.ALPHA.-OLEFINS AND OLEFIN POLYMERS AND PROCESSES THEREFOR

POLYMERES D'OLEFINES ET DE .ALPHA.-OLEFINES ET PROCEDES DE POLYMERISATION

English Abstract

Disclosed herein are processes for polymerizing ethylene, acyclic olefins,
and/or selected cyclic olefins, and optionally selected olefinic
esters or carboxylic acids, and other monomers. The polymerizations ate
catalysed by selected transition metal compounds, and sometimes
other co-catalysts. Since some of the polymerizations exhibit some
characteristics of living polymerizations, block copolymers can be
readily made. Many of the polymers produced are often novel, particularly in
regard to their microstructure, which gives some of them
unusual properties. Numerous novel catalysts are disclosed, as well as some
novel processes for making them. The polymers made are
useful as elastomers, molding resins, in adhesives, etc. Also described herein
is the synthesis of linear .alpha.-olefins by the oligomerization
of ethylene using as a catalyst system a combination of a nickel compound
having a selected .alpha.-diimine ligand and a selected Lewis or
Bronsted acid, or by contacting selected S(a)-diimine nickel complexes with
ethylene.

Claims

What is claimed is:
1. A polyolefin, which contains about 80 to about
150 branches per 1000 methylene groups, and which
contains for every 100 branches that are methyl, about
30 to about 90 ethyl branches, about 4 to about 20
propyl branches, about 15 to about 50 butyl branches,
about 3 to about 15 amyl branches, and about 30 to
about 140 hexyl or longer branches.
2. The polyolefin as recited in claim 1 which
contains about 100 to about 130 branches per 1000
methylene groups, and which contains for every 100
branches that are methyl, about 50 to about 75 ethyl
branches, about 5 to about 15 propyl branches, about 24
to about 40 butyl branches, about 5 to about 10 amyl
branches, and about 65 to about 120 hexyl or longer
branches.
3. The polyolefin as recited in claim 1 which is
an ethylene homopolymer.
4. A polyolefin which contains about 20 to about
150 branches per 1000 methylene groups, and which
contains for every 100 branches that are methyl, about
4 to about 20 ethyl branches, about 1 to about 12
propyl branches, about 1 to about 12 butyl branches,
about 1 to about 10 amyl branches, and 0 to about 20
hexyl or longer branches.
5. The polyolefin as recited in claim 4 which
contains about 40 to about 100 branches per 1000
methylene groups, and which contains for every 100
branches that are methyl, about 6 to about 15 ethyl
branches, about 2 to about 10 propyl branches, about 2
to about 10 butyl branches, about 2 to about 8 amyl
branches, and about 2 to about 15 hexyl or longer
branches.
6. The polyolefin as recited in claim 4 which is
an ethylene homopolymer.
7. A polymer, consisting essentially of units
derived from the monomers ethylene and a compound of
the formula CH2=CH(CH2)m CO2R1, wherein R1 is hydrogen,
408

hydrocarbyl or substituted hydrocarbyl, and is 0 or
an integer from 1 to 16, and which contains about 0.01
to about 40 mole percent of repeat units derived from
said compound, and provided that said repeat units
derived from said compound are in branches of the
formula -CH(CH2)n CO2R1, in about 30 to about 70 mole
percent of said branches n is 5 or more, in about 0 to
about 20 mole percent n is 4, in about 3 to 60 mole
percent n is 1, 2 and 3, and in about 1 to about 60
mole percent n is 0.
8. The polymer as recited in claim 7 wherein m is
0.
9. The polymer as recited in claim 7 wherein R1 is
hydrocarbyl or substituted hydrocarbyl.
10. The polymer as recited in claim 7 wherein R1
is alkyl containing 1 to 10 carbon atoms.
11. The polymer as recited in claim 8 wherein R1
is hydrocarbyl or substituted hydrocarbyl.
12. The polymer as recited in claim 7 wherein
about 0.1 to about 20 mole percent of said units are
derived from said compound.
13. A process for the polymerization of olefins,
comprising, contacting a transition metal complex of a
bidentate ligand selected from the group consisting of
<IMG>
409

<IMGS>
with an olefin wherein:
said olefin is selected from the group
consisting of ethylene, an olefin of the formula
R17CH=CH2 or R17CH=CHR17, cyclobutene, cyclopentene,
norbornene, or a substituted norbornene,;
said transition metal is selected from the
group consisting of Ti, Zr, Sc, V, Cr, a rare earth
metal, Fe, Co, Ni or Pd;
R2 and R5 are each independently hydrocarbyl or
substituted hydrocarbyl, provided that the carbon atom
bound to the imino nitrogen atom has at least two
carbon atoms bound to it;
R3 and R4 are each independently hydrogen,
hydrocarbyl, substituted hydrocarbyl, or R3 and R4
taken together are hydrocarbylene or substituted
hydrocarbylene to form a carbocyclic ring;
R44 is hydrocarbyl or substituted hydrocarbyl,
and R28 is hydrogen, hydrocarbyl or substituted
hydrocarbyl or R44 and R28 taken together form a ring;
410

R45 is hydrocarbyl or substituted hydrocarbyl,
and R29 is hydrogen, substituted hydrocarbyl or
hydrocarbyl, or R45 and R29 taken together form a ring;
each R30 is independently hydrogen, substituted
hydrocarbyl or hydrocarbyl, or two of R30 taken
together form a ring;
R46 and R47 are each independently hydrocarbyl or
substituted hydrocarbyl, provided that the carbon atom
bound to the imino nitrogen atom has at least two
carbon atoms bound to it;
R48 and R49 are each independently hydrogen,
hydrocarbyl, or substituted hydrocarbyl;
R31 is independently hydrogen, hydrocarbyl or
substituted hydrocarbyl;
R20 and R23 are independently hydrocarbyl or
substituted hydrocarbyl;
R21 and R23 are each in independently hydrogen,
hydrocarbyl or substituted hydrocarbyl;
each R17 is independently hydrocarbyl or
substituted hydrocarbyl provided that any olefinic bond
in said olefin is separated from any other olefinic
bond or aromatic ring by a quaternary carbon atom or at
least two saturated carbon atoms;
R1 is hydrogen, hydrocarbyl or substituted
hydrocarbyl;
n is 2 or 3;
and provided that:
when said bidentate ligand is (XXX) M is not
Pd;
when M is Pd a diene is not present; and
said transition metal also has bonded to it a
ligand that may be displaced by said olefin or add to
said olefin;
when norbornene or substituted norbornene is
used no other olefin is present.
14. The process as recited in claim 13 wherein
said transition metal is Co, Fe, Ni or Pd.
'
411

15. The process as recited in claim 13 wherein
said transition metal is Ni or Pd.
16. The process as recited in claim 13 wherein
said olefin is ethylene, R17CH=CH2, or cyclopentene,
wherein R17 is n-alkyl.
17. The process as recited in claim 13 wherein
said olefin comprises cyclopentene.
18. The process as recited in claim 13, 14, 15, or
16 wherein said bidentate ligand is (VIII).

19. The process as recited in claim 18 wherein
said olefin is ethylene.
20. The process as recited is in claim 18 wherein
said olefin is propylene.
21. The process as recited in claim 18 wherein
said olefin. is a combination of ethylene and propylene.
22. The process as recited in claim 18 wherein
said olefin is contained in a mixed butenes stream.
23. The process as recited in claim 18 wherein R2
and R5 are each independently hydrocarbyl provided that
the carbon atom-bound to the imino nitrogen atom has at
least two carbon atoms bound to it; R3 and R4 are each
independently hydrogen, hydrocarbyl, or R3 and R4 taken
together are hydrocarbylene to form a carbocyclic ring.
24. The process as recited in claim 18 wherein. R3
and R4 are each independently hydrogen or methyl or
together are 1,8-naphthylylene, and both R2 and R5 are
2,6-diisopropylphenyl.
25. The process as recited in claim 18 wherein
said olefin comprises cyclopentene.
26. A process for the copolymerization of an
olefin and a fluorinated olefin, comprising, contacting
a transition metal complex of a bidentate ligand
selected from the group consisting of
<IMG>
with an olefin, and a fluorinated olefin wherein:
said olefin is selected from the group
consisting of ethylene and an olefin of the formula
R17CH=CH2 or R17CH=CHR17;
said transition metal is selected from the
group consisting of Ni and Pd;
412

said fluorinated olefin is of the formula
H2C=CH(CH2)a R f R42
a is an integer of 2 to 20; R f is
perfluoroalkylene optionally containing one or more
ether groups;
R42 is fluorine or a functional group;
R2 and R5 are each independently hydrocarbyl or
substituted hydrocarbyl, provided that the carbon atom
bound to the imino nitrogen atom has at least two
carbon atoms bound to it;
R3 and R4 are each independently hydrogen,
hydrocarbyl, substituted hydrocarbyl, or R3 and R4
taken together are hydrocarbylene or substituted
hydrocarbylene to form a carbocyclic ring;
each R17 is independently saturated
hydrocarbyl;
and provided that said transition metal also has
bonded to it a ligand that may be displaced by said
olefin or added to said olefin.
27. The process as recited in claim 26 wherein R42
is fluorine, ester or sulfonyl halide.
28. The process as recited in claim 26 wherein R f
is -(CF2)b-, wherein b is 2 to 20, or -(CF2)d OCF2CF2-
wherein d is 2 to 20.
29. The process as recited in claim 26 or 27
wherein said olefin is ethylene or wherein said olefin
is R17CH=CH2, wherein R17 is n-alkyl.
30. The process as recited in claim 26 wherein R2
and R5 are each independently hydrocarbyl, provided
that the carbon atom bound to the imino nitrogen atom
has at least two carbon atoms bound to it; and R3 and
R4 are each independently hydrogen, hydrocarbyl, or R3
and R4 taken together are hydrocarbylene to form a
carbocyclic ring.
31. A copolymer of an olefin of the formula
R17CH=CHR17 and a fluorinated olefin of the formula
H2C=CH(CH2)a R f R42, wherein:
413

each R17 is independently hydrogen or saturated
hydrocarbyl;
a is an integer of 2 to 20; R f is
perfluoroalkylene optionally containing one or more
ether groups; and
R42 is fluorine or a functional group;
provided that when both of R17 are hydrogen and R42
is fluorine, R f is -(CF2)b- wherein b is 2 to 20 or
perfluoroalkylene containing at least one ether group.
32. The copolymer as recited in claim 31 wherein
R42 is fluorine, ester, sulfonic acid, or sulfonyl
halide.
33. The copolymer as recited in claim 31 wherein
R f is -(CF2)b-, wherein b is 2 to 20, or -(CF2)d OCF2CF2-
wherein d is 2 to 20.
34. The copolymer as recited in claim 31 or 32
wherein said olefin is ethylene or wherein said olefin
is R17CH=CH2, wherein R17 is n-alkyl.
35. The copolymer as recited in claim 31 wherein
said fluorinated olefin is about 1 to 20 mole percent
of repeat units in said copolymer.
36. An acid catalyst of the composition of claim
31, wherein R42 is sulfonic acid.
37. A process for the polymerization of olefins,
comprising, contacting, at a temperature of about
-100°C to about +200°C:
a first compound W, which is a neutral Lewis
acid capable of abstracting either Q- or S- to form WQ-
or WS-, provided that the anion formed is a weakly
coordinating anion; or a cationic Lewis or Bronsted
acid whose counterion is a weakly coordinating anion;
a second compound of the formula
414

<IMG>
and one or more monomers selected from the
group consisting of ethylene, an olefin of the formula
R17CH=CH2 or R17CH=CHR17, cyclobutene, cyclopentene,
substituted norbornene, or norbornene;
wherein:
M is Ti, Zr, Sc, V, Cr, a rare earth metal, Fe,
Co, Ni or Pd in the m oxidation state;
y + z = m
R2 and R5 are each independently hydrocarbyl or
substituted hydrocarbyl, provided that the carbon atom
bound to the imino nitrogen atom has at least two
carbon atoms bound to it;
R3 and R4 are each independently hydrogen,
hydrocarbyl, substituted hydrocarbyl, or R3 and R4
taken together are hydrocarbylene or substituted
hydrocarbylene to form a carbocyclic ring;
each R17 is independently hydrocarbyl or
substituted hydrocarbyl provided that any olefinic bond
in said olefin is separated from any other olefinic
bond or aromatic ring by a quaternary carbon atom or at
least two saturated carbon atoms;
Q is alkyl, hydride, chloride, iodide, or
bromide;
S is alkyl, hydride, chloride, iodide, or
bromide; and
provided that;
when norbornene or substituted norbornene is
present, no other monomer is present;
when M is Pd a diene is not present; and
415

except when M is Pd, when both Q and S are each
independently chloride, bromide or iodide W is capable
of transferring a hydride or alkyl group to M.
38. The process as recited in claim 37 wherein
said monomer is ethylene only.
39. The process as recited in claim 37 wherein
said monomer is an .alpha.-olefin only.
40. The process as recited in claim 39 wherein
said a-olefin is propylene.
41. The process as recited in claim 37 done in the
presence of a solvent.
42. The process as recited in claim 41 wherein R3
and R4 are each independently hydrogen or methyl, or R3
and R4 taken together are 1,8-naphthylylene, and both
R2 and R5 are 2,6-diisopropylphenyl.
43. The process as recited in claim 37 used to
make a block polymer.
44. The process as recited in claim 37 wherein:
M is Ti(IV), Q and S are chloride, and y and z are
2;
M is Zr(IV), Q and S are chloride, and y and z are
2;
M is Co(II), Q and S are bromide, and y and z are
1;
M is Fe(II), Q and S are chloride, and y and z are
1;
M is Sc(III), Q and S are chloride, y is 1 and z
is 2;
M is Ni(II), Q and S are bromide or chloride, and
y and z are 1;
M is Pd(II), Q and S are methyl, and y and z are
1;
M is Pd(II), Q and S are chloride,.and y and z are
1;
M is Ni(I), Q is methyl, chloride, bromide, iodide
or acetylacetonate, y is 1, and z is 0;
M is Pd(II), Q is methyl and S is chloride, and y
and z are 1; or
416

M is Ni(II), Q and S are methyl, and y and z are
1.
45. The process as recited in claim 37 wherein
ethylene and propylene are the monomers.
46. The process as recited in claim 37 wherein
said monomers are part of a crude butenes stream.
47. The process as recited in claim 37 wherein R2
and R5 are each independently hydrocarbyl, provided
that the carbon atom bound to the imino nitrogen atom
has at least two carbon atoms bound to it; R3 and R4
are each independently hydrogen, hydrocarbyl, or R3 and
R4 taken together are hydrocarbylene to form a
carbocyclic ring.
48. The process as recited in claim 37 wherein
said monomer comprises cyclopentene.
49. A process for the production of polyolefins,
comprising, contacting, at a temperature of about -
100°C to about +200°C, one or more monomers selected
from the group consisting of ethylene, an olefin of the
formula R17CH=CH2 or R17CH=CHR17, cyclobutene,
cyclopentene, substituted norbornene, and norbornene;
and a compound of the formula
<IMGS>
or
417

<IMG>
wherein:
R2 and R5 are each independently hydrocarbyl or
substituted hydrocarbyl, provided that the carbon atom
bound to the imino nitrogen atom has at least two
carbon atoms bound to it;
R3 and R4 are each independently hydrogen,
hydrocarbyl, substituted hydrocarbyl, or R3 and R4
taken together are hydrocarbylene or substituted
hydrocarbylene to form a carbocyclic ring;
T1 is hydrogen, hydrocarbyl not containing
olefinic or acetylenic bonds, R15C(=O)- or R15OC(=O)-;
Z is a neutral Lewis base wherein the donating
atom is nitrogen, sulfur or oxygen, provided that if
the donating atom is nitrogen then the pKa of the
conjugate acid of that compound is less than about 6;
X is a weakly coordinating anion;
R15 is hydrocarbyl not containing olefinic or
acetylenic bonds;
each R17 is independently hydrocarbyl or
substituted hydrocarbyl provided that any olefinic bond
in said olefin is separated from any other olefinic
bond or aromatic ring by a quaternary carbon atom or at
least two saturated carbon atoms;
M is Ni(II) or Pd(II);
each R16 is independently hydrogen or alkyl
containing 1 to l0 carbon atoms;
n is 1, 2, or 3;
R8 is hydrocarbyl; and
T2 is hydrogen, hydrocarbyl not containing
olefinic or acetylenic bonds, hydrocarbyl substituted
418

with keto O~ ester groups but not containing olefinic
or acetylenic bonds, R15C(=O)- or R15OC(=O)-;
provided that:
when M is Pd, or (II) or (VII) are present, a
diene is not present; and
when norbornene or substituted norbornene is
used no other monomer is present.
50. The process as recited in claim 49 wherein
said monomer is ethylene only.
51. The process as recited in claim 49 wherein
said monomer is an .alpha.-olefin only.
52. The process as recited in claim 51 wherein
said .alpha.-olefin is propylene.
53. The process as recited in claim 49 wherein
said compound is (II), (IV) or (VII), M is Pd(II), and
a comonomer selected from the group consisting of: a
compound of the formula CH2=CH (CH2)m CO2R1, wherein R1 is
hydrogen or, hydrocarbyl or substituted hydrocarbyl
containing 1 to 10 carbon atoms, and m is 0 or an
integer of 1 to 16; CO; and a vinyl ketone, is also
present.
54. The process as recited in claim 53 wherein m
is 0, and R1 is hydrocarbyl or substituted hydrocarbyl.
55. The process as recited in claim 49 done in the
presence of a solvent.
56. The process as recited in claim 49 done in the
absence of a solvent.
57. The process as recited in claim 49 wherein R3
and R4 are each independently hydrogen or methyl, or R3
and R4 taken together are 1,8-naphthylylene, and both
R2 and R5 are 2,6-diisopropylphenyl.
58. The process as recited in claim 49 used to
make a block polymer.
59. The process as recited in claim 49 wherein X
is BAF, SbF6, PF6, or BF4.
60. The process as recited in claim 57 wherein X
is BAF, SbF6, PF6, or BF4.
419

61. The process as recited in claim 60 wherein a
monomer is ethylene or propylene.
62. The process as recited in claim 49 wherein the
monomers are ethylene and propylene.
63. The process as recited in claim 49 wherein
said monomers are part of a crude butenes stream.
64. The process as recited in claim 49 wherein R2
and R5 are each independently hydrocarbyl, provided
that the carbon atom bound to the imino nitrogen atom
has at least two carbon atoms bound to it; R3 and R4
are each independently hydrogen, hydrocarbyl, or R3 and
R4 taken together are hydrocarbylene to form a
carbocyclic ring.
65. A process for the production of polyolefins,
comprising contacting, at a temperature of about -100°C
to about +200°C, one or more monomers selected from the
group consisting of ethylene, an olefin of the formula
R17CH=CH2 or R17CH=CHR17, cyclobutene, cyclopentene,
substituted norbornene, and norbornene; with a compound
of the formula
420

<IMGS>
wherein:
R44 is hydrocarbyl or substituted hydrocarbyl,
and R28 is hydrogen, hydrocarbyl or substituted
hydrocarbyl or R44 and R28 taken together form a ring;
R45 is hydrocarbyl or substituted hydrocarbyl,
and R29 is hydrogen, substituted hydrocarbyl or
hydrocarbyl, or R45 and R29 taken together form a ring;
each R30 is independently hydrogen, substituted
hydrocarbyl or hydrocarbyl or two of R30 taken together
form a ring;R20 and R23 are independently hydrocarbyl or
substituted hydrocarbyl;
R21 and R22 are each in independently hydrogen,
hydrocarbyl or substituted hydrocarbyl;
n is 2 or 3;
T1 is hydrogen, hydrocarbyl not containing
olefinic or acetylenic bonds, R15C(=O)- or R15OC(=O)-;
M is Ti, Zr, Sc, Cr, a rare earth metal, V, Fe,
Co, Ni or Pd the m oxidation state;
for (XVII), y + z = m;
421

for (XIII), n is 2;
Q is alkyl, hydride, chloride, iodide, or
bromide;
S is alkyl, hydride, chloride, iodide, or
bromide;
T2 is hydrogen, hydrocarbyl not containing
olefinic or acetylenic bonds, hydrocarbyl substituted
with keto or ester groups but not containing olefinic
or acetylenic bonds, R15C (=O) - or R15OC (=O) - ;
Z is a neutral Lewis base wherein the donating
atom is nitrogen, sulfur or oxygen, provided that if
the donating atom is nitrogen then the pKa of the
conjugate acid of that compound is less than about 6;
and
X is a weakly coordinating anion; and
provided that:
when said compound is (XVII) M is not Pd; and
except when M is Pd, when both Q and S are each
independently chloride, bromide or iodide W is capable
of transferring a hydride or alkyl group to M.
66. The process as recited in claim 65 wherein
said monomer is ethylene only.
67. The process as recited in claim 65 wherein
said monomer is an .alpha.-olefin only.
68. The process as recited in claim 67 wherein
said .alpha.-olefin is propylene.
69. The process as recited in claim 66 wherein M
is Pd(II) and one or more comonomer is selected from
the group consisting of: a compound of the formula
CH2=CH (CH2) m CO2R1, wherein R1 is hydrogen or, hydrocarbyl
or substituted hydrocarbyl containing 1 to 10 carbon
atoms, and m is 0 or an integer of 1 to 16; CO; and a
vinyl ketone is also present.
70. The process as recited in claim 69 wherein m
is 0, and R1 is hydrocarbyl or substituted hydrocarbyl.
71. The process as recited in claim 65 done in the
presence of a solvent.
422

72. The process as recited in claim ~ done in the
absence of a solvent.
73. The process as recited in claim 65 used to
make a block polymer.
74. The process as recited in claim 65 wherein X
is BAF , SbF6 , PF6 , or BF4.
75. The process as recited in claim 74 wherein a
monomer is ethylene or propylene.
76. The process as recited in claim 75 wherein the
monomers are ethylene and propylene.
77. The process as recited in claim 65 wherein
said monomers are part of a crude butenes stream.
78. The process as recited in claim 65 wherein:
R49 is hydrocarbyl, and R28 is hydrogen or
hydrocarbyl, or R44 and R28 taken together form a ring;
R45 is hydrocarbyl, and R29 is hydrogen or
hydrocarbyl, or R45 and R29 taken together form a ring;
each R30 is independently hydrogen or
hydrocarbyl, or two of R30 taken together form a ring;
R21 and R22 are each in independently hydrogen
or hydrocarbyl; and
R20 and R23 are independently hydrocarbyl.
79. A process for the production of polyolefins,
comprising contacting, at a temperature of about -100°C
to about +200°C, one or more monomers selected from the
group consisting of ethylene, an olefin of the formula
R17CH=CH2 or R17CH=CHR17, cyclobutene, cyclopentene,
substituted norbornene, and norbornene; with a compound
of the formula
<IMG>
423

wherein:
R20 and R23 are independently hydrocarbyl or
substituted hydrocarbyl;
R21 and R22 are each in independently hydrogen,
hydrocarbyl or substituted hydrocarbyl;
X is a weakly coordinating anion;
each R17 is independently hydrocarbyl or
substituted hydrocarbyl provided that any olefinic bond
in said olefin is separated from any other olefinic
bond or aromatic ring by a quaternary carbon atom or at
least two saturated carbon atoms;
M is Ni (II) or Pd(II) ;
T2 is hydrogen, hydrocarbyl not containing
olefinic or acetylenic bonds, hydrocarbyl substituted
with keto or ester groups but not containing olefinic
or acetylenic bonds, R15C(=O)- or R15OC(=O)-;
and provided that:
when M is Pd a diene is not present; and
when norbornene or substituted norbornene is
used no other monomer is present.
80. The process as recited in claim 79 wherein
said monomer is ethylene only.
81. The process as recited in claim 79 wherein
said monomer is an .alpha.-olefin only.
82. The process as recited in claim 81 wherein
said .alpha.-olefin is propylene.
83. The process as recited in claim 79 wherein T2
is methyl; R20 and R23 are independently hydrocarbyl;
and R21 and R22 are each in independently hydrogen or
hydrocarbyl.
84. A process for the production for polyolefins,
comprising contacting, at a temperature of about -100°C
to about +200°C,
a first compound W, which is a neutral Lewis
acid capable of abstracting either Q- or S- to form WQ-
or WS-, provided that the anion formed is a weakly
coordinating anion; or a cationic Lewis or Bronsted
acid whose counterion is a weakly coordinating anion;
424

a second compound of the formula
<IMG>
and one or more monomers selected from the
group consisting of ethylene, an olefin of the formula
R17CH=CH2 or R17CH=CHR17, cyclobutene, cyclopentene,
substituted norbornene, or norbornene;
wherein:
M is Ti, Zr, V, Cr, a rare earth metal, Co, Fe,
Sc, or Ni, of oxidation state m;
R44 is hydrocarbyl or substituted hydrocarbyl,
and R28 is hydrogen, substituted hydrocarbyl or
hydrocarbyl, or R44 and R28 taken together form a ring;
R45 is hydrocarbyl or substituted hydrocarbyl,
and R29 is hydrogen, substituted hydrocarbyl or
hydrocarbyl, or R45 and R29 taken together form a ring;
each R30 is independently hydrogen, substituted
hydrocarbyl or hydrocarbyl, or two of R30 taken
together form a ring;
n is 2 or 3;
y and z are positive integers;
y+z = m;
each R17 is independently hydrocarbyl or
substituted hydrocarbyl provided that any olefinic bond
in said olefin is separated from any other olefinic
bond or aromatic ring by a quaternary carbon atom or at
least two saturated carbon atoms;
Q is alkyl, hydride, chloride, iodide, or
bromide;
S is alkyl, hydride, chloride, iodide, or
bromide; and
425

provided that;
when norbornene or substituted norbornene is
present, no other monomer is present.
85. The process as recited in claim 84 wherein
R28, R29, and each of R30 are hydrogen.
86. The process as recited in claim 84 wherein
said monomer is ethylene only.
87. The process as recited in claim 84 wherein
said monomer is an .alpha.-olefin only.
88. The process as recited in claim 87 wherein
said .alpha.-olefin is propylene.
89. The process as recited in claim 84 done in the
presence of a solvent.
90. The process as recited in claim 84 wherein
both R44 and R45 are 2,4,6-trimethylphenyl.
91. The process as recited in claim 84 used to
make a block polymer.
92. The process as recited in claim 90 wherein a
monomer is ethylene or propylene.
93. The process as recited in claim 84 wherein:
M is Ti(IV), Q and S are chloride, and y and z are
2;
M is Zr(IV), Q and S are chloride, and y and z are
2;
M is Co(II), Q and S are bromide, and y and z are
1;
M is Fe(II), Q and S are chloride, and y and z are
1;
M is Sc(III), Q and S are chloride, y is 1 and z
is 2; ~
M is Ni(II), Q and S are bromide or chloride, and
y and z are 1;
M is Pd(II), Q and S are chloride, and y and z are
1;
M is Pd(II), Q and S are methyl, and y and z are
1;
M is Ni(I), Q is methyl, chloride, bromide, iodide
or acetylacetonate, y is 1, and z is 0;
426

M is Pd (II), Q is methyl and S is chloride, and y
and z are 1; or
M is Ni(II), Q and S are methyl, and y and z are
1.
94. The process as recited in claim 84 wherein
ethylene and propylene are the monomers.
95. The process as recited in claim 84 wherein
said monomers are part of a crude butenes stream.
96. The process as recited in claim 84 wherein:
R44 is hydrocarbyl, and R28 is hydrogen or
hydrocarbyl, or R44 and R28 taken together form a ring;
R45 is hydrocarbyl, and R29 is hydrogen or
hydrocarbyl, or R45 and R29 taken together form a ring;
and
each R30 is independently hydrogen or
hydrocarbyl, or two of R30 taken together form a ring.
97. A process for the production of polyolefins,
comprising, contacting, at a temperature of about -
100°C to about +200°C, one or more monomers selected
from the group consisting of ethylene, an olefin of the
formula R17CH=CH2 or R17CH=CHR17, cyclobutene,
cyclopentene, substituted norbornene, and norbornene;
optionally a source of X-, and a compound of the
formula
<IMG>
wherein:
R2 and R5 are each independently hydrocarbyl or
substituted hydrocarbyl, provided that the carbon atom
bound directly to the imino nitrogen atom has at least
two carbon atoms bound to it;
R3 and R4 are each independently hydrogen,
hydrocarbyl, substituted hydrocarbyl, or R3 and R4
427

taken together are hydrocarbylene or substituted
hydrocarbylene to form a carbocyclic ring;
each R17 is independently hydrocarbyl or
substituted hydrocarbyl provided thatR17 contains no
olefinic bonds;
T1 is hydrogen, hydrocarbyl not containing
olefinic or acetylenic bonds, R15C (=O) - or R15OC (=O) -;
R15 is hydrocarbyl not containing olefinic or
acetylenic bonds;
E is halogen or -OR18;
R18 is hydrocarbyl not containing olefinic or
acetylenic bonds; and
X is a weakly coordinating anion;
provided that when norbornene or substituted
norbornene is present no other monomer is present.
98. The process as recited in claim 97 wherein
said monomer is ethylene only.
99. The process as recited in claim 97 wherein
said monomer is an .alpha.-olefin only.
100. The process as recited in claim 99 wherein
said .alpha.-olefin is propylene.
101. The process as recited in claim 97 wherein E
is chlorine.
102. The process as recited in claim 97 wherein
T1 is alkyl.
103. The process as recited in claim 97 done in
the presence of a solvent.
104. The process as recited in claim 98 wherein E
is chlorine and T1 is alkyl.
105. The process as recited in claim 104 wherein
R3 and R4 are each independently hydrogen or methyl or
R3 and R4 taken together are 1,8-naphthylylene, both R2
and R5 are 2,6-diisopropylphenyl, and T1 is methyl.
106. The process as recited in claim 97 used to
make a block polymer.
107. The process as recited in claim 105 wherein
X is BAF, SbF6, PF6, or BF4.
428

108. The process as recited in claim 107 wherein a
monomer is ethylene or propylene.
109. The process as recited in claim 97 wherein
the monomers are ethylene and propylene.
110. The process as recited in claim 97 wherein
said monomers are part of a crude butenes stream.
111. The process as recited in claim 97 wherein R2
and R5 are each independently hydrocarbyl or
substituted hydrocarbyl, provided that the carbon atom
bound directly to the imino nitrogen atom has at least
two carbon atoms bound to it; and R3 and R4 are each
independently hydrogen, hydrocarbyl, substituted
hydrocarbyl, or R3 and R4 taken together are
hydrocarbylene or substituted hydrocarbylene to form a
carbocyclic ring.
112. A process for the polymerization of olefins,
comprising, contacting, at a temperature of about -
100°C to about +200°C:
a first compound W, which is a neutral Lewis
acid capable of abstracting either Q- or S- to form WQ-
or WS-, provided that the anion formed is a weakly
coordinating anion; or a cationic Lewis or Bronsted
acid whose counterion is a weakly coordinating anion;
a second compound of the formula
<IMG>
and one or more monomers selected from the
group consisting of ethylene, an olefin of the formula
R17CH=CH2 or R17CH=CHR17, 4-vinylcyclohexene,
cyclobutene, cyclopentene, substituted norbornene, and
norbornene;
wherein:
429

M is Ni(II), Co(II), Fe(II) or Pd(II);
R2 and R5 are each independently hydrocarbyl or
substituted hydrocarbyl, provided that the carbon atom
bound to the imino nitrogen atom has at least two
carbon atoms bound to it;
R3 and R4 are each independently hydrogen,
hydrocarbyl, substituted hydrocarbyl, or R3 and R4
taken together are hydrocarbylene or substituted
hydrocarbylene to form a carbocyclic ring;
each R17 is independently hydrocarbyl or
substituted hydrocarbyl provided that any olefinic bond
in said olefin is separated from any other olefinic
bond or aromatic ring by a quaternary carbon atom or at
least two saturated carbon atoms;
Q is alkyl, hydride, chloride, iodide, or
bromide;
S is alkyl, hydride, chloride, iodide, or
bromide; and
provided that:
when norbornene or substituted norbornene is
present, no other monomer is present, and further
provided that when 4-vinylcyclohexene is present M is
Ni;
when M is Pd a diene is not present; and
except when M is Pd, when both Q and S are each
independently chloride, bromide or iodide W is capable
of transferring a hydride or alkyl group to M.
113. The process as recited in claim 112 wherein
said monomer is ethylene only.
114. The process as recited in claim 112 wherein
said monomer is an .alpha.-olefin only.
115. The process as recited in claim 114 wherein
said .alpha.-olefin is propylene.
116. The process as recited in claim 112 done in
the presence of a solvent.
117. The process as recited in claim 112 wherein
R3 and R4 are each independently hydrogen or methyl or
430

both of R3 and R4 taken together are 1,8-naphthylylene,
and both R2 and R5 are 2,6-diisopropylphenyl.
118. The process as recited in claim 112 used to
make a block polymer.
119. The process as recited in claim 112 wherein a
monomer is ethylene or propylene.
120. The process as recited in claim 112 wherein
the molar ratio of said first compound: said second
compound (I) is about 5 to about 1000.
121. The process as recited in claim 112 wherein
the molar ratio of said first compound: said second
compound (I) is about 10 to about 100.
122. The process as recited in claim 112 wherein
said first compound is R9AlCl2, R9 2AlCl, R9 3Al2Cl3, or an
alkylaluminoxane in which the alkyl group has 1 to 4
carbon atoms, and wherein R9 is alkyl containing 1 to 4
carbon atoms.
123. The process as recited in claim 120 wherein
said first compound is R9AlCl2, R9 2AlCl, R9 3Al2Cl3, or an
alkylaluminoxane in which the alkyl group has 1 to 4
carbon atoms, and wherein R9 is alkyl containing 1 to 4
carbon atoms.
124. The process as recited in claim 112 wherein
the monomer comprises cyclopentene.
125. The process as recited in claim 112 wherein
said monomers are part of a crude butenes stream.
126. The process as recited in claim 112 wherein
R2 and R5 are each independently hydrocarbyl, provided
that the carbon atom bound to the imino nitrogen atom
has at least two carbon atoms bound to it; and R3 and
R4 are each independently hydrogen, hydrocarbyl, or R3
and R4 taken together are hydrocarbylene to form a
carbocyclic ring.
127. A polymerization process, comprising,
contacting a compound of the formula [Pd(R13CN)4]X2, or
a combination of Pd[OC(O)R40]2 and HX, with a compound
of the formula
431

<IMG>
and one or more monomers selected from the group
consisting of ethylene, an olefin of the formula
R17CH=CH2 or R17CH=CHR17, cyclopentene, cyclobutene,
substituted norbornene, and norbornene, wherein:
R2 and R5 are each independently hydrocarbyl or
substituted hydrocarbyl, provided that the carbon atom
bound to the imino nitrogen atom has at least two
carbon atoms bound to it;
R3 and R4 are each independently hydrogen,
hydrocarbyl, substituted hydrocarbyl, or R3 and R4
taken together are hydrocarbylene or substituted
hydrocarbylene to form a carbocyclic ring;
each R17 is independently hydrocarbyl or
substituted hydrocarbyl providedR17 contains no
olefinic bonds;
R13 is hydrocarbyl;
R40 is hydrocarbyl or substituted hydrocarbyl;
and
X is a weakly coordinating anion;
provided that when norbornene or substituted
norbornene, is present no other monomer is present.
128. The process as recited in claim 127 wherein
said monomer is ethylene only.
129. The process as recited in claim 127 wherein
said monomer is an .alpha.-olefin only.
130. The process as recited in claim 129 wherein
said a-olefin is propylene.
131. The process as recited in claim 127 wherein
one or more comonomer selected from the group
consisting of: a compound of the formula
432

CH2=CH(CH2)m CO2R1, wherein R1 is hydrogen or, hydrocarbyl
or substituted hydrocarbyl containing 1 to 10 carbon
atoms, and m is 0 or an integer of 1 to 16; CO; and a
vinyl ketone is also present.
132. The process as recited in claim 131 wherein m
is 0, and R1 is hydrocarbyl or substituted hydrocarbyl.
133. The process as recited in claim 127 done in
the presence of a solvent.
134. The process as recited in claim 127 wherein
R3 and R4 are each independently hydrogen or methyl or
both R3 and R4 taken together are 1,8-naphthylylene,
and both R2 and R5 are 2,6-diisopropylphenyl.
135. The process as recited in claim 127 used to
make a block polymer.
136. The process as recited in claim 127 wherein X
is BAF, SbF6, PF6, or BF4.
137. The process as recited in claim 134 wherein
X i s BAF or BF4.
138. The process as recited in claim 137 wherein a
monomer is ethylene or propylene.
139. The process as recited in claim 127 wherein
the monomers are ethylene and propylene.
140. The process as recited in claim 127 wherein
said monomers are part of a crude butenes stream.
141. The process as recited in claim 127 wherein
R2 and R5 are each independently hydrocarbyl, provided
that the carbon atom bound to the imino nitrogen atom
has at least two carbon atoms bound to it; and R3 and
R4 are each independently hydrogen, hydrocarbyl, or R3
and R4 taken together are hydrocarbylene to form a
carbocyclic ring.
142. A polymerization process, comprising,
contacting:
a Ni[0], Pd[0] or Ni[I] compound containing a
ligand which may be displaced by a ligand of the
formula (VIII), (XXX), (XXXII) or (XXIII);
a second compound of the formula
433

<IMGS>
an oxidizing agent;
a source of a relatively weakly coordinating
anion;
434

and one or more monomers selected from the
group consisting of ethylene, an olefin of the formula
R17CH=CH2 or R17CH=CHR17, cyclopentene, cyclobutene,
substituted norbornene, and norbornene;
wherein:
R2 and R5 are each independently hydrocarbyl or
substituted hydrocarbyl, provided that the carbon atom
bound to the imino nitrogen atom has at least two
carbon atoms bound to it;
R3 and R4 are each independently hydrogen,
hydrocarbyl, substituted hydrocarbyl or R3 and R4 taken
together are hydrocarbylene or substituted
hydrocarbylene to form a ring;
each R17 is independently hydrocarbyl or
substituted hydrocarbyl provided that any olefinic bond
in said olefin is separated from any other olefinic
bond or aromatic ring by a quaternary carbon atom or at
least two saturated carbon atoms;
each R31 is independently hydrogen, hydrocarbyl
or substituted hydrocarbyl;
R44 is hydrocarbyl or substituted hydrocarbyl,
and R28 is hydrogen, hydrocarbyl or substituted
hydrocarbyl or R44 and R28 taken together form a ring;
R45 is hydrocarbyl or substituted hydrocarbyl,
and R29 is hydrogen, substituted hydrocarbyl or
hydrocarbyl, or R45 and R29 taken together form a ring;
each R30 is independently hydrogen, substituted
hydrocarbyl or hydrocarbyl, or two of R30 taken
together form a ring;
R46 and R47 are each independently hydrocarbyl
or substituted hydrocarbyl, provided that the carbon
atom bound to the imino nitrogen atom has at least two
carbon atoms bound to it;
n is 2 or 3;
R48 and R49 are each independently hydrogen,
hydrocarbyl, or substituted hydrocarbyl;
R20 and R23 are independently hydrocarbyl or
substituted hydrocarbyl;
435

R21 and R22 are each in independently hydrogen,
hydrocarbyl or substituted hydrocarbyl; and
provided that;
when norbornene or substituted norbornene is
present, no other monomer is present;
when a Pd[0] compound is used, a diene is not
present; and
when said second compound is (XXX) only an Ni[0]
or Ni[I] compound is used.
143. The process as recited in claim 142 wherein
said monomer is ethylene only.
144. The process as recited in claim 142 wherein
said monomer is an .alpha.-olefin only.
145. The process as recited in claim 144 wherein
said a-olefin is propylene.
146. The process as recited in claim 142 done in
the presence of a solvent.
147. The process as recited in claim 142 used to
make a block polymer.
148. The process as recited in claim 142 wherein
the monomers are ethylene and propylene.
149. The process as recited in claim 142 wherein
said monomers are part of a crude butenes stream.
150. The process as recited in claim 142 wherein:
R2 and R5 are each independently hydrocarbyl,
provided that the carbon atom bound to the imino
nitrogen atom has at least two carbon atoms bound to
it;
R3 and R4 are each independently hydrogen,
hydrocarbyl, or R3 and R4 taken together are
hydrocarbylene to form a ring;
each R17 is independently hydrocarbyl provided
that any olefinic bond in said olefin is separated from
any other olefinic bond or aromatic ring by a
quaternary carbon atom or at least two saturated carbon
atoms;
each R32 is independently hydrogen or
hydrocarbyl;
436

R44 is hydrocarbyl, and R28 is hydrogen or
hydrocarbyl or R44 and R28 taken together form a ring;
R45 is hydrocarbyl, and R29 is hydrogen, or
hydrocarbyl, or R45 and R29 taken together form a ring;
each R30 is independently hydrogen or
hydrocarbyl, or two of R30 taken together form a ring;
R46 and R47 are each independently hydrocarbyl,
provided that the carbon atom bound to the imino
nitrogen atom has at least two carbon atoms bound to
it;
R48 and R49 are each independently hydrogen or
hydrocarbyl;
R20 and R23 are independently hydrocarbyl; and
R21 and R22 are each in independently hydrogen or
hydrocarbyl.
151. The process as recited in claim 142 wherein
said olefin comprises cyclopentene.
152. A polymerization process, comprising,
contacting an Ni[0] complex containing a ligand or
ligands which may be displaced by (VIII), oxygen, an
alkyl aluminum compound, and a compound of the formula
<IMG>
and one or more monomers selected from the group
consisting of ethylene, an olefin of the formula
R17CH=CH2 or R17CH=CHR17, cyclopentene, cyclobutene,
substituted norbornene, and norbornene; wherein:
R2 and R5 are each independently hydrocarbyl or
substituted hydrocarbyl, provided that the carbon atom
bound to the imino nitrogen atom has at least two
carbon atoms bound to it;
437

R3 and R4 are each independently hydrogen,
hydrocarbyl, substituted hydrocarbyl or R3 and R4 taken
together are hydrocarbylene or substituted
hydrocarbylene to form a ring; and
each R17 is independently hydrocarbyl or
substituted hydrocarbyl provided that any olefinic bond
in said olefin is separated from any other olefinic
bond or aromatic ring by a quaternary carbon atom or at
least two saturated carbon atoms;
provided that, when norbornene or substituted
norbornene is present, no other monomer is present.
153. The process as recited in claim 152 wherein
R2 and R5 are each independently hydrocarbyl, provided
that the carbon atom bound to the imino nitrogen atom
has at least two carbon atoms bound to it; and R3 and
R4 are each independently hydrogen, hydrocarbyl, or R3
and R4 taken together are hydrocarbylene to form a
carbocyclic ring.
154. The process as recited in claim 152 wherein
said Ni(0] complex is a 1,5-cyclooctadiene complex.
155. The process as recited in claim 152 wherein
said monomer is ethylene only.
156. The process as recited in claim 152 wherein
said olefin comprises cyclopentene.
157. The process as recited in claim 152 wherein
said monomer is an .alpha.-olefin only.
158. The process as recited in claim 157 wherein
said .alpha.-olefin is propylene.
159. The process as recited in claim 152 done in
the presence of a solvent.
160. The process as recited in claim 156 used to
make a block polymer.
161. The process as recited in claim 152 wherein
the monomers are ethylene and propylene.
162. The process as recited in claim 152 wherein
said monomers are part of a crude butenes stream.
163. A polymerization process, comprising,
contacting oxygen and an alkyl aluminum compound, or a
438

compound of the formula HX, and a compound of the
formula
<IMGS>
and one or more monomers selected from the group
consisting of ethylene, an olefin of the formula
R17CH=CH2 or R17CH=CHR17, cyclopentene, cyclobutene,
substituted norbornene, and norbornene; wherein:
R2 and R5 are each independently hydrocarbyl or
substituted hydrocarbyl, provided that the carbon atom
bound to the imino nitrogen atom has at least two
carbon atoms bound to it;
R3 and R4 are each independently hydrogen,
hydrocarbyl, substituted hydrocarbyl or R3 and R4 taken
together are hydrocarbylene or substituted
hydrocarbylene to form a ring; and
each R17 is independently hydrocarbyl or
substituted hydrocarbyl provided that any olefinic bond
in said olefin is separated from any other olefinic
bond or aromatic ring by a quaternary carbon atom or at
least two saturated carbon atoms;
X is a weakly coordinating anion; and
provided that, when norbornene or substituted
norbornene is present, no other monomer is present.
164. The process as recited in claim 163 wherein
R2 and R5 are each independently hydrocarbyl, provided
439

that the carbon atom bound to the imino nitrogen atom
has at least two carbon atoms bound to it; and R3 and
R4 are each independently hydrogen, hydrocarbyl, or R3
and R4 taken together are hydrocarbylene to form a
carbocyclic ring.
165. The process as recited in claim 142 wherein
said Ni[0] compound is bis(1,5cyclooctadiene)nickel or
bis(o-tolylphosphito)nickel(ethylene) or said Pd[0]
compound is tris(dibenzylideneacetone)dipalladium[0].
166. The process as recited in claim 163 wherein
said monomer is ethylene only.
167. The process as recited in claim 163 wherein
said olefin comprises cyclopentene.
168. The process as recited in claim 163 wherein
said monomer is an .alpha.-olefin only.
169. The process as recited in claim 168 wherein
said .alpha.-olefin is propylene.
170. The process as recited in claim 163 done in
the presence of a solvent.
171. The process as recited in claim 163 used to
make a block polymer.
172. The process as recited in claim 163 wherein
the monomers are ethylene and propylene.
173. The process as recited in claim 163 wherein
said monomers are part of a crude butenes stream.
174. The process as recited in claim 164 wherein
said olefin comprises cyclopentene.
175. The process as recited in claim 164 wherein
said monomer is ethylene only.
176. A polymerization process, comprising,
contacting an Ni[0] complex containing a ligand or
ligands which may be displaced by (VIII), HX or a
Bronsted acidic solid, and a compound of the formula
440

<IMG>
and one or more monomers selected from the group
consisting of ethylene, an olefin of the formula
R17CH=CH2 or R17CH=CHR17, cyclopentene, cyclobutene,
substituted norbornene, and norbornene; wherein:
R2 and R5 are each independently hydrocarbyl or
substituted hydrocarbyl, provided that the carbon atom
bound to the imino nitrogen atom has at least two
carbon atoms bound to it;
R3 and R4 are each independently hydrogen,
hydrocarbyl, substituted hydrocarbyl or R3 and R4 taken
together are hydrocarbylene or substituted
hydrocarbylene to form a ring;
each R17 is independently hydrocarbyl or
substituted hydrocarbyl provided that any olefinic bond
in said olefin is separated from any other olefinic
bond or aromatic ring by a quaternary carbon atom or at
least two saturated carbon atoms; and
X is a weakly coordinating anion;
provided that, when norbornene or substituted
norbornene is present, no other monomer is present.
177. The process as recited in claim 176 wherein
R2 and R5 are each independently hydrocarbyl, provided
that the carbon atom bound to the imino nitrogen atom
has at least two carbon atoms bound to it; and R3 and
R4 are each independently hydrogen, hydrocarbyl, or R3
and R4 taken together are hydrocarbylene to form a
carbocyclic ring.
178. The process as recited in claim 176 wherein
said Ni[0] complex is bis(1,5-cycloocatidene)nickel or
bis(o-tolylphosphito)nickel(ethylene)
441

179. The process as recited in claim 176 wherein
said monomer is ethylene only.
180. The process as recited in claim 176 wherein
said olefin comprises cyclopentene.
181. The process as recited in claim 176 wherein
said- monomer is an .alpha.-olefin only.
182. The process as recited in claim 181 wherein
said .alpha.-olefin is propylene.
183. The process as recited in claim 176 done in
the presence of a solvent.
184. The process as recited in claim 176 used to
make a block polymer.
185. The process as recited in claim 176 wherein
the monomers are ethylene and propylene.
186. The process as recited in claim 176 wherein
said monomers are part of a crude butenes stream.
187. A process for the polymerization of olefins,
comprising, contacting, at a temperature of about
-100°C to about +200°C:
a first compound W, which is a neutral Lewis
acid capable of abstracting either Q or S to form WQ-
or WS-, provided that the anion formed is a weakly
coordinating anion; or a cationic Lewis or Bronsted
acid whose counterion is a weakly coordinating anion;
a second compound of the formula
<IMG>
and one or more monomers selected from the
group consisting of ethylene, an olefin of the formula
442

R17CH=CH2 or R17CH=CHR17, cyclobutene, cyclopentene,
substituted norbornene, or norbornene;
wherein:
M is Ni(II) or Pd(II);
R20 and R22 are independently hydrocarbyl or
substituted hydrocarbyl;
R21 and R22 are each in independently hydrogen,
hydrocarbyl or substituted hydrocarbyl;
each R17 is independently hydrocarbyl or
substituted hydrocarbyl provided that any olefinic bond
in said olefin is separated from any other olefinic
bond or aromatic ring by a quaternary carbon atom or at
least two saturated carbon atoms;
Q is alkyl, hydride, chloride, iodide, or
bromide;
S is alkyl, hydride, chloride, iodide, or
bromide;
provided that;
when norbornene or substituted norbornene is
present, no other monomer is present;
when M is Pd a diene is not present; and
except when M is Pd, when both Q and S are each
independently chloride, bromide or iodide W is capable
of transferring a hydride or alkyl group to M.
188. The process as recited in claim 187 wherein
said monomer is ethylene only.
189. The process as recited in claim 187 wherein
said monomer is an .alpha.-olefin only.
190. The process as recited in claim 189 wherein
said .alpha.-olefin is propylene.
191. The process as recited in claim 187 done in
the presence of a solvent.
192. The process as recited in claim 187 used to
make a block polymer.
193. The process as recited in claim 191 wherein a
monomer is ethylene or propylene.
443

194. The process as recited in claim 187 wherein
the molar ratio of said first compound: said second
compound (I) is about 5 to about 1000
195. The process as recited in claim 187 wherein
the molar ratio of said first compound: said second
compound (I) is about 10 to about 100.
196. The process as recited in claim 187 wherein
the monomers are ethylene and propylene.
197. The process as recited in claim 187 wherein
said monomers are part of a crude butenes stream.
198. The process as recited in claim 187 wherein
R20 and R23 are independently hydrocarbyl; R21 and R22
are each in independently hydrogen or hydrocarbyl; and
each R17 is independently hydrocarbyl provided that any
olefinic bond in said olefin is separated from any
other olefinic bond or aromatic ring by a quaternary
carbon atom or at least two saturated carbon atoms.
199. A process for the polymerization of olefins,
comprising, contacting, at a temperature of about -
100°C to about +200°C, a compound of the formula
<IMG>
and one or more monomers selected from the group
consisting of ethylene, an olefin of the formula
R17CH=CH2 or R17CH=CHR17, cyclopentene, cyclobutene,
substituted norbornene, and norbornene; wherein:
R2 and R5 are each independently hydrocarbyl or
substituted hydrocarbyl, provided that the carbon atom
bound to the imino nitrogen atom has at least two
carbon atoms bound to it;
444

R3 and R4 are each independently hydrogen,
hydrocarbyl, substituted hydrocarbyl, or R3 and R4
taken together are hydrocarbylene or substituted
hydrocarbylene to form a carbocyclic ring;
each R17 is independently hydrocarbyl or
substituted hydrocarbyl provided that R17 does not
contain any olefinic bonds; and
each R27 is independently hydrocarbyl;
each X is a weakly coordinating anion;
provided that, when norbornene or substituted
norbornene is present, no other monomer is present.
200. The process as recited in claim 199 wherein
both R27 are methyl.
201. The process as recited in claim 199 wherein
said monomer is ethylene only.
202. The process as recited in claim 199 wherein
said monomer is an .alpha.-olefin only.
203. The process as recited in claim 202 wherein
said .alpha.-olefin is propylene.
204. The process as recited in claim 199 wherein
one or more comonomer selected from the group
consisting of: a compound of the formula
CH2=CH(CH2)m CO2R1, wherein R1 is hydrogen or, hydrocarbyl
or substituted hydrocarbyl containing 1 to 10 carbon
atoms, and m is 0 or an integer of 1 to 16; CO; and a
vinyl ketone is also present.
205. The process as recited in claim 204 wherein m
is 0, and R1 is hydrocarbyl or substituted hydrocarbyl.
206. The process as recited in claim 199 done in
the presence of a solvent.
207. The process as recited in claim 199 wherein
R3 and R4 are each independently hydrogen or methyl,
and both R2 and R5 are 2,6-diisopropylphenyl.
208. The process as recited in claim 199 used to
make a block polymer.
209. The process as recited in claim 199 wherein X
is BAF, SbF6, PF6, or BF4.
445

210. The process as recited in claim 207 wherein
X is BAF or BF4.
211. The process as recited in claim 210 wherein a
monomer is ethylene or propylene.
212. The process as recited in claim 199 wherein
the monomers are ethylene and propylene.
213. The process as recited in claim 199 wherein
said monomers are part of a crude butenes stream.
214. The process as recited in claim 199 wherein
R2 and R5 are each independently hydrocarbyl, provided
that the carbon atom bound to the imino nitrogen atom
has at least two carbon atoms bound to it; and R3 and
R4 are each independently hydrogen, hydrocarbyl, or R3
and R4 taken together are hydrocarbylene to form a
carbocyclic ring, and each R17 is hydrocarbyl.
215. The process as recited in claim 199 wherein
said olefin comprises cyclopentene.
216. A process for the polymerization of olefins,
comprising, contacting, at a temperature of about -
100°C to about +200°C:
a first compound W, which is a neutral Lewis
acid capable of abstracting either Q- or S- to form WQ-
or WS-, provided that the anion formed is a weakly
coordinating anion; or a cationic Lewis or Bronsted
acid whose counterion is a weakly coordinating anion;
a second compound of the formula
<IMG>
and one or more monomers selected from the group
consisting of ethylene, an olefin of the formula
446

R17CH=CH2 or R17CH=CHR17, cyclopentene, cyclobutene,
substituted norbornene, and norbornene; wherein:
R46 and R47 are each independently hydrocarbyl
or substituted hydrocarbyl, provided that the carbon
atom bound to the imino nitrogen atom has at least two
carbon atoms bound to it;
R48 and R49 are each independently hydrogen,
hydrocarbyl, or substituted hydrocarbyl;
each R31 is independently hydrocarbyl,
substituted hydrocarbyl, or hydrogen;
M is Ti, Zr, V, Cr, a rare earth metal, Co, Fe,
Sc, Ni, or Pd of oxidation state m;
y and z are positive integers;
y+z = m;
each R17 is independently hydrocarbyl or
substituted hydrocarbyl provided that any olefinic bond
in said olefin is separated from any other olefinic
bond or aromatic ring by a quaternary carbon atom or at
least two saturated carbon atoms;
Q is alkyl, hydride, chloride, iodide, or
bromide;
S is alkyl, hydride, chloride, iodide or
bromide; and
provided that;
when norbornene or substituted norbornene is
present, no other monomer is present;
when M is Pd a diene is not present; and
except when M is Pd, when both Q and S are each
independently chloride, bromide or iodide W is capable
of transferring a hydride or alkyl group to M.
217. The process as recited in claim 216 wherein
eachR31 is hydrogen.
218. The process as recited in claim 216 wherein
said monomer is ethylene only.
219. The process as recited in claim 216 wherein
said monomer is an .alpha.-olefin only.
220. The process as recited in claim 219 wherein
said .alpha.-olefin is propylene.
447

221. The process as recited in claim 216 done in
the presence of a solvent.
222. The process as recited in claim 216 wherein
R48 and R49 are each independently hydrogen or methyl,
both R46 and R47 are 2,6-diisopropylphenyl, and T1 is
methyl.
223. The process as recited in claim 216 used to
make a block polymer.
224. The process as recited in claim 216 wherein M
is Ni (II).
225. The process as recited in claim 216 wherein
M is Pd(II).
226. The process as recited in claim 225 wherein a
monomer is ethylene or propylene.
227. The process as recited in claim 216 wherein:
M is Ti(IV), Q and S are chloride, and y and z are
2;
M is Zr(IV), Q and S are chloride, and y and z are
2;
M is Co(II), Q and S are bromide, and y and z are
1;
M is Fe(II), Q and S are chloride, and y and z are
1;
M is Sc(III), Q and S are chloride, y is 1 and z
is 2;
M is Ni(II), Q and S are bromide or chloride, and
y and z are 1; M is Pd(II), Q and S are methyl, and y
and z are 1;
M is Ni(I), Q is methyl, chloride, bromide, iodide
or acetylacetonate, y is 1, and z is 0;
or
M is Ni(II), Q and S are methyl, and y and z are
1.
228: The process as recited in claim 216 wherein
the monomers are ethylene and propylene.
229. The process as recited in claim 216 wherein
said monomers are part of a crude butenes stream.
448

230. The process as recited in claim 216 wherein:
R46 and R47 are each independently hydrocarbyl
or substituted hydrocarbyl, provided that the carbon
atom bound to the imino nitrogen atom has at least two
carbon atoms bound to it;
R48 and R49 are each independently hydrogen,
hydrocarbyl, or substituted hydrocarbyl;
each R31 is independently hydrocarbyl,
substituted hydrocarbyl, or hydrogen; and
each R17 is hydrocarbyl.
231. The process as recited in claim 216 wherein
said olefin comprises cyclopentene.
232. A compound of the formula
<IMG>
wherein:
R2 and R5 are each independently hydrocarbyl or
substituted hydrocarbyl, provided that the carbon atom
bound to the imino nitrogen atom has at least two
carbon atoms bound to it;
R3 and R4 are each independently hydrogen,
hydrocarbyl, substituted hydrocarbyl, or R3 and R4
taken together are hydrocarbylene or substituted
hydrocarbylene to form a carbocyclic ring;
T1 is hydrogen, hydrocarbyl not containing
olefinic or acetylenic bonds, R15C(=O)- or R15OC(=O)-;
Z is a neutral Lewis base wherein the donating
atom is nitrogen, sulfur or oxygen, provided that if
the donating atom is nitrogen then the pKa of the
conjugate acid of that compound is less than about 6;
X is a weakly coordinating anion; and
449

R15 is hydrocarbyl not containing olefinic or
acetylenic bonds;
provided that when R3 and R4 taken together are
hydrocarbylene to form a carbocyclic ring Z is not an
organic nitrile.
233. The compound as recited in claim 232 wherein
T1 is methyl, and Z is R6 2O or R7CN wherein each R6
independently hydrogen or hydrocarbyl and R7 is
hydrocarbyl.
234. The compound as recited in claim 232 wherein
R3 and R4 are each independently hydrogen or methyl or
R3 and R4 taken together are 1,8-naphthylylene, and
both R2 and R5 are 2,6-diisopropylphenyl.
235. The compound as recited in claim 233 wherein
R3 and R4 are each independently hydrogen or methyl,
and both R2 and R5 are 2,6-diisopropylphenyl, and
wherein X is BAF, SbF6, PF6, or BF4.
236. The compound as recited in claim 232 wherein
X is BAF-, SbF6-, PF6-, or BF4-.
237. The compound as recited in claim 232 wherein
R2 and R5 are each independently hydrocarbyl, provided
that the carbon atom bound to the imino nitrogen atom
has at least two carbon atoms bound to it; and R3 and
R4 are each independently hydrogen, hydrocarbyl, or R3
and R4 taken together are hydrocarbylene to form a
carbocyclic ring.
238. The compound as recited in claim 232 wherein
each of R2, R3, R4, R5, T1, Z, and X are as follows:
450

R2 R3 R4 R5 T1 Z X
2,6-i-PrPh Me Me 2,6-i-PrPh Me OEt2 BAF
2,6-i-PrPh H H 2,6-i-PrPh Me OEt2 BAF
2,6-MePh H H 2,6-MePh Me OEt2 BAF
2,6-MePh Me Me 2,6-MePh Me OEt2 BAF
2,6-i-PrPh Me Me 2,6-i-PrPh Me OEt2 SbF6
2,6-i-PrPh Me Me 2,6-i-PrPh Me OEt2 BF4
2,6-i-PrPh Me Me 2,6-i-PrPh Me OEt2 PF6
2,6-i-PrPhH H H 2,6-i-PrPh Me OEt2 SbF6
2,4,6-MePh Me Me 2,4,6-MePh Me OEt2 SbF6
2,6-i-PrPh An An 2,6-i-PrPh Me OEt2 SbF6
2,6-i-PrPh Me Me 2,6-i-PrPh Me NCMe SbF6
Ph Me Me Ph Me NCMe SbF6
2,6-EtPh Me Me 2,6-EtPh Me NCMe BAF
2,6-EtPh Me Me 2,6-EtPh Me NCMe SbF6
2-t-BuPh Me Me 2-t-BuPh Me NCMe SbF6
1-Np Me Me 1-Np Me NCMe SbF6
Ph2CH H H Ph2CH Me NCMe SbF6
2-PhPh Me Me 2-PhPh Me NCMe SbF6
Ph a a Ph Me NCMe BAF
Ph Me Me Ph Me NCMe SbF6
Ph Ph Ph Ph Me NCMe BAF
Ph2CH H H Ph2CH Me NCMe SbF6
Ph2CH H H Ph2CH Me SMe2 SbF6
a -CMe2CH2CMe2-.
239. A compound of the formula
<IMG>
wherein:
R50 is substituted phenyl;
R51 is phenyl or substituted phenyl;
451

R3 and R4 are each independently hydrogen,
hydrocarbyl, substituted hydrocarbyl or R3 and R4 taken
together are hydrocarbylene or substituted
hydrocarbylene to form a ring;
and provided that groups in the 2 and 6 positions
of R50 have a difference in E S of about 0.15 or more.
240. The compound as recited in claim 239 wherein
groups in the 2 and 6 of R51 have a difference in E S of
about 0.60 or more.
241. The compound as recited in claim 239 wherein
the group in the 2 position of R50 is t-butyl and the
group in 6 position of R50 is methyl or hydrogen.
242. The compound as recited in claim 241 wherein
the group in the 2 position of R51 is t-butyl and the
group in 6 position of R51 is methyl or hydrogen.
243. A compound of the formula
<IMG>
wherein:
R52 is substituted phenyl;
R53 is phenyl or substituted phenyl;
R3 and R4 are each independently hydrogen,
hydrocarbyl, substituted hydrocarbyl or R3 and R4 taken
together are hydrocarbylene or substituted
hydrocarbylene to form a ring;
Q is alkyl, hydride, chloride, bromide or
iodide;
S is alkyl, hydride, chloride, bromide or
iodide;
and provided that;
groups in the 2 and 6 positions of R52 have a
difference in E S of 0.15 or more; and
452

except when M is Pd, when both Q and S are each
independently chloride, bromide or iodide W is capable
of transferring a hydride or alkyl group to M.
244. The compound as recited in claim 243 wherein
said difference is about 0.20 more.
245. The compound as recited in claim 243 wherein
groups in the 2 and 6 of R51 have a difference in E S of
0.15 or more.
246. The compound as recited in claim 243 wherein
the group in the 2 position of R52 is i-propyl or
t-butyl and the group in the 6 position of R52 is methyl
or hydrogen.
247. The compound as recited in claim 246 wherein
the group in the 2 position of R53 is i-propyl or
t-butyl and the group in 6 position of R52 is methyl or
hydrogen.
248. A compound of the formula
<IMG>
wherein:
R2 and R5 are each independently hydrocarbyl or
substituted hydrocarbyl, provided that the carbon atom
bound to the imino nitrogen atom has at least two
carbon atoms bound to it;
R3 and R4 are each independently hydrogen,
hydrocarbyl, substituted hydrocarbyl, or R3 and R4
taken together are hydrocarbylene or substituted
hydrocarbylene to form a ring;
T1 is hydrogen, hydrocarbyl not containing
olefinic or acetylenic bonds, R15C(=O) - or R15OC (=O) -;
453

R15 is hydrocarbyl not containing an olefinic
or acetylenic bond;
Z is a neutral Lewis base wherein the donating
atom is nitrogen, sulfur or oxygen, provided that if
the donating atom is nitrogen then the pKa of the
conjugate acid of that compound is less than about 6;
X is a weakly coordinating anion.
249. The compound as recited in claim 248 wherein
T1 is methyl, Z is R6 2O wherein each R6 is independently
alkyl, and X is BAF, SbF6, PF6, or BF4.
250. The compound as recited in claim 248 wherein
R3 and R4 are each independently hydrogen or methyl,
and both R2 and R5 are 2,6-diisopropylphenyl.
251. The compound as recited in claim 249 wherein
R3 and R4 are each independently hydrogen or methyl,
and both R2 and R5 are 2,6-diisopropylphenyl.
252. The compound as recited in claim 248 wherein
R2 and R5 are each independently hydrocarbyl provided
that the carbon atom bound to the imino nitrogen atom
has at least two carbon atoms bound to it; and R3 and
R4 are each independently hydrogen, hydrocarbyl, or R3
and R4 taken together are hydrocarbylene to form a
ring.
253. A compound of the formula
<IMG>
454

wherein:
R2 and R5 are each independently hydrocarbyl or
substituted hydrocarbyl, provided that the carbon atom
bound to the imino nitrogen atom has at least two
carbon atoms bound to it;
R3 and R4 are each independently hydrogen,
hydrocarbyl, substituted hydrocarbyl, or R3 and R4
taken together are hydrocarbylene or substituted
hydrocarbylene to form a ring;
M is Ni(II) or Pd(II);
each R16 is independently hydrogen or alkyl
containing 1 to 10 carbon atoms;
n is 1, 2, or 3;
X- is a weakly coordinating anion; and
R8 is hydrocarbyl.
254. The compound as recited in claim 253 wherein
R3 and R4 are each independently hydrogen or methyl,
both R2 and R5 are 2,6-diisopropylphenyl, M is Pd(II),
and X i s BAF, SbF6, PF6, or BF4.
255. The compound as recited in claim 254 wherein
each R16 is hydrogen and n is 3.
256. The compound as recited in claim 253 wherein
M is Pd(II).
257. The compound as recited in claim 253 wherein
each R16 is hydrogen and n is 3.
258. The compound as recited in claim 253 wherein
R2 and R5 are each independently hydrocarbyl, provided
that the carbon atom bound to the imino nitrogen atom
has at least two carbon atoms bound to it; and R3 and
R4 are each independently hydrogen, hydrocarbyl, or R3
and R4 taken together are hydrocarbylene to form a
ring.
259. A compound of the formula
455

<IMG>
wherein:
R2 and R5 are each independently hydrocarbyl
or substituted hydrocarbyl, provided that the carbon
atom bound directly to the imino nitrogen atom has at
least two carbon atoms bound to it;
R3 and R4 are each independently hydrogen,
hydrocarbyl, substituted hydrocarbyl, or R3 and R4
taken together are hydrocarbylene or substituted
hydrocarbylene to form a ring;
E is halogen or -OR18;
R18 is hydrocarbyl not containing olefinic or
acetylenic bonds;
T1 is hydrogen, hydrocarbyl not containing
olefinic or acetylenic bonds, R15C (=O) - or R15OC (=O) -;
R15 is hydrocarbyl not containing olefinic or
acetylenic bonds; and
X- is a weakly coordinating anion.
260. The compound as recited in claim 259 wherein
R2 and R5 are each independently hydrocarbyl, provided
that the carbon atom bound to the imino nitrogen atom
has at least two carbon atoms bound to it; and R3 and
R4 are each independently hydrogen, hydrocarbyl, or R3
and R4 taken together are hydrocarbylene to form a
ring.
261. The compound as recited in claim 259 wherein
T1 is methyl, and E is chlorine.
262. The compound as recited in claim 261 wherein
R3 and R4 are each independently hydrogen or methyl,
and both R2 and R5 are 2,6-diisopropylphenyl.
456

263. The compound as recited in claim 262 wherein
X is BAF, SbF6, PF6, or BF4.
264. A compound of the formula [(~4-1,5-
COD)PdT1Z]+X-, wherein:
T1 is hydrocarbyl not containing olefinic or
acetylenic bonds;
X- is a weakly coordinating anion;
COD is 1,5-cyclooctadiene;
Z is R10CN; and
R10 is hydrocarbyl not containing olefinic or
acetylenic bonds.
265. The compound as recited in claim 264 wherein
T1 is methyl.
266. The compound as recited in claim 265 wherein
Z is methyl and X is BAF, SbF6, PF6, or BF4.
267. A compound of the formula
<IMG>
wherein:
M is Ni(II) or Pd(II);
R2 and R5 are hydrocarbyl or substituted
hydrocarbyl, provided that the carbon atom bound
directly to the imino nitrogen atom has at least two
carbon atoms bound to it;
R3 and R4 are each independently hydrogen,
hydrocarbyl, substituted hydrocarbyl, or R3 and R4
taken together are hydrocarbylene or substituted
hydrocarbylene to form a ring;
each R11 is independently hydrogen, alkyl or
-(CH2)m CO2R1;
457

T3 is hydrogen, hydrocarbyl not containing
olefinic or acetylenic bonds, or -CH2CH2CH2CO2R8;
P is a divalent group containing one or more
repeat units derived from the polymerization of one or
more of ethylene, an olefin of the formula R17CH=CH2 or
R17CH=CHR17, cyclobutene, cyclopentene, substituted
norbornene, or norbornene and, when M is Pd(II),
optionally one or more of: a compound of the formula
CH2=CH (CH2) mCO2R1, CO, or a vinyl ketone ;
R8 is hydrocarbyl;
m is 0 or an integer from 1 to 16;
R1 is hydrogen, or hydrocarbyl or substituted
hydrocarbyl containing 1 to 10 carbon atoms;
and X is a weakly coordinating anion.
268. The compound as recited in claim 267 wherein
R1 is hydrocarbyl or substituted hydrocarbyl.
269. The compound as recited in claim 267 wherein
T3 is hydrogen or alkyl.
270. The compound as recited in claim 267 wherein
M is Pd(II).
271. The compound as recited in claim 269 wherein
M is Pd(II).
272. The compound as recited in claim 267 wherein
R3 and R4 are each independently hydrogen or methyl,
and both R2 and R5 are 2,6-diisopropylphenyl.
273. The compound as recited in claim 271 wherein
R3 and R4 are each independently hydrogen or methyl,
and both R2 and R5 are 2,6-diisopropylphenyl.
274. The compound as recited in claim 267 wherein
R2 and R5 are each independently hydrocarbyl, provided
that the carbon atom bound to the imino nitrogen atom
has at least two carbon atoms bound to it; and R3 and
R4 are each independently hydrogen, hydrocarbyl, or R3
and R4 taken together are hydrocarbylene to form a
ring.
275. A compound of the formula
458

<IMG>
wherein:
R2 and R5 are each independently hydrocarbyl or
substituted hydrocarbyl, provided that the carbon atom
bound to the imino nitrogen atom has at least two
carbon atoms bound to it;
R3 and R4 are each independently hydrogen,
hydrocarbyl, substituted hydrocarbyl, or R3 and R4
taken together are hydrocarbylene or substituted
hydrocarbylene to form a ring;
T2 is hydrogen, hydrocarbyl not containing
olefinic or acetylenic bonds, hydrocarbyl substituted
with keto or ester groups but not containing olefinic
or acetylenic bonds, R15C (=O) - or R15OC (=O) -;
R15 is hydrocarbyl not containing olefinic or
acetylenic bonds; and
X is a weakly coordinating anion.
276. The compound as recited in claim 275 wherein
T2 is methyl.
277. The compound as recited in claim 276 wherein
R3 and R4 are each independently hydrogen or methyl or
R3 and R4 taken together are 1,8-naphthylylene, and
both R2 and R5 are 2,6-diisopropylphenyl.
278. The compound as recited in claim 276 wherein
X i s BAF, SbF6, PF6, or BF4.
279. The compound as recited in claim 275 wherein
R2 and R5 are each independently hydrocarbyl, provided
that the carbon atom bound to the imino nitrogen atom
has at least two carbon atoms bound to it; and R3 and
R4 are each independently hydrogen, hydrocarbyl, or R3
459

and R4 taken together are hydrocarbylene to form a
ring.
280. A process for the production of polyolefins,
comprising, contacting, at a temperature of about
- 100°C to about +200°C, a compound of the formula
<IMG>
with one or more monomers selected from the group
consisting of ethylene, an olefin of the formula
R17CH=CH2 or R17CH=CHR17, cyclobutene, cyclopentene,
substituted norbornene, and norbornene,
wherein:
M is Ni (II) or Pd(II);
R2 and R5 are hydrocarbyl or substituted
hydrocarbyl, provided that the carbon atom bound
directly to the imino nitrogen atom has at least two
carbon atoms bound to it;
R3 and R4 are each independently hydrogen,
hydrocarbyl, substituted hydrocarbyl, or R3 and R4
taken together are hydrocarbylene or substituted
hydrocarbylene to form a ring;
each R11 is independently hydrogen, alkyl or
- (CH2),nCO2R1;
T3 is hydrogen, hydrocarbyl not containing
olefinic or acetylenic bonds, or -CH2CH2CH2CO2R8;
P is a divalent group containing one or more
repeat units derived from the polymerization of one or
monomers selected from the group consisting of
ethylene, an olefin of the formula R17CH=CH2 or
R17CH=CHR17, cyclopentene, cyclobutene, substituted
norbornene, and norbornene, and, when M is Pd(II),
460

optionally one or more of: a compound of the formula
CH2=CH(CH2) mCO2R1, CO, or a vinyl ketone;
R8 is hydrocarbyl;
each R17 is independently hydrocarbyl or
substituted hydrocarbyl provided that any olefinic bond
in said olefin is separated from any other olefinic
bond or aromatic ring by a quaternary carbon atom or at
least two saturated carbon atoms;
R1 is hydrogen, or hydrocarbyl or substituted
hydrocarbyl containing 1 to 10 carbon atoms;
m is 0 or an integer of 1 to 16;
and X is a weakly coordinating anion;
provided that when norbornene or substituted
norbornene is present no other monomer is present;
when M is Pd a diene is not present; and
further provided that when M is Ni(II) R11 is not
-CO2R8.
281. The compound as recited in claim 280 wherein
R2 and R5 are each independently hydrocarbyl, provided
that the carbon atom bound to the imino nitrogen atom
has at least two carbon atoms bound to it; and R3 and
R4 are each independently hydrogen, hydrocarbyl, or R3
and R4 taken together are hydrocarbylene to form a
ring; and each R17 is hydrocarbyl.
282. The process as recited in claim 280 wherein
T3 is methyl.
283. The process as recited in claim 282 wherein
said monomer is ethylene only, and R11 is hydrogen.
284. The process as recited in claim 282 wherein
said monomer is an .alpha.-olefin only, and R11 is alkyl.
285. The process as recited in claim 284 wherein
said .alpha.-olefin is propylene, and R11 is methyl.
285. The process as recited in claim 280 wherein M
is Pd(II), and one or more comonomers selected from the
group consisting of: a compound of the formula
CH2=CH(CH2) mCO2R1, wherein R1 is hydrogen or, hydrocarbyl
or substituted hydrocarbyl containing 1 to 10 carbon
461

atoms, and ~ is 0 or an integer of 1 to 16; CO; and a
vinyl ketone is also present.
287. The process as recited in claim 286 wherein m
is 0, and R2 is hydrocarbyl or substituted hydrocarbyl.
288. The process as recited in claim 287 wherein m
is 0, and R1 is hydrocarbyl.
289. The process as recited in claim 280 done in
the presence of a solvent.
290. The process as recited in claim 280 done in
the absence of a solvent.
291. The process as recited in claim 282 wherein
R3 and R4 are each independently hydrogen or methyl or
R3 anal R4 taken together are 1,8-naphthylylene, and
both R2 and R5 are 2,6-diisopropylphenyl.
292. The process as recited in claim 280 used to
make a block polymer.
293. The process as recited in claim 280 wherein X
is BAF, SbF6, PF6, or BF4.
294. The process as recited in claim 291 wherein
X is BAF, SbF6, PF6, or BF4.
295. The process as recited in claim 294 wherein a
monomer is ethylene or propylene.
296. The process as recited in claim 280 wherein
the monomers are ethylene and propylene.
297. The process as recited in claim 280 wherein
said monomers are part of a crude butenes stream.
298. The process as recited in claim 280 wherein
said monomers comprise cyclopentene.
299. A process for the production of polyolefins,
comprising, contacting, at a temperature of about
- 100°C to about +200°C, a compound of the formula
462

