GROUP 8, 9 OR 10 OLEFIN COPOLYMERIZATION CATALYST

CATALYSEUR DE COPOLYMERISATION D'OLEFINES CONTENANT UN METAL DU GROUPE 8, 9 OU 10

English Abstract

Olefin co- or homopolymers having a good molecular weight and short chain branching may be prepared in the presence of a pyridyl bridged bisphosphinimine complex of a Group 8, 9 or 10 metal.

French Abstract

Il est possible de préparer des co- ou homopolymères d'oléfine dotés d'un bon poids moléculaire et une ramification de courte chaîne en présence d'un complexe de bisphosphinimine ponté de pyridyle contenant un métal du groupe 8, 9 ou 10.

Claims

The embodiments of the invention in which an exclusive property or
privilege is claimed are defined as follows:
1. A ligand of formula I:
<IMG>
wherein R2, R3, R4 and R5 are independently selected from the group
consisting of a hydrocarbyl radical which is unsubstituted or further
substituted and an inert functional group; R6 and R7 are independently
selected from the group consisting of a hydrocarbyl radical which is
unsubstituted or further substituted, a trialkyl silyl radical and an inert
functional group; and R8, R9 and R10 are independently selected from the
group consisting of a hydrogen atom, a hydrocarbyl radical which is
unsubstituted or further substituted, and an inert functional group.
2. The ligand according to claim 1, wherein R8, R9 and R10 are
independently selected from the group consisting of a hydrogen atom and
a C1-4 alkyl radical.
3. The ligand according to claim 2, wherein R2, R3, R4 and R5 are
independently selected from the group consisting of a C1-10 alkyl and an
aryl radical.
34

4. The ligand according to claim 3, wherein R6 and R7 are
independently selected from the group consisting of tri C1-6 alkyl silyl
radicals and phenyl radicals which are unsubstituted or substituted by up
to five substituents independently selected from the group consisting of a
C1-10 hydrocarbyl radical and two hydrocarbyl radicals, wherein said two
hydrocarbon radicals may be taken together to form a ring
5. The ligand according to claim 4, wherein R2, R3, R4 and R5 are
independently selected from the group consisting of a t-butyl radical or a
phenyl radical.
6. The ligand according to claim 5, wherein R6 and R7 are
independently selected from the group consisting of a trimethyl silyl radical
and a 2,6-di-isopropyl phenyl radical.
7. The ligand according to claim 6, wherein R8, R9 and R10 are a
hydrogen atom.
8. The ligand according to claim 6, wherein R8, R9 and R10 are
independently selected from the group consisting of C1-4 alkyl radicals.
9. The ligand according to claim 8, wherein R8, R9 and R10 are the
same.

10. A process for the polymerization of one or more C2-12 alpha olefins
in the presence of:
(a) a complex comprising a Group 8, 9 or 10 metal and ligand of
formula I:
<IMG>
wherein R2, R3, R4 and R5 are each independently selected from the group
consisting of a hydrocarbyl, a substituted hydrocarbyl and an inert
functional group; R6 and R7 are each independently selected from
hydrocarbyl, substituted hydrocarbyl, trialkyl silyl and substituted or
unsubstituted aryl; and R8, R9 and R10 are each independently selected
from hydrogen, hydrocarbyl, substituted hydrocarbyl, an inert functional
group; and
(b) an activator at a temperature from 20 to 250° C and at a
pressure from 15 to 15000 psi.
11. The process according to claim 10, wherein the activator is selected
from the group consisting of:
(i) aluminoxane compounds R20 2AIO(R20AIO)m AIR20 2 wherein
each R20 is independently selected form the group consisting of C1-20
hydrocarbyl radical and m is from 5 to 30 to provide a molar ratio of
aluminum to Group 8, 9 or 10 metal from 20:1 to 1000:1;
36