<IMG>
and one or more monomers selected from the group
consisting of ethylene, an olefin of the formula
R17CH=CH2 or R17CH=CHR17, cyclobutene, cyclopentene,
substituted norbornene, and norbornene,
wherein:
M is Zr, Ti, Sc, V, Cr, a rare earth metal, Fe,
Co, Ni or Pd of oxidation state m;
R2 and R5 are each independently hydrocarbyl or
substituted hydrocarbyl, provided that the carbon atom
bound directly to the imino nitrogen atom has at least
two carbon atoms bound to it;
R3 and R4 are each independently hydrogen,
hydrocarbyl, substituted hydrocarbyl, or R3 and R4
taken together are hydrocarbylene or substituted
hydrocarbylene to form a ring;
each R11 is independently hydrogen or alkyl, or
both of R11 taken together are hydrocarbylene to form a
carbocyclic ring;
T3 is hydrogen, hydrocarbyl not containing
olefinic or acetylenic bonds, or -CH2CH2CH2CO2R8; Q is a
monoanion;
P is a divalent group containing one or more
repeat units derived from the polymerization of one or
monomers selected from the group consisting of
ethylene, an olefin of the formula R17CH=CH2 or
R17CH=CHR17, cyclopentene, cyclobutene, substituted
norbornene, and norbornene, and, when M is Pd(II),
optionally one or more of: a compound of the formula
CH2=CH(CH2) mCO2R1, CO, or a vinyl ketone;
R8 is hydrocarbyl;
463

a is 1 or 2;
y + a + 1 = m;
each R17 is independently hydrocarbyl or
substituted hydrocarbyl provided that any olefinic bond
in said olefin is separated from any other olefinic
bond or aromatic ring by a quaternary carbon atom or at
least two saturated carbon atoms;
R1 is hydrogen, or hydrocarbyl or substituted
hydrocarbyl containing 1 to 10 carbon atoms;
m is 0 or an integer of 1 to 16;
and X is a weakly coordinating anion;
provided that, when norbornene or substituted
norbornene is present, no other monomer is present;
when M is Pd a diene is not present; and
further provided that, when M is Ni(II), T3 is not
- CH2CH2CH2CO2R8.
300. The process as recited in claim 299 wherein
R2 and R5 are each independently hydrocarbyl, provided
that the carbon atom bound to the imino nitrogen atom
has at least two carbon atoms bound to it; and R3 and
R4 are each independently hydrogen, hydrocarbyl, or R3
and R4 taken together are hydrocarbylene to form a
ring; and each R17 is hydrocarbyl.
301. The process as recited in claim 299 wherein
T3 is methyl.
302. The process as recited in claim 301 wherein
said monomer is ethylene only, and R11 is hydrogen.
303. The process as recited in claim 301 wherein
said monomer is an .alpha.-olefin only, and R11 is alkyl.
304. The process as recited in claim 303 wherein
said .alpha.-olefin is propylene, and each R11 is methyl or
hydrogen.
305. The process as recited in claim 299 wherein M
is Pd(II), and one or more comonomer selected from the
group consisting of: a compound of the formula
CH2=CH(CH2)mCO2R1, wherein R1 is hydrogen or, hydrocarbyl
or substituted hydrocarbyl containing 1 to 10 carbon
464

atoms, and m is 0 or an integer of 1 to 16; CO; and a
vinyl ketone is also present.
306. The process as recited in claim 305 wherein m
is 0, and R1 is hydrocarbyl or substituted hydrocarbyl.
307. The process as recited in claim 299 done in
the presence of a solvent.
308. The process as recited in claim 299 done in
the absence of a solvent.
309. The process as recited in claim 301 wherein
R3 and R4 are each independently hydrogen or methyl,
and both R2 and R5 are 2,6-diisopropylphenyl.
310. The process as recited in claim 299 used to
make a block polymer.
311. The process as recited in claim 299 wherein X
i s BAF, SbF6, PF6, or BF4.
312. The process as recited in claim 309 wherein
X i s BAF, SbF6, PF6, or BF4.
313. The process as recited in claim 312 wherein a
monomer is ethylene or propylene.
314. The process as recited in claim 299 wherein
the monomers are ethylene and propylene.
315. The process as recited in claim 299 wherein
said monomers are part of a crude butenes stream.
316. The process as recited in claim 299 wherein
said monomer comprises cyclopentene.
317. A compound of the formula
<IMG>
wherein:
M is Zr, Ti, Sc, V, Cr, a rare earth metal, Fe,
Co, Ni or Pd of oxidation state m;
465

R2 and R5 are each independently hydrocarbyl or
substituted hydrocarbyl, provided that the carbon atom
bound directly to the imino nitrogen atom has at least
two carbon atoms bound to it;
R3 and R4 are each independently hydrogen,
hydrocarbyl, substituted hydrocarbyl, or R3 and R4
taken together are hydrocarbylene or substituted
hydrocarbylene to form a ring;
each R11 is independently hydrogen, or alkyl, or
both of R11 taken together are hydrocarbylene to form a
carbocyclic ring;
T3 is hydrogen, hydrocarbyl not containing
olefinic or acetylenic bonds, or -CH2CH2CH2CO2R8;
P is a divalent group containing one or more
repeat units derived from the polymerization of one or
monomers selected from the group consisting of
ethylene, an olefin of the formula R17CH=CH2 or
R17CH=CHR17, cyclopentene, cyclobutene, substituted
norbornene, and norbornene, and optionally, when M is
Pd(II), one or more of: a compound of the formula
CH2=CH (CH2) mCO2R1, CO, or a vinyl ketone;
Q is a monovalent anion;
R8 is hydrocarbyl;
a is 1 or 2;
y + a + 1 = m;
each R17 is independently hydrocarbyl or
substituted hydrocarbyl provided that any olefinic bond
in said olefin is separated from any other olefinic
bond or aromatic ring by a quaternary carbon atom or at
least two saturated carbon atoms;
R1 is hydrogen, or hydrocarbyl or substituted
hydrocarbyl containing 1 to 10 carbon atoms;
m is 0 or an integer of 1 to 16; and
and X is a weakly coordinating anion;
and provided that when M is Pd a diene is not
present;.
318. The compound as recited in claim 317 wherein
R1 is hydrocarbyl or substituted hydrocarbyl.
466

319. The compound as recited in claim ~7 wherein
T3 is hydrogen or alkyl.
320. The compound as recited in claim 317 wherein
R2 and R5 are each independently hydrocarbyl, provided
that the carbon atom bound to the imino nitrogen atom
has at least two carbon atoms bound to it; and R3 and
R4 are each independently hydrogen, hydrocarbyl, or R3
and R4 taken together are hydrocarbylene to form a
ring; and each R17 is hydrocarbyl.
321. The compound as recited in claim 317 wherein
M is Pd(II).
322. The compound as recited in claim 319 wherein
M is Pd(II).
323. The compound as recited in claim 317 wherein
R3 and R4 are each independently hydrogen or methyl,
and both R2 and R5 are 2,6-diisopropylphenyl.
324. The compound as recited in claim 317 wherein
both of R11 taken together form a five-membered
carbocyclic ring.
325. The compound as recited in claim 317 wherein
both of R11 taken together are hydrocarbylene to form a
carbocyclic ring.
326. A process, comprising, contacting, at a
temperature of about -40°C to about +60°C, a compound
of the formula [(~4-1, 5-COD) PdT1Z] +X- and a diimine of
the formula
<IMG>
to produce a compound of the formula
467

<IMG>
wherein:
T1 is hydrogen, hydrocarbyl not containing
olefinic or acetylenic bonds, R15C(=O)- or R15OC(=O)-;
X is a weakly coordinating anion;
COD is 1,5-cyclooctadiene;
Z is R10CN;
R10 is hydrocarbyl not containing olefinic or
acetylenic bonds;
R15 is hydrocarbyl not containing olefinic or
acetylenic bonds;
R2 and R5 are each independently hydrocarbyl or
substituted hydrocarbyl, provided that the carbon atom
bound to the imino nitrogen atom has at least two
carbon atoms bound to it; and
R3 and R4 are each independently hydrogen,
hydrocarbyl, substituted hydrocarbyl, or R3 and R4
taken together are hydrocarbylene or substituted
hydrocarbylene to form a ring.
327. The process as recited in claim 326 wherein
R10 is alkyl, and T1 is methyl.
328. The process as recited in claim 326 carried
out in a solvent of the formula R10CN, wherein R10 is
hydrocarbyl not containing olefinic or acetylenic
bonds.
329. The process as recited in claim 327 wherein
R3 and R4 are each independently hydrogen or methyl,
and both R2 and R5 are 2,6-diisopropylphenyl.
330. The process as recited in claim 326 wherein X
is BAF, SbF6, PF6, or BF4.
468

331. The process as recited in claim 326 wherein
R2 and R5 are each independently hydrocarbyl, provided
that the carbon atom bound to the imino nitrogen atom
has at least two carbon atoms bound to it; and R3 and
R4 are each independently hydrogen, hydrocarbyl, or R3
and R4 taken together are hydrocarbylene to form a
ring.
332. An ethylene homopolymer with a density of
0.86 g/ml or less.
333. The ethylene homopolymer as recited in claim
332 wherein said density is about 0.85 or less.
334. A compound of the formula
<IMG>
wherein:
R2 and R5 are each independently hydrocarbyl or
substituted hydrocarbyl, provided that the carbon atom
bound to the imino nitrogen atom has at least two
carbon atoms bound to it;
R3 and R4 are each independently hydrogen,
hydrocarbyl, substituted hydrocarbyl, or R3 and R4
taken together are hydrocarbylene or substituted
hydrocarbylene to form a ring;
each R27 is hydrocarbyl; and
each X is a weakly coordinating anion.
335. The compound as recited in claim 334 wherein
R2 and R5 are each independently hydrocarbyl, provided
that the carbon atom bound to the imino nitrogen atom
has at least two carbon atoms bound to it; and R3 and
R4 are each independently hydrogen, hydrocarbyl, or R3
469

and R4 taken together are hydrocarbylene to form a
ring.
336. The compound as recited in claim 334 wherein
both of R27 are methyl.
337. The compound as recited in claim 334 wherein
R3 and R4 are each independently hydrogen or methyl or
R3 and R4 taken together are 1,8-naphthylylene, and
both R2 and R5 are 2,6-diisopropylphenyl.
338. The compound as recited in claim 334 wherein
X i s BAF, SbF6, PF6, or BF4.
339. A compound of the formula
<IMG>
wherein:
M is Ni(II) or Pd(II);
R2 and R5 are each independently hydrocarbyl or
substituted hydrocarbyl, provided that the carbon atom
bound directly to the imino nitrogen atom has at least
two carbon atoms bound to it;
R3 and R4 are each independently hydrogen,
hydrocarbyl, substituted hydrocarbyl, or R3 and R4
taken together are hydrocarbylene or substituted
hydrocarbylene to form a ring;
each R14 is independently hydrogen, alkyl or
- (CH2) mCO2R1;
R1 is hydrogen, or hydrocarbyl or substituted
hydrocarbyl containing 1 to 10 carbon atoms;
T4 is alkyl, -R60C (O) OR8, R15 (C=O) - or R15OC (=O) -
470

R15 is hydrocarbyl not containing olefinic or
acetylenic bonds;
R60 is alkylene not containing olefinic or
acetylenic bonds;
R8 is hydrocarbyl;;
and X is a weakly coordinating anion;
and provided that when R14 is - (CH2)mCO2R1, or T4
is not alkyl, M is Pd(II).
340. The compound as recited in claim 339 wherein
R2 and R5 are each independently hydrocarbyl, provided
that the carbon atom bound to the imino nitrogen atom
has at least two carbon atoms bound to it; and R3 and
R4 are each independently hydrogen, hydrocarbyl, or R3
and R4 taken together are hydrocarbylene to form a
ring.
341. The compound as recited in claim 339 wherein
T4 is methyl and M is Pd(II).
342. The compound as recited in claim 339 wherein
each R14 is independently hydrogen or - (CH2) mCO2R1 and M
is Pd(II).
343. A homopolypropylene with a glass transition
temperature of -30°C or less, provided that said
homopolypropylene has at least 50 branches per 1000
methylene groups.
344. The homopolypropylene as recited in claim 343
wherein said glass transition temperature is about
- 35°C or less.
345. A homopolymer of cyclopentene having a degree
of polymerization of about 30 or more and an end of
melting point of about 100°C to about 320°C, provided
that said homopolymer has less than 5 mole percent of
enchained linear olefin containing pentylene units.
346. The homopolymer as recited in claim 345
wherein at least 90 percent of repeat units are
1,3-cyclopentylene repeat units.
347. The homopolymer as recited in claim 345
wherein at least 90 percent of repeat units are
cis-1,3-cyclopentylene repeat units.
471

348 . The homopolymer as recited in claim 345
wherein an X-ray powder diffraction pattern thereof
has reflections at approximately 17.3°, 19.3°, 24.2°,
and 40.7° 2.theta..
349. A homopolymer of cyclopentene that has an X-
ray diffraction pattern with reflections at
approximately 17.3°, 19.3°, 24.2°, and 40.7°
2.theta..
350. The homopolymer as recited in claim 349 which
has a monoclinic unit cell of the approximate
dimensions: a=0.561 nm; b=0.607 nm; c=7.37 nm; and
g=123.2°.
351. The homopolymer as recited in claim 349
wherein at least 90 percent of repeat units are 1,3-
cyclopentylene repeat units.
352. The homopolymer as recited in claim 351
wherein at least 90 percent of repeat units are cis-
1,3-cyclopentylene repeat units.
353. A homopolymer of cyclopentene wherein at
least 90 mole percent of enchained cyclopentylene units
are 1,3-cyclopentylene units, and said homopolymer has
an average degree of polymerization of 30 more.
354. A homopolymer of cyclopentene wherein at
least 90 mole percent of enchained cyclopentylene units
are cis-1,3-cyclopentylene, and said homopolymer has an
average degree of polymerization of about 10 or more.
355. A copolymer of cyclopentene and ethylene
wherein at least 75 mole percent of enchained
cyclopentylene units are 1,3-cyclopentylene units.
356. The copolymer as recited in claim 355 wherein
at least 50 mole percent of the repeat units are
derived from cyclopentene.
357. The copolymer as recited in claim 355 wherein
there are at least 20 branches per 1000 methylene
carbon atoms.
358. A copolymer of cyclopentene and ethylene
wherein there are at least 20 branches per 1000
methylene carbon atoms.
472

359. The copolymer as recited in claim 358 wherein
at least 50 mole percent of the repeat units are
derived from ethylene.
360. A copolymer of cyclopentene and ethylene
wherein at least 50 mole percent of the repeat units
are derived from cyclopentene.
361. A copolymer comprising repeat units of
cyclopentene and an .alpha.-olefin.
362. The copolymer as recited in claim 361 wherein
repeat units derived from ethylene are also present.
363. The copolymer as recited in claim 361 wherein
said .alpha.-olefin is a linear .alpha.-olefin.
364. The copolymer as recited in claim 361 wherein
at least 90 mole percent of repeat units derived from
cyclopentene are 1,3-cyclopentylene units.
365. The copolymer as recited in claim 364 wherein
at least 90 mole percent of repeat units derived from
cyclopentene are cis-1,3-cyclopentylene units.
366. A fiber made from the polymer of claim 345,
349, 353, 354, 355, 356, 357, 358, 360 or 361.
367. A polymerization process, comprising,
contacting an olefin of the formula R17CH=CH2 or
R17CH=CHR17, each R17 is independently hydrogen,
hydrocarbyl, or substituted hydrocarbyl provided that
any olefinic bond in said olefin is separated from any
other olefinic bond or aromatic ring by a quaternary
carbon atom or at least two saturated carbon atoms with
a catalyst, wherein said catalyst:
contains a nickel or palladium atom in a
positive oxidation state;
contains a neutral bidentate ligand coordinated
to said nickel or palladium atom, and wherein
coordination to said nickel or palladium atom is
through two nitrogen atoms or a nitrogen atom and a
phosphorous atom; and
said neutral bidentate ligand, has an Ethylene
Exchange Rate of less than 20,000 L-mol-1s-1 when said
catalyst contains a palladium atom, and less than
473

50,000 L-mol-1s-1 when said catalyst contains a nickel
atom;
and provided that when M is Pd a dime is not
present.
368. The polymerization process as recited in
claim 367 wherein said Ethylene Exchange Rate is less
than 10,000 L-mol-1s-1 when said catalyst contains a
palladium atom, and less than 25,000 L-mol-1s-1 when
said catalyst contains a nickel atom.
369. The process as recited in claim 367 wherein
said bidentate ligand is coordinated to said nickel or
palladium atom through two nitrogen atoms.
370. The process as recited in claim 369 wherein
said ligand is an .alpha.-diimine.
371. The process as recited in claim 367 wherein
said olefin has the formula R17CH=CH2, wherein R17 is
hydrogen or n-alkyl.
372. A process for the polymerization of olefins,
comprising, contacting, at a temperature of about
-100°C to about +200°C:
a first compound which is a source of a
relatively noncoordinating monoanion;
a second compound of the formula
<IMG>
and one or more monomers selected from the
group consisting of ethylene, an olefin of the formula
R17CH=CH2 or R17CH=CHR17, cyclobutene, cyclopentene,
substituted norbornene, or norbornene;
wherein:
474

R2 and R5 are each independently hydrocarbyl or
substituted hydrocarbyl, provided that the carbon atom
bound to the imino nitrogen atom has at least two
carbon atoms bound to it;
R3 and R4 are each independently hydrogen,
hydrocarbyl, substituted hydrocarbyl, or R3 and R4
taken together are hydrocarbylene or substituted
hydrocarbylene to form a ring;
each R17 is independently hydrocarbyl or
substituted hydrocarbyl provided that R17 does not
contain any olefinic bonds;
T1 is hydrogen, hydrocarbyl not containing
olefinic or acetylenic bonds, R15C(=O)- or R15OC(=O)-;
S is chloride, iodide, or bromide; and
provided that, when norbornene or substituted
norbornene is present, no_other monomer is present.
373. The process as recited in claim 372 wherein
R2 and R5 are each independently hydrocarbyl, provided
that the carbon atom bound to the imino nitrogen atom
has at least two carbon atoms bound to it; and R3 and
R4 are each independently hydrogen, hydrocarbyl, or R3
and R4 taken together are hydrocarbylene to form a
ring; and each R17 is saturated hydrocarbyl.
374. The process as recited in claim 372 wherein
said source is an alkali metal salt of said anion.
375. The process as recited in claim 372 wherein
T1 is methyl.
376. The process as recited in claim 372 wherein
said monomer is ethylene only, and R11 is hydrogen.
377. The process as recited in claim 372 wherein
one or more comonomer selected from the group
consisting of: a compound of the formula
CH2=CH(CH2)m CO2R1, wherein R1 is hydrogen or, hydrocarbyl
or substituted hydrocarbyl containing 1 to 10 carbon
atoms, and m is 0 or an integer of 1 to 16; CO; and a
vinyl ketone is also present.
378. The process as recited in claim 372 done in
the presence of a solvent.
475

379. The process as recited in claim 368 used to
make a block polymer.
380. The process as recited in claim 368 wherein
said monoanion is BAF, SbF6, PF6, or BF4.
381. The process as recited in claim 374 wherein
said monoanion is BAF-, SbF6-, PF6-, or BF4-.
382. The process as recited in claim 377 wherein a
monomer is ethylene or propylene.
383. The process as recited in claim 372 wherein
the monomers are ethylene and propylene.
384. A polyolefin, comprising, a polymer made by
polymerizing one or more monomers of the formula
H2C=CH(CH2)e G by contacting said monomers with a
transition metal containing coordination polymerization
catalyst, wherein:
each G is independently hydrogen or -CO2R1;
each a is independently 0 or an integer of 1 to
20;
each R1 is independently hydrogen, hydrocarbyl
or substituted hydrocarbyl;
and provided that:
said polymer has at least 50 branches per 1000
methylene groups;
in at least 50 mole percent of said monomers G
is hydrogen;
except when no branches should be theoretically
present, the number of branches per 1000 methylene
groups is 90% or less than the number of theoretical
branches per 1000 methylene groups, or the number of
branches per 1000 methylene groups is 110% or more of
theoretical branches per 1000 methylene groups; and
when there should be no branches theoretically
present, said polyolefin has 50 or more branches per
1000 methylene groups;
and provided that said polyolefin has at least
two branches of different lengths containing less than
6 carbon atoms each.
476

395. The polyolefin as recited in claim 384
wherein except when no branches should be theoretically
present the number of branches per 1000 methylene
groups is 80% or less than the number of theoretical
branches per 1000 methylene groups, or the number of
branches per 1000 methylene groups is 1200 or more of
theoretical branches per 1000 methylene groups; and
when there should be no branches theoretically
present, said polyolefin has 75 or more branches per
1000 methyl ene groups .
385. A polyolefin, comprising, a polymer made by
polymerizing one or more monomers of the formula
H2C=CH(CH2)e G by contacting said monomers with a
transition metal containing coordination polymerization
catalyst, wherein:
each G is independently hydrogen or -CO2R1;
each a is independently 0 or an integer of 1 to
20;
R1 is independently hydrogen, hydrocarbyl or
substituted hydrocarbyl;
and provided that:
said polymer has at least 50 branches per 1000
methylene groups;
in at least 50 mole percent of said monomers G
is hydrogen;
said polymer has at least 50 branches of the
formula -(CH2)f G per 1000 methylene groups, wherein
when G is the same as in a monomer and e~f, and/or for
any single monomer of the formula H2C=CH(CH2)e G there
are less than 90% of the number of theoretical branches
per 1000 methylene groups, or more than 110% of the
theoretical branches per 1000 methylene groups of the
formula -(CH2)f G and f=e, and wherein f is 0 or an
integer of 1 or more;
and provided that said polyolefin has at least two
branches of different lengths containing less than 6
carbon atoms each.
477

387. The polyolefin as recited in claim 386
wherein when G is the same as in a monomer and e~f,
and/or for any single monomer of the formula
H2C=CH(CH2)e G there are less tan 80% of the number of
theoretical branches per 1000 methylene groups, or more
than 120% of the theoretical branches per 1000
methylene groups of the formula -(CH2)f G and f=e.
388. A tackifier for an adhesive comprising the
polymer of claim 1, 2, 3, 5, 6 or 7.
389. An oil additive for smoke suppression in two-
stroke gasoline engines comprising the polymer of claim
1, 2, 3, 4, 5, 6, or 7.
390. A base resin for a hot melt adhesive, a
pressure sensitive adhesive or a solvent applied
adhesive comprising the polymer of claim 1, 2, 3, 4, 5,
6 or 7.
391. A viscosity modifier for lubricating oils
comprising the polymer of claim 1, 2, 3, 4, 5, 6 or 7.
392. A coating or penetrant comprising the polymer
of claim 1, 2, 4, 5, 6 or 7.
393. A base polymer for caulking comprising the
polymer of claim 1, 2, 3, 4, 5, 6 or 7.
394. The polymer of claim 1, 2, 4, 5, 6 or 7 which
is grafted so it contains functional groups.
395. A toughener for a thermoplastic or a
thermoset comprising the polymer of claim 1-4.
396. A modifier for asphalt comprising the polymer
of claim 1, 3, 4, 6, 7, 332 or 343.
397. The polymer of claim 1, 3, 4, 6, 7, 332 or
343 which is chlorinated or chlorosulfonated.
398. The polymer of claim 17 which is elastomeric.
399. A wire insulation or jacketing comprising the
polymer of claim 1, 3, 4, 6, 7, 332 or 343.
400. A toughener for polyolefins comprising the
polymer of claim 1, 3, 4, 6, 7, 332 or 343.
401. A base for a synthetic lubricant comprising
the polymer of claim 1, 4, 6, 7, 332 or 343.
478

402. A drip suppressant for synthetic polymers
comprising the polymer of claim 1, 3, 4, 6, 7, 332 or
343.
403. A blown or cast film, or a sheet comprising
the polymer of claim 1, 3, 4, 6, 7, 332 or 343.
404. An additive for wax candles for smoke
suppression or drip control comprising the polymer of
claim 1, 4, 6, 7, 332 or 343.
405. A base resin for carpet backing comprising
the polymer of claim 1, 3, 4, 6, 7, 332 or 343.
406. A capliner resin comprising the polymer of
claim 1, 3, 4, 6, 7, 332 or 343.
407. A thermal transfer imaging resin comprising
the polymer of claim 1, 4, 6, 7, 332 or 343.
408. An extrusion or coextrusion onto a plastic,
metal, textile or paper web comprising the polymer of
claim 1, 3, 4, 6, 7, 332 or 343.
409. A laminating adhesive for glass comprising
the polymer of claim 1, 3, 4, 6, 7, 332 or 343.
410. A foamed object comprising the polymer of
claim 1, 3, 4, 6, 7, 332 or 343.
411. A powder used to coat an object comprising
the polymer of claim 1, 3, 4, 6, 7, 332 or 343.
412. A hose comprising the polymer of claim 1, 3,
4, 6, 7, 332 or 343.
413. A pour point depressant for a fuel or oil
comprising the polymer of claim 1, 3, 4, 6, 7, 332 or
343.
414. A nonwoven fabric comprising the polymer of
claim 1, 3, 4, 6, 7, 332 or 343.
415. A roofing membrane comprising the polymer of
claim 1, 3, 4, 6, 7, 332 or 343.
416. A reactive diluent for an automotive finish
comprising the polymer of claim 7, 8, 9, 10, 11 or 12.
417. An ionomer comprising the polymer of claim 7,
8, 9, 10, 11 or 12.
418. A molding resin comprising the ionomer of
claim 417.
479

419. A core for the initiation of condensation
polymerizations yielding a grafted branched polymer,
comprising the polymer of claim 7, 8, 9, 10, 11, or 12.
420. A compatiblizing agent comprising the polymer
of claim 3, 6 or 7.
421. A toughener for a thermoplastic or thermoset
comprising the polymer of claim 1, 3, 4, 6, 7, 332 or
343.
422. An internal plasticizer for polymers
comprising the polymer of claim 1, 3, 4, 6, 7, 332 or
343.
423. An adhesive for adhering a polymer comprising
the polymer of claim 3, 6, 7, 332 or 343.
424. A curing agent for a polymer containing
complimentary functional groups comprising the polymer.
of claim 3, 6 or 7.
425. An additive to thermoplastic polymers to
improve the adhesion of paint thereto comprising the
polymer of claim 3, 6 or 7.
426. A polymer blend comprising the polymer of
claim 1, 3, 4, 6, 7, 332 or 343 and at least one other
polymer.
427. A polymer of one or more alpha-olefins of the
formula CH2=CH(CH2)a H wherein a is an integer of 2 or
more, which contains the structure
<IMG>
wherein R35 is an alkyl group and R36 is an alkyl group
containing two or more carbon atoms, and provided that
R35 is methyl in at least about 2 mole percent of the
total amount of (XXV) in said polymer.
428. The polymer as recited in claim 427 wherein a
structure in which R35 is methyl is about 5 mole
percent or more of the total amount of (XXV) in said
polymer.
480

429. The polymer as recited in claim 4~7 wherein a
structure in which R35 is methyl is about 50 mole
percent or more of the total amount of (XXV) in said
polymer.
430. A polymer of one or more alpha-olefins of the
formula CH2=CH(CH2)a H wherein a is an integer of 2 or
more, wherein said polymer contains methyl branches and
said methyl branches are about 25 to about 75 mole
percent of the total branches in said polymer.
431. The polymer as recited in claim 430 which
contains branches of the formula -(CH2)a H.
432. The polymer as recited in claim 430 which
contains branches of the formula -(CH2)n H wherein n is
an integer of 6 or greater.
433. The polymer as recited in claim 431 which
contains the structure
<IMG>
and wherein (XXVI) is present in an amount of 0.5
branches of (XXVI) or more per 1000 methylene atoms
greater than can be accounted for by end groups.
434. A polyethylene containing the structure
(XXVII) in an amount greater than can be accounted for
by end groups.
<IMG>
435. The polyethylene as recited in claim 434
which contains about 2 or more of (XXVII) per 1000
methylene groups in said polymer.
436. A polypropylene containing one or both of the
structures (XXVIII) and (XXIX), provided that:
(XXIX), if present is present in an amount
greater than or equal to 0.5 of (XXIX) per 1000
481

methylene groups greater than can be accounted for by
end groups;
or the polymer contains at least 0.5 or more of
(XXVIII) per 1000 methylene groups, if (XXVIII) is
present.
<IMG>
437. The polypropylene as recited in claim, 436
which contains about 15 or more groups of structure
(XXVIII) per 1000 methylene groups in said
polypropylene.
438. The polypropylene as recited in claim 436
which contains about 15 or more groups of structure
(XXIX) per 1000 methylene groups in said polypropylene.
439. A process for the formation of linear .alpha.-
olefins, comprising, contacting, at a temperature of
about -100°C to about +200°C:
ethylene;
a first compound W, which is a neutral Lewis acid
capable of abstracting X- to form WX-, provided that
the anion formed is a weakly coordinating anion, or a
cationic Lewis or Bronsted acid whose counterion is a
weakly coordinating anion; and
a second compound of the formula
<IMG>
wherein:
482

R2 and R5 are each independently hydrocarbyl or
substituted hydrocarbyl;
R3 and R4 are each independently hydrogen,
substituted hydrocarbyl, hydrocarbyl, or R3 and R4
taken together are hydrocarbylene or substituted
hydrocarbylene to form a ring; and
Q and S are each independently chlorine,
bromine, iodine or alkyl; and
wherein an .alpha.-olefin containing 4 to 40 carbon
atoms is produced.
440. The process as recited in claim 439 wherein
said linear .alpha.-olefin has the formula H2C=CHR1, wherein
R1 is n-alkyl containing 2 to 30 carbon atoms.
441. The process as recited in claim 439 wherein
R2 and R5 are phenyl.
442. The process as recited in claim 439 wherein
R3 and R4 are hydrogen, methyl or 1,8-naphthylylene.
443. The process as recited in claim 440 wherein
R3 and R4 are hydrogen, methyl or 1,8-naphthylylene.
444. The process as recited in claim 439 wherein
said second compound is an alkyl aluminum compound.
445. The process as recited in claim 444 wherein
said alkyl aluminum compound is R93Al, R92AlCl, R9AlCl2,
R93Al2Cl3, or R9AlO, wherein R9 is alkyl containing 1 to
25 carbon atoms.
446. The process as recited in claim 445 wherein
R9 contains 1 to 4 carbon atoms.
447. The process as recited in claim 443 wherein
said second compound is R93Al, R92AlCl, R9AlCl2, or
R9AlO, R93Al2Cl3, wherein R9 is alkyl containing 1 to 25
carbon atoms.
448. The process as recited in claim 439 carried
out at a temperature of about 25°C to about 100°C.
449. The process as recited in claim 439 wherein a
partial pressure of said ethylene is about atmospheric
pressure to about 275 MPa.
450. The process as recited in claim 439 wherein
R2 and R5 are each independently hydrocarbyl, provided
483

that the carbon atom bound to the imino nitrogen atom
has at least two carbon atoms bound to it; and R3 and
R4 are each independently hydrogen, hydrocarbyl, or R3
and R4 taken together are hydrocarbylene to form a
ring.
451. A process for the formation of linear .alpha.-
olefins, comprising, contacting, at a temperature of
about -100°C to about +200°C:
ethylene and a compound of the formula
<IMGS>
wherein:
R2 and R5 are each independently hydrocarbyl or
substituted hydrocarbyl;
R3 and R4 are each independently hydrogen,
substituted hydrocarbyl, hydrocarbyl, or R3 and R4
taken together are hydrocarbylene or substituted
hydrocarbylene to form a ring;
T1 is hydrogen or n-alkyl containing up to 38
carbon atoms;
Z is a neutral Lewis base wherein the donating
atom is nitrogen, sulfur, or oxygen, provided that if
the donating atom is nitrogen then the pKa of the
484

conjugate acid of that compound (measured in water) is
less than about 6;
U is n-alkyl containing up to 38 carbon atoms;
and
X is a noncoordinating anion;
and wherein an .alpha.-olefin containing 4 to 40 carbon
atoms is produced.
452. A process for the production of polyolefins,
comprising, contacting, at a temperature of about 0°C
to about +200°C, a compound of the formula.
<IMG>
and one or more monomers selected from the group
consisting of ethylene, an olefin of the formula
R17CH=CH2 or R17CH=CHR17, cyclobutene, cyclopentene,
substituted norbornene, and norbornene,
wherein:
M is Ni(II) or Pd(II);
A is a .pi.-allyl or .pi.-benzyl group;
R2 and R5 are each independently hydrocarbyl or
substituted hydrocarbyl, provided that the carbon atom
bound directly to the imino nitrogen atom has at least
two carbon atoms bound to it;
R3 and R4 are each independently hydrogen,
hydrocarbyl, substituted hydrocarbyl or R3 and R4 taken
together are hydrocarbylene or substituted
hydrocarbylene to form a ring;
each R17 is independently hydrocarbyl or
substituted hydrocarbyl provided that any olefinic bond
in said olefin is separated from any other olefinic
bond or aromatic ring by a quaternary carbon atom or at
485

least two saturated carbon atoms; R3 is hydrogen or
hydrocarbyl or substituted hydrocarbyl containing 1 to
10 carbon atoms;
and X is a weakly coordinating anion;
and provided that;
when norbornene or substituted norbornene is
present, no other monomer is present; and
when M is Pd a diene is not present.
453. The process as recited in claim 452 wherein
said temperature is about 20°C to about 100°C.
454. The process as recited in claim 452 wherein
said olefin is ethylene or a linear .alpha.-olefin.
455. The process as recited in claim 452 wherein
said olefin is ethylene.
456. The process as recited in claim 452 wherein
R2 and R5 are each independently hydrocarbyl, provided
that the carbon atom bound to the imino nitrogen atom
has at least two carbon atoms bound to it; and R3 and
R4 are each independently hydrogen, hydrocarbyl, or R3
and R4 taken together are hydrocarbylene to form a
ring.
457. The process as recited in claim 452 or 454
wherein a Lewis acid is also present.
458. The process as recited in claim 452 wherein M
is Ni(II).
459. The process as recited in claim 452 wherein M
is PD(II).
460. The process as recited in claim 452 wherein
said .pi.-allyl or .pi.-benzyl group is selected from the
group consisting of
486

<IMGS>
wherein R is hydrocarbyl.
461. A compound of the formula
<IMG>
wherein:
M is Ni(II) or Pd(II);
A is a .pi.-allyl or .pi.-benzyl group;
R2 and R5 are each independently hydrocarbyl or
substituted hydrocarbyl, provided that the carbon atom
bound directly to the imino nitrogen atom has at least
two carbon atoms bound to it;
R3 and R4 are each independently hydrogen,
hydrocarbyl, substituted hydrocarbyl or R3 and R4 taken
together are hydrocarbylene or substituted
hydrocarbylene to form a ring;
each R17 is independently hydrocarbyl or
substituted hydrocarbyl provided that any olefinic bond
in said olefin is separated from any other olefinic
bond or aromatic ring by a quaternary carbon atom or at
least two saturated carbon atoms; R1 is hydrogen, or
487

hydrocarbyl or substituted hydrocarbyl containing 1 to
10 carbon atoms;
and X is a weakly coordinating anion;
and provided that when M is Pd a diene is not
present.
462. The compound as recited in claim 461 wherein
R2 and R5 are each independently hydrocarbyl, provided
that the carbon atom bound to the imino nitrogen atom
has at least two carbon atoms bound to it; and R3 and
R4 are each independently hydrogen, hydrocarbyl, or R3
and R4 taken together are hydrocarbylene to form a
ring.
463. The compound as recited in claim 461 wherein
M is Ni(II).
464. The compound as recited in claim 461 wherein.
M is Pd(II).
465. The compound as recited in claim 461 wherein
said .pi.-allyl or .pi.-benzyl group is selected from the
group consisting of
<IMGS>
wherein R is hydrocarbyl.
466. A compound of the formula
488

<IMG>
wherein:
R3 and R4 are each independently hydrogen,
hydrocarbyl, substituted hydrocarbyl or R3 and R4 taken
together are hydrocarbylene or substituted
hydrocarbylene to form a ring;
R54 is hydrocarbyl or substituted hydrocarbyl,
provided that the carbon atom bound directly to the
imino nitrogen atom has at least two carbon atoms bound
to it;
each R55 is independently hydrogen,
hydrocarbyl, substituted hydrocarbyl, or a functional
group;
M is Ni or Pd;
W is alkylene or substituted alkylene
containing 2 or more carbon atoms;
Z is a neutral Lewis base wherein the donating
atom is nitrogen, sulfur, or oxygen, provided that if
the donating atom is nitrogen then the pKa of the
conjugate acid of that compound (measured in water) is
less than about 6, or an olefin of the formula
R17CH=CHR17;
each R17 is independently hydrogen, saturated
hydrocarbyl or substituted saturated hydrocarbyl; and
X is a weakly coordinating anion;
and provided that when M is Ni, W is alkylene and
each R17 is independently hydrogen or saturated
hydrocarbyl.
467. The compound as recited in claim 466 wherein
R3 and R4 are each independently hydrogen or
489

hydrocarbyl, or R3 and R4 taken together are
hydrocarbylene to form a ring; and R54 is hydrocarbyl.
468. The compound as recited in claim 466 or 467
wherein each R55 is independently hydrogen or alkyl
containing 1 to 10 carbon atoms.
469. The compound as recited in claim 466 wherein
Z is neutral Lewis base.
470. The compound as recited in claim 469 wherein
Z is a dialkyl ether.
471. The compound as recited in claim 466 wherein
Z is R17CH=CHR17.
472. The compound as recited in claim 471 wherein
each R17 is independently hydrogen or alkyl.
473. The compound as recited in claim 471 wherein
both of R17 are hydrogen.
474. The compound as recited in claim 466 wherein
W is -CH(CH3)CH2- or -C(CH3)2CH2-.
475. The compound as recited in claim 471 wherein
W is a divalent polymeric radical derived from the
polymerization of R17CH=CHR17.
476. A process for the production of a compound of
the formula
<IMG>
comprising, heating a compound of the formula
490

<IMG>
at a temperature of about -30°C to about +I00° for a
sufficient time to produce (XXXVIII), and wherein:
R3 and R4 are each independently hydrogen,
hydrocarbyl, substituted hydrocarbyl or R3 and R4 taken
together are hydrocarbylene or substituted
hydrocarbylene to form a ring;
R54 is hydrocarbyl or substituted hydrocarbyl,
provided that the carbon atom bound directly to the
imino nitrogen atom has at least two carbon atoms bound
to it;
each R55 is independently hydrogen,
hydrocarbyl, substituted hydrocarbyl, or a functional
group;
R56 is alkyl containing 2 to 30 carbon atoms;
M is Ni or Pd;
T5 is alkyl;
W is alkylene containing 2 to 30 carbon atoms;
Z is a neutral Lewis base wherein the donating
atom is nitrogen, sulfur, or oxygen, provided that if
the donating atom is nitrogen then the pKa of the
conjugate acid of that compound (measured in water) is
less than about 6; and
X is a weakly coordinating anion.
477. The process as recited in claim 476 wherein
R3 and R4 are each independently hydrogen or
hydrocarbyl, or R3 and R4 taken together are
hydrocarbylene to form a ring; and R54 is hydrocarbyl.
478. The process as recited in claim 476 or 472
wherein each R55 is independently hydrogen or alkyl
containing 1 to 10 carbon atoms.
491

479. The process as recited in claim 4 wherein Z
is a dialkyl ether.
480. The process as recited in claim 476 wherein W
is -CH(CH3)CH2- or -C(CH3)2CH2-
481. The process as recited in claim 476, 477, 479
or 480 wherein T5 is methyl.
482. A process for the polymerization of olefins,
comprising, contacting a compound of the formula
<IMG>
and one or more monomers selected from the group
consisting of ethylene, an olefin of the formula
R17CH=CH2 or R17CH=CHR17, cyclobutene, cyclopentene,
substituted norbornene, and norbornene,
wherein:
R3 and R4 are each independently hydrogen,
hydrocarbyl, substituted hydrocarbyl or R3 and R4 taken
together are hydrocarbylene or substituted
hydrocarbylene to form a ring;
R54 is hydrocarbyl or substituted hydrocarbyl,
provided that the carbon atom bound directly to the
imino nitrogen atom has at least two carbon atoms bound
to it;
each R55 is independently hydrogen,
hydrocarbyl, substituted hydrocarbyl, or a functional
group;
M is Ni or Pd;
W is alkylene or substituted alkylene
containing 2 or more carbon atoms;
492

Z is a neutral Lewis base wherein the donating
atom is nitrogen, sulfur, or oxygen, provided that if
the donating atom is nitrogen then the pKa of the
492a

conjugate acid of that compound (measured in water) is
less than about 6, or an olefin of the formula
R17CH=CHR17;
each R17 is independently hydrogen, saturated
hydrocarbyl or substituted saturated hydrocarbyl; and
X is a weakly coordinating anion;
and provided that:
when M is Ni, W is alkylene and each R17 is
independently hydrogen or saturated hydrocarbyl;
and when norbornene or substituted norbornene is
present, no other monomer is present.
483. The process as recited in claim 482 wherein
R3 and R4 are each independently hydrogen or
hydrocarbyl, or R3 and R4 taken together are
hydrocarbylene to form a ring; and R54 is hydrocarbyl.
484. The process as recited in claim 482 or 483
wherein each R55 is independently hydrogen or alkyl
containing 1 to 10 carbon atoms.
485. The process as recited in claim 482 wherein Z
is a dialkyl ether.
486. The process as recited in claim 482 wherein Z
is R17CH=CHR17.
487. The process as recited in claim 482 wherein
each R17 is independently saturated hydrocarbyl or
hydrogen.
488. The process as recited in claim 482 wherein
both of R17 are hydrogen.
489. The process as recited in claim 482 wherein W
is -CH(CH3)CH2- or -C(CH3)2CH2-.
490. The process as recited in claim 482 wherein
said temperature is about 20°C to about 100°C.
491. The process as recited in claim 482 wherein
said olefin is ethylene or a linear .alpha.-olefin.
492. The process as recited in claim 482 wherein
said olefin is ethylene, propylene or a combination of
ethylene and propylene.
493

493. The process as recited in claim 486 wherein
said olefin is ethylene, propylene or a combination of
ethylene and propylene.
494. The process as recited in claim 489 wherein
said olefin is cyclopentene.
495. The process as recited in claim 482 wherein
said olefin is cyclopentene.
496. A homopolypropylene containing about 10 to
about 700 .delta.+ methylene groups per 1000 methylene
groups.
497. The homopolypropylene as recited in claim 496
containing about 25 to about 300 .delta.+ methylene groups
per 1000 methylene groups.
498. A homopolypropylene wherein a ratio of .delta.+.gamma.
methylene groups is about 0.5 to about 7.
499. The homopolypropylene as recited in claim 498
wherein said ratio is about 0.7 to 2Ø
500. A homopolypropylene in which about 30 to
about 85 mole percent of monomer units are enchained in
an .omega.,1 fashion.
501. The homopolypropylene as recited in claim 500
wherein about 30 to about 60 mole percent of the
monomer units are enchained in an .omega.,1 fashion.
502. A process for the formation of linear .alpha.-
olefins, comprising, contacting, at a temperature of
about -100°C to about +200°C:
ethylene;
and a Ni [II] compound of
<IMG>
R2 and R5 are each independently hydrocarbyl or
substituted hydrocarbyl, provided that the carbon atom
494

bound to the imino nitrogen atom has-at least two
carbon atoms bound to it;
R3 and R4 are each independently hydrogen,
hydrocarbyl, substituted hydrocarbyl, or R3 and R4
taken together are hydrocarbylene or substituted
hydrocarbylene to form a carbocyclic ring and
wherein an .alpha.-olefin containing 4 to 40 carbon
atoms is produced.
503. The process as recited in claim 502 wherein
said linear .alpha.-olefin has the formula HOC=CHR1, wherein
R1 is n-alkyl containing 2 to 30 carbon atoms.
504. The process as recited in claim 502 wherein
R2 and R5 are phenyl.
505. The process as recited in claim 502 wherein
R3 and R4 are hydrogen, methyl or 1,8-naphthylylene.
506. The process as recited in claim 503 wherein
R3 and R4 are hydrogen, methyl or 1,8-naphthylylene.
507. The process as recited in claim 502 carried
out at a temperature of about 25°C to about 100°C.
508. The process as recited in claim 502 wherein a
partial pressure of said ethylene is about atmospheric
pressure to about 275 MPa.
509. The process as recited in claim 502 wherein
R2 and R5 are each independently hydrocarbyl, provided
that the carbon atom bound to the imino nitrogen atom
has at least two carbon atoms bound to it; and R3 and
R4 are each independently hydrogen, hydrocarbyl, or R3
and R4 taken together are hydrocarbylene to form a
ring.
510. A polymer blend comprising the polymer of
claim 345, 349, 353, 354, 355, 358, 360 or 361 and one
other polymer.
511. A nonwoven fabric wherein at least some
fibers comprise the polymer of claim 345, 349, 353,
354, 355, 358, 360 or 361.
512. A shaped part comprising the polymer of claim
345, 349, 353, 354, 355, 358, 360 or 361.
495

513. A sheet or film comprising the polymer of
claim 345, 349, 353, 354, 355, 358, 360 or 361.
514. A nonwoven fabric or microfiber comprising
the polymer of claim 345, 349, 353, 354, 355, 358, 350
or 361.
515. A laminate wherein one or more of the layers
comprises the polymer of claim 345, 349, 353, 354, 355,
358, 350 or 361.
516. The laminate as recited in claim 511 wherein
a barrier layer is present.
517. A fiber comprising the polymer of claim 345,
349, 353, 354, 355, 358, 360 or 361.
518. A foam or foamed object comprising the
polymer of claim 345, 349, 353, 354, 355, 358, 360 or
361.
519. A microporous membrane comprising the polymer
of claim 345, 349, 353, 354, 355, 358, 360 or 361.
520. The polymer of claim 345, 349, 353, 354, 355,
358, 360 or 361 which is crosslinked.
521. The polymer of claim 345, 349, 353, 354, or
355 which is heat treated.
522. The polymer as recited in claim 521 which has
20 percent or more crystallinity.
523. A composition comprising the polymer of claim
345, 349, 353, 354, 355, 358, 360 or 361 and a
nucleating agent.
524. A composition comprising the polymer of claim
345, 349, 353, 354, 355, 358, 360 or 361 and a flame
ralardant.
525. A composition comprising the polymer of claim
345, 349, 353, 354, 355, 358, 360 or 361 and an
antioxidant.
526. A composition comprising the polymer of claim
345, 349, 353, 354, 355, 358, 360 or 361 and a filler
or reinforcer.
527. A composition comprising the polymer of claim
345, 349, 353, 354, 355, 358, 360 or 361 which is
electrically conductive.
496

528. A process, comprising, contacting, at a
temperature of about -80°C to about +20°C, a compound
of the formula (~4-1,5-COD)PdMe2 and a diimine of the
formula
<IMG>
to produce a compound of the formula
<IMG>
wherein:
COD is 1,5-cyclooctadiene;
R2 and R5 are each independently hydrocarbyl or
substituted hydrocarbyl, provided that the carbon atom
bound to the imino nitrogen atom has at least two
carbon atoms bound to it; and
R3 and R4 are each independently hydrogen,
hydrocarbyl, substituted hydrocarbyl or R3 and R4 taken
together are hydrocarbylene or substituted
hydrocarbylene to form a ring.
529. The process as recited in claim 528 wherein
said temperature is about -50°C to about +10°C.
530. The process as recited in claim 528 wherein
R2 and R5 are both 2-t-butylphenyl or 2,5-di-t-
butylphenyl, and R3 and R4 taken together are 1,8-
497

naphthylylene, or R3 and R4 are both hydrogen or
methyl.
531. The process as recited in claim 528 wherein
R2 and R5 are each independently hydrocarbyl, provided
that the carbon atom bound to the imino nitrogen atom
has at least two carbon atoms bound to it; and R3 and
R4 are each independently hydrogen, hydrocarbyl, or R3
and R4 taken together are hydrocarbylene to form a
ring.
532. The compound as recited in claim 232, 248,
253, 259, 267, 317, 334, 339, 461 or 466 wherein X is
part of a heterogeneous support.
533. The compound as recited in claim 532 wherein
said heterogeneous support is montmorillonite.
534. The process as recited in claim 49, 97, 176,
199, 280, 299, 451, 452 or 482 wherein X is part of a
heterogeneous support.
535. The process as recited in claim 49, 97, 176,
199, 280, 299, 451, 452 or 482 wherein a polymerization
catalyst is supported on a heterogeneous support.
536. The compound as recited in claim 232, 248,
253, 259, 267, 317, 334, 339, 461 or 466 which is
supported on a heterogeneous support.
537. The process as recited in claim 49, 97, 176,
199, 280, 299, 451, 452 or 482 wherein the
polymerization is run in the gas phase.
538. The process as recited in claim 537 which is
run in a fluidized bed reactor.
539. A flexible pouch made from a single or
multilayer film which comprises the polymer of claim 1,
3, 9, 6, 7, 332 or 343.
540. The polymer of claim 1, 3, 4, 6, 332 or 343
grafted with a compound containing ethylenic
unsaturation and a functional group.
541. The polymer as recited in claim 540 wherein
said functional group is carboxyl, carboxylic
anhydride, ester or a carboxylate salt.
498

542. A wrap packaging film having differential
cling, comprising a film laminate having at least two
layers;
an outer reverse layer which comprises a
polymer of claim 1, 3, 4, 6, 7, 332 or 343, and a
tackifier present in sufficent amount to impart cling
properties; and
an outer obverse layer which has a density of
at least about 0.916 g/mL and which has little or no
cling; and
provided that a density of said outer reverse
layer is at least 0.008 g/mL less than that of a
density of said outer obverse layer.
543. A fine denier fiber comprising the polymer of
claim 1, 3, 4, 6, 7, 332 or 343.
544. A composition, comprising, a polymer of claim
1, 3, 4, 6, 7, 332 or 343 and an antifogging agent.
545. The process as recited in claim 13, 15 or 142
wherein said bidentate ligand or second compound is
(XXX) and n is 2, all of R30, R28 and R29 are hydrogen,
and both of R44 and R45 are 9-anthracenyl.
546. The process as recited in claim 65 or 84
wherein said compound or said second compound is (XVII)
and n is 2, all of R30, R28 and R29 are hydrogen, and
both of R44 and R45 are 9-anthracenyl.
547. The process as recited in claim 65 or 84
wherein said compound or said second compound is (XVII)
and n is 2, all of R30, R28 and R29 are hydrogen, both of
R44 and R45 are 9-anthracenyl, M is Ni, and n is 2.
548. The compound or process as recited in claim
299 or 317 wherein M is Ni or Pd and m is 2.
549. The process as recited in claim 299 wherein M
is Ni.
550. The process as recited in claim 49 wherein
said olefin comprises cyclopentene.
551. The process as recited in claim 65 wherein
said olefin comprises cyclopentene.
499

552. The process as recited in claim 452 wherein
said olefin comprises cyclopentene.
553. The process as recited in claim 548 wherein
said monomer comprises cyclopentene.
554. The process as recited in claim 17, 48, 124,
151, 156, 167, 180, 232, 298, 316, 550, 551, 552 or 553
wherein cyclopentene is a solvent.
555. The process as recited in claim 37 wherein:
R2 and R5 are both 2,4,6-trimethylphenyl or
2,6-dimethylphenyl;
R3 and R4 taken together are 1,8-naphthylylene;
y and z are both 1;
M is Ni;
Q and S are both chloride, iodide or bromide;
and
m is 2.
556. The process as recited in claim 555 wherein
said first compound is an alkylaluminum compound.
557. The process as recited in claim 556 wherein
said alkylaluminum compound is ethylaluminum dichloride
or methylaluminoxane.
556. The process as recited in claim 555, 556 or
557 wherein said monomer comprises cyclopentene.
559. The process as recited in claim 558 wherein
cyclopentene is a solvent.
560. The polymer as recited in claim 1, 3, 4, 6,
332 or 343 which has:
a melt flow ratio, I10/I2 ~ 5.63;
a molecular weight distribution, Mw/Mn, defined
by the equation: Mw/Mn ~ (I10/I2)-4.63; and
a critical shear rate at onset of surface melt
fracture of at least 50 percent greater than the
critical shear rate at the onset of surface melt
fracture of a linear olefin polymer having about the
same I2 and Mw/Mn.
561. A composition comprising:
the polymer as recited in claim 1, 3, 4, 6, 332 or
343 which has:
500

a melt flow ratio, I10/I2, > or = 5.63;
a molecular weight distribution, Mw/Mn, defined
by the equation: Mw/Mn < OR = (I10/I2)-4.63; and
a critical shear rate at onset of surface melt
fracture of at least 50 percent greater than the
critical shear rate at the onset of surface melt
fracture of a linear olefin polymer having about the
same I2 and Mw/Mn; and
at least one of: natural polymer; a synthetic
polymer chosen from the polymer of claims 1, 3, 4, 6,
332, or 343; or a conventional high density
polyethylene, low density polyethylene or linear low
density polyethylene polymer.
562. The polymer as recited in claim 1, 3, 4, 6,
332, 343, 383, 384, 385, 386 or 387 which has a melt
flow ratio, I10/I2 ~ 5.63, a molecular weight
distribution, Mw/Mn, defined by the equation: Mw/Mn ~
(I10/I2)-4.63, and a critical shear stress at onset of
gross melt fracture of greater than about 400 kPa.
563. A compound of the formula
<IMG>
wherein:
R2 and R5 are each independently hydrocarbyl or
substituted hydrocarbyl, provided that the carbon atom
bound to the imino nitrogen atom has at least two
carbon atoms bound to it; and
R3 and R4 are each independently hydrogen,
hydrocarbyl, substituted hydrocarbyl; and
Me is methyl.
564. The compound as recited in claim 563 wherein
R2 and R5 are both 2-t-butylphenyl, 2,6-
501

diisopropylphenyl, or 2,5-di-t-butylphenyl, and R3 and
R4 are both hydrogen or methyl.
565. The compound as recited in claim 563 wherein
R2 and R3 are each independently hydrocarbyl, provided
that the carbon atom bound to the imino nitrogen atom
has at least two carbon atoms bound to it; and R3 and
R4 are each independently hydrogen or hydrocarbyl.
566. A compound of the formula
<IMG>
wherein:
R2 and R5 are each independently hydrocarbyl or
substituted hydrocarbyl, provided that the carbon atom
bound to the imino nitrogen atom has at least two
carbon atoms bound to it; and
R3 and R4 are each independently hydrogen,
hydrocarbyl, substituted hydrocarbyl or R3 and R4 taken
together are hydrocarbylene or substituted
hydrocarbylene to form a ring.
501a

568. A compound of the formula
<IMG>
wherein:
M is Ti, Zr, Sc, V, Cr, or a rare earth metal
in the m oxidation state;
y + z = m
R2 and R5 are each independently hydrocarbyl or
substituted hydrocarbyl, provided that the carbon atom
bound to the imino nitrogen atom has at least two
carbon atoms bound to it;
R3 and R4 are each independently hydrogen,
hydrocarbyl, substituted hydrocarbyl, or R3 and R4
taken together are hydrocarbylene or substituted
hydrocarbylene to form a carbocyclic ring;
each Q is independently alkyl, hydride,
chloride, iodide, or bromide; and
each S is independently alkyl, hydride,
chloride, iodide, or bromide.
569. The compound as recited in claim 568 wherein
R3 and R4 are each independently hydrogen or methyl, or
R3 and R4 taken together are 1,8-naphthylylene, and
both R2 and R5 are 2,6-diisopropylphenyl.
570. The compound as recited in claim 568 wherein:
M is Ti(IV), Q and S are chloride, and y and z are
both 2;
M is Zr(IV), Q and S are chloride, and y and z are
both 2;
M is Sc(III), Q and S are chloride, y is 1 and z
is 2;
M is Cr(III), Q and S are chloride, y is 1 and s
is 2;
M is Cr(II), Q and S are chloride, y is 1 and s is
1; and
501b

Q ~~ alkyl, hydride, chloride, iodide, or
bromide; and
S is alkyl, hydride, chloride, iodide, or
bromide.
574. The compound as recited in claim 573 wherein
R29, R2~, and each of R30 are hydrogen.
575. The compound as recited in claim 573 wherein
both R44 and R45 are 2,4,6-trimethyl phenyl.
576. The compound as recited in claim 573 wherein:
M is Ni(II) and all of Q and S ara halogen; or
M is Ti(IV) and all of Q and S are halogen.
577. The compound as recited in claim 573 wherein
all of R28, R29 and R30 are hydrogen.
501d

M is V(III), Q and S are chloride, y is 1 and s is
2.
571. The compound as recited in claim 568 wherein
R2 and R5 are each independently hydrocarbyl, provided
that the carbon atom bound to the imine nitrogen atom
has at least two carbon atoms bound to it; R3 and R4
are each independently hydrogen, hydrocarbyl, or R3 and
R4 taken together are hydrocarbylene to form a
carbocyclic ring.
572. The compound as recited in claim 568 wherein:
M is Fe and m is 2;
M is Co and m is 2;
M is Zr and m is 4;
M is Sc and m is 3;
M is Cr and m is 2 or 3; or
M is V and m is 3.
573. A compound of the formula
<IMG>
wherein:
M is Ti, Zr, V, Cr, a rare earth metal, Co, Fe,
So, Pd, or Ni, of oxidation state m;
R44 is hydrocarbyl or substituted hydrocarbyl,
and R28 is hydrogen, substituted hydrocarbyl or
hydrocarbyl, or R44 and R28 taken together form a ring;
R45 is hydrocarbyl or substituted hydrocarbyl,
and R29 is hydrogen, substituted hydrocarbyl or
hydrocarbyl, or R45 and R29 taken together form a ring;
each R30 is independently hydrogen, substituted
hydrocarbyl or hydrocarbyl, or two of R30 taken
together form a ring;
n is 2 or 3;
y and z are positive integers;
y+z = m;
501c

Description

CA 02338581 2001-03-O1
' s
f
DEMANDES OU BREVETS VOLUMINEUX
LA PRESENTE PART1E DE CETTE DEMANDE OU CE BREVET
COMPREND PLUS D'UN TOME.
CEC1 EST LE TOME ~ DE
NOTE: Pour les tomes additionels, veuiilez coritacter le Bureau canadien des
brevets
JUMBO APPLICATiONSIPATENTS
THIS SECTION OF THE APPLICATtON/PATENT CONTAINS MORE
THlS 1S VOLUME OF
PIOTE:.For additional volumes'piease contact'the Canadian Patent Office

CA 02338581 2001-03-O1
..
a-OLEFINS AND OLEFIN POLYMERS AND PROCESSES THEREFOR
This application is a continuation-in-part of
pending prior application Serial No. 60/002,654, filed
August 22, 1995, is also a continuation-in-part of
pending application Serial No. 60/007,375, filed
November 15, 1995, is also a continuation-in-part of
pending application Serial No. 08/473,590, filed
June 7, 1995, which is a continuation-in-part of prior
pending application Serial No. 08/415,2$3, filed
April 3, 1995, which is a continuation-in-part of
pending prior application Serial No. 08/378,044 filed
January 24, 1995.
FIELD OF THE INVENTION
The invention concerns novel homo- and copolymers
oz ethylene and/or one or more acyclic olefins, and/or
selected cyclic olefins, and optionally selected ester,
carboxylic acid, or other functional group containing
olefins as comonomers; selected transition metal
containing polymerization catalysts; and processes for
making such polymers, intermediates for such catalysts,
and new processes for making such catalysts. Also
disclosed herein is a process for the production of
linear alpha-olefins by contacting ethylene with a
nickel compound of the formula [DAB]NiXz wherein DAB is
a selected a-diimine and X is chlorine, bromine, iodine
or alkyl, and a selected Lewis or Bronsted acid, or by
contacting ethylene with other selected a-diimine
nickel complexes
BACKGRODND OF THE INVENTION
Homo- and copolymers of ethylene (E) and/or one or
more acyclic olefins, and/or cyclic olefins, and/or
substituted olefins, and optionally selected olefinic
esters or carboxylic acids, and other types of
monomers, are useful materials, being used as plastics
for packaging materials, molded items, films, etc., and
as elastomers for molded goods, belts of various types,
in tires, adhesives, and for other uses. It is well
1
AMENDED SHEET

CA 02338581 2001-03-O1 PCTI(JS96101282
WO 96123010
"S':at 'i''e St=uC "°_ ,~r.= "bass sarl.~'_:S
~° ar t tL:_
~::OW .~. i:: ~ ,. .. ...
D:IVTLIers, and hence t~°_=r prOpertles a::uses, are
..ic~:ly dependent on the catal yst and specif is .
co~ditions used durinc their synthesis. In addition to
~~ese =asters processes ir. w~:ic~: thes_ types of
._ ,
y~ers car. be made at reduced cost are also
ir~,ocrta::t. Therefore, improved processes for maicir.c
suc'.~. inew! polymers are of interest. ~._so discloses .
here- a=a uses Lcr t~°_ novel polymers.
u-0=e=ins are cor,:mercial materials beinc
_ca=t__~_Gr_v useful as monomers and as chemical
=e--~;=s- tes. For a review of a-olefi.~.s, _-..._us~ra
____ _ .a
., .,
__.___ us=s and precar==io.~., see L . E 1 vers, et a=d
:.__..,~_._.' s Encyclopedia ct Industrial C~e~rist~y, ~=h
1 _~ , .__. _._ v'~verlacsgesellschaft m:.~.ri, weinh°-i~.
., _
236-251. They are use=ul as c~e:.~.ica:
~9, _ .
_._te--~~~d_ates and they are often made by the
c;~;~=r_za=ion of ethylene usin3 varioss types cf
catalw=~s. Therefore catalysts which are capable cr
?p _Jrmir_ a-olefins f~om ethylene are cor.stantl.,r soup t.
~~p,Rv pF ~ . TNVE'Ir'TZQ13
_._i= invention concerns a pciyolefin, which
....._ta_n.= about 60 to about =~0 branches per '_000
which contains ~~r every 100
~;___~._,_e-a Groups, and
-~~~ are methyl, about 30 tc about °~ °-=hv-
..__::c. --__ _.
2v ~~r, .~ t,.rS~C~cc, a::C::= __
b=a_nc__, about to about F_~~i_ - --
aDcu~ :~J buty,_ branches, about 3 to about __ ar,.y_
and about 30 to abo~~t 1=0 hexyi c= -cnQer
=a..~.ches.
3p _.__s _nvention also concer.~.s a pclyol e'-z which
cc-ta_-s about 20 to about 150 branches per 1000
methv_e.~.e groups, and which contains fcr every 100
.._~_...°_-- t::at a_-e methyl , about 4 to about 2G ethy,
~_anc=s, about I to abo::t 12 p-opyl branches, abou_ _
3~ to about .2 butyl branches, about 1 to about ~0 amyl
branc::es, and~0 to about 20 hexyl or longer branches.
~_sclosed herein is a polymer, consisting
peat units derived from the mcno~~er_=,
a=son=_a__y of r°-
- _. .~~t ,.., m r ~.G\

WO 96/23010 ~ 02338581 2001-03-O1 pCTNS96/01282
ethylene and a compound of the forrnuia
CH2=CH(CH2)mCO2Rl, wherein R1 is hydrogen, hydrocarbyl or
substituted hydrocarbyi, and m is 0 or an integer from
1 to 16, and which contains about 0.01 to about 40 mole
percent of repeat units derived from said compound, and
provided that said repeat units derived from said
compound are in branches of the formula -CH(CTi~)nCO~R',
in about 30 to about 70 mole percent of said branches n
is 5 or more, in about 0 to about 20 mole percent n is
4, in abcut 3 to~60 mole percent n is 1, 2 and 3, and
in about 1 to about 60 mole percent n is 0.
This invention concerns a polymer of one or more
alaha-olefins of the formula CH2=CH(CH2)aH wherein a is
an integer cf 2 or more, which contains the s~ructure
I~ ;XXV
R35 R36
-CH-CH2-CH- (XXV)
wherein R35 is an alkyl group and R36 is an alkyl group
?0 containing two or more carbon atoms, and provided that
R35 is methyl in about 2 mole percent or more of the
total amount of (XXV) in said polymer.
This invention also includes a polymer of one or
more alaha-olefins of the formula CH2=CH(CHz)aH wherein
'_'~ a is an integer of 2 or more, wherein said polymer
contains methyl branches and said methyl branches
comprise about 25 to about 75 mole percent of the total
branches.
This invention also concerns a polyethylene
s0 containing the structure (XXVII) in an amount greater
than can be accounted for by end groups, and preferably
at least 0.5 or more of such branches per 1000
methylene groups than can be accounted for by end
groups.
3;
.w ~nnTrrv rTr e~uccT tDl 11 C 9~',1

CA 02338581 2001-03-O1
WO 96/23010 PCT/US96/01282
CH3
-CH2-CH-CH2CH3 (XXVII)
This invention also concerns a polypropylene
containing one or both of the structures (XXVIII) and
lXXIX) and in the case of lXXIX) in amounts greater
than can be accounted for by end groups. Preferably at
least 0.5 more of (XXIX) branches per 1000 methylene
groups than can be accounted for by end groups, and/or
at least 0.5 more of (XXVIII) per 1000 methylene groups
are present in the polypropylene.
CH3
~CH\
CH2 CH3
-CH- (XXVIiI)
CH3
-CH2CH2 CH-CH3 (XXIX)
I~ Also described herein is an ethylene homopolymer
with a density of 0.86 g/ml or less.
Described herein is a process for the
polymerization of olefins, comprising, contacting a
transition metal complex of a bidentate iigand selected
~0 from the group consisting of
R2
R3 N
R4 ~ N
R~
(VIII)
4
_.._~.~..~.. .,~ mrr rm n r nev

WO 96/23010 ~ 02338581 2001-03-O1 p~/US96/01282
28
R (CR3~2)n R2s
R4~=N~ 1~=GR4s
(xxx)
Rae Ras
R' i _N
R31 ag N
R ~a~
(VIII)
R2o
O ~-H
R2~ -N
R22 -N
O H
'23
R
(XXXII)
with an elafin wherein:
said olefin is selected from the g~ou~
consisting of ethylene, an olefin of the formula
R'~CH=CH; or R' CH=CHR1', cyclobutene, cyclopentene,
norbornene, or substituted norbornene;
said transition metal is selected from the
group consisting of Ti, Zr, Sc, V, Cr, a rare earth
metal, =e, Co, Ni or Pd;
R' and RS are each independently hydrocarbyl or
1~ substituted hydrocarbyl, provided that the carbon atom
bound to the imino nitrogen atom has at least two
carbon atoms bound to it;
R~ and R4 are each independently hydrogen,
hydrocarb~~_, substituted hydrocarbyl, or R3 and RQ
w rnm~rrT~ rTr eW ~t°PT lf'\111 C nC\

CA 02338581 2001-03-O1
WO 96123010 PCTNS96101282
taker. together are hydrocarbylene substituted
hydrocarbyiene to form a carbocyclic ring;
R44 is hydrocarbyl or substituted hydrocarbyi,
and R28 is hydrogen, hydrocarbyl or substituted
S hydrocarbyl or R44 and R'e taken together form a ring;
R45 is hydrocarbyl or substituted hydrocarbyl,
and R'9 is hydrogen, substituted hydrocarbyl cr
hydrocarbyl, or R45 and R'~ taken together form a ring;
each RJ° is independently hydrogen, substituted
hydrocarbyl or hydrocarbyl, or two of R3° taken
together form a ring;
R'° and R'~ are independently hydrocarbyl or
substituted hydrocarbyl;
R" and R" are each in independently hydrogen,
is hydrccarbyi cr substituted hydrocarbyl;
each R1~ is independently hydrocarbyl or
substituted hydrocarbyl provided that any olefinic bond
in said olefin is separated from any other olefinic
bond or aromatic ring by a quaternary carbon atom or at
least two saturated carbon atoms;
n is 2 or 3 ;
R1 is hydrogen, hydrocarbyl or substituted
hydrocarbyl;
and provided that:
?5 said transition metal a-~so has bonded to it a
iigand t'-.at may be displace by said olefin or add to
said olefin;
when M is Pd, said biden~ate ligand is iViII),
(XXXII) or (XXIII);
30 when M is Pd a diene is not present; and
when norbornene or substituted norbornene is
used no other olefin is present.
Described herein is a process for the
copolymerization of an olefin a:.d a fluorinated olefin,
3~ comprising, contacting a transition metal complex of a
bidentate ligand selected from the group consisting of
6

WO 96/23010 ~ 02338581 2001-03-O1 pC'f/17g9610I282
R2
Rs I
,N
Ra ~ N
R5
(VIII)
with an olefin, and a fluorinated olefin wherein:
said olefin is selected from the group
consisting cf ethylene and an olefin of the formula
R''CH=~.H~ or R'~CH=CHRy~;
said transition metal is selected from the
groin consisting of Ni and Pd;
sai='.~~~ori:~ate oleiir_ is of the formula
.-.'=C=CH ; Ci-i~ i ar~_r'~'-,
a is a:. integer cf 2 to 20; RF is
perflaoroalkylene optionally containing one or more
ether groups;
1~ R~' is fluorine or a functional group;
RZ and RS are each independently hydrocarbyl or
substituted hydrocarbyi, provided that the carbon atom
bound to the imino nitrogen atom has at least two
carbon atoms bound to it;
R' and RS are each independently hydrogen,
hydrocarbyl, substituted hydrocarbyl, or R- and R'
taken together are hydrocarbylene substituted
hydrocarbylene to form a carbocyclic ring;
each R' is independently saturated
::ydrocarbyl ;
and provided that said transition metal also has
bonded to it a ligand that may be displaced by said
olefin or add to said olefin.
This invention also concerns a copolymer of an
,0 olefin of the formula R' CH=CHR'' and a fluorinated
olefin ef the formula H~C=CH(CHz)aRfR°z, wherein:
each R''' is independently hydrogen or saturated
hydrocarbyl;
7
ww~n~rm rTr Ntlr~T lD111 C ~IR~

CA 02338581 2001-03-O1
WO 96/23010 PCT/US96I01282
a is ar, integer of 2 to 20; of is
perfluoroalkylene optionally containing one cr more
ether groups; and
R°2 is fluorine or a functional group;
5 provided that when both of R1' are hydrogen and R4'
is fluorine, Ra is -(CF~)b- wherein b is 2 to 20 or
perfluoroalkyiene containing at least one ether group.
Described herein is a process for the
polymerization e~ olefins, comprising, cc~tacting, at a
tem~_erature of about -100°C to about +200'C.
a firs compound W, which is a neutral Lewis
acid capable cf abstracting either Q or S to form WQ-
or WS , provided that the anicn formed is a weakly
coordinatincr anion; or a cationic Lewis cr Bronsted
1~ acid whose ceunterion is a weakly coordinating anion;
a seccnd compound of the formula
R2
R3 ~ N\ j Q)r
M
R4
(~5
(XI)
'_' 0
and one or more monomers selected ==om the
group consisting of ethylene, an olefin e. the formula
R1 CH=CH, or R- CH=CHR1', cyclobutene, cyclcpentene,
substituted norbornene, or norbornene;
'?5 wherein
M is Ti, Zr, Sc, V, Cr, a rare earth metal, Fe,
Co, Ni or Pd the m oxidation state;
y + z = m
R' and R~ are each independently hydrocarbyl or
30 substituted hydrocarbyl, provided that the carbon atom
bound to the imino nitrogen atom has at least two
carbon atoms bound to it;
8
_.._ _.....~.. .., ~~r! m n r nc~

CA 02338581 2001-03-O1
WO 96/23010 PCT/US96/01282
R- and R~' a=a each independently hydrogen,
hydrocarbyl, substituted hydrocarbyl, or R3 and RS
taken together are hydrocarbylene or substituted
hydrocarbylene to form a ring;
each R1' is independently hydrocarbyl or
substituted hydrocarbyl provided that any olefinic bond
in said olefin is separated from any other olefinic
bona cr aromatic ring by a auaternary carbcn atom or at
least two saturated carbon atoms;
Q is alkyl, :~ydride, chloride, iodide, or
bromide;
S is alkyl, hydride, chloride, iodide, or
bromide; and
provided that:
1~ when norbornene cr substituted norbornene is
prese.~.~, no other monomer is present;
when M is Pd a diene is not present; and
except when M is Pd, when both Q and S are each
independently chloride, bromide or iodide w is capable
?0 of transferring a hydride or alkyl group to M.
This invention includes a process for the
production of polyolefins, comprising contacting, at a
temperature of about -100°C to about +200°C, one or
more monomers selected from the group consisting of
ethylene, an olefin cf the formula R- CH=CH_, or
R CH=CHR- , cyclobutene, cyclopentene, subs~_tuted
norbornene, and norbornene; with a compound of the
f ormul a
9
_.._ -_._. ._ _. ._~ ,." " ,. .""

CA 02338581 2001-03-O1
PCT/US96/01282
WO 96/23010
R2 R2
Rs ~ R3 I
,- N. ~ Ti ~ N~ / T~
\ ~Pd~ ~ N~~Z
Ra N Z Ra N
R5 X_ Rs X_
R2 OR8
R3 N O=C
M
Ra ~ N~ ~~CHR~6)n
X_
R5
(II) (III) (IV)
or
R2
R3 N TZ
~Pd~
Ra ~ N X
R5
(VII)
wherein:
R' and RS are each independently hydrocarbyl or
substituted hydrocarbyl, provided that the carbon atom
hounc t.. the imino nitrogen atom has at least two
carbo.~. atoms bound to it;
R- and R~ are each independently hydrogen,
Is ~vdrccarbyl, substituted hydrocarbyl, or R' and R4
taker. together are hydrocarbyiene or substituted
::ydrccarbylene to form a ring;
T' is hydrogen, hydrocarbyl not containing
-ef=_-_; ~ cr acetylenic bonds, R15C (=O) - or R150C (=O) - ,
?p n is 2 or 3 ;
Z is a neutral Lewis base wherein the donating
atom is nitrogen, sulfur or oxygen, provided that i'
r'~:e dc:~ating atom is nitrogen then the pKa of the
conjugate acid of that compound is less than about 6;

CA 02338581 2001-03-O1
WO 96123010 PCTIUS96/01282
X is a weakly cocrdinating anion;
R15 is hydrocarbyl not.containing olefinic or
acetylenic bonds;
each R1' is independently hydrocarbyl or
substituted hydrocarbyl provided that any olefinic bond
in said olefin is separated from any other olefinic
bond or aromatic ring by a quaternary carbon atom or at
least two saturated carbon atoms;
M is Ni(II) or Pd(II);
each R16 is independently hydrogen cr alkyl
containing 1 to 10 carbon atoms;
n is 1, 2, or 3;
RB is hydrocarbyi; and
T2 is hydrogen, hydrocarbyl not containing
l~ olefinic or acetyienic bonds, hydrocarbyl substituted
with keto or ester groups but not containing oiefinic
or acetylenic bonds, R15C(=O)- or R150C(=O)-;
and provided that:
when M is Pd a diene is not present; and
when norbornene or substituted norbornene is
used no other monomer is present.
This invention includes a process for the
production of polyolefins, comprising contacting, at a
temperature of about -100°C to about +200°C, one or
more monomers selected from the group consisting of
ethylene, an olefin of the formula R1'CH=CH: or
R1'CH=CHR1', cyclobutene, cyclopentene, substituted
norbornene, and norbornene; with a compound o. the
formula
~..~.,~.... r~r nWrrT bet t1 t'R1

CA 02338581 2001-03-O1
WO 96123010 PCT/US96I01282
RZo
O IH
R2i -N, T2
is '
R (CR3o2)n R2s
R4~=N' Tl=~ R45 R22 ~=N X
~M~ O~H
(Q>y/ ~ (S>z R23
(XVII) (XVlll) or
R2o
O IH
R2~ -N T~
~M~
RZZ -N' ~ Z
O~H X
R23
(X111)
wherein:
R4q is h}~drocarbyl or substituted hydrocarbyl,
and Rz8 is hydrogen, hydrocarbyl or substituted
hydrccarhyl or R44 and R~e taken together form a ring;
R4' is hydrocarbyl or substituted hydrocarbyl,
and R'~ is hydrogen, substituted hydrocarbvl or
10 :~:ycirocarby-" or R45 and R'9 taken together form a ring;
each R'° is independently hydroge.~., substituted
hydrocarbyl or hydrocarbyl, or two of R~~ taken
together form a ring;
each R'' is independently hydrocarbyl cr
l~ substituted hydrocarbyl provided that any clefir.ic bond
in said olefin. is separated from any other olefinic
bond or aromatic ring by a auaternary caric:: atom or at
least two saturated carbon atoms;
R" and R'' are independently hydrocarbyi or
'_'0 substituted hydrocarbyl;
R" and R" are each in independently hydrogen,
hydrocarbyl cr substituted hydrocarbyl;
1 '_'

CA 02338581 2001-03-O1
WO 96123010 PCTNS96/01282
'~' is hydrogen, hydrocarbyl not conta_r.inc
olefinic or acetylenic bonds, R15C (=O) - or R'-;.C (=0) -;
Z is a neutral Lewis base wherein the donating
atom is nitrogen, sulfur or oxygen, provided that if
the donating atom is nitrogen then the pKa of the
conjugate acid of that compound is less than Gbout 6;
and
X is a weakly coordinating anion; ana
provided that:
when. M is Pd or (XVIII) is used a diene is not
prese.~_r ; and
in (XVIi) M is not Pd.
This invention includes a process fc= the
production cf polyolefins, comprising contac~_::g, at a
temperature c= about .00°C to about +200°C, c~:e c~
more monomers selected from the group consisting cf
ethylene, an olefin of the formula R1~CH=CHI cr
Rl~CH=CHRl~, 4-vinylcyclohexene, cyclobutene,
cyclopentene, substituted norbornene, and nor~crnene;
with a compound of the formula
R2o
O IH
R2~ -N. T2
Pd\
R22 -N X
O H
~23
R
(XVIII)
wherein:
R20 and R23 are independently hydroca=byl or
substi~uted ~ydrocarbyl;
R" and Rz~ are each in independently ?:ydrogen,
hydrocarbyl er substituted hydrocarbyl;
T1 is hydrogen, hydrocarbyl not containing
olefinic or acetylenic bonds, R15C (=O)- or RI~OC(=O)-, .
13

CA 02338581 2001-03-O1
WO 96/23010 PCT/US96/01282
Z is a neutral Lewis base wherein the donating
atom is nitrogen, sulfur or oxygen, provided trat if
the donating atom is nitrogen then the pKa of the
conjugate acid of that compound is less than about 6;
j X is a weakly coordinating anion;
R15 is hydrocarbyl not containing olefinic or
acetylenic bonds;
each R''' is independently hydrocarbyl or
substituted hydrocarbyi provided that any olefinic bond
,~n said olefin is separated from any other olefinic
bond cr _aromatic ring by a auaternary carbon atom or at
'east two saturated carbon atoms;
M is Ni(IT_) or Pd(II);
T2 is hydrogen, hydrocarbyl not containing
is olefinic or acetylenic bonds, hydrocarbyl substituted
with keto or ester groups but not containing olefinic
or acetyienic bonds, R~SC(=O)- or R150C(=O)-;
and provided that:
when M is Pd a diene is not present; and
20 when norbornene or substituted norbornene is
used no other monomer is present.
Described herein is a process for the production
for polyolefins, comprising contacting, at a
temperature of about -100°C to about +200°C,
'_'S a first compound w, which is a neutral Lewis
acid cap_abie of abstracting either Q or S t~ fcrm WQ
or wS , provided that the anion formed is a weakly
cocrdvnating anion; or a cationic Lewis or Bror.sted
acid whose ccunterion is a weakly coordinating anion;
30 a second compound of the formula
R28 /(CR3p2)n R29
T~=~ R4s
\M/
~(S)z
(XVII)
.-_ _..~~ ...~ w r nw

CA 02338581 2001-03-O1
WO 96/23010 PCT/US96101282
and one or more monomers selected from t'ne
group, consisting of ethylene, an olefin of the formula
R1'CH=CH~ or R1'CH=CHR'', cyclobutene, cyclopentene,
substituted norbornene, or norbornene;
wherein:
M is Ti, Zr, V, Cr, a rare earth meta=, Co, Fe,
Sc, e= Ni, of oxidation. state m;
Rs4 is hydrocarbyl or substituted.h.ydrocarby2,
and R'' is hydrogen, substituted hydrocarbyl er
hydrocarbyl , cr R44 and R2e taker. together form a r ing;
R4' is hydrocarbyl or substituted hydrocarbyi,
and R" is hydrogen, substituted hydrocarbyl or
hydrocarbyl, or R45 and R'~ taken together form a ring;
I' each Rj' is independently hydrogen, su:ostitv.:ted
hydrocarbyl or hydrocarbyl, or two of R'° taken
together form a ring;
n is 2 or 3;
y and z are positive integers;
?0 y+z = m;
each R1' is independently hydrocarbyl or
substituted hydrocarbyl provided that any olefinic bond
in said olefin is separated from any other olefinic
bond or aromatic ring by a auaternary carbon atom or at
least two saturated carbon atoms;
Q is alkyl, hydride, chloride, iodide, .._
bromide;
S is alkyl, hydride, chloride, iodide, of
bromide; and
30 provided that;
when norbornene or substituted norbornene is
present, no other monomer is present.
Disclosed herein is a process for the production
of polyolefins, comprisinc, contacting, at a
temperature of about -100°C to about +200°C, one or
more monomers selected from the group consistine_ o
ethylene, an olefin of the formula R1'CH=CH2 or
R1 CH=CHR1', cyclobutene, cyclopentene, substituted
1~

CA 02338581 2001-03-O1
PCTNS96101282
WO 96123010
norbornene, a::d r.crbornene; optionally a so;:rce of R;
with a compound of the formula
R2 R2
R3 N T1 N Rs
~Pd~ E T1/Pd\N
Ra ~ N ~ Ra
Rs R$ X-
j (V)
wherein:
R' and R~ are each independently hydrocarbyl or
substituted hvdrocarbyl, provided that the carboy. atom
10 bound directlw ~. the imino : _troger. atcm ::GS at least
twc carbon ato-r.s bound to it ;
R3 and :~' a=a each independently hydrogen,
hydrocarbyl, substituted hydrocarbyl or R3 ar.d R4 taken
together are hydrocarbylene substituted hydrccarbylene
lj to form a ring;
each z'~ is independently hydrocarbyl or
substituted hydrocarbyl provided that R-~ contains no
olefinic bonds;
T1 is hydrogen, hydrocarbyl not containing
'_'0 olefinic or acetvienic bonds, R15C(=0)- or R--OC(=O)-,
.s
R is i:ydrocarbyl not containi.~.g c~=_finic or
acetylenic bonds;
E is halogen or -ORle;
Rie is hydrocarbyl not containing olefinic cr
''j acetylenic bonds; and
X is a weakly coordinating anion;
provided that, when norbornene or substituted
norbcrnene -is present, no other monomer is present.
Described herein is a process for the
30 polymerization of olefins, comprising, contacting, at a
temperature o~~abcut -100°C to about +200°C:
a first compound W, which is a neutral Lewis
acid capable c~ abstracting either Q or S to form WQ
16

WO 96/23010 ~ 02338581 2001-03-O1
PCT/US96/01282
or wS , provided t~:at t!e anion formed is a weakly
coordinating anion; or a cationic Lewis or Bronsted
acid whose counterion is a weakly coordinatirc anion;
a second compound of the formula
R2
R3 t
N.MIQ
i \
Ra ~ N S _
R5
(I)
and one or more monomers selected from the
grou~ co.~_sisting of et:~ylene, an ole=in of the formula
R' CH=CH_ or R' CH=CHR', 4-vinylcyclohexene,
cyclobutene, cyclopentene, substituted norbornene, or
norbornene;
wherein:
M is Ni(II), Co(II), Fe(II), or Pd(II);
R' and R5 are each independently hydrocarbyl or
substituted hydrocarbyl, provided that the carbon atom
bound to the imino nitrogen atom has at least two
carbon atoms bound to it;
''0 R' and R; are each independently hydrogen,
hydrocarbyi, substituted hydrocarbyi or R' and RQ taken
together are hydrocarbylene or subst_tuted
hydrocarbylene to form a ring;
each R1' is independently hydrocarbyl or
''~ substituted hydrocarbyl provided that any olefinic bond
in said olefin is separated from any other olefinic
bond cr aromatic ring by a quaternary carbon atom or at
least two saturated carbon atoms;
Q is alkyl, hydride, chloride, iodide, or
30 bromide;
S is alkyl, hydride, chloride, iodide, or
bromide; and
provided that;
17
_..___._..__ ." .....T m ii r ncv

CA 02338581 2001-03-O1
WO 96/23010 PCT/US96/01282
when norbornene cr substituted norbornene is
present, no other monomer is present;
when M is Pd a dime is not present; and
except when M is Pd, when both Q and S are each
independently chloride, bromide or iodide w is capable
of transferring a hydride or alkyl group to M.
Included herein is a polymerization process,
comprising, contacting a compound of the formula
fad (R -"CN) 4] Xz or a combination of Pd [OC (O) R;°] ; and HX; a
compound of the formula
R2
_N
Ra~N
I
R5
(VIII)
1~ and one or more monomers selected from the group
consisting of ethylene, an olefin of the formula
Rl CH=CH, or R1'CH=CHR", cyclopentene, cyclobutene,
substituted norbornene, and norbornene; wherein:
R2 and RS are each independently hycirocarbyl or
''0 substituted hydrocarbyl, provided that the carbon atom
bound ~o the imino nitrogen atom has at least two
carbon atoms bound to it;
R' and R~ are each independently hydrogen,
hydrocarbyl, substituted hydrocarbyl or R3 and R' taken
together are hydrocarbylene or substituted
hydrocarbylene to form a ring;
each R1' is independently hydrocarbyl or
substituted hydrocarbyl provided that R1' contains no
olefinic bonds;
30 R13 is hydrocarbyl ;
R4° is hydrocarbyl or substituted hydrocarbyl
and
X is a weakly coordinating anion;
18
___-..-_ _. .....~ "m n r nee

CA 02338581 2001-03-O1
WO 96/23010 PCT/US96/01282
provided that, when norbornene cr substituted
norbornene is present, no other monomer is present.
Also described herein is a polymerization process,
comprising;
contacting Ni [0) , Pd[0J or Ni [I) compound
containing a iigand which may be displaced by a ligand
of the formula (VIII), (XXX), (XXXII) cr (XXIII);
a second compound of the formula
R2
Rs I
N
R4 ~ N
R5
(VIII)
28
R (CR3~2)n R29
R°~=N~ T~l=G~ R4s
(xxx)
R48 R4s
R' ~ -N
R'~
R4 rS47
(XXIII)
1~
or
19
_........ .". ," vrrT inl 11 C ~7C\

CA 02338581 2001-03-O1
WO 96/23010 PCTNS96/01282
R2o
0 ~-H
R2 i ~N
R22 ~=N
H
~23
R
(XXXiI)
an oxidizing agent;
a source of a relatively weakly coordinating
anion;
and one or more monomers selected from the
group consisting of ethylene, an olefin o~ the formula
R' C =C~~ o~ :~- ~._-CriR'-~, cycl~~entene, cycl cbutene,
substituted norbornene, and norbornene;
wnereln:
R' and R' are each independently hydrocarbyl or
substituted hydrocarbyl, provided that the carbon atom
bound to the imino nitrogen atom has at least two
carbon atoms bound to it;
R3 and R' are each independently hydrogen,
1~ hydrocarbyl, substituted hydrocarbyl or R- and R~' taken
together are hydrocarbylene or substituted
hydrocarbyiene to form a ring;
each R- is independently hydrocarbyl or
substituted hydrocarbyl provided that any olefinic bond
..~. said olefin is separated from any other olefinic
bond or aromatic ring by a auaternary carbon atom or at
least two saturated carbon atoms;
R13 is hydrocarbyl;
R'' is hydrocarbyl or substituted '.~.ydrocarbyl,
and R26 is hydrogen, hydrocarbyl or substi~uted
hydrocarbyl or R'~' and R28 taken together corm a ring;
R45 is hvdrocarbyl or substituted hvdrocarbyl,
and R'S is hydrogen, substituted hydrocarbvi or
hydrocarbyl, or Rqs and Rz5 taken together =crm a ring;
?0
_..___._..~~ .., r..~ rni n r ~c~

CA 02338581 2001-03-O1
each R'° is independ~. .ly hydrogen, ,substituted' ~ ~'
hydrocarbyl or hydrocarbyl, or two of R'° taken
together form a ring;
R31 is independently hydrogen, hydrocarbyl or
substituted hydrocarbyl;
R46 and R" are each independently hydrocarbyl
or substituted hydrocarbyl, provided that the carbon
atom bound to the imino nitrogen ato~~ has at least two
carbon atoms bound to it;
R48 and R'9 are each independently hydrogen,
hydrocarbyl, or substituted hydrocarbyl;
Rz° and R2' are independently hydrocarbyl or
substituted hydrocarbyl;
n is 2 or 3;
1~ Rz' and R2~ are each in independently hydrogen,
hydrocarbyl or substituted hydrocarbyl; and
X is a weakly coordinating anion;
provided that;
when norbornene or substituted norbornene is
present, no other monomer is present;
when said Pd[0] compound is used, a diene is not
present; and
when said second compound is (XXX) only an Ni[0]
or Ni [ I ] compound is used .
Described herein is a polymerization process,
comprising, contacting an Ni[0] complex containing a
ligand or ligands which may be displaced by (VIII),
oxygen, an alkyl aluminum compound, and a compound of
the formula
R2
R3 N
R4 ~ N
R5
(VIII)
21
AMEHOED SHEET

CA 02338581 2001-03-O1
and one or more monomers selected f: ~n the~group
consisting of ethylene, an olefin of the formula
21a
AGAENOED SHEEP

WO 96123010 r~ 02338581 2001-03-O1 PCTILiS9610128=
:c' ~-=C'.-'.'.= e. R' C'.-'.'.=C'.-'_'_~ , cyclepentene,
cy~_~bu~e.~.°,
5::.~.~L~tu:.°.". ::OrDOrnenc, anC n02'bOrnene; Where-r.:
and RS are e3C : _..~.dependentl V f:ydrOCar~'L'Vi : _
subs titutea hydrocarbyl , provided that t:~e ca=bc.~. atc.-....
bou :d tc t'.~.e ir,.i~o ritrocer. atom has at Teas= twc
Ca=.~.n0:: Gtv':J bOLi:::I t0 1t;
hvdrcca=byi, .substituted hydrocarbyl or R' and n' take:
=cc~-!-:e_ a-= ~:ydrcca=bylene o. substituted
~w~_~carW'len~ to form a =ing; and
each is independently hydrocarbyl .._
su~st~_..t?d hVdrocarbyl provided that any olefi.~..c :.c::..
ir: sa_c cl efin .s separate3 =rpm a::y ether o_ef_..~.ic
i,.~..~_.. C- a-Oisla=='. r~n~ Dy a C;:at°~r.a~V Car~J' C~ a.~vm C. a_
1~ _east two saturated carbcr: atoms;
o=cwided ti'.at, whe:: ncrborne.~.e o. substi=::_ed
nC=~.~,.~.=:'.°.':° 1S D.eSent , nC Other mOnOmer .5 D~
e5°_~ t .
A pClViTterlZdLlOn prOCe55, COmprlSlng, COtaCL=
OXVQ~?:1 c: a.~. alkyl aiur"_~um co;rpou.~.~, Or a C :.T,OL: : : : _
'0 the fcr;~:::a :T.X, ar.d a compound o' the formula
Rz
I R:
R '~-N R~ i I \ ~~ R:
Ni COD N ~N\
Ni ~ I O
~N~ \// \
R~ I. R< I N
R- R' ~ ~ o~,~
(VIII) cxxxxin rxxxxut~
Rz , RI Rs
R~ R I Ra
N N N
/\ / \
N,~ (7_
\ \ /
~N ~N N
R< I R< I s I: ~R~
RS R R
fXXX\I~'1 or (XXXX1'1
and one o_- more monomers selected from the group
co:aisti.~.~ of ethylene, an ole'in of the formula
'_'~ R' CH=C:i, or R''CH=CHR1', cyciopArte.~.e , cyclobuce.~.e ,
,.:, ~-= ~ ~"T'~ and r.OrbOr~ene; wl'lere;.~.:
s..~s_~tut_d norbo_.._ne,
," n~r~ ,n, n r rC\

WO 96123010 ~ 02338581 2001-03-O1 pCT/US96/01282
R2 and RS are each independently hydrocarbyl or
substituted hydrocarbyl, provided that the carbon atom
bound to the imino nitrogen atom has at least two
carbon atoms bound to it;
R3 and R4 are each independently hydrogen,
hydrocarbyl, substituted hydrocarbyl or R3 and R9 taken
together are hydrocarbylene or substituted
hydrocarbylene to form a ring; and
each R'' is independently hydrocarbyl cr
substituted hydrocarbyl provided that any olefinic bond
in said olefin is separated from any other olefinic
bond or aromatic ring by a auaternary carbon atom or at
least two saturated carbon atoms;
X is a weakly coordinating anion; and
is provided that, when norbornene or substituted
norbornene is present, no other monomer is present.
Described herein is a polymerization process,
comprising, contacting an Ni[0) complex containing a
ligand or ligands which may be displaced by (VIII), HX
or a Bronsted acidic solid, and a compound of the
formula
R2
Rs
,N
Ra ~ N
Rs
(VIII)
>>
and one or more monomers selected from the group
consisting of ethylene, an olefin of the formula
R1'CH=CH2 or R1'CH=CHR1', cyclopentene, cyclobutene,
substituted norbornene, and norbornene; wherein.:
R~ and RS are each independently hydrocarbyl or
substituted hydrocarbyl, provided that the carbon. atom
bound to the imino nitrogen atom has at least two
carbon atoms bound to it;
?3
... ... m~..n .~ m ~ rrT r n t N C ~ C\

CA 02338581 2001-03-O1
WO 96/23010 PCTIUS96/01282
R3 and n' are each irdepe.~.dent~y ~~~gen,
hydrocarbyl, substituted hydrocarbyl or R3 and RS taker_
together are hydrocarbylene or substituted
hydrocarbylene to form a ring;
5 each Rl is independently hydrocarbyl or
substituted hydrocarbyl provided that any olefinic bond
in said olefin is separated from any other olefinic
bond or aromatic ring by a quaternary carbon atom or at
least two saturated carbon atoms; and
X is a weakly coordinating anion;
provided that, when norbornene or substituted
norbornene is present, no other monomer is present
Described herein is a process for the
polymerization e~ olefins, comprising, contacting, at a
i~ temperature c~ about -i00°C to about X200°C:
a first compound W, which is a neutral Lewis
acid capable of abstracting either Q or S to form wQ-
or WS , provided that the anion formed is a weakly
coordinating anion; or a cationic Lewis or Bronsted
?0 acid whose counterion is a weakly coordinating anion;
a seccnd compound of the formula
Rzo
O~H
R2i -N D
R22 / N/ \S
O' LH
~R23
XIX
and ene er more monomers selected from the
croup consisting of ethylene, an olefin of the formula
R1'CH=CH, or R' CH=CHR1', cyclobutene, cyclopentene,
substituted norbornene, or norbornene;
wherein:
30 M is Ni(II) or Pd(II);
_ . ._ _.....__ .., .~~~ .n. m r ncv

CA 02338581 2001-03-O1
WO 96123010 PCTIUS96/01282
R~° and R'' are independently hydrocarDyi or
substituted hydrocarbyl;
R~1 and RZ' are each in independently hydrogen,
hydrocarbyl cr substituted hydrocarbyl;
j each R1' is independently hydrocarbyl or
substituted hydrocarbyl provided that any olefinic bond
in said olefin is separated from any other oiefinic
bond or aromatic ring by a quaternary carbon atom or at
least two saturated carbon atoms;
IO Q is alkyl, hydride, chloride, iodide, or
bromide;
S is alkyl, hydride, chloride, iodide, or
bromide; and
provided that;
l, when norbornene or substituted norbornene is
present, no other monomer is present;
when M is Pd a dime is not present; and
except when M is Pd, when both Q and S are each
independently chloride, bromide or iodide W is capable
?0 of transferring a hydride or alkyl group to M.
This invention also concerns a process for the
polymerization of olefins, comprising, contacting, at a
temperature of about -100°C to about +200°C, a compound
of the formula
'_' S
R2
R3 N NCRz'
~Pd~
R4 ~ ~j ~NCRZ'
2X
(XIV)
30 and one or more monomers selected from the group
consisting of ethylene, an olefin of the formula
R1~CH=CHI or R1'CH=CHR'', cyclopentene, cyclobutene,
substituted norbornene, and norborne.~.e; wherein:
-_ _. ._~ .... n r ncv

CA 02338581 2001-03-O1
WO 96/23010 PCTIUS96I01282
RZ and R~ are each independently ny~~~:srbyl or
substituted hydrocarbyl, provided that the carbon atom
bound to the imino nitrogen atom has at least two
carbon atoms bound to it;
R' and R4 are each independently hydrogen,
hydrocarbyl, substituted hydrocarbyl or R3 and R4 taken
~egether are hydrocarbylene or substituted
:~ydrocarbylene to form a ring;
each R' is independently hydrocarbyl er
10 substituted hydrccarbyl provided that R1' contains no
olefinic bonds; and
each R2' is independently hydrocarbyl;
each X is a weakly coordinating anion;
provided that, when norbornene or substituted
1~ ~orbornene is present, no other monomer is present.
This invention also concerns a process fcr the
polymerization of olefins, comprising, contacting, at a
temperature of about -100°C to about +200°C:
a first compound W, which is a neutral Lewis
''0 acid capable of abstracting either Q or S to form WQ-
cr WS , provided that the anion formed is a weakly
coordinating anion; or a cationic Lewis or Bronsted
acid whose counterion is a weakly coordinating anion;
a second compound of the formula
R48 Ras
R'~ N
wi'cn~
R~ ~ ~1~
R4g K47
and one or more monomers selected from the group
consisting of ethylene, an olefin of the formula
30 R''CH=CHz or R1'CH=CHR1', cyclopentene, cyclobutene,
substituted norbornene, and norbornene; wherein:
~6

WO 96/23010 ~ 02338581 2001-03-O1 p~/pg96/01282
R~'~ and R4' are each independer.~iy hydrocarbyl
or substituted hydrocarbyl, provided that the carbon
atom bound to the imino nitrogen atom has at least two
carbon atoms bound to it;
R48 and R'9 are each independently hydrogen,
hydrocarbyl, or substituted hydrocarbyl;
each R31 is independently hydrocarbyl,
substituted hydrocarbyl or hydrogen;
M is Ti, Zr, Co, V, Cr, a rare earth metal, Fe,
Sc, Ni, or Pd of oxidation state m;
y and z are positive integers;
y+z = m;
each R1' is independently hydrocarbyl or
substituted hydrocarbyl provided that any olefinic bond
1~ in said olefin is separated from any other olefir.ic
bond or aromatic ring by a quaternary carbon atom or at
least two saturated carbon atoms;
Q is alkyl, hydride, chloride, iodide, or
bromide;
S is alkyl, hydride, chloride, iodide, or
bromide; and
provided that;
when norbornene or substituted norbornene is
present, no other monomer is present;
'_'S when M is Pd a diene is not present; and
except whey. M is Pd, when both Q and S are each
independently chloride, bromide or iodide w is capable
of transferring a hydride or alkyl group to M.
Disclosed herein is a compound of the formula
R2
Rs I
N
a ~ N Pd 2
R
R5 X-
(II)
'' 7
~. ~~n~r~~ rrr PurrT lDl 11 C ~R1

CA 02338581 2001-03-O1
WO 96/23010 PCTNS96101282
wherein:
R2 and RS are each independently hydrocarbyl or
substituted hydrocarbyl, provided that the carbon atom
bound to the imino nitrogen atom has at least two
carbon atoms bound to it;
R3 and R4 are each independently hydrogen,
hydrocarbyl, substituted hydrocarbyl or R3 and R4 taken
together are hydrocarbylene or substituted
hydrocarbylene to form a ring;
10 T1 is hydrogen, hydrocarbyl not containing
olefinic or acetylenic bonds, R15C(=O)- or R150C(=O)-;
Z is a neutral Lewis base wherein the donating
atom is nitrogen, sulfur or oxygen, provided that if
the donating atom is nitrogen then the pKa of the
1~ conjugate acid of that compound is less than about 6;
X is a weakly coordinating anion; and
R15 is hydrocarbyl not containing olefinic or
acetylenic bonds;
provided that wher_ R~ and R9 taken together are
?0 hydrocarbylene to form a carbocyclic ring, Z is not an
organic :.itrile .
Described herein is a compound of the formula
R5o
R3 N
~N
[.~51
wherein:
R5° is substituted phenyl;
R51 is phenyl or substituted phenyl;
R~ and R~ are each independently hydrogen,
hydrocarbyl, substituted hydrocarbyl or R' and R~ taken
together are hydrocarbylene or substituted
30 hydrocarbylene to form a ring;
and provided that groups in the 2 and 5 positions
of RS° have a difference in ES of about 0.60 or more.
Described herein is a compound of the formula
28
~..~~~.~..~m.....r~ rw a r nW

WO 96/23010 ~ 02338581 2001-03-O1 pr~'/US96101282
R52
R3 N
/Q
i
Ra ~ f~ ~ S
~53
(XXXVI)
wherein:
RS~ is substituted phenyl;
Rs' is phenyl or substituted phenyl;
R3 and R4 are each independently hydrogen,
hydrocarbyl, substituted hydrocarbyl or R3 and R9 taken
together are hydrocarbylene or substituted
hydrocarbylene to form a ring;
Q is alkyl, hydride, chloride, bromide or
iodide;
S is alkyl, hydride, chloride, bromide or
iodide;
I~ and provided that;
groups in the 2 and 6 positions of RS' have a
difference in ES of 0.15 or more; and
when both Q and S are each independently chloride,
bromide or iodide W is capable of transferring a
?0 hydride or alkyl group to Ni.
T~:is invention includes a compound of the formula
R2
R3 r
N\ T
Nib
Ra ~ N Z
R5 X-
(IIi)
wherein:
R' and RS are each independently hydrocarbyl or
substituted hydrocarbyl, provided that the carbon atom
~9
w~~w~w~ lvl IPrT /A111 C ~

CA 02338581 2001-03-O1
WO 96123010 PCT/US96/01282
bound to the imino nitrogen atom has at '_east two
carbon atoms bound to it;
R3 and R5 are each independently hydrogen,
hydrocarbyl, or substituted hydrocarbyl or R3 and R4
taken together are hydrocarbylene or substituted
hydrocarbylene to form a ring;
T1 is hydrogen, hydrocarbyl not containing
olefinic or acetylenic bonds, R15C(=O)- or R150C(=O)-;
R15 is hydrocarbyl not containing an olefinic
cr acetylenic bond;
Z is a neutral Lewis acid wherein the donating
atom is nitrogen, sulfur or oxygen, provided that, if
the donating atom is nitrogen, then the pKa o~ the
conjugate acid of that compound is less tran about 6;
1~ and
X is a weakly coordinating anion.
This invention also concerns a compound c. the
formula
R2 ORs
R3 ~ N~ ~O=C
M I
R4 ~ N ~(CHR~s)n
R5
'_' U
(IV)
wherein:
R' and RS are each independently hydrocarbyl or
'_'~ substituted hydrocarbyl, provided that the carbon atom .
bound to the imino nitrogen atom has at least two
carbon atoms bound tc it;
R3 and R4 are each indeper_dently hydrogen,
hydrocarbyl, substituted hydrocarbyl or R3 and R' taken
30 together are hydrocarbylene or substituted
hydrocarbylene to form a ring;
M is Ni(II) or Pd(II);
-_ __ _.....__ ....~~~ .nm r nee

CA 02338581 2001-03-O1
WO 96/23010 PCT/US96I0128Z
each R1~ is independently hydrogen or alkyl
containing 1 to to carbon atoms;
n is l, 2, or 3;
X is a weakly coordinating anion; and
RB is hydrocarbyl.
Also disclosed herein is a compound of the formula
R2 R2
R3 ~ ~ N Rs
N T
~Pd~ E' Pd~
R4 ~ Ni T~/ ~N
~s Ra
Rs R X-
(V)
wherein:
R' and RS are each independently hydrocarbyl or
substituted hydrocarbyl, provided that the carbon atom
bound directly to the imino nitrogen atom has at least
1~ two carbon atoms bound to it;
R' and R4 are each independently hydrogen,
hydrocarbyl, substituted hydrocarbyl or R3 and R' taken
together are hydrocarbylene or substituted
hydrocarbylene to form a ring;
0 E is halogen or -ORle.
R16 is hydrocarbyl not containing olefinic or
acetylenic bonds;
T1 is hydrogen, hydrocarbyl not containing
olefinic or acetylenic bonds, R'SC(=O)- or R150C(=O)-;
R15 is hydrocarbyl not containing olefir_ic or
acetylenic bonds; and
X is a weakly coordinating anion.
Included herein is a compound of the formula [(r)4-
i,5-COD)PdTIZJfX , wherein:
30 T1 is hydrocarbyl not containing olefinic or
acetylenic bonds;
X is a weakly coordinating anion;
COD is 1,5-cyclooctadiene;
31
_. __ _-._. .~~ .,. ...~T m n r ~e~

CA 02338581 2001-03-O1
WO 96123010 PCT/US96I01282
Z is R-°CN; and
R1° is hydrocarbyl not containing oiefinic or
acetylenic bonds.
Also included herein is a compound of the formula
R2
R3 ~ N. ,P~
i~~~CHR~~
R4 \ N R' ~ HC X-
Rs
(VI)
wherein:
N~ is Ni(II) cr Pd(TI);
R2 and RS are each independently hydrocarbyl or
substituted hydrocarbyl, provided that the carbon atom
bound directly to the imino nitrogen atom has at least
two carbon atoms bound to it;
15 R' and R4 are each independently hydrogen,
hydrocarbyl, substituted hydrocarbyl or R' and R9 taken
together are hydrocarbylene or substituted
hydrocarbylene to form a ring;
each R1' is independently hydrogen, alkyl or
?0 - ( CHZ ) ~,CO~R1;
T3 is hydrogen, hydrocarbyl not containing
olefinic or acetylenic bonds, or -CHzCH,CH2CG~R6;
P is a divalent group containing one or more
repeat units derived from the polymerization of one or
'_5 more of ethylene, an olefin of the formula R'''CH=CHz or
R1'CH=CHR1', cyclobutene, cyclopentene, substituted
norbornene, or norbornene and, when M is Pd(II),
optionally one or more of: a compound of the formula
CHz=CH t CHz? mC02R'', CO, or a vinyl ketone ;
30 R8 is hydrocarbyl;
m is 0 or an integer from 1 to 16;
R1 is hydrogen, or hydrocarbyl or substituted
hydrocarbyl containing 1 to 10 carbon atoms;
32
_ _ __ _~ .r _. ._~ ,... ,. ~ .,..,

WO 96123010 ~ 02338581 2001-03-O1 pCTIUS96/01282
and X is a weakly coordinating anion;
provided that, when M is Ni(II), R11 is not -C02R~.
Also described herein is a compound of the formula
Rz
R3 ~ N\ /T2
~Pd~
R4 ~ N X
R5
(VII)
wherein:
R' and RS are each independently hydrocarbyl or
subst_tuted hydrocarbyl, provided that the carbon atom
bound to the imino nitrogen atom has at least two
carbon. atoms bound to it;
Rj and R9 are each independently hydrogen,
hydrocarbyl, substituted hydrocarbyl or R3 and R~ taken
1~ together are hydrocarbylene or substituted
hydrocarbylene to form a ring;
T2 is hydrogen, hydrocArbyl not containing
olefinic or acetylenic bonds, hydrocarbyl substituted
with keto or ester groups but not containing olefinic
or acetvlenic bonds, R'SC(=O)- or R''OC(=0)-,
R'S is hydrocarbyl not containing olefinic or
acetyienic bonds; and
X is a weakly coordinating anion..
Included herein is a process for the production of
?5 polyoiefins, comprising, contacting, at a temperature
of about -100°C to about +200°C, a compound of the
formula
R2
R3 ~ N. ~Pl'3
i~~~CHR> >
R° 'N R'~HC X-
R5
(vI>
>;
~..~.,~.~ ear m ~rr-T !DI 11 C ~7R\

WO 96/23010 ~ 02338581 2001-03-O1 pC'f/~TS96/01282
and one or more monomers selected from the group
consisting of ethylene, an olefin of the formula
R1 CH=CH2 or R1'CH=CHR1', cyclobutene, cyclopentene,
substituted norbornene, and norbornene,
wherein:
M is Ni(II) or Pd(II);
R2 and RS are each independently hydrocarbyl or
substituted hydrocarbyl, provided that the carbon atom
10 bound directly to the imino nitrogen atom has at least
twc carbon atoms bound to it;
R3 and R' are each independently hydrogen,
hydrocarbyl, substituted hydrocarbyl or R3 and R' taken
together are hydrocarbylene or substituted
1~ :.ydrocarbylene to form a ring;
each R" is independently hydrogen, alkyl or
- ( CH~ ) mC02R1 ;
T3 is hydrogen, hydrocarbyl not containing
olefinic or acetylenic bonds, or -CH2CHzCHzCO2R8;
20 P is a divalent group containing one or more
repeat units derived from the polymerization of one or
monomers selected from the group consisting of
ethylene, an olefin of the formula R1'CH=CHI or
R' CH=CHR1', cyclopentene, cyclobutene, substituted
__~rbornene, and norbornene, and, when M is Pd(II),
o~tior.ally one or more of: a compound of the formula
CH~=CH ( CHz ) mC02R' , CO or a vinyl ketone ;
RB is hydrocarbyl;
each R1' is independently hydrocarbyl or
30 substituted hydrocarbyl provided that any olefinic bond
in said olefin is separated from any other olefinic
bcnd or aromatic ring by a quaternary carbon atom or at
least two saturated carbon atoms; R1 is hydrogen, or
hydrecarbyl or substituted hydrocarbyl containing 1 to -
3~ 10 carbon atom ;
m is 0 or an integer of 1 to 16; _
and X is a weakly coordinating anion;
34
.., ~.,r~~T, rrr cuccT roW c ~Rt

WO 96/23010 ~ 02338581 2001-03-O1 pCTIUS96/01282
provided that:
when M is Pd a dime is not present;
when norbornene or substituted norbornene is
present, no other monomer is present; and
further provided that, when M is Ni(II), R11 is
not
-CO~R~ .
Included herein is a process fer the production of
polyolefins, comprising, contacting, at a temperature
ef about -100°C to about +200°C, a compound of the
formula
Rz
3
R
N
%Q)y ~
/
\
M- C-R"
w /
a C-R"
N s
H- P
R
R5 T
(XVI) (X )a
l~ and one or more monomers selected from the group
consisting of ethylene, an olefin of the formula
R1'CH=CH, or Ri'CH=CHR'~, cyclobutene, cyclopentene,
substituted norbornene, and norbornene,
wherein:
M is Zr, : , Sc, V, Cr, a rare earth metal, Fe,
Co, Ni or Pd of oxidation state m;
R' and RS are each independently hydrocarbyl or
substituted hydrocarbyl, provided that the carbon atom
bound directly to the imino nitrogen atom has at least
two carbon atoms bound to it;
R3 and R4 are each independently hydrogen,
hydrocarbyl, substituted hydrocarbyl or R' and R' taken
together are hydrocarbylene or substituted
hydrocarbylene to form a ring;
~0 each R'1 is independently hydrogen, or alkyl,
or both of R-' take~ together are hydrocarbylene to
form a carbocyclic ring;
3~
m rn~TrTmTC cuLCT IC71 II F ~Rl

CA 02338581 2001-03-O1
WO 96/23010 PCT/US96/01282
Ty is hydrogen, hydrocarbyl not co:?ta~ntng
olefinic or acetylenic bonds, or -CH2CHZCH~CO2R6;
P is a divalent group containing one or more
repeat units derived from the polymerization of one or
monomers selected from the group consisting of
ethylene, an olefin of the formula R1'CH=CH; or
R1'CH=CHR1~, cyciopentene, cyclobutene, substituted
norbornene, and norbornene, and, when M is Pd(II),
optionally one er more o~: a compound of the formula
l0 CH,=CH t CHI ) ~,CO~R' , CO, or a vinyl ketone ;
Re is hydrocarbyl;
a is 1 or 2 ;
y + a t ~ - m;
each R- is independently hydrocarbvi or
l~ substituted hydrocarbyl provided that any ciefinic bond
in said olefin is separated from any other olefinic
bond or aromatic ring by a auaternary carbon. atom or at
least two saturated carbon atoms; R1 is hydrogen, or
hydrocarbyl or substituted hydrocarbyl containing 1 to
?0 10 carbon atoms;
m is 0 or an integer cf 1 to 16;
and X is a weakly coordinating anio.~.;
provided that:
when norbornene or substituted norbornene is
present, .no other monomer is present;
when M is Pd a diene is not present; and
further provided that, when M is Ni(II), R'1 is
not
-CO~Re .
30 Also described herein is a compound of the formula
R2
3
R ~N\ %C)y I
M-C-R~ ~
',
H-C-R ~ ~
R Rs PTa
(XVI) (x )a
36

WO 96/23010 ~ 02338581 2001-03-O1
PCT/US96/01282
wherein:
M is Zr, Ti, Sc, V, Cr, a rare earth metal, Fe,
Co, Ni or Pd of oxidation state m;
R' and RS are each independently hydrocarbyl or
subst_tuted hydrocarbyl, provided that the carbor. atom
bound directly to the imino nitrogen atom has at least
two carboy. atoms bound to it;
n- and R4 are each independently hydrogen,
hydrocarbyl, substituted hydrocarbyl or R3 and R4 taken
togeter a=a hydrocarbyiene or substituted
hydrccarbylene to form a ring;
each R'' is independently hydrogen, o= alky;,
or bo~h of R11 taken together are hydrocarbylene to
is form a carbocyclic ring;
T' is hydrogen, hydrocarbyl not containing
olefir:ic cr acetylenic bonds, or -CHZCH~CH~CO_Re;
P is a divalent group containing one or mere
repeat units derived from the polymerization of one or
?0 monomers selected from the group consisting of
ethylene, an olefin of the formula R''CH=CH2 or
R1'CH=CHR', cyclopentene, cyclobutene, substi~uted
norbcrner.~, and norbornene, and optionally, when M is
Pd(II!, one or more of: a compound of the formula
CH~=C.T:!Cr-'~.CO,R', CO, or a vi~yl ketone;
is a monovalent anion;
:~' is hydrocarbyl;
a is 1 or 2;
y + a + 1 = m;
30 each R1' is independently hydrocarbyi or
subst_tuted hydrocarbyl provided that any olefinic bond
in said olefin is separated from any other olefinic
bond cr aromatic ring by a quaternary carbon atom cr at
least twc saturated carbon atoms;
3~ R' is hydrogen, or hydrocarbyl or substituted
hydrocarbyi containing 1 to 10 carbon atoms;
m is 0 or an integer of 1 to 16; and
and X is a weakly coordinating anion;
-,
__.___._..~~ ~..~r.. .wn r nw

CA 02338581 2001-03-O1
WO 96!23010 PCT/US96/01282
and provided that when M is Pd a aiene is not
present.
Described herein is a process, comprising,
contacting, at « temperature of about -40°C to about
+60°C, a compound of the formula [ (r14-1, 5-COD) PdTlZ)'X
and a diimine of the formula
R2
R3 N
R4 ~ N
R5
(VIiI)
to prcduce a compound of the formula
R2
Rs i
N, T~
Pd~
R4 ~ N Z
RS X-
(II)
1;
wherein:
is hydrogen, hydrocarbyl not containing
olefinic or acetylenic bonds, R15C (=O) - or R150C (=O) -;
X is a weakly coordinating anion;
?0 COD is 1,5-cyclooctadiene;
Z is R1°ChT;
R'° is hydrocarbyl not containing olefinic or
acetylenic bonds;
R15 is hydrocarbyl not containing olefinic or
acetv_lenic bonds;
R~ and RS are each independently hydrocarbyl or
substituted hydrocarbyl, provided that the carbon atom
bound to the imino nitrogen atom has at least two
carbcn atoms bound to it; and
38
_ _._.

WO 96123010 ~ 02338581 2001-03-O1 pCT/US96I01282
R~ and R4 are each independently ~yu~c~g~n,
hydrocarbyl, substituted hydrocarby2 or R3 and R4 taken
together are hydrocarbylene or substituted
hydrocarbylene to form a ring.
Described herein is a process, comprising,
contacting, at a temperature of about -80°C to about
+2C°C, a compound of the formula (r)'-1, ~-COD? PdMe2 and a
diimine cf the formula
Rz
Rs I
,N
Ra ~ N
R5
(VIII)
to produce a compound of the formula
Rz
R
Me
Pd
\N/ ~ Me
R'
Rs
(XXXXI)
wherein:
COD is 1,5-cyclooctadiene;
Rz and RS are each independently hydrocarbyl or
?0 substituted hydrocarbyl, provided that the carbon atom
bound to the imino nitrogen atom has at least two
carbon atoms bound to it; and
R3 and R4 are each independently hydrogen,
hydrocarbyl, substituted hydrocarbyl or R' and R' taken
together are hydrocarbylene or substituted
hydrocarbylene to form a ring.
Also disclosed herein is a compound of the formula ..
39
e~meeTtTtn'C cu~CT ft7111 ~ ~Rl

CA 02338581 2001-03-O1
WO 96/23010 PCT'/US96/01282
R2
R3 N NCRz'
~Pd~
R4 ~ ~ ~NCRz'
2X
(XIV)
wherein:
R' ar.d RS are each independently hydrecarbyl or
substituted hydrocarbyl, provided that the carbon atom
bound tc the imino nitrogen atom has at least two
carboy ator~.s bound to i t ;
R- and R~ are each independently hydrogen,
hydrocarbyl, substituted hydrocarbyl or R- anc R' taker.
together are hydrocarbylene or substituted
hydrocarbylene to form a ring;
1 s each R' ~ i s hydr ocarbyl ; and
each X is a weakly coordinating anio:.
This invention includes a compound of ti:e formula
R2
R3 N -I-4
i~~CHR~°
Ra N RiaHC~ X-
R5
?0 (IX)
whet eir.:
M is Ni(II) or Pd(II);
R' and R~ are each independently hydrocarbyl or
substituted hydrocarbyl, provided that the carbon atom
bound directly to the imino nitrogen atom has at least
two carbon atoms bound to it;
R- and R' are each independently hydrogen,
hydrocarby~, substituted hydrocarbyl or R' and R4 taken
_..___._..~~ .., ,rr-T rm n c nc~

WO 96123010 ~ 02338581 2001-03-O1 PCT/US96/01282
together are hydrocarbylene cr substituted
hydrocarbylene to form a ring;
each R14 is independently hydrogen, alkyl or
- ( CHZ ) mC0,R1:
R' is hydrogen, or hydrocarbyl or substituted
hydrocarbyl containing 1 to 10 carbon atoms;
T' is alkyl, -R6°C (O) ORB, R15 (C=0) - or R150C (=0) -
R'S is hydrocarbyl not containing olefinic or
acetylenic bonds;
R6o .~s alkylene not containing olefinic or
acetylenic bends;
RB is hydrocarbyl;;
and X is a weakly coordinating anion;
1 ~ and provided that when R" is - ( CH2 ) mCO,R' , or T'
is not alkyl, M is Pd(II).
Described herein is a homopolypropylene with a
glass transition temperature of -30°C or less, and
containing at least about 50 branches per 1000
?0 methyiene groups.
This invention also concerns a homopolymer of
cyclopentene having a degree of pclymerization of about
30 or more and an end of melting point of about 100°C
to about 320°C, provided that said homopolymer has less
than 5 mole percent of enchained linear olefin.
containing pentylene units.
In addition, disclosed herein is a homopolymer or
copolymer of cyclopentene that has an X-ray powder
diffraction pattern that has reflections at
approximately 17.3°, 19.3°, 24.2°, and 40.7° 2A.
Another novel polymer is a homopolymer of
cyclopentene wherein at least 90 mole percent of
enchained cyclopentylene units are 1,3-cyclopentylene
units, and said homopolymer has an average degree of
3~ polymerization of 30 more.
Described herein is a homopolymer of cyclopentene
wherein at least 90 mole percent of enchained
cyciopentylene units are cis-1,3-cyclopentylene, and
41
n. ~eeT~Ti tTC cucCT rCtl II G ~R1

CA 02338581 2001-03-O1
WO 96/23010 PCT/US96/01282
said homopoiymer has an average decree c~$'
polymerization of about 10 or more.
Also described is a copolymer of cyclopentene and
ethylene wherein at least 75 mole percent of enchained
cyciopentylene units are 1,3-cyclopentyiene units.
This invention concerns a copolymer of
cyclopentene and ethylene wherein there are at least 20
branches per 1000 methylene carbon. atoms.
Described herein is a copolymer of cyciopentene
10 and ethylene wherein at least 50 mole percent of the
repeat units are derived from cyclopentene.
Disclosed herein is a copolymer of cyclopentene
and an a-of e~in.
This invention also concerns a polymerization ~r:y.
l~ rocess, comprising, contacting an olefin of the
~orrr~ula R' CH=CHz or R1'CH=CHR1', wherein. each R'~ is
independently hydrogen, hydrocarbyl, or substituted
hydrccarbyl provided that any olefinic bond in said
olefin is separated from any other olefinic bond or
20 aromatic ring by a quaternary carbon atom or at least
two saturated carbon atoms with a catalyst, wherein
said catalyst:
contains a nickel or palladium atom in a
positive oxidation state;
contains a neutral bidentate ligand coordinated
~o said nickel er palladium atom, and wherein
coordination to said nickel or palladium atom is
trough two nitrogen atoms or a nitrogen atom and a
p~.osphorous atom; and
30 said neutral bidentate ligand, has an Ethylene
exchange Rate of less than 20,000 L-mol is 1 when said
catalyst contains a palladium atom, and less than
X0,000 L-mol -s ' when said catalyst contains a nickel
atom;
3~ and provided that when Pd is present a diene is
not present.
4?
_.._ __.....r.. .., ~~rT m n r nc~

WO 96123010 ~ 02338581 2001-03-O1 p~/US96/01282
Described herein is a process for the
polymerization of olefins, comprising, contacting, at a
temperature of about -100°C to about +200°C:
a first compound which is a salt of an alkali
metal cation and a relatively noncocrdinating
monoanion;
a second compound of the formula
RZ
R3 N T'
~Pc~
R4 ~ N~ ~S
~5
!XX)
and one or more monomers selected from the
group consisting of ethylene, an olefin of the formula
R1'CH=CHZ or R''CH=CHR1', cyclobutene, cyclopentene,
1~ substituted norbornene, or norbornene;
wherein:
R~ and RS are each independently hydrocarbyl or
substituted hydrocarbyl, provided that the carbon atom
bound to the imino nitrogen atom has at least two
'_0 carbon atoms bound to it;
R3 and R' are each independently hydrogen,
hydrocarbyl, substituted hydrocarbyl or R3 and R' taken
together are hydrocarbylene or substituted
hydrocarbylene to form a ring;
each R1' is independently hydrocarbyl or
substituted hydrocarbyl provided that R'' contains no
olefinic bond;
T1 is hydrogen, hydrocarbyl not containing
olefinic or acetylenic bonds, R15C(=0)- or R'SOCt=O)-,
30 S is chloride, iodide, or bromide; and
provided that, when norbornene or substituted
norbornene is present, no_other monomer is present.
43
~wnr~~r~T~ eTr e~uL~T IDI II C ~C1

CA 02338581 2001-03-O1
WO 96/23010 PCTNS96/01282
Described '.:erein is a polyolefin, comprising, a
polymer made by polymerizing one or more monomers of
the formula HOC=CH(CH~)eG by contacting said monomers
with a transition metal containing coordination
polymerization catalyst, wherein:
each G is independently hydrogen or -C02R1;
each a is independently 0 or an integer of 1 to
20;
each R- is independently hydrogen, hydrocarbyl
or substituted hydrocarbyl;
and crovided that:
said polymer has at least SO branches per 1000
methylene Groups;
in at least 50 mole percent of said monomers G
1 ~ i s hvdrocte~. ; an d
except when no branches should be theoreticGlly
present, the number of branches per 1000 methylene
groups is 900 or less than the number of theoretical
branches per 1000 methylene groups, or the number of
20 branches per 1000 methylene groups is 110% or more of
theoretical branches per 1000 methylene groups, and
when there should be no branches theoretically
present, said polyolefin has 50 or more branches per
1000 methylene groups;
and provided that said polyoiefi:.:~as at least
two branches of different lengths ccntair._::c less t ha::
6 carbon atoms each.
Also described herein is a polyoiefi::, comprising,
a polymer made by polymerizing one or more monomers c
30 the formula HOC=CH(CH2)eG by contacting said monomers
with a transition metal containing coordination
polymerization catalyst, wherein:
each G is independently hydrogen cr -C02R';
each a is independently 0 or an i~:teger ef 1 to
35 2 0 ;
R' is independently hydrogen, hydrocarbyl or
substituted hydrocarbyl;
and provided that:
44
_.._ __._..~ ....~~ .ni m r nev

WO 96123010 ~ 02338581 2001-03-O1 pC1'/tJS96/01282
said polymer has at least 50 branches per 1000
methylene groups;
in at least 50 mole percent of said monomers G
is hydrogen;
said polymer has at least 50 branches of the
formula -(CHZ)fG per 1000 methylene groups, wherein
when G is the same as in a monomer and e~f, and/or for
any single monomer of the formula HOC=CH(CH2)eG there.
are less than 90% of the number of theoretical branches
per 1000 methylene groups, cr more than 1100 of the
theoretical branches per 1000 methylene groups of the
formula -lCH2)fG and f=e, and wherein f is 0 or an
intecrer of 1 or more;
and provided that said poiyolefin has at leas:. two
I~ branches of d,~fferent lengths containing less than 6
carbo:. atoms.
This invention concerns a process for the
formation of linear a-olefins, comprising, contacting,
at a temperature of about -100°C to about +200°C:
ethylene;
a first compound W, which is a neutral Lewis acid
capable ef abstracting X to form wX , provided that
the anion formed is a weakly coordinating anion, c. a
cationic Lewis or Bronsted acid whose counterion is a
'_'~ weakly coordinating anion; and
a second compound of the formula
R2
R3 N Q
~N~
~S
R4 ~ N
~s
(XXXI)
wherein:
R' and RS are each independently hydrocarbyl or
substituted hydrocarbyl;
R3 and R' are each independently hydrogen,
hydrocarbyl, substituted hydrocarbyl or R3 and R4 taken
4~
~..~..~.r".rr m ~rrT ~D111 C ~7F.'~

CA 02338581 2001-03-O1
WO 96!23010 PCT/US96/01282
together are hydrocarbylene or substituted
hydrocarbylene to form a ring; and
Q and S are each independently chlorine, bromine,
iodine or alkyl; and
5 wherein an a-olefin containing 4 to 40 carbon
atoms is produced.
This invention also concerns a process for the
formation of linear a-olefins, comprising, contacting,
at a temperature of about -100°C to about +200°C:
ethylene and a compound of the formula
R2 ~ +
3
R ~ N T'
~N~
Ra/~N ~Z X'
~s
(III)
or
1
N~Ni~U
(XXXIV)
wherein:
R2 and Ri are each independently hydrocarbyl or
substituted hydrocarbyl;
R3 and R' are each independently hydrogen,
hydrocarbyl, substituted hydrocarbyl or R3 and R' taken
together are hydrocarbylene or substituted
hydrocarbylene to form a ring;
T1 is hydrogen or n-alkyl containing up to 38
carbon atoms;
Z is a neutral Lewis base wherein the donating
atom is nitrogen, sulfur, or oxygen, provided that if
46
_..___.~..~~ .,".-~ rni n c nc~

WO 96123010 ~ 02338581 2001-03-O1 p~/tIS96/01282
the donating atom is nitrogen then the pKa of the
conjugate acid of that compound (measured in water) is
less than about 6;
U is n-alkyl containing up to 38 carbon atoms;
and
X is a noncoordinating anion;
and wherein an a-olefin containing 4 to 40 carbon
atoms is produced.
Another novel process is a process for the
formation of linear a-olefins, comprising, contacting,
at a temperature of about -100°C to about +200°C:
ethylene;
and a Ni [ I I ) of
R2
R3 N
R4 ~ N
R5
(VIII)
1;
R2 and RS are each independently hydrocarbyl or
substituted hydrocarbyl, provided that the carbon atom
bound to the imino nitrogen atom has at least two
carbon atoms bound to it;
'_0 R' and R4 are each independently hydrogen,
hydrocarbyl, substituted hydrocarbyl, or R~ and R'
taken together are hydrocarbylene substituted
hydrocarbylene to form a carbocyclic ring and
wherein an a-olefin containing 4 to 40 carbon
'_'~ atoms is produced..
Also described herein is a process for the
production of polyolefins, comprising, contacting, at a
temperature of about 0°C to about +200°C, a compound of
the formula
47
~..~..~.~wr m W >-T' ID111 C'!.'\

CA 02338581 2001-03-O1
WO 96123010 PCTIUS96I01282
R2
R=
M - ,a
~N~
R" ~ S;
5
XXXVII
and one or more monomers selected from the croup
consisting of ethylene, an olefin of the ~,.rmula
R1'CH=Ch, or R'~CH=CHR1', cyclobutene, cyclepentene,
substituted norbornene, and norbornene,
wherein:
M is Ni(~=i or Pd(II);
A is a ;,-allyl or ~-benzyl group;
10 R- and R- are each independently hydrocarbyl or
substituted hydrocarbyl, provided that tha carbon atom
bound directly to the imino nitrogen atom has at least
two carbon atoms bound to it;
R' and R' are each independently hydrogen,
I~ hydrocarbyl, substituted hydrocarbyl or R~ and R4 taken
together are hydrocarbylene or substituted
hydrocarbylene to form a ring;
each R'' is independently hydrocarbyl or
substituted hydrocarbyl provided that any olefinic bond
i_~. said olefin is separated from any ot'.~.er olefinic
bond or aromatic ring by a quaternary carbon atom or at
least two saturated carbon atoms;
and X is a weakly coordinating anion;
and provided that:
when M is Pd a diene is not present; and
when norbornene or substituted norbornene is
present, no other monomer is present.
The inventior_ also includes a compou.~.d of the
formula
30
48
w m.~~» ~r m trTT IPfI I1 C nC\

WO 96/23010 ~ 02338581 2001-03-O1
PCT/US96/01282
R'
R'
N
M- .A
N
R' h-
Rs
XXXVII
wherein:
M is Ni(II) or Pd(II);
A is a ~-allyl or n-benzyl group;
R' and R~. are each independently hydrocarbyl or
substituted hydrocarbyl, provided that the carbon atom
bound directly to the imino nitrogen. atom has at least
two carbon atoms bound to it;
Rl and R4 are each independently hydrogen,
hydrocarbyl, substituted hydrocarbyl or R' and R' taken
together are hydrocarbylene or substituted
hydrocarbylene to form a ring;
each R1' is independently hydrocarbyl or
substituted hydrocarbyl provided that any olefinic bond
1~ in said olefin is separated from any other olefinic
bond cr aromatic ring by a quaternary carbon atom or at
least two saturated carbon atoms;
and X is a weakly coordinating anion;
and r~rovided that when M is Pd a diene is not
'_'0 prese:.~ .
'j'his invention also includes a compound of the
f ormui a
Rss
R55
R'
Rs
R3 V W
\ ' N\ /
M
wN \Z X.
R° i
Rsa
(XXXViIt)
49
_.._ __.-..~ ~..~,.~ ..,w r nr~

CA 02338581 2001-03-O1
WO 96123010 PCT/US96/01282
wherein:
R3 and R' are each independently hydrogen,
hydrocarbyl, substituted hydrocarbyl or R3 and R' taken
S together are hydrocarbylene or substituted
hydrocarbylene to form a ring;
R54 is hydrocarbyl or substituted hydrocarbyl,
provided that the carbon atom bound directly to the
_mino nitrogen atom has at least two carbon atoms bound
to it;
each R55 is independently hydrogen,
hydrocarbyl, substituted hydrocarbyl, or a functional
croup;
W is alkyiene cr substituted alkylene
1~ containing 2 or more carbon atoms;
Z is a neutral Lewis base wherein the donating
atom is nitrogen, sulfur, or oxygen, provided that if
the donating atom is nitrogen then the pKa of the
conjugate acid of that compound (measured in water) is
?0 less than about 6, or an olefin of the formula
R''CH=CHR1' ;
each R1' is independently hydrogen, saturated
hydrocarbyl or substituted saturated hydrocarbyl; and
X is a weakly coordinating anion;
and provided that when M is Ni, W is alkylene anti
each R1~ is independently hydrogen or saturated
'_hydrocarbyl.
This invention also includes a process for the
production of a compound of the formula
Rss
R55 R55
y
R
R3 N W
M
~N/ Z X.
R' I
Rs,
(XXXVIiI)
_ _-_-..r _..~~ .r,. a r nW

CA 02338581 2001-03-O1
WO 96123010 PCT/US96I01282
comprising, heating a compound of the formula
Rss
R55
RS~~ R56
R
~~ T5
~~ \z x.
R
~s~
(xxxix)
at a temperature of about -30°C to about +100° for a
sufficient time to produce (XXXVIII), and wherein:
R- and R" are each independently hydrogen,
hvdrocarbvl, substituted hydrocarbyl or R~ and R~ taken
together are hydrocarbylene or substituted
hydrocarbylene to form a ring;
RS'' is hydrocarbyl or substituted hydrocarbyl,
provided that the carbon atom bound directly to the
imino nitrogen atom has at least two carbon atoms bound
to it;
each R~' is independently hydrogen,
hydrocarbyl, substituted hydrocarbyl, or a functional
group;
R56 is alkyl containing 2 to 30 carbon atoms;
is alkyl;
W is alkylene containing 2 to 30 carbon atoms;
Z is a neutral Lewis base wherein the donating
atom is nitrogen, sulfur, or oxygen, provided that if
the donating atom is nitrogen then the pKa of the
conjugate acid of that compound (measured in wateri is
less than about 6; and
X is a weakly coordinating anion.
This invention also concerns a process for the
polymerization of olefins, comprising, contacting a
compound of the. formula
~l

CA 02338581 2001-03-O1
WO 96/23010 PCTlUS96101282
Rss
Rss
Rss
Rs
R3 ~ W
~ N\
M
/ \ X.
N Z
Ra I
Rsa
(XXXVIII)
and one or more monomers selected from the group
consisting of ethylene, an olefin of the formula
.,- CH=CHZ or R1'CH=CHR1', cyclobutene, cyclopentene,
substituted norbornene, and norbornene,
wherein:
R- and R' are each independently hydrogen,
ydrocarbyl, substituted hydrocarbyl or R' and R' taken
together are hydrocarbylene or substituted
10 ydrocarbylene to form a ring;
RS' is hydrocarbyl or substituted hydrocarbyl,
provided that the carbon atom bound directly to the
imino nitrogen atom has at least two carbon atoms bound
to it;
1~ each R~5 is independently hydrogen,
'.,:vdrocarbyl, substituted hydrocarbyl, or a functional
group;
W is alkylene or substituted alkylene
....::tai..~.ing 2 cr more carbon atoms;
'_'0 Z is a neutral Lewis base wherein the donating
atom is nitrogen, sulfur, or oxygen, provided that ==
the donating atom is nitrogen then the pKa of the
ccn~ugate acid of that compound (measured in water! is
less than about 6, or an olefin of the formula
..- CH=CHR1' ;
each R1' is independently hydrogen, saturated
::y~rocarbyl or substituted saturated hydrocarbyl; and
X is a weakly coordinating anion;
and provided that: .
30 when M is Ni, w is alkylene and each R1~ is
__-:dependently hydrogen or saturated hydrocarbyl;
_ . ._ __._. ~_ _.._~ ,..... ~ .,..,

WO 96123010 ~ 02338581 2001-03-O1 PCTIUS96101282
and whet. norbornene or substituted norbornene
is present, no other monomer is present.
This invention also concerns a homopoiypropylene
containing about 10 to about 700 ~+ methyiene groups
~ per 1000 total methylene groups in said
homopolypropylene.
Described herein is a homopolvpropylene wherein
the ratio of b+:y methylene groups is about 0.5 to
about 7.
Also included herein is a homopolypropylene in
which. about 30 to about B5 mole percent of the monomer
units are enchained in an c~,l fashion.
1~RTATLS OF THE T_I~TVEIVTION
Herein certain terms are used to define certain
1~ chemical groups or compounds. These terms are defined
below.
~ A "hydrocarbyl group" is a univalent group
containing only carbon and hydrogen. If not otherwise
stated, it is preferred that hydrocarbyl groups herein.
contain. 1 to about 30 carbon atoms.
~ By "not containing olefinic or acetylenic
bonds" is meant the grouping does not contain olefinic
carbon-carbon double bonds (but aromatic rings are not
excluded) and carbon-carbon triple bonds.
?~ ~ By "substituted hydrocarbyl" herein is meant
a hydrocarbyl group which contains one or more
substituent groups which are inert under the process
conditions to which the compound containing these
groups is subjected. The substituent groups also do
not substantially interfere with the process. If not
otherwise stated, it is preferred that substituted
hydrocarbyl groups herein contain 1 to about 30 carbon
atoms. Included in the meaning of "substituted" are
heteroaromatic rings.
;~ . By an alkyl aluminum compound is meant
a compound in which at least one alkyl group is bound
to an aluminum atom. Other groups such as alkoxide,
;3
m iocTtTt tTC CNFFT f R1 II F 261

CA 02338581 2001-03-O1
WO 96/23010 PCT/US96/01282
oxygen, and halogen may also be bound tc aluminum atoms
in the compound.
~ By "hydrocarbylene" herein is meant a
divalent group containing only carbon and hydrogen.
Typical hydrocarbylene groups are -(CH2)4-, -
CHZCH (CH~CH3) CH2CH~- and
\ \
/ /
(An)
10
If not otherwise stated, it is preferred that
hydrocarbylene groins herein contain 1 to about 3G
carbon atoms.
~ By "substituted hydrocarbylene" herein is
1~ meant a hydrocarbylene group which contains one or more
substituent groups which are inert under the process
conditions to which the compound containing these
groups is subjected. The substituent groups also do
not substantially interfere with the process. If not
?0 otherwise stated, it is preferred that substituted
hydrocarbylene groups herein contain 1 to about 30
carboy. atoms. Included within the meaning of
"substituted" are heteroaromatic rincrs.
~ Bv substituted norbornene is meant a
norbornene which is substituted with one cr more groups
whicdoes not interfere substantially with the
polymerization. It is preferred that subsrituent
groups (if they contain carbon atoms) contain 1 to 30
carbon atoms. Examples of substituted norbornenes are
:0 ethylidene norbornene and methylene norbornene.
~ By "saturated hydrocarbyl" is meant a
univalent group containing only carbon and hydrogen
which contains no unsaturation, such as oiefinic,
acetylenic, or aromatic groups. Examples of such
>> groups include alkyl and cycloalkyl. If not otherwise
;4
~t tr~n~tTt rn Pt Ir>-T 1D1 II C t7C.'\

WO 96!23010 ~ 02338581 2001-03-O1 PCT/US96101282
stated, ,;t is preferred that saturated hydrocarby-_
groups herein contain 1 to about 30 carbon atoms.
~ By "neutral Lewis base" is meant a compound,
which is not an ion, which can act as a Lewis base.
Examples of such compounds include ethers, amines,
sulfides, and organic nitriles.
~ By "cationic Lewis acid" is meant a catien
whit: can act as a Lewis acid. Examples of such
catior_s are sodium and silver cations.
~ By "a-olefin" is meant a compound of the
formal a ~r,=CHR'9, wherein R'9 is n-alkyl or bra~ched
alkyl, ~re~erably n-alkyl.
~ By "linear a-olefin" is meant a compound cf
the formula CH,=CHRi~, wherein R19 is n-alkyl. It is
preferre~ that the linear a-olefir. have 4 to ~~ carbcr.
atoms.
~ By a "saturated carbon atom" is meant a
carbon atom which is bonded to other atoms by single
bonds only. Not included in saturated carbon atoms are
?0 carbon atoms which are part of aromatic rings.
~ By a quaternary carbon atom is meant a
saturated carbon atom which is not bound to anv
hydroaer. atoms. A preferred quaternary carbor_ atom, is
bound tc four other carbon atoms.
~ By an olefinic bond is meant a carbon-carbo.~.
double be~d, but does not _..~.clude bonds y.. arc-~,atlc
rinQS.
~ By a rare earth metal is meant one of
lanthanum, cerium, praeseodymium, neodymium,
30 promethium, samarium, europium, gadolinium, terbium,
dysprosium, holmium, erbium, thulium, ytterbium or
lutetium.
:'his invention concerns processes for making
polymers, comprising, contacting ore or more selected
3~ olefins cr cycloolefins, and optionally an ester or
carboxylic acid of the formula CH2=CH(CHZ)mCO~R', and
other selected monomers, with a transition metal
eortainir.Q catalyst (and possibly other catalyst
nr reeTrTr tTC cuLCT lCtl il C'7R1

CA 02338581 2001-03-O1
WO 96/23010 PCT/US96/01282
components). Such catalysts are, for instance, various
complexes of a diimine with these metals. By a
"polymerization process herein (and the polymers made
therein)" is meant a process which produces a polymer
with a degree of polymerization (DP) cf about 20 or
more, preferably about 40 or more [except where
otherwise noted, as in P in compound (VI)] By "DP" is
meant the average number of repeat (monomer) units i:.
the polymer.
Cne ef these catalysts may generally be written as
R2
R3 ~ N\ ,Q
Ra~Ni S
i
R5
(I)
1~ wherein: M is Ni(II), Co(II), Fe(II) or Pd(II); R' and
RS are each independently hydrocarbyl or substituted
hydrocarbyl, provided that the carbon atom bound to the
imino nitrogen atom has at least two carbon atoms bound
to it; R3 and R4 are each independently hydrogen,
'_'0 hydrocarbyl , substituted hydrocarbyl or R' and R' taken
toget:~er are hydrocarbylene or substituted
::ydrocarbylene tc form a ring; Q is alkyl, hydride, .
chloride, iodide, or bromide; and S is alkyl, hydride,
chloride, iodide, or bromide. Preferably M is Ni(I=)
or Pd(II).
In a prefers ed form of ( I ) , R3 and R4 are each
independently hydrogen or hydrocarbyl. If Q and/or S
is alkyl, it is preferred that the alkyl contains ~ to
4 carbon atoms, and more preferably is methyl.
,0 Another useful catalyst is
~6
." ",~Tm ~r cuccT rai n F ~Rl

WO 96/23010 ~ 02338581 2001-03-O1 p~'/pS96/01281
R2
R3 I
T~
Pd~
Ra ~N ~Z
Rs X'
(II)
wherein: R' and RS are each independently hydrocarbyl
or substituted hydrocarbyl, provided that the carbon
atom bound to the imino nitrogen atom has at least two
carbon atoms bound to it; Rj and R4 are each
independently hydrogen, hydrocarbyl, substituted
hydrocarbyl or R' and RS taken together are
rydrocarbylene or substituted hydrocarbylene to form a
ring; T1 is hydrogen, hydrocarbyl not containing
olefinic or acetylenic bonds, R'SC(=O)- or R'SOC(=O)-; Z
is a neutral Lewis base wherein the donating atom is
nitrogen, sulfur or oxygen, provided that, if the
l~ donating atom is nitrogen, then the pKa of the
conjugate acid of that compound is less than about 6; X
is a weakly coordinating anion; and R15 is hydrocarbyl
not containing olefinic or acetylenic bonds.
In one preferred form of (II), R' and R9 are each
?0 independently hydrogen or hydrocarbyl. In a more
preferred form of (II), T~ is alkyl, and T' is
especially preferably methyl. It is preferred that Z
is R6~0 or R'CN, wherein each R6 is independently
hydrocarbyl and R' is hydrocarbyl. It is preferred that
R~ and R~ are alkyl, and it is more preferred that they
are methyl or ethyl. It is preferred that X is BAF,
SbF6 , PFa or BF4 .
Another useful catalyst is
57
nmn~TrTt rTr ~uccT 1Q1 II C ~R\

CA 02338581 2001-03-O1
WO 96/23010 PCTNS96/01282
R2
R3 I
N Ti
Nib
R4 ~ N Z
RS X'
(III)
wherein: R2 and RS are each independently hydrocarbyl
or substituted hydrocarbyl, provided that t::e carbon
atom bound to the imino nitrogen atom has at '-east two
carbcn atoms bound to it; R'' and R4 are each
inde~e:~dently hydrogen, hydrocarbyl, cr subs=ituted
hydrocarbyiene, or R3 and R9 taken together Gre
10 hydrocarbyiene er substitute.''. i:ydrocarbylene t.. form a
ring; T~' is hydrogen, hydrocarbyl not conta,_ning
olefi~ic or acetylenic bonds, R15C(=O)- or R-'OC(=O)-; Z
is a neutral Lewis base wherein the donating atom is
nitrogen, sulfur or oxygen, provided that if the
1~ donating atom is nitrogen then the pKa of the conjugate
acid of that compound is less than about 6; X is a
weakly coordinating anion; and R15 is hydrocarbyl not
containing olefinic or acetylenic bonds.
In one preferred form of ( III ) , R' and :~- are each
~0 independently hydrogen, hydrocarbyl. In a mere
pre~erred form of (III) T' is alkyl, and T- =s
especially preferably methyl. It is preferred that Z '
is R',O or R Ch, wherein each R6 is independe__~.t l y
hydrocarbyl and R'' is hydrocarbyi. It is pre=erred
that R6 and R are alkyl, and it is especially preferred.
that they are methyl or ethyl. It is preferred that X
is BAF- , SbF 4- , PF6- or BFQ' .
Relatively weakly coordinating anions are known tc
the artisan. Such anions are often bulky anions,
30 particularly those that may delocalize their negative
charge. Suitable weakly coordinating anions in this
Application i::clude (Ph)4B (Ph = phenyli,
tetrakis[3,5-bis(trifluoromethyl)phenyl]borate (herein.
~8
_ .._ __._..~~ ~..~r~ ,rwm r ncv

WO 96123010 ~ 02338581 2001-03-O1 pC'f/US96/01282
abbre~riated BAF) , PFE , 3F4 , SbFE ,
trifluoromethanesulfonate, p-toluenesulfonate,
(RfSOz) 2N-, and (C6F5) 9B . Preferred weakly coordinating
anions include BAF , PF6 , BF4 , and SbF6
Also useful as a polymerization catalyst is a
compound of the formula
R2 OR8
Rs I I
N~ ,O=C - -
M I
R4 ~ Ni ~~CHR~6)n
I X_
Rs
(IV)
wherein: R2 and RS are each independently hydrocarbyi
or substituted hydrocarbyl, provided that the carbon
atom bound to the imino nitrogen atom has at least two
carbon atoms bound to it; R3 and R4 are each
independently hydrogen, hydrocarbyl, substituted
hydrocarbyl or R3 and R4 taken together are
hydrocarbylene or substituted hydrocarbylene to form a
ring; M is Ni(II) or Pd(II); each R16 is independently
hydrogen or alkyl containing 1 to 10 carbon atoms; n is
'?0 1, 2, or 3; X is a weakly coordinating anion; and RB is
hyd=ccarbyl.
It is preferred that n is 3, and all of R16 are
hydrogen. Tt is also preferred that RB is alkyl or
substituted alkyl, especially preferred that it is
alkyl, and more preferred that R8 is methyl.
Another useful catalyst is
R2 R2
R3 I ~ I Rs
~N~ ~T ,N~
~Pd E 1/Pd\
a N T
N
R I Ra
Rs R5 X_
(v)
~9
w mrwrm rTr HLJr~1' IDI I) C'R~

CA 02338581 2001-03-O1
WO 96123010 PCT/US96/01282
wherein: R~ and RS are hydrocarbyl or substituted
hydrocarbyl, provided that the carbon atom bound
directly to the imino nitrogen atom has at least two
carbon atoms bound to it ; R' and R'' are each
independently hydrogen, hydrocarbyl, substituted
hydrocarbyl or R3 and R4 taken together are
hydrocarbylene or substituted hydrocarbylene to form a
ring; T' is hydrogen, hydrocarbyl not containing w
clefinic or acetylenic bonds, R15C(=O)- or R1'OC(=O)-;
z'S is hydrocarbyl not containing olefinic or
acetylenic bonds; E is halogen or -OR18; R18 is
hydrocarbyl not containing olefinic or acetyienic
bonds; and X is a weakly coordinating anion. It is
I~ ~referred that T~ is alkyl containing 1 to 4 carboy.
atoms, and more preferred that it is methyl. In other
preferred compounds (~), R3 and R4 are methyl or
hydrogen and R~ and RS are 2,6-diisopropylphenyl and X
is BAF. It is also preferred that E is chlorine.
20 Another useful catalyst is a compound of the
f ormul a
R2
R3 ~ N~ ~Tz
Pd~
R4
R5
(VII)
wherein: R2 and RS are each independently hydrocarbyl
or substituted hydrocarbyl , provided that the carbon
atom bound to the imino nitrogen atom has at least twc
30 carbon atoms bound to it; R3 and R' are each
independently hydrogen, hydrocarbyl, substituted
hydrocarbyl or R3 and R4 taken together are
hydrocarbylene or substituted hydrocarbylene to form a
_.._.,~.~, .~.. ..~ ~~.-T gin, i~ r nc~

WO 96/23010 ~ 02338581 2001-03-O1 PCT/US96/01282
ring; T' is hydrogen, hydrocarbyl not containing
olefinic or acetylenic bonds, hydrocarbyl substituted
with keto or ester groups but not containing eiefinic
or acetylenic bonds, R15C (=O) - or R150C (=O) -, R~-y is
~ hydrocarbyl not containing olefinic cr acetylenic
bonds; and X is a weakly coordinating anion. In a more
preferred form of (VII), T2 is alkyl containing 1 to 4
carbon atoms and T' is especially preferably methyl.
It is preferred that X is perfluoroalkylsulforate,
especially trifluoromethanesulfonate (triflate;~. If X
is an extremely weakly coordinating anion such as BAF,
(VII) may not form. Thus it may be said that ;VII)
forms usually with weakly, but perhaps not extremely
weakly, coordinating anions.
1~ Ir. all compounds, intermediates, catalysts,
processes, etc. ,;n which they appear .,. is preferred
that R' and R~ are each independently hydrocarbyl, and
in one form it is especially preferred that R' and RS
are both 2,6-diisopropylphenyl, particularly when R3
?0 and R' are each independently hydrogen or methyl. It
3 4
is also preferred that R and R are each independently
hydrogen, hydrocarbyl or taken together hydrocarbylene
to form a carbocyclic ring.
Compounds c~ the formula (I) wherein M is Pd, Q is
'~ alkyl and S is halogen may be made by the reaction of
the ccrrespor.ding 1,5-cycloectadiene (COD) Pte' complex
wit'_: the appropriate diimine. When M is Ni, -) can be
made by the displacement of a another ligand, such as a
dialkylether or a polyether such as 1,2-
~0 dimethoxyethane, by an appropriate diimine.
Catalysts of formula (III, wherein X is BAF , ;nay
be made by reacting a compound of formula (I) wherein Q
is alkyl and S is halogen, with about one equivalent of
an alkali metal salt, particularly the sodium salt, of
3~ HBAF, in the presence of a coordinating ligand,
particularly a nitrite such as acetonitrile. When X
is an anion such as BAF , SbF6~ or BFQ the same
61
w ~rwTVT~ rTr cuccT l01 II C ~R1