(ii) anions of the formula [B(R18)4]- wherein each R18 is
independently selected from the group consisting of phenyl radicals which
are unsubstituted or substituted by up to 5 substituents selected from the
group consisting of a fluorine atom, a C1-4 alkyl or alkoxy radical which is
unsubstituted or substituted by a fluorine atom and a silyl radical of the
formula -Si(R19)3; wherein each R19 is independently selected from the
group consisting of a hydrogen atom and a C1-4 alkyl radical; and an
activator of the formula [B(R18)3] wherein R18 is as defined above and to
provide a molar ratio of Group 8, 9 or 10 metal to boron from 1:1 to 1:3;
and
(iii) a mixture of activators (i) and (ii) and an aluminum
compound selected from the group consisting of aluminum alkyls of the
formula AIR3-n X n in which R is independently selected from the group
consisting of a C1-8 alkyl radical, X is a halogen atom and n is 0, 1, 2 or 3
to provide a ratio of Group 8, 9 or 10 metal to aluminum to boron from
1:1:1 to 1:100:5.
12. The process according to claim 11, wherein said one or more
olefins are selected from the group consisting of ethylene, propylene,
butene, hexene and octene.
13. The process according to claim 12, wherein R8, R9 and R10 are
independently selected from the group consisting of a hydrogen atom and
a C1-4 alkyl radical.
37

14. The process according to claim 13, wherein R2, R3, R4 and R5 are
independently selected from the group consisting of a C1-10 alkyl and an
aryl radical.
15. The process according to claim 14, wherein R6 and R7 are
independently selected from the group consisting of tri C1-6 alkyl silyl
radicals and phenyl radicals which are unsubstituted or substituted by up
to five substituents independently selected from the group consisting of a
C1-10 hydrocarbyl radical and two hydrocarbyl radicals, wherein said two
hydrocarbon radicals may be taken together to form a ring.
16. The process according to claim 15, wherein said group 8, 9 or 10
metal is selected from the group consisting of Fe, Co, Ni and Pd.
17. The process according to claim 16, wherein the temperature is from
120 to 250°C, the pressure is from 100 to 4,500 psig, the activator is
an
aluminoxane in which each R20 is selected from the group consisting of
C1-4 alkyl radicals and m is from 5 to 30.
18. The process according to claim 17, wherein R20 is a methyl radical.
19. The process according to claim 18, wherein R2, R3, R4 and R5 are
independently selected from the group consisting of a t-butyl radical or a
phenyl radical.
38

20. The process according to claim 19, wherein R6 and R7 are
independently selected from the group consisting of a trimethyl silyl radical
and a 2,6-di-isopropyl phenyl radical.
21. The process according to claim 20, wherein R8, R9 and R10 are a
hydrogen atom.
22. The process according to claim 20, wherein R8, R9 and R10 are
independently selected from the group consisting of C1-4 alkyl radicals.
23. The process according to claim 22, wherein R8, R9 and R10 are the
same.
24. The process according to claim 16, wherein the temperature is from
20 to 120°C, the pressure is from 15 to 4,500 psig, the activator is an
aluminoxane in which each R20 is selected from the group consisting of
C1-4 alkyl radicals and m is from 5 to 30.
25. The process according to claim 24, wherein R20 is a methyl radical.
26. The process according to claim 25, wherein R2, R3, R4 and R5 are
independently selected from the group consisting of a t-butyl radical or a
phenyl radical.
39

27. The process according to claim 26, wherein R6 and R7 are
independently selected from the group consisting of a trimethyl silyl radical
and a 2,6-di-isopropyl phenyl radical.
28. The process according to claim 27, wherein R8, R9 and R10 are a
hydrogen atom.
29. The process according to claim 27, wherein R8, R9 and R10 are
independently selected from the group consisting of C1-4 alkyl radicals.
30. The process according to claim 29, wherein R8, R9 and R10 are the
same.
31. The process according to claim 16, wherein the temperature is from
120 to 250°C, the pressure is from 100 to 4,500 psig and the activator
is
an activator capable of ionizing the Group 8, 9 or 10 metal complex and
which is selected from the group consisting of
N,N-dimethylaniliniumtetrakispentafluorophenyl borate, triphenylmethylium
tetrakispentafluorophenyl borate and trispentafluorophenyl boron.
32. The process according to claim 31, wherein R2, R3, R4 and R5 are
independently selected from the group consisting of a t-butyl radical or a
phenyl radical.