CA 02338581 2001-03-O1
WO 96/23010 PCT/US96/01282
starting palladiua, compound can be reacted with the
silver salt AgX.
However, sometimes the reaction of a diimine with
a 1,5-COD Pd complex as described above to make
~ compounds of formula (II) may be slow and/or give poor
conversions, thereby rendering it difficult to make the
starting material for (II) using the method described
in the preceding paragraph. For instance when:
R'=RS=Ph-,Cr- and R'=R'=H; R'=RS=Ph- and R3=R4=Ph; R'=RS=2_
10 t-butylphenyi and R3=R~=CH,; R2=RS=a-naphthyl and
R'-- _R'=CH, ; and R'=R~=2 -phenylphenyl and R3=R4=CH,
difficulty may be encountered in making a compound of
formula (=I).
In these instances it has been found more
1> convenient to prepare (II) by reacting [(r~s-1,~-
COD)PdT'Z)fX~, wherein T~- and X are as defined above and
Z is an organic nitrite ligand, preferably in an
organic nitrite solvent, with a diimine of the formula
R2
Rs I
,N
Ra ~ N
R5
?0
(VIII)
By a "nitrite solvent" is meant a solvent that is
at least 20 volume percent nitrite compound. The
?~ product of this reaction is (II?, in which the Z ligand
is the nitrite used in the synthesis. In a preferred
synthesis, Tl is methyl and the r.itrile used is the
same as i~ the starting palladium compound, and is more
preferably acetonitrile. The process is carried out in
30 solution, preferably when the nitrite is substantially
all of the solvent, at a temperature of about -40°C to
about +60°C, preferably about 0°C to about 30°C. It is
6?
~..~~~.~. r~r m ~rrT ~f71 tt C ~7C\

WO 96123010 ~ 02338581 2001-03-O1 p(°f/US96l01282
preferred that the reactants be used in substantially
equimolar quantities.
The compound [(~~-1,5-COD)PdTlZ1+X , wherein ~_" is
alkyl, Z is an organic nitrite and X is a weakly
coor::,ir~ating anion may be made by the reaction of [ (>14-
1,5-COD)PdTlA, wherein A is C1, Br or I and T1 is alkyl
with the silver salt of X , AgX, or if X is BAF with an
alka~i metal salt of HBAF, in the presence of an
organic r.i~riie, which of course will become the ligand
T'. In a preferred process A is C1, T1 is alkyl, more
pre=erGbly methyl, and the organic nitrite is a.z alkyl
r.itri~e, more preferably acetonitrile. The starting
mateYia~_s are p=eferably present in approximately
equi-~:olar amounts, except for the nitrite which is
is present preferably in excess. The solvent is
preferably a non-coordinating solvent such as a
halecarbo.~.. Methylene chloride is useful as such a
solvent. ~he process preferably is carried out at a
temperature of about -40°C to about +50°C. It is
?'Q preferred to exclude water and other hydroxyl
contair_ing compounds from the process, and this may be
done by purification of the ingredients and keeping the
process mass under an inert gas such as nitrogen.
ComDOUnds of formula (II) [or (III) when the metal
is n=ckel] car. also be made by the reaction of
R2
Rs~N T'
Ra~N~ ~T~
i
[~5
(X)
30 wit:. G source of the conjugate acid of the anion X, the
acid HX or its equivalent (such as a trityl salt) in
the presence of a solvent which is a weakly
coordinating ligand such as a dialkyl ether or an alkyl
63
w ~r,nTr~ ~r ruccT rflt tt C ~R\

CA 02338581 2001-03-O1
WO 96/23010 PCT/US96/01282
nitrite. It is preferred to carry out this reaction at
about -80°C to about 30°C.
Compounds of formula (XXXXI) can be made by a
process, comprising, contacting, at a temperature of
about -80°C to about +20°C, a compound cf the formula
rl4-1,5-COD)PdMez and a diimine of the formula
R2
R3 N
R4 ~ N
R5
(VIII)
wherein: COD is 1,5-cyclooctadiene; R' and R'
are each independently hydrocarbyl or substituted
hydrocarbyl, provided that the carbon atom bound to the
1~ imino nitrogen atom has at least two carbor. atoms bound
to it; and R3 and Rq are each independently hydrogen,
hydrocarbyl, substituted hydrocarbyl or R3 and R4 taken
together are hydrocarbylene or substituted
hydrocarbylene to form a ring.._It is preferred that
the temperature is about -50°C to about +10°C. ;t is
also preferred that the two starting materials be used
in approximately equimolar quantities, and/or that the
reaction be carried out in solution. It is preferred
that R~ and RS are both 2-t-butylphenyl or 2,5-di-t-
butylphenyl and that R3 and R4 taken together are A.n,
or R3 and R4 are both hydrogen or methyl.
ComDOUnds of formula (IV) can be made by several
routes. In one method a compound of formula (II) is
reacted with an acrylate ester of the formula
30 CH~=CHCO~R1 wherein R1 is as defined above. This
reaction is carried out in a non-coordinating solvent
such as methylene chloride, preferably using a greater
than 1 to 50 fold excess of the acrylate ester. In a
6~
_.._ __._..~~ .., ,..~ m, n r nev

CA 02338581 2001-03-O1
WO 96123010 PCTIUS96I01282
preferred reaction, Q is methyl, and R' is alkyl
containing 1 to 4 carbon atoms, more preferably methyl.
The process is carried out at a temperature of about -
100°C to about +100°C, preferably about 0°C to about
50°C. It is preferred to exclude water and other
hydroxyl containing compounds from the process, and
this may be done by purification of the ingredients and
keeping the process mass under an inert gas such as
nitrogen
Alternatively, (IV) may be prepared by reacting
(I), wherein Q is alkyl and S is C1, Br or I with a
source of an appropriate weakly coordinating anion such
as AgX or an alkali metal salt of BAF and an acrylate
ester (formula as immediately above) in a single step.
1~ Approximately eauimolar auantities of (I) and the
weakly coordinating anion source are preferred, but t::e
acrylate ester may be present in greater than 1 to 50
fold excess. In a preferred reaction, Q is methyl, and
R' is alkyl containing 1 to 4 carbon atoms, more
preferably methyl. The process is preferably carried
out at a temperature of about -100°C to about +100°C,
preferably about 0°C to about 50°C. It is preferred to
exclude water and other hydroxyl containing compounds
from the process, and this may be done by purification
cf the ingredients and keeping the process mass under
an inert gas such as nitrogen.
In another variation of the preparation of (IV)
from (I> the source of the weakly coordinating anion is
a compound which itself does not contain an anion, :,ut
which can combine with S [of (I)] to form such a weakly
coordinating anion. Thus in this type of process by
"source of weakly coordinating anion" is meant a
compound which itself contains the anion which will
become X , or a compound which during the process can
3~ combine with other process ingredients to form such an
anion.
Catalysts of formula (V), wherein X is BAF , may
be made by reacting a compound of formula (I) wherein Q
6~
_ _.-..__ _. ._~ ~m n r nee

CA 02338581 2001-03-O1
WO 96/23010 PC'TIUS96I01282
is alkyl and S is halogen, with about one-':~-~' oL an
equivaler:t of an alkali metal salt, particularly the
sodium salt, of HBAF. Alternatively, (V) containing
other anions may be prepared by reacting (I), wherein Q
is alkyl and S is C1, Br or I with one-half equivalent
of a source of an appropriate weakly coordinating anion
such as AgX.
Some of the nickel and palladium compounds
described above are ~,a eful in processes for
10 polymerizing vaYious olefins, and optionally also
copo~ymeri~~na olefinic esters, carboxylic acids, or
other func~ional olefins, with these olefins. When (I)
is used as a catalyst, a neutral Lewis acid or a
cationic Lewis or Bronsted acid whose counterion is a
1~ weakly coordinating anion. is also present as part of
the catalyst system (sometimes called a "first
compound" in the claims). By a "neutral Lewis acid" is
meant a compound which is a Lewis acid capable for
abstracting Q or S from (I) to form a weakly
'_'0 coordination anion. The neutral Lewis acid is
originally uncharged (i.e., not ionic). Suitable
neutral Lewis acids include SbFs, Ar3B (wherein Ar is
aryl), and BF,. By a cationic Lewis acid is meant a
canon with a positive charge such as Ag', ._ , and Na'.
In those instances in which (I) (and similar
catalysts whic:: require the presence of a neutral Lewis
acid or a cationic Lewis or Bronsted acid), does not
contain ar: alkyl or hydride group already bonded to the
metal (i.e., neither Q or S is alkyl or hydride), the
30 neutral Lewis acid or a cationic Lewis or Bronsted acid
also alkylates or adds a hydride to the metal, i.e.,
causes an alkyl group or hydride to become bonded to
t~e metal atom.
A preferred neutral Lewis acid, which can alkylate
3~ the metal, is a selected alkyl aluminum compound, such
as R9~A1 , :c'_AlCl , R9A1C12 , and "R9A10"
(alkylaluminoxanes), wherein R9 is alkyl containing 1
to 25 carbon atoms, preferably 1 to 4 carbon atoms.
66

CA 02338581 2001-03-O1
WO 96/23010 PCT/US96101282
Suitable alkyl aluminum compounds include
methylaluminoxane (which is an oligomer with the
general formula [MeAlO] n) , (CzHs) ~AlCl, C,H~A1C1~, and
[ (CH3) zCHCH2] 3A1 .
S Metal hydrides such as NaBH4 may be used to bond
hydride groups to the metal M.
The first compound and (I) are contacted, usually
in the liquid phase, and in the presence of the olefin,
and/or 4-vinylcyclohexene, cyclopentene, cyclobutene,
substituted norbornene, or norbornene. The liquid
phase may include a compound added just as a solvent
and/or may include the monomers) itself. The molar
ratio of first compound:nickel or palladium ccmplex is
about 5 to about 1000, preferably about 10 to about
1~ 100. The temperature at which the polymerizatio~ is
carried out is about -100°C to about +200°C, preferably
about -20°C to about +80°C. The pressure at which the
polymerization is carried out is not critical,
atmospheric pressure to about 275 MPa, or more, being a
?0 suitable range. The pressure may affect the
microstructure of the polyolefin produced (see below).
When using (I) as a catalyst, it is preferred that
R3 and R4 are hydrogen, methyl, or taken together are
\ \
/ /
?5
(An)
It is also preferred that both R2 and RS are 2,6-
diisopropylphenyl, 2,6-dimethylphenyl, 2,6-
30 diethylphenyl, 4-methylphenyl, phenyl, 2,4,6-
trimethylphenyl, and 2-t-butylphenyl. When M is
Ni(II), it is preferred that Q and S are each
independently chloride or bromide, while when M is
Pd(II) it is preferred that Q is methyl, chloride, or _.
~5 bromide, and S is chloride, bromide or methyl. In
67

CA 02338581 2001-03-O1
WO 96123010 PCTIUS96/01282
addition, the specific combinations of groups" ~n't~:e-
catalysts listed in Table I are especially preferred.
Table I
R- R' R' RS Q S M
2,6-i-PrPh H H 2,6-i-PrPh Me C1 Pd
2,6-i-PrPh Me Me 2,6-i-PrPh Me C1 Pd
2,6-~-PrPh An An 2,6-i-PrPh Me C1 Pd
2,6-MePh H H 2,6-MePh Me C1 Pd
4-MePh H H 4-MePh Me Cl Pd
4-MePh Me Me 4-MePh Me C1 Pd
2,6-~-PrPI: Me Me 2,6-i-PrPh Me Me Pd
2,6-i-PrPh H i-i 2,6-i-PrPh Me Me Pd
2,6-MePh H H 2,6-MePh Me Me Pd
2,6-i-PrPh H H 2,6-i-PrPh Br Br Ni
2,6-i-PrPh Me Me 2,6-i-PrPh Br Br Ni
2,6-MePh H H 2,6-MePh Br Br Ni
Ph Me Me Ph Me C1 Pd
2,6-EtPh Me Me 2,6-EtPh Me C1 Pd
2,4,6-MePh Me Me 2,4,6-MePh Me Cl Pd
2,6-MePh Me Me 2,6-MePh Br Br Ni
2,6-i-PrPh An An 2,6-i-PrPh Br Br Ni
2,6-Meph An An 2,6-MePh Br Br 1i
2-t-BuPh An An 2-t-BuPh Br Br Ni
2,5-t-BuPh An An 2,5-t-BuPh Br Br Ni
~-i-Pr-6-MePh An An 2-i-Pr-6-MePh Br Br Ni
~-i-Pr-6-MePh Me Me 2-i-Pr-6-MePh Br Br Ni
2,6-t-BuPh H H 2,6-t-BuPh Br Br Ni
c,6-t-BuPh Me Me 2,6-t-BuPh Br Br Ni
2,6-t-BuPh An An 2,6-t-BuPh Br Br Ni
2-t-BuPh Me Me 2-t-BuPh Br Br Ni
Note - In Tables and II, and elsewhere here-n,
I
the following convention and abbreviations ed.
are us
For R~ and RS, when a ring is .
substituted
phenyl
present, the a mountof ubstitution is by the
s indicated
~umber of numb ers tina positions pheny~
indica on the
68
_. __ _. ._~ ..., " . "..,

WO 96123010 ~ 02338581 2001-03-O1
PCTlUS96/01282
ring, so that, for example, 2,6-i-PrPh is 2,6-
diisopropylphenyl. The following abbreviations are
used: i-Pr = isopropyl; Me = methyl; Et = ethyl; t-Bu =
t-butyl; Ph = phenyl; Np = naphthyl; An = 1,8-
naphthylylene (a divalent radical used for both R3 and
R4, wherein R' and R4 taken together form a ring, which
is part cf an acenaphthylene group); OTf = triflate;
and BAF = tetrakis[3,5-
bis(trifluoromethyl)phenyi]borate.
Preferred olefins in the polymerization are one or
more of ethylene, propylene, 1-butene, 2-butene, 1-
hexene 1-octene, 1-pentene, 1-tetradecene, norbornene,
and cvclonentene, with ethylene, propylene and
1~ cyclopentene being more preferred. Ethylene (alone as
a homopolymer) is especially preferred.
The polymerizations with (I) may be run in the
presence of various liquids, particularly aprotic
organic liquids. The catalyst system, monomer(s), and
?0 polymer may be soluble or insoluble in these liquids,
but obviously these liquids should not prevent the
polymerization -from occurring. Suitable liquids include
alkanes, cycloalkanes, selected halogenated
hydrocarbons, and aromatic hydrocarbons. Specific
useful solvents include hexane, toluene anti benzene.
whether such a liquid is used, and which and how
much liquid is used, may affect the product obtained.
It may affect the yield, microstructure, molecular
weight, etc., of the polymer obtained.
30 Compounds of formulas (XI), (XIII), (XV) and (XIX)
may also be used as catalysts for the polymerization of
the same monomers as compounds of formula (I). The
polymerization conditions are the same fcr (XI),
(XIII), (XV) and (XIX) as for (I), and the same Lewis
35 and Bronsted acids are used as co-catalysts. Preferred
groupings R2, R3, R~, and RS (when present) in (XI) and
(XIII) are the same as in (I), both in a polymerization
process and as compounds in their own right.
69
~..~~~.~..~~ m ~rrr ~m tt r rfC1

CA 02338581 2001-03-O1
WO 96123010 PCT/US96/01282
Preferred (XI) compounds have the metals Sc(III),
Zr(IV), Ni(II), Ni(I), Pd(II), Fe(II), and Co(II).
When M is Zr, Ti, Fe, and Sc it is preferred that all
of Q and S are chlorine or bromine more preferably
chlorine. When M is Ni or Co it is preferred that all
of Q and S are chlorine, bromine or iodine, more
preferably bromine.
Ir. (XVII) preferred metals are Ni(II) and Ti(IV).
It is preferred that all of Q and S are halogen. It is
also preferred that all of R28, R~9, and R3° are
hydrogen, and/or that both R44 and R95 are 2,4,6-
trimethyiphenyl cr 9-anthracenyl.
In (XV) it is preferred that both of R~' are
hydrogen.
In (XIII), (XXIII) and (XXXII) (as polymerization
catalysts and as no~,rel compounds) it is preferred that
all of R-°, R'1, R'~ and R~3 are methyl. It is also
preferred that T1 and T' are methyl. For (XIII), when
M is Ni(I) or (II), it is preferred that both Q and S
20 are bromine, while when M is Pd it is preferred that Q
is methyl and S is chlorine.
Compounds (II), (IV) or (VII) will each also
cause the polymerization of one or more of an olefin,
and/or a selected cyclic olefin such as cyclobutene,
cvcloDentene or norbornene, and, when it is a Pd(II)
complex, optionally copolymerize an ester or carboxylic
acid of the formula CHI=CH(CHZ)mC02R1, wherein m is 0 or
an integer of 1 to 16 and R1 is hydrogen or hydrocarbyl
or substituted hydrocarbyl, by themselves (without
30 cocatalysts). However, (III) often cannot be used when
the ester is present. When norbornene or substituted
norbornene is present no other monomer should be
present.
Other monomers which may be used with compounds
35 (II), (IV) or (VII) (when it is a Pd(II) complex) to
form copolymers with olefins and selected cycloolefins
are carbon monoxide (CO), and vinyl ketones of the
general formula H,C=CHC (O) Rzs, wherein R'5 is alkyl
_......_." ...r r., ,rrT m a c nc~

CA 02338581 2001-03-O1
WO 96/23010 PCT/US96/01282
containing 1 to 20 carbon atoms, and it is preferred
that R25 is methyl. In the case of the vinyl ketones,
the same compositional limits on the polymers produced
apply as for the carboxylic acids and esters described
as comonomers in the immediately preceding paragraph.
CO forms alternating copolymers with the various
olefins and cycloolefins which may be polymerized with
compounds (II), (IV) or (VII). The polymerization to
form the alternating copolymers is done with both CO
l0 and the olefin simultaneously in the process mixture,
and available to the catalyst. It is also possible to
form block copolymers containing the alternating
CO/(cyclo)olefin copolymers and other blocks containing
just that olefin or other olefins or mixtures thereof.
I~ This may be done simply by sequentially exposing
compounds (II), (IV) or (VII), and their subsequent
living polymers, to the appropriate monomer cr mixture
of monomers to form the desired blocks. Copolymers of
CO, a (cyclo)olefin and a saturated carboxylic acid or
20 ester ef the formula CHz=CH(CHZ)mC02R1, wherein m is 0
or an integer of 1 to 16 and R1 is hydrogen or
hydrocarbyl or substituted hydrocarbyl, may also be
made by simultaneously exposing the polymerization
catalyst or living polymer to these 3 types of
'_'s monomers .
The polymerizations may be carried out with (i~i,
(III), (IV) or tVII), and other catalyst molecules or
combi:~ations, initially in the solid state (assuming
(IIi, (III) (IV) or (VII) is a solid] or in solution.
30 The olefin and/or cycloolefin may be in the gas or
liauid state (including gas dissolved in a solvent). A
liquid, which may or may not be a solvent for any or
all of the reactants and/or products may also be
present. Suitable liquids include alkanes,
3~ cycloalkanes, halogenated alkanes and cycloalkanes,
ethers, water, and alcohols, except that when (III) is
used, hydrocarbons should preferably be used as
solvents. Specific useful solvents include methylene
71
_..___ ._... ..,...

CA 02338581 2001-03-O1
WO 96/23010 PCT/US96/01282
chloride, hexane, CO~, chloroform, perfiuoro-(n-
butyltetrahydrofuran) (herein sometimes called FC-75),
toluene, dichlorobenzene, 2-ethylhexanol, and benzene.
It is particularly noteworthy that one of the
liquids which can be used in this polymerization
process with (II), (III), (IV) or (VII) is water, see
for instance Examples 213-216. Not only can water be
present but the polymerization "medium" may be largely
water, and various types of surfactants may be employed
so that an emulsion polymerization may be done, along
with a suspe.~.sion polymerization when surfactants are
not employed.
Preferred olefins and cycloolefins in the
Dolvmerization using (II), (III) or (IV) are one or
I~ more c= ethylene, propylene, 1-butene, 1-hexene, i-
octene, 1-butene, cyclopentene, 1-tetradecene, and
norbornene; and ethylene, propylene and cyciopentene
are more preferred. Ethylene alone is especially
preferred.
Olefin~c esters or carboxylic acids of the formula
CHz=CH ( CH2 ) mC02R1, where in R- is hydrogen , hydrocarbyl ,
or substituted hydrocarbyi, and m is 0 or an integer of
1 to 16. T_t is preferred if R' hydrocarbyl or
substituted hydrocarbyl and it is more preferred if it
is alkyl containing 1 to 10 carbon atoms, or glycidyl.
It is also preferred if m is 0 and/or R' is alkyl
containing 1 to 10 carbon atoms. It is preferred to
make copolymers containing up to about 60 mole percent,
preferably up to about 20 mole percent of repeat uni~~
derived from the olefinic ester or carboxylic acid.
Total repeat unit units in the polymer herein refer not
only to those in the main chain from each monomer unit,
but those in branches or side chains as well.
When using (II), (III), (IV) or (VII) as a
3~ catalyst it is.preferred that R' and R4 are hydrogen,
methyl, or taken together are

WO 96/23010 ~ 02338581 2001-03-O1 p~~7g96/01282
\ \
/ /
(An)
It is also preferred that both R2 and RS are 2,6-
diisopropylphenyl, 2,6-dimethylphenyl, 4-methylphenyl,
phenyl, 2,6-diethylphenyl, 2,4,6-trimethylphenyl and 2-
t-butylphenyl. When (II) is used, it is preferred that
T1 is methyl, R~ is methyl or ethyl and R~ is methyl.
When (III) ,;s used it is preferred that ~1 is methyl
and said Lewis base is 8620, wherein R6 is methyl or
ethyl. When (IV) is used it is preferred that RB is
methyl, n is 3 and R1~ is hydrogen. In addition in
Table II are listed all particularly preferred
combinations as catalysts for (II), (III), (IV) and
1~ (VII) .
73
~..~..~.~...~ ... .rte .n~ m r nrv

CA 02338581 2001-03-O1
WO 96!23010 PCT/US96/01282
Table II
Com- R~ R3 R' R' T'/TZ/ Z M X
pound Re
Type
(II) 2,6-i- Me Me 2,6-i- Me OEt, ?d BAF
PrPh PrPh
(II) 2,6-i- H H 2,6-i- Me OEt_ ad BAF
PrPh PrPh
(III) i- Me Me 2,6-i- Me OEt~ ~i BAF
2,6- _
PrPh PrPh
(III 2,6-i- H H 2,6-i- Me OEt~ vi BAF
i
prph PrPh
(II) 2,6- H H 2,6-MePh Me OEt= .d BAF
Meph
(II) 2,6- Me Me 2,6-MePh Me OEt, ?d BAF
_
MePh
(II) 2,6-i- Me Me 2,6-i- Me OEt2 Pd SbFS
PrPh PrPh
(II) 2,6-i- Me Me 2,6-i- Me OEtz Pd BF4
PrPh PrPh
(II) 2,6-i- Me Me 2,6-i- Me OEt~ Pd PF6
PrPh PrPh
(II) 2,6-i- H H 2,6-i- Me OEt_ ?d SbF
PrPh PrPh
( I 2 , Me Me 2 , 4 Me OEt= ?~? SbF:
I 4 , , 6 -
) o -
MePh MePh
(II) 2,6-_ An An 2,6-i- Me OEt, .d SbFE
-
PrPh PrPh
(II) 2,6-i- Me Me 2,6-i- Me NCMe Pd SbFS
PrPh PrPh
(II) Ph Me Me Ph Me NCMe Pd SbF6
(II) 2,6- Me Me 2,6-EtPh Me NCMe ?d BAF
EtPh
(II) 2,6- Me Me 2,6-EtPh Me NCMe Pd SbFE
EtPh
(II) 2-t- Me Me 2-t-BuPh Me NCMe Pd SbF6 .
BuPh
74
_ _ ._ _-.-. .__ ... .~~ .... a r nev

WO 96/23010 ~ 02338581 2001-03-O1 PCT/US96/01282
(II) 1-Np Me Me 1-Np Me NCMe Pd SbF6
( Ph2CH H H Ph2CH Me NCMe Pd SbFs
I
I
)
(II) 2-PhPh Me Me 2-PhPh Me NCMe Pd SbF6
(II) Ph a a Ph Me NCMe Pd BAF
(IV) 2,6-i- Me Me 2,6-i- Me b Pd SbF6
PrPh PrPh
(IV) 2,6-i- Me Me 2,6-i- Me b Pd BAF
PrPh PrPh
(IVi 2,6-i- H H 2,6-i- Me b Pd SbFE
PrPh PrPh
(IV) 2,6-i- Me Me 2,6-i- Me b Pd B(C6
PrPh PrPh FS),C
1
(Ii) Ph Me Me Ph Me NCMe Pd SbF
iVII 2,6-~ Me Me 2,6-i- Me - Pd OTf
PrPh PrPh
(II) Ph Ph Ph Ph Me NCMe Pd BAF
( Ph2CH H H Ph2CH Me NCMe Pd SbF6
I
I
)
a This up is
gro -CMe2CHzCMe~-
b This is (CHz)3CO2Me
group -
47hen using (II), (III), (IV) or (VII) the
temperature at which the polymerization is carried out
is abcut -100°C to about +200°C, preferably about 0°C to
about X50°C, more preferably about 25°C to about 100°C.
The pressure at which the polymerization is carried o~.:t
is nct critical, atmospheric pressure to abou:. 275 MPa
beino a suitable range. The pressure can affect the
microstructure of the polyolefin produced (see below).
Catalysts of the formulas (II), (III), (IV) and
(VII) may also be supported on a solid catalyst (as
opposed to just being added as a solid or in solution),
I~ fcr instance on silica gel (see Example 98). By
supported is meant that the catalyst may simply be
carried physically on the surface of the solid support,
may be adsorbed, or carried by the support by other
means.
7
nme~~rrnrrc cuGCT IC7111 C ~Rl

CA 02338581 2001-03-O1
WO 96123010 PCT/US96/01282
When using (XXX) as a ligand or in any process or
reaction herein it is preferred that n is 2, all of
Ri', R'8 and R'9 are hydrogen, and both of R~'' and R45 are
9-anthracenyl.
Another polymerization process comprises
contacting a compound cf the formula [Pd (R13CN) 4] X2 or a
combination of Pd [OC (O) R4°] 2 and HX, with a compound of
the formula
R2
Rs
,N
Ra ~ N
R5
IU
(VIII)
and one or more monomers selected from the group
consisting of ethylene, an olefin of the formula
I~ R''CH=CHI or R1'CH=CHR1', cyciopentene, cyclobutene,
substituted norbornene and norbornene, wherein: R' and
RS are each independently hydrocarbyl or substituted
hydrocarbyl, provided that the carbon atom bound to the
imino nitrogen atom has at least two carbon atoms bound
~0 ~c it; R3 and Ra are each independently hydrogen,
hydrocarbyl, substituted hydrocarbyl or R- and R' taken
l:
together are hydrocarbyiene or substituted
hydrocarbylene to form a carbocyclic ring; each R- is
independently hydrocarbyl or substituted hydrocarbyl
provided that R1' contains no olefinic bonds; R4° is
hydrocarbyl or substituted hydrocarbyl; and X is a
weakly coordinating anion; provided that when
norbornene or substituted norbornene is present no
other monomer is present.
30 It is believed that in this process a catalyst
similar to (II) may be initially generated, and this
then causes the polymerization. Therefore, ail cf the -
conditions, monomers (including olefinic esters and
76
w~ wrwn rTr 1"~t 1rt~T /DI II C ~7C.\

WO 96123010 ~ 02338581 2001-03-O1 p~'/~IS96/01282
carboxylic acids), etc., which are applicable to the
process using (II) as a polymerization catalyst are
applicable to this process. All preferred items are
also the same, including appropriate groups such as R~,
~ R? , R' , R5, and combinations thereof . This process
however should be run so that all of the ingredients
car contact each other, preferably in a single phase.
Initially at least, it is preferred that this is done
in solution. The molar ratio of (VIII) to palladium
compound used is-not critical, but for most economical
use of the compounds, a moderate excess, about 25 to
1000 excess, of (VIII) is preferably used.
As mentioned above, it is believed that in the
polymerization using (VIII ) and (Pd (Rl'C:~T) 4] X~ or a
1~ Pd[II] carboxylate a catalyst similar to (II) is
formed. Other combinations of starting materials that
can combine into catalysts similar to (iI), (III),
(IV) and (VII) often also cause similar
polymerizations, see for instance Examples 238 and 239.
~0 Also combinations of a-diimines or other diimino
ligands described herein with: a nickel [~] cr nickel
[I] compound, oxygen, an alkyl aluminum compound and an
olefin; a nickel (0] or nickel [I] compou.~.d, an acid
such as HX and an olefin; or an a-diimine Ni[0] or
'_'~ nickel [I] complex, oxygen, an alkyl aluminum compound
and ar, olefin. Thus active catalysts from a-diimines
and other bidentate imino compounds can be formed
beforehand or in the same "pot" (in situ; in which the
polymerization takes place. In all of the
30 polymerizations in which the catalysts a=a formed in
situ, preferred groups on the a-diimines are the same
as for the preformed catalysts.
In general Ni(C], Ni[I]' or Ni(II) compounds may be
used as precursors to active catalyst species. They
:~ must have ligands which can be displaced by the
appropriate bidentate nitrogen ligand, or must already
contain such a bidentate ligand already bound to the
nickel atom. Ligands which may be displaced include
77
..~ '..r.T~Ti rrr e~uecT rod ~i C ~~~

CA 02338581 2001-03-O1
WO 96123010 PCT/US96/01282
1,5-cyclooctadiene and tris(o-tolyl)phosphite, which
may be present in Ni[0) compounds, or
dibenzylideneacetone, as in the useful Pd[0] precursor
tris(dibenzylideneacetone)dipalladium[0]. These lower
valence nickel compounds are believed to be converted
into active Ni[II] catalytic species. As such they
must also be contacted (react with) with an oxidizing
agent and a source of a weakly coordinating anion (X ).
Oxidizing agents include oxygen, HX (wherein X is a
10 weaklv coordinating anion), and other well known
oxidizing agents. Sources of X- include HX,
alkylaluminum compounds, alkali metal and silver salts
of X . As can be seen above, some compounds such as HX
may act as both an oxidizing agent and a source of X . ,
1~ Compounds containing other lower valent metals may be
converted into active catalyst species by similar
methods.
When contacted with an alkyl aluminum compound or
HX useful Ni[O] compounds include
?0
R2 Rz
R3 N R3 ~ R
/ \~ ~ ~N~ R'
NI COD N~ /N~
R4 \~ R \N~ . \N~N~ I O
R
s
R 5 0~1t
(X7i.)iII I)
~xxxxn~ ~xxxxun
R' R~ R5
Ra ~ R3 ~ Rs
/N\ /N~ N~
\Ni- O:
\ /
,N wN N
R~ 15 Ra I5 12 R3
R R
(XXXXIVI Or IXXXXV)
Various types of Ni[0] compounds are known in the
literature. Below are listed references for the types
25 shown immediately above.
78
~..~..~.~ .~~ n~ ~rrr W n C ~fC\

WO 96123010 ~ 02338581 2001-03-O1 PCT/US96/01282
~ (XXXIII) G. van Koten, et al., Ate.
Organometal. Chem., vol. 21, p. 151-239 (1982).
~ (XXXXII) W. Bonrath, et al., Angew. Chem.
Int. Ed. Engl., vol. 29, p. 298-300 (1990).
~ (XXXXIV) H. tom Dieck, et al., Z.
Natruforsch., vol. 366, p. 823-832 (1981); and M.
Svoboda, et al., J. Organometal. Chem., vol. 191, p.
321-328 (1980).
~ (XXXXV) G. van Koten, et ai., Adv.
Organcmetal. Chem., vol. 21, p. 151-239 (1982).
polymerizations using (XIV), the same preferred
monomers and groups ( such as R' , R' , Ry , RS and X ) as
are preferred for the polymerization using (II) are
used and preferred. Likewise, the conditions used and
1~ ~refe~red for polymerizations with (XIV) are similar tc
those used and preferred for (II), except tha:. higher
olefin pressures !when the olefin is a gas) are
preferred. Preferred pressures are about 2.0 to about
MPa. (XIV) may be prepared by the reaction of one
20 mcle of (Pd (R1'CI~') q] Xz with one mole of (VIII ) in
acetonitrile or nitromethane.
Novel compound (XIV) is used as an oiefir.
polymerization catalyst. In preferred forms o' (XIV),
the preferred groups R', R3, R~', R' and X are the same
as are ~referred for compound (II).
A:.other type of compound whic is an clef~:~
polymerization catalyst are n-ally! and n-benzyl
compounds of the formula
R~
R
N
M- A
N
R' ~ X
Rs
XXXVII
wherein M is Ni~(II) or Pd(II); R' and RS are
hydrocarbyl or substituted hydrocarbyl, provided that
the carbon atom bound directly to the imino nitrogen
79
........~,~ rrr nuCCT ~DW C 9R1

CA 02338581 2001-03-O1
WO 96123010 PCTIUS96/01282
atom has at least two carbon atoms bound to it; R' ann
R4 are each independently hydrogen, hydrocarbyl,
substituted hydrocarbyl or R3 and R; taken together are
hydrocarbylene or substituted hydrocarbylene to form a
ring; X is a weakly coordinating anion; and A is a n-
allyi or n-benzyl group. By a n-allyl group is meant a
monoanionic with 3 adjacent sp2 carbon atoms bound to a
metal center in an r13 fashion. The three spy carbon
atoms may be substituted with other hydrocarbyl groups
cr functional groups. Typical n-allyl groups include
~ co,R
CO, R
Ph ~ ~ CI
wherein R is hydrocarbyl. By a n-benzyl group is meant
l~ n-allyl ligand in which two of the spz carbon atoms are
part of an aromatic ring. Typical ~-benzyl groups
include
F
F
F
?0
F .
n-Benzyl compounds usually initiate polymerization
of the olefins fairly readily even at room temperature,
but n-allyl compounds may not necessarily do so.
......~~.~mr ~utcT m n C ~R1

WO 96/23010 ~ 02338581 2001-03-O1 p~'/US96/01282
Initiation of ~-ailyl compounds can be improved by
using cne or more of the following methods:
~ Using a higher temperature such as about
80°C.
~ Decreasing the bulk of the a-diimine ligand,
such as RZ and R' being 2,6-dimethylphenyl instead of
2,6-diisopropyiphenyl.
~ Making the n-allyl ligand more bulky, such
as usina
rather than the simple n-allyl group itself.
~ Having a Lewis acid present while using a
functional z-allyl or r-benzyl group. Relatively weak
1~ Lewis acids such a triphenylborane,
tris(pentafluorophenyl)borane, and tris(3,5-
trifluoromethylphenyl)borane, are preferred. Suitable
functional groups include chloro and ester. "Solid"
acids such as montmorillonite may also be used.
When using (XXXVII) as a polymerization catalyst,
it is preferred that ethylene and/or a linear a-olefin
is the monomer, or cyclopentene, more preferred if the
monomer is ethylene and/or propylene, and ethylene is
especially preferred. A preferred temperature for the
polymerization process using (XXXVII) is about +20°C to
about 100°C. It is also preferred that the partial
pressure due to ethylene or propylene monomer is at
least about 600 kPa.It is also noted that (XXXVII) is a
novel compound, and preferred items for (XXXVII) for
the polymerization process are also preferred for the
compound itself.
Another catalyst for the polymerization of olefins
is a compound of the formula
81
r~ ~ecTm tTC CLJCCT fAl Il F ~Rl

CA 02338581 2001-03-O1
WO 96/23010 PC'T/US96/01282
R55
R55 R55
R5
R3 I W
N\
M
wN \Z X.
R< I
R~
(XXXVIII)
and one cr more monomers selected from the. group
consisting ef ethylene, an olefin of the formula
R1'CH=CH_ or R1'CH=CHR1', cyclobutene, cyclopentene,
substituted norbornene, and norbornene,
wherei: : k3 and R4 are each independert_y
hydrogen, hydrocarbyl, substituted hydrocarbyl or Ry .
and R' taker together are hydrocarbylene cr substituted
hydrocarbylene to form a ring; R54 is hydrocarbyl or
substituted hydrocarbyl, provided that the carbon atom
bound directly to the imino nitrogen atom has at least
two carbon atoms bound to it; each R55 is independently
hydroge.~. , i~:ydrocarbyl , substi tuted hydrocarbyl , or a
functional group; w is alkylene cr substituted alkylene
l~ containing 2 or more carbon atoms; Z is a neutral Lewis
base where~:~ the donating atom is nitrogen, sulfur, or
oxygen, provided that i~ the donating atom is nitrogen
then the ~_Ka of the conjugate acid of that comDOUnd
(measured in water) is less than about 6, cr an clefin
?0 of the formula R1'CH=CHR1'; each Rl' is independently
alkyl c. substituted alkyl; and X is a weakly
coordinating anion. It is preferred that i.~. compound
(XXXVII=; that: R54 1S phenyl or substituted phenyl, and
preferred substituents are alkyl groups; each RSS is
'_'~ independently hydrogen or alkyl containing 1 to 1C
carbon atoms; W contains 2 carbon atoms between the
phenyl ring and metal atom it is bonded to or W is a
divalent ~~lymeric group derived from the
polymerization of R''CH=CHR'', and it is especially
30 preferred that it is -CH(CH~)CH~- or -C(CH~)~CH~-; and Z
is a diaikvi ether or an olefin of the formula
8''
~..~~~.~.~~ IW vrrl ~1~111i r nC\

WO 96/23010 ~ 02338581 2001-03-O1 pCT/US96101282
..' CH=CHR1'; and combinations thereof . W is a_~: alkylene
crroun in which each of the two free valencies are to
different carbon atoms of the alkylene group.
When W is a divalent group formed by the
pclymerization of R1'CH=CHR1', and Z is R1'CH=CHR'', the
compound (XXXVIII) is believed to be a living ended
polymer. That end of W bound to the phenyl ring
actually is the original fragment from R56 from which
the "bridge" w originally formed, and the remaining
part of W is formed from the olefin (s) R''~CH=CHR1'. In
a sense this compound is similar in function to
compound (VI).
By substituted phenyl in (XXXVIII) and (XXXIX) is
meant the Dhenyl ring can be substituted wit: any
l~ Qrouping which does not interfere with the coTpound's
stability or any of the reactions the compound
undergoes. Preferred substituents in substituted
phenyl are alkyl groups, preferably containing 1 to 10
carbon atoms.
~0 Preferred monomers for this polymerization are
ethvlene and linear a-olefins, or cyclopentene,
particularly propylene, and ethylene and propylene or
both are more preferred, and ethylene is especially
preferred.
'_', Tt is noted that (XXXVII_) is a novel cc~:~ound,
and preferred compounds and groupings are the same as
in the polymerization process.
Compound (XXXVIII) can be made by heatin= compound
(XXXIX),
R55
Rss RSS
Rs ~ ~ Rss
R
'M
R~
~5~
w ~~w~.W n~P nl irrT !fly ~~ C'~i,

CA 02338581 2001-03-O1
WO 96123010 PCT/US96/01282
wherein: R' and R' are each independently
hydrogen, hydrocarbyl, substituted hydrocarbyl or R3
and R' taken together are hydrocarbylene or substituted
hydrocarbylene to form a ring; R54 is hydrocarbyl or
substituted hydrocarbyl, provided that the carbon atom
bound directly to the imino nitrogen atom has at least
two carbon atoms bound to it; each R55 is independently
hydrogen, hydrocarbyl, substituted hydrocarbyl, or a
_unctional group; R56 is alkyl containing 2 to 30
10 carbon atoms; T' is alkyl; Z is a neutral Lewis base
w::ereir. the donating atom is nitrogen, sulfur, or
oxyge_~., provided that if the donating atom is nitrogen
t:~e:: ~.:-~__ pKa cf the conjugate acid of that compound
imeasured in water) is less than about 6; and X is a
l~ weakiv coordinating anio.~.. Preferred groups are the
same as those ~n (XXXVIII). In addition it is
),referred that T~ contain 1 to 10 carbon atoms, and
more preferred that it is methyl. A preferred
temperature for the conversion of (XXXIX) to (XXXVIII)
'?0 is about -30°C to about SO°C. Typically the reaction
takes about ~0 min. to about 5 days, the higher the
temperature, the faster the reaction. Another facto
which affects the reaction rate is the nature of Z.
The weaker the Lewis basicity of Z, the faster the
desired reaction will be.
Y~Then (II) , (ITI) , (IV) , (V) , (VII) , (VIII) or a
combination of compounds that will generate similar
co~pounds, (subject to the conditions described above)
.s used in tre polymerization of olefins, cyclole=ins,
:0 a:.d oNtionally olefinic esters or carboxylic acids,
polymer having what is believed to be similar to a
"living end" is formed. This molecule is that from
whit:. the polymer crows to its eventual molecular
weig:~.t. This compound may have the structure
3~
84
........mT~ tTr rurrT ~D111 L ~R\

WO 96123010 ~ 02338581 2001-03-O1 PCT/US96/01282
Rz
R3 N PT3
~M~
~CHR»
Ra ~ N Ri i HCi~ X_
~5
(VI)
wherein: M is Ni(II) or Pd(II); R~ and R- are
hydrocarbyl c. substituted hydrocarbyl, provided that
the carbon atom bound directly to the imino nitrogen
atom has at least two carbon atoms bound to it; R' and
R~ are each independently hydrogen, hvdrocarbyl,
substituted hydrocarbyl or R3 and R' take_~, together are
hydrccarbyiene or substi~uted ::ydrccarby;e.~_e tc fcrm a
ring; each R" is independently hydrogen, alkyl or
-(CH2)mC02R1; _ is hydrogen, hydrocarbyl not containing
olefinic or acetylenic bonds, R'S(C=O)-, R''"O(C=O)-, or
-CH2CHZCH~CO2Re; R'S is hydrocarbyl not containing
1~ olefinic or acetylenic unsaturation; P is a divalent
group containing one or more repeat units derived from
the polymerization of one or more of ethylene, ar.
olefin of the formula R-'CH=CHz or R1'CH=CHR'~,
cyclobutene, cyclopentene, substituted ncrbornene, or
_'0 norbornene ana, when M is Pd(IT_), optionally one cr
more compounds of the formula CHI=CH (CH: ) ~CO~R-; RE is
hydrocarbyl; each Rl' is independently hydrocarbyl or
substituted hydrocarbyl provided that any olefinic bond
in said olefin is separated from any other olefinic
bond or aromatic ring by a quaternary carbon atom or at
least two saturated carbon atoms; m is 0 or an integer
from 1 to 16; R1 is hydrogen, or hydrocarbyl or
substituted hydrocarbyl containing 1 to l0 carbon
atoms; and X is a weakly coordinating anion; and that
30 when M is Ni(II), R11 is not -COzRe and when M is Pd a
dime is not present. By an "olefinic ester or
carboxylic acid" is meant a compound of the formula
8
~..~~~.~........."r~rT in~,~ c nc\

CA 02338581 2001-03-O1
WO 96/23010 PCTIUS96J01282
CH2=CH ( CHI ) ~.,C02R- , where in m and R1 ar a as def inea
immediately above.
This molecule will react with additional monomer
(olefin., cyclic olefin, olefinic ester or olefinic
carboxylic acid) to cause further polymerization. In
other words, the additional monomer will be added to P,
extending the length cF the polymer chain. '~hus P may
be o~ any size, from one "repeat unit" to many repeat
units, and when the polymerization is over and P is
removed from M, as by hydrolysis, P is essentially the
polymer product o~ the polymerizaticn. Polymerizations
with (Vi), that =~s contact of additional monomer with
this r.:oiecule takes place under the same conditions as
described above for the Dolymerization process using
1~ (II) , ,=I~) , (IV) , (V) , (VII) or (VIII) , or
combinGticns of compounds that will generate similar
molecules, and where appropriate preferred ccnditions
and structures are the same.
The group T' in (VI) was originally the group T1
?0 in (;I) or (III), or the group which included R8 in
(IV). ;t in essence will normally be one of the end
groins ef the eventual polymer product. The oiefinic
groin which is coordinated to M, R'~'CH=CHR11 is normally
one of the monomers, olefin, cyclic olefin, or, if
Pd(;=v .s M, an olefinic ester or carboxylic acid. If
more t:.an one of these monomers is present __. the
reaction, it may be any one of them. It is preferred
that 'I is alkyl and especially preferred that « is
methyl, and it is also preferred that R11 is hydroger_
30 or n-alkyl. It is also preferred that M is Pd(II).
Another "form" for the living end is (XVI).
R2
3
R N ~Q)r H
-~_R,
wtr ,,H_C_R,
5
R4 ~ ~T3
(XVI) ~h )a
86
_ . __ __._..~ ......~ .r,m r nr~

WO 96/23010 ~ 02338581 2001-03-O1 p~~g96101282
This type of compound is sometimes referred to as a
compound in the "agostic state". In fact both (VI) and
(XVI) may coexist together in the same polymerization,
both types of compound representing living ends. It is
believed that (XVI)-type compounds are particularly
favored when the end of the growing polymer chain bound
tc the transition metal is derived from a cyclic olefin
=uch as cyclopentene. Expressed in terms of the
structure of (XVI) this is when both of R11 are
vdrocarbylene to form a carbocyclic ring, and it is
_referred that this be a five-membered carbocyclic
r incr .
1~ ~cr both the polymerization process using (XVI)
a::d the structure of (XVI) itself, the same conditions
and groups as are used and preferred for (VI) are also
used and preferred for (XVI), with the exception that
for R'1 it is preferred in (XVI) that both of R11 are
?0 :~ydrocarbylene to form a carbocyclic ring.
This invention also concerns a compound cf the
f ormul a
Rz
R3~ N,
i~~~CHR~a
R° \ N R~4HC X'
Rs
(IX)
wherein: M is Ni(Ih) or PdtII); RZ and RS are
~:ydrocarbyl or substituted hydrocarbyl, provided that
tie carbon atom bound directly to the imino nitrogen
30 atom has at least two carbon atoms bound to it; R' and
R' are each independently hydrogen, hydrocarbyl,
substituted hydrocarbyl or R3 and R4 taken together are
hydrocarbylene or substituted hydrocarbylene to form a
87
~..~w~w. wr f~l N'rT II'!1 II C r7Q~

CA 02338581 2001-03-O1
WO 96123010 PCT/US96/01282
ring; each R14 is independently hydrogen, alkyl or
[when M is Pd ( II ) ] - (CHz ) mC02R1; R' is hydrogen, or
hydrocarbyl or substituted hydrocarbyl containing 1 to
10 carbon atoms; T° is alkyl, -R6°C (O) ORB, R15 (C=O) - or
R150C(=O)-; R15 is hydrocarbyl not containing olefinic
or acetylenic bonds; R6° is alkylene not containing
olefinic or acetylenic bonds; RB is hydrocarbyl; and X
is a weakly coordinating anion.
(IX) may also be used to polymerize olefins,
10 cyclic olefins, and optionally olefinic esters and
carboxylic acids. The same conditions (except as noted
below) apply to the polymerizations using (IX) as they
do for (VI). It is preferred that M is Pd(II) and T~
is methyl.
1~ A compound of formula (V) may also be used as a
catalyst for the pclymerization of olefins, cyclic
olefins, and optionally olefinic esters and/or
carboxylic acids. In this process (V) is contacted
with one or more of the essential monomers. Optionally
20 a source of a relatively weakly coordinating anion may
also be present. Such a source could be an alkali
metal salt of BAF or AgX (wherein X is the anion), etc.
Preferably about 1 mole of the source of X, such as
AgX, will be added per mole of (V). This will usually
?~ be done in the liquid phase, preferably in which (V)
and the source of the anion are at least partially
soluble. The conditions of this polymerization are
otherwise the same as described above for (IIi, (III),
(IV) and (VII), including the preferred conditions and
30 ingredients.
In polymerizations using (XX) as the catalyst,
a first compound which is a source of a relatively
noncoordinating monoanion is present. Such a source
can be an alkali metal or silver salt of the monoanion.
3~
88
__ __ _~~.r _..

WO 96/23010 ~ 02338581 2001-03-O1 pCTlUS96l01282
R2
_ R3 N T'
~P~
~S
R4 ~ N
~5
(XX)
It is preferred that the alkali metal can on is sodium
or potassium. It is preferred that the monoanion is
SbF6 , BAF, PFE , or BF4 , and more preferred that it is
BAF. It is preferred that '_" is methyl and/or S is
chlorine. All other preferred groups and conditions
for these polymerizatiens are the same as for
polymerizations with (II).
In aii of the above poiymerizations, and the
catalysts for making them it is preferred that R' and
R', if present, are 2,6-diisopropylphenyl and R3 and R4
are hydrogen or methyl. When cyclopentene is
1~ polymerized, is preferred that R2 and RS (if present)
are 2,6-dimethylphenyl or 2,4,6-trimethylphenyl and
that R3 and R~ taken together are An. R', R~, R4 and R
and other groups herein may also be substituted
hydrocarbyl. As previously defined, the substituent
?0 groups in substituted hydrocarbyl groups (there may be
one or more substituent groups) should not
substantially interfere witr. the polymerization or
other reactions that the compound is undergoing.
Whether a particular group will interfere can first be
?~ judged from the artisans general knowledge and the
particular polymerization or other reaction that is
involved. For instance, in polymerizations where an
alkyl aluminum compound is used may not be compatible
with the presence of groups containing an active
30 (relatively acidic) hydrogen atom, such as hydroxyl or
carboxyl because of the known reaction of alkyl
aluminum compounds with such active hydrogen containing
groups (but such polymerizations may be possible if
89
~..~~~..r...... w ~rrT rni n C HC\

CA 02338581 2001-03-O1
WO 96/23010 PCT/US96101282
enough "extra" alkyl aluminum compound is added to
react with these groups). However, in very similar
polymerizations where alkyl aluminum compounds are not
present, these groups containing active hydrogen may be
present. Indeed many of the polymerization processes
described herein are remarkably tolerant to the
presence of various functional groups. Probably the
most important considerations as to the operability of
compounds containing any particular functional group
10 are the effect of the group on the coordination of the
metal atom (if present), and side reaction or the group
with other process ingredients (such as noted above).
Therefore c: course, the further away from the metal
atom the f~.::~ctional group is, the less likely ~~ is to
l~ influence, say, a polymerization. If there is doubt as
to whether a particular functional group, in a
particular position, will affect a reaction, simple
minimal experimentation will provide the requisite
answer. Functional groups which may be present in R',
?0 R~, R~, R', and other similar radicals herein include
hydroxy, halo (fluoro, chloro, bromo and iodo), ether,
ester, dialkylamino, carboxy, oxo (keto and aldehyo),
nitre, amide, thioether, and imino. Preferred
functional groups are hydroxy, halo, ether and
diaikvlamino.
I-also ~_. ail of the polymerizations, the
(cycio)olefin may be substituted hydrocarbyl. Suitable
substituent_= include ether, keto, aldehyde, ester,
carboxylic acid.
30 In ail of the above polymerizations, with the
exceptions noted below, the following monomer(s), to
produce the corresponding homo- or copolymers, are
preferred to be used: ethylene; propylene; ethylene anti
propylene; ethylene and an a-olefin; an a-olefin;
3~ ethylene and an, alkyl acrylate, especially methyl
acrylate; ethylene and acrylic acid; ethylene and
carbon monoxide; ethylene, and carbon monoxide and an
acrylate ester or acrylic acid, especially methyl
-_ ._ __._.._~ ." ,~.-T .r., " ~ nc~

WO 96123010 ~ 02338581 2001-03-O1 p~'NS96101282
acrylate; propylene and alkyl acrylate, especially
methyl acrylate; cyciopentene; cyclopentene and
ethylene; cyclopentene and propylene. Monomers which
contain a carbonyl group, including esters, carboxylic
~ acids, carbon monoxide, vinyl ketones, etc., can be
polymerized with Pd(Ii) containing catalysts herein,
with the exception of those that require the presence
of a neutral or cationic Lewis acid or cationic
Bronsted acid, which is usually called the "first
compound" in claims describing such polymerization
processes.
Another useful "monomer" for these polymerization.
processes is a C4 refinery catalytic cracker stream,
which will often contain a mixture of n-butane,
1~ isobutane, isobutene, 1-butene, 2-butenes and small
amounts of butadiene. This type of stream is referred
to herein as a "crude butenes stream". This stream
may act as both the monomer source and "solvent" for
the polymerization.. It is preferred that the
'0 concentration of 1- and 2-butenes in the stream be as
high as possible, since these are the preferred
compounds to be polymerized. The butadiene content
should be minimized because it may be a polymerization
catalyst poison. The isobutene may have been
'_'~ creviously removed for other uses. After being used in
the pciymerization (during which much or most ef the ;
butene would have been polymerized), the butenes stream
can be returned to the refinery for further processing.
In many cf the these polymerizations certain
30 genera= trends may be noted, although for all cf these
trends there are exceptions. These trends (and
exceptions) can be gleaned from the Examples.
Pressure of the monomers (especially gaseous
monomers such as ethylene) has an effect on the
3~ polvmerizations in many instances. Higher pressure
often affects the polymer microstructure by reducing
branching, especially in ethylene containing polymers.
This effect is more pronounced for Ni catalysts than Pd
9l
....~..~.~. ~r m irrT m II C ~~\

CA 02338581 2001-03-O1
WO 96123010 PCTlUS96/01282
catalysts. Under certain conditions higher pressures
also seem to give higher productivities and higher
molecular weight. When an acrylate is present and a Pd
catalyst is used, increasing pressure seems to decrease
the acrylate content in the resulting copolymer.
Temperature also affects these poiymerizatiors.
Higher temperature usually increases branching with Ni
catalysts, but often has little such effect using Pd
catalysts. With Ni catalysts, higher temperatures
l0 appear to often decrease molecular weight. with Pd
catalysts, when acrylates are present, increasing
temperature usually increases the acrylate content of
the polymer, but also often decreases the product,_vity
and molecular weight of the polymer.
1~ Anions surprisingly also often affect molecular
weight of the polymer formed. More highly coordinating
anions often give lower molecular weight polymers.
Although all of the anions useful herein are relatively
weakly coordinating, some are more strongly
?0 coordinating than others. The coordinating ability of
such anions is known and has been discussed ir. the
literature, see for instance W. Beck., et al., Chem.
Rev., vol. 88 p. 1405-1421 (1988), and S. H. Strauss,
Chem. Rev., vol. 93, p. 927-942 (1993), both of which
'_'~ are hereby included by reference. The results found
herein in which the molecular weight of the polymer
produced is related to the coordinating ability c. the
anion used, is in line with the coordinating abil_ties
of these anions as described in Beck (p. 1411) and
~0 Strauss (p. 932, Table II).
In addition to the "traditional" weakly
coordinating anions cited in the paragraph immediately
above, heterogeneous anions may also be employed. In
these cases, the true nature of the counterion is
3~ poorly defined or unknown. Included in this group are
MAO, MMAO and related aluminoxanes which do not form
true solutions. The resulting counterions are thought
to bear anionic aluminate moieties related to those
92
-..~ ~~.~. r.n m w~T 111111 r ~1C~

WO 96123010 ~ 02338581 2001-03-O1 PCTIUS96101282
cited in to pa=a==a~~ iTa=_diately above. ?o_ymerl..
drilC.~.1C tTldte.' .S SL1C~: aS ~aflOn~ DO1V~1 ::J=CS~_ZOnlC
acid Can -ilr.Ct:On aS nOn-CJOrQl.~.atlnQ COI~rW.e.lO.~.S. In
addtio.~., a wide variety o= here=ogeneous inorga.~..c
T~~at2~lalS CcD2 iP3u°_ '..O I;.: :: tlOn aS : J::_CJOr :_ atl: ~
COL:.n ter lOnS . =Xa:.~.aleS wOUl d lnCl ude al :l.~.,i:laS , Si11C3S ,
S_1=,.a~a_u",:;..,~ , ....._...°=It°S, C_aV=, :~~JL;.~, a=:J
ma.~:V
others ut_lized as traditional supports for Z_egier-
i~Tatta Olefl:': _"iVT°r_ZatlO:: CatalyStS. TheS°_ are
a~neral'v r.:at___a;s whic~. have Lewis c. _=Jnsted
ac~.d'_ty. ..ig s;:r=Gce area is usua 1 ly desired and
often these T~3te=ia_s will ::aye been activated through
some heat_na p=Jces=. Leafing may remove excess
Ssl~~G'v.~. ~h3~~- G .r v. ~rl~~ ...:'~ cJ'1..~_3. ~ ...~_...--V
1~ ..,rOnS:.e,~.. :.J _°~h=S ~VJ°. "'IGZe=IGiS wnlC.~. c=e
.'...... aCtlV°
in t'.:e role r:a;: of_e~ be mach activa b-_ svr=ac_
treatment. ~C= 1_~.StanC°_, a Surface-hVd=dv°_Q S__lCa,
ZInC OXlde C. Car DC.~. Can b°_ treaLdd wlth a:l
Cr ga: Oal L::.',_~:.:.~, C.~r:;;DOS.~.d tC TJ~OVId°_ tl:e
re~:lire.".
''0 ~unctiorality.
The cata_vsts descr'_bed here..~. ca:. be
heteroge~ized th=oug~ a Va=iety c' mea.~.s. 'T_'he
hate=o=~nec~= acic:a :: t::e paraJ=ap:: _-::~edia=e_y above
will all serve to heteroge~ize the catalysts.
vata~yStS C._.. c:SJ Ce hat°_=O''-Je.~.lzed '~-~ expJSl.'- L~':erl tC
Sti~a__ C::a: ~_ti°S O: a ~Ø~.O.~.:e_' t0 e:lCa: S::_alc _
:°_,'.: _.. a
polymeric ma_erial tl~.rouQh which additio:.a'_ mc.~.ome=s
wi'_ diffuse. ~-~ot'.~.er methcd is to spra~l-d:y the
catalyst wit:: its suitable non-coordinati::g counter: on
~0 cntJ a Dolvme=is suoDOrt. -etero~ene;,:a Vers=o:.s of
the catalyst are pa=ticularly useful for running gas-
phase poivmerizations. The catalyst is s~~tabiy
,.._"~~°_.~. a::C ..=S.~,°-rS°_ : C.~. ~~°_
S::«aCe C_ _.'.°_ Cd_a~yS=
S:lu.~.;~~ .. W CJ ~s-.._ ~ .e hea.. CL pOly~1°_C 1ZG..lv...
V's~'1°_~
aDp_ied to f'_u~ize~-bed poiymerizations, the
heterogeneous ~suppcr~s provide a convenie:t means o'
catalyst introduction.
9~
........~,T, rT- ~~ ~~:-T roW c ~W

CA 02338581 2001-03-O1
Another item ray effect the irco~porat_ r.~ of pole--
monomers such as acrylic esters in olefin copolymers.
It has been found that catalysts containing Less bulky
a-diimines incorporate more of the polar monomer into
the polymer (one obtains a polymer with a higher
percentage o~ polar monomer) than a catalyst cor.taini:.c
a more bulky a-diimine, particularly when ethylene is
the olefin comonomer. For instance, in a~ a-diimin~ c.
formula (VIII), if Rz and RS are 2,6-dimethylphenyl
instead of 2,6-diisopropylphenyl, more acrylic monomer
will be incorporated into the polymer. However,
another commor, effect of using a less bulky catalyst is
to produce a polymer with lower molecular weight.
Therefore one may have to make a compromise between.
1~ polar monomer content in the polymer and polymer nY
molecular weight.
When an olefinic carboxylic acid is polymerized
into the polymer, the polymer will of course contain
carboxyl groups. Similarly in an ester containing
polymer, some or all of the ester groups may be
hydrolyzed to carboxyl groups (and vice versa). The
carboxyl groups may be partially or completely
converted into salts such as metallic salts. Such
polymeric salts are termed ionomers. Ionomers are
2~ useful in adhesives, as ionomeric elastomers, and as
molding resins. Salts may be made with ions of metals
such as Na, K, Zn, Mg, A1, etc. The polymeric salts
may be made by methods known to the artisan, for
instance reaction of the carboxylic acid containing
polymers with various compounds of the metals such as
bases (hydroxides, carbonates, etc.) or other
94
AMENDED SHEET

WO 96/23010 ~ 02338581 2001-03-O1
pCTIUS96101282
compounds, such as acetylacetonates. Novel polymers
that contain carboxylic acid groups herein, also form
novel ionomers when the carboxylic acid groups are
partially or fully converted to carboxylate salts.
When copolymers of an olefinic carboxylic acid or
olefinic ester and selected olefins are made, they may
be crosslinked by various methods known in the art,
depending on the specific monomers used to make the
polymer. For instance, carboxyl or ester containing
polymers may be crosslinked by reaction with diamines
to form bisamides. Certain functional groups which may
be present on the polymer may be induced to react to
crosslink the polymer. For instance epoxy groups
(which may be present as glycidyl esters) may be
I~ crosslinked by reaction of the epoxy groups, see For
instance Example 135.
It has also been found that certain fluorinated
olefins, some of them containing other functional
groups may be polymerized by nickel and palladium
catalysts. Note that these fluorinated olefins are
included within the definition of HzC=CHR1', wherein R1'
can be considered to be substituted hydrocarbyl, the
substitution being fluorine and possibly other
substituents. Olefins which may be polymerized include
H>C-- _CH(CHz)aRfR42 wherein a is an integer of 2 to 20, R<
is perfluoroalkylene optionally containing one or more
ether groups, and R42 is fluorine or a functional
group. Suitable functional groups include hydrogen,
chlorine, bromine or iodine, ester, sulfonic acid (-
S03H), and sulfonyl halide. Preferred groups for R4'
include fluorine, ester, sulfonic acid, and sulfonyl
fluoride. A sulfonic acid croup containing monomer
does not have to be polymerized directly. It is
preferably made by hydrolysis of a sulfonyl halide
3~ group already present in an already made polymer. It
is preferred that the perfluoroalkylene group contain 2
to 20 carbon atoms and preferred perfluoroalkylene
groups are -(CF2?b- wherein b is 2 to 20, and -
9~
_.._ __._. _

CA 02338581 2001-03-O1
WO 96/23010 PCTIUS96/01282
(CFA) dOCF2CF 2- wherein d is 2 to 20 . A preferred
olefinic comonomer is ethylene or a linear a-olefin,
and ethylene is especially preferred. Polymerizations
may be carried out with many of the catalysts~described
herein, see Examples 284 to 293.
As described herein, the resulting fluorinated
polymers often don't contain the expected amount of
branching, and/or the lengths of the branches present
are not those expected for a simple vinyl
polymerization.
The resulting polymers may be useful for
compatibilizing fluorinated and nonfluorinated
polymers, for changing the surface characteristics of
Fluorinated or nonfluorinated polymers (by being mixed
1~ with themi, as melding resins, etc. Those polymers
containing functional groups may be useful where those
functional groups may react or be catalysts. For
instance, if a polymer is made with a sulfonyl fluoride
group (R°z is sulfonyl fluoride) that group may be
20 hydrolyzed to a sulfonic acid, which being highly
fluorinated is well known to be a very strong acid.
Thus the polymer may be used as an acid catalyst, for
example for the polymerization of cyclic ethers such as
tetrahydrofuran.
=n this use it has been found that this polymer is
more effective than a completely fluorinated sulfonic
acid containing polymer. For such uses the sulfonic
acid content need not be high, say only 1 to 20 mole
percent, preferably about 2 to 10 mole percent of the
30 repeat units in the polymer having sulfonic acid
groups. The polymer may be crosslinked, in which case
it may be soluble in the medium (for instance
tetrahydrofuran), or it may be crosslinked so it
swollen but not dissolved by the medium, Or it may be
35 coated onto a substrate and optionally chemically
attached and/or crosslinked, so it may easily be
separated from the other process ingredients.
96

WO 96/23010
CA 02338581 2001-03-O1
pCT/US96/OI282
One of the monomers that may be polymerizes by the
above catalysts is ethylene (E), either by itself to
form a homopolymer, or with a-olefins and/or olefinic
esters or carboxylic acids. The structure of the
polymer may be unique in terms of several measurable
properties.
These polymers, and others herein, can have unique
structures in terms of the branching in the polymer..
Branching Tay be determined by NMR spectroscopy (see
the Examp-ies for details), and this analysis can
determine the total number of branches, and to some
extent the length of the branches. Herein the amount
of branching is expressed as the number of branches per
1000 of the total methylene (-CH,-) groups in the
1~ polymer, with one exception. Methylene groups that are
in an ester grouping, i.e. -CO2$, are not counted as
part of the 1000 methylenes. These methylene groups
include those in the main chain and in the branches.
These polymers, which are E homopolymers, have a branch
content of about 80 to about 150 branches per 1000
methylene groups, preferably about 100 to about 130
branches per 1000 methylene groups. These branches do
not include polymer end groups. In addition the
distribution of the sizes (lengths) of the branches is
uniaue. OF the above total branches, For every 100
that are methyl, about 30 to about 90 are ethy-~, about
4 to about 20 are propyl, about 15 to about 50 butyl,
about 3 to about 15 are amyl, and about 30 to about 140
are hexyl or longer, and it is preferred that for every
100 that are methyl, about 50 to about 75 are ethyl,
about 5 to about 15 are propyl, about 24 to about 40
are butyl, about 5 to 10 are amyl, and about 65 to
about 120 are hexyl or larger. These E homopolymers
are often amorphous, althougz in some there may be a
3~ small amount o~ crystallinity.
Another polyolefin, which is an E homopolymer that
can be made by these catalysts has about 20 to about
150 branches per 1000 methylene groups, and, per 100
97
__ _..~~~ ...~ w r nW

CA 02338581 2001-03-O1
WO 96123010 PCT/US96/01282
methyl groups, about 4 to about 20 ethyl groups, about
1 to about 12 propyl groups, about 1 to about 12 butyl
group, about 1 to about 10 amyl groups, and ~ to about
20 hexyl or larger groups. Preferably this polymer has
about 40 to about 100 methyl groups per 1000 methylene
groups, and per 100 methyl groups, about 6 to about 15
ethyl groups, about 2 to about 10 propyl groins, about
2 to about 10 butyl groups, about 2 to about 9 amyl
groups, and about 2 to about 15 hexyl or larger groups.
Many of the~polyolefins herein, including
homopolyethylenes, may be crosslinked by various
methods known in the art, for instance by the use of
peroxide or other radical generating species which can
crosslink these polymers. Such crosslinked polymers ,
l~ are novel when the uncrosslinked polymers frc~~ whic'r!
they are derived are novel, because for the mcst part
the structural features) of the uncrosslinked polymers
which make them novel will be carried over into the
crosslinked forms.
?0 In addition, some of the E homopolymers :nave an
exceptionally low density, less than about 0.66 g/mL,
preferably about 0.85 g/mL or less, measured at 25°C.
This density is based on solid polymer.
Homopelymers of polypropylene (F) can also have
unusual structures. Similar effects have been observed
wits other a-olefins (e.g. 1-hexene). A "normal" P
homopolvmer will have one methyl group for each
methylene group (or 1000 methyl groups per 1000
methylene groups), since the normal repeat uit is -
30 CH(CH;iCHZ-. However, using a catalyst of formula (I)
in whic!: M is Ni(II) in combination with an alkyl
aluminum compound it is possible to produce a P
homopolvmer with about 400 to about 600 methyl groups
per 1000 methylene groups, preferably about 450 to
3~ about 550 methyl groups per 1000 methylene groups.
Similar effects have been observed with other a-olefins ,
(e. g. 1-hexene).
98
_.._......~ .,~ '..~~ .n'" ~ nev

WO 96/23010 ~ 02338581 2001-03-O1 p~/Ug96/01282
In the polymerization processes described herein
olefinic esters and/or carboxylic acids may also be
present, and of course become part of the copolymer
formed. These esters may be copolymerized with one or
more of E and one or more a-olefins. When
copolymerized with E alone polymers with unique
structures may be formed.
In many such E/olefinic ester and/or carboxylic
acid copolymers the overall branching level and the
distribution of branches of various sizes are unusual.
In addition, where and how the esters or carboxylic
acids occur in the polymer is also unusual. A
relatively high proportion of the repeat units derived
from the olefinic esters are at the ends of branches.
I~ In such copclymers, it is preferred that the repeat
units derived from the olefinic esters and carboxylic
acids are about 0.1 to 40 mole percent of the total
repeat units, more preferably about 1 to about 20 mole
percent. In a preferred ester, m is 0 and R1 is
hydrocarbyl or substituted hydrocarbyl. It is
preferred that R1 is alkyl containing 1 to 20 carbon
atoms, more preferred that it contains 1 to 4 carbon
atoms, and especially preferred that R1 is methyl.
One such preferred dipolymer has about 60 to 100
methyl groups (excluding methyl groups which are
esters) per 1000 methylene groups in the polymer, and
contains, per 100 methyl branches, about 45 to about
65 ethyl branches, about 1 to about 3 propyl branches,
about 3 to about 10 butyl branches, about 1 to about 3
amyl branches, and about 15 to about 25 hexyl or longer
branches. In addition, the ester and carboxylic acid
containing repeat units are often distributed mostly at
the ends of the branches as follows. If the branches,
and the carbon atom to which they are attached to the
main chain, are of the formula -CH (CHZ) nCO~Rl, wherein
the CH is part of the main chain, then in some of these
polymers about 40 to about 50 mole percent of ester
groups are found in branches where n is 5 or more,
99
~.._~1.~..~~ .,..nrT ~n~ ~~ r nc~

CA 02338581 2001-03-O1
WO 96123010 PCT/US96I01282
about to to about 20 mole percent when n is 4, about 20
to 30 mole percent when n is 1, 2 and 3 and about 5 to
about 15 mole percent when n is 0. When n is 0, an
acrylate ester has polymerized "normally" as part of
the main chain, with the repeat unit -CH2-CHCOZR1-.
These branched polymers which contain olefin and
olefinic ester monomer units, particularly copolymers
of ethylene and methyl acrylate and/or other acrylic
esters are particularly useful as viscosity modifiers
10 fcr lubricating oils, particularly automotive
lubricating oils.
Under certain polymerization. conditions, some of
the polymerization catalysts described herein produce
polymers whose structure is unusual, especially
l~ considering from what compounds (monomers) the polymers
were made, and the fact that polymerization catalysts
used herein are so-called transition metal coordination
catalysts (more than one compound may be involved in
the catalyst system, one of which must include a
20 transition metal). Some of these polymers were
described in a somewhat different way above, and they
may be described as "polyolefins" even though they may
contain other monomer units which are not olefins
(e.g., olefinic esters). In the polymerization of an
'~ unsaturated compound of the formula H~C=CH(CHz)eG,
wherein a is 0 or an integer of 1 or more, and G is
hydrogen or -COZR1, the usual ("normal") polymeric
repeat unit obtained would be -CHZ-CH[(CHz)eG1-, wherein.
the branch has the formula -(CHZ)~G. However, with soanz
30 of the instant catalysts a polymeric unit may be -CH,-
CH[(CH~)fG]-, wherein f ~ e, and f is 0 or an integer
of 1 or more. If f<e, the "extra" methylene groups may
be part of the main polymer chain. If f>e (parts cf)
additional monomer molecules may be incorporated into
3~ that branch. Ip other words, the structure of any
polymeric unit.may be irregular and different for
monomer molecules incorporated into the polymer, and
the structure of such a polymeric unit obtained could
100
~..~~~.~. r1. w w~ inl 11 r r1C\

WO 96/23010 ~ 02338581 2001-03-O1 p~'/1TS96101282
be rationalized as the result of "migration. c_ the
active polymerizing site" up and down the po;ymer
chain, although this may not be the actual mechanism.
This is highly unusual, particularly for
pclvmerizations employing transition metal coordination
catalysts.
For "normal" polymerizations, wherein the
polymeric unit -CHI-CH[(CHZ)eG)- is obtained, the
theoretical amount of branching, as measured by the
number of branches per 1000 methylene (-CHz-) groups
can be calculated as follows which defines terms
"theoretical branches" or "theoretical branching"
herein:
I ~ Theo:et;:o: brancnes - 1000~Tetal mile faction of a-olef--s
l[~(2~mole fraction e=0)).[=(mole fraction u-olefin~en
In this equation, an a-olefin is any olefinic compound
HOC=CH(CHZ)eG wherein e~0. Ethylene or an acrylic
~0 compound are the cases wherein e=0. Thus to calculate
the number ef theoretical branches in a polymer made
from 50 mole percent ethylene (e=0), 30 mole percent
propylene (e=1) and 20 mole percent methyl 5-heptenoate
(e=4) would be as follows:
,:
':heorec:cai cranches . ~n0D~C ~ = 238 lbranchesilDC= aechyienes
((2~C.5?1~[(D.30~11.t0.20~411f
The "1000 methylenes" include all of the methylene
,0 groups in the polymer, including methylene groups i.~.
the branches.
For some of the polymerizations described herein,
the actual amount of branching present in the polymer
is considerably greater than cr less than the above
theoretical branching calculations would indicate. For
instance, when an ethylene homopolymer is made, there
should be no branches, yet there are often many such
branches. When an a-olefin is polymerized, the
101
~..~.,~.~"Tr nl Ir>-T !DI 11 C ~R1

CA 02338581 2001-03-O1
WO 96123010 PCT/US96/01282
branc~ing level may be much lower or higher than t:he
theoretical branching level. It is preferred that the
actual branching level is at 90% or less of the
theoretical branching level, more preferably about SOo
~ or less of the theoretical branching level, or 110% or
more of the theoretical branching level, more
preferably about 1200 or more of the theoretical
branching level. The polymer should also have at least
about 50 branches per 1000 methylene units, preferably
10 about 75 branches per 1000 methylene units, and more
preferably about 100 branches per 1000 methylene snits.
In cases where there are "0" branches theoretically
present, as in ethylene homopolymers or copolymers with
acrylics, excess branches as a percentage cannot be
1~ calculated. In that instance if the polymer has =C or
more, preferably 75 or more branches per 1000 met?:y,~ene
groups, it has excess branches (i.e. in branches in
which f >0 ) .
These polymers also have "at least two branches of
'?0 different lengths containing less than 6 carbon atoms
each." By this is meant that branches of at least two
different lengths (i.e. number of carbon atoms), and
containing less than 6 carbon atoms, a=a present ._. the
polymer. For instance the polymer may contain ethyl
and butyl branches, or methyl and amyl branches.
As will be understood from the above discussio:-:,
the lencrths of the branches ("f") do not necessarily
correspond to the original sizes of the monomers used
("e"). Indeed branch lengths are often present which
~0 do not correspond to the sizes of any of the monomers
used and/or a branch length may be present "in excess".
By "in excess" is meant there are more branches c= a
particular length present than there were monomers
which corresponded to that branch length in the
polymer. For instance, in the copolymerization of 75
mole percent ethylene and 25 mole percent 1-butene -;t ,
would be expected that there would be 125 ethyl
branches per 1000 methylene carbon atoms. If there
102
_..__-.~..~~ w..r.~ rw w r nev

WO 96/23010 ~ 02338581 2001-03-O1 PCT/US96/01282
were mere etryl branches than that, the~~bb~3 b~ z:r
excess compared to the theoretical branching. There
may also be a deficit of specific length branches. If
there were less than 125 ethyl branches per 1000
methylene groups in this polymer there would be a
deficit. Preferred polymers have 90% or less or 110%
or more of the theoretical amount of any branch length
present in the polymer, and it is especially preferred
if these branches are about e0a or less or about 1200
or more of the theoretical amount of any branch length.
In the case c~ the 75 mole percent ethylene/25 mole
percent i-butene polymer, the 90o would be about 113
ethyl branches or less, while the 1100 would be about
138 ethyl branches or more. Such polymers may also or
l~ exclusively ccntain at least 50 branches per 1000
methylene atoms with. lengths which should not
theoretically (as described above) be present at all.
These polymers also have "at least two branches of
differe=.t lengths containing less than 6 carbon atoms
?0 each." Bv this is meant that branches of at least two
different lengths (i.e. number of carbon atoms), and
containing less than 6 carbon atoms, are present in the
polymer. For instance the polymer may contain ethyl
and butyl branches, or methyl and amyl branches.
Some of the polymers produced herein are novel
because of unusual structural features. Normally, i:
polymers of alpha-olefins of the formula CHI=CH(CH2)aH
wherein a is an integer of 2 or more made by
coordination polymerization, the most abundant, and
30 often the only, branches present in such pciymers have
the structure -(CH2)aH. Some of the polymers produced
herein are novel because methyl branches comprise about
25% to about 750 of the total branches in the polymer.
Such polymers are described i.~. Examples 139, 162, 173
3~ and 243-245. Some of the polymers produced herein are
novel because in addition to having a high percentage
(25-750) of methyl branches (of the total branches
present), they also contain linear branches of the
103
r.. ~nn~~ rre euccT got tt C ~R1

CA 02338581 2001-03-O1
WO 96/23010 PCT/US96/01282
structure -(CHZ)nH wherein n is an integer c~ six or
greater. Such polymers are described in Examples 139,
173 and 243-245. Some of the polymers produced herein
are novel because in addition to having a high
percentage (25-75%) of methyl branches (of the total
branches present), they also contain the structure
(XXVI), preferably in amounts greater than can be
accounted for by end groups, and more preferably
greater than 0.5 (XXVI) groups per thousand methyl
grour~s in the polymer greater than can be acccunted for
by end groups.
CH3
-CH2-CH-(CH2)aH (XXVI)
l~ Normally, homo- and copolymers ef one er more
alpha-olefins of the formula CH2=CH(CH2)aH wherein a is
an integer of 2 or more contain as part of the polymer
backbone the structure (XXV)
R35 R36
.,0 -CH-CH2-CH- (XXV)
whereon R35 and R36 are alkyl groups. In most such
polymers of alpha-olefins of this formula (especially
those produced by coordination-type polymerizationsl,
boti: of R35 and R36 are - (CH2)aH. However, in certain
of these polymers described herein, about 2 mole
percent or more, preferably about 5 mole percent or
more and more preferably about 50 mole percent or more
of the total amount of (XXV) in said polymer consists
30 of the structure where one of R35 and R36 is a methyl
groin and the other is an alkyl group containing two or
more carbon atoms. Furthermore, in certain of these
polymers described herein, structure (XXV) may occur in
side chains as well as in the polymer backbone.
3~ Structure (XXV) can be detected by '-3C NMR. The signal
104
r.. ~r,nTm err ~ureT rCl 11 C ~R\

WO 96/23010 ~ 02338581 2001-03-O1 pCT/US96101282
_ the carbon atom of the methylene group between the
two methine carbons in (XXV) usually occurs in the 13C
i~WR at 41.9 to 44.0 ppm when one of R35 and R36 is a
methyl croup and the other is an alkyl group containing
J two or more carbon atoms, while when both R35 and R3s
contain. 2 or more carbon atoms, the signal for the
methyiene carbon atom occurs at 39.5 to 41.9 ppm.
Integration. provides the relative amounts of these
structures present ir. the polymer. If there are
10 .~terfering signals from other carbon atoms in these
regions, they must be subtracted from the total
_=~tecrals to give correct values for structure (XXV).
Normally, homo- and copolymers of one or more
~loha-olefins of the formula CHI=CH(CH2)aH wherein a is
1 ~ ~.. _..teaer of 2 or more (especial ly those made by
coordination polymerization) contain as part of the
oolvmer backbone structure (XXIV) wherein n is 0, 1, or
2. When n is 0, this structure is termed "head to
:head" polymerization. When n is 1, this structure is
?0 termed "head to tail" polymerization. When n is 2,
t:.is structure is termed "tail to tail" polymerization.
Ir. most such polymers of alpha-olefins of this formula
especially those produced by coordination-type
ooivmerizations), both of R3~ and R38 are -(CHZ)ah.
..owever some cf the polymers of alpha-olefins of this
_crmua described herein are novel in that they also
contain structure (XXIV) wherein n = a, R3~ is a methyl
~ro;:~., and R3g is an alkyl group with 2 or more carbon
atoms.
~0
R37 R38
I I
-CH-(CH2)~-CH-
(XXN)
Normally polyethylene made by coordination
~civmerization has a linear backbone with either no
10~
m ~nnT~T~ tTr CLJCCT ICI il C ~R~

CA 02338581 2001-03-O1
WO 96123010 PCTlUS96/01282
branching, or small amounts of linear branches. Some
of the polyethylenes described herein are unusual in
that they contain structure (XXVII) which has a methine
carbon that is not part of the main polymer backbone.
CH3
-CH2-CH-CH2CH3 (XXVII)
Normally, polypropylene made by coordination
polymerization has methyl branches and few if any
10 branches of other sizes. Some of the polypropylenes
described herein are unusual in that they contain one
or both of the structures (XXVIII) and (XXIX).
CH3
~ CH'
CH2 CH3
-CH- (XXVIII)
CH3
I
-CH2CH2 CH-CH3 (XXIX)
As the artisan understands, in coordination
polymerization alpha-olefins of the formula
CH2=CH(CH2)aH may insert into the growing polymer chain
'_'0 in a 1,2 or 2,1 manner. Normally these insertion steps
lead to 1,2- enchainment or 2,1-enchainment of the
monomer. Both of these fundamental steps form a -
(CH2)aH branch. However, with some catalysts herein,
some of the initial product of 1,2 insertion can
rearrange by migration of the coordinated metal atom to
the end of the last inserted monomer before insertion
of additional monomer occurs. This results in omega,2-
enchainment and the formation of a methyl branch.
106
_..__~,~"~ r.",~rT rn, n c nab

WO 96/23010 ~ 02338581 2001-03-O1
PCT/US96/01282
1.2 insertion
polymer-M + CHZ=CH(CH2)aH
M
CH2 CH3
i
polymer~CH~(CHz)aH rearrangement polymer~CH~(CH2)aM
1,2-enchainment ro.2-enchainment
-(CHZ)aH branch -CH~ branch
It is also known that with certain other
catalysts, some of the initial product of 2,1 insertion
can rearrange in a similar manner by migraticn of the
coordinated metal atom to the end of the last inserted
monomer. This results in omega,l-enchainme::t and no
branch is formed.
2.1 insertion
polymer-M + CHZ=CH(CH2)aH
M
i
polymer ,CH rearrangement
CHz ~(CHZ)aH ~ polymer
CH~ CHz~ (CH2),M
2.1-enchainment ~~~.1-enchamment
-(CH2)aH branch no branch
Of the four types of alpha-olefin enchainment,
omega,l-enchainment is unique in that it does not
generate a branch. In a polymer made from an alpha-
1~ olefin of the formula CHZ=CH(CH2)aH, the total number
of branches per 1000 methylene groups (=' can be
expressed as:
B = (1000) (1-Xw, 1) / [ (1-XW,1) a + X,~,1 (a + 2) ]
where X«,1 is the fraction of omega,l-enchainment
Solving this expression for Xw,l gives:
X~,1 = (1000 - aB)/(1000 + 2B)
This equation provides a means of calculating the
fraction of omega,l-enchainment in a polymer of a
linear alpha-olefin from the total branching B. Total
~5 branching can be measured by 1H NMR or ~~C NMR.
Similar equations can be written for branched alpha-
107
_.._ _-.-..__ ~..~~~ .... n r nw

CA 02338581 2001-03-O1
WO 96/23010 PCT/US96/01282
olefin=. For example, the equl~tic,n f.or 4-methyl-.~
pentene is:
Xw,l = (2000 - 2B)/(1000 + 2B)
Most polymers of alpha-olefins made by other
coordination polymerization methods have less than S%
omega,l-enchainment. Some of the alpha-olefin polymers
described herein have unusually large amounts (say >5~)
of omega,i-enchainment. In essence this is similar to
~ statinc t:,:at a polymer made from an a-olefin has much
less tl-:a~ the "expected" amount of branching. Although
many c~ ~he polymerizations described herein give
substar:t~~Gl amounts of w,l- and other unusual forms of
enchainmen: cf olefinic monomers, it has surprisingly
been fov.:nC that "unsymmetrical" a-diimine ligands of
1~ formul.--, aVIII) give especially high amounts of c~, 1-
enchainment. In particular when R2 and RS are phenyl,
and one c_ both of these is substituted in such a way
as different sized groups are present in the 2 and 6
position cf the phenyl ring(s), w,l-enchainment is
enhances. For instance, if one or both of R~ and R
are 2-t-butylphenyl, this enchainment is enhanced. In
this ccntext when R' and/or RS are "substituted" phenyl
the substitution may be not only ir_ the 2 and/or 6
positions, but on any other position in the phenyl
rinc. _.._ instance, 2,5-di-t-butylphenyl, and 2-t-
butyl-~,5-cichiorophenyl would be included in
substi~uted phenyl.
steric effect of various groupings has been
quan~ified by a parameter called ES, see R. W. Taft,
Jr., ~. Am. Chem. Soc., vol. 74, p. 3120-3128, and M.S.
Newman, Steric Effects in Organic Chemistry, John Wiley
& Sons, New York, 1956, p. 598-603. For the purposes
herei_~., the ES values are those fcr o-substituted
benzoat~s described ir. these publications. If the
3~ value fcr ES for any particular group is not known, it
can be determined by methods described in these
publica~ic.~.s. For the purposes herein, the value of
hvdroQen is defined to be the same as for methyl. It
108
__ _.._~ ...", . .".,

WO 96123010 ~ 02338581 2001-03-O1 pCZ'/US96/01282
is preferred that difference in ES, when R" a.-:'~
preferably also RS) is phenyl, between the groups
substituted in the 2 and 6 positions of the phenyl ring
is at least 0.15, more preferably at least about 0.20,
and especially preferably about 0.6 or more. These
phenyl groups may be unsubstituted or substituted in
any other manner in the 3, 4 or 5 positions.
These differences in ES are preferred in a diimine
such as (VIII), and in any of the polymerization
processes herein wherein a metal complex containing an
a-diimine ligand is used or formed. The synthesis and
use of such a-diimines is illustrated in Examples 454-
463.
Because of the relatively large amounts of c~,l-
1~ enchainment that may be obtained using some c~ the
polymerization catalysts reported herein novel polymers
can be made. Among these homopolypropylene (PP). In
some of the PP's made herein the structure
?0
CaHCHZCH2CdH2(CbH2)~CdH2CHZCH~CaH
may be found. In this structure each C° is a methine
carbon atom that is a branch point, while each Cb is a
methylene group that is more than 3 carbon atoms
removed from any branch point (Ca). Herein methylene
groups of the type -CbHz- are termed 8+ (or delta+)
methylene groups. Methylene groups of the type -C°H:-,
which are exactly the third carbon atom from a branch
point, are termed y (gamma) methylene groups. The NMR
.0 signal for the b+ methylene groups occurs at about
29.75 ppm, while the NMR signal for the y methylene
groups appears at about 30.15 ppm. Ratios of these
types of methylene groups to each other and the total
number of methylene groups in the PP is done by the
usual NMR integration techniaues.
109
~..~..~.~..~r m ~rrT ini n r ~C\

CA 02338581 2001-03-O1
WO 96/23010 PCT/US96/01282
It is preferred that PP's made herein have about
25 to about 300 8+ methylene groups per 1000 methylene
groups (total) in the PP.
It is also preferred that the ratio of b+:y
methylene groups in the PP be 0.7 to about 2Ø
The above ratios involving b+ and f methylene
groups in PP are of course due to the fact that high
relatively high w,l enchainment can be obtained. It is
preferred that about 30 to 60 mole percent of the
10 monomer units in PP be enchained in an w,l fashion.
Using the above equation, the percent w,l enchainment
for polypropylene can be calculated as:
o w,l = (100)(1000-B)/(1000+2B)
wherein B is the total branching (number of methyl
1~ groups) per 1000 methylene groups in the polymer.
Homo- or copolymers of one or more linear a-
olefins containing 3 to 8 carbon atoms may also have b+
carbon atoms in them, preferably at least about 1 or
more cS+ carbon atoms per 1000 methylene groups.
''0 The above polymerization processes can of course
be used to make relatively random copolymers (except
for certain CO copolymers) of various possible
monomers. However, some of them can also be used to
make block polymers. A block polymer is conventionally
defined as a polymer comprising molecules in which
there is a linear arrangement of blocks, a block being
a portion of a polymer molecule which the monomeric
units have at least one constitutional or
configurational feature absent from adjacent portions
.0 (definition from H. Mark, et al., Ed., Encyclopedia of
Polymer Science and Engineering, Vol. 2, John Wiiey &
Sons, New York, 1985, p. 324). Herein in a block
copolymer, the constitutional difference is a
difference in monomer units used to make that block,
while in a block homopolymer the same monomers) are
used but the repeat units making up different blocks
are different structure and/or ratios of types of
structures.
110
_ _ ._ __._. .~ ... .~..r ..wn r nev

WO 96123010 ~ 02338581 2001-03-O1 PCT/US96/01282
Since it is believed that many of the
polymerization processes herein have characteristics
that often resemble those of living polymerizations,
making block polymers may be relatively easy. One
method is to simply allow monomers) that are being
polymerized to be depleted to a low level, and then
adding different monomers) or the same combination of
monomers in different ratios. This process may be
repeated to obtain polymers with many blocks.
Lower temperatures, say about less than. 0°C,
preferably about -10° to about -30°, tends to enhance
the iivingness of the polymerizations. Under these
conditions narrow molecular weight distrib;:tion
pclymers may be obtained (see Examples 357-359 and
I~ 37~., and block copolymers may also be made ,Example
370) .
As pointed out above, certain polymerization
conditions, such as pressure, affect the microstructure
of many polymers. The microstructure in turn affects
?0 many polymer properties, such as crystallization.
Thus, by changing polymerization conditions, such as
the pressure, one can change the microstructure of the
part cf the polymer made under those conditions. This
of course leads to a block polymer, a polymer have
defined portions having structures differe.~.: =rom other
defined portions. This may be done with mcre than one
monomer to obtain a block copolymer, or may be done
with a single monomer or single mixture of monomers to
obtain a block homopolymer. For instance, in the
:0 polymerizaticn of ethylene, high pressure sometimes
leads to crystalline polymers, while lower pressures
give amorphous polymers. Changing the pressure
repeatedly could lead to an ethylene homopoiymer
containing blocks of amorphous polyethylene and blocks
3~ of crystalline polyethylene. If the blocks were of the
correct size, and there were enough of them, a
thermoplastic elastomeric homopolyethylene could be
nr mn~r~Tt tTC cuCCT lDi il G ~R1

CA 02338581 2001-03-O1
WO 96/23010 PCT/US96/01282
oreduced. Similar polymers could possibly be made from
other monomer(s), such as propylene.
Homopolymers oz a-olefins such as propylene, that
is polymers which were made from a monomer that
consisted essentially of a single monflmer such as
propylene, which are made herein, sometimes exhibit
unusual properties compared to their "normal"
homopciymers. For instance, such a homopolypropylene
usually would have about 1000 methyl groups per 1000
10 met>,yiene groups. Polypropylenes made herein typically
have about half that many methyl groups, and in
addition have some longer chain branches. Other a-
olefins often. give polymers whose microstructure is
analogous to these polypropylenes when the above
l~ cata_vsts are used for the polymerization.
These polypropylenes often exhibit exceptionally
low glass transition temperatures (Tg's). "Normal"
polypropylene has a Tg of about -17°C, but the
polyprooyienes herein have a Tg of -30°C or less,
'?D~ preferably about -35°C or less, and more preferably
about -~0°C or less. These Tg's are measured by
Differential Scanning Calorimetry at a heating rate of
~;0°C/min, and the Tg is taken as the midpoint of the
traps=tion. These polypropylenes preferably have at
yeast =~ branches (methyl groups) per 1000 carbon
atoc~a, more preferably at least about 100 bra..~.ches per
1000 methylene groups.
Previously, when cyclopentene was coordination
polymerized tc higher molecular weights, the resulting
:0 polymer was essentially intractable because of its very
hig'.~. m=_lting point, greatly above 300°C. Using the
catalysts here to homopolymerize cyclopentene results
in a ~oiymer that is tractable, i.e., may be reformed,
as :;y me'_t forming. Such polymers have an end of
3~ melti:~g point of about 320°C or less, preferably about
300°C or less, or a melting point of about 275°C or
less, preferably about 250°C or less. The melting
t~oi:.t is determined by Differential Scanning
11?
_ __ _-_-..-_ _..~~~ .r., " r nev

WO 96123010 CA 02338581 2001-03-O1 PCT/US96l01282
Calorimetry at a heating rate of 15°C/min, and taking
the maximum of the melting endotherm as the melting
point. However these polymers tend to have relatively
diffuse melting points, so it is preferred to measure
the "melting point" by the end of melting point. The
method is the same, except the end of melting is taken
as the end (high temperature end) of the melting
endotherm which is taken as the point at which the DSC
signal returns to the original (extrapola.ted) baseline.
Such polymers have an average degree of polymerization
;average number of cyclopentene repeat units per
wolymer chain) of about 10 or more, preferably about 30
or more, and more preferably about 50 or more.
In these polymers, enchainment of the cyclopencene
1~ =epeat units is usually as cis-1,3-pentylene units, i::
contrast to many prior art cyclopentenes which were
enchained as 1,2-cyclopentylene units. It is preferred
that about 90 mole percent or more, more preferably
about 95 mole percent or more of the enchained
cyclopentene units be enchained as 1,3-cyclopentylene
units, which are preferably cis-1,3-cyclopentylene
units.
The X-ray powder diffraction pattern of the
instant poly(cyclopentenes) is also unique. To produce
~yclopentene polymer samples of uniform thickness fer
X-ray measurements, powder samples were compressed i:.cc
disks approximately 1 mm thick and 32 mm in diameter.
X-ray powder diffraction patterns of the samples were
collected over the range 10-50° 28. The diffraction
data were collected using an automated Philips 8-8
diffractometer (Philips X'pert System) operating in the
symmetrical transmission mode (Ni-filtered CuKa
radiation, equipped with a diffracted beam collimator
(Philips Thin Film Collimator system), Xe filled
3~ proportional detector, fixed step mode (0.05°/step),
12.5 sec./step, 1/4° divergence slit). Reflection
positions were identified using the peak finding .
routine in the APD suite of programs provided with the
113
ci iac~~n t~ ~NFFT fRl il E 261

CA 02338581 2001-03-O1
WO 96!23010 PCTIUS96101282
X'pert System. The X-ray powder diffraction pattern
had reflections at approximately 17.3°, 19.3°, 24.2°,
and 40.7° 2B, which correspond to d-spacings of
approximately 0.512, 0.460, 0.368 and 0.222 nm,
respectively. These polymers have a monoclinic unit
cell of the approximate dimensions: a=0.561 nm; b=0.607
nm; c=7.37 nm; and g=123.2°.
Copolymers of cyclopentene and various other
olefins may also be made. For instance a copolymer of
ethylene and cyclopentene may also be made. In such a
copolymer ~t is preferred that at least 50 mole
percent, more preferably at least about 70 mole
perce:a, of the repeat units are derived from
cyclopentene. As also noted above, many of the
I~ polymerization systems described herein produce
polyethylenes that have considerable branching in them.
Likewise the ethylene units which are copolymerized
with the cyclopentene herein may also be branched, so
it is preferred that there be at least 20 branches per
~0 1000 methylene carbon atoms in such copolymers. In
this instance, the "methylene carbon atoms" referred to
in the previous sentence do not include methylene
grouDS in the cyclopentene rings. Rather it includes
methylene groups only derived from ethylene or other
'_'~ olefin, but not cyciopentene.
Another copolymer that may be prepared is one from
cyclopentene and an a-olefin, more preferably a linear
a-olefin. It is preferred in such copolymers that
repeat units derived from cyclopentene are 50 mole
30 percent or more ef the repeat units. As mentioned
above, a-olefins may be enchained in a l,c.~ fashion,
and it is preferred that at least l0 mole percent of
the repeat units derived from the a-olefin be enchained
in such a fashion. Ethylene may also be copolymerized
3~ with the cyclopentene and a-olefin.
Poly(cyclopentene) and copolymers of cyclopentene,
especially those that are (semi)crystalline, may be
used as molding and extrusion resins. They may contain
114
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WO 96123010 ~ 02338581 2001-03-O1 p~'/US96/01282
various materials normally found in resins, such as
fillers, reinforcing agents, antioxidants,
antiozonants, pigments, tougheners, compatibilizers,
dyes, flame retardant, and the like. These polymers
may also be drawn cr melt spun into fibers. Suitable
tougheners and compatibilizers include polycyclopentene
resin which has been grafted with malefic anhydride, an
grafted EPDM rubber, a grafted EP rubber, a
functiona~ized styrene/butadiene rubber, or other
rubber w:~ch i:as been modified to selectively bond to
components ef the two phases.
In a,~l cf the above homo- and copolymers of
cycloaentene, where appropriate, any of the preferred
state rr~av be ccmbined any other preferred states?.
1~ The homo- and copolymers of cyclopentene described
above may used or made into certain forms as described
below:
1. The cyclopentene polymers described above
may be part of a polymer blend. That is they may be
mixed in any proportion with one or more other polymers
which may be thermoplastics and/or elastomers.
Suitable polymers for blends are listed below in the
listing ~er blends of other polymers described herein.
One preferred type of polymer which may be blended is a
toughening agent or com>Jatibilizer, which is often
elastomeric and/or contains functional grouts which may
help compatibilize the mixture, such as epoxy or
carboxyl.
2. The polycyclopentenes described herein are
~0 useful in a nonwoven fabric comprising fibrillated
three-dimensional network fibers prepared by using of a
polycyclopentene resin as the principal component. It
can be made by flash-spinning a homogeneous solution
contain i ng a polycyclopente.~.e . The resulta.~.t nonwoven
3~ fabric is excellent fir. heat resistance, dimensional
stability and solvent resistance.
3. A shaped part of any of the cyc~opentene
containing resins. This part may be formed by
ll~
m w,nT~Ti rTr nut~T JDI 11 C ~R1

CA 02338581 2001-03-O1
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injection molding, extrusion, and thermoform=:.g.
Exemplary uses include molded part for automotive use,
medical treatment container, microwave-range container,
food package container such as hot packing cc_ntainer,
oven container, retort container, etc., and heat-
resisting transparent container such as heat-resisting
bottle.
4. A sheet or film of any of the oyciopentene
containing resins. This sheet or film may be clear and
10 may be used for optical purposes (i.e. breakage
resistant glazing). The sheet or film may be oriented
or unoriented. Orientation may be carried opt by any
of the known methods such a uniaxial or biaxial
drawing. The sheet or film may be stampable or
1~ thermoformable.
5. The polycyclopentene resins are useful i:~
nonwoven fabrics or microfibers which are produced by
melt-blowing a material containing as a main component
a polycyclopentene. A melt-blowing process for
?0 producing a fabric or fiber comprises supplying a
polycyclopentene in a molten form from at least one
orifice of a nozzle into a gas stream which attenuates
the molten polymer into microfibers. The nonwoven
fabrics are excellent in heat-resistant and chemical
resistant characteristics, and are suitable =or use as
medical fabrics, industrial filters, battery separator=
and so forth. The microfibers are particularly useful
in the field of high temperature filtration, coalescing
and insulation.
30 6. A laminate in which one or more ca the
layers comprises a cyclopentene resin. The laminate
may also contain adhesives, and other polymers in some
or all of the layers, or other materials such as paper,
metal foil, etc. Some or all of the layers, may be
3~ oriented in the same or different directions. The
laminate as a whole may also be oriented. Such
materials are useful for containers, or other uses ..
where barrier properties are required.
116
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WO 96J23010 ~ 02338581 2001-03-O1 p~'/17S96J01282
7. A fiber of a cyclopentene polymer. This
fiber may be undrawn or drawn to further orient it. It
is useful for apparel and in industrial application
where heat resistance and/or chemical resistance are
important.
8. A foam or foamed object of a cyclopentene
polymer. The foam may be formed in any conve.~.tional
manner such as by using blowing agents.
9. The cyclopentene resins may be.microporous
membranes. They may be used in process wherein semi-
permeable membranes are normally used.
Ir. addition, the cyclopentene resins may be
treated or mixed with other materials to improve
certain properties, as follows:
l~ 1. They may further be irradiated wits electron
rays. This often improves heat resistance and/or
chemical resistance, and is relatively inexpensive.
Thus the molding is useful as a material required to
have high heat resistance, such as a structural
?0 material, a food container material, a food wrapping
material or an electric or electronic part material,
particularly as an electric or electronic part
material, because it is excellent in soldering
resistance.
2. Parts with a crystallinity of at 'east 200
may be obtained by subjecting cyclopentene pciymers
having an end of melting point between 240 and 300°C to
heat treatment (annealing) at a temperature of 120°C to
just below the melting point of the polymer. Preferred
.0 conditions are a temperature of 150 to 280°C. for a
period of time of 20 seconds to 90 minutes, preferably
to give a cyclopentene polymer which has a heat
deformation temperature of from 200 to 260°C. These
parts have good physical properties such as heat
resistance and chemical resistance, and thus are useful
for, for example, general construction materials,
electric or electronic devices, and car parts.
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CA 02338581 2001-03-O1
WO 96123010 PCTlUS96/01282
3. Cyclopentene resins may be nucleated to
promote crystallization during processing. An example
would be a poiycyclopentene resin composition
containing as main components (A) 100 parts by weight
of a pelycyclopentene and (B) 0.01 to 25 parts by
weigh c~ one or more nucleating agents selected from
the group consisting of (1) metal salts of organic
acids, (2i inorganic compounds, (3) organophosphorus
compounds, and/or (4) metal salts of ionic hydrocarbon
10 copolymer. Suitable nucleating agents may be sodium
methyienebis(2,4-di-tertbutylphenyl) acid phosphate,
sodium bis(4-tent-butylphenyl) phosphate, aluminum p-
(tert-butyl) benzoate, talc, mica, or related species.
These could be used in a process for producing
1~ polycycioeentene resin moldings by molding the above
polycyclopentene resin composition at a temperature
above them melting point.
4. Flame retardants and flame retardant
combinations may be added to a cyclopentene polymer.
?0 Suitable flame retardants include a halogen-based or
phosphorus-based flame retardant, antimony trioxide,
antimony pentoxide, sodium antimonate, metallic
antimony, antimony trichloride, antimony pentachloride,
antimony trisulfide, antimony pentasulfide, zinc
borate, barium metaborate or zirconium oxide. Thev may
be used in conventional amounts.
5. Antioxidants may be used ir. conventional
amounts to improve the stability of the cyclopentene
polymers. For instance 0.005 to 30 parts by weight,
30 per 100 parts by weight of the cyclopentene polymer, of
an antioxidant selected from the group consisting of a
phosphorous containing antioxidant, a phenolic
antioxidant or a combination thereof. The phosphorous
containing antioxidant may be a monophosphite or
diphosphite or.mixture thereof and the phenolic
antioxidant may be a dialkyl phenol, trialkyl phenol,
diphenylmonoalkoxylphenol, a tetraalkyl phenol, or a
mixture thereof. A sulfur-containing antioxidant may
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WO 96/23010 ~ 02338581 2001-03-O1 PCT/US96101282
also be used alone or in combination with o~~-
antioxidants.
6. various fillers or reinforcers, such as
particulate or fibrous materials, may be added to
~ improve various physical properties.
7. "Special" physical properties car. be
obtained by the use of specific types of materials.
Electrically conductive materials such as f-~:e metallic
wires or graphite may be used to render the polymer
electrically conductive. The temperature coefficient
of expansion may be regulated by the use of appropriate
fillers, and it may be possible to even obtain
materials with positive coefficients of expa~:sion.
Such materials are particularly useful ir_ e-_ectricai
1~ anti electronic parts.
8. The polymer may be crosslinked by
irradiation or chemically as by using peroxides,
optionally in the presence of suitable coagents.
Suitable peroxides include benzoyl peroxide, lauroyl
'?0 peroxide, dicumyl peroxide, tert-butyl peroxide, tert-
butylpercxybenzoate, tent-butylcumyl peroxide, tert-
butylhydroperoxide, 2,5-dimethyl-2,5-di(tert-
butylperoxy)hexane, 2,5-dimethyl-2,5-di(tert-
butylperoxy)hexyne-3,1,1-bis(tert-
'_'~ butylperoxyisopropyl)benzene, 1,1-bis(tert-
butylpercxy)-3,3,5- trimethyicyclohexane, n-butyl-4,~-
bis(tert-butylperoxy)valerate, 2,2-bis(tert-
butyiperoxy)butane and tert-butylperoxybenzene.
When polymerizing cyclopentene, it has been found
30 that some ef the impurities that may be found in
cyclopentene poison or otherwise interfere with the
pclymerizations described herein. Compounds such as
1,3-pentadiene (which can be removed by passage through
5A molecu'ar sieves), cyclopentadiene (which can be
3~ removed by distillation from Na), and
methylenecyclobutane (which can be removed by
distillation from polyphosphoric acid), may interfere
119
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CA 02338581 2001-03-O1
WO 96/23010 PCT/US96101282
with the polymerization, and their level shou~_d be kept
as low as practically possible.
The above polymers (in general) are useful in many
applications. Crystalline high molecular weight
polymers are useful as molding resins, and for films
for use in packaging. Amorphous resins are usefu_ as
elastomers, and may be crosslinked by known methods,
such as by using free radicals. When such amorphous
resins contain repeat units derived from polar monomers
10 they are oil resistant. Lower molecular weight
polymers are useful as oils, such as in polymer
processing aids. When they contain polar groups,
particularly carboxyl groups, they are useful in
adhesives.
I~ In many of the above polymerizations, the
transition metal compounds employed as (part of the)
catalysts contains) (a) metal atoms) in a positive
oxidation state. In addition, these complexes may have
a square planar configuration about the metal, and the
20 metal, particularly nickel or palladium, may have a d8
electronic configuration. Thus some of these catalysts
may be said to have a metal atom which is cationic and
has a de-square planar configuration.
In addition these catalysts may have a bidentate
liaand wherein coordination to the transition metal is
through two different nitrogen atoms or throug:: a
nitrogen atom and a phosphorus atom, these nitrogen and
phosphorus atoms being part of the bidentate ligand.
~t is believed that some of these compounds herein are
30 effective polymerization catalysts at least partly
because the bidentate ligands have sufficient steric
bulk or. both sides of the coordination plane (of the
square planar complex). Some of the Examples herein
wit.': the various catalysts of this type illustrate the
3~ degree of steric bulk which may be needed for such
catalysts. If such a complex contains a bidentate
ligand which has the appropriate steric bulk, it is
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WO 96/23010 ~ 02338581 2001-03-O1 pCT/US96/01282
believed that it produces polyethylene with a de~~'ee ~'
~olymerization of at least about 10 or more.
It is also believed that the polymerization
catalysts herein are effective because unpolymerized
olefir_ic monomer can only slowly displace from the
complex a coordinated olefin which may be formed by ~3-
hydride elimination from the growing polymer chain
which is attached to the transition metal. The
~isnlacement can occur by associative exchange.
_..creasing the steric bulk of the ligand slows the rate
assec_ative exchange and allows polymer c:-~air.
=owth. A ctuar.titative measure of the steric bulk of
~:e b=dentate liaand can be obtained by measuring at -
_=°~. the rate of exchange of free ethylene with
l~ ~:,mpiexed ethylene in a complex of formula (XI) as
shown ;n equation 1 using standard 1H NMR techniques,
which is called herein the Ethylene Exchange Rate
,EER). The neutral bidentate ligand is represented by
Yv where Y is Zither N or P. The EER is measured in
?0 ~::is system. In this measurement system the metal is
a~~ways Pd, the results being applicable to other metals
as noted below. Herein it is preferred for catalysts
tc contain bidentate ligands for which the second order
.ate constant for Ethylene Exchange Rate is about
,OCO L-mol-ls-1 or less when the metal used in the
lymerizatior. catalyst is palladium, more preferably
about 10,000 L-mcl-ls-1 or less, and more preferably
about 5,000 L-moi 's ' or less. When the meta~~ in the
_~lymerization catalyst is nickel, the second order
30 .ate constant (~or the ligand in EER measurement' is
abOUt 50,000 L-mol is I, more preferably about 25,000 L-
moi is 1 or less, and especially preferably about 10,000
=-mol is ' cr less . Herein the EER is measured usir~y the
_~mpound (XI1 in a procedure !including temperature''
described in Examples 21-23.
1 '_' I
m ~ncTt~ tTC cuCC? fCll 11 F ~F~l

CA 02338581 2001-03-O1
WO 96/23010 PCT/US96/01282
_.
_a
CH3 ~ -. k X\ ~CH3
Pd~ + Pd
N~ \ II ~N~ \ II.
(XI) X=N or P
In these polymerizations it is preferred if the
bidentate ligand is an a-diimine. T_t is also preferred
if the olefin has the formula R1'CH=Ch~, wherein R1' is
hydrogen or n-alkyl.
In general fer the polymers described herein,
blends may be prepared with other polymers, and such
other polymers may be elastomers, thermoplastics or
thermosets. By elastomers are generally meant polymers
10 whose Ta (glass transition temperature) and Tm (melting
point) , ~_ prese:.t, are below ambie__~.t temperature,
usually considered ro be about 20''C. Thermoplastics
are those polymers whose Tg and/or Tm are at or above
ambient temperature. Blends can be made by any of the
1~ common techniques known to the artisan, such as
solution blending, or melt blending in a suitable
apparatus such as a single or twin-screw extruder.
Specific uses for the polymers of this application in
the blends or as blends are listed below.
'_'0 Blends may be made with almost any kind of
elastomer, such as EP, EPDM, SBR, natural rubber,
polyisoprene, poiybutadiene, neoprene, butyl rubber,
styrene-butadiene block copolymers, segmented
polyester-polyether copolymers, elastomeric
polyurethanes, chlorinated or chlorosulfonated
polyethylene, (per)fluorinated elastomers such as
copolymers of vinylidene fluoride, hexafluoropropylene
and optionally tetrafluoroethylene, copolymers of
tetrafluoroethylene and perfluoro(methyl vinyl ether),
30 and ccpolymers of tetrafluoroethylene and propylene.
Suitable thermoplastics which are useful for
blending with the polymers described herein include:
polyesters such as polyethylene terephthalate),
poly(butylene tereDhthalate), and polyethylene
m tn~TtTt sTr cuCLT IRI II F ~Rl

WO 96/23010 ~ 02338581 2001-03-O1 pCT/U596/01282
adipate); polyamides such as nylon-6, nylon-~,~, nylon-
12, nylon-12,12, nylon-11, and a copolymer of
hexamethylene diamine, adipic acid and terephthaiic
acid; fluorinated polymers such as copolymers of
ethylene and vinylidene fluoride, copolymers of
tetrafluoroethylene and hexafluoropropylene, copolymers
of tetrafluoroethylene and a perfluoro(alkyl vinyl
ether) such as perfluoro(propyl vinyl ether), and
polyvinyl fluoride); other halogenated polymers such a
polyvinyl chloride) and poly(vinylidene chloride) and
its copolymers; polyolefins such as polyethylene,
polypropylene and polystyrene, and copolymers thereof;
(meth)acrylic polymers such a poly(methyl methacrylate)
' and copolymers thereof; copolymers of olefins such as
I~ ethylene with various (meth) acrylic monomers such as
alkyl acrylates, (meth)acrylic acid and ionomers
thereof, and glycidyl (meth)acrylate); aromatic
polyesters such as the copolymer of Bisphenol A and
terephthalic and/or isophthalic acid; and liquid
crystalline polymers such as aromatic polyesters or
aromatic polyester-amides).
Suitable thermosets for blending with the polymers
described herein include epoxy resins, phenol-
formaldehyde resins, melamine resins, and unsaturated
polyester resins (sometimes called thermoset
polyesters). Blending with thermoset polymers will
often be done before the thermoset is crosslinked,
using standard techniques.
The polymers described herein may also be blended
with uncrosslinked polymers which are not usually
considered thermoplastics for various reasons, for
instance their viscosity is too high and/or their
melting point is so high the polymer decomposes below
the melting temperature. Such polymers include
3~ poiy(tetrafluoroethylene), aramids such as poly(p
phenylene terephthalate) and poly(m-phenyiene
isophthalate), liquid crystalline polymer such as ..
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CA 02338581 2001-03-O1
WO 96123010 PCT/US96/01282
po~iy(benzoxazoles), and non-melt processinle polyW saes
which are often aromatic polyimides.
Ail of the polymers disclosed herein may be mixed
with various additives normally added to eiastomers and
thermoplastics [see EPSE (below), vol. 14, p. 327-410].
For i-:stance reinforcing, non-reinforcing and
conductive fillers, such as carbon black, glass fiber,
minerals such as clay, mica and talc, glass spheres,
barium sulfate, zinc oxide, carbon fiber, and aramid
10 fiber cr fibrids, may be used. Antioxidants,
antiozo:.arts, pigments, dyes, delusterants, compounds
to nroT~cte crosslinking may be added. Plasticizers
suc:. as various hydrocarbon oils may also be used.
The =ollowing listing is of some uses for
I~ noivoleri::s, which are made from linear olefins and do
not _..clucie polar monomers such as acrylates, which are
disclosed herein. In some cases a reference is given
whic=~ discusses such uses for polymers in general. All
of these references are hereby included by reference.
?0 For the references, "TJ" refers to W. Gerhartz, et al.,
Ed., ~l,~mann's Encyclopedia of Industrial Chemistry,
5th Ed. VCH Verlagsgesellschaft mBH, Weinheim, for
which the volume and page number are given, "ECT3"
refers t.. the H. F. Mark, et al., Ed., Kirk-Othmer
Encvclo~edia of Chemical Technology, 4th Ed., John
Wilev & Sc.~.s, New York, "ECT4" refers to the J.
Kroschwi~z, et al., Ed., Kirk-Othmer Encyclopedia of
Che:r:ical '_'echnoiogy, 4th Ed. , John Wiley & Sons, New
York, fer which the volume and page number are given,
30 "EPS'_"" reTers to H-. F. Mark, et al., Ed., Encyclopedia
of =~lymer Science and Technology, 1st Ed., John Wiley
& Sons, New York, for which the volume and page number
are ~ive~, "EPSE" refers to H. F. Mark, et al., Ed.,
Encycicpedia of Polymer Science and Engineering, 2nd
3~ Ed., ooh.~. Wiley & Sons, New York, for which volume and
page numbers are given, and "PM" refers to J. A. ,
Brydscn, ed., Plastics Materials, 5 Ed., Butterworth-
Heinema~:=, Oxfo=d, L'K, 1989, and the page is given. In
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WO 96123010 ~ 02338581 2001-03-O1 pCT/US96/01282
these uses, a polyethylene, polypropylene and a
copolymer of ethylene and propylene are preferred.
1. Tackifiers for low strength adhesives (U,
vol. A1, p. 235-236) are a use for these polymers.
Elastomeric and/or relatively low molecular weight
polymers are preferred.
2. An oil additive for smoke suppression in
single-stroke gasoline engines is another use.
Elastomeric polymers are preferred.
3. The pclymers are useful as base resins for
hct melt adhesives (U, vol. A1, p. 233-234), pressure
sensitive adhesives (U, vol. A1, p. 235-236) or solvent
applied adhesives. Thermoplastics are preferred for
hot melt adhesives. The polymers may also be used in a
1~ carpet installation adhesive.
4. Lubricating oil additives as Viscosity Index
Improvers for multigrade engine oil (ECT3, Vol 14, p.
495-496) are another use. Branched polymers are
preferred. Ethylene copolymer with acrylates or other
'_'0 polar monomers will also function as Viscosity Index
Improvers for multigrade engine oil with the additional
advantage of providing some dispersancy.5. Polymer for
coatings and/or penetrants for the protection of
various porous items such as lumber and masonry,
particularly out-of-doors. The polymer may be in a
suspension or emulsion, or may be dissolved ~.. a
solvent.
6. Base polymer for caulking of various kinds
is another use. An elastomer is preferred. Lower
~0 molecular weight polymers are often used.
7. The polymers may be grafted with various
compounds particularly those that result in functional
groups such as epoxy, carboxylic anhydride (for
instance as with a free radically polymerized reaction
with malefic anhydride) or carboxylic acid (EPSE, vol.
12, p. 445). Such functionaiized polymers are
particularly useful as tougheners for various
thermoplastics and thermosets when blended. When the
I_
ei ioeTiTt rrC cNCCT IRI I) F 761

CA 02338581 2001-03-O1
WO 96123010 PCT/US96/01282
polymers are elastomers, the functional groups whlcr_
are grafted onto them may be used as curesites to
crosslink the polymers. Malefic anhydride-grafted
randomly-branched polyolefins are useful as tougheners
for a wide range of materials (nylon, PPO, PPO/styrene
alloys, PET, PBT, POM, etc.); as tie layers in
multiiayer constructs such as packaging barrier films;
as hct melt, moisture-curable, and coextrudable
adhesives; or as polymeric plasticizers. The malefic
10 andhydride-grafted materials may be post reacted with,
for example; amines, to form other functional
materials. Reaction with aminopropyl trimethoxysilane
would allow for moisture-curable materials. Reactions
with di- and tri-amines would allow for viscosity
1~ modifications.
8. The polymers, particularly elastomers, may
be used for modifying asphalt, to improve the physical
properties of the asphalt and/or extend the life of
asphalt paving.
?0 9. The polymers may be used as base resins for
chlorination or chlorosulfonation for making the
corresponding chlorinated cr chlorosulfonated
elastomers. The unchlorinated polymers need not be
elastomers themselves.
10. Wire insulation and jacketing may be made
from ar_-~ of the pclyolefins (see EPSE, vol. 17, _. 828-
842). ~n the case of elastomers it may be preferable
to crosslink the polymer after the insulaticn or
jacketing is formed, for example by free radicals.
30 11. The polymers, particularly the elastomers,
may be used as tougheners for other polyolefins such as
polypropylene and polyethylene.
12. The base for synthetic lubricants (motor
oils) may be the '.highly bunched polyolefins described
3~ herein (ECT3, vol. 14, p. 496-501).
13. The branched pelyolefins herein can be used
as drip suppressants when added to other polymers.
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WO 96/23010 ~ 02338581 2001-03-O1 PCT/US96/01282
14. The branched polyolefins herein. are
especially useful in blown film applications because of
their particular rheological properties (EP~~, vol. 7,
p. 88-106). It is preferred that these polymers have
some crystallinity.
15. The polymer described herein can be used to
blend with wax fen candles, where they would provide
smoke suppression and/or drip control.
16. The polymers, especially the.branched
polymers, are useful as base resins for carpe backing,
especially for autcmobile carpeting.
17. The polymers, especially those wrich are
relatively flexible, are useful as capliner resins for
carbonated and noncarbonated beverages.
1~ 18. The polymers, especially those having a
relatively low melting point, are useful as ~::ermal
transfer imaging resins (for instance for imaging tee-
shirts or signs).
19. The polymers may be used for extrusion or
?0 coextrusior_ coatings onto plastics, metals, textiles or
paper webs.
20. The polymers may be used as a laminating
adhesive for glass.
21. The polymers are useful as for blown or
cast films or as sheet (see EPSE, vol. 7 p. 88-106;
ECT4, vol. 11, p. 843-856; PM, p. 252 and p. 432ff).
The films may be single layer or multilayer, the
multilayer Films may include other polymers, adhesives,
etc. For packaging the films may be stretch-wrap,
30 shrink-wrac or cling wrap. The films are useful form
many applications such as packaging foods, geomembranes
and pond liners. It is preferred that these polymers
have some crystallinity.
G2. The polymers may be used to form flexible
3~ or rigid foamed objects, such as cores for various
sports items such as surf boards and liners for
protective headgear. Structural foams may also be
made. It is preferred that the polymers have some
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~t ~eer~ rre cuGCT Ipl II F ~Rl

CA 02338581 2001-03-O1
WO 96/23010 PCT/C1S96/01282
crystallinity. The polymer of the foams may be
crosslinked.
23. In powdered form the polymers may be used
to coat objects by using plasma, flame spray or
fluidized bed technicrues.
24. Extruded films may be formed from these
polymers, and these films may be treated, for example
drawn. Such extruded films are useful for packaging of
various sots .
10 25. The polymers, especially those that are
elastomeric, may be used in various types of hoses,
such as automotive heater hose.
26. The polymers, especially those that are
branched, are useful as pour point depressants for
l~ fuels and cils.
27. These polymers may be flash spun to
nonwoven fabrics, particularly if they are crystalline
(see EPSE vol. 10, p. 202-253) They may also be used
to form spunbonded polyolefins (EPSE, vol. 6, p. 756-
20 760). These fabrics are suitable as house wrap and
geotextiles.
28. The highly branched, low viscosity
polyolefins would be good as base resins for master-
batching of pigments, fillers, f'_ame-retardants, and
?~ related additives for polyolefins. 29. The polymers
may be grafted with a compound containing ethylenic
unsaturation and a functional group such as a carboxyl
group or a derivative of a carboxyl group, such as
ester, carboxylic anhydride of carboxylate salt. A
30 minimum grafting level of about 0.01 weight percent of
grafting agent based on the weight of the grafted
polymer is preferred. The grafted polymers are useful
as compatibilizers and/or tougheners. Suitable
grafting agents include malefic, acrylic, methacrylic,
3~ itaconic, crotonic, alpha-methyl crotonic and cinnamic
acids, anhydrides, esters and their metal salts and
fumaric acid and their esters, anhydrides (when
appropriate) and metal salts.
I?8
i,w,n~rm err r~ueLT IOI 11 C ~R1

WO 96!23010 ~ 02338581 2001-03-O1 PCTNS96/01282
Copolymers of linear olefins with 4-
-;inylcyclohexene and other dienes may generally be used
or all of the applications for which the linear
olefins polymers(listed above) may be used. In
addition they may be sulfur cured, so they generally
can be used for any use for which EPDM polymers are
~ssed, assuming the olefin/4-vinylcyclohexene polymer is
~iastomeric.
Also described herein are novel copolymers of
_inear olefins with various polar monomers such as
acrylic acid and acrylic esters. Uses for these
polymers are given below. Abbreviations fcr reference=
Describing these uses ir, general with polymers are the
same as listed above for polymers made from linear
1~ olefins.
1. Tackifiers for low strength adhesives (U,
vol. A1, p. 235-236) are a use for these polymers.
Elastomeric and/or relatively low molecular weight
olymers are preferred.
?0 2. The polymers are useful as base resins for
::ot melt adhesives (U, vol. A1, p. 233-234), pressure
sensitive adhesives (U, vol. A1, p. 235-236) or solve.~.~
applied adhesives. Thermoplastics are preferred for
of melt adhesives. The polymers may also be used in a
carpet installation adhesive.
3. Base polymer for caulking of vario~.:s kinds
.s another use. An elastomer is preferred. Lower
,oiecular weight polymers are often used.
4. The polymers, particularly elastomers, may
:0 ~e used for modifying asphalt, to improve the physical
properties of the asphalt and/or extend the life of
asphalt paving, see U.S. patent 3,980,598.
5. Wire insulation and jacketing may be made
rpm any of the polymers Osee EPSE, vol. 17, p. 828
3~ 342). In the case of elastomers it may be preferable
to crosslink the polymer after the insulation or
acketing is formed, for example by free radicals.
129
ci mcTIT~ ITF ~HFFT (RULE 261

CA 02338581 2001-03-O1
WO 96/23010 PC T/US96/01282
6. The polymers, especially the branched
polymers, are useful as base resins for carpet backing,
especially for automobile carpeting.
7. The polymers may be used for extrusion or
5 coextrusion coatings onto plastics, metals, textiles or
paper webs.
8. The polymers may be used as a laminating
adhesive for glass.
9. The polymers are useful as for blown or cast
Films cr as sheet (see EPSE, vol. 7 p. 88-106; ECT4,
vol. ~ , p. 843-855; PM, p. 252 and p. 432ff). The
films may be single layer or multilayer, the multilayer
films may include other polymers, adhesives, etc. For
packaginc the films may be stretch-wrap, shrink-wrap or
l~ cii:.a wrap. The Films are useful form many
applications such as packaging foods, geomembranes and
pond liners. It is preferred that these polymers have
some crystallinity.
10. The polymers may be used to form flexible
?0 or rigid foamed objects, such as cores for various
sports items such as surf boards and liners for
protective headgear. Structural foams may also be
made. It is preferred that the polymers have some
crystallinity. The polymer of the foams may be
crosslinked.
1~. In powdered form the polymers may be used
to coat objects by using plasma, flame spray or
fluicized bed tech:.iques.
12. Extruded films may be formed from these
30 polymers, and these films ma~~ be treated, for example
drawn. Such extruded films are useful for packaging of
various sorts.
13. The pciymers, especially those that are
elastomeric, may be used in various types of hoses,
3~ such as automotive heater hose.
14. The polymers may be used as reactive
diluents in automotive finishes, and for this purpose .
130
m ~ecTiTt TTC CLJRCT IRI 11 F ~Rl

WO 96/23010 ~ 02338581 2001-03-O1 PCT/US96/01282
it is preferred that they have a relatively iow
molecular weight and/or have some crystallinity.
15. The polymers can be converted to ionomers,
which when the possess crystallinity can be used as
molding resins. Exemplary uses for these ionomeric
molding resins are golf ball covers, perfume caps,
sporting goods, film packaging applications, as
tougheners in other polymers, and usually extruded)
detcnator cords.
16. The functional groups on the poivmers can
be used tc initiate the polymerization of other types
of monomers or to copolymerize with other types of
monomers. If the polymers are elastomeric, they can
act as toughening agents.
I~ 7. The polymers can act as compatibilizing
agents between various other polymers.
18. The polymers can act as tougheners for
various other polymers, such as thermoplastics and
thermosets, particularly if the olefin/polar monomer
?0 polymers are elastomeric.
19. The polymers may act as internal
plasticizers for other polymers in blends. A polymer
which may be plasticized is polyvinyl chloride).
20. The polymers can serve as adhesives between
other oolvmers.
2i. With the appropriate functional groups, the
polymers may serve as curing agents for other polymers
with complimentary functional groups (i.e., the
functional groups of the two polymers react with each
30 other) .
22. The polymers, especially those that are
branched, are useful as pour point depressants for
fuels and oils.
23. Lubricating oil additives as Viscosity
3~ Index Improvers for multigrade engine oil (ECT3, Vol
14, p. 495-496) are another use. Branched polymers are
preferred. Ethylene copolymer with acrylates or other
polar monomers will also function as Viscosity Index
131
m toeTrn tTC cuCCT 1011 II F ~R1

CA 02338581 2001-03-O1
WO 96123010 PCTIUS96/01282
improvers for multigrade engine oil with the additicral
advantage of providing some dispersancy.
24. The polymers may be used for roofing
membranes.
25. The polymers may be used as additives to
various molding resins such as the so-called
thermcplastic olefins to improve paint adhesicn, as ir.
automctive uses.
10 Polymers with or without polar monomers present
are useful in the following uses. Preferred polymers
with cr without polar monomers are those listed above
n t~~ uses for each "type".
1. A flexible pouch made from a single layer cr
l~ mult=layer film ias described above) which may be usea
for packaging various liquid products such as milk, cr
powder such as hot chocolate mix. The pouch may be
heat sealed. It may also have a barrier layer, such as
a metal foil layer.
~0 2. A wrap packaging film having differential
cling is provided by a film laminate, comprising at
least two layers; an outer reverse which is a polymer
(or a blend thereof) described herein, which contains a
tackifier in sufficent amount to impart cling
properties; and an outer obverse which has a density ef
at least about 0.916 g/mL which has little or ne cling,
provided that a density of the outer reverse layer is
at -;east 0.008 g/mL less than that of the density of
the outer obverse layer. It is preferred that the
30 outer cbverse layer is linear low density polyethylene,
and the polymer of the outer obverse layer have a
density of less than 0.90 g/mL. All densities are
0
meas~.:red at 25 C.
3. Fine denier fibers and/or multifilaments.
3~ 'These ,~~ay be mel t spun. They may be in the form of a
filament bundle, a non-woven web, a woven fabric, a
knitted fabric or staple fiber.
13'_'
r~ ~ecT~T~ tTL cWC>=T loll II F 'JRl

WO 96/23010 CA 02338581 2001-03-O1 pCTNS96/OI282
4. A composition comprising a mixture of the
polymers herein and an antifogging agent. This
composition is especially useful in film or sheet form
because of its antifogging properties.
~. Elastic, randomly-branched olefin polymers are
disclosed which have very good processability,
including processing indices (PI's) less than or equal
to 70 percent of those of a comparative linear olefin
polymer and a critical shear rate at onset of surfac a
melt =racture of at least 50 percent greater than the
criticGl shear rate at the onset of surface melt
fracture of a traditional linear olefin polymer at
abollt the same I2 and Mw/Mn. The novel polymers may
have higher low/zero shear viscosity and lower high
1~ shear .iscosity than comparative linear olefin polymers
made by other means. These polymers may be
characterized as having: a) a melt flow ratio, I10/I2,
>_ 5.53, b) a molecular weight distribution, Mw/Mn,
defined by the equation: Mw/Mn < (I10/I2)-4.63, and c)
~0 a critical shear rate at onset of surface melt fracture
of at /east 50 percent greater than the critical shear
rate at the onset of surface melt fracture of a linear
olefin polymer having about the same I2 and Mw/Mn.
Some blends of these polymer are characterized as
~~ having: a) a melt flow ratio, I10/I2, > 5.63, b) a
molecular weight distribution, Mw/Mn, defined b~~ ti:e
equation: Mw/Mn <_ (I10/I2)-4.63, and c) a critical
shear rate at onset of surface melt fracture of at
least 50 percent greater than the critical shear rate
0 at the onset of surface melt fracture of a linear
olefin polymer having about the same I2 and Mw/Mn and
(b) at least one other natural or synthetic polymer
chosen from the polymer of claims 1, 3, 4, 6, 332, or
343, a conventional high density polyethylene, low
_~ density polyethylene or linear low density polyethylene
polymer. The polymers may be further characterized as
having a melt flow ratio, I10/I2, ? 5.63, a molecular
weight distribution, Mw/Mn, defined by the equation:
I ~~
CI IACTITI tTF CNFFT lRl II F ~Rl

CA 02338581 2001-03-O1
WO 96123010 PCT/US96/01282
Mw/Mn 5 (I10/I2)-4.63, and a critical shear stress at
onset of gross melt fracture of greater than about 400
kPa (4x106 dyne%cmz) and their method of manufacture
are disclosed. The randomly-branched olefin polymers
preferably have a molecular weight distribution from
about 1.5 to about 2.5. The polymers described herein
often. have improved processability over conventional
olefin polymers and are useful in producing fabricated
articles such as fibers, films, and molded parts. For
10 this paragraph, the value I2 is measured in accordance
with ASTM D-1238-190/2.16 and I10 is measured in
accordance with ASTM D-1238-190/10; critical shear rate
at onset of surface melt fracture and processing index
(PI) are defined in U.S. Patent 5,278,272, which is
l~ hereby included by reference.
In another process described herein, the product
of the process described herein is an a-olefin. It is
preferred that in the process a linear a-olefin is
produced. It is also preferred that the a-olefin
?0 contain 4 to 32, preferably 8 to 20, carbon atoms.
Rz
R3 N Q
~N~
Ra ~.Ni \S
~5
( XXXI )
When (XXXI) is used as a catalyst, a neutral Lewis
acid or a cationic Lewis cr Bronsted acid whose
's counterion is a weakly coordinating anion is also
present as part of the catalyst system (sometimes
called a "first compound" in the claims).. By a
"neutral Lewis acid" is meant a compound which is a
Lewis acid capable for abstracting X from (I) to form
30 a weakly coordinating anion. The neutral Lewis acid is
originally uncharged (i.e., not ionic). Suitable
neutral Lewis acids include SbFS, Ar~B (wherein Ar is
134
~..~r.~wTmTr nurLT ~Df ~t C ~R\

WO 96/23010 CA 02338581 2001-03-O1 PCT/US96/01282
aryl), and BF:. By a cationic Lewis acid _s meanW a
cation with a positive charge such as Ag', J', and Na'.
A preferred neutral Lewis acid is an alkyl
aluminum compound, such as R~,Al, R92A1C1, R~A1C1~, and
"R9A10" (alkylaluminoxane), wherein R9 is alkyl
containing 1 to 25 carbon atoms, preferably 1 to 4
carboy. atoms. Suitable alkyl aluminum ccmpounds
include methylaluminoxane, (C~HS) 2A1C1 , C=H_A1C1_, and
[(CH3)~CHCH~),Al.
Relatively noncoordinating anions are known in the
art, and the coordinating ability of such anions is
known and has been discusses in the literature, see for
instance W. Beck., et al., Chem. Rev., vol. 88 p. 1405-
1421 (1988), and S. H. Strauss, Chem. Rev., vol. 93, p._
I~ 927-942 ;19931, both of whic:~ are hereby _ncluded by
reference. Amona such anions are those formed from the
aluminum compounds in the immediately preceding
paragraph and X , including R'~A1X , Rs2A1C1X , R~A1C12X ,
and "R9AlOX-". Other useful noncoordinatina anions
include BAF {BAF = tetrakis[3,5-
bis(trifluoromethyl)phenyl)borate}, SbF6-, YFS~, and BF9-
trifluoromethanesulfonate, p-toluenesulfonate,
(R~SO~),N , and (C6F5)qB .
The temperature at which the process is carried
out is about -100°C to about +200°C, preferably about
0°C to about 150°C, more preferably about 25'C to about
100°C. Tt is believed that at higher temperatures,
lower molecular weight a-olefins are produced, all
other factors being equal. The pressure at which the
polymerization is carried out is not critical,
atmospheric pressure to about 275 MPa being a suitable
range. .t is also believed that increasing the
pressure increases the relative amount of a-olefin (as
opposed to internal olefin) produced.
The process to make a-olefins may be run in a
solvent (liquid), and that is preferred. The solvent
may in fact be the a-olefin produced. Such a process
may be started by using a deliberately added solvent
135
suBSTITUTE SHEET (RULE 26)

WO 96/23010 ~ 02338581 2001-03-O1
PCT/US96/01282
which is gradually displaced as the reaction proceeas.
By solvent it is not necessarily meant that any or all
cf the starting materials and/or products are soluble
in the (liquid) solvent.
s In (I) it is preferred that R3 and R5 are both
hydrogen cr methyl or R~ and R4 taken together are
\ \
/ /
(An)
10 =c is also preferred that each of Q and S is
independently chlorine or bromine, and it is more
preferred that both o~ Q and S in (XXXI) are chlorine
or bromine.
In (XXXI) R' and RS are hydrocarbyl or substituted
1~ hydrocarbyl. What these groups are greatly determines
whether the a-olefins of this process are made, or
whether higher polymeric materials, i.e., materials
containing over 25 ethylene units, are coproduced or
produced almost exclusively. If R2 and RS are highly
?0 statically hindered about the nickel atom, the tendency
is to produce higher polymeric material. For instance,
when R- and R5 are both 2,6-diisopropylphenyl mostly
higher polymeric material is produced. However, when
R' and RS are both phenyl, mostly the a-olefins of this
process are produced. Of course this will also be
influenced by other reaction conditions such as
temperature and pressure, as noted above. Useful
groups for R' and RS are phenyl, and p-methylphenyl.
As is understood by the artisan, in
.0 ..-iaomerization reactions of ethylene to produce a-
olefins, usually a mixture of such a-olefins is .
obtained containing a series of such a-olefins
differing from one another by two carbon atoms (an y
ethylene unit). The process for preparing a-olefins
3~ described herein produces products with a high
136
m ioeTiTt tTC c4.IFFT lRl ll F 261

WO 96/23010 ~ 02338581 2001-03-O1 pCTIUS96101282
percentage of terminal olefinic groups (as opposed to
nternal olefinic groups). The product mixture also
contains a relatively high percentage of molecules
which are linear. Finally relatively high catalyst
efficiencies can be obtained.
The a-olefins described as being made herein may
also be made by contacting ethylene with one of the
compounds
R2 ~ +
Rs~N T'
~N ~Z
R4 N
~s
(III)
or
l~
R2 ~ +
_N U
Ra ~ f~N
(XXXIV)
wherein R' , R' , Ra , and RS are as de f fined ( and
preferred) as described above (for the preparation of a
-olefins), and T' is hydrogen or n-alkyl containing up
:0 38 carbon atoms, Z is a neutral Lewis base wherein
?0 :.ae donating atom is nitrogen, sulfur, or oxygen,
provided that if the donating atom is nitrogen then the
pKa of the conjugate acid of that compound (measured in
water) is less than about 6, U is n-alkyl containing up
to 38 carbon atoms, and X is a noncoordinating anion
2~ ;see above). The process conditions for making a-
oiefins using (III) or (XXXIV) are the same as for
using (XXXI) to make these compounds except a Lewis or
Bronsted acid need not be present. Note that the
double line in (XXXIV> represents a coordinated
137
e~ ~oeTiTi tTC cG.IGCT lGtl II F ~Rl

WO 96/23010 ~ 02338581 2001-03-O1 pC'f/US96/01282
ethylene molecule. (XXXIV) may be made'~rom (II) by
reaction of (III) with ethylene. In other words,
(XXXIV) may be considered an active intermediate in the
formation of a-olefin from (III). Suitable groups for
Z include dialkyl ethers such as diethyl ether, and
alkyl nitrites such as acetonitrile.
In general, a-olefins can be made by this process
using as a catalyst a Ni[II] complex of an a-diimine of
formula (VIII), wherein the Ni[II] complex.is made by
10 any of the methods which are described above, using
Ni [ 0 ] , Ni ( I ] or Ni [ I I ] precursors . Al l of the proces s
conditions, and preferred groups on (VIII), are the
same as described above in the process for making a-
olefins.
l~
In the Examples, the following convention is used
for naming a-diimine complexes of metals, and the a-
diimine itself. The a-diimine is indicated by the
?0 letters "DAB". To the left of the "DAB" are the two
groups attached to the nitrogen atoms, herein usually
called R2 and R5. To the right of the "DAB" are the
groups or_ the two carbon atoms of the a-diimine group,
herein usually termed R3 and R4. To the right of all
this appears the metal, ligands attached to the metal
(such as Q, S and T), and finally any anions (X), which
when "free" anions are designated by a superscript
minus sign (i.e., X-). Of course if there is a "free"
anion present, the metal containing moiety is cationic.
30 Abbreviations for these groups are as described in the
Specification in the Note after Table ?. Analogous
abbreviations are used for a-diimines, etc.
In the Examples, the following abbreviations are
used:
35 ~-if - heat of fusion
acac - acetylacetonate
Bu - butyl
t-BuA - t-butyl acrylate
138
c~ ~aeTr~ rTC cNCCT lRl II F 7R1

WO 96/23010 ~ 02338581 2001-03-O1 PCT/L1S96/01282
DMA - Dynamic Mechanical Analysis
DME - 1,2-dimethoxyethane
DSC - Differential Scanning Calorimetry
E - ethylene
EOC - end of chain
Et - ethyl
FC-75 - perfluoro(n-butyltetrahydrofuran)
FOA - fluorinated octyl acrylate
GPC - gel permeation chromatography
MA - methyl acrylate
MAO - methylaluminoxane
Me - methyl
MeOH - methanol
MMAO - a modified methylaluminoxane in which
1~ about 25 e percent of the methyl groups have
mol been
replaced isobutyl groups
by
M-MA O - see MMAO
MMAO -3A - see MMAO
Mn - number average molecular weight
MVK - methyl vinyl ketone
Mw- weight
average
molecular
weight
Mz - viscosity average molecular weight
PD or P/D
- polydispersity,
Mw/Mn
Ph - phenyl
'S PMAO - see MAO
PMMA - poly(methyl methacrylate)
Pr - propyl
PTFE - polytetrafluoroethylene
RI - refractive index
30 RT (or rt)
- room temperature
TCE - 1,1,2,2-tetrachloroethane
Tc - temperature of crystallization
Td - temperature of decomposition.
Tg - glass transition temperature
>> TGA - Thermogravimetric Analysis
THF - tetrahydrofuran
Tm - melting temperature
139
SUBSTITUTE SHEET (RULE 26)

PCT/US96/01282
WO 96/23010 ~ 02338581 2001-03-O1
TO - turnovers , the number of mdl'~3 "~° mo~iotii'e=
polymerized per g-atom of metal in the catalyst used
Uv - ultraviolet
Unless otherwise noted, all pressures are gauge
pressures.
In the Examples, the following procedure was used
to quantitatively determine branching, and the
distribution of branch sizes in the polymers (but not
necessarily the simple number of branches as measured
10 by total number ~f methyl groups per 1000 methylene
groups). 100 MHz 13C NMR spectra were obtained on a
Varian Unity 400 MHz spectrometer using a 10 mm probe
on typically 15-20 wt% solutions of the polymers and
0.05 M Cr(acetylacetonate)3 in 1,2,4-trichlorobenzene
1~ lTCB) unlocked at 120-140°G using a 90 degree pulse of
12.5 to 18.5 sec, a spectral width of 26 to 35 kHz, a
relaxation delay of 5-9 s, an acquisition time of 0.64
sec and gated decoupling. Samples were preheated for
at least 15 min before acquiring data. Data
20 acquisition time was typically 12 hr. per sample. The
T1 values of the carbons were measured under these
conditions to be all less than 0.9 s. The longest T1
measured was for the Bu+, end of chain resonance at 14
ppm, which was 0.84 s. Occasionally about 16 vol. o
benzene-d~ was added to the TCB and the sample was run
locket. Some samples were run in chloroform-dl, CDCl:-
dl, !locked) at 30°C under similar acquisition
parameters. T1's were also measured in CDC13 at
ambient temperature on a typical sample with 0.05 M
,0 Cr(acetylacetonate)3 to be all less than 0.68 s. In
rare cases when Cr(acetylacetonate)3 was not used, a
30-40 s recycle delay was used to insure quantitation.
The alycidyl acrylate copolymer was run at 100°C with
Crlacetylacetonate)3. Spectra are referenced to the .
3~ sclver.t - either the TCB highfield resonance at 127.8
ppm cr the chloroform-dl triplet at 77 ppm. A DEPT 135
spectrum was done on most samples to distinguish
methyls and methines from methylenes. Methyls were
140
CI IRSTITI lTF SHEET (RULE 26)

WO 96/23010 ~ 02338581 2001-03-O1 PCT/US96l01282
_.~istinguished from methines by chemical shift. EOC is
end-of-chain. Assignments reference to following
naming scheme:
1. xBy: By is a branch of length y carbons; x is
the carbon being discussed, the methyl at the end of
the branch is numbered 1. Thus the second carbon from
the end of a butyl branch is 2B4. Branches of length y
or greater are designated as y+.
2. xEBy: EB is an ester ended branch containing y
methylenes. x is the carbon being discussed, the first
methylene adjacent to the ester carbonyl is labeled 1.
Thus the second methylene from the end of a 5 methylene
ester terminated branch would be 2EB5. 13C NMR of
model compounds for EBy type branches for y=0 and y=5'
1~ confirm the peak positions. and assignments of these
branches. In addition, a model compound for an EB1
branch is consistent with 2 dimensional NMR data using
the well know 2D NMR techniques of hsqc, hmbc, and
hsqc-tocsy; the 2D data confirms the presence of the
EB5', EBO, EB1 and other intermediate length EB
branches
3. The methylenes in the backbone are denoted
with Greek letters which determine how far from a
branch point methine each methylene is. Thus X3(3 (beta
beta) B denotes the central methylene in the following
PCHRCH2CH2CH2CHRP. Methylenes that are three or more
carbons from a branch point are designated as y+
( gamma+ ) .
4. When x in xBy or xEBy is replaced by a M, the
:0 methine carbon of that branch is denoted.
Integrals of unique carbons in each branch were
measured and were reported as number of branches per
1000 methylenes (including methylenes in the backbone
and branches). These integrals are accurate to +/- 50
relative for abundant branches and +/- 10 or 200
relative for branches present at less than 10 per 1000
methylenes.
141
SUBSTITUTE SHEET (RULE 26)

WO 96/23010 ~ 02338581 2001-03-O1 pCT/US96l01282
Such types of analyses are gene rall~~ mown, see
for instance "A Quantitative Analysis of Low Density
(Branched) Polyethylenes by Carbon-13 Fourier Transform
Nuclear Magnetic Resonance at 67.9 MHz", D. E. Axelson,
5 et al., Macromolecules 12 (1979) pp. 41-52; "Fine
Branching Structure in High-Pressure, Low Density
Polyethylenes by 50.10-MHz 13C NMR Analysis", T. Usami
et al., Macromolecules 17 (1984) pp. 1757-1761; and
"Quanti~ication of Branching in Polyethylene by 13C NMR
10 Using Paramagnetic Relaxation Agents", J. V. Prasad, et
al., Eur. Polym. J. 27 (1991) pp. 251-254 (Note that
this latter paper is believed to have some significant
typographical errors in it).
~t is believed that in many of the polymers
l~ described herein which have unusual branching, i.e.,
they have more or fewer branches than would be expected
for "normal" coordination polymerizations, or the
distribution of sizes of the branches is different from
that expected, that "branches on branches" are also
20 present. By this is meant that a branch from the main
chain or_ the polymer may itself contain one or more
branches. It is also noted that the concept of a "main
chain" may be a somewhat semantic argument if there are
sufficient branches on branches in any particular
polymer.
By a polymer hydrocarbyl branch is meant a methyl
group to a methine or quaternary carbon atom or a group
of consecutive methylenes terminated at one end by a
methyl group and connected at the other end to a
30 methine or quaternary carbon atom. The length of the
branch is defined as the number of carbons from and
including the methyl group to the nearest methine or
quaternary carbon atom, but not including the methine
or auaternarv carbon atom. T_f the number of .
s~ consecutive methylene groups is "n" then the branch
contains (or the branch length is) n+1. Thus the
structure (which represents part of a polymer) -
l4'
~t tR~~iTtITE SHEET (RULE 26)

WO 96/23010 CA 02338581 2001-03-O1 PCT/US96/01282
=HzCH2CH(CH~CHZCHZCH~CH(CH3)CH2CH3]CH2CH~CH2CH,- contains 2
branches, a methyl and an ethyl branch.
For ester ended branches a similar definition is
used. An ester branch refers to a group of consecutive
methyiene groups terminated at one end by an ester -
COOR group, and connected at the other end tc a methine
or quaternary carbon atom. The length of t::e branch is
defined as the number of consecutive methylene groups
from the ester group to the nearest methine or
10 quaternary carbon atom, but not including the methine
or quaternary carbon atom. If the number e~ methylene
groins is "n", then the length of the branc~ is n.
Thus -CH_CH~CH (CH~CH2CH~CH~CH (CHz) CH~COOR] CH,CH~CH2CH2-
contains 2 branches, a methyl and an n=1 es:.er branch.
l~ The -3C NMR peaks for.copolymers of cyclopentene
and ethylene are described based on the labeling scheme
and assignments of A. Jerschow et al, Macromolecules
1995, 28, 7095-7099. The triads and pentads are
described as 1-eme, 1,3-ccmcc, 1,3-cmc, 2-cme, 2-cmc,
20 i,3-eme,3-cme, and 4,5-cmc, where a = ethylene, c =
cyclopentene, and m = meta cyclopentene (i.e. 1,3
enchainment). The same labeling is used for
cyclopentene/1-pentene copolymer substituting p =
pentane for e. The synthesis of diimines is reported
in the literature (Tom Dieck, H.; Svoboda, M.; Grieser,
T. Z. Naturfcrsch 1981, 36b, 823-832. Klieaman, J. M.;
Barnes, R. K. J. Org. Chem. 1970, 35, 3140-3143.)
Exam l~
[(2,6-i-PrPh)2DABMe~]PdMeCl
30 Et20 (75 mL) was added to a Schlenk flask
containing CODPdMeCl (COD = 1,5-cyclooctadiene) (3.53
g, 13.3 mmol) and a slight excess of (2,6-i-
PrPh)2DABMe, (5.43 g, 13.4 mmol, 1.01 equiv). An
orange precipitate began to form immediately upon
3~ mixine. The reaction mixture was stirred overnight and
the Et20 and free COD were then removed via filtration.
The product was washed with an additional 25 mL of Et20
and then dried overnight in vacuo. A pale orange
143
SUBSTITUTE SHEET (RULE 26)

WO 96/23010 ~ 02338581 2001-03-O1 PCT/US96/01282
powder (7.18 g, 95.80) was isolated: '-H NMR (CD2Ci~,
400 MHz) b 7.4 - 7.2 (m, 6, Hary1), 3.06 (septet, 2, J -
6.81, CHMe2), 3.01 (septet, 2, J = 6.89, C'HMe~), 2.04
and 2.03 (N=C(Me)-C'(Me)=N), 1.40 (d, 6, J = 6.79,
C'HMeMe'), 1.36 (d, 6, J = 6.76, CHMeMe'), 1.19 (d, 6,
J = 6.83, CHMeMe'), 1.18 (d, 6, J = 6.87, C'HMeMe'),
0.36 (s, 3, PdMe); 13C NMR (CD2Clz, 400 MHz) b 175.0 and
17D.3 (N=C-C'=N), 142.3 and 142.1 (Ar, Ar': Cipso),
138.9 and 138.4 (Ar, Ar': Co), 128.0 and 127.1 (Ar,
10 Ar': Cp), 124.3 and 123.5 (Ar, Ar': Cm), 29.3 (CHMe2),
28.8 (C'HMe2), 23.9, 23.8, 23.5 and 23.3 (CHMeMe',
C'HMeMe'), 21.5 and 20.1 (N=C(Me)-C'(Me)=N), 5.0 (J~H =
135.0, PdMe).
14.~
sugsT~TUTE SHEET (RULE 26)