33. The process according to claim 32, wherein R6 and R7 are
independently selected from the group consisting of a trimethyl silyl radical
and a 2,6-di-isopropyl phenyl radical.
34. The process according to claim 33, wherein R8, R9 and R10 are a
hydrogen atom.
35. The process according to claim 33, wherein R8, R9 and R10 are
independently selected from the group consisting of C1-4 alkyl radicals.
36. The process according to claim 35, wherein R8, R9 and R10 are the
same.
37. The process according to claim 16, wherein the temperature is from
20 to 120°C, the pressure is from 15 to 4,500 psig and the activator is
an
activator capable of ionizing the Group 8, 9 or 10 metal complex and which
is selected from the group consisting of
N,N-dimethylaniliniumtetrakispentafluorophenyl borate, triphenylmethylium
tetrakispentafluorophenyl borate and trispentafluorophenyl boron.
38. The process according to claim 37, wherein R2, R3, R4 and R5 are
independently selected from the group consisting of a t-butyl radical or a
phenyl radical.
41

39. The process according to claim 38, wherein R6 and R7 are
independently selected from the group consisting of a trimethyl silyl radical
and a 2,6-di-isopropyl phenyl radical.
40. The process according to claim 39, wherein R8, R9 and R10 are a
hydrogen atom.
41. The process according to claim 39, wherein R8, R9 and R10 are
independently selected from the group consisting of C1-4 alkyl radicals.
42. The process according to claim 41, wherein R8, R9 and R10 are the
same.
43. The process according to claim 16, wherein the temperature is from
120 to 250°C, the pressure is from 15 to 4,500 psig and the activator
is a
combination of:
(i) an activator capable of ionizing the Group 8, 9 or 10 metal
complex and which is selected from the group consisting of
N,N- dimethylaniliniumtetrakispentafluorophenyl borate,
triphenylmethylium tetrakispentafluorophenyl borate and
trispentafluorophenyl boron, and
(ii) an aluminum alkyl compound.
42

44. The process according to claim 43, wherein R2, R3, R4 and R5 are
independently selected from the group consisting of a t-butyl radical or a
phenyl radical.
45. The process according to claim 44, wherein R6 and R7 are
independently selected from the group consisting of a trimethyl silyl radical
and a 2,6-di-isopropyl phenyl radical.
46. The process according to claim 45, wherein R8, R9 and R10 are a
hydrogen atom.
47. The process according to claim 45, wherein R8, R9 and R10 are
independently selected from the group consisting of C1-4 alkyl radicals.
48. The process according to claim 47, wherein R8, R9 and R10 are the
same.
49. The process according to claim 16, wherein the temperature is from
20 to 120°C, the pressure is from 15 to 4,500 psig and the activator is
a
combination of:
(i) an activator capable of ionizing the Group 8, 9 or 10 metal
complex and which is selected from the group consisting of
N,N- dimethylaniliniumtetrakispentafluorophenyl borate,
triphenylmethylium tetrakispentafluorophenyl borate and
trispentafluorophenyl boron; and
43

(ii) an aluminum alkyl compound.
50. The process according to claim 49, wherein R2, R3, R4 and R5 are
independently selected from the group consisting of a t-butyl radical or a
phenyl radical.
51. The process according to claim 50, wherein R6 and R7 are
independently selected from the group consisting of a trimethyl silyl radical
and a 2,6-di-isopropyl phenyl radical.
52. The process according to claim 51, wherein R8, R9 and R10 are a
hydrogen atom.
53. The process according to claim 51, wherein R8, R9 and R10 are
independently selected from the group consisting of C1-4 alkyl radicals.
54. The process according to claim 53, wherein R8, R9 and R10 are the
same.
55. A process comprising reacting a compound of formula II:
<IMG>
44

wherein R2, R3, R4 and R5 are independently selected from the group
consisting of a hydrocarbyl radical which is unsubstituted or further
substituted and an inert functional group; R6 and R7 are independently
selected from the group consisting of a hydrocarbyl radical which is
unsubstituted or further substituted, a trialkyl silyl radical and an inert
functional group; and R8, R9 and R10 are independently selected from the
group consisting of a hydrocarbyl radical which is unsubstituted or further
substituted and an inert functional group; M is a Group 8, 9 or 10 metal; X
is a halogen atom or a C1-10 alkoxy radical; and n is an integer from 1 to 3;
with an alkylating agent at a temperature from -50 to 200°C.
56. The process according to claim 55, wherein the alkylating agent is
selected from the group consisting of a Grignard reagent of the formula
RMgX wherein R is a C1-10 alkyl radical and X is a halide; LiR wherein R is
a C1-10 alkyl agent; and alkyl aluminum reagents.
57. A process for reacting one or more C2-12 alpha olefins in the
presence of a catalyst of formula III:
<IMG>