WO 96/23010 ~ 02338581 2001-03-O1 PCT/US9610I282
Exams
[(2,6-i-PrPh)zDABH2)PdMeCl
Following the procedure of Example 1, an orange
powder was isolated in 97.1% yield: 1H NMR (CDzCl2,
400 MHz) b 8.31 and 8.15 (s, 1 each, N=C(H)-C'(H)=N),
7.3 - 7.1 (m, 6, Hary1), 3.22 (septet, 2, J = 6.80,
CHMe2), 3.21 (septet, 2, J = 6.86, C'HMe2), 1.362,
1.356, 1.183 anti 1.178 (d, 6 each, J = 7.75 - 6.90;
CHMeMe', C'HMeMe'), 0.67 (s, 3, PdMe); 13C NMR
(CD2C12, 100 MHz) 8 164.5 (JcH = 179.0, N=C(H)), 160.6
(J~H = 178.0, N=C'(H)), 144.8 and 143.8 (Ar, Ar'
Cipso), 140.0 and 139.2 (Ar, Ar': Co), 128.6 and 127.7
(Ar, Ar': Cp), 124.0 and 123.4 (Ar, Ar': Cm), 29.1
(CHMe2), 28.6 (C'HMe2), 24.7, 24.1, 23.1 and 22.7
1 ~ , ~: HMeMe ' , C ' HMeMe ' ) , 3 . 0 ( JcH = 13 4 . 0 , PdMe ) . Ana 1 .
Calcd for (C2~H39C1N2Pd): C, 60.79; H, 7.37; N, 5.25.
Found: C, 60.63; H, 7.24; N, 5.25.
F-xamn 1~
[(2,6-MePh)zDABMe2]PdMeCl
-'0 Following the procedure of Example 1, a yellow
powder was isolated in 90.6a yield: 1H NMR (CD2C12,
400 MHz) b 7.3 - 6.9 (m, 6, Haryl), 2.22 (s, 6, Ar, Ar':
Me), 2.00 and 1.97 (N=C(Me)-C'(Me)=N), 0.25 (s, 3,
PdMe ) .
>>
[ (2, 6-MePh) zDABMez] PdMeCl
Following the procedure of Example 1, an orange
powder was isolated in 99.0% yield: 1H NMR (CD2C1-,,
400 MHz, 41 °C) b 8.29 and 8.14 (N=C(H)-C'(H)=N), 7.2 -
30 7.1 (m, 6, Haryl). 2.33 and 2.30 (s, 6 each, Ar, Ar'
Me) , 0.61 (s, 3, PdMe) ; 13C NMR (CD2C12, 100 MHz, 41
°C) 8 165.1 (Jcg = 179.2, N=C(H)), 161.0 (Jcg = 177.8
(N=C'(H)), 147.3 and 146.6 (Ar, Ar': Cipso). 129.5 and
128.8 (Ar, Ar': Co), 128.8 and 128.5 (Ar, Ar'~ Cm),
3~ i27.9 and 127.3 (Ar, Ar': Cp), 18.7 and 18.2 (Ar, Ar':
Me), 2.07 (JcH = 136.4, PdMe).
145
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WO 96/23010 ~ 02338581 2001-03-O1 pCT/US96/01282
Example 5
[4-MePh) 2DABMez] PdMeCl
Following the procedure of Example 1, a yellow
powder was isolated in 92.10 yield: 1H NMR (CD2C12,
400 MHz) S 7.29 (d, 2, J = 8.55, Ar: Hi"), 7.26 (d, 2, J
- 7.83, Ar': Hn,), 6.90 (d, 2, J = 8.24, Ar': Ho), 6.83
(d, 2, J = 8.34, Ar: Ho), 2.39 (s, 6, Ar, Ar': Me),
2.15 and 2.05 (s, 3 each, N=C(Me)-C'(Me)=N), 0.44 (s,
3, PdMe); 13C NMR (CD2C12, 100 MHz) 8 176.0 and 169.9
10- (N=C-C'=N) , 144.9 and 143.7 (Ar, Ar' : Cipso) , 137.0 and
136.9 (Ar, Ar': Cp), 130.0 and 129.3 (Ar, Ar': Cm),
122.0 and 121.5 (Ar, Ar': Co), 21.2 (N=C(Me)), 20.1
(Ar, Ar': Me), 19.8 (N=C'(Me)), 2.21 (J~g = 135.3,
PdMe). Anal. Calcd for (C19Ha3C1N2Pd): C, 54.17; H,
1~ 5.50; N, 6.65. Found: C, 54.41; H, 5.37; N, 6.69.
Exarn~le 6
[ (4-MePh) 2DABH~) PdMeCl
Following the procedure of Example 1, a burnt
orange powder was isolated in 90.5% yield: Anal. Calcd
20 for (C1~H19C1NZPd): C, 51.93; H, 4.87; N, 7.12. Found:
C, 51.36; H, 4.80; N, 6.82.
xa ale 7
({ [ (2, 6-i-PrPh) 2DABMe~) PdMe}2 (~-Cl) ~BAF'
Et20 (25 mL) was added to a mixture of [(2,6-i-
2~ PrPh)zDABMez]PdMeCl (0.81 g, 1.45 mmol) and 0.5 equiv
of NaBAF (0.64 g, 0.73 mmol) at room temperature. A
golden yellow solution and NaCl precipitate formed
immediately upon mixing. The reaction mixture was
stirred overnight and then filtered. After the EtzO
30 was removed in vacuo, the product was washed with 25 mL
of hexane. The yellow powder was then dissolved in 25
mL of CHzCl2 and the resulting solution was filtered in
order to removed traces of unreacted NaBAF. Removal of
CH2C12 in vacuo yielded a golden yellow powder (1.25 g,
j 88.20) : 1H NMR (CD2C12, 400 MHZ) S 7.73 (S, 8, BAF:
Ho) , 7.57 (s, 4; BAF: Hp) , 7.33 (t, 2, J = 7.57, Ar: ,
Hp), 7.27 (d, 4, J = 7.69, Ar: Ho), 7.18 (t, 2, J =
7.64, Ar: Hp), 7.10 (d, 4, J = 7.44, Ar': Ho), 2.88
146
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WO 96/23010 ~ 02338581 2001-03-O1 PCT/US96/01282
tseptet, 4, J - 6.80, CHMe2), 2.75 (septet, 4, J =
6 82, C'HMe2), 2.05 and 2.00 (s, 6 each, N=C(Me)-
C'(Me)=N), 1.22,
1.13, 1.08 and
1.01 (d, 12 each,
J =
6.61-6.99, CHMeMe',
C'HMeMe'), 0.41
(s, 6, PdMe); 13C
NMR (CD2C12, 10 0 MHz) 8 177.1 and 171.2 (N=C-C'=N),
162.2 (q, Jg~ = 49.8, BAF: Cipso), 141.4 and 141.0 (Ar,
Ar': Cipso), 138.8
and 138.1 (Ar,
Ar': Co), 135.2
(BAF:
Cp), 129.3 (q, J~F = 31.6, BAF: Cm), 128.6 and 127.8
(Ar, Ar': Cp), 125.0 (q, J~p = 272.5, BAF: CF3), 124.5
and 123 . 8 (Ar,Ar' : Cm) , 117 . 9 (BAF : Cp) , 29
. 3 ( CHMez ) ,
29.0 (C'HMe2), 23.8, 23.7, 23.6 and 23.0 (CHMeMe',
C'HMeMe'), 21.5 and 20.0 (N=C(Me)-C'(Me)=N), 9.8 (Jcx
=
136.0, PdMe) . Anal. Calcd for (C9pH98BC1F24N4Pd2)
: C,
55.41; H, 5.06; N, 2.87. Found: C, 55.83; H, 5.09; N,
I~ 2.63.
Examt~l_e 8
({ [ (2, 6-i-PrPh) ZDABHz] PdMe}2 (~-C1) )BAF-
The procedure of Example 7 was followed with one
exception, the removal of CH2C12 in vacuo yielded a
20 product that was partially an oil. Dissolving the
compound in Et20 and then removing the Et20 in vacuo
yielded a microcrystalline red solid (85.5%): 1H NMR
(CD2C12, 400 MHz) 8 8.20 and 8.09 (s, 2 each, N=C(H)-
C'(H)=N), 7.73 (s, 8, BAF: Ho), 7.57 (s, 4, BAF: Hp),
25 7.37 (t, 2, J = 7.73, Ar: Hp), 7.28 (d, 4, J = 7.44,
Ar: Hm), 7.24 (t, 2, Ar': Hp), 7.16 (d, 4, J = 7.19,
Ar': Hm), 3.04 (septet, 4, J = 6.80, CFIMe2), 2.93
(septet, 4, J = 6.80, C'HMe2), 1.26 (d, 12, J = 6.79,
CHMeMe'), 1.14 (d, 12, J = 6.83, CHMeMe'), 1.11 (d, 12,
30 J = 6.80, C'HMeMe'), 1.06 (d, 12, J = 6.79, C'HMeMe'),
0.74 (s, 6, PdMe); 13C NMR (CDZC12 , 100 MHz) b 166.0
(J~H = 180.4, N=C(H)), 161.9 (q, JeC = 49.6, BAF:
Cipso), 160.8 (Jcg = 179.9, N=C'(H)), 143.5 and 143.0
(Ar, Ar': Cipso), 139.8 and 138.9 (Ar, Ar': Co), 135.2
35 (BAF: Co), 129.3 (q, J~p = 31.4, BAF. Cn,), 129.3 and
128.5 (Ar, Ar': Cp), 125.0 (q, J~F = 272.4, BAF: CF3),
124.3 and 123.7 (Ar, Ar': Cm), 117.9 (BAF: Cp), 29.2
and 28.9 (CHMe2, C'HMe2), 24.5, 24.1, 23.0, and 22.5
147
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WO 96/23010 ~ 02338581 2001-03-O1 pCT/US96101282
(CHMeMe', C'HMeMe'), 10.3 (PdMe). Anal. Calcd for
(C86H9pBC1F24N4Pd2): C, 54.52; H, 4.97; N, 2.96.
Found: C, 54.97; H, 4.72; N, 2.71.
Example 9
5 Alternatively, the products of Examples 7 and 8
have been synthesized by stirring a 1:1 mixture of the
appropriate PdMeCl compound and NaBAF in Et20 for -1 h.
Removal of solvent yields the dimer + 0.5 equiv of
Na+(OEt2)2BAF-. Washing the product mixture with
10 hexane yields ether-free NaBAF, which is insoluble in
CH2C12. Addition of CH2C12 to the product mixture
and filtration of the solution yields salt-free dimer:
1H NMR spectral data are identical with that reported
above.
15 For a synthesis of CODPdMe2, see: Rudler-
Chauvin, M., and Rudler, H. J. Organomet. Chem. 1977,
134, 115-119.
Example 10
[(2,6-i-PrPh)ZDABMez]PdMe2
20 A Schlenk flask containing a mixture of [(2,6-i-
PrPh)2DABMe2]PdMeCl (2.00 g, 3.57 mmol) and 0.5 equiv
of Me2Mg (97.2 mg, 1.79 mmol) was cooled to -78 °C, and
the reaction mixture was then suspended in 165 mL of
Et20. The reaction mixture was allowed to warm to room
25 temperature and then stirred for 2 h, and the resulting
brown solution was then filtered twice. Cooling the
solution to -30 °C yielded brown single crystals (474.9
mg, 24.6%, 2 crops): 1H NMR (C6D6, 400 MHz) 8 7.2-7.1
(m, 6, Haryl) , 3.17 (septet, 4, J = 6.92, CI~Me2) , 1.39
30 (d, 12, J = 6.74, CHMeMe'), 1.20 (N=C(Me)-C(Me)=N),
1.03 (d, 12, J = 6.89, CHMeMe'), 0.51 (s, 6, PdMe); 13C
NMR (C6D6, 100 MHz) b 168.4 (N=C-C=N), 143.4 (Ar:
Cipso) ~ 138.0 (Ar: Co) , 126.5 (Ar: Cp) , 123.6 (Ar: Cn,) ,
28.8 (CHMe2), 23.6 and 23.5 (CHMeMe'), 19.5 (N=C(Me)-
35 C(Me)=N), -4.9 (JcH = 127.9, PdMe). Anal. Calcd for
(C3pHQ6N2Pd): C, 66.59; H, 8.57; N, 5.18. Found: C,
66.77; H, 8.62; N, 4.91.
148
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WO 96/23010 CA 02338581 2001-03-O1 PCT/US96I01282
Fxamgl_e
[(2,6-i-PrPh)2DABH2]PdMe2
The synthesis of this compound in a manner
analogous to Example 10, using 3.77 mmol of ArN=C(H)-
C(H)=NAr and 1.93 mmol of Me2Mg yielded 722.2 mg
(37.4%) of a deep brown microcrystalline powder upon
recrystallization of the product from a hexane/toluene
solvent mixture.
This compound was also synthesized by the
10 following method: A mixture of Pd(acac)2 (2.66 g, 8.72
mmol) and corresponding diimine (3.35 g, 8.90 mmol) was
suspended in 100 mL of Et20, stirred for 0.5 h at room
temperature, and then cooled to -78°C. A solution of
Me2Mg (0.499 g, 9.18 mmol) in 50 mL of Et20 was then
15 added via cannula to the cold reaction mixture. After
stirring for 10 min at -78°C, the yellow suspension was
allowed to warm to room temperature and stirred for an
additional hour. A second equivalent of the diimine
was then added to the reaction mixture and stirring was
20 continued for -4 days. The brown Et20 solution was
then filtered and the solvent was removed in vacuo to
yield a yellow-brown foam. The product was then
extracted with 75 mL of hexane, and the resulting
solution was filtered twice, concentrated, and cooled
25 to -30°C overnight to yield 1.43 g (32.0%) of brown
powder: 1H NMR (C6D6, 400 MHz) 8 7.40 (s, 2, N=C(H)-
C (H) =N) , 7.12 (s, 6, Ha~,l) , 3 .39 (septet, 4, J = 6 .86,
CHMe2), 1.30 (d, 12, J = 6.81, CHMeMe'), 1.07 (d, 12, J
- 6.91, CHMeMe'), 0.77 (s, 6, PdMe); 13C NMR (C6D6, 100
30 MHz) b 159. 9 (J~H = 174.5, N=C(H) -C(H) =N) , 145.7 (Ar:
Cipso) ~ 138.9 (Ar: Co) , 127.2 (Ar: Cp) , 123.4 (Ar: Cue) ,
28 . 5 ( CHMe2) , 24 .4 and 22,. 8 (CHMeMe' ) , -5. 1 (J~x =
128.3, PdMe). Anal. Calcd for (CzeH42N2Pd): C, 65.55,
H, 8.25; N, 5.46. Found: C, 65.14; H, 8.12; N, 5.14.
149
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WO 96/23010 ~ 02338581 2001-03-O1 PCT/US96/01282
Exams
[(2,6-MePh)2DABHz]PdMez
This compound was synthesized in a manner similar
to the second procedure of Example 11 (stirred for 5 h
5 at rt) using 5.13 mmol of the corresponding diimine and
2.57 mmol of Me2Mg. After the reaction mixture was
filtered, removal of Et20 in vacuo yielded 1.29 g
(62.2%) of a deep brown microcrystalline solid: 1H NMR
(C6D6, 100 MHz, 12°C) 8 6 . 98 (s, 2, N=C (H) -C (H) =N) ,
10 6. 95 (s, 6, Haz-},1) , 2.13 (s, 12, Ar: Me) , 0.77 (s, 6,
PdMe); 13C NMR (CsD6, 400 MHz, 12°C) b 160.8 (J~H =
174 . 6, N=C(H) -C(H) =N) , 147. 8 (Ar: Cipso) , 128.2 (Ar:
Cm) , 128.15 (Ar: Co) , 126.3 (Ar: Cp) , 18.2 (Ar: Me) , -
5.5 (J~H = 127.6, Pd-Me) .
15 Example 13
[(2,6-i-PrPh)2DABH2]NiMe2
The synthesis of this compound has been reported
(Svoboda, M.; tom Dieck, H. J. Organomet. Chem. 1980,
191, 321-328) and was modified as follows: A mixture
20 of Ni(acac)Z (1.89 g, 7.35 mmol) and the corresponding
diimine (2.83 g, 7.51 mmol) was suspended in 75 mL of
Et20 and the suspension was stirred for 1 h at room
temperature. After cooling the reaction mixture to -
78°C, a solution of Me2Mg (401 mg, 7.37 mmol) in 25 mL
2~ of Et20 was added via cannula. The reaction mixture
was stirred for 1 h at -78°C and then for 2 h at 0°C to
give a blue-green solution. After the solution was
filtered, the Et20 was removed in vacuo to give a blue-
green brittle foam. The product was then dissolved in
30 hexane and the resulting solution was filtered twice,
concentrated, and then cooled to -30°C to give 1.23 g
!35.90 , one crop) of small turquoise crystals.
Example 14
[ (2, 6-i-PrPh) 2DABMez] NiMe~
35 The synthesis of this compound has been reported
(Svoboda, M.; tom Dieck, H. J. Organomet. Chem. 1980,
191, 321-328) and was synthesized according to the
above modified procedure !Example 13) using Ni(acac)2
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SUBSTITUTE SHEET (RULE 26)

WO 96/23010 CA 02338581 2001-03-O1 PCT/US96/01282
X3.02 g, 11.75 mmol ) , the corresponding diilzt~'Ne T4.80
g, 11.85 mmol) and Me2Mg (640 mg, 11.77 mmol). A
turquoise powder was isolated (620 mg, 10.70).
Fxam~ 15
[ (2, 6-MePh) zDABMe2J PdMe (MeCN) ;BAF
To a mixture of [(2,6-MePh)zDABMe2]PdMeCl (109.5
mg, 0.244 mmol) and NaBAF (216.0 mg, 0.244 mmoll were
added 20 mL each of Et20 and CHZC12 and 1 mL of CH3CN.
The reaction mixture was then stirred for 1.5 h and
10 then. the NaCl was removed via filtration. Removal of
the solvent in vacuo yielded a yellow powder, which was
washed with 50 mL cf hexane. The product (269.6 mg,
83.80 was then dried in vacuo: 1H NMR (CD~C12, 400
MHz) c7 7.73 (s, 8, BAF: Ho), 7.57 (s, 4, BAF: Hp),
1~ % .22- ~ .16 (m, 6, Hary1) , 2..23 (s, 6, Ar: Me) , 2.17 (s,
6, Ar~: Me), 2.16, 2.14, and 1.79 (s, 3 each, N=C(Me)-
C'(Me)=N, NCMe), 0.38 (s, 3, PdMe); 13C NMR (CD2C12,
100 Mi-Iz) ~ 180.1 and 172.2 (N=C-C'=N) , 162.1 (q, JBC =
49.9, BAF: Cipso) , 142.9 (Ar, Ar' : Co) , 135.2 (BAF: Co) ,
20 129.3 (Ar: Cm), 129.2 (q, Jig = 30.6, BAF: Cm), 129.0
(Ar': Cm), 128.4 (Ar: Cp), 128.2 (Ar: Co), 127.7 (Ar':
Cp), 127.4 (Ar': Co), 125.0 (q, JCg = 272.4, BAF: CF3),
121.8 (NCMe), 117.9 (BAF: Cp), 20.2 and 19.2 (N=C(Me)-
C'(Me)=N), 18.0 (Ar: Me),17.9 (Ar'~ Me), 5.1 and 2.3
(NCMe, PdMe) . Anal. Calcd for (C55H42BF24N3Pd) : C,
50.12; H, 3.21; N, 3.19. Found: C, 50.13; H, _.13, N,
2.99.
Example 16
((4-MePh)~DABMe=]PdMe(MeCN)}BAF
30 Following the procedure of Example 15, a yellow
powder was isolated in 85o yield: 1H NMR (CD2C1~, 400
MHz) 8 7.81 (s, 8, BAF: Ho), 7.73 (s, 4, BAF: Hp), 7.30
(d, 4, J - 8.41, Ar, Ar': Hm), 6.89 (d, 2, J = 8.26,
Ar: Ho), 6.77 (d, 2, J = 8.19, Ar': Ho), 2.39 (s, 5,
3~ Ar, Ar': Me), 2.24, 2.17 and 1.93 (s, 3 each, N=C(Me)-
C'(Me)=N, NCMe)Pd-Me; 13C NMR (CDZC12, 100 MHz) ~ i80.7
and 171.6 (N=C-C'=N), 162.1 (q, Jgc = 49.8, BAF: Cipso),
143.4 and 142.9 (Ar, Ar': Cipso). 138.6 and 138.5 (Ar,
1~1
SUBSTITUTE SHEET (RULE 26)

WO 96/23010 ~ 02338581 2001-03-O1 p~'/11596/01282
-~r' : Cp) , 135.2 (BAF: Co) , 130.6 and 130.4 (Ar, Ar'
Cm) , 129.3 (q, J~F = 31.6, BAF: Cm) , 125.0 (q, J~F =
272.5, BAF: CF3), 122.1 (NCMe), 121.0 and 120.9 (Ar,
Ar': Co), 117.9 (BAF: Cp), 21.5 (ArN=C(Me)), 21.1 (Ar,
Ar': Me), 19.7 (ArN=C'(Me)), 6.2 and 3.0 (NCMe, PdMe).
Anal. Calcd for (C53H38BF24N3Pd): C, 49.34; H, 2.97: N,
3.26. Found: C, 49.55; H, 2.93; N, 3.10.
Example 17
[ (2, 6-MePh) 2DABMe~] PdMe (Et20J BAF
10 A Schlenk flask containing a mixture of ((2,6-i-
PrPh)~DABMez]PdMe2 (501 mg, 0.926 mmol) and
H+(OEt2)zBAF- (938 mg, 0.926 mmol) was cooled to -78°C.
Following the addition of 50 mL of Et20, the solution
was allowed to warm and stirred briefly (-.15 min) at
l~ room temperature. The solution was then filtered and
the solvent was removed in vacuo to give a pale orange
powder (1.28 g, 94.50), which was stored at -30°C under
an inert atmosphere: 1H NMR (CDZC12, 400 MHz, -60°C)
S 7.71 (s, 8, BAF: Ho), 7.58 (s, 4, BAF: Hp), 7.4 - 7.0
30 (m, 6, Haryl), 3.18 (q, 4, J = 7.10, O(CH2CH3)2), 2.86
(septet, 2, J = 6.65, CHMe2), 2.80 (septet, 2, J =
6.55, C'HMe2), 2.18 and 2.15 (N=C(Me)-C'(Me)=N), 1.34,
1.29, 1.14 and 1.13 (d, 6 each, J = 6.4-6.7, CHMeMe',
C ' HMeMe ' ) , 1 . 0 6 ( t , J = 6 . 9 , O (-CH2 CH3 ) 2 ) , 0 . 3 3 ( s , 3
,
PdMe); '-3C NMR (CD2C12, 100 MHz, -60°C) S 179.0 and
172.1 (N=C-C'=N) , 161.4 (q, Jg~ = 49.7, BAF: Cipso)
140.21 and 140.15 (Ar, Ar': Cipso), 137.7 and 137.4
(Ar, Ar': Co), 134.4 (BAF: Cp), 128.3 (q, J~F = 31.3,
BAF: Cm), 128.5 and 128.2 (Ar, Ar': Cp), 124.2 (q, J~F
30 - 272.4, BAF: CF3), 117.3 (BAF: Cp), 71.5 (O(CH2CH3)2),
28.7 (CHMe2), 28.4 (C'HMe2), 23.7, 23.6, 23.1 and 22.6
(CHMeMe', C'HMeMe'), 21.5 and 20.7 (N=C(Me)-C'(Me)=N),
14.2 (O(CHZCH3)2'~~, 8.6 (PdMe). Anal. Calcd for
(C65HE5BF24N20Pd): C, 53.35; H, 4.48; N, 1.91. Found:
3~ C, 53.01; H, 4.35; N, 1.68.
15?
~11R~TITI 1TF SHFFT (RULE 261

WO 96/23010 CA 02338581 2001-03-O1 PCT/US96I01282
Rxam~
[(2,6-MePh)zDABH~]PdMe(Et20)BAF
Following the procedure of Example 17, an orange
powder was synthesized in 94.3% yield and stored at -
30°C: 1H NMR (CD2C1~, 400 MHz, -60°C) cS 8.23 and 8.20
(s, i each, N=C(H)-C'(H)=N), 7.72 (s, 8, BAF: Ho), 7.54
(S, 4, BAF: Ho) , 7.40 - 7.27 (m, 6, Haryl) , 3.32 (q, 4,
J = 6.90, O(CH2CH3)2), 3.04 and 3.01 (septets, 2 each,
J = 6.9 - 7.1, CHMe2 and C'HMe2), 1.32, 1.318, 1.14 and
10 1.10 (d, 6 each, J = 6.5 - 6.8, CHMeMe' and C'HMeMe'),
1.21 (t, 6, J = 6.93, O(CHzCH3)Z) , 0.70 (s, 3, PdMe) ;
i3C NMR (CD2C12, 100 MHz, -60°C) b 166.9 (J~H = 182.6,
N= C ( H ) ) , 1 61 . 5 ( Jgc = 4 9 . 7 , BAF : Cipso ) , 161 . 3 ( Jcg =
181.6, N=C'(H)), 143.0 and 141.8 (Ar, Ar': Cipso),
1> 138.7 a:~d -x.37.8 (Ar, Ar' : ~o) , 134.4 (BAF: Co) , 129.1
and 128.8 (Ar, Ar': Cp), 128.3 (Jcg = 31.3, BAF: Cm),
124.0 and 123.9 (Ar, Ar': Cm), 117.3 (BAF: Cp), 72.0
(O(CH2CH3)~), 28.5 and 28.4 (CHMez, C'HMe2), 25.2, 24.1,
21 . 9 and 21 . 7 ( CHMeMe ' , C ' HMeMe ' ) , 15 . 2 ( O ( CH2 CH3 ) a ) ,
~0 11.4 (JcH = 137.8, PdMe) . Anal. Calcd for
(Cs3HsIBFz.~N20Pd): C, 52.72; H, 4.28; N, 1.95. Found:
C, 52.72; H, 4.26; N, 1.86.
Example 19
[ (2, 6-MePh) ~DABMe~) NiMe (Et,O) BAF
Following the procedure of Example 17, a magenta
powder was isolated and stored at -30°C: 1H NMR
(CD2C12, 400 MHz, -60°C; A H20 adduct and free Et20
were observed.) cS 7.73 (s, 8, BAF: Ho), 7.55 (s, 4,
BAF: Hp) , 7.4 - 7.2 (m, 6, Haryl) , 3.42 (s, 2, OH2) ,
30 3.22 (q, 4, O(CH2CH3)2), 3.14 and 3.11 (septets, 2
each, J = 7.1, CHMe2, C'HMe2), 1.95 and 1.78 (s, 3
each, N=C(Me)-C'(Me)=N), 1.42, 1.39, 1.18 and 1.11 (d,
6 each, "' - 6.6 - 6.9, CHMeMe' and C'HMeMe'), 0.93 (t,
J = 7.5, C(CH2CH3)2), -0.26 (s ,3, NiMe); 13C NMR
~~ (CD2C12 100 MHz, -58°C) 8 175.2 and 170.7 (N=C-C'=N),
161.6 (q, Jgc = 49.7, BAF: Cipso). 141.2 (Ar: Cinso).
139.16 and 138.68 (Ar, Ar': Co), 136.8 (Ar': Cipso)
134.5 (BAF: Co), 129.1 and 128.4 (Ar, Ar': Cp), 128.5
153
SUBSTITUTE SHEET (RULE 26)

WO 96/23010 ~ 02338581 2001-03-O1 p~/17596/01282
(q, Jcp = 32.4, BAF: Cm), 125.0 and 124.2 (Ar, Ar':
Cm), 124.3 (q, Jcg = 272.5, BAF: CF3), 117.4 (BAF: Cp),
66.0 (0(CHZCH3)2), 29.1 (CHMe2), 28.9 (C'HMe~i, 23.51,
23.45, 23.03, and 22.95 (CHMeMe', C'HMeMe'), 21.0 and
19 .2 (N=C (Me) -C' (Me) =N) , 14 . 2 (OCH2CH3) ~) , -0. 86 (JcH =
131.8, NiMe). Anal. Calcd for (Cs5Hs5BF24N2Ni0): C,
55.15; H, 4.63; N, 1.98. Found: C, 54.74; H, 4.53; N,
2.05.
Example 20
10 [-(2, 6-MePh) ZDABHZ] NiMe (Et~O) BAF
Following the procedure of Example 17, a purple
powder was obtained and stored at -30°C: 1H NMR
(CD2C12, 400 MHz, -80°C; H20 and Et20 adducts were
observed in an 80:20 ratio, respectively.) b 8.31 and
is 8.13 (s, 0.8 each, N=C(H)-.C'(H)=N; H20 Adduct), 8.18
and 8.00 (s, 0.2 each, N=C(H)-C'(H)=N; Et20 Adduct),
7.71 (s, 8 BAF: Co), 7.53 (s, 4, BAF: Cp), 7.5 - 7.0
(m, 6, Haryl) , 4.21 (s, 1.6, OH2) , 3.5 - 3.1 (m, 8,
O(CH2CH3)2, CHMe2, C'f~Ie2), 1.38, 1.37, 1.16 and 1.08
20 (d, 4.8 each, CHMeMe', C'HMeMe'; H20 Adduct; These
peaks overlap with and obscure the CHMe2 doublets of
the Ft20 adduct.), 0.27 (s, 2.4, PdMe; H20 Adduct),
0.12 (s, 0.6, PdMe: EtzO Adduct).
Examples 21-23
The rate of exchange of free and bound ethylene
was determined by 1H NMR line broadening experiments at
-85°C for complex (XI), see the Table below. The NMR
instrument was a 400 MHz Varian~ NMR spectrometer.
Samples were prepared according to the following
30 procedure: The palladium ether adducts {[(2,6-i-
PrPh) 2DABMe2] PdMe (OEtz) }BAF, { [ (2, 6-i-
PrPh)ZAn]PdMe(OEt2)}BAF, and ([(2,6-i-
PrPh)2DABH2]PdMe(OEt2)}BAF were used as precursors to
(XI), and were weighed (-15 mg) in a tared 5 mm dia.
NMR tube in a nitrogen-filled drybox. The tube was
then capped with a septum and Parafilm~ and cooled to
-80°C. Dry, degassed CD2C12 (700 ~L) was then added to
the palladium complex via gastight syringe, and the
i ~-1
citQCTITITTF SHFFT lRlILE 261

WO 96/23010 CA 02338581 2001-03-O1 PCTIUS96/01282
_ube was shaken and warmed briefly to giv~'a
homogeneous solution. After acquiring a -85°C NMR
spectrum, ethylene was added to the solution via
gastight syringe and a second NMR spectrum was acquired
~ at -85°C. The molarity of the BAF counterion was
calculated according to the moles of the ether adduct
placed in the NMR tube. The molarity of (XI) and free
ethylene were calculated using the BAF peaks as an
internal standard. Line-widths (w) were measured at
10 half-height in units of Hz for the complexes ethylene
signal (usually at 5 to 4 ppm) and were corrected for
line widths (wo) in the absence of exchange.
For (XI) the exchange rate was determined
from the standard equation for the slow exchana_e
1~ approximation:
k = (W - Wo) n/ f=) ,
where [_] is the molar concentration of ethylene.
These experiments were repeated twice and an average
value is reported below.
Rate Constants for Ethylene Exchanges
k
Ex. (XI) (L_M-ls-lv
21 ~[(2,6-i-PrPh)2DABMe2]PdMe(=)}BAF45
22 {[(2,6-i-PrPh)2An)PdMe(=)}BAF 5~0
23 ~[(2,6-i-PrPh)2DABH2]PdMe(=)~BAF 8100
aThe T1 of free ethylene is 15 sec. A pulse delay of 6o sec and a
30° pulse width were used.
Example 2424
Anhydrous FeCl2 (228 mg, 1.8 mmol) and (2,6-i-
PrPh)zDABAn (1.0 g, 2.0 mmol) were combined as solids
and dissolved in 40 ml of CHzCl2. The mixture was
°
stirred at 25 C for 4 hr. The resulting green scl;:tion
was removed from the unreacted FeCl~ via filter
cannula. The solvent was removed under reduced
I~
CI IR~TITI tTF ~HFFT fRl ILE 261

WO 96/23010 ~ 02338581 2001-03-O1 PCT/US96/01282
pressure resulting in a green solid (0.95 g, 84a
yield).
A portion of the green solid (40 mg) was
immediately transferred to another Schlenk flask and
dissolved in 50 ml of toluene under 1 atm of ethylene.
The solution was cooled to 0°C, and 6 ml of a loo MAO
solution in toluene was added. The resulting purple
solution was warmed to 25°C and stirred for 11 hr. The
polymerization was quenched and the polymer
10 precipitated by acetone. The resulting polymer was
washed with 6M HC1, water and acetone. SubseQUent
drying of the polymer resulted in 60 mg of white
polyethylene. 'H NMR (CDC13, 200 MHz) 81.25 (CHz, CH) S
0 . 85 (m, CH, ) .
1~ ample 25
(2-t-BuPh)2DABMe~
A Schlenk tube was charged with 2-t-butylaniline
(5.00 mL, 32.1 mmol) and 2,3-butanedione (1.35 mL, 15.4
mmol). Methanol (10 mL) and formic acid (1 mL) were
?0 added and a yellow precipitate began to form almost
immediately upon stirring. The reaction mixture was
allowed to stir overnight. -The resulting yellow solid
was collected via filtration and dried under vacuum.
The solid was dissolved in ether and dried over Na2S04
for 2-3 h. The ether solution was filtered, condensed
and placed into the freezer (-30°C). Yellow crystals
were isolated via filtration and dried under vacuum
overnight (4.60 g, 85.7e): 1H NMR (CDC13, 250 MHz) cS
7.41(dd, 2H, J = 7.7, 1.5 Hz, Hm), 7.19 (td, 2H, J= 7.5,
30 1.5 Hz, Hm or Hp),.7.07 (td, 2H, J = 7.6, 1.6 Hz, Hm or
Hp), 6.50 (dd, 2H, J = 7.7, 1.8 Hz, Ho), 2.19 (s, 6H,
N=C(Me)-C(Me)=N), 1.34 (s, 18H, C(CH3)3).
~nles 26 and 27
General Polymerization Procedure for Examples 26
3~ and 27: In the drybox, a glass insert was loaded with
[(r13-C3H5)Pd(~-C1)l2 (11 mg, 0.03 mmol), NaBAF (53 mg,
0.06 mmol), and an a-diimine ligand (0.05 mmol). The
insert was cooled to -35°C in the drybox freezer, 5 mL
156
et mcTt~ tTF SHFFT !RI ii F ?fl

WO 96/23010 ~ 02338581 2001-03-O1 PCT/US96/01282
~f C5D6 was added to the cold insert, and the insert
was then capped and sealed. Outside of the drybox, the
cold tube was placed under 6.9 MPa of ethylene and
allowed to warm to RT as it was shaken mechanically for
18 h. An aliquot of the solution was used to acquire a
1H NMR spectrum. The remaining portion was added to
-20 mL of MeOH in order to precipitate the polymer.
The polyethylene was isolated and dried under vacuum
Exam
a-Diimine was (2,6-i-PrPh)zDABMe~. Polyethylene
(50 mg) was isolated as a solid. 1H NMR spectrum
(C6D6) is consistent with the production of 1- and 2-
butenes and branched polyethylene.
Rxam 1~
u-Diimine was (2,6-i-PrPh)ZDABAn. Polyethylene
(17 mg) was isolated as a solid. 1H NMR spectrum
(C6D6) is consistent with the production of branched
polyethylene.
Examnl_e 28
[ ( 2 , 6 - i - PrPh ) 2DABH2 ] NiBr2
The corresponding diimine (980 mg, 2.61 mmol) was
dissolved in 10 mL of CH2C12 in a Schlenk tube under a
N~ atmosphere. This solution was added via cannula to
a suspension of (DME)NiBrz (DME = 1,2-dimethoxyethane)
(787 mg, 2.55 mmol) in CHZC12 (20 mL). The resulting
red/brown mixture was stirred for 20 hours. The
solvent was evaporated under reduced pressure resulting
in a red/brown solid. The product was washed with 3 x
10 mL of hexane and dried in vacuo. The product was
30 isolated as a red/brown powder (1.25 g, 82% yield).
Exams
[ (2, 6-i-PrPh) ZDABMe2] NiBrz
Using a procedure similar to that of Example 28,
500 ma (1.62 mmol) (DME)NiBrz and 687 mg (1.70 mmol) of
3~ the corresponding diimine were combined. The product
was isolated as an orange/brown powder (670 mg, 67%
yield).
157
R1IFIRTiTIITF SHFFT fRlil F ~Rl

WO 96123010 ~ 02338581 2001-03-O1
PCTIUS96101282
Example 30
[ (2, 6-MePh) zDABHz] NiBr
Using a procedure similar to that of Example 28,
500 mg (1.62 mmol) (DME)NiBr2 and 448 mg (1.70 mmol) of
the corresponding diimine were combined. The product
was isolated as a brown powder (622 mg, 80o yield).
Examx~le 31
[(2,6-i-PrPh)2DABAn]NiBr2
Using a procedure similar to that cf Example 28,
10 500 mg (1.62 mmol) (DME)NiBr2 and 850 mg (1.70 mmol) of
the corresponding diimine were combined. The product
was isolated as a red powder (998 mg, 86o yield).
Anal. Calcd. for C36H4oN2Br2Ni: C, 60.12; H, 5.61; N,
3.89. Found C, 59.88; H, 5.20; N, 3.52.
1~ Example 32
[(2,6-MePh)zDABAn]NiBr~
The corresponding diimine (1.92 g, 4.95 mmol) and
(DME)NiBr2 (1.5 g, 4.86 mmol) were combined as solids
in a flame dried Schlenk under an argon atmosphere. To
20 this mixture 30 mL of CH2C12 was added giving an orange
solution. The mixture was stirred for 18 hours
resulting in a red/brown suspension. The CHZC12 was
removed via filter cannula leaving a red/brown solid.
The Droduct was washed with 2 x 10 mL of CFi2Clz and
dried under vacuum. The product was obtained as a
~ed/~rown powder (2.5 g, 83% yield).
Example 33
[ (2, 6-MePh) 2DABMez] NiBr2
Using a procedure similar to that of Example 32,
30 the t=tle compound was made from 1.5 g (4.86 mmol)
(DME'NiBr2 and 1.45 g (4.95 mmol) of the corresponding
diimine. The product was obtained as a brown powder
(2.0~ a, 81o yield).
Rxam~ 34
3~ [(2,6-i-PrPh)~DABMe~]PdMeCl
(COD)PdMeCl (9.04 g, 34.1 mmol) was dissolved in
200 mi of methylene chloride. To this solution was
added. the corresponding diimine (13.79 g, 34.1 mmol).
1~8
m tacTt~ tTC c>aFFT IRI II F 261

V4'O 96123010 PCTlLiS96/01283
CA 02338581 2001-03-O1
.= __ r_s~a? ~i: so ~ idly c'.3. a _...
.g 1 ~.ticz rap_ r ~. °d co_c_ __
yellow to oranc~-red. rafter stir=_:~g at :oom
temperature fcr several hours it was corc_::tr3te.. to
orm a saturated scl~ation of the cesired product, and
:c_ed tc - _,;'C c~~e=- __. .~-L-: o=a. ~~ ...__..
crystallize3 from t'le SClut_on, and was isolated by
__._____..-., was'.~.ec w_t.. petrcleu;n et~», a::c ~__ed _..
a==C=C _2 . ~G g CL t~°_ tltl °_ COiTIDOI.::W aS au Cran=c
powder . Second a.~.~ third crops of crystals cbta:.~.e~
frcc. the mother liQUOr afforded ar ad;:itio::al 3.~2 c ~=
:'Oral V.eIC = 870.
_ ~~X2-'-, i ~ i ~ _ 7 c
ii
a.v_~~wlnC. ~,~;L.~~ui:.~..s were Il.alie a~.~~ G metTi.~..~
s:r-:____ tc t:.at used _.. ExamD~ a 3~ .
!~
Lxamc;e Comcound
3S [ (2, 5-i-Pr?h):D~:::) PdMeC'_
35 [ (2, 6-i-Pr?h) zDP~Anj P~'MeC_
37 [ (Ph) 2DABMJ:) ?dMeC=
?0 38 [(2,6-EtPh):DA3Me:)PdMeC;
39 [ (2, ~, 6-Me?'.~.) zD.~.3Me=J ?di~leC?
rote: '.'he dieti:vl ether complexes describe: =..
Exa-p_es 4i-~o are unstable in~ no:~-cocrdirating
S :W'C::_S S ::C.. as met~vle~e C~lOrlCe a: ,~. C;,~rrO~C=:.'..
mt.°~. Y=° ~ :aras.ter;Z°_(1 by j:: NMR S-
.~.°.~.t=a rc~CC'.rQeC _:u
C~~Cr:; under these conditio~s the aceto::itrile a~auct
cf t~e Pd methyl cation is formed. Typically, less
than a whole equivalent of free diethylether is
.i0 ..~=e= :-e-? i-~:. ':: NMR whe:: [ (R) 2DA5 (R' i 2) ?.''.Me (n~~ ~ ~: .s
.,
dissolved in CD3CN. Therefore, it is believed the
cc..,«lexes designated as " { [ (R) 2DAH (R' ) 2; PdM_ (OEt~ ) }X"
ce:ot~ a=a 1 _kel v mixt~a=es cf
l ~ ~ )' a ~')')p ° i W [( ~~r~~; W anr~v .
.. (.. dM_ (0= , ..t~) , X a..c =) ~D. .. ,_ .._. , a.~.c
3' ___ _~:~ ' a t te. : .~.LTI~.~..~ eXeS the X llga::'~ ( cE.rc D ~ y v_
P. ~i is weakly coorcinated to paLlaciu~;.. A forc;,.:_a of
the type " ( [ (R) 2DAB (R' ) z) PdMe (~Et2) }X" ' S a "formal"
way C_' CO::Ve;:~:lg the aOprOximate cverall COii:DOS:t=O:1 O'_.
1.9
SUBSTITUTE SHEET (RU! E 26)

CA 02338581 2001-03-O1
. . , .
this compound, but may not accurately depict the ea
coordination to the metal atom.
Listed below are the 13C NMR data for Example 36.
13C NMR data
Tcs, l2oc, a.osM cracac
i
frea ocm intens
' 46.5568 ty 1 cmp and/or 1,3 ccmcc
24.6005
44.9321 3.42517 1,3 cmc
40.8118 55.4341 2 pmp
40.3658 145.916 1,3 pmp
39.5693 18.458 methylenes from~~ cmp and/or 2 cmc
38.7782 4.16118
38.6295 5.84037
38.2844 8.43098
38.1198 8.29802
37.8384 3.83966
37.5198 13.4977
37.2384 23.4819
37.1163 16.8339
36.7446 114.983
36.0012 6.19217
35.7198 5.17495
34.2278 4.83958
32.9216 20.2781 386+, 3EOC
32.619 3.6086
32.4172 2.98497
32.1995 10.637
31.9765 42.2547
31.8809 143.871
30.4686 27.9974
30.3199 47.1951
30.022 36.1409
29.7411 102.51 -'
29.311 4.83244
28.7111 117.354 __
28.2597 9.05515
27.1659 22.5725
27.0067 5.81855
26.1146 13.5772
24.5642 2.59695 p~38
22.6368 12.726 2B5+, 2EOC
20.1413 3.7815 283
19.7271 20.0959 181
17.5236 7.01554 end group
14.2528 3.03535 1B3
13.8812 12.3535 184+, lEOC
Ex~~ls
[ (4-MezNPh) 2DABMe2] PdMe (MeCN) }SbF6~MeCN
160
AMENDED SHEET

WO 96/23010 CA 02338581 2001-03-O1 PCT'/US96/01282
A procedure analogous to that used in Example 54,
using (~-Me2NPh)2DABMe2 in place of (2-C6H4-tBu)2DABMe2,
afforded ~ [ (4-NMe2Ph) 2DABMe2] PdMe (MeCN) }SbF6~MeCN as a
purple solid (product was not recrystallized in this
instance). 1H NMR (CD2C12) 8 6.96 (d, 2H, Haryl). 6.75
(mutt, 6H, Haryl)~ 3.01 (s, 6H; NMe2), 2.98 (s, 6H,
NMe'2), 2.30, 2.18, 2.03, 1.96 (s's, 3H each, N=CMe,
N=CMe', and free and coordinated N--CMe), 0.49 (s, 3H,
Pd-Me).
~ Example 41
[ (2, 6-i-PrPh) ~DABMez] PdMe (Et~O) n}SbFS
[(2,6-i-PrPh)2DABMe2]PdMeCl (0.84 g, 1.49 mmol) was
suspended in 50 mL of diethylether and the mixture
cooled t:~ -40"C. To this was added AgSbF6 (0.52 g,
l~ 1.50 mmo-_:. The reaction mixture was allowed to warm
to room temperature, and stirred at room temperature
for 90 min. The reaction mixture was then filtered,
giving a pale yellow filtrate and a bright yellow
precipitate. The yellow precipitate was extracted with
?0 4 x 20 mL 50/50 methylene chloride/diethyl ether. The
filtrate and extracts were then combined with an
additional 30 mL diethyl ether. The resulting solution
was they. concentrated to half its original volume and
100 mL cf petroleum ether added. The resulting
precipitate was filtered off and dried, affording 1.04
a of the title compound as a yellow-orange powder (830
yield). =H NMR (CD3CN) 8 7.30 (mutt, 6H, Haryi), 3.37
[q, free O(CH~CH3)z], 3.05-2.90 (overlapping sept's,
4H, CHMe~), 2.20 (s, 3H, N=CMe), 2.19 (s, 3H, N=CMe'),
30 1.35-1.14 (overlapping d's, 24H, CHMe2), 1.08 (t, free
O(CH2CH;)~], 0.28 (s, 3H, Pd-Me). This material
contained 0.4 equiv of Et20 per Pd, as determined by 1H
NMR integration.
Exarrnle 42
3~ ~ [ (2 , 6-i-PrPh) 2DABMez] PdMe (EtzO) n~BF4
A procedure analogous to that used in Example 41,
using AaBF.~ in place of AgSbF6, afforded the title
compound as a mustard yellow powder in 61% yield. This
161
c~ iac~~n rrc ~HFFT rRULE 261

WO 96/23010 ~ 02338581 2001-03-O1 pC'f/US96/01282
material contained 0.3 equiv of Et20 per Pd, as
determined by 1H NMR integration. 1H NMR in CD3CN was
otherwise identical to that of the compound made in
Example 41.
5
Rxample x343
([(2,6-i-PrPh)zDABMe2]PdMe(Et20)n}PF6
A procedure analogous to that used in Example 41,
using AgPF6 in place of AgSbFs, afforded the title
10 compound as a yellow-orange powder in 72o yield. This
material contained 0.4 equiv of Et20 per Pd, as
determined by 1H NMR integration. 1H NMR in CD3CN was
identical to that of the compound of Example 41.
Example 4a
1~ {[(2,6-i-PrPh)zDABH~]PdMe(Et20)n}SbFS
A procedure analogous to that used in Example 41,
using [(2,6-i-PrPh)2DABH2]PdMeCl in place of [(2,6-i-
PrPh)ZDABMe2]PdMeCl, afforded the title compound in 710
yield. 1H NMR (CD3CN) 8 8.30 (s, 2H, N=CH and N=CH'),
20 7.30 (s, 6H, Haryi) , 3.37 [q, free O(CH2CH3)2] , 3.15
(br, 4H, Cl~le2) , 1.40-1.10 (br, 24H, CHMe2) , 1.08 (t,
free O(CH2CH3)2], 0.55 (s, 3H, Pd-Me). This material
contained 0.5 equiv of Et20 per Pd, as determined by 1H
NMR integration.
amble 45
[(2,4,6-MePh)ZDABMe2]PdMe(EtzO)r)SbF6
j(2,4,6-MePh)ZDABMe2]PdMeCl (0.50 g, 1.05 mmol)
was partially dissolved in 40 mL 50/50 methylene
chloride/diethylether. To this mixture at room
30 temperature was added AgSbF6 (0.36 g, 1.05 mmol). The
resulting reaction mixture was stirred at room
temperature for 45 min. It was then filtered, and the
filtrate concentrated in vacuo to afford an oily solid.
The latter was washed with diethyl ether and dried to
3~ afford the title compound as a beige powder. 1H NMR
(CD3CN) b 6.99 (s, 4H, Hary1) , 3.38 [q, free
O(CH2CH3)2], 2.30-2.00 (overlapping s's, 24H, N=CMe,
N=CMe' and aryl Me's), 1.08 (t, free O(CH2CH3)2], 0.15
16Z
e~ ~oe~Tmc cu~GT IRI II F ~R1

WO 96123010 CA 02338581 2001-03-O1 PCT/US96/01282
_.s, 3H, Pd-Me). This material contained~B:', equiv of
Et20 per Pd, as determined by 1H MR integration.
Example 46
( [ (2, 6-i-PrPh) 2DABAn] PdMe (Et20) n~SbF6
A procedure analogous to that used in Example 41,
using [(2,6-i-PrPh)ZDABAn]PdMeCl in place of [(2,6-i-
PrPh)2DABMe~]PdMeCl, afforded the title compound in 92%
yield. 1H NMR (CD3CN) 8 8.22 (br t, 2H, Haryl). 7.60-
7.42 (br mult, 8H, Haryl) , 6.93 (br d, 1H, Haryl) , 6.53
10 (br d, 1H, Haryl) , 3 .38 (q, free 0 (CH2CH3) 2] , 3 .30 (br
mult, 4H, CHMe2), 1.36 (br d, 6H, CHMe2), 1.32 (br d,
6H, CHMe2) , 1. 08 (t, free O (CHZCH3) 2] , 1.02 (br d, 6H,
CHMe2), 0.92 (br d, 6H, CHMe2), 0.68 (s, 3H, Pd-Me).
The amount of ether contained in the product could not
I~ be determined precisely by~lH NMR integration, due to
overlapping resonances.
Example 47
[ (2, 6-i-PrPh) 2DABMez] PdMe (OS02CF3)
A procedure analogous to that used in Example 41,
20 using AgOS02CF3 in place of AgSbFs, afforded the title
compound as a yellow-orange powder. '-H NMR in CD3CN
was identical to that of the title compound of Example
41, but without free ether resonances.
Example 48
[ ( 2 , 6 - i - PrPh ) 2DABMe2 ] PdMe ( MeCN ) ) SbF6
[(2,6-i-PrPh)2DABMe2]PdMeCl (0.40 g, 0.71 mmoii
was dissolved in 15 mL acetonitrile to give an orange
solution. To this was added AgSbF6 (0.25 g, 0.71 mmol)
at room temperature. AgCl immediately precipitated
30 from the resulting bright yellow reaction mixture. The
mixture was stirred at room temperature for 3 h. It
was then filtered and the AgCl precipitate extracted
with 5 mL of acetonitrile. The combined filtrate and
extract were concentrated to dryness affording a yellow
.~ solid. This was recrystallized from methylene
chloride/petroleum ether affording 0.43 g of the title
compound as a bright yellow powder (Yield = 75%). 1H
NMR (CDC13) S 7.35-7.24 (mult, 6H, Haryl). 2.91 (mult,
163
ci iac~iTt TTF ~NFFT 1R11LE 261

WO 96/23010 ~ 02338581 2001-03-O1 PCT/US96/01282
. 4H, CHMe2) , 2.29 (s, 3H, N=CMe) , 2.28 (s, 3'H; ~=CMS") , _ _ _
1.81 (s, 3H, N=CMe), 1.37-1.19 (overlapping d's, 24H,
CHMe's), 0.40 (s, 3H, Pd-Me). This compound can also
be prepared by addition of acetonitrile to {[(2,6-i-
PrPh ) 2DABMe2 ) PdMe ( Et~O ) ~ SbF6 .
Example 49
[ (Ph) 2DABMe2] PdMe (MeCN) )SbF6
A procedure analogous to that used in Example 48,
using [(Ph)ZDABMe2)PdMeCl in place of [(2,6-1-
10 PrPh)2DABMe2]PdMeCl, afforded the title compound as a
yellow microcrystalline solid upon recrystallization
from methylene chloride / petroleum ether. This
complex crystallizes as the acetonitrile solvate from
acetonitrile solution at -40°C. 1H NMR of material
l~ recrystallized from methylene chloride/petroleum ether:
(CDC13) ~ 7.46 (molt, 4H, Haryl). 7.30 (t, 2H, Haryl)~
7.12 (d, 2H, Haryl), 7.00 (d, 2H, Haryl), 2.31 (s, 3H,
N=CMe), 2.25 (s, 3H, N=CMe'), 1.93 (s, 3H, N=CMe), 0.43
(s, 3H, Pd-Me) .
20 Example 50
{ [ (2, 6-EtPh) zDABMe2] PdMe (MeCN) ~BAF
[(2,6-EtPh)ZDABMe2JPdMeCl (0.200 g, 0.396 mmol)
was dissolved in l0 mL of acetonitrile to give an
orange solution. To this was added NaBAF (0.350 g,
0.396 mmol). The reaction mixture turned bright yellow
and NaCi precipitated. The reaction mixture was
stirred at room temperature for 30 min and then
filtered through a Celite~ pad. The Celite~ pad was
extracted with 5 mL of acetonitrile. The combined
30 filtrate and extract was concentrated in vacuo to
afford an orange solid, recrystallization of which from
methylene chloride / petroleum ether at -40°C afforded
0.403 g of the title compound as orange crystals (Yield
- 74 0) . 1H NMR (CDC13) b 7.68 (s, 8H, Hortho of anion) ,
35 7.51 (s, 4H, Hpara of anion), 7.33-7.19 (mult, 6H, Haryl
of cation), 2.56-2.33 (mult, 8H, CHZCH3), 2.11 (s, 3H, .
N=CMe), 2.09 (s, 3H, N=CMe'), 1.71 (s, 3H, N=CMe),
1.27-1.22 (mutt, 12H, CH2CH3), 0.41 (s, 3H, Pd-Me).
164
~~ iRSTITIITE SHEET (RULE 26)

WO 96123010 CA 02338581 2001-03-O1 PCT/US96/01282
Exam~le 5~
[ (2, 6-EtPh) ZDABMe~] PdMe (MeCN) ~SbFE
A procedure analogous to that used in Example 50,
using AgSbF6 in place of NaBAF, afforded the title
compound as yellow crystals in 99o yield after
recrystailization from methylene chloride/petroleum
ether at -40°C.
Examp~e 52
[ ( COD ) PdMe ( NCMe ) ] SbF6
10 To (COD)PdMeCl (1.25 g, 4.70 mmol) was added a
solution of acetonitrile (1.93 g, 47.0 mmol) in 20 mL
methylene chloride. To this clear solution was added
AgSbF6 (1.62 g, 4.70 mmol). A white solid immediately
precipitated. The reaction mixture was stirred at room
1~ temperature for 45 min, and then filtered. The yellow
filtrate was concentrated to dryness, affording a
yellow solid. This was washed with ether and dried,
affording 2.27 g of ((COD)PdMe(NCMe)]SbF6 as a light
yellow powder (yield = 950). iH NMR (CD2C12) cS 5.84
20 (mult, 2H, CH=CH), 5.42 (mutt, 2H, CH'=CH'), 2.65
(mult, 4H, CHH'), 2.51 (mult, 4H, CHH'), 2.37 (s, 3H,
NCMe), 1.18 (s, 3H, Pd-Me).
$xample 53
[(COD)PdMe(NCMe)]BAF
A procedure analogous to that used in Example
52, using NaBAF in place of AgSbF6, afforded the title
compound as a light beige powder in 96% yield.
16~
c1 ICICT1T11T~ CNFFT f RULE 26)

WO 96123010 ~ 02338581 2001-03-O1 pCT/US96/01282
~'xam~le 54
[ (2-t-BuPh) 2DABMe2] PdMe (MeCN) ]SbFS
To a suspension of (2-t-BuPh)2DABMe2 (0.138 g,
0.395 mmol) in 10 mL of acetonitrile was added
[(COD)PdMe(NCMe)]SbF6 (0.200 g, 0.395 mmoi). The
resulting yellow solution was stirred at room
temperature for S min. It was then extracted with 3 x
10 mL of petroleum ether. The yellow acetonitrile
phase was concentrated to dryness, affording a bright
10 yellow powder. Recrystallization from methylene
chloride/petroleum ether at -40 °C afforded 180 mg of
the title product as a bright yellow powder (yield =
61 0 ) . 1H NMR (CD2C12) b 7.57 (dd, 2H, Haryl) , 7.32
(mutt, 4H, Haryl). 6.88 (dd, 2H, Haryl), 6.78 (dd, 2H,
Harv1), 2.28 (s, 3H, N=CMe), 2.22 (s, 3H, N=CMe'), 1.78
(s, 3H, N=CMe), 1.48 (s, 18H, tBu), 0.52 (s, 3H, Pd-
Me ) .
Example 55
~ [ (Np) ~DABMe2] PdMe (MeCN) } SbF6
20 A procedure analogous to that used in Example 54,
using (Np)~DABMe2 in place of (2-t-BuPh)~DABMe2,
afforded the title compound as an orange powder 520
in
yield after two recrystallizations from methylene
chlcride/petroleum ether. 1H NMR (CD2C12) c~ 8.20-7.19
(molt, 14 H, Haromatic) , 2.36 (d, J = 4.3 Hz,
3H,
N=CMe), 2.22 (d, J = 1.4 Hz, 3H, N=CMe'), i.32 3H,
(s,
NCMe), 0.22 (s, 3H, Pd-Me).
l
56
e
Examp
[ (PhzCH) zDABH~] PdMe (MeCN) }SbFs
30 A procedure analogous to that used in Example 54,
using (Ph~CH)2DABH2 in place of (2-t-BuPh)2DABMe2,
afforded the title compound as a yellow
r~,icrccrystalline solid. =H NMR (CDC13) 8 7.69 1H,
(s,
N=CH), 7.65 (s, 1H, N=CH'), 7.44-7.08 (muit, 20H,
Haryl). 6.35 (2, 2H, CHPh2), 1.89 (s, 3H, NCMe), 78
0.
(s, 3H, Pd-Me). ,
166
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WO 96123010 CA 02338581 2001-03-O1 PCT/US96/01282
Examrl_e 5757
[ (2-PhPh) 2DABMe~] PdMe (MeCN) )SbF6
A procedure analogous to that used in Example 54,
using (2-PhPh)2DABMe2 in place of (2-t-BuPh)2DABMe2,
afforded the title compound as a yellow-orange powder~
in 90o yield. Two isomers, due to cis or trans
orientations of the two ortho phenyl groups on either
side of the square plane, were observed by 1H NMR. 1H
NMR (CD2C12) cS 7.80-5.82 (mult, 18H, Haryl). 1.98, 1.96,
10 1.90, 1.83, 1.77, 1.73 (singlets, 9H, N=CMe, N=CMe',
NCMe for cis and trans isomers), 0.63, 0.61 (singlets,
3H, Pd-Me for cis and trans isomers).
Example 58
{[(Ph)DAB(cycio-CMe~CHzCMez-)]PdMe(MeCN)}BAF
l~ To a solution of [(COD)PdMe(NCMe)]BAF (0.305 g,
0.269 mmol) dissolved in 15 mL of acetonitrile was
added N,N'-diphenyl-2,2',4,4'-tetramethyl-
cyclopentyldiazine (0.082 g, 0.269 mmol). A gold
colored solution formed rapidly and was stirred at room
20 temperature for 20 min. The solution was then
extracted with 4 x 5 mL petroleum ether, and the
acetonitrile phase concentrated to dryness to afford a
yellow powder. This was recrystallized from methylene
chloride/petroleum ether at -40°C to afford 0.323 g
2~ (90%) of the title compound as a yellow-orange,
crystalline solid. 1H NMR (CDC13) 8 7.71 (s, 8H, Hortho
of anion), 7.54 (s, 4H, Hpara of anion), 7.45-6.95
(mult, lOH, Haryl of cation), 1.99 (s, 2H, CH2), 1.73
(s, 3H, NCMe) , 1.15 (s, 6H, Me2) , 1.09 (s, 6H, Me'2) ,
30 0.48 (s, 3H, Pd-Me).
Exanlnle 59
{[(2,6-i-PrPh)2DABMe2]Pd(CH2CHzCH2C02Me)}SbF6
Under a nitrogen atmosphere ~[(2,6-i-
PrPh)~DABMe,]PdMe(Et,O)}SbFE (3.60 g, 4.30 mmol) was
3~ weighed into a round bottom flask containing a magnetic
stirbar. To this was added a -40°C solution of methyl
acrylate (1.85 g, 21.5 mmol) dissolved in 100 ml of
methylene chloride. The resulting orange solution was
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WO 96123010 ~ 02338581 2001-03-O1 PCTIUS96/01282
stirred for 10 min, while being allowed to warm to room
temperature. The reaction mixture was then
concentrated to dryness, affording a yellow-brown
solid. The crude product was extracted with methylene
chloride, and the orange-red extract concentrated,
layered with an equal volume of petroleum ether, and
cooled to -40°C. This afforded 1.92 g of the title
compound as yellow-orange crystals. An additional 1.39
g was obtained as a second crop from the mother liquor;
10 total yield = 910. 1H NMR (CD2C12) 8 7.39-7.27 (mult,
6H, Hary1), 3.02 (s, 3H, OMe), 2.97 (sept, 4H, CHMe2),
2.40 (mule, 2H, CH2), 2.24 (s, 3H, N=CMe), 2.22 (s, 3H,
N=CMe'), 1.40-1.20 (mult, 26H, CHMe2 and CH2'), 0.64
(mult, 2H, CHZ" ) .
1~ Example 60
([(2,6-i-PrPh)2DABH2)Pd(CH2CHZCHzCOZMe)}SbF6
AgSbFs (0.168 g, 0.489 mmol) was added to a -40°C
solution of {[(2,6-i-PrPh)2DABH2)PdMeCl (0.260 g, 0.487
mmol) and methyl acrylate (0.210 g, 2.44 mmol) in 10 mL
'?0 methylene chloride. The reaction mixture was stirred
for 1 h while warming to room temperature, and then
filtered. The filtrate was concentrated in vacuo to
give a saturated solution of the title compound, which
was then layered with an equal volume of petroleum
ether and cooled to -40°C. Red-orange crystals
precipitated from the solution. These were separated
by filtration and dried, affording 0.271 g of the title
compound (68% yield). 1H NMR (CD2C12) 8 8.38 (s, 1H,
N=CH), 8.31 (s, 1H, N=CH'), 7.41-7.24 (mult, 6H,
30 Hary1), 3.16 (mult, 7H, OMe and CHMe2), 2.48 (mult, 2H,
CHz), 1.65 (t, 2H, CH2'), 1.40-1.20 (mult, 24H, CHMe2),
0.72 (mult, 2H, CH2" ) .
Example 61
{[(2,6-i
3~ PrPh) ZDABMe2) Pd (CHZCH2CH2C02Me) ) [B (C6F5) 3C1)
[(2,6-i-PrPh)2DABMe2]PdMeCl (0.038 g, 0.067 mmol)
and methyl acrylate (0.028 g, 0.33 mmol) were dissolved
in CD2C12. To this solution was added B(C6F5)3 (0.036
168
suBSTmITE SHEET (RULE 26)

WO 96/23010 CA 02338581 2001-03-O1 PCT/US96/01282
g, 0.070 mmol). 1H NMR of the resulting reaction
mixture showed formation of the title compound.
Example 62
A 100 mL autoclave was charged with chloroform (50
~ mL), {[(2-t-BuPh)2DABMe2]PdMe(NCMe)}SbF6- (0.090 g, 0.12
mmol), and ethylene (2.1 MPa). The reaction mixture
was stirred at 25°C and 2.1 MPa ethylene for 3 h. The
ethylene pressure was then vented and volatiles removed
from the reaction mixture in vacuo to afford 2.695 g of
10 branched polyethylene. The number average molecular
weight (Mn), calculated by 1H NMR integration of
aliphatic vs. olefinic resonances, was 1600. The
degree of polymerization, DP, was calculated on the
basis of the 1H NMR spectrum to be 59; for a linear
I~ polymer this would result .in 18 methyl-ended branches
per 1000 methylenes. However, based on the iH NMR
spectrum the number of methyl-ended branches per LOGO
methylenes was calculated to be 154. Therefore, it may
be concluded that this material was branched
?0 polyethylene. 1H NMR (CDC13) 8 5.38 (mult, vinyl H's),
1.95 (mult, allylic methylenes), 1.62 (mult, allylic
methyls), 1.24 (mutt, non-allylic methylenes and
methines), 0.85 (mult, non-allylic methyls).
Example 63
A suspension of {[(2-t-
BuPh)2DABMe2]PdMe(NCMe)}SbF6 (0.015 g, 0.02 mmol) in 5
mL FC-75 was agitated under 2.8 MPa of ethylene for 30
min. The pressure was then increased to 4.1 MPa and
maintained at this pressure for 3 h. During this time
30 the reaction temperature varied between 25 and 40°C. A
viscous oil was isolated from the reaction mixture by
decanting off the FC-75 and dried in vacuo. The
number average molecular weight (Mn), calculated by 1H
NMR integration of aliphatic vs. olefinic resonances,
3~ was 2600. DP for this material was calculated on the
basis of the 1H NMR spectrum to be 95; for a linear
polymer this would result in 11 methyl-ended branches
per 1000 methylenes. However, based on the 1H NMR
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WO 96/23010 ~ 02338581 2001-03-O1
PCT/US96/01281
,spectrum the number of methyl-ended branches per 1000
methylenes was calculated to be 177.
Example 64 '
A 100 mL autoclave was charged with chloroform (55
mL), (((2-PhPh)2DABMe2]PdMe(NCMe)}SbF6 (0.094 g, 0.12
mmol), and ethylene (2.1 MPa). The reaction mixture
was stirred at 25°C and 2.1 MPa ethylene for 3 h. The
ethylene pressure was then vented and volatiles removed
from the reaction mixture in vacuo to afford 2.27 g of
10 a pale yellow oil. Mn was calculated on the basis of
1H NMR integration of aliphatic vs. olefinic resonances
to be 200. The degree of polymerization, DP, was
calculated on the basis of the 1H NMR spectrum to be
7.2; for a linear polymer this would result in 200
1~ methyl-enaed branches per .1000 methylenes. However,
based on the 1H NMR spectrum the number of methyl-ended
branches per 1000 methylenes was calculated to be 283.
Exan~nle 65
A suspension of [(2-PhPh)2DABMe2]PdMe(NCMe)}SbF6
20 (0.016 g, 0.02 mmol) in 5 mL FC-75 was agitated under
1.4 MPa of ethylene for 3 h 40 min. During this time
the reaction temperature varied between 23 and 41°C. A
viscous oil (329 mg) was isolated from the reaction
mixture by decanting off the FC-75 and dried in vacuo.
Mn was calculated on the basis of 1H NMR integration of
aliphatic vs. olefinic resonances to be 700. The degree
of polymerization, DP, was calculated on the basis of
the 1H NMR spectrum to be 24.1; for a linear polymer
this would result in 45 methyl-ended branches per 1000
30 methylenes. However, based on the 1H NMR spectrum the
number of methyl-ended branches per 1000 methylenes was
calculated to be 173.
ample 66
A 100 mL autoclave was charged with FC-75 (50 mL),
3~ t(Ph2DABMe2)PdMe(NCMe)}SbF6 (0.076 g, 0.12 mmol) and
ethylene (2.1 MPa). The reaction mixture was stirred
at 24°C for 1.5 h. The ethylene pressure was then
vented, and the FC-75 mixture removed from the reactor.
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c~ mc~t~ tT~ ~HFFT IRI II E 261

WO 96123010 CA 02338581 2001-03-O1 P~~1S96/01282
small amount of insoluble oil was isolated fro~mtl~e
mixture by decanting off the FC-75. The reactor was
washed out with 2 x 50 mL CHC13, and the washings added
to the oil. Volatiles removed, from the resulting
solution in vacuo to afford 144 mg of an oily solid.
Mn was calculated on the basis of 1H NMR integration of
aliphatic vs. olefinic resonances to be 400. The
degree of polymerization, DP, was calculated or. the
basis of the 1H NMR spectrum to be I3.8; for a linear
polymer this would result in 83 methyl-ended branches
per 1000 methylenes. However, based on the iH NMR
spectrum the number of methyl-ended branches per 1000
methylenes was calculated to be 288.
Examnie 67
1~ A 100 mL autoclave was charged with chlercfe~m (50
mL), {[(2,6-EtPh)2DABMe2]PdMe(NCMe)}BAF (0.165 Q, O.i2
mmol), and ethylene (2.1 MPa). The reaction mixture
was stirred under 2.1 MPa of ethylene for 60 min;
during this time the temperature inside the reactcr
increased from 22 to 48°C. The ethylene pressure was
then vented and volatiles removed from the reaction
mixture in vacuo to afford 15.95 g of a viscous oil.
1H NMR of this material showed it to be branched
polyethylene with 135 methyl-ended branches per 1000
methylenes. GPC analysis in trichlorobenzene (vs. a
linear polyethylene standard) gave Mn = 10,400,
22,100.
~~le 68
This was run identically to Example 67, but with
{[(2,6-EtPh)2DABMez]PdMe(NCMe)}SbF6 (0.090 g, 0.12
mmol) in place of the corresponding BAF salt. The
temperature of the reaction increased from 23 to 30°C
during the course of the reaction. 5.25 g of a ~~iscous
oil was isolated, 1H NMR of which showed it to be
3~ branched polyethylene with 119 methyl-ended branches
per 1000 methylenes.
171
SUBSTITUTE SHEET (RULE 26)

WO 96/23010 ~ 02338581 2001-03-O1 PCT/US96/01282
Example 69
A suspension of ~[(Np)2DABMe2]PdMe(NCMe)}SbF6
(0.027 g, 0.02 mmol) in 5 mL FC-75 was agitated under '
1.4 MPa of ethylene for 3 h; during this time the
temperature inside the reactor varied between 25 and
40°C. Two FC-75 insoluble fractions were isolated from
the reaction mixture. One fraction, a non-viscous oil
floating on top of the FC-75, was removed by pipette
and shown by 1H NMR to be branched ethylene oligomers
10 for which Mn = 150 and with 504 methyl-ended branches
per 1000 methylenes. The other fraction was a viscous
oil isolated by removing FC-75 by pipette; it was shown
by 1H NMR to be polyethylene for which Mn = 650 and
with 240 methyl-ended branches per 1000 methylenes.
1~ Example 70
A suspension of {[(PhzCH)ZDABHZ)PdMe(NCMe)}SbF6
(0.016 g, 0.02 mmol) in 5 mL FC-75 was agitated under
1.4 MPa of ethylene for 3 h 40 min. During this time
the reaction temperature varied between 23 and 41°C. A
?0 viscous oil (43 mg) was isolated from the reaction
mixture by decanting off the FC-75 and dried in vacuo.
Mn was calculated on the basis of 1H NMR integration of
aliphatic vs. olefinic resonances to be approximately
2000. The degree of polymerization, DP, was calculated
on the basis of the 1H NMR spectrum to be 73; for a
linear polymer this would result in 14 methyl-ended
branches per 1000 methylenes. However, based on the 1H
NMR spectrum the number of methyl-ended branches per
1000 methylenes was calculated to be 377.
30 Example 71
A 100 mL autoclave was charged with FC-75 (50 mL),
~(Ph2DAB(cyclo -CMezCH2CMe2-))PdMe(MeCN))BAF (0.160 g,
0.12 mmol) and ethylene (2.1 MPa). The reaction
mixture was stirred at 24-25°C for 3.5 h. The ethylene
pressure was then vented, and the cloudy FC-75 mixture
removed from the reactor. The FC-75 mixture was '
extracted with chloroform, and the chloroform extract
concentrated to dryness affording 0.98 g of an oil. Mn
172
SUBSTfTU?E SHEET (RULE 26)

WO 96123010 ~ 02338581 2001-03-O1 pCT'1US96101282
aas calculated on the basis of 1H NMR integration of
aliphatic vs. olefinic resonances to be 500. The
degree of polymerization, DP, was calculated on the
basis of the 1H NMR spectrum to be 19.5; for a linear
polymer this would result in 57 methyl-ended branches
per 1000 methylenes. However, based on the 1H NMR
spectrum the number of methyl-ended branches per 1000
methylenes was calculated to be 452.
Example 72
A 100 mL autoclave was charged with FC-75 (50 mL),
[ (4-NMe,Ph) 2DABMe2] PdMe (MeCN) )SbF6 (MeCN) (0. 091 g,
0.12 mmol) and ethylene (2.1 MPa). The reaction
mixture was stirred at 24°C for 1.5 h. The ethylene
pressure was then vented, and the cloudy FC-75 mixture
1~ removed from the reactor. The FC-75 was extracted with
3 x 25 mL of chloroform. The reactor was washed out
with 3 x 40 mL CHC13, and the washings added to the
extracts. Volatiles removed from the resulting
solution in vacuo to afford 556 mg of an oil. Mn was
calculated on the basis of 1H NMR integration of
aliphatic vs. olefinic resonances to be 200. The
degree of polymerization, DP, was calculated on the
basis cf the 1H NMR spectrum to be 8.4; for a linear
polymer this would result in 154 methyl-ended branches
per 1000 methylenes. However, based on the 1H NMR
spectrum the number of methyl-ended branches per 1000
methylenes was calculated to be 261.
Example 73
Under nitrogen, a 250 mL Schlenk flask was charged
with '_0.0 g of the monomer CH2=CHCOZCH2CH2(CFz)nCF3 (avg
n = 9), 40 mL of methylene chloride, and a magnetic
stirbar. To the rapidly stirred solution was added
[(2,5-i-PrPh)2DABMe2]PdMe(OEt2)}SbFE (0.075 g, 0.089
mmol) in small portions. The resulting yellow-orange
3~ solution was stirred under 1 atm of ethylene for 18 h.
The reaction mixture was then concentrated, and the
viscous product extracted with - 300 mL of petroleum
ether. The yellow filtrate was concentrated to
173
m ~ee~T rrr cuCCT IRI II F 9R1

WO 96123010 ~ 02338581 2001-03-O1 p~'~S96/01282
3ryness, and extracted a second time with - 15D mL
petroleum ether. -. 500 mL of methanol was added to the
filtrate; the copolymer precipitated as an oil which
adhered to the sides of the flask, and was isolated by
decanting off the petroleum ether/ methanol mixture.
The copolymer was dried, affording 1.33 g of a slightly
viscous oil. Upon standing for several hours, an
additional 0.70 g of copolymer precipitated from the
petroleum ether/ methanol mixture. By 1H NMR
integration, it was determined that the acrylate
content of this material was 4.2 mole%, and that it
contained 26 ester and 87 methyl-ended branches per
1000 methylenes. GPC analysis in tetrahydrofuran (vs.
a PMMA standard) gave Mn = 30,400, MW = 40,200. 1H NMR.
l~ (CDC13) d 4.36 (t, CH2CH2C02CH2CH2Rg) , 2.45 (mult,
CH~CHzC02CH2CH2Rf), 2.31 (t, CH2CH2C02CH~CH2Rg), 1.62
(mult, CH2CH2C02CH2CHZRfi, 1.23 (mult, other methylenes
and methines), 0.85 (mult, methyls). 13C NMR gave
branching per 1000 CH2: Total methyls (91.3), Methyl
;32.8), Ethyl(20), Propyl (2.2), Butyl (7.7), Amyl
(2.2), >_Hex and end of chains (22.1). GPC analysis in
THF gave Mn = 30,400, Mw = 40,200 vs. PMMA.
Example 74
A 100 mL autoclave was charged with
~Pd(CH3CH2CN)4](BF4)2 (0.058 g, 0.12 mmol) and
chloroform (40 mL). To this was added a solution of
;2,6-i-PrPh)zDABMe2 (0.070 g, 0.17 mmol) dissolved in
.0 mL of chloroform under ethylene pressure (2.1 MPa).
The pressure was maintained at 2.1 MPa for 1.5 h,
during which time the temperature inside the reactor
increased from 22 to 35°C. The ethylene pressure was
then vented and the reaction mixture removed from the
reactor. The reactor was washed with 3 x 50 mL of
chloroform, the washings added to the reaction mixture,
3~ and volatiles removed from the resulting solution in
vacuo to afford 9.77 g of a viscous oil. 1H NMR of
this material showed it to be branched polyethylene
with 96 methyl-ended branches per 1000 methylenes.
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WO 96/23010 CA 02338581 2001-03-O1 PCT/US96/01282
Fxam~le 75
A 100 mL autoclave was charcred with
[Pd(CH3CN)4~(BF4)2 (0.053 g, 0.12 mmol) and chloroform
(50 mL). To this was added a solution of (2,6-i-
PrPh)2DABMe2 (0.070 a, 0.17 mmol) dissolved in 10 mL of
chloroform under ethylene pressure (2.1 MPa). The
pressure was maintained at 2.1 MPa for 3.0 h, during
which time the temperature inside the reactor increased
from 23 to 52°C. The ethylene pressure was then vented
10- and the reaction mixture removed from the reactor. The
reactor was washed with 3 x 50 mL of chloroform, the
washings added to the reaction mixture, and volatiles
removed from the resulting solution in vacuo to afford
25.98 g of a viscous oil. 1H NMR of this material
1~ showed it to be branched polyethylene with 103 methyl-
ended branches per 1000 methylenes. GPC analysis in
trichlorobenzene gave Mn = 10,800, MW = 21,200 vs.
linear polyethylene.
Example 76
20 A mixture of 20 mg (0.034 mmol) of [(2,6-i-
PrPh)DABH~]NiBr2 and 60 mL dry, deaerated toluene was
magnetically-stirred under nitrogen in a 200-mL three-
necked flask with a gas inlet tube, a thermometer, and
a gas exit tube which vented through a mineral oil
bubbler. To this mixture, 0.75 mL (65 eq) of 3M
poly(methylalumoxane) (PMAO) in toluene was added via
syringe. The resulting deep blue-black catalyst
solution was stirred as ethylene was bubbled through at
about 5 ml and 1 atm for 2 hr. The temperature of the
30 mixture rose to 60°C in the first 15 min and then
dropped to room temperature over the course of the
reaction.
The product sclution was worked up by blending
with methanol; the resulting white polymer was washed
3~ with 2N HC1, water, and methanol to yield after drying
(50°C/vacuum/nitrogen purge) 5.698 (6000 catalyst
turnovers) of polyethylene which was easily-soluble in
hot chlorobenzene. Differential scanning calorimetry
17~
c~ iacTiTi r~ SNFFT (RULE 261

WO 96/23010 ~ 02338581 2001-03-O1 p~'~596/01282
.exhibited a broad melting point at 107°C (67 J/g). Gel
permeation chromatography (trichlorobenzene, 135°C,
polystyrene reference, results calculated as
polyethylene using universal calibration theory):
Mn=22,300; MW=102,000; MW/Mn=4.56. 13C NMR analysis:
branching per 1000 CH2: total Methyls (60), Methyl
( 41 ) , Ethyl ( 5 . 8 ) , Propyl ( 2 . 5 ) , Butyl ( 2 . 4 ) , Amyl
(1.2), ?Hexyl and end of chain (5); chemical shifts
were referenced to the solvent: the high field carbon
10 of 1,2,4-trichlorobenzene (127.8 ppm). A film of
polymer (pressed at 200°C) was strong and could be
stretched and drawn without elastic recovery.
Example 77
In a Parry 600-mL stirred autoclave under
nitrogen was combined 23 mg (0.039 mmol) of ((2,6-i-
PrPh)DABH~]NiBr2, 60 mL of dry toluene, and 0.75 mL of
poly(methylalumoxane) at 28°C. The mixture was
stirred, flushed with ethylene, and pressurized to 414
kPa with ethylene. The reaction was stirred at 414 kPa
20 for 1 hr; the internal temperature rose to 31°C over
this time. After 1 hr, the ethylene was vented and 200
mL of methanol was added with stirring to the
autoclave. The resulting polymer slurry was filtered;
the polymer adhering to the autoclave walls and
impeller was scraped off and added to the filtered
polymer. The product was washed with methanol and
acetone and dried (80°C/vacuum/nitrogen purge) to yield
S.lOg (4700 catalyst turnovers) of polyethylene.
Differential scanning calorimetry exhibited a melting
3O point at 127°C (170 J/g). Gel permeation
chromatography (trichlorobenzene, 135°C, polystyrene
reference, results calculated as polyethylene using
universal calibration theory): Mn=49,300; MW=123,000;
MW/Mn=2.51. Intrinsic viscosity (trichlorobenzene,
3~ 135°C): 1.925 dL/g. Absolute molecular weight averages
corrected for branching: Mn=47,400; MW=134,000;
Mw/Mn=2.83. 13C NMR analysis; branching per 1000 CH2:
total Methyls (10.5), Methyl (8.4), Ethyl (0.9), Propyl
176
m iec~rrnrr cuctz nal It G 9R1

WO 96/23010 ~ 02338581 2001-03-O1 PGT/US96/01282
(0), Butyl (0), >_Butyl and end of chain (1.1); chemical
shifts were referenced to the solvent: the high field
carbon of 1,2,4-trichlorobenzene (127.8 ppm). A film
of polymer (pressed at 2o0°C) was strong and stiff and
could be stretched and drawn without elastic recovery.
This polyethylene is much more crystalline and linear
than the polymer of Example 76. This example shows that
only a modest pressure increase from 1 atm to 414 kPa
allows propagation to successfully compete with
10 rearrangement and isomerization of the polymer chain by
this catalyst, thus giving a less-branched, more-
crystal_ine polyethylene.
Exam 78
A mixture of 12 mg (0.020 mmol) of [(2,6-i-
1~ PrahiDABZ,)NiBr2 and 40 mL.dry, aeaerated toluene was
magne~ically-stirred under nitrogen at 15°C in a 100-mL
three-necked flask with an addition funnel, a
thermometer, and a nitrogen inlet tube which vented
throug:~ a mineral oil bubbler. To this mixture, 0.5 mL
?0 of poiy(methylalumoxane) in toluene was added via
syringe; the resulting burgundy catalyst solution was
stirred for 5 min and allowed to warm to room
temperature. Into the addition funnel was condensed
(via a Dry Ice condenser on the top of the funnel) 15
~ mL (abou~ lOg) of cis-2-butene. The catalyst solution
was s~irred as the cis-2-butene was added as a liquid
all at once, and the mixture was stirred for 16 hr.
The product solution was treated with 1 mL of methanol
and was filtered through diatomaceous earth; rotary
30 evaporation yielded 0.35g (300 catalyst turnovers) of a
light yellow grease, poly-2-butene. 13C NMR analysis;
branc~.i:~g per 1000 CHZ: total Methyls (365), Methyl
(285), ethyl (72), ?Butyl and end of chain (8);
chemical shifts were referenced to the solvent
>> chloroform-dl (77 ppm).
Listed below are the 13C NMR data upon which the
above analysis is based.
177
SUBSTITUTE SHEET (RULE 26)

WO 96/23010 CA 02338581 2001-03-O1 PCT/US96/01282
13C ~ Data
CDC13, RT, 0.05M CnAcAc
Freq ppm Intensity
41.6071 11.2954
41.1471 13.7193
38.6816 3.55568
37.1805 7.07882
36.8657 33.8859
36.7366 35.1101
36.6196 33.8905
36.2645 12.1006
35.9094 13.3271
35.8004 11.8845
35.5785 4.20104
34.7351 24.9682
34.4325 39.3436
34.3114 59.2878
34.1177 125.698
33.9886 121.887
33.8837 120.233
33.5326 49.8058
33.004 132.842
32.7377 51.2221
32.657 55.6128
32.3705 18.1589
31.5876 9.27643
31.3818 16.409
31.0066 15.1861
30.0946 41.098
29.9736 42.8009
29.7672 106.314
29.3602 60.0884
29.2512 35.0694
29.114 26.6437
28.9769 29.1226
27.9358 3.57351
27.7501 3.56527
27.0682 14.6121
26.7333 81.0769
26.3257 14.4591
26.015 11.8399
25.3008 8.17451
25.0627 5.98833
22.4801 3.60955 284
22.3308 10.4951 2B5+, EOC
19.6192 90.3272 1B1
19.4618 154.354 1B1
19.3085 102.085 1B1
18.9937 34.7667 181
18.8525 38.7651 1B1
13.7721 11.2148 184+, EOC, 1B3
11.0484 54.8771 182
10.4552 10.8437 182
10.1283 11.0735 1B2
9.99921 9.36226 182
SUBSTITUTE SHEET (RULE 26)

WO 96/23010 CA 02338581 2001-03-O1 PCTIUS96101282
Example 79
A mixture of 10 mg (0.017 mmol) of [(2,6-i-
PrPh)DABH2]NiBr2 and 40 mL dry, deaerated toluene was
magnetically-stirred under nitrogen at 5°C in a 100-mL
three-necked flask with an addition funnel, a
thermometer, and a nitrogen inlet tube which vented
through a mineral oil bubbles. To this mixture, 0.5 mL
of 3M poly(methylalumoxane) in toluene was added via
10 syringe; the resulting burgundy catalyst solution was
stirred at 5°C for 40 min. Into the addition funnel
was condensed (via a Dry Ice condenser on the top of
the funnel) 20 mL (about 15 g) of 1-butene. The
catalyst solution was stirred as the 1-butene was added
l~ as a liquid ail at once. The reaction temperature rose
to 50°C over 30 min and then dropped to room
temperature as the mixture was stirred for 4 hr. The
product solution was treated with 1 mL of methanol and
was filtered through diatomaceous earth; rotary
20 evaporation yielded 6.17 g (1640 catalyst turnovers) of
clear, tacky poly-1-butene rubber. Gel permeation
chromatography (trichlorobenzene, 135°C, polystyrene
reference, results calculated as polyethylene using
universal calibration theory): Mn=64,700; Mw=115,000;
?~ MW/Mn=1.77. 13C NMR analysis; branching per 1000 CHI:
total Methyls (399), Methyl (86), Ethyl (272), >_BUtyl
and end of chain (41); chemical shifts were referenced
to the solvent chloroform-dl (77 ppm). This example
demonstrates the polymerization of an alpha-olefin and
30 shows the differences in branching between a polymer
derived from a 1-olefin (this example) and a polymer
derived from a 2-olefin (Example 78). This difference
shows that the internal olefin of Example 78 is not
first isomerized to an alpha-olefin before
3~ polymerizing; thus this catalyst is truly able tc
polymerize internal olefins.
Listed below are the 1'C NMR data upon which the
above analysis is based.
179
SI IRSTITtiTE SHEET (RULE 26)

WO 96123010 CA 02338581 2001-03-O1 PCT/US96/01282
13C ~R Data
CDC13, RT, CrAcAc
0.05M
Freq Intensity
ppm
43.8708 6.42901
41.5304 11.1597
41.0825 16.1036
38.7623 103.647
38.1247 50.3288
37.3338 24.6017
36.81?3 30.0925
35.756 55.378
35.0337 22.3563
34.1419 64.8431
33.8514 55.3508
33.4116 90.2438
33.0645 154.939
32.7094 51.3245
32.431 23.0013 385
30.946 12.8866 386+
30.1551 26.1216
29.7516 54.6262
29.4248 40.7879
27.6008 8.64277
27.2417 20.1564
27.1207 21.9735
26.7777 45.0824
26.0755 66.0697
25.6599 77.1097
24.3807 8.9175
23.4809 32.0249 284, 2B5+, 2EOC
22.8393 8.06774
22.1372 16.4732
19.4981 57.7003 1B1
19.3609 70.588 1B1
15.132 17.2402 1B4+
13.8448 7.9343 184+
12.2509 27.8653
12.037 27.0118
11.0766 6.61931 182
10.2938 98.0101 1B2
10.1364 104.811 182
Examl, l a 8 0
A 22-mg (0.037-mmol) sample of [(2,6-i-
PrPh) DABH2] NiBr~, was introduced into a 600-mL stirred
ParrO autoclave under nitrogen. The autoclave was
sealed and 75 mL of dry, deaerated toluene was .
introduced into the autoclave via gas tight syringe
10 through a port on the autoclave head. Then 0.6 mL of '
3M poly(methylalumoxane) was added via syringe and
stirring was begun. The autoclave was pressurized with
180
ct IacTITI 1TF CNFFT fRi il E 261

WO 96!23010 ~ 02338581 2001-03-O1 PCT/LTS96/01282
;~:ropyiene to 414 kPa and stirred with continuous
propylene feed. There was no external cooling. The
internal temperature quickly rose to 33°C upon initial
propylene addition but gradually dropped back to 24°C
~ over the course of the polymerization. After about 7
min, the propylene feed was shut off and stirring was
continued; over a total polymerization time of 1.1 hr,
the pressure dropped from 448 kPa to 358 kPa. The
propylene was vented and the product, a thin, honey-
10 colored solution, was rotary evaporated to yield 1.65g
of a very thick, brown semi-solid. This was dissolved
in chloroform and filtered through diatomaceous earth;
concentration yielded 1.3 g (835 catalyst turnovers) of
tacky, yellow polypropylene rubber. Gel permeation
Is chromatography ltrichiorobenzene, 135°C, polystyrene
reference, results calculated as polypropylene using
universal calibration theory): Mn=7,940; Mw=93,500;
Mw/Mn=11.78.
Example 81
20 A mixture of 34 mg (0.057 mmol) of [(2,6-i-
PrPh)DABH~]NiBrz and 20 mL dry, deaerated toluene was
magnetically-stirred under nitrogen at 5°C in a 100-mL
three-necked flask with a thermometer and a nitrogen
inlet tube which vented through a mineral oil bubbler.
~ To this mixture, 0.7 mL of 3M poly(methylalumoxane) in
toluene was added via syringe and the resulting deep
blue-black solution was stirred for 30 min at 5°C. To
this catalyst solution was added 35 mL of dry,
deaerated cyclopentene, and the mixture was stirred and
30 allowed to warm to room temperature over 23 hr. The
blue-black mixture was filtered through alumina to
remove dark blue-green solids (oxidized aluminum
compounds from PMAO); the filtrate was rotary
evaporated to yield 1.2 g (310 catalyst turnovers) of
35 clear liquid cyclopentene oligomers.
Example 82
A 20-mg (0.032 mmol) sample of ((2,6-i-
PrPh)DABMe2]NiBr2 was placed in Parr~ 600-mL stirred
181
SUBSTITUTE SHEET (RULE 26)

WO 96/23010 CA 02338581 2001-03-O1 PCT/US9G/01282
autoclave under nitrogen. The autoclave was sealed and
100 mL of dry, deaerated toluene and 0.6 mL of 3M
poly(methylalumoxane) were injected into the autoclave
through the head port, and mixture was stirred under
nitrogen at 20°C for 50 min. The autoclave body was
immersed in a flowing water bath and the autoclave was
then pressurized with ethylene to 2.8 MPa with stirring
as the internal temperature rose to 53°C. The
autoclave was stirred at 2.8 MPa (continuous ethylene
10 feed) for 10 min as the temperature dropped to 29°C,
and the ethylene was then vented. The mixture stood at
1 atm for 10 min; vacuum was applied to the autoclave
for a few minutes and then the autoclave was opened.
The product was a stiff, swollen polymer mass
I~ whic~~ was scraped out, cut. up, and fed in portions to
500 mL methanol in a blender. The polymer was then
boiled with a mixture of methanol (200 mL) and
trif~uoroacetic acid (10 mLl, and finally dried under
high vacuum overnight to yield 16.8g (18,700 catalyst
20 turnovers) of polyethylene. The polymer was somewhat
heterogeneous with respect to crystallinity, as can be
seen from the differential scanning calorimetry data
below; amorphous and crystalline pieces of polymer
could be picked out of the product. Crystalline
polyethylene was found in the interior of the polymer
mass; amorphous polyethylene was on the outside. The
crystalline polyethylene was formed initially when the
ethylene had good access to the catalyst; as the
polymer formed limited mass transfer, the catalyst
30 became ethylene-starved and began to make amorphous
polymer. Differential scanning calorimetry:
(crystalline piece of polymer): mp: 130°C (150J/g);
(amorchous piece of polymer): -48°C (Tg); mp: 42°C ,
(3J/a), 96°C (11J/g). Gel-permeation chromatography
~f (tric'.~.lorobenzene, 135°C, polystyrene reference,
results calculated as polyethylene using universal
calibration theory): Mn=163,000; MW=534,000;
MW/MT=3.27. This example demonstrates the effect of
18~
SIIBSTfTUTE SHEET (RULE 26)

WO 96/23010 CA 02338581 2001-03-O1 PCT/US96101282
ethylene mass transrer on the polymerization and~shows
that the same catalyst can make both amorphous and
crystalline polyethylene. The bulk of the polymer was
crystalline: a film pressed at 200°C was tough and
~ stiff.
Fxamp~
A 29-mg (0.047 mmol) sample of [(2,6-i-
PrPh)DABMe2)NiBrz was placed in ParrO 600-mL stirred
autoclave under nitrogen. The autoclave was sealed and
100 mL of dry, deaerated toluene and 0.85 mL of 3M
poly(methylalumoxane) were injected into the autoclave
through the head port. The mixture was stirred under
nitrogen at 23°C for 30 min. The autoclave body was
immersed in a flowing water bath and the autoclave was
l~ pressurized with ethylene .to 620 kPa with stirring.
The internal temperature peaked at 38°C within 2 min.
The autoclave was stirred at 620 kPa (continuous
ethylene feed) for 5 min as the temperature dropped to
32°C. The ethylene was then vented, the regulator was
20 readjusted, and the autoclave was pressurized to 34.5
kPa (gauge) and stirred for 20 min (continuous ethylene
feed) as the internal temperature dropped to 22°C. In
the middle of this 20 min period, the ethylene feed was
temporarily shut off for 1 min, during which time the
'_'~ autoclave pressure dropped from 34.5 kPa (gauge) to
13.8 kPa; the pressure was then restored to 34.5 kPa.
After stirring 20 min at 34.5 kPa, the autoclave was
once again pressurized to 620 kPa for 5 min; the
internal temperature rose from 22°C to 34°C. The
30 ethylene feed was shut off for about 30 sec before
venting; the autoclave pressure dropped to about 586
kPa.
The ethylene was vented; the product was a dark,
thick liquid. Methanol (200 mL) was added to the
35 autoclave and the mixture was stirred for 2 hr. The
polymer, swollen with toluene, had balled up on the
stirrer, and the walls and bottom of the autoclave were
coated with white, fibrous rubbery polymer. The
183
S178STITlITE SHEET (RULE 261

WO 96!23010 ~ 02338581 2001-03-O1 PCT/US96/01282
polymer was scraped out, cut up, and blended with
methanol in a blender and then stirred with fresh
boiling methanol for 1 hr. The white rubber was dried
under high vacuum for 3 days to yield 9.6 g (7270
catalyst turnovers) of rubbery polyethylene. 1H NMR
analysis (CDC13): 95 methyl carbons per 1000 methylene
carbons.
Differential scanning calorimetry: -51°C (Tg); mp:
3°.5°C (4J/g); mp: 76.4°C (7J/g). Gel permeation
10 chromatography (trichlorobenzene, 135°C, polystyrene
reference, results calculated as polyethylene using
universal calibration theory): Mn=223,000; Mw=487,000;
Ni~,/Mn=2 . 19 .
The polyethylene of Example 83 could be cast from
1~ ::ot chlorobenzene or press-ed at 200°C to give a strong,
stretchy, hazy, transparent film with good recovery.
It was not easily chloroform-soluble. This example
demonstrates the use of the catalyst's ability (see
Example 82) to make both amorphous and crystalline
?0 polymer, and to make both types of polymer within the
same polymer chain due to the catalyst's low propensity
to chain transfer. With crystalline blocks (due to
higher ethylene pressure) on both ends and an amorphous
region (due to lower- pressure, mass transfer-limited
polymerization) in the center of each chain, this
polymer is a thermoplastic elastomer.
$xample 84
A Schlenk flask containing 147 mg EO.i00 mmol) of
{ [ (2, 6-i-PrPh) DABMe2] PdMe (OEt2) }BAF was cooled to -
30 78°C, evacuated, and placed under an ethylene
atmosphere. Methylene chloride (100 ml) was added to
the flask and the solution was then allowed to warm to
room temperature and stirred. The reactic.~. vessel was
warm during the first several hours of mixing and the
3~ solution became viscous. After being stirred for 17.4
h, the reaction mixture was added to -600 mL of MeOH in
order to precipitate the polymer. Next, the MeOH was
decanted off of the sticky polymer, which was then
184
e~ iac~t rr~ cu>:~ SRI 11 E 261

WO 96/23010 ~ 02338581 2001-03-O1 PCT/US96/01282
dissolved in -.600 mL of petroleum ether. After being
filtered through plugs of neutral alumina and silica
gel, the solution appeared clear and almost colorless.
The solvent was then removed and the viscous oil (45.31
g) was dried in vacuo for several days: 1H NMR (CDC13,
400 MHz) cS 1.24 (CH2, CH), 0.82 (m, CH3); Branching:
-128 CH3 per 1000 CH2; DSC: Tg = -67.7°C. GPC: Mn =
29,000; Mw = 112,000.
Fxam ~pl_e 85
10 Following the procedure of Example 84 ([(2,6-i-
PrPh)DABMe2] PdMe (OEtz) }BAF (164 mg, 0.112 mmol)
catalyzed the polymerization of ethylene for 24 h in 50
mL of CH2C12 to give 30.16 g of polymer as a viscous
o i 1 . =:? NMR ( C6D6 ) d 1 . 41 ( CH2 , CH ) , 0 . 94 ( CH3 ) ;
1~ Branc:~~ing: -115 CH3 per 1000 CH2; GPC Analysis (THF,
PMMA standards, RI Detector): Mw = 262,000; Mn =
121,000; PDI = 2.2; DSC: Tg = -66.8°C.
Example 86
The procedure of Example 84 was followed using 144
?0 mg (0.100 mmol) of ( [ (2, 6-i-PrPh)DABH2] PdMe (OEtz) }BAF
in 50 mL of CH2C12 and a 24 h reaction time. Polymer
(9.68 a) was obtained as a free-flowing oil. 1H NMR
(CDC1~, 400 MHz) cS 5.36 (m, RHC=CHR'), 5.08 (br s,
RR'C=CHR "), 4.67 (br s, H2C=CRR'), 1.98 (m, allylic
~~ H), 1.25 (CH2, CH), 0.83 (m, CH3); Branching: -149
CH3 per 1000 CHz; DSC: Tg = -84.6°C.
Example 87
A 30-mg (0.042-mmol) sample of [(2,6-i-
PrPh)DABAn]NiBrz was placed in ParrO 600-mL stirred
30 autoclave under nitrogen. The autoclave was sealed and
150 mL of dry toluene and 0.6 mL of 3M
polymet'.~.ylalumoxane were injected into the autoclave
through the head port. The autoclave body was immersed
in a flowing water bath and the mixture was stirred
3~ under nitrogen at 20°C for 1 hr. The autoclave was
then pressurized with ethylene to 1.31 MPa with
stirring for 5 min as the internal temperature peaked
at 30°C. The ethylene was then vented to 41.4 kPa
185
SUBSTITUTE SHEET (RULE 26)

WO 96123010 ~ 02338581 2001-03-O1 pCT/US96/01282
w gauge) and the mixture was stirred and fed ethylene at
41.4 kPa for 1.5 hr as the internal temperature dropped
to 19°C. At the end of this time, the autcclave was
again pressurized to 1.34 MPa and stirred for 7 min as
the internal temperature rose to 35°C.
The ethylene was vented and the autoclave was
briefly evacuated; the product was a stiff, solvent-
swollen gel. The polymer was cut up, blended with 500
mL methanol in a blender, and then stirred overnight
10 with 500 mL methanol containing 10 mL of 6N HC1. The
stirred suspension in methanol/HC1 was then boiled for
4 hr, filtered, and dried under high vacuum overnight
to yield 26.1 g (22,300 catalyst turnovers) of
polyethylene. Differential scanning calorimetry: -49°C
I~ (Tg); mp: 115°C (42J/g). The melting transition was
very broad and appeared to begin around room
temperature. Although the melting point temperature is
higher in this Example than in Example 76, the area
under the melting endotherm is less in this example,
20 implying that the polymer of this Example is less
crystalline overall, but the crystallites that do exist
are more ordered. This indicates that the desired
block structure was obtained. Gel permeation
chromatography (trichlorobenzene, 135°C, polystyrene
reference, results calculated as polyethylene using
universal calibration. theory): Mn=123,000; Mw=601,000;
MW/Mn=4.87. The polyethylene of this example could be
pressed at 200°C to give a strong, tough, stretchy,
hazy film with ~,artial elastic recovery. When the
30 stretched film was plunged into boiling water, it
completely relaxed to its original dimensions.
Example 88
A 6.7-mg (0.011-mmol) sample of [(2,6-i-
PrPh)DABMe2]NiBrz was magnetically-stirred under
nitrogen in a 50-mL Schlenk flask with 25 mL of dry,
deaerated toluene as 0.3 mL of 3M poly(methylalumoxane)
was injected via syringe. The mixture was stirred at
23°C for 40 min to give a deep blue-green solution of
186
~r iac~Tt tTF RHFFT (RI tl E 261

WO 96/23010 CA 02338581 2001-03-O1 PCT/US96101282
atalyst. Dry, deaerated cyclopentene (10 mL) was
injected and the mixture was stirred for 5 min. The
flask was then pressurized with ethylene at 20.7 MPa
and stirred for 22 hr. The resulting viscous solution
was poured into a stirred mixture of 200 mL methanol
and 10 mL 6N HC1. The methanol was decanted off and
replaced with fresh methanol, and the polymer was
stirred in boiling methanol for 3 hr. The tough,
stretchy rubber was pressed between paper towels and
dried under vacuum to yield l.Og of
poly[ethylene/cyclopentene). By 1H NMR
analysis(CDC13): 100 methyl carbons per 1000 methylene
carbons. Comparison of the peaks attributable to
cyclopentene (0.65 ppm and 1.75 ppm) with the standard
Is polyethylene peaks (0.9 ppm and 1.3 ppm) indicates
about a 10 molo cyclopentene incorporation. This
polymer yield and composition represent about 2900
catalyst turnovers. Differential scanning calorimetry:
-44°C (Tg). Gel permeation chromatography
(trichlorobenzene, 135°C, polystyrene reference,
results calculated as polyethylene using universal
calibration theory): Mn=122,000; Mw=241,000;
Mw/Mn=1.97.
Listed below are the 13C NMR data upon which the
above analysis is based.
13C ~R data
TCB, 120C, 0.05M CrAcAc
Freq ppm Intensity
50.9168 5.96663
46.3865 3.27366 1 cme and/or 1,3
ccmcc
40.7527 40.5963 2 eme
40.567 41.9953 1,3 eme
40.3336 45.8477 1,3 eme
37.1985 60.1003
36.6998 41.2041
36.0579 12.2879
35.607 25.169
34.4771 19.0834
34.0845 22.8886
33.1293 20.1138
32.8962 27.6778
31.8406 75.2391
30.0263 76.2755
187
ci ~ac~r~ rr>= ~HFFT fRl II F ~R1

WO 96/23010 ~ 02338581 2001-03-O1 pC'1'/US96101282
29.6921 170.41
28.9494 18.8754
28.647 25.8032
27.4588 22.2397
27.1086 48.0806
24.3236 3.31441
22.5783 4.64411 2B5+, 2 EOC
19.6712 43.1867 1B1
17.5546 1.41279 end group
14.3399 1.74854 1B3
13.8518 5.88699 184+, lEOC
10.9182 2.17785 2B1
Example 89
A 7.5-mg (0.013-mmol) sample of [(2,6-t-
BuPh)DABMe~)NiBr2 was magnetically stirred under
nitrogen in a 50-mL Schlenk flask with 40 mL of dry,
deaerated toluene as 0.5 mL of 3M poly(methylalumoxane).
was injected via syringe. The mixture was stirred at
23°C for 1 hr to give a deep blue-green solution of
catalyst. The flask was pressurized with ethylene at
10 20.7 kPa (gauge) and stirred for 20 hr. The solution,
which had become a reddish-brown suspension, was poured
into a stirred mixture of 200 mL methanol and 10 mL 6N
HCl and was stirred at reflux for 1 hr. The methanol
was decanted off and replaced with fresh methanol, and
15 the white polymer was stirred in boiling methanol for 1
hr. The stiff, stretchy rubber was pressed between
paper towels and then dried under vacuum to yield 1.25
g (3380 catalyst turnovers) of polyethylene. 1H-1 NMR
analysis (C6D6): 63 methyl carbons per 1000 methylene
20 carbons. Differential scanning calorimetry: -34°C
(Tg); mp: 44°C (31J/g); mp: 101°C (23J/g).
Example 90
A 5.5 mg (0.0066 mmol) sample of ([(2,6-i-
PrPh)2DABMe2]PdMe(Et,O)}SbF6 was allowed to stand at
room temperaLUre in air for 24 hr. A 100-mL three-neck
flask with a magnetic stirrer and a gas inlet dip tube
was charged with 40 mL of reagent methylene chloride
and ethylene gas was bubbled through with stirring to
saturate the solvent with ethylene. The sample of
30 { [ (2, 6-i-PrPh) ~DABMe2) PdMe (Et20) }SbF6 was then rinsed
188
e~racTmt~ cuccT rQtil F 761

WO 96/23010 CA 02338581 2001-03-O1 PCT/US96/01282
,Lnto the flask with 5 mL of methylene chloride~and
ethylene was bubbled through with stirring for 5 hr.
The clear yellow solution was rotary evaporated to
yield 0.20 g (1080 catalyst turnovers) of a thick
yellow liquid polyethylene.
Example 91
A 600-mL stirred Parry autoclave was sealed and
flushed with nitrogen, and 100 mL of dry, deaerated
toluene was introduced into the autoclave via gas tight
syringe through ~ port on the autoclave head. The
autoclave was purged with propylene gas to saturate the
solvent with propylene. Then 45 mg (0.054 mmol) of
(((2,6-i-PrPh)2DABMe~]PdMe(Et20)~SbF6 was introduced
into the autoclave in the following manner: a 2.5-mL
1~ gas tight syringe with a syringe valve was loaded with
45 mg of([(2,6-i-PrPh)2DABMe2)PdMe (Et20)?SbF6 under
nitrogen in a glove box; then 1-2 mL of dry, deaerated
methylene chloride was drawn up into the syringe and
the contents were quickly injected into the autoclave
?0 through a head port. This method avoids having the
catalyst in solution with no stabilizing ligands.
The autoclave was pressurized with propylene to
414 MPa and stirred for 2.5 hr, starting with
continuous propylene feed. The autoclave was cooled in
a running tap water bath at 22°C. The internal
temperature quickly rose to 30°C upon initial propylene
addition but soon dropped back to 22°C. After 0.5 hr,
the propylene feed was shut off and stirring was
continued. Over 2 hr, the pressure dropped from 41.4
:0 MPa to 38.6 MPa. The propylene was then vented. The
product was a thin, honey-colored solution. Rotary
evaporation yielded 2.3 g (1010 catalyst turnovers) of
very thick, dark-brown liquid polypropylene which was
almost eiastomeric when cool. Gel permeation
>> chromatography (trichlorobenzene, 135°C, polystyrene
reference, results calculated as polypropylene using
universal calibration theory): Mn=8,300; Mw=15,300;
Mw/Mn=1.84. 13C NMR analysis; branching per 1000 CH2:
189
SI IRCTiTI iTF SHFFT (RULE 261

WO 96/23010 CA 02338581 2001-03-O1 pCT/iJS96101282
total Methyls (545), Propyl (1.3), _>Butv~ and end cf
chain (9.2); chemical shifts. The polymer exhibited a
glass transition temperature of -44°C by differential
scanning calorimetry.
Listed below are the 13C NMR data upon which the
above analysis is based.
13C ~R data
CDC13, RT, 0.05M CrAcAc
Freq ppm Intensity
46.4978 13.2699 Methylenes
45.8683 11.9947 Methylenes
45.3639 10.959 Methvlenes
45.1783 11.3339 Methylenes
44.5568 8.41708 Methylenes
44.4398 7.69019 Methylenes
44.3026 6.29108 Methylenes
44.1372 6.73541 Methylenes
43.5036 5.49837. Methylenes
42.4262 5.03113 Methylenes
41.6918 3.72552 Methylenes
39.1537 4.23147 Methines Methvlenes
and
38.7179 25.2596 Methines Methylenes
and
37.8664 10.0979 Methines Methylenes
and
37.6727 14.3755 Methines Methylenes
and
37.0755 17.623 Methines Methylenes
and
36.781 42.0719 Methines Methylenes
and
36.559 10.0773 Methines Methylenes
and
34.5495 5.34388 Methines Methvlenes
and
34.3195 7.48969 Methines Methylenes
and
33.5488 12.6148 Methines Methylenes
and
33.351 20.5271 Methines Methylenes
and
32.7982 4.10612 Methines Methylenes
and
32.4108 22.781 Methines Methylenes
and
31.8701 5.90488 Methines Methvlenes
and
31.5957 10.6988 Methines Methylenes
and
29.8364 44.4935 Methines Methylenes
and
29.7072 103.844 Methines Methylenes
and
29.3925 152.645 Methines Methvlenes
and
29.0293 6.71341 Methines Methylenes
and
27.6089 38.7993 Methines Methylenes
and
27.4193 10.3543 Methines Methylenes
and
27.0763 66.8261 Methines Methylenes
and
26.9552 92.859 Methines Methylenes
and
26.7615 55.7233 Methines Methylenes
and
26.3661 20.1674 Methines Methv_lenes
and
24.8529 16.9056 Methine Carbon
of XXVIII
23.1217 12.5439 Methine carbons
of XX~~'T_II
and
XXIX, 2B4+,
EOC
22.6779 13.0147 Methine carbons
of XXL~III
and
XXIX, 2B4+,
EOC
22.5245 9.16236 Methine carbons
of XXVIII
and
XXIX, 2B4+,
EOC
190
ct tacTtTt tT~ ~H~FT lRIILE 261

WO 96/23010 CA 02338581 2001-03-O1PCTlUS96101282
22.3389 77.3342 Methine carbons of XXVIII
and
XXIX, 2B4+, EOC
21.9757 9.85242 Methine carbons of XXVT_II
and
XXIX, 2B4+, EOC
21.1405 10.0445 Methyls
20.4182 8.49663 Methyls
19.9743 25.8085 Methyls
19.825 31.4787 Methyls
19.3811 44.9986 Methyls
19.1995 31.3058 Methyls
13.8569 6.37761 Methyls
13.8004 7.67242 Methyls
137.452 22.0529 Methvls
128.675 44.6993 Methyls
127.88 43.8939 Methyls
124.959 22.4025 Methyls
122.989 3.3312 Methyls
Examn
A 600-mL stirred Parrv autoclave was sealed,
flushed with nitrogen, and heated to 60°C in a water
bath. Fifty mL (48 g; 0.56 mol) of dry, deaerated
methyl acrylate was introduced into the autoclave via
gas tight syringe through a port on the autoclave head
and ethylene gas was passed through the autoclave at a
low rate to saturate the solvent with ethylene before
catalyst addition. Then 60 mg (0.07 mmol) of ([(2,6-1-
10 PrPh)2DABMe2]PdMe(Et20)~SbF6 was introduced into the
autoclave in the following manner: a 2.5-mL gas tight
syringe with a syringe valve was loaded with 60 mg of
([(2,6-i-PrPh)2DABMe2]PdMe(Et20)}SbF6 under nitrogen
in a glove box; then 1 mL of dry, deaerated methyiene
1~ chloride was drawn up into the syringe and the contents
were quickly injected into the autoclave through a head
port. This method avoids having the catalyst in
solution with no stabilizing ligands.
The autoclave-was pressurized with ethylene to 689
20 kPa and continuously fed ethylene with stirring for 4.5
hr; the internal temperature was very steady at 60°C.
The ethylene was vented and the product, a clear yellow
solution, was rinsed out of the autoclave with
chloroform, rotary evaporated, and held under high
2~ vacuum overnight to yield 1.56 g of thin light-brown
liquid ethylene/methyl acrylate copolymer. The
191
sin~n~r~ SHF>=r rRULE 267

WO 96123010 ~ 02338581 2001-03-O1 PCT/US96/01282
infrared spectrum of the product exhibited a strong
ester carbonyl stretch at 1740 cm-1. 1H-1 NMR analysis
(CDC13): 61 methyl carbons per 1000 methylene carbons.
Comparison of the integrals of the ester methoxy
(3.67ppm) and ester methylene (~2COOMe; 2.30ppm) peaks
with the integrals of the carbon chain methyls (0.8-
0.9ppm) and methylenes (1.2-l.3ppm) indicated a methyl
acrylate content of 16.6 mol% (37.9 wt°s). This product
yield and composition represent 480 ethylene turnovers
10 and 96 methyl acrylate turnovers. 13C NMR analysis;
branching per 1000 CH2: total methyls (48.3), Methyl
(20.8i, Ethyl (10.5), Propyl (1), Butyl (8), _>Amyl and
End of Chair (18.1), methyl acrylate (94.4); ester-
bearina -CH(CH2)nCO~CH~ branches as a % of total ester:
1~ n?5 (35.9), n=4 (14.3), n=i,2,3 (29.5), n=0 (20.3);
chemical shifts were referenced to the solvent: the
high field carbon of 1,2,4-trichlorobenzene (127.8
ppm). Gel permeation chromatography (tetrahydrofuran,
30°C, poiymethylmethacrylate reference, results
20 calculated as polymethylmethacrylate using universal
calibration theory): Mn=3,370; Mw=5,450; Mw/Mn=1.62.
Listed below are the 13C NMR data upon which the
above analysis is based.
192
S11RSTIT11TF SHEET (RULE 261

WO 96/23010 cA 02338581 2001-03-O1 PCT/US96/01282
13
C NMR data
TCB 120C, 0.05M CrAcAc
Freq ppm Intensity
53.7443 2.19635 CH2C12 solvent
impurity
50.9115 8.84408
50.641 132.93
45.5165 7.55996 MEBO 43.8 ppm :2 adjacent MEBO
39.6917 2.71676
39.2886 7.91933
38.1639 13.843
37.7926 26.6353
37.1666 20.6759
36.6733 8.65855
34.6256 17.6899
34.4612 16.7388
34.1429 85.624
33.9095 124.997 lEB4+
33.676 40.0271 Contributions from EB
33.2888 11.4719 Contributions from EB
32.8644 14.4963 Contributions from E9
3 .3458 17.5883 . Contributionsfrom EB
32.04'75 9.83096 Contributions from EB
31.8459 30.9676 Contributions from EB
31.7079 12.7737 Contributions from EB
31.5912 13.8792 Contributions from EB
31.0873 19.6266 Contributions from EB
30.6258 10.5512
30.1324 58.6101
29.6497 169.398
29.4322 48.5318
29.1934 95.4948
27.8619 8.70181
27.4269 32.9529
26.92E3 78.0563
26.5145 27.0608
26.3554 14.0683
25.4568 21.9081 2EB4 (tent)
X5.33_5 9.04646 2EB4 (tent)
24.9761 64.2333 2EB5+
24.2069 10.771 BBB (beta-beta-H)
23.0451 9.50073 2B4
22.9337 6.90528 2B4
22.5518 30.0427 285+, EOC
19.9842 1.87415 283
19.6288 17.125 181
19.1673 6.0427 1B1
16.7695 2.23642
14.3 - 183
13.7882 34.0749 1B4+, EOC
11.07'%4 4.50599 1B2
10.8705 10.8817 1B2
189.989 1.04646 EBO Carbonyl
175.687 3.33867 EBO Carbonyl
175.406 14.4124 EBO Carbonyl
175.22 5.43832 EBO Carbonyl
175.061 3.53125 EBO Carbonyl
193
~I IRSTITI tTF SHFFT (RULE 261

WO 96123010 ~ 02338581 2001-03-O1 pCT/US96/01282
172.859 11.2356 EB1+ Carbonyl
172.605 102.342 EB1+ Carbonyl
172.09 7.83303 EB1+ Carbonyl
170.944 3.294 EB1+ Carbonyl
Example 93
A 45-mg (0.048-mmol) sample of {[(2,6-i-
PrPh) 2DABAn] PdMe (Et20) ? SbF6 was placed in a 600-mL Parr
~ stirred autoclave under nitrogen. To this was added
50 mL of dry, deaerated methylene chloride, and the
autoclave was pressurized to 414 kPa with ethylene.
Ethylene was continuously fed at 414 kPa with stirring
at 23-25°C for 3 hr; then the feed was shut off and the
10 reaction was stirred for 12 hr more. At the end of
this time, the autoclave was under 89.6 kPa (absolute).
The autoclave was repressurized to 345 kFa with
ethylene and stirred for 2 hr more as the pressure
dropped to 255 kPa, showing that the catalyst was still
1~ active; the ethylene was then vented. The brown
solution in the autoclave was rotary evaporated, taken
up in chloroform, filtered through alumina to remove
catalyst, and rotary evaporated and then held under
high vacuum to yield 7.35 g of thick, yellow liquid
?0 polyethylene. 1H NMR analysis (CDC13): 131 methyl
carbons per 1000 methylene carbons. Gel permeation
chromatography (trichlorobenzene, 135°C, polystyrene
reference, results calculated as polyethylene using
universal calibration theory): Mn=10,300; Mw=18,100;
Mw/Mr=1.76.
Example 94
A 79-mg (0.085-mmol) sample of {[(2,6-i-
PrPh) zDABAn] PdMe (Et20) }SbF6 was placed in a 600-mL Parr
~ stirred autoclave under nitrogen. To this was added
30 50 mL of dry, deaerated methyl acrylate, and the
autoclave was pressurized to 689 kPa with ethylene.
The autoclave was warmed to 50°C and the reaction was
stirred at 689 kPa for 70 hr; the ethylene was then
vented. The clear yellow solution in the autoclave was
filtered through alumina to remove catalyst, rotary
194
ct tacTtTt tTF ~HFFT IRI ii E 261

WO 96/23010 CA 02338581 2001-03-O1 pCT/US96/01282
evaporated, and held under high vacuum to yield C.27 g -
of liquid ethylene/methyl acrylate copolymer. The
infrared spectrum of the product exhibited a strong
ester carbonyl stretch at 1740cm-1. 1H NMR analysis
(CDC13): 70 methyl carbons per 1000 methylene carbons;
13.5 mol% (32 wt%) methyl acrylate. This yield and
composition represent 12 methyl acrylate turnovers and
75 ethylene turnovers.
Exams
10 A 67-mg (0.089-mmol) of {[(2,4,6-
MePh) 2DABMe~] PdMe (Et20) }SbF6 was placed in a 200-mL
glass centrifuge bottle with a magnetic stir bar under
nitrogen. To this was added 40 mL of dry, deaerated
methyiene chloride. The bottle was immediatelv
pressurized to 207 kPa with ethylene. Ethylene was
continuously fed at 207 kPa with stirring at 23-25°C
for 4 hr. After 4 hr, the ethylene feed was shut off
and the reaction was stirred for 12 hr more. At the
end of this time, the bottle was under zero pressure
?0 (gauge). The brown solution was rotary evaporated and
held under high vacuum to yield 5.15 g of thick, brown
liquid polyethylene. 1H NMR analysis (CDC13): 127
methyl carbons per 1000 methylene carbons. Gel
permeation chromatography (trichlorobenzene, 135°C,
-'~ polystyrene reference, results calculated as
polyethylene using universal calibration theory):
Mn=20,200; Mw=32,100; Mw/Mn=1.59.
ExamDlP 6
A 56-mg (0.066-mmol) sample of {[(2,6-1-
30 PrPh) 2DABMe~] PdCHzCH2C (0) CH3) }SbF6 was placed in a 600-
mL Parr~ stirred autoclave under nitrogen. To this
was added 30 mL of dry, deaerated
perfluoro(propyltetrahydrofuran). The autoclave was
stirred and pressurized to 5.9 MPa with ethylene. The
3~ internal temperature peaked at 29°C; a cool water bath
was placed around the autoclave body. The reaction was
stirred for 16 hr at 23°C and 5.9 MPa and the ethv_iene
was then vented. The autoclave contained a licrht
19~
e~ mc~nr~ tTr cucrT roe ii c ~R1

WO 96/23010 ~ 02338581 2001-03-O1 PCT/US96101282
yellow granular rubber; this was scraped out ef the
autoclave and held under high vacuum to yield 29.0 g
(15,700 catalyst turnovers) of spongy, non-tacky,
rubbery polyethylene which had good elastic recovery
and was very strong; it was soluble in chloroform or
chlorobenzene.
The polyethylene was amorphous at room
temperature: it exhibited a glass transition
temperature of -57°C and a melting endotherm of -16°C
10 (35J/g) by diffeYential scanning calorimetry. On
cooling, there was a crystallization exotherm with a
maximum at 1°C (35J/g). Upon remelting and recooling
the melting endotherm and crystallization exotherm
persisted, as did the glass transition. Dynamic
I~ mechanical analysis at lHz showed a tan b peak at -51°C
and a peak in the loss modulus E" at -65°C; dielectric
analysis at 1000 Hz showed a tan d peak at -35°C. 1H
NMR analysis (CDC13): 86 methyl carbons per 1000
methylene carbons. 13C NMR analysis: branching per
20 1000 CH2: total Methyls (89.3), Methyl (37.2), Ethyl
(14), Propyl (6.4), Butyl (6.9), ?Am and End Of Chain
(23.8); chemical shifts were referenced to the solvent:
the high field carbon of 1,2,4-trichlorobenzene (127.8
ppm). Gel permeation chromatography (trichlorobenzene,
135°C, polystyrene reference, results calculated as
polyethylene using universal calibration theory):
Mn=137,000; Mw=289,000; Mw/Mn=2.10. Intrinsic
viscosity (trichlorobenzene, 135°C): 2.565 dL/g.
Absolute molecular weight averages corrected for
30 branching: Mn=196,000; Mw=425,000; Mw/Mn=2.77. Density
(determined at room temperature with a helium gas
displacemen~ pycnometer): 0.8546 ~ 0.0007 g/cc.
Example 97
A 49-mg (0.058 mmol) sample of {[(2,6-i-
3~ PrPh)~DABMe:]PdCHzCHzC(O)CH3}SbF6 was placed in a 600-mL
Parr~ stirred autoclave under nitrogen. To this was
added 30 mL of dry, deaerated hexane. The autoclave
was stirred and pressurized to 5.9 MPa with ethylene.
196
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WO 96/23010 CA 02338581 2001-03-O1 pCT/US96I01282
The internal temperature peaked briefly at 34°C; a cool
water bath was placed around the autoclave body. The
reaction was stirred for 16 hr at 23°C. At 14 hr, the
ethylene feed was shut off; the autoclave pressure
5 dropped to 5.8 MPa over 2 hr; the ethylene was then
vented. The autoclave contained a light yellow, gooey
rubber swollen with hexane, which was scraped out of
the autoclave and held under high vacuum to yield 28.2
g (17,200 catalyst turnovers) of spongy, non-tacky,
10 rubbery polyethylene which had good elastic recovery
and which was very strong.
The polyethylene was amorphous at room
temperature: it exhibited a glass transition
temperature of -61°C and a melting endotherm of -12°C
1~ (27J/g) by differential scanning calorimetry. Dynamic
mechanical analysis at 1Hz showed a tan d peak at -52°C
and a peak in the loss modulus E" at -70°C; dielectric
analysis at 1000 Hz showed a tan d peak at -37°C. 1H
NMR analysis (CDC13): 93 methyl carbons per 1000
?0 methylene carbons. 13C NMR analysis: branching per
1000 CH2: total Methyls (95.4), Methyl (33.3), Ethyl
(17.2), Propyl (5.2), Butyl (10.8), Amyl (3.7), >_Hex
and End Of Chain (27.4); chemical shifts were
referenced to the solvent: the high field carbon of
'_J 1,2,4-trichlorobenzene (127.8 ppm). Gel permeation
chromatography (trichlorobenzene, 135°C, polystyrene
reference, results calculated as polyethylene using
universal calibration theory): Mn=149,000; Mw=347,000;
Mw/Mn=2.33. Density (determined at room temperature
30 with a helium gas displacement pycnometer): 0.8544 ~
0.0007 g/cc.
xample 98
Approximately 10-mesh silica granules were dried
at 200°C and were impregnated with a methylene chloride
3~ solution of ( [ (2, 6-i-PrPh) 2DABMez] PdCH2CH2C (O) CH3)SbF6
to give a 10 wt% loading of the catalyst on silica.
A 0.53-g (0.063 mmol) sample of silica gel
containing 10 wto ([(2,6-i-
197
e~ mcr~ tTr curt? IQI 11 C 9Rl

CA 02338581 2001-03-O1
WO 96/23010 PCT/US96/01282
PrPh)~DABMez]PdCH2CH2C(O)CH3}SbFs was placed in a 600-mL
ParrO stirred autoclave under nitrogen. To this was
added 40 mL of dry, deaerated hexane. The autoclave
was stirred and pressurized to 5.5 MPa with ethylene;
the ethylene feed was then turned off. The internal
temperature peaked briefly at 31°C. The reaction was
stirred for 14 hr at 23°C as the pressure dropped to
5.3 MPa; the ethylene was then vented. The autoclave
contained a clear, yellow, gooey rubber swollen with
10 hexane. The product was dissolved in 200 mL
chloroform, filtered through glass wool, rotary
evaporated, and held under high vacuum to yield 7.95 a
(4500 catalyst turnovers) of gummy, rubbery
polyethylene. 1H NMR analysis (CDC13): 96 methyl
I~ carbons per 1000 methylene~ carbons. Gel permeation
chromatography (trichlorobenzene, 135°C, polystyrene
reference, results calculated as polyethylene using
universal calibration theory): Mn=6,900; Mw=118,000;
Mw/Mn=17.08.
20 Example 99
A 108-mg (0.073 mmol) sample of ~[(2,6-i-
PrPh) ZDABMe~) PdCH2CH2C (O) CH3 }BAF was placed i:~ a 600-mL
Parr~ stirred autoclave under nitrogen. To this was
added via syringe 75 mL of deaerated reagent grade
methyl acrylate containing 100 ppm hydroquinone
monomethyl ether and 100 ppm of phenothiazine. The
autoclave was pressurized to 5.5 MPa with ethylene and
was stirred at 35°C as ethylene was continuously fed
for 90 hr; the ethylene was then vented. The product
30 consisted of a swollen clear foam wrapped around the
impeller; 40 mL of unreacted methyl acrylate was poured
off the polymer. The polymer was stripped off the
impeller and was held under high vacuum to yield 38.2 g
ef clear, grayish, somewhat-tacky rubber. 1H NMR
3~ analysis (CDC13): 99 methyl carbons per 1000 methylene
carbons. Comparison of the integrals of the ester
methoxy (3.67ppm) and ester methylene (~i2COOMe;
2.3oppm) peaks with the integrals of the carbon chain
198
m~nnTmnr ~urrT mm c ~C~

WO 96/23010 CA 02338581 2001-03-O1 PCT/US96I01282
nethyls 10.8-0.9ppm) and methylenes (1.2-l.3ppm)
indicated a methyl acrylate content of 0.9 mol% (2.6
wt%). This product yield and composition represent
18,400 ethylene turnovers and.158 methyl acrylate
turnovers. 13C NMR analysis: branching per 1000 CH2:
total Methyls (105.7), Methyl (36.3), Ethyl (22),
Propyl (4.9), Butyl (10.6), Amyl (4), >_Hex and End Of
Chain (27.8), methyl acrylate (3.4); ester-bearing
-CH(CH2)nC02CH3 branches as a a of total ester: n?5
(40.6), n=1,2,3 (2.7), n=0 (56.7); chemical shifts were
referenced to the solvent: the high field carbon of
1,2,4-trichlorobenzene (127.8 ppm). Gel permeation
chromatography (tetrahydrofuran, 30°C,
polymethylmethacrylate reference, results calculated as
1~ polymethyimethacrylate using universal calibration
theory): Mn=151,000; Mw=272,000; Mw/Mn=1.81.
Rxam~1_e X00
A 62-mg (0.074-mmol) sample of
[ (2, 6-i-PrPh) 2DABMe2] PdMe (Et~O) ?SbF6 was placed in a
600-mL Parr~ stirred autoclave under nitrogen with 200
mL of deaerated aqueous 10% (v/v) n-butanol. The
autoclave was pressurized to 2.8 MPa with ethylene and
was stirred for 16 hr. The ethylene was vented and the
polymer suspension was filtered. The product consisted
of a fine gray powdery polymer along with some larger
particles of sticky black polymer; the polymer was
washed with acetone and dried to yield 0.60 g (290
catalyst turnovers) of polyethylene. The gray
polyethylene powder was insoluble in chloroform at RT;
it was soluble in hot tetrachloroethane, but formed a
gel on cooling to RT_. 1H NMR analysis
(tetrachloroethane-d2; 100°C): 43 methyl carbons per
1000 methylene carbons. Differential scanning
calorimetry exhibited a melting point at 89°C (78J/g)
with a shoulder at 70°C; there was no apparent glass
transition.
199
et tac~~n trF ~HFFT lRl II F 261

WO 96/23010 ~ 02338581 2001-03-O1 p~yLIS96!01281
A 78-mg (0.053-mmol) sample of {[(2,6-i-
PrPh) ZDABMe2] PdCHzCH2C (O) CH3 }BAF was placed in a 600-mL
ParrO stirred autoclave under nitrogen. To this was
added 40 mL of dry, deaerated t-butyl acrylate
containing 100 ppm hydroquinone monomethyl ether. The
autoclave was pressurized with ethylene to 2.8 MPa and
was stirred and heated at 35°C as ethylene was
continuously fed at 2.8 MPa for 24 hr; the ethylene was
then vented. The product consisted of a yellow, gooey
10 polymer which was dried under high vacuum to yield 6.1
g of clear, yellow, rubbery ethylene/t-butyl acrylate
copolymer which was quite tacky. 1H NMR analysis
(CDC13): 102 methyl carbons per 1000 methylene carbons.
Comparison of the integral of the ester t-butoxy (1.44
Is ppm) peak with the integrals of the carbon chain
methyls (0.8-0.9ppm) and methylenes (1.2-l.3ppm)
indicated a t-butyl acrylate content of 0.7 molo (3.3
wto). This yield and composition represent 3960
ethylene turnovers and 30 t-butyl acrylate turnovers.
20 Gel permeation chromatography (tetrahydrofuran, 30°C,
polymethylmethacrylate reference, results calculated as
polymethylmethacrylate using universal calibration
theory): Mn=112,000; Mw=179,000; Mw/Mn=1.60.
Example 102
A 19-mg (0.022-mmol) sample of
[ (2, 6-i-PrPh) ZDABMe2] PdCH2CH~C (0) CH3}SbF6 was placed in
a 600-mL ParrO stirred autoclave under nitrogen. The
autoclave was pressurized to 5.2 MPa with ethylene and
was stirred for 2 hr; the ethylene feed was then shut
30 off. The autoclave was stirred for 16 hr more as the
ethylene pressure dropped to 5.0 MPa; the ethylene was
then vented. The autoclave contained a light yellow,
granular sponge rubber growing all over the walls and
head of the autoclave; this was scraped out to yield
3~ 13.4 g (21,800 catalyst turnovers) of spongy, non-
tacky, rubbery polyethylene which was very strong and
elastic. 1H NMR analysis (CDC13): 90 methyl carbons
per 1000 methylene carbons.
200
e~ ~e~~~ err cuGCT lcti tl F ~Rl