wherein R2, R3, R4 and R5 are each independently selected from the group
consisting of a hydrocarbyl, a substituted hydrocarbyl and an inert
functional group; R6 and R7 are each independently selected from
hydrocarbyl, substituted hydrocarbyl, trialkyl silyl and substituted or
unsubstituted aryl; R8, R9 and R10 are each independently selected from
hydrogen, hydrocarbyl, substituted hydrocarbyl, an inert functional group
and an activator; M is a Group 8, 9, or 10 metal; L1 is a neutral
monodenate ligand which is displaced by one or more activators; L2 is an
activatable ligand; x is from 0 to 12; and y is equal to the oxidation state
of
the metal; with an activator at a temperature from 20 to 250°C and at a
pressure from 15 to 15000 psi.
58. The process according to claim 57, wherein the activator is selected
from the group consisting of:
(i) aluminoxane compounds R20 2AlO(R20AlO)m AlR20 2 wherein
each R20 is independently selected form the group consisting of C1-20
hydrocarbyl radical and m is from 5 to 30 to provide a molar ratio of
aluminum to Group 8, 9 or 10 metal from 20:1 to 1000:1;
(ii) anions of the formula [6(R18)4]- wherein each R18 is
independently selected from the group consisting of phenyl radicals which
are unsubstituted or substituted by up to 5 substituents selected from the
group consisting of a fluorine atom, a C1-4 alkyl or alkoxy radical which is
unsubstituted or substituted by a fluorine atom and a silyl radical of the
formula -Si(R19)3 wherein each R19 is independently selected from the
group consisting of a hydrogen atom and a C1-4 alkyl radical; and an
46

activator of the formula [B(R18)3] wherein R18 is as defined above and to
provide a molar ratio of Group 8, 9 or 10 metal to boron from 1:1 to 1:3;
and
(iii) a mixture of activators (i) and (ii) and an aluminum
compound selected from the group consisting of aluminum alkyls of the
formula AlR3-n X n in which R is independently selected from the group
consisting of a C1-8 alkyl radical and a C1-8 alkoxy radical, X is a halogen
atom and n is 0, 1, 2 or 3 to provide a ratio of Group 8, 9 or 10 metal to
aluminum to boron from 1:1:1 to 1:100:5.
59. The process according to claim 58, wherein L1 is selected from the
group consisting of water and tetrahydrofuran.
60. The process according to claim 59, wherein L2 is selected from the
group consisting of C1-4 alkyl radical, C1-4 alkoxy radical and a halogen
atom.
61. The process according to claim 60, wherein y is 2 or 3.
62. The process according to claim 61, wherein said one or more
olefins are selected from the group consisting of ethylene, propylene,
butene, hexene and octene.
63. The process according to claim 62, wherein the temperature is from
120 to 250°C and the pressure is from 100 to 4,500 psig.
47

64. The process according to claim 63, wherein R8, R9 and R10 are
independently selected from the group consisting of a hydrogen atom and
a C1-4 alkyl radical.
65. The process according to claim 64, wherein in R2, R3, R4 and R5 are
phenyl radicals.
66. The process according to claim 65, wherein R6 and R7 are selected
from the group consisting of 2,6-di-isopropyl phenyl radicals and trimethyl
silyl radicals.
67. The process according to claim 66, wherein M is selected from the
group consisting of Fe, Co, Ni and Pd.
68. The process according to claim 67, wherein the activator is an
aluminoxane in which each R20 is selected from the group consisting of
C1-4 alkyl radicals and m is from 5 to 30.
69. The process according to claim 68, wherein R20 is a methyl radical.
70. The process according to claim 67, wherein the activator is an
activator capable of ionizing a Group 8, 9 or 10 metal complex and which
is selected from the group consisting of
N,N-dimethylaniliniumtetrakispentafluorophenyl borate, triphenylmethylium
tetrakispentafluorophenyl borate and trispentafluorophenyl boron.
48