WO 96/23010 CA 02338581 2001-03-O1 PCT/I;S96;01282
Li;=erentia_ scar..ni~~ calorimetry ex:.ibite~ a
class transition at -50°C. Gel permeatio~
....romatograohy (trick lorobenzene, 135°C, polystyre:~e
re=ere~ce, resu'_ts calculated as ~olvethvlene usinc
~ ~,:::_ver_=a= cal i.._..tio.. tspry? : h'n=i75, OCC; h~w=4 70', 0~.~,
bic,,i/M-,=2 .72 .
-.w-~-:
t: 70-mg (0.047-mmoi) sample of {[(2,6-i-
Fr?h) =O.=W"e=J PdCa:~:i:C (O) C~3 ~BRF was placed in a 600-
T,=
_ __rG s=irred au=ccl aye under nitroge.~.. To this was
added 70 mL o. deaerated reagent grade methyl acr~~late
contai:=::g lOC ppm each hydroquinone monomethyl ether
a
a..~.d p~~~ot::iazine and 0 . 7 mL ( 1 wt a , 4 . 7 mol o )
d=aera=ed, deio:.ized water. The autoclave was stirred
I~ Gt 35°C as ethylene was continuously fed at 4.8 M?a .,._
hr~ the ethylene was then vented. The product
consisted of a clear solution. Rotary evaporation
yielded 1.46 g o. ethylene/methyl acrylate copolymer as
a clear oil. T::e i~=cared spectrum of the product
ex'.~.ibited a strong ester carbonyl stretch at 1740cm''-.
1:? uMR ~ralysis (CDC13): 118 methyl carbons per 1000
methyle.~.e carbons. Comparison of the intecrals c~ ti:e
es_er methoxy (3.e7ppm) and ester methylene (~::2COO~:e;
2.30po-::~ peaks with the integrals of the carbon chaff.-..
~~ ~~et~v_s (0.8-0.9oom) and methvienes (1.2-_.3oom)
_r.dicated a methyl acryiate content of 0.7 moi% (2.2
wt°s). _..is product yield and composition represent
1090 e~'.~.yle.~.e turnovers and a methyl acrylate
turnovers. Gel permeation chromatography
.i0 ,__ic::'_orobenze.~.e, 135°C, polystyrene reference,
results calculated as polyethylene using universal
calibration theory): Mn=362; Mw=908; Mw/Mn=2.51.
~xa.~.'a,_~ ~'J~
n ._-my (C.C3o-mmol) sample c_' {[(2,5--
3~ P=?hi ;D~-.~:~ie=) ?dC: _"~zC (O) C:~~ }BF~R was placed in a 600-~:.L
?arrG stirred autoclave under .nitrogen. To this was
added 100 mL o~ d=y, deaerated methylene chloride. The
~~~ i:. a cool water bath and stir=ed
a~tocl a r_ was ir,....__ sed
201
r.. ",..Tw, rr~ cu~~ tDl tl C ~~1

CA 02338581 2001-03-O1 '
.. .. ,. ,.
as it was pressurized to 4.8 MPa with ethylene.
Ethylene was continuously fed with stirring at 4.8 MPa
and 23°C for 23 hr; the ethylene then was vented. The
product consisted of a clear rubber, slightly swollen
with methylene chloride. The polymer was dried under
high vacuum at room temperature to yield 34.5 g (34,100
catalyst turnovers) of clear rubbery polyethylene. 1H
NMR analysis (CDC13): 110 methyl carbons per 1000
methylene carbons. Gel permeation chromatography
(trichlorobenzene, 135°C, polystyrene reference,
results calculated as polyethylene using universal
calibration theory) : Mn=243, 000; Mi,,~=676, 000;
Mw/Mn=2.78.
Example 104A
1S A 83-mg (0.056-mmol) sample of {[(2,6-i-
PrPh) 2DABMe2} PdCH2CH2C (O) CH3}BAF was placed in a 600-mL
Parr~ stirred autoclave under nitrogen. To this was
added 70 mL of dry, deaerated, ethanol-free chloroform.
The autoclave was immersed in a cool water bath and
stirred as it was pressurized to 4.7 MPa with ethylene.
Ethylene was continuously fed with stirring at 4.7 MPa
and 23°C for 21 hr; the ethylene then was vented. The
product consisted of a pink, rubbery, foamed
polyethylene, slightly swollen with chloroform. The
polymer was dried under vacuum at 40°C to yield 70.2 g
(44,400 catalyst turnovers) of pink, rubbery
polyethylene which was slightly tacky. 1H NMR analysis
(CDC13): 111 methyl carbons per 1000 methylene carbons.
Gel permeation chromatography (trichlorobenzene, 135°C,
polystyrene reference, results calculated as
polyethylene using universal calibration theory):
Mn=213,000; Mw=728,000; Mw/Mn=3.41.
Example 105
A 44-mg (0.052-mmol) sample of {[(2,6-1-
PrPh) ZDABMe2} PdCH2CH2C (O) CHj}SbF6 was magnetically
stirred under nitrogen in a 50-mL Schlenk flask with 20
mL of dry, deaerated methylene chloride. To this was
added S mL (5.25 g; 73 mmol) of freshly distilled
202
AMENDED SHEET

WO 96/23010 CA 02338581 2001-03-O1 PCT/US96/01282
,acrylic acid (contains a few ppm of phenotr.iazine as a
radical polymerization inhibitor) via syringe and the
mixture was immediately pressurized with ethylene at
5.52 kPa and stirred for 40 hr. The dark yellow
solution was rotary evaporated and the residue was
stirred with 50 mL water for 15 min to extract any
acrylic acid homopolymer. The water was drawn off with
a pipette and rotary evaporated to yield 50 mg of dark
residue. The polymer which had been water-extracted
was heated under high vacuum to yield 1.30 g of
ethylene/acrylic acid copolymer as a dark brown oil.
The infrared spectrum showed strong COOH absorbances at
3400-2500 and at 1705cm-1, as well as strong methylene
absorbances at 3000-2900 and 1470cm-1.
A 0.2-g sample of the. ethylene/acrylic acid
copclymer was treated with diazomethane in ether to
esterify the COOH groups and produce an ethyiene/methyl
acrylate copolymer. The infrared spectrum of the
ester_fied copolymer showed a strong ester carbonyl
abscrbance at 1750cm-l; the COOH absorbances were gone.
1H NMR analysis (CDC13): 87 methyl carbons per 1000
methylene carbons. Comparison of the integrals of the
ester methoxy (3.67ppm) and ester methylene (~2COOMe;
2.30ppm) peaks with the integrals of the carbon chain
methyis (0.8-0.9ppm) and methylenes (1.2-l.3ppm)
indicated a methyl acrylate content of 5.3 molo (14.7
wt°s methyl acrylate => 12.3 wt°s acrylic acid in the
original copolymer). This product yield and
composition represent 780 ethylene turnovers and 43
acrylic acid turnovers. Gel permeation chromatography
(tetrahydrofuran, 30°C, polymethylmethacrylate
reference, results calculated as polymethylmethacrylate
usi:= universal calibration theory): Mn=25,000;
Mw=X2,800; Mw/Mn=1.71.
Listed below are the 13C ~R data upon which the
above analysis is based.
I3C ~ Data
CDC13, 0.05M CrAcAc, 30C
Freq ppm Intensity
~03
SUBSTITUTE SHEET (RULE 26)

WO 96123010 ~ 02338581 2001-03-O1
PCT/US96101282
51.0145 24.9141
45.434 1.11477 MEBo
38.8925 2.29147
38.5156 6.51271
37.3899 10.7484
37.0713 17.3903
36.7634 17.6341
36.4182 3.57537
36.2961 6.0822 -
34.459 2.158
34.0289 9.49713
33.7369 34.4456
33.3705 49.2646
32.8926 18.2918
32.3935 10.5014
32.0271 3.5697 3B5
31.5705 30.6837 386+, 3EOC
31.1723 1.54526
29.813 46.4503
29.3511 117.987
29.1387 21.034
28.9953 30.603
28.613 7.18386
27.2007 8.02265
26.744 23.8731
26.3777 46.8498
26.006 5.42389
25.5547 8.13592
25.0609 5.46013 2 EB4(tentative)
24.9175 2.30355 2 EB4(tentative)
24.6042 15.7434 2 EB5+
23.7547 2.78914
23.3777 5.63727
22.7936 8.07071 284
22.6768 3.78032 284
22.3211 33.1603 285+, 2EOC
19.3477 15.4369 181
18.8645 5.97477 1B1
14.1814 1.99297 183
13.7407 38.5361 1B4+, lEOC
11.0274 6.19758 1B2
10.5124 10.4707 1B2
176.567 9.61122 EBo carbonyl
174.05 9.03673 EB1+ carbonyl
173.779 85.021 EB1+ carbonyl
F~RI a 10 6
A 25-mg (0.029-mmol) sample of {[(2,6-i-
PrPh) zDABMe2] PdCH2CH2C (O) CH3}SbF6 was magnetically
stirred under 55.2 kPa of ethylene in a 50-mL Schlenk
flask with 20 mL of dry methylene chloride and 5 mL
(4.5 g; 39 mmol) of methyl 4-pentenoate for 40 hr at
room temperature. The yellow solution was rotary
204
ei meTtTt t~ cHFFT (RULE 261

WO 96/23010 CA 02338581 2001-03-O1 PCT/US96/01282
evaporated to yield 3.41 g of ethylene/methyl 4-
pentenoate copolymer as a yellow oil. The infrared
spectrum of the copolymer showed a strong ester
carbonyl absorbance at 1750cm-1. 1H NMR analysis
(CDC13): 84 methyl carbons per 1000 methylene carbons.
Comparison of the integrals of the ester methoxy
(3.67ppm) and ester methylene (~2COOMe; 2.30ppm) peaks
with the integrals of the carbon chain methyls (0.8-
0.9ppm) and methylenes (1.2-l.3ppm) indicated a methyl
10 4-pentenoate content of 6 mol% (20 wt%). This yield
and composition represent about 3400 ethylene turnovers
and 200 methyl 4-pentenoate turnovers. 13C NMR
quantitative analysis: branching per 1000 CH2: total
Methyls (93.3), Methyl (37.7), Ethyl(18.7), Propyl (2),
is Butyl (8.6), ?Am and end of chains (26.6), >_Bu and end
of chains (34.8); ester-bearing branches -CH(CH~)nCOzCHj
as a o of total ester: n>_5 (38.9), n=4 (8.3), n=1,2,3
(46.8), n=0 (6); chemical shifts were referenced to the
solvent: chloroform-dl (77 ppm). Gel permeation
20 chromatography (tetrahydrofuran, 30°C,
polymethylmethacrylate reference, results calculated as
polymethylmethacrylate using universal calibration
theory): Mn=32,400; Mw=52,500; Mw/Mn=1.62.
Example 107
A 21-mg (0.025-mmol) sample of {[(2,6-i-
PrPh)2DABMe~]PdCH~CH~C(O)CH3}SbF6 was magnetically
stirred under nitrogen in a 50-mL Schlenk flask with 5
mL of dry methylene chloride and 5 mL (4.5 g; 39 mmol)
of methyl 4-pentenoate for 74 hr. The yellow solution
30 was rotary evaporated to yield 0.09 g of a yellow oil,
poly[methyl 4-pentenoate]. The infrared spectrum
showed a strong ester carbonyl absorbance at 1750cm-1.
The 1H NMR (CDC13) spectrum showed olefinic protons at
5.4-5.5ppm; comparing the olefin integral with the
3~ integral of the ester methoxy at 3.67ppm indicates an
average degree of polymerization of 4 to 5. This
example demonstrates the ability of this catalyst to
205
SIIHSTITInE SHEET (RULE 26)

WO 96/23010 ~ 02338581 2001-03-O1 PC'T/US96/01282
'lomopoiymerize alpha olefins bearing pol~f'°~~ctional
groups not conjugated to the carbon-carbon double bond.
Exams a 108
A 53-ma (0.063-mmol) sample of ~[(2,6-i-
PrPh) 2DABMe-] PdCH2CHZC (O) CH3 ) SbF6 was placed in a 600-mL
Parr~ stirred autoclave under nitrogen. To this was
added 25 mL of dry, deaerated toluene and 25 mL (26 g;
0.36 mol) cf freshly distilled acrylic acid containing
about 100 pam phenothiazine. The autoclave was
10 pressurized to 2.1 MPa with ethylene and was stirred
for 68 hr at 23°C; the ethylene was then vented. The
autoclave contained a colorless, hazy solution. The
solution was rotary evaporated and the concentrate was
taken up i:: 50 mL of chloroform, filtered through
1~ diatomaceous earth, rotary. evaporated, and then held
under high vacuum to yield 2.23 g of light brown, very
viscous liquid ethylene/acrylic acid copolymer. The
infrared spectrum showed strong COON absorbances at
3400-2500 and at 1705cm-1, as well as strong methylene
20 absorbances at 3000-2900 and 1470cm-1.
A 0.3-g sample of the ethylene/acrylic acid
copolymer was treated with diazomethane in ether to
esterify the COOH groups and produce an ethylene/methyl
acrylate copolymer. The infrared spectrum showed a
strong ester carbonyl absorbance at 1750cm-1; the COOH
absorbances were gone. 1H NMR analysis (CDC13): 96
methyl carbons per 1000 methylene carbons. Comparison
of the integrals of the ester methoxy (3.67ppm) and
ester methylene (~i2COOMe; 2.30ppm) peaks with the
30 integrals cf the carbon chain methyls (0.8-0.9ppm) and
methylenes (1.2-l.3ppm) indicated a methyl acrylate
content of 1.8 molo (5.4 wto methyl acrylate => 4.5 wto
acrylic acid in the original copolymer). This product
yield and composition represent 1200 ethylene turnovers
35 and 22 acrylic acid turnovers. Gel permeation
chromatography (trichlorobenzene, 135°C, polystyrene
reference, results calculated as polyethylene using
206
~t 1R~TITt 1TE SHEET (RULE 26)

WO 96/23010 CA 02338581 2001-03-O1 PCT/US96/01282
sniversal calibration theory): Mn=5,330; taw=~~,000;
Mw/Mn=2.82.
E.~l~ ~
A 600-mL stirred Parr~ autoclave was sealed and
flushed with nitrogen. Fifty mL (48 g; 0.56 mcl) of
dry, deaerated methyl acrylate was introduced into the
autoclave via gas tight syringe through a port on the
autoclave head. Then 60 mg (0.07 mmol) of {((2,6-i-
PrPh)~DABMez]PdMe(EtzO))BAF was introduced into the
autoclave in the following manner: a 2.5-mL gas tight
syringe with a syringe valve was loaded with 60 mg of
{[(2,6-i-PrPh)~DABMe2]PdMe(Et20)}BAF under nitrogen in
a glove box; then 1 mL of dry, deaerated methviene
chloride was drawn up into the syringe and the contents
1~ were uuickly injected into. the autoclave through a head
port. This method avoids having the catalyst in
solution with no stabilizing ligands.
The autoclave body was immersed in a running tap
water bath; the internal temperature was very steady at
22°C. The autoclave was pressurized with ethvlene to
2.8 MPa and continuously fed ethylene with stirring for
4.5 hr. The ethylene was then vented and the product,
a mixture of methyl acrylate and yellow gooey polymer,
was rinsed out of the autoclave with chloroform, rotary
evaporated, and held under high vacuum overnia_ht to
yield 4.2 g of thick, light-brown liquid
ethylene/methyl acrylate copolymer. The infrared
spectrum of the product exhibited a strong ester
carbonyl stretch at 1740em-1. 1H NMR analysis (CDC13):
82 methyl carbons per 1000 methylene carbons.
Comparison of the integrals of the ester methoxy
(3.67ppm) and ester methylene (~2COOMe; 2.30ppm) peaks
with the integrals of the carbon chain methyls (0.8-
0.9ppm) and methylenes (1.2-=.3ppm) indicated a methyl
acrylate content of 1.5 mol% (4.4 wto). This product
~ yield and composition represent 2000 ethylene turnovers
and 31 methyl acrylate turnovers. 13C NMR analysis:
branching per 1000 CH2: total Methyls (84.6), Methyl
207
Sl IRSTITI fTF SHEET fRlILE 261

WO 96123010 ~ 02338581 2001-03-O1 pCT/US96101282
( 28 . 7 ) , Ethyl ( 15 . S ) , Propyl ( 3 . 3 ) , Butyl ( 8 .-2 ) , ?riex
and End Of Chain (23.9), methyl acrylate (13.9). Ester-
bearing -CH(CH2)nC02CH3 branches as a o of total ester:
n?5 (34.4), n=4 (6.2), n=1,2,3 (13), n=0 (46.4). Molex:
ethylene (97.6), methyl acrylate (2.4); chemical shifts
were referenced to the solvent: the high field carbon
of 1,2,4-trichlorobenzene (127.8 ppm). Gel permeation
chromatography (tetrahydrofuran, 30°C,
polymethylmethacrylate reference, results.calculated as
10 polymethylmethacrylate using universal calibration
theory): Mn=22,000; Mw=45,500; Mw/Mn=2.07.
A mixture of 1.45 g of this ethylene/methyl
acrylate copolymer, 20 mL dioxane, 2 mL water, and 1
mL of 50o aqueous NaOH was magnetically stirred at
I~ reflux under nitrogen for 4.5 hr. The liquid was then
decanted away from the swollen polymer and the polymer
was stirred several hours with three changes of bciling
water. The polymer was filtered, washed with water and
methanol, and dried under vacuum (80°C/nitrogen purge)
20 to yield 1.2 g soft of ionomer rubber, insoluble in hot
chloroform. The FTIR-ATR spectrum of a pressed film
(pressed at 125°C/6.9 MPa) showed a strong ionomer peak
at 1570cm-1 and virtually no ester carbonyl at 1750cm-
1. The pressed film was a soft', slightly tacky rubber
with about a 50o elongation to break. This example
demonstrates the preparation of an ionomer from this
ethylene/methyl acrylate polymer.
Example 110
The complex [(2,6-i-PrPh)2DABMe2]PdMeCl (0.020 g,
30 0.036 m-nol) was weighed into a vial and dissolved in 6
ml CH2C12. NaBAF (0.0328, 0.036 mmol) was rinsed into
the stirring mixture with 4 ml of CH2C12. There was an
immediate color change from orange to yellow. Tre
solution was stirred under 6.2 MPa ethylene in a Fisher
3~ Porter tube with temperature control at 19°C. The
internal temperature rose to 22°C during the first 15
minutes. The temperature controller was raised to
30°C. After 35 minutes, the reaction was consuming
208
c~ iacmi >TC ~NFFT raWE 261

WO 96/23010 CA 02338581 2001-03-O1 PCT/US96/01282
:thylene slowly. After a total reactior.~ tifie of about
20 h, there was no longer detectable ethylene
consumption, but the liquid level in the tube was
noticeably higher. Workup by addition to excess MeOH
gave a viscous liquid precipitate. The precipitate was
redissolved in CH2C12, filtered through a 0.5 micron
PTFE filter and reprecipitated by addition to excess
MeOH to give 7.208 g dark brown viscous oil (7180
equivalents of ethylene per Pd). 1H NMR (CDC13) 0.8-
1.0 (m, CH3); 1.0-1.5 (m, CH and CH2). Integration
allows calculation of branching: 118 methyl carbons per
1000 methylene carbons. GPC in THF vs. PMMA standard:
Mn=12,700, Mw=28,800, Mw/Mn=2.26.
Example 111
1~ The solid complex {((2,6-i-
PrPh)~DABMe2]PdMe(Et20)}SbF6 (0.080 g, 0.096 mmol) was
placed in a Schlenk flask which was evacuated and
refilled with ethylene twice. Under one atm of
ethylene, black spots formed in the center of the solid
complex and grew outward as ethylene was polymerized in
the solid state and the resulting exotherm destroyed
the complex. Solid continued to form on the solid
catalyst that had not been destroyed by the exotherm,
and the next day the flask contained considerable solid
'~ and the reaction was still slowly consuming ethylene.
The ethylene was disconnected and 1.808 g of light gray
elastic solid was removed from the flask (644
equivalents ethylene per Pd). The 1H NMR in CDC13 was
similar to example 110 with 101 methyl carbons per 1000
methylene carbons. Differential Scanning Calorimetry
(DSC): first heat 25 to 150°C, 15°C/min, no events;
second heat -150 to 150°C, Tg = -53°C with an
endothermic peak centered at -20°C; third heat -150 to
275°" Tg = -51°C with an endothermic peak centered at
3~ -20°C. GPC (trichlorobenzene, 135°C, polystyrene
reference, results calculated as linear polyethylene
using universal calibration theory): Mn=13,000
Mw=313,000 Mw/Mn=24.
209
e~ ~ce~Tt tT~ CNFFT !Rl It F 961

WO 96/23010 ~ 02338581 2001-03-O1 PCTlUS96/01282
Example 11
The complex ~ [ (2, 6-i-PrPh) ZDABMe,] PdMe (Et20) )SbF6
(0.084 g, 0.100 mmol) was loaded into a Schlenk flask
in the drybox followed by 40 ml of dry dioxane. The
septum-capped flask was connected to a Schlenk line and
the flask was then briefly evacuated and refilled with
ethylene. The light orange mixture was stirred under
an ethylene atmosphere at slightly above 1 atm by using
a mercury bubbler. There was rapid uptake of ethylene.
10 A room temperature water bath was used to control the
temperature of the reaction. After 20 h, the reaction
was worked up by removing the solvent in vacuo to give
10.9 g of a highly viscous fluid (3870 equivalents of
ethylene per Pd). Dioxane is a solvent for the Pd
1~ complex and a non-solvent.for the poivmer product. 1H
NMR (CDC13) 0.8-1.0 (m, CH3); 1.0-1.5 (m, CH and CH2).
Integration allows calculation of branching: 100 methyl
carbons per 1000 methylene carbons. GPC
(trichlorobenzene, 135°C, polystyrene reference,
20 results calculated as linear polyethylene using
universal calibration theory): Partially resolved
trimodal distribution with Mn=16300, Mw=151000
Mw/Mn=9.25. DSC (second heat,-150°C to 150°C,
15°C/min) Tg=-63°C, endothermic peak centered at -
30°C.
Example ~~
Polymerization of ethylene was carried out
according to example 112, using pentane as solvent.
Pentane is a non-solvent for the Pd complex and a
30 solvent for the polymer product. The reaction gave
7.47 g of dark highly viscous fluid (2664 equivalents
of ethylene per Pc3). 1H NMR analysis (CDC13): 126
methyl carbons per 1000 methylene carbons. 13C NMR
analysis, branching per 1000 CH2: Total methyls
3~ (128.8), Methyl (37.8), Ethyl (27.2), Propyl (3.5),
Butyl (14.5), Amyl (2.5), ?Hexyl and end of chain
(44.7), average number of carbon atoms for ?Hexyl
branches = 16.6 (calculated from intrinsic viscosity
210
SiIBSTiTLtTE SHEET (RULE 26)

WO 96/23010 CA 02338581 2001-03-O1 PCT/US96/01282
and GPC molecular weight data). Quantitation of the -
CHZCH(CH3)CHZCH3 structure per 1000 CH2's: 8.3. These
side chains are counted as a Methyl branch and an Ethyl
branch in the quantitative branching analysis. GPC
S (trichlorobenzene, 135°C, polystyrene reference,
results calculated as linear polyethylene using
universal calibration theory): Mn=9,800, Mw=16,100,
Mw/Mn=1.64. Intrinsic viscosity (trichlorobenzene,
135°C) - 0.125 g/dL. Absolute molecular weights
10 calculated by GPC (trichlorobenzene, 135°C, polystyrene
reference, corrected for branching using measured
intrinsic viscosity): Mn=34,900, Mw=58,800, Mw/Mn=1.68.
DSC (second heat, -150°C to 150°C, 15°C/min) Tg = -
71°C, endothermic peak centered at -43 °C.
I~ Example 114
Polymerization of ethylene was carried out
according to example 112, using distilled degassed
water as the medium. Water is a non-solvent for both
the Pd complex and the polymer product. The mixture
20 was worked up by decanting the water from the product
which was then dried in vacuo to give 0.427 g of dark
sticky solid (152 equivalents of ethylene per Pd). 1H
NMR analysis (CDC13): 97 methyl carbons per 1000
methylene carbons. GPC (trichlorobenzene, 135°C,
polystyrene reference, results calculated as linear
polyethylene using universal calibration theory):
Mn=25,100, Mw=208,000, Mw/Mn=8.31.
Example 1~5
Polymerization of ethylene was carried out
30 according to example 112, using 2-ethylhexanol as the
solvent. The Pd complex is sparingly soluble in this
solvent and the polymer product is insoluble. The
polymer product formed small dark particles of high
viscosity liquid suspended in the 2-ethylhexanol. The
35 solvent was decanted and the polymer was dissolved in
CHC13 and reprecipitated by addition of excess MeOH.
The solvent was decanted, and the reprecipitated .
polymer was dried in vacuo to give 1.66 g of a dark
211
ci lacim rrc cN~~ r SRI II F ?61

WO 96123010 ~ 02338581 2001-03-O1 p~'~7s96101282
;:ighly viscous fluid (591 equivalents of ethylene per
Pd). 1H NMR analysis (CDC13): 122 methyl carbons per
1000 methylene carbons. GPC (trichlorobenzene, 135°C,
polystyrene reference, results calculated as linear
5 polyethylene using universal calibration theory):
Mn=7,890, Mw=21,600, Mw/Mn=2.74.
Example 116
The solid complex {[(2,6-i-
PrPh) zDABMe2] PdMe (Et20) } SbF6 ( 0 . 084 g, 0 . 100 mmol ) was
10 loaded into a Schlenk flask in the drybox. The flask
was connected to a Schlenk line under 1 atm of
ethylene, and cooled to -78°C. Solvent,(CH2C12, 40 ml)
was added by syringe and after equilibrating at -78°C
under ethylene, the mixture was warmed to room
I~ temperature under ethylene: The mixture was stirred
under an ethylene atmosphere at slightly above 1 atm by
using a mercury bubbler. There was rapid uptake of
ethylene. A room temperature water bath was used to
control the temperature of the reaction. After 24 h,
20 the reaction was worked up by removing the solvent in
vacuo to give 24.5 g of a highly viscous fluid (8730
equivalents of ethylene per Pd). CH2C12 is a good
solvent for both the Pd complex and the polymer
product. The polymer was dissolved in CH2C12, and
2~ reprecipitated by addition to excess MeOH in a tared
flask. The solvent was decanted, and the
reprecipitated polymer was dried in vacuo to give 21.3
g of a dark highly viscous fluid. 1H NMR analysis
(CDC13): 105 methyl carbons per 1000 methylene carbons.
30 C-13 NMR analysis, branching per 1000 CH2: Total
methyls (118.6), Methyl (36.2), Ethyl (25.9), Propyl
(2.9), Butyl (11.9), Amyl (1.7), ?Hexyl and end of
chains (34.4), average number of carbon atoms for
Hexyl branches = 22.5 (calculated from intrinsic
3~ viscosity and GPC molecular weight data). Quantitation
of the -CH2CH(CH3)CH2CH3 structure per 1000 CH2's: 8.1.
These side chains also counted as a Methyl branch and
an Ethyl branch in the quantitative branching analysis.
?12
e~ ioe~Tt tTC Cu~cT IR111 F 9R1

WO 96/23010 CA 02338581 2001-03-O1 PCT/LTS96/01282
.~PC (trichlorobenzene, 135°C, polystyrene reference,
results calculated as linear polyethylene using
universal calibration theory): Mn=25,800, Mw=45,900,
Mw/Mn=1.78. Intrinsic viscosity (trichlorobenzene,
5 135°C) - 0.24 g/dL. Absolute molecular weights
calculated by GPC (trichlorobenzene, 135°C, polystyrene
reference, corrected for branching using measured
intrinsic viscosity): Mn=104,000, Mw=188,000,
Mw/Mn=1.81.
10 Listed below are the 13C NMR data upon which the
above analysis is based.
213
Sl IRS"fITIITE SHEET (RULE 26)

WO 96/23010 ~ 02338581 2001-03-O1
PCTIUS96/01282
13C ~R Data
TCB, 120C, 0.06M CrAcAc
Freq ppm Intensity
39.7233 5.12305
39.318 17.6892 MH2
38.2022 17.9361 MB3+
37.8369 32.3419 MB3+
37.2469 43.1136 a81, 383
36.8335 10.1653 aBl, 383
36.7452 14.674 aBl, 383
34.9592 10.3554 ay+B, (484, etc.)
585,
34.6702 24.015 ay+B, (4B4, etc.)
5B5,
34.5257 39.9342 ay+B, (4B4, etc.)
585,
34.2006 109.158 ay+B, (4B4, etc.)
585,
33.723 36.1658 ay+B, (4B4, etc.)
585,
33.3136 12.0398 MB1
32.9323 20.7242 MB1
32.4266 6.47794 3B5
31.9409 96.9874 3B6+, 3EOC
31.359 15.2429 ,i+y+B,3B4
31 .09E1 19.29Ei i+y+B, 3B4
30.6606 15.8689 y+y+B, 384
30.2271 96.7986 -r+y+B,3B4
30.1188 54.949 y+y+B, 3B4
29.7455 307.576 y+y+B, 3B4
29.5809 36.2391 y+y+B, 384
29.3361 79.3542 y+y+B, 3B4
29.2157 23.0783 y+y+B, 3B4
27.6424 24.2024 ~iy+B, 2B2,(4B5,etc.)
27.526 29.8995 py+B, 2B2,(4B5,etc.)
27.3534 23.1626 (3y+H, 2B2,(4B5,etc.)
27.1607 70.8066 py+B, 2B2,(4B5,etc.)
27.0042 109.892 py+B, 2B2,(485,etc.)
26.5908 7.13232 py+B, 2B2,(4B5,etc.)
26.3941 23.945 (3y+B, 2B2,(485,etc.)
25.9446 4.45077 ~3y+B, 2B2,(4B5,etc.)
24.4034 9.52585 ppB
24.2428 11.1161 ~ipB
23.1391 21.2608 2B4
23.0227 11.2909 2B4
22.6494 103.069 2B5+, 2EOC
20.0526 5.13224 283
19.7355 37.8832 1B1
19.2017 19.8043 181, Structure
XXVII
14.4175 4.50604 1B3
13.9118 116.163 1B4+, lEOC
11.1986 18.5867 182, Structure
XXVII
10.9617 32.3855 1B2
214
c~ veeTm rTF ~ta>:FT IR1JLE 267

WO 96123010 CA 02338581 2001-03-O1 PCTIUS96/01282
Examr~
Polymerization of ethylene was carried out
according to example 116, at a reaction temperature of
0°C and reaction time of several hours. The polymer
product formed a separate fluid phase on the top of the
mixture. The reaction was quenched by addi:~g 2 ml
acrylonitrile. The product was moderately v_scous
fluid, 4.5 g (1600 equivalents of ethylene per Pd). 1H
NMR analysis (CDC13): 108 methyl carbons.per 1000
methylene carbons. 13C NMR analysis, branc!:iag per
1000 CH2: Total methyls (115.7), Methyl (35.7), Ethyl
(24.7), Propyl (2.6), Butyl (11.2), Amyl (3.2), >_Hexyl
and end of chain (37.1). Quantitation of the -
CH2CH(CH3)CHzCH3 structure per 1000 CH2's: 7.~. These
l~ side chains are counted as a Methyl branch and an Ethyl
branch in the quantitative branching analysis. GPC
(trichlorobenzene, 135°C, polystyrene reference,
results calculated as linear polyethylene using
universal calibration theory: Mn=15,200, Mw=23,700,
Mw/Mn=1.56.
Exam ~~e
The Pd complex ~[(2,6-i-
PrPh) zDABMe2] PdCHzCHzCH2C (O) OCH~ }SbF6 (0 . 084 g, 0 . 100
mmol) was loaded into a Schlenk flask in the drybox,
and 40 ml of FC-75 was added. ~'he septum-caeped flask
was connected to a Schlenk line and the flas)c was then
briefly evacuated and refilled with ethylene from the
Schlenk line. The mixture was stirred under an
ethylene atmosphere at slightly above 1 atm by using a
mercury bubbler. Both the Pd initiator and the polymer
are insoluble in FC-75. After 15 days, the reaction
flask contained a large amount of gray elastic solid.
The FC-75 was decanted, and the solid polymer was then
dissolved in CHC13 and precipitated by addition of the
3~ solution to excess MeOH. The polymer was dried in
vacuo, and then dissolved in o-dichlorobenzene at
100°C. The hot solution was filtered through a 10 ~m
FTFE filter. The filtered polymer solution was shaken
21~
ci tRCTITI tTF SHFFT lRl II F 261

WO 96/23010 ~ 02338581 2001-03-O1 PCT/US96/01282
,:n a separatory funnel with concentrated sulfuric acid,
followed by distilled water, followed by 5% NaHC03
solution, followed by two water washes. The polymer
appeared to be a milky suspension in the organic layer
during this treatment. After washing, the polymer was
precipitated by addition to excess MeOH in a blender
and dried at room temperature in vacuo to give 19.6 g
light gray elastic polymer fluff (6980 equivalents of
ethylene per Pd). 1H NMR analysis (CDC13): 112 methyl
10 carbons per 1000 methylene carbons. 13C NMR analysis,
branching per 1000 CH2: Total methyls (114.2), Methyl
(42.1), Ethyl (24.8), Propyl (5.1), Butyl (10.2), Amyl
(4), >_Hexyl and end of chain (30.3), average number cf
carbon atoms for >_Hexyl branches = 14.4 (calculated
1~ from intrinsic viscosity and GPC molecular weight
data). GPC (trichlorobenzene, 135°C, polystyrene
reference, results calculated as linear polyethylene
using universal calibration theory: Mn=110,000,
Mw=265,000, Mw/Mn=2.40. Intrinsic viscosity
20 (trichlorobenzene, 135°C) - 1.75 g/dL. Absolute
molecular weights calculated by GPC (trichlorobenzene,
135°C, polystyrene reference, corrected for branching
using measured intrinsic viscosity): Mn=214,000,
Mw=535,000, Mw/Mn=2.51.
Fxamnle 119
Polymerization of ethylene was carried out
according to example 112, using the complex {((2,6-i-
PrPh) 2DABMe2] PdCH2CH2CH2C (O) OCH3 ) SbF6 ( 0 . 084 g, 0 . 100
mmol) as the initiator and CHC13 as the solvent. The
30 reaction gave 28.4 g of dark viscous fluid (10,140
equivalents of ethylene per Pd). 1H NMR analysis
(CDC13): 108 methyl carbons per 1000 methylene carbons.
13C NMR analysis, branching per 1000 CH2: Total methyls
(119.5), Methyl (36.9), Ethyl (25.9), Propyl (2.1),
3~ Butyl (11), Amyl (1.9), >_Hexyl and end of chain
(38.9). GPC (.trichlorobenzene, 135°C, polystyrene
reference, results calculated as linear polyethylene
216
Ct taC~tTI 1TF SNFFT (Rl 1l E 261

WO 96/23010 CA 02338581 2001-03-O1 PCT/US96/01282
;.sing universal calibration theory): Mn=10,800,
Mw=26,800, Mw/Mn=2.47.
Examble 120
Polymerization of ethylene was carried out
according to example 112, using the complex [(2,6-i-
PrPh) zDABMe2] PdMe (OS02CF3) (0.0688, 0.10 mmol) as the
initiator and CHC13 as the solvent. The reaction gave
5.98 g of low viscosity fluid (2130 equivalents of
ethylene per Pd). 1H NMR (CDC13) 0.8-1.0 (m, CH3);
10 1.0-1.5 (m, CH and CH2); 1.5-1.7 (m, C~3CH=CH- ); 1.9-
2.1 (broad, -C~2CH=CHC~2- ); 5.3-5.5 (m, -CH=CH- ).
Integration of the olefin end groups assuming one
olefin per chain gives Mn = 630 (DP = 24). A linear
polymer with this molecular weight and methyl groups at
l~ both ends should have 46 methyl carbons per 1000
methylene carbons. The value measured by integration
is 161, thus this polymer is highly branched.
Exam~l ~
Polymerization of ethylene was carried out
20 according to example 112, using the complex {[(2,6-i-
PrPh) 2DABHz] PdCH~CH2CH2C (O) OCH3 } SbF6 ( 0 . 082 g, 0 . 10 mmol )
as the initiator and CHC13 as the solvent. The
reaction gave 4.47 g of low viscosity fluid (1600
equivalents of ethylene per Pd). 1H NMR (CDC13) is
similar to example 120. Integration of the olefin end
groups assuming one olefin per chain gives Mn = 880 (DP
- 31). A linear polymer with this molecular weight and
methyl groups at both ends should have 34 methyl
carbons per 1000 methylene carbons. The value measured
30 by integration is 156, thus this polymer is highly
branched.
Exam~e 122
Polymerization of ethylene was carried out
according to example 112, using the complex {[(2,6-i-
3o PrPh) ~DABMe~] PdCH,CH2CH~C (O) OCH3}BC1 (C6F5) 3 (0. 116 g,
0.10 mmol) as the initiator and CHC13 as the sclvent.
The reaction gave 0.278 g of low viscosity fluid, after
correcting for the catalyst residue this is 0.160 g (57
?17
SU8STITlITE SHEET (RULE 261

WO 96/23010 ~ 02338581 2001-03-O1 PCT/US96/01282
equivalents of ethylene per Pd) . Mn estimatea~~~o~
integration of olefin end groups is 300.
Examz~
The complex [(2,6-i-PrPh)2DABMe2)PdMeCl (0.056 g,
0.10 mmol) was loaded into a Schlenk flask in the
drybox followed by 40 ml of dry toluene. A solution of
ethyl aluminum dichloride (1.37 ml of 0.08 M solution
in o-dichlorobenzene) was added while stirring.
Polymerization of ethylene was carried out using this
10 solution according to example 112. The reaction gave
0.255 g of low viscosity fluid, after correcting for
the catalyst residue this is 0.200 g (71 equivalents of
ethylene per Pd). Mn estimated by integration of
olefin end groups is 1300.
Exams a 124
Methyl acrylate was sparged with argon, dried over
activated 4A sieves, passed through activity 1 alumina
B in the drybox, and inhibited by addition of 20 ppm
phenothiazine. The solid complex {[(2,6-1-
20 PrPh)zDABMe2)PdMe(Et20)}SbF6 (0.084 g, 0.100 mmol) was
loaded into a Schlenk flask in the drybox. The flask
was connected to a Schlenk line under 1 atm of
ethylene, and cooled to -78°C. Forty ml of CH2C12 was
added by syringe and after equilibrating at -78°C under
ethylene, 5 ml of methyl acrylate was added by syringe
and the mixture was warmed to room temperature under
ethylene. After 40 h, the reaction was worked up by
removing the solvent in vacuo to give 3.90 g of
moderately viscous fluid. Integration of the 1H NMR
30 spectrum showed that this copolymer contained 6.9 mole
% methyl acrylate. No poly(methyl acryiate)
homopolymer could be detected in this sample by 1H NMR.
1H NMR shows that a significant fraction of the ester
groups are located at the ends of hydrocarbon branches:
35 3.65(s, -C02CH3, area=4.5), 2.3(t, -C$2C02CH3, ester
ended branches, area=3), 1.6(m, -C$2CH2C02CH3, ester
ended branches, area=3), 0.95-1.55(m, CH and other CH2,
area=73), 0.8-0.95(m, CH3, ends of branches or ends of
218
ci ~ac~~n rTC cu~cT fRl II F 9R1

WO 96123010 CA 02338581 2001-03-O1 PCT/IJS96101282
chains, area=9.5) his is confirmed by the i3C NMR
quantitative analysis: Mole%: ethylene (93.1), methyl
acrylate (6.9), Branching per 1000 CH2: Total methyls
(80.2), Methyl (30.1), Ethyl (16.8), Propyl (1.6),
Butyl (6.8), Amyl (1.3), ?Hexyl and end of chain
(20.1), methyl acrylate (41.3), Ester branches
CH(CH~)nC02CH3 as a o of total ester: n?5 (47.8), n=4
(17.4), n=1,2,3 (26.8), n=0 (8).
GPC of this sample was done in THF vs. PMMA
standards using a dual UV/RI detector. The outputs of
the two detectors were very similar. Since the Uv
detector is only sensitive to the ester functionality,
and the RI detector is a relatively nonselective mass
detector, the matching of the two detector outputs
1~ shows that the ester functionality of the methyl
acrylate is distributed throughout the entire molecular
weight range of the polymer, consistent with a true
copolymer of methyl acrylate and ethylene.
A 0.503 g sample of the copolymer was fractionated
by dissolving in benzene and precipitating partially by
slow addition of MeOH. This type of fractionation
experiment is a particularly sensitive method for
detecting a low molecular weight methyl acrylate rich
component since it should be the most soluble material
unde_ the precipitation conditions.
The precipitate 0.349 g, (69%) contained 6.9 mole
% methyl acrylate by 1H NMR integration, GPC (THF, PMMA
standard, RI detector): Mn=19,600, Mw=29,500,
Mw/Mn=1.51. The soluble fraction 0.1808 (36%)
contained 8.3 mole % methyl acrylate by 1H NMR
integration, GPC (THF, PMMA standard, RI detector):
Mn=11,700, Mw=19,800, Mw/Mn=1.70. The
characterization of the two fractions shows that the
acrylate content is only slightly higher at lower
molecular weights. These results are also consistent
with a true copolymer of the methyl acrylate with
ethylene.
219
ct ~acm t~~ ~NF~ !Rl 11 E 261

WO 96/23010 ~ 02338581 2001-03-O1 PCT/US96/01282
Example 125
Methyl acrylate was sparged with argon, dried over
activated 4A sieves, passed through activity 1 alumina
B in the drybox, and inhibited by addition of 20 ppm
phenothiazine. The complex [(2,6-i-
PrPh) 2DABMez] PdMe (OSO~CF3) (0. 068 g, 0.10 mmol ) was
loaded into a Schlenk flask in the drybox, and 40 ml of
CHC13 was added followed by 5 ml of methyl acrylate..
The septum capped flask was connected to a Schlenk line
10 and the flask was then briefly evacuated and refilled
with ethylene from the Schlenk line. The light orange
mixture was stirred under an ethylene atmosphere at
slightly above 1 atm by using a mercury bubbler. After
20 h, the reaction was worked up by removing the
1~ solvent and unreacted methyl acrylate in vacuo to give
1.75 g or a low viscosity copolymer.
i3C NMR quantitative analysis: Molex: ethylene
(93), methyl acrylate (7), Branching per 1000 CH2:
Total methyls (100.9), Methyl (33.8), Ethyl (19.8),
20 Propyl (1.9), Butyl (10.1), Amyl (7.3), ?Hexyl and end
of chains (28.4), methyl acrylate (41.8). This sample
is low molecular weight - total methyls does not
. include end of chain methyls. Ester branches -
CH(CH2)nC02CH3 as a % of total ester: n>_5 (51.3), n=4
(18.4), n=1,2,3 (24), n=0 ( 6.3).
Fxamnle 126
Ethylene and methyl acrylate were copolymerized
according to example 125 with catalyst {[(2,6-i-
PrPh) 2DABMe2] PdCH,CH2CH2C (O) OCH3 }BAF (0 . 136 g, 0. 10
30 mmol) in CH2C12 solvent with a reaction time of 72
hours to give 4.93 g of copolymer.
Example 127
Ethylene and methyl acrylate were copolymerized ~
according to example 125 with catalyst {[(2,6-i-
3~ PrPh)2DABMe,]PdCH2CH2CH2C(O)OCH3}SbF6 (0.084 g, 0.10
mmol) with a reaction time of 72 hours to give 8.19 g
of copolymer.
220
~i ~R~~n r~ ~HF~ rRU~E 26)

WO 96123010 ~ 02338581 2001-03-O1 pCTlUS96101282
Rxamola 128
Ethylene and methyl acrylate were copolymerized
according to example 125 with catalyst {[(2,6-i-
PrPh) zDABH2) PdCH2CH2CH2C (O) OCH3 } SbF6 ( 0 . 082 g, 0 . 10 mmol )
to give 1.97 g of copolymer.
Exa~r~le ~ ~9
Ethylene and methyl acrylate were copolymerized
according to example 125 with catalyst {[(2,6-i-
PrPh) zDABMe~) PdMe (CH3CN) ?SbF6 (0.080 g, 0.10 mmol) to
give 3.42 g of copolymer. The 1H NMR shows primarily
copolymer, but there is also a small amount of
poly(methyl acrylate) homopolymer.
Examoie X30
Ethylene and methyl acrylate (20 ml) were
1~ copoiymerized in 20 ml of CHCl3 according to example
125 using catalyst {[(2,6-i-
PrPh) ~DABMe2) PdCHzCH2CH2C (O) OCH3 } SbF6 ( 0 . 339 g, 0 . 40
mmol) to give 2.17 g of copolymer after a reaction time
of 72 hours. 13C NMR quantitative analysis: Mole%:
'?0 ethylene (76.3), methyl acrylate (23.7). Branching per
1000 CH2: Total methyls (28.7), Methyl (20.5), Ethyl
(3.8), Propyl (0), Butyl (11), ?Amyl and end of chains
(13.6), methyl acrylate (138.1). Ester branches -
CH(CH2)nC02CH3 as a % of total ester: n>_5 (38.8), n=4
(20), n=1,2,3 (15.7), n=0 (25.4).
Example 131
Ethylene and methyl acrylate (20 ml) were
copolymerized in 20 ml of CHC13 at 50°C for 20 hours
according to example 125 using catalyst {[(2,6-1-
30 PrPh)ZDABMe2)PdCH;CH2CH2C(O)OCH3)SbF6 (0.339 g, 0.40
mmol) to give 0.795 g of copolymer. DSC (two heats,
150 to +150°C, 15°C/min) shows Tg= -48°C.
Example 132
A solution of the ligand (2,6-i-PrPh)2DAB(Me2)
3~ (0.045 g, 0.11 mmol) dissolved in 2 ml of CHC13 was
added to a solution of the complex [PdMe(CH3CN)(1,5-
cyclooctadiene))+SbF6- (0.051 g, 0.10 mmol) in 2 ml of
CHC13. This mixture was combined with 35 ml of
2?1
n, ~ne~Trr rrc ~uccT rQl ll ~ 9R1

CA 02338581 2001-03-O1
WO 96123010 PCT/US96/01282
additional CHC13 and 5 ml cf methyl acryiate in a
Schlenk flask in a drybox, and then a copolymerization
with ethylene was carried out according to example 125
to give 1.94 g of copolymer.
Examr~le 133
Methyl acrylate (5 ml) was added to the solid
catalyst ( ( (2, 6-i-PrPh) 2DABMez] PdMe (Et20) }BF9 ( C . 069g,
0.10 mmol) followed by 40 ml of CHC13. The addition of
methyl acrylate before the CHC13 is often.important to
10 avoid deactivation of the catalyst. A copolymerization
with ethylene was carried out according to example 125
to give 2.&7 g of copolymer.
Characters zation of ~Ol y tethytl_ene-co-meth~rl acryi a
~~H NMR
NMR spectra in CDC13 were integrated and the
polymer compositions and branching ratios were
calculated. See example 124 for chemical shifts and
assignments.
20
ExampleYieldtg) methyl acrylateCH3 per C02CH3 per
tmole o) 1000 CH2 l
1000 CHI
124 3.9 6.9 80 42
125 1.75 7.1 104 45
126 4.93 5.6 87 34
127 8.19 6.1 87 37
128 1.97 7.3 159 50
129 3.42 9.5 86 59
130 2.17 22.8 29 137
131 0.795 41 14 262
132 1.94 6.1 BO 36
133 2.87 8.2 70 49
Molecular Weight Characterization
GPC was done in THF using PMMA standards and an RI
detector except for example 133 which was done in
~5 trichlorobenzene at 135°C vs. polystyrene reference
m mnTrrt tTe euccT SDI il C ~R1

WO 96/23010 CA 02338581 2001-03-O1 PCT/US96101282
with results calculated as linear polyethylene using
universal calibration theory. When polymer end groups
could be detected by 1H NMR (5.4 ppm, multiples, -
CH=CH-, internal double bond), Mn was calculated
assuming two olefinic protons per chain.
Example Mr MW MW/Mn Mn (1H NMR)
124 15,500 26,400 1.70
125 1,540 2,190 1.42 850
126 32,500 49,900 1.54
127 12,300 22,500 1.83
128 555 595 1.07 360
129 16,100 24,906 1.55
13C B00 3,180 3.98 1,800 -
131 1,100
132 15,200 26,000 1.71
133 5,010 8,740 1.75
Example 134
Ethylene and t-butyl acrylate (20 ml) were
10 copolymerized according to example 130 to give 2.039 g
of viscous fluid. 1H NMR of the crude product showed
the desired copolymer along with residual unreacted t-
butyl acrylate. The weight of polymer corrected for
monomer was 1.84 g. The sample was reprecipitated to
15 remove residual monomer by slow addition of excess MeOH
to a CHC13 solution. The reprecipitated polymer was
dried in vacuo. 1H NMR (CDC13): 2.2(t, -CH2C02C(CH3)3.
ester ended branches), 1.6(m, -C$2CH2C02C(CH3)3, ester
ended branches), 1.45(s, -C(CH3)3), 0.95-1.45(m, CH and
20 other CH2), 0.75-0.95(m, CH3, ends of hydrocarbon
branches or ends of chains). This spectrum shows that
the esters are primarily located at the ends of
hydrocarbon branches; integration gave 6.7 mole % t-
butyl acrylate. 13C NMR quantitative analysis,
branching per 1000 CH2: Total methyls (74.8), Methyl
(27.7), Ethyl (15.3), Propyl (1.5), Butyl (8.6), ?Amyl
e~ ~e~Tt~ tTC cucCT !RI II F ~Rl

WO 96/23010 ~ 02338581 2001-03-O1
PCT/US96/01282
,:nd end of chains (30.8), -C02C(CH3)3 ester (43.2).
Ester branches -CH(CH2)nC02C(CH3)3 as a % of total
ester: n>_5 (44.3), n=1,2,3,4 (37.2), n=0 (18.5). GPC
(THF, PMMA standard): Mn=6000 Mw=8310 Mw/Mn = 1.39.
S Example 135
Glycidyl acrylate was vacuum distilled and
inhibited with 50 ppm phenothiazine. Ethylene and
glycidyl acrylate (5 ml) were copolymerized according
to Example 125 using catalyst {[(2,6-1-
PrPh) 2DABMe2) PdCH2CH2CH2C (O) OCH3 } SbF6 ( 0 . 084 g, 0 . 10
mmol). The reaction mixture was filtered through a
fritted glass filter to remove chloroform insolubles,
and the chloroform was removed in vacuo to give 14.1 a
viscous yellow oil which still contained residual
l~ unreacted glycidyl acrylate. The sample was
reprecipitated to remove residual monomer by slow
addition of excess acetone to a CHC13 solution. The
reprecipitated polymer was dried in vacuo to give 9.92
g of copolymer containing 1.8 mole % glycidyl acrylate.
20 1H NMR (CDC13): 4.4, 3.9, 3.2, 2.85,
2.65 (multiplets, 1 H each -CH2CH[ CH2 i ) 2.35 (t,
-CH2C02CHZCHI CH2 i , ester ended branches), 1.65(m,
-CH2CH2COZCH2CHCH20, ester ended branches), 0.95-1.5(m.CH
U
and other CH2), 0.75-0.95(m, CH3, ends of hydrocarbon
branches or ends of chains). This spectrum shows that
the epoxide ring is intact, and that the glycidyl ester
groups are primarily located at the ends of hydrocarbon
branches. GPC (THF, PMMA standard): Mn=63,100
Mw=179,000 Mw/Mn = 2.85.
30 13C NMR quantitative analysis, branching per 1000
CH2: Total methyls (101.70 , Methyl (32.5), Ethyl ,
(21.3), Propyl (2.4), Butyl (9.5), Amyl (1.4), >_vexyl
and end of chains (29.3), Ester branches -CH(Cr2)nC02R
as a % of total ester: n?5 (39.7), n=4 (small amount),
3~ n=1,2,3 (50.7), n=0 (9.6).
224
cl lccT1T11TC CNFFT (R111 F 261

WO 96/23010 CA 02338581 2001-03-O1 PCT/US96I01282
A 3.24-g sample of the copolymer was dissolved in
50 mL of refluxing methylene chloride. A solution of
0.18 g oxalic acid dihydrate in 5 mL of 1:1 chloroform-
acetone was added to the solution of copolymer and the
solvent was evaporated off on a hot plate. The thick
liquid was allowed to stand in an aluminum pan at room
temperature overnight; the pan was then placed in an
oven at 70°C for 1.5 hr followed by 110°C/vacuum for 5
hr. The cured polymer was a dark, non-tacky soft
10 rubber which tore easily (it had a very short
elongation to break despite its rubberiness).
Exam 36
1-Pentene (20 ml) and methyl acrylate (5 ml) were
copolymerized in 20 ml chloroform for 96 hours using
I~ catalyst { [ (2, 6-i-PrPh) 2DABMe2] PdCH2CH2CHzC (O) OCH, }SbFE
(0.084 g, 0.10 mmol). The solvent and unreacted
monomers were removed in vacuo to give 0.303 g
copolymer (0.219 g after correcting for catalyst
residue). The 1H NMR spectrum was similar to the
20 ethylene/methyl acrylate copolymer of example 124
suggesting that many of the ester groups are located at
the ends of hydrocarbon branches. Integration shows
that the product contains 21 mole % methyl acrylate.
There are 65 acrylates and 96 methyls per 1000
methylene carbons. GPC (THF, PMMA standard): Mn=6400
Mw=11200 Mw/Mn = 1.76.
Fxam~le i37
Benzyl acrylate was passed through activity 1
alumina B, inhibited with 50 ppm phenothiazine, and
30 stored over activated 4A molecular sieves. Ethylene
and benzyl acrylate (5 ml) were copolymerized according
to example 135 to give 11.32 g of viscous fluid. 1H
NMR of the crude product showed a mixture of copolymer
and unreacted benzyl acrylate (35 wt ~) The residual
3~ benzyl acrylate was removed by two reprecitations, the
first by addition of excess MeOH to a chloroform
solution, and the second by addition of excess acetone _
to a chloroform solution. 1H NMR (CDC13): 7.35 (broad
225
ClliiCTfTl1'fF CNFFT fRl II F 961

WO 96/23010 CA 02338581 2001-03-O1 pC'fNg96101282
~,_ -CH2C6H5), 5.1(s, -CH2C6H5), 2.35(t, -CH2C02CH2C6H5,
ester ended branches), 1.6(m, -CIj2CH2C02CH2C6H5, ester
ended branches), 0.95-1.5(m, CH and other CH2), 0.75-
0.95(m, CH3, ends of hydrocarbon branches or ends of
chains). Integration shows that the product contains
3.7 mole % benzyl acrylate. There are 21 acrylates and
93 methyls per 1000 methylene carbons. GPC (THF, PMMA
standard): Mn=46,200 Mw=73,600 Mw/Mn = 1.59.
13C ~,R quantitative analysis, Branching per 1000
10 CH2: Total methyls (97.2), Methyl (32.9), Ethyl (20.3),
Propyl (2.4), Butyl (9.7), Amyl (2.9), >_Hexyl and end
of chains (35.2), benzyl acrylate (17.9), Ester
branches -CH(CH2)nC02R as a o of total ester: n?5
(44.51, n=4 (7.2), n=1,2,3 (42.3), n=0 (6)
1~ Example 138
1-Pentene (10 ml) and ethylene (1 atm) were
copolymerized in 30 ml chloroform according to example
125 using catalyst {[(2,6-i-
PrPh)~DABMe~]PdCH2CH2CH2C(O)OCH3}SbF6 (0.084 g, 0.10
20 mmol) to give 9.11 g highly viscous yellow oil The 1H
NMR spectrum was similar to the polyethylene) of
example 110 with 113 methyl carbons per 1000 methylene
carbons. 13C NMR quantitative analysis, branching per
1000 CH2: Total methyls (119.5), Methyl (54.7), Ethyl
(16.9), Propyl (8.4), Butyl (7.7), Amyl (7.2), ?Hexyl
and end of chains (30.9). GPC (trichlorobenzene,
135°C, polystyrene reference, results calculated as
linear polyethylene using universal calibration
theory): Mn=25,000, Mw=44,900, Mw/Mn=1.79.
30 Listed below are the 13C NMR data upon which the
above analysis is based.
13C ~ Data
TCB, 120C, 0.05M
CrACAc
Freq Intensity
ppm
39.60125.53532
39.43136.33425 MB2
38.30048.71403 MB3+
37.944617.7325 MB3+
37.280936.416 CtBl,
383
36.76595.10586 aBl,
3B3
226
c> >ocTt~ tT~ cuGtT rR111 E 261

WO 96/23010 ~ 02338581 2001-03-O1 PCT/C1S96/01282
34.3181 56.1758 ay+B
33.8243 15.6271 ay+B
33.3942 8.09189 MB,
32.9854 20.3523 MB1
32.6721 4.35239 MB1
32.327 4.06305 385
31.9394 27.137 3B6+, 3
EOC
31.4031 9.62823 y+y+B, 384
30.235 52.8404 Y+y+B, 384
29.7518 162.791 y+y+B, 384
29.3164 26.506 y+y+B, 384
27.5695 15.4471 By+H, 2B2
27.1341 59.1216 By+B, 282
26.4811 8.58222 By+B, 2B2
24.4475 5.93996 (3(38
23.12 5.05181 284
22.6369 29.7047 2B5+, 2
EOC
20.1626 6.29481 283
19.7378 31.9342 1B1
19.2068 3.93019 181
14.2582 5.59441 1B3
13.8706 36.3938 1B4+, _
EOC
10.9768 9.89028 1B~
Exams
1-Pentene (20 ml) was polymerized in 20 ml
chloroform according to example 138 to give 2.59 g of
viscous fluid (369 equivalents 1-pentene per Pd).
Integration of the 1H NMR spectrum showed 118 methyl
carbons per 1000 methylene carbons. DSC (two heats, -
150 to +150°C, 15°C/min) shows Tg= -58°C and a low
temperature melting endotherm from
-50°C to 30°C (32 J/g).
13C NMR quantitative analysis, branching per 1000
CH2: Total methyls (118), Methyl (85.3), Ethyl (none
detected), Propyl (15.6), Butyl (non detected), _>Amyl
and end of chains (17.1). GPC (trichlorobenzene,
1J 135°C, polystyrene reference, results calculated as
linear polyethylene using universal calibration
theory): Mn=22,500, Mw=43,800, Mw/Mn=1.94.
Listed below are the 13C NMR data upon which the
above analysis is based.
~?7
SUBSTfTUTE SHEET (RULE 26)

WO 96/23010 CA 02338581 2001-03-O1 PCT/LJS96/01282
13C ~ data
TCB, 120C, 0.05M CrAcAc
FreQ t
I
i
~~m n
42.6277 ens as for Me & Et+
ty
4.69744 '
39.5428 9.5323 3rd carbon of a 6+ carbon
side chain that has a
methv_1
branch at the 4 position
38.1357 3.59535
37.8384 13.9563 MB3+
37.5888 28.4579
37.2224 54.6811 aB1,3B3
35.5287 6.51708
35.2419 3.55603
34.6366 7.35366
34.2437 22.3787
32.911 45.2064 MB1
32.5977 10.5375
32.38 4.02878
31.8809 14.1607 3B6+, 3EOC
30.6916 8.44427 y+y+B
30.0703 63.1613 y+v+B
29.6987 248 y+y+B
29.2633 17.9013 y+y+B
28.8916 3.60422
27.1182 66.2971 py+B, (4B5, etc.)
24.5324 16.8854
22.5784 16.0395 2B5+, 2EOC
20.1041 13.2742
19.6952 54.3903 181, 2B3
14.2104 12.2831
13.8281 16.8199 1B4+,EOC,1B3
Integration of the CH2 peaks due to the structure
s -CH(R)CH2CHlR')- , where R is an alkyl group, and R' is
an alkyl group with two or more carbons showed that in
690 of these structures, R = Me. The region integrated
for the structure where both R and R' are >_Ethyl was
39.7 ppm to 41.9 ppm to avoid including an interference
10 from another type of methylene carbon on a side chain.
Exa~le 140
[(2,6-i-PrPh)ZDABMe=]PdMeCl 10.020 g, 0.036 mmol)
was dissolved in 4 ml CH2C12 and methyl acrylate
IS (0.162 g, 0.38 mmol, inhibited with 50 ppm
phenothiazine) was added while stirring. This sclution
was added to a stirred suspension of NaBAF (0.033 g,
0.038 mmol) in 4 ml of CH2C12. After stirring for 1
~?g
SUBSTITUTE SHEET (RULE 26)

WO 96/23010 CA 02338581 2001-03-O1 PCT/US96I01282
'our, the mixture was filtered through a 0.5 ~m PTFE
membrane filter to remove a flocculant gray
precipitate. The solvent was removed from the filtrate
in vacuo to give a solid which was recrystallized from
a CH2C12/pentane mixture at -40°C to give 0.39 g (750
yield) of orange crystalline {[(2,6-i-
PrPh)zDABMe~]PdCH2CHzCHZC(O)OCH3)BAF . 1H NMR (CDC13)
0.65(m, CH2, 2H); 1.15-1.45(four sets of doublets for
-CH(C~3)2 and multiplet at 1.4 for a CH2,.total area =
26H); 2.19,2.21 (s, s, CH3 of ligand backbone, 6H);
2.40(m, CH2, 2H); 2.90 (m, -C$(CH3)2, 4H); 3.05(s, -
C02CH;, 3H); 7.25-7.75(m, aromatic H of ligand and
counterior~, 19H).
All GPC data reported for examples 141-170, 177,
1~ and 204-212 were run in trichlorobenzene vs.
polyethylene standards unless otherwise indicated. All
DSC data reported for examples 141-170, 177, and 204-
212 (second heat, -150°C to 150°, 10 or 15°C/min).
Examt~le 141
A Schlenk flask containing {[(2,6-i-
PrPh)ZDABHZ]NiMe(EtzO)~BAF (1.3 mg, 8.3 x 10-~ mol)
under an argon atmosphere was cooled to -78°C. Upon
cooling, the argon was evacuated and the flask
backfilled with ethylene (1 atm). Toluene (75 mL) was
added via syringe. The polymerization mixture was then
warmed to 0°C. The solution was stirred for 30 minutes
Polymer began to precipitate from the solution
within minutes. After 30 minutes, the polymerization
was terminated upon exposing the catalyst to air. The
polymer was precipitated from acetone, collected by
filtration and washed with 6 M HC1, water, and acetone.
The polymer was dried in vacuo. The polymerization
yielded 1.53 g of polyethylene (1.3 x 105 TO). Mn =
91, 900; M,a = 279, 000; M,,,/Mn = 3.03; Tm = 129°C. 1H NMR
(CED5C1, 142°C) 0.6 methyls per 100 carbons.
Example 142
The reaction was done in the same way as in
Example 141 using 1.3 mg of {[(2,6-1-
229
c~ iacTm ~c cucFT fRl tl F 9R1

WO 96123010 ~ 02338581 2001-03-O1 p~/pg96/01282
_vrPh) zDABMe;] NiMe (EtZO) }BAF ( 8 . 3 x 10-7 mol ) . The
polymer was isolated as a white solid (0.1 g).
Examples 143-148
General procedure for the polymerization of
ethylene by the methylaluminoxane (MAO) activation of
nickel complexes containing bidentate diimine ligands:
Polymerization at 0°C: The bisimine nickel dihalide
complex (1.7 x 10-5 mol) was combined with toluene (100
mL) in a flame dried Schlenk flask under 1 atmosphere
10 ethylene pressure. The polymerization was cooled to
0°C in an ire-water bath. The mixture was stirred at
0°C for 15 ;~.inutes prior to activation with MAO.
Subseauent~_~~, 1.5 mL of a loo MAO (100 eq) solution in
toluene was added onto the nickel dihalide suspension.
The solutic-: was stirred at 0°C for 10, 30, or 60
minutes. Within minutes increased viscosity and/or
precipitation of polyethylene was observed. The
polymerization was quenched and the polymer
precipitated from acetone. The polymer was collected
20 by suction Filtration and dried under vacuum for 24
hours. See Table I for a detailed description of
molecular weight and catalyst activity data.
Example No. Catalyst
143 [ (2, 6-i-PrPh) zDABH2] NiBr~
?5 144 [(2,6-i-PrPh)~DABMe~]NiBr2
145 [ (2, 6-MePh) ~DABH2] NiBr2
146 [(2,6-i-PrPh)ZDABAn]NiBr2
147 [(2,6-MePh)zDABAn]NiBr2
148 [ (2, 6-MePh) 2DABMe2] NiBrz
30
Exam. Condi- Yield TO/ Mn MW MW/Mn Thermal
tionsl (g) hr~mol Analysis
catalyst (C)
143 0'C..iO5.3 22,700 80,900 231,000 2.85 119 (Tm~
m
144 0'C,30m3.8 16,300 403,000795,000 1.97 115 (Tm)
145' 0'C.30 3.4 14,300 42,900 107,000 2.49 131 (Tm)
m
146' O~C.3Um7.0 29,900 168,000389,000 2.31 107 (Tm;
.
147 0"C 3 . 47, 500 125, 362, 2 . 122 (Tm)
.10 7 OQO 000 89
m
14B 0'C.10 5.1 65,400 171,000440,000 2.58 115 (Tm)
m
230
el IDCTIT1 tTC CI-IC1:T loll il F ~Rl

WO 96/23010 CA 02338581 2001-03-O1 PCT/US96/01282
1 Polymerization reactions run at 1 atmosphere
ethylene pressure.
2 Branching Analysis by 13C NMR per 1000 CH2:
Ex. 144: Total methyls (54.3), Methyl (43.4),
Ethyl (3.3), Propyl (2), Butyl (1.3), >_Butyl and end of
chains ( 5 . 7 ) .
Ex. 146: Total methyls (90.9), Methyl (65.3),
Ethyl (7.2), Propyl (4.5), Butyl (3.5), Amyl (4.5), >_
Hexyl and end of chains (10.2).
3 Ex. 145: '1H NMR (CEDSC1) , 142°C) 0.1 methyl per
100 carbon atoms.
Exam~ies 149-154
Polymerization at Ambient Temperature
The general procedure described for the MAO
li activation of the diimine~nickel dihalides was followed
in the polymerizations detailed. below, except all
polymerizations were run between 25-30°C.
Exarnnle No . Cata first
149 [ (2, 6-i-PrPh) zDABH2] NiBr2
150 [(2,6-i-PrPh)2DABMez]NiBrz
151 [(2,6-MePh)2DABH~]NiBrz
152 [(2,6-i-PrPh)=DABAn]NiBr~
153 [(2,6-MePh)zDABAn]NiBr~
2~ 154 [(2,6-MePh)zDABMe2]NiBr~
Exam.Condi- Yield TO/ Mn MW MW/Mn Thermal
tionsl (g) hr~mol Analysis
catalyst (C)
149 30C.30 2.5 12,200 15,500 34,900 2.25 --
m
i50~ 25C,.iO 3.4 14,500 173,000 248,OOG1.44 -51 (Tg)
m
151' 25C.30 7.2 30.800 13,900 39,900 2.88 90,122
m (Tm)
152 25C.30 4.2 18,000 82,300 175,0002.80 39 (Tm)
m
153 25C,10 4.9 62,900 14,000 25,800 1.85 --
m
154 25C.10 3.7 47,500 20,000 36,000 1.83 --
m
231
~t ita~TtTIITE SHEET (RULE 26)

WO 96/23010 ~ 02338581 2001-03-O1
PCTIUS96/01282
1 Polymerization reactions run at 1 atmosphere
ethylene pressure.
2 Branching Analysis by 13C NMR per 1000 CH2:
Ex. 150: Total methyls (116.3), Methyl (93.5),
Ethyl (6.2), Propyl (3.2), Butyl (2.9), Am (6.6), ?Hex
and end of chains (11.2).
Ex. 152: Total methyls (141.9), Methyl (98.1),
Ethyl (15.9), Propyl (5.6), Butyl (6.8), Amyl (4.1), >
Hex and end of chains (10.7). Quantitation of the -
l0 CH2CH(CH3)CHZCH3 structure per 1000 CH2's: 8.
' Ex. 151: 1H NMR (C6DSC1) , 142°C) 3 methyl per 100
carbon atoms.
Example 155
A standard solution of [(2,6-i-PrPh)~DABAn]NiBr~
Is was prepared as follows: 1,2-difluorobenzene (10 mL)
was added to 6.0 mg of [(2,6-i-PrPh)2DABAnJNiBrz (8.4 x
10-6 mol) in a 10 mL volumetric flask. The standard
solution was transferred to a Kontes flask and stored
under an argon atmosphere.
20 The standard catalyst solution (1.0 mL, 8.4 x
10-~ mol catalyst) was added to a Schlenk flask which
contained 100 mL toluene, and was under 1 atmosphere
ethylene pressure. The solution was cooled to 0°C, and
1.5 mL of a 10% solution of MAO (?1000 eq) was added.
The solution was stirred for 30 minutes. Polymer began
to precipitate within minutes. The polymerization was
quenched and the polymer precipitated from acetone.
The resulting polymer was dried in vacuo (2.15 g, 1.84
x 105 TO) . Mn = 489, 000; M,", = 1, 200, 000; M,~,/Mn = 2.47
30 Examr~le 156
The polymerization of ethylene at 25°C was
accomplished in an identical manner to that described
in Example 155. The polymerization yielded 1.8 g of
polyethylene (1.53 x 105 TO). Mn = 190,000; MW =
3~ 410,000; Mw/Mn = 2.16; 1H NMR (C6D5C1, 142°C) 7 methyls
per 100 carbons.
232
Ct tacTtTt 1TF SHFFT (RI il E 261

WO 96/23010 CA 02338581 2001-03-O1 PCT/US96/01282
A standard solution of [(2,6-MePh)zDABAn)NiBr~ was
prepared in the same way as described for the complex
in Example 155 using 5.0 mg of [(2,6-MePh)2DABAn]NiBr~
( 8 . 4 x 10-6 mol ) .
5 Toluene (100 mL) and 1.0 mL of the standard
solution of complex 5 (8.3 x 10-~ mol catalyst) were
combined in a Schlenk flask under 1 atmosphere ethylene
pressure. The solution was cooled to 0°C, and 1.5 mL
of a loo solution of MAO(>_1000 eq) was added. The
10 polymerization mixture was stirred for 30 minutes. The
polymerization was terminated and the polymer
precipitated from acetone. The reaction yielded 1.60 a
of polyethylene (1.4 x 105 TO). Mn = 590,000; Mw =
1,350,000; Mw/Mn = 2.29.
1~ Example X58
Toluene (200 mL) and 1.0 mL of a standard solution
of [(2,6-i-PrPh)ZDABAn)NiBrz (8.3 x 10-~ mol catalyst)
were combined in a Fisher-Porter pressure vessel. The
resulting solution was cooled to 0°C, and 1.0 mL of a
20 10% MAO (?1000 eq) solution in toluene was added to
activate the polymerization. Subsequent to the MAO
addition, the reactor was rapidly pressurized to 276
kPa. The solution was stirred for 30 minutes at 0°C.
After 30 minutes, the reaction was quenched and polymer
?~ precipitated from acetone. The resulting polymer was
dried under reduced pressure. The polymerization
yielded 2.13 g of white polyethylene (1.82 x 105 TO).
Mn = 611,000; MW = 1,400,000; MW/Mn = 2.29; Tm = 123°C;
1H NMR (C6D5C1, 142°C) 0.5 methyls per 100 carbons.
30 Examples 159-160
Polymerization of Propylene
The diimine nickel dihalide complex (1.7x10'5 mol)
was combined with toluene (100 mL) in a Schlenk flask
under 1 atmosphere propylene pressure. The
35 polymerization was cooled to 0°C, and 1.5 mL of a 10%
MAO (100 eq) solution in toluene was added. The
solution was stirred for 2 hours. The polymerization
?3~
ci iacTm rr~ SHEET rRULE 261

WO 96/23010 ~ 02338581 2001-03-O1 pC'fIUS96/01282
~as quenched and the polymer precipitated from a~Ctone.
The polymer was dried under vacuum.
Example No. Catalyst
159 [(2,6-i-PrPh)~DABHz]NiBr2
160 [(2,6-i-PrPh)~DABAn)NiBr2
Exam.Condi- Yield TO/ Mn MW MW/Mn Thermal
tionsl (g) hr-mol Analysis
catalyst (C)
159 0C.2h 1.3 900 131,000 226,000 1.72 -20 (Tg)
a
160 0C.2h 4.3 2,900 147,000 35,000 1.60 -78,
-20
(T )
aGPC (toluene, polystyrene standard)
Ex. 159: 'H NMR (C5D5C1), 142°C) 30 methyls per 100
carbon atoms.
10 Ex. 160: 1H NMR (CEDSC1) , 142°C) 29 methyls per 100
carbon atoms. Quantitative 13C NMR analysis, branching
per 1000 CH2: Total methyls (699). Based on the total
methyls, the fraction of 1,3-enchainment is 130.
Analysis of backbone carbons (per 1000 CH2): 8+ (53),
b+/Y ( 0 . 98 ) .
Listed below are the 13C NMR data upon which the
above analysis is based.
13
C NMR Data
20 TCH, 140C, 0.05M CrACAc
Freq ppm Intensity
47.3161 53.1767
46.9816 89.3849
46.4188 82.4488
45.84 23.1784
38.4702 12.8395
38.0985 29.2643
37.472 18.6544
37.2915 24.8559
35.3747 15.6971
34.5623 14.6353
33.3145 14.2876
32.996 12.2454
30.9464 24.2132
30.6703 57.4826
30.081 30.122 y to single branch
234
ct iR~Tm 1TF SHFFT f RlILE 261

WO 96/23010 CA 02338581 2001-03-O1 PCT/US96/01282
29.6987 29.2186 8+ to branch
28.3659 298.691
27.4792 33.2539
27.1235 29.7384
24.5324 9.45408
21.1554 20.0541
20.6244 110.077
19.9926 135.356
16.9342 8.67216
16.4829 8.81404
14.9962 8.38097
RxamP
[(2,6-i-PrPh)2DABH2JNiBrz (10 mg, 1.7 x 10-5 mol)
was combined with tcluene (40 mL) under a N2
atmosphere. A loo solution of MAO (1.5 mL, 100 eq) was
added to the solution. After 30 minutes, the Schlenk
flask was backfilled with propylene. The reaction was
stirred at room temperature for 5.5 hours. The
polymerization was quenched, and the resulting polymer
dried under vacuum (670 mg, 213 TO/h). Mn = 176,000;
MW = 299,000; Mw/Mn = 1.70. Quantitative 13C NMR
analysis, branching per 1000 CH2: Total methyls (626),
Methyl (501), Ethyl (1), >_Butyl and end of chain (7).
Based on the total methyls, the fraction of 1,3-
enchainment is 220. Analysis of backbone carbons (per
1~ 1000 CH2) : 8+ (31) , 8+/y (0.76) .
Exams 16"-X65
The diimine nickel dihalide catalyst precursor
(1.7x10-5 mol) was combined with toluene (40 mL) and 1-
hexe.~.e (10 mL) under a N2 atmosphere. Polymerization
'_'0 reactions of 1-hexene were run at both 0°C and room
temperature. A 10% solution of MAO (1.5 mL, 100 eq) in
toluene was added. Typically the polymerization
reactions were stirred for 1-2 hours. The polymer was
precipitated from acetone and collected by suction
filtration. The resulting polymer was dried under
vacuum.
235
S1 IR4TITlITE SHEET f RULE 267

WO 96/23010 ~ 02338581 2001-03-O1 p~'/pS96101282
Ex. No. Catalyst
162 [ (2, 6-i-PrPh) 2DABH2] NiBr=
163 [(2,6-i-PrPh)2DABAn]NiBr~
164 [ (2 , 6-i-PrPh) 2DABH2] NiBr
165 [ (2, 6-i-PrPh) 2DABAn] NiBr
Exam. Condi- Yield TO/ Mna MW MW/Mn Thermal
tionsl (g) hr~mol Analysis
catalyst (C)
162 25C.Ih 3.0 2100 173,000318,000 1.84 -48 (T
)
163 25C,lh 1.2 860 314,000642,000 2.05 -54 (Tg)
-19 (Tm)
164 0C.2h 3.0 1100 70,800 128,000 1.80 -45 (TQ)
165 0C.2h 1.5 540 91,700 142,000 1.55 -49 (T~)
aGPC (toluene, polystyrene standards).
Branching Analysis Ex. 162: by 13C NMR per 1000
CH 2
10 Total methyls (157.2), Methyl (47), Ethyl (1.9),
Propyl (4.5), Butyl (101.7), ?Am and end of chain
(4.3) .
236
c, iacTiT~ tTF ~NFFT rRULE 261

WO 96123010 CA 02338581 2001-03-O1 PCT/US96/01282
13C ~,,IR data (Example 162)
TCB, 120C, 0.05MCrAcAc
Frees i
~Dm Intens
42.8364 ty Methine
7.99519
41.3129 27.5914 as to tw o h+ branches
Et
40.5759 19.6201 as to tw o h+ branches
Et
37.8831 14.7864 Methines andMethylenes
37.2984 93.6984 Methines andMethylenes
36.6684 6.99225 Methines andMethylenes
35.5773 36.067 Methines andMethylenes
34.655 55.825 Methines andMethylenes
34.3091 63.3862 Methines andMethylenes
33.8356 24.1992 Methines andMethylenes
33.428 53.7439 Methines andMethylenes
32.9957 51.1648 Methines andMethylenes
31.9169 17.4373 Methines andMethylenes
31.5546 14.008 Methines andMethylenes
31.1552 10.6667 Methines andMethylenes
30.5993 34.6931 Methines andMethylenes
30.274 56.8489 Methines andMethylenes.
30.1258 42.1332 Methines andMethylenes
29.747 97.9715 Methines andMethylenes
29.1047 47.1924 Methines andMethylenes
28.8823 64.5807 Methines andMethylenes
28.1289 13.6645 Methines andMethylenes
27.5648 61.3977 Methines andMethylenes
27.1777 50.9087 Methines andMethylenes
27.0213 31.6159 Methines andMethylenes
26.9142 31.9306 Methines andMethylenes
26.4572 4.715666 Methines andMethylenes
23.2085 154.844 284
22.6074 12.0719 2B5+,EOC
20.0669 8.41495 181
19.6963 57.6935 1B1
15.9494 17.7108
14.3477 8.98123
13.8742 248 184+,EOC
Example 166
((2,6-i-PrPh)zDABMez]NiBr2 (10.4 mg, 1.7 x 10-5
mol) was combined with toluene (15 mL) and 1-hexene (40
mL) under 1 atmosphere ethylene pressure. The solution
was cooled to 0°C, and 1.5 mL of a loo MAO (100 eq)
solution in toluene was added. The reaction was
10 stirred at 0°C for 2.5 hours. The polymerization was
quenched and the polymer precipitated from acetone.
The resulting polymer was dried under reduced pressure
(1.4g). Mn = 299,000; Mw = 632,000; Mw/Mn = 2.12.
237
e~ ~acTm rrc cuFFT IRt lI E 261

WO 96/23010 ~ 02338581 2001-03-O1 pC?IUS96/01282
Branching Analysis by 13C NMR per 1000 CHz: Total
methyls (101.3), Methyl (36.3), Ethyl (1.3), Propyl
(6.8), Butyl (47.7), ?Amyl and end of chains (11.5).
Example 167
[(2,6-i-PrPh)2DABH2)NiBrz (10 mg, 1.7 x 10-5 mol)
was added to a solution which contained toluene (30 mL)
and 1-octene (20 mL) under 1 atm ethylene. A 10%
solution of MAO (1.5 mL, 100 eq) in toluene was added.
The resulting purple solution was allowed to stir for 4
10 hours at room temperature. Solution viscosity
increased over the duration of the polymerization. The
polymer was precipitated from acetone and dried under
vacuum resulting in 5.3 g of copolymer. Mn = 15,200,
Mw = 29,100, Mn/MW = 1.92.
xample X68
[(2,6-i-PrPh)2DABAn)NiBr, (12 mg, 1.7x10-5 mol) was
combined with toluene (75 mL) in a Schlenk flask under
1 atmosphere ethylene pressure. The mixture was cooled
to 0°C, and 0.09 mL of a 1.8 M solution in toluene of
20 Et2A1C1 (10 eq) was added. The resulting purple
solution was stirred for 30 minutes at 0°C. The
polymerization was quenched and the polymer
precipitated from acetone. The resulting polymer was
dried under reduced pressure (6.6 g, 2.8 x 104 TO). Mn
- 105, QvO; M~,~ = 232, 000; M,"~/Mn = 2.21
Example 159
[(2,6-i-PrPh)ZDABAn)NiBrz (12 mg, 1.7x10-5 mol) was
combined with toluene (75 mL) under 1 atmosphere
propylene pressure. The solution was cooled to 0°C and
30 0.1 mL of Et2AlCl (>_10 eq1 was added. The reaction was
stirred at 0°C for 2 hours. The polymerization was
quenched and the polymer precipitated from acetone.
The resulting polymer was dried under reduced pressure
(3.97 c, 2800 TO).
Exanlnle 170
[(2,6-i-PrPh)ZDABAn)NiBr2 (12 mg, 1.7x10-5 mol) was
combined with toluene (50 mL) and 1-hexene (25 mL)
under a N~ atmosphere. Et2A1C1 (0.01 mL, 10 eq) was
238
SI IRSTtTtITF SHEET (RULE 261

WO 96/23010 CA 02338581 2001-03-O1 PCT/US96/01282
added to the polymerization mixture . The- resu°'tifrg
purple solution was allowed to stir for 4 hours. After
4 hours the polymerization was quenched and the polymer
precipitated from acetone. The polymerization yielded
1.95 g poly(1-hexene) (348 TO/h). Mn = 373,000; MW =
680, 000; M,";/Mn = 1. 81.
Examp 7~
1-Tetradecene (20 ml) was polymerized in methylene
chloride (10 ml) for 20 hr using catalyst {[(2,6-1-
PrPh)~DABMe~]PdCH2CHzCH2C(O)OCH3}SbF6 (0.04 g, 0.05
mmol). The solvent and reacted monomer were removed in
vacuo. The polymer was precipitated to remove
unreacted monomer, by the addition of acetone to a
chloroform solution. The precipitated polymer was
1~ dried in vacuo to give a 10.2 g yield. i'C NMR
(trichlorobenzene, 120°C) integrated to give the
following branching analysis per 1000 methylene
carbons: Total methyls (69.9), methyl (24.5), ethyl
(11.4), propyl (3.7), butyl (2.3) amyl (0.3), >_Hexyl
and end of chain (24.2). Thermal analysis showed Tg =
-42.7°C, and Tm = 33.7°C (15.2 J/g).
Listed below are the 13C NMR data upon which the
above analysis is based.
239
ct tac~~ tTt: cN~cT IRI II F 9R1

WO 96/23010 ~ 02338581 2001-03-O1 p~'NS96/01282
13
C NMR Data
TCB, 120C, 0.05M
CrAcAc
Freq ppm Intensity
39.3416 7.78511 MB2
38.2329 5.03571 MB3+
37.8616 9.01667 MB3+
37.5857 3.33517 MB3+
37.2462 31.8174 aBl, 3B3
36.6415 2.92585 aBl, 383
34.668 5.10337 ay+B
34.2384 38.7927 aY+B
33.7397 16.9614 3B5
33.3471 3.23743 3B6+, 3EOC
32.9387 16.0951 Y+Y+B, 3$4
31.9148 27.6457 Y+y+B, 384
31.1297 6.03301 y+Y+B, 384
30.212 59.4286 y+y+B, 384
29.7398 317.201 y+y+B, 384
29.3101 32.1392 Y+y+B, 3B4
27.1511 46.0554 (3y+B, 2B2
27.0185 53.103 . (3y+B, 2B2
26.419 9.8189 ~iy+B, 2B2
24.244 2.46963 (3[3B
22.6207 28.924 2B5+, 2EOC
20.0479 3.22712 2B3
19.7084 18.5679 181
14.3929 3.44368 1B3
13.8677 30.6056 1B4+, lEOC
10.9448 9.43801 182
Example 172
4-Methyl-1-pentene (20 ml) was polymerized in
methylene chloride (10 ml) for 19 hr using catalyst
[(2,6-i-PrPh)~DABMe~]PdCH~CHzCH2C(O)OCH3}SbF6 (0.04 g,
0.05 mmol). The solvent and unreacted monomer were
removed in vacuo. The polymer was precipitated tc
10 remove residual monomer by addition of excess acetone
to a chloroform solution. The precipitated polymer was
dried in vacuo to Give a 5.7 g yield. 13C NMR
(trichlorobenzene, 120°C) integrated to give 518
methyls per 1000 methylene carbon atoms. Thermal
1~ analysis showed Tg -30.3°C.
Listed below are the 13C NMR data upon which ~he
above analysis is based.
240
..~ ~..r.~,~, rtc euccT got tt C 9R1

WO 96/23010 CA 02338581 2001-03-O1 PCT/L1S96/01282
13C ~R Data
TCB, 120C, 0.05M CrAcAc
Freq ppm Intensity
47.8896 13.3323
47.4011 8.54293
45.7127 26.142
45.1392 17.4909
43.9658 13.9892
43.1375 12.7089
42.6171 11.5396
41.8207 9.00437
39.203 64.9357
37.9712 24.4318
37.3075 87.438
35.4862 16.3581
34.9553 24.5286
34.35 31.8827
33.3624 25.7696
33.0226 42.2982
31.4403 25.3221
30.6226 38.7083
28.504 26.8149
27.989 . 81.8147
27.7341 78.3801
27.5802 94.6195
27.458 75.8356
27.0864 35.5524
25.6103 97.0113
23.4333 59.6829
23.0563 41.5712
22.536 154.144
21.9944 5.33517
20.7307 16.294
20.4971 34.7892
20.2953 29.9359
19.7378 62.0082
Example 173
1-Eicosene (19.0 g) was polymerized in methylene
chloride (15 ml) for 24 hr using catalyst {[(2,6-i-
PrPh) ZDABMe~l PdCH2CH2CHzC (O) OCH3)SbF6 (0. 047 g, 0 . 05
mmol). The solvent and unreacted monomer were removed
in vacuo. The polymer was precipitated to remove
residual monomer by addition of excess acetone to a
chloroform solution of the polymer. The solution was
10 filtered to collect the polymer. The precipitated
polymer was dried in vacuo to give a 5.0 g yield. 13C
NMR quantitative analysis, branching per 1000 CH2:
Total methyls (27), Methyl (14.3), Ethyl (0), Propyl
241
~~ nom r~ sHEET rRmE 2s1

WO 96/23010 CA 02338581 2001-03-O1 pCT/US96/01282
_,0.2), Butyl (0.6), Amyl (0.4), >_Hexyl and end of
chains (12.4).
Integration of the CH2 peaks due to the structure
-CH(R)CH2CH(R')- , where R is an alkyl group, and R' is
5 an alkyl group with two or more carbons showed that in
820 of these structures, R = Me.
Listed below are the '3C NMR data upon which the
above analysis is based.
13C NMR data
TCB, 120C, 0.05M CrAcAc
37.7853 13.978 MB-,+
37.1428 52.1332 aB
34.1588 41.067 aB4+
32.826 26.6707 MB1
31.8066 24.9262 3B6+,3EOC
30.0703 96.4154 y+y+B 384
29.6243 1239.8 y+~+B 384
27.0013 78.7094 By+B, (4B5, etc.)
22.5041 23.2209 2B5+,2EOC
19.605 30.1221 1B1
13.759 23.5115 184+,EOC
Example 174
The complex [(2,6-i-PrPh)2DABH2]PdMeCl (0.010
g, 0.019 mmol) and norbornene (0.882 g, 9.37 mmol) were
weighed into a vial and dissolved in 2 ml CH2C12.
NaBAF (0.0328, 0.036 mmol) was rinsed into the stirring
mixture with 2 ml of CH2C12 After stirring about 5
minutes, there was sudden formation of a solid
20 precipitate. Four ml of o-dichlorobenzene was added
and the solution became homogenous and slightly
viscous. After stirring for 3 days, the homogeneous
orange solution was moderately viscous. The polymer
was precipitated by addition of the solution to excess
MeOH, isolated by filtration, and dried in vacuo to
give 0.285 g (160 equivalents norbornene per Pd) bright
orange glassy solid. DSC (two heats, 15°C/min) showed
no thermal events from -50 to 300°C. This is
consistent with addition type poly(norbornene). Ring-
30 opening polymerization of norbornene is known to
242
~1 IRSTITI ITF SHEET (RULE 26)

WO 9GI23010 ~ 02338581 2001-03-O1 pC'f/US96/01282
,produce an amorphous polymer with a glass transition
temperature of about 30-55°C.
Rxam~~,~
The solid complex {[(2,6-1-
PrPh) 2DABHz] PdMe (Et20) }SbF6 (0.080 g, 0.10 mmol) was
added as a solid to a stirring solution of norbornene
(1.865 g) in 20 ml of o-dichlorobenzene in the drybox.
About 30 min after the start of the reaction, there was
sligr~t viscosity (foam on shaking) and the homogeneous
mixture was dark orange/red. After stirring for 20 h,
the solvent and unreacted norbornene were removed in
vacuo to give 0.508 g orange-red glassy solid (54
equivalents norbornene/Pd). 1H NMR (CDC13): broad
featureless peaks from 0.8-2.4 ppm, no peaks in the
l~ olefi~ic region. This spectrum is consistent with
addition type poly(norbornene). GPC (trichlorobenzene,
135°C, polystyrene reference, results calculated as
linear polyethylene using universal calibration
theory): Mn=566 Mw=1640 Mw/Mn=2.90.
FxamPle X76
4-Methyl-1-pentene (10 ml) and ethylene (1 atm)
were copolymerized in 30 ml of chloroform according to
example 125 using catalyst {[(2,6-i-
PrPh) ~DABMez) PdCH2CH2CHzC (O) OCH3 } SbF6 ( 0 . 084- g, 0 . 10
mmol) to give 23.29 g highly viscous yellow oil. The
lI-I NMR spectrum was similar to the polyethylene) of
example 110 with 117 methyl carbons per 1000 methylene
carbons. 13C NMR quantitative analysis, branching per
1000 CH2: Total methyls (117.1), Methyl (41.5), Ethyl
(22.7), Propyl (3.3), Butyl (13), Amyl (1.2), ?Hexyl
and end of chains (33.1), ~.myl and end of chains
(42.3), By 13C NMR this sample contains two
identifiable branches at low levels attributable to 4-
methyl-1-pentene. The Bu and ?Amyl peaks contain small
3~ contributions from isopropyl ended branch structures.
Example 177
CoCl2 (500 mg, 3.85 mmol) and (2,6-i-PrPh)2DABAn
(2.0 g, 4.0 mmol) were combined as solids and dissolved
243
SUBSTITUTE SHEET (RULE 26)

WO 96/23010 CA 02338581 2001-03-O1 PCT/US96101282
~n 50 mL of THF. The brown solution was stirred for
hours at 25°C. The solvent was removed under reduced
pressure resulting in a brown solid (1.97 g, 820
yield) .
A portion of the brown solid (12 mg) was
immediately transferred to another Schlenk flask and
dissolved in 50 mL of toluene under 1 atmosphere of
ethylene. The solution was cooled to 0°C, and 1.5 mL
of a 10% MAO solution in toluene was added. The
10 resulting purple solution was warmed to 25°C and
stirred for 12 hours. The polymerization was quenched
and the polymer precipitated from acetone. The white
polymer (200 mg) was collected by filtration and dried
under reduced pressure. Mn = 225,000, M,~, = 519,000,
l~ Mw/Mn = 2.31, Tg = -42°, Tm = 52°C and 99.7°C.
Example 178
Ethyl 10-undecenoate (10 ml) and ethylene (1 atm)
were copolymerized in 30 ml of CH2C12 according to
example 125 using catalyst {[(2,6-1-
20 PrPh) ~DABMe2) PdCH2CHzCH2C (O) OCH3)SbF6 (0. 084 g, 0. 10
mmol). The copolymer was precipitated by removing most
of the CH2C12 in vacuo, followed by addition of excess
acetone. The solution was decanted and the copolymer
was dried in vacuo to give 1.35 g viscous fluid. 1H
NMR (CDC13): 0.75-0.95(m, CH3); 0.95-1.5(m,
C(O)OCH2CH3, CH2, CH); 1.5-1.7(m, -C$2CH2C(O)OCH2CH3);
1.9-2.0(m, -C$2CH=CH-); 2.3(t, -CH2C$2C(O)OCH2CH3);
4.15(q, -CH2CH2C(O)OCFi2CH3); 5.40(m, -CH=CH-). The
olefinic and allylic peaks are due to isomerized ethyl
30 10-undecenoate which has coprecipitated with the
copolymer. Adjusting for this, the actual weight of
copolymer in this sample is 1.18 g. The copolymer was
reprecipitated by addition of excess acetone to a
chloroform solution. 1H NMR of the reprecipitated
35 polymer is similar except there are no peaks due to
isomerized ethyl 10-undecenoate at 1.9-2.0 and 5.40
ppm. Based on integration, the reprecipitated
copolymer contains 7.4 mole % ethyl 10-undecenoate, and
244
SIIRSTITItTE SHEET (RULE 26)

WO 96/23010 CA 02338581 2001-03-O1 PCT/US96101282
,-;3 methyl carbons per 1000 methylene carbons. 13C NMR
quantitative analysis, branching per 1000 CH2: Total
methyls (84.5), Methyl (31.7), Ethyl( 16.9), Propyl
(1.5), Butyl (7.8), Amyl (4.4), ?Hexyl and end of
5 chains (22.3). GPC (THF, PMMA standard): Mn=20,300
Mw=26,300 Mw/Mn = 1.30. 13C NMR quantitative
analysis, branching per 1000 CH2: ethyl ester (37.8),
Ester branches -CH(CH2)nC02CH2CH3 as a °s of total
ester: n?5 (65.8), n=4 (6.5), n=1,2,3 (26.5), n=0
l0 (1.2) .
Listed below are the 13C NMR data upon which the
above analysis is based.
245
S! IBSTITL>TF SHEET (RULE 26)

WO 96/23010 cA 02338581 2001-03-O1 pCT/US96/01282
13~ ~~ Data
Freq ppm Intensity
59.5337 53.217
39.7234 2.57361
39.3145 7.80953
38.2207 11.9395
37.8437 20.3066
37.2225 29.7808
36.7181 5.22075
34.6792 17.6322
34.265 107.55
33.7181 21.9369
33.3093 8.22574
32.9164 15.0995
32.396 8.52655
32.0828 5.79098
31.9075 37.468
31.127 13.8003
30.6757 8.38026
30.2084 52.5908
29.9961 27.3761
29.72 151.164
29.5076 39.2815
29.2899 69.7714
28.727 6.50082
27.5164 20.4174
26.9908 64.4298
26.5713 9.18236
26.3749 11.8136
25.5519 4.52152
25.0528 43.7554
24.2457 7.9589
23.1094 10.0537
22.9926 4.71618
22.6156 37.2966
20.0245 2.4263
19.6847 25.9312
19.1643 5.33693
17.5183 2.20778
14.2954 66.1759
13.8653 43.8215
13.414 2.52882
11.1521 5.9183
10.9237 14.9294
174.945 3.27848
172.184 125.486
171.695 4.57235
Example 179
The solid complex {[(2,6-i-
PrPh)2DABHz)PdMe(Et20)~SbF6 (0.080 g, 0.10 mmol) was
added as a solid to a stirring solution of cyclopentene
(1.35 g, 20 mmol) in 20 ml of dichlorobenzene in the
246
sugSTmITE SHEET (RULE 26)

WO 96J23010 CA 02338581 2001-03-O1 PGT/US96101282
drybox. After stirring 20 h, the sligYitr~ viscous
solution was worked up by removing the solvent in vacuo
~to give 1.05 g sticky solid (156 equivalents of
cyclopentene per Pd). 1H NMR (CDC13): complex spectrum
5 from 0.6-2.6 ppm with maxima at 0.75, 1.05, 1.20, 1.55,
1.65, 1.85, 2.10, 2.25, and 2.50. There is also a
multiplet for internal olefin at 5.25-5.35. This is
consistent with a trisubstituted cyclopentenyl end
group with a single proton (W. M. Kelly et. al.,
10 Macromolecules 1994, 27, 4477-4485.) Integration
assuming one olefinic proton per polymer chain gives
DP=8.0 and Mn=540. IR (Thin film between NaCl plates,
cm-1): 3048 (vw, olefinic end group, CH stretch),
1646(vw, olefinic end group, R2C=CHR trisubstituted
15 double bond stretch), 1464(vs), 1447(vs), 1364(m),
1332(m), 1257(w), 1035(w), 946(m), 895(w), 882(w),
803(m, cyclopentenyl end group,. R2C=CHR trisubstituted
double bond, CH bend), 721(vw, cyclopentenyl end group,
RHC=CHR disubstituted double bond, CH bend). GPC
20 (trichlorobenzene, 135°C, polystyrene reference,
results calculated as linear polyethylene using
universal calibration theory): Mn=138 Mw=246
Mw/Mn=1.79.
R~amnlP 180
25 The solid complex {[(2,6-i-
PrPh) ZDABMe2] PdCH2CHzCHzC (0) OCH3 } SbFs ( 0 . 084 g, 0 . 10
mmol) was added to a stirring solution of 10.0 ml
cyclopentene in 10 ml CHC13 in the drybox. After
stirring for 20 h, the mixture appeared to be separated
30 into two phases. The solvent and unreacted monomer
were removed in vacuo leaving 2.20 g off-white solid
(323 equivalents cyclopentene per Pd). DSC (25 to
300°C, 15°C/min, first heat): Tg = 107°C, Tm (onset) -
165 °C, Tm (end) - 260 °C, Heat of fusion = 29 J/g.
35 Similar results were obtained on the second heat.
GPC (trichlorobenzene, 135°C, polystyrene reference,
results calculated as linear polyethylene using
247
SUBSTITUTE SHEET (RULE 26)

CA 02338581 2001-03-O1
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