71. The process according to claim 67, wherein the activator is a
combination of:
(i) an activator capable of ionizing a Group 8, 9 or 10 metal
complex and which is selected from the group consisting of
N,N-dimethylaniliniumtetrakispentafluorophenyl borate,
triphenylmethylium tetrakispentafluorophenyl borate and
trispentafluorophenyl boron, and
(ii) an aluminum alkyl.
72. The process according to claim 67, wherein the temperature is from
20 to 120°C and the pressure is from 15 to 4,500 psig.
73. The process according to claim 72, wherein R8, R9 and R10 are
independently selected from the group consisting of a hydrogen atom and
a C1-4 alkyl radical.
74. The process according to claim 73, wherein R2, R3, R4 and R5 are
phenyl radicals.
75. The process according to claim 74, wherein R6 and R7 are selected
from the group consisting of 2,6-di-isopropyl phenyl radicals and trimethyl
silyl radicals.
49

76. The process according to claim 75, wherein the activator is an
aluminoxane in which each R20 is selected from the group consisting of
C1-4 alkyl radicals and m is from 5 to 30.
77. The process according to claim 76, wherein R20 is a methyl radical.
78. The process according to claim 75, wherein the activator is an
activator capable of ionizing a Group 8, 9 or 10 metal complex and which
is selected from the group consisting of N,N-
dimethylaniliniumtetrakispentafluorophenyl borate, triphenylmethylium
tetrakispentafluorophenyl borate and trispentafluorophenyl boron.
79. The process according to claim 75, wherein the activator is a
combination of:
(i) an activator capable of ionizing a Group 8, 9 or 10 metal
complex and which is selected from the group consisting of
N, N- dimethylaniliniumtetrakispentafluorophenyl borate,
triphenylmethylium tetrakispentafluorophenyl borate and
trispentafluorophenyl boron, and
(ii) an aluminum alkyl.
80. A polyolefin having a weight average molecular weight (Mw) from 5
× 10 4 to 10 7 and a degree of short chain branching from 1-30 per 1000
carbon atoms when prepared by a process according to claim 10.

81. The polyolefin according to claim 80, having a weight average
molecular weight (Mw) from 10 5 to 10 7.
82. The polyolefin according to claim 81, having a degree of short chain
branching from 1-20 per 1000 carbon atoms.
83. The polyolefin according to claim 82, comprises at least 80 weight
% of ethylene and up to 20 weight % of one or more monomers selected
from the group consisting of propylene, 1-butene, 1-hexene and 1-octene.
51

Description

CA 02285523 2008-05-20
FIELD OF THE INVENTION
The present invention relates to late transition metal complexes, a
process for their preparation and their use in the polymerization of olefins.
BACKGROUND OF THE INVENTION
The papers in Organometallics, 10, 1421-1431, 1991; Inorg. Chem.,
34, 4092-4105, 1995; J. Organomet. Chem., 527(1-2), 263-276, 1997; and
Inorg. Chem., 35(6), 1518-28, 1996, report the reaction of bis
(iminophosphoranyl) methane (BIPM) which are typically aryl substituted
on the phosphorus atom and the nitrogen with Group 8, 9 or 10 metal
halides (chlorides) further comprising at two weakly coordinating ligands
(L) such as nitriles or cyclooctadiene, afforded several products depending
on the reaction time, type of ligand or nature of the metal. The product
could be a N-C chelating type product or a N-N chelating product (similar
to those of the present invention).
a. N-C chelating b. N-N chelating
A A
H N A~ / A
'`~/\iX
A \` / ~ x X
i X R-C
R /M\\x
P` ~
A ~
A A ~ ~ A A
A
The products contain alkyl bridges between the phosphinimine
groups and the references do not disclose the pyridyl bridged compounds
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CA 02285523 2008-05-20
of the present invention. Further, none of the references teach or suggest
the use of such compounds for the polymerization of alpha olefins.
United States patent 5,557,023 issued September, 1996 teaches
the use of some phosphinimines complexes to oligomerize alpha olefins.
However, the complexes disclosed are not bisphosphinimine complexes.
Rather, the complexes are of the structure indicated below.
R \ /Rto
s
R,\P/ M/x~ Y\/F
RZ/ \ R7t~~F\ / \G
Rts
S t N\
(R8)y
Re\ /Rto
n /Li
M
L4 M-LZ
Rtt / \ LS
N
Rtz Ii
wherein R, Q, etc. are as defined in the patent. The structures disclosed
in the patent are not the bisphosphinimines of the present invention. While
the reference does teach oligomerization, it does not suggest
polymerization.
WO 98/30609 patent application published July 16, 1998 assigned
to E.I. du Pont de Nemours teaches the use of various complexes of nickel
to polymerize alpha olefins. The most structurally similar complex in the
disclosure is compound XXXXI at the middle of page 9 and the associated
description of the various substituents. However, the compound does not
contain a pyridyl bridge. Rather, the nickel atom completes the cyclic
structure in the middle of the compound. The reference does not
contemplate or disclose compounds of the present invention which have a
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CA 02285523 2008-05-20
pyridyl bridge between the bisphosphinimine functionality. The reference
fails to disclose the subject matter of the present invention.
There are a number of patents and papers by Brookhart and/or
Gibson disclosing the use of Group 8, 9 or 10 metals to polymerize olefins.
However, such papers did not teach the copolymerizations (e.g. WO
98/27124). The present invention provides olefin copolymerization using
an iron based catalyst.
SUMMARY OF THE INVENTION
The present invention provides a process for the polymerization of
one or more C2_12 alpha olefins in the presence of an activatable complex
of a Group 8, 9 or 10 metal and ligand of formula I:
R ~ / R 3
8 p~~Rs
R9 N
R1o N
R4 Ps R7
R
wherein R2, R3, R4 and R5 are independently selected from the group
consisting of a hydrocarbyl radical which is unsubstituted, further
substituted or an inert functional group; R6 and R' are independently
selected from the group consisting of a hydrocarbyl radical which is
unsubstituted or further substituted, trialkyl silyl radical and an inert
functional group; and R8, R9 and R10 are independently selected from the
group consisting of a hydrogen atom, a hydrocarbyl radical which is
unsubstituted or further substituted and an inert functional group.
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A further aspect of the present invention provides a process for the
polymerization of one or more C2_12 alpha olefins in the presence of:
(a) a complex comprising a Group 8, 9 or 10 metal and ligand of
formula I:
R 2 R3
8 p\' / Rs
N
R9
N
R R4\ 5R~
5 R
wherein R2, R3, R4 and R5 are each independently selected from the group
consisting of hydrocarbyl, substituted hydrocarbyl or an inert functional
group; R6 and R' are each independently selected from hydrocarbyl,
substituted hydrocarbyl, trialkyl silyl and substituted or unsubstituted aryl;
10 and R8, R9 and R10 are each independently selected from hydrogen,
hydrocarbyl, substituted hydrocarbyl, an inert functional group; and
(b) an activator at a temperature from 20 to 250 C and at a
pressure from 15 to 15000 psi.
In a further aspect, the present invention provides a process for
reacting one or more C2_12 alpha olefins in the presence of a catalyst of
formula III:
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CA 02285523 2008-05-20
2R\ Fe
P-~
~(OX
(L2~
R~ f
4
R F~ F~
wherein R2 to R10 and M are defined above; L' is a neutral monodenate
ligand which is displaced by one or more of an activator, a scavenger or a
monomer; x is from 0 to 12; L2 is an activatable ligand; and y is the
oxidation state of the metal; with an activator at a temperature from 20 to
250 C and at a pressure from 15 to 15000 psi.
The present invention further comprises reacting a compound of
formula II:
8 2R~ R3 ~R6
zz:== N
\
R9 \ / N MXn
Rio PrN
aR~ R5 R7
wherein R2, R3, R4, R5,R6, R7, R8, Rg, R10 and M are as defined above, X is
a halogen and n is an integer from 1 to 3 with an alkylating agent at a
temperature from -50 to 250 C to produce a compound of formula III as
defined above.
The present invention also provides an olefin co- or homopolymer
having a weight average molecular weight (Mw) from 5 x 104 to 107 and a
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degree of short chain branching from 1-30 per 1000 carbon atoms
prepared in the presence of an iron (or cobalt) containing catalyst.
DETAILED DESCRIPTION
The term "scavenger" as used in this specification is meant to
include those compounds effective for removing polar impurities from the
reaction solvent. Such impurities can be inadvertently introduced with any
of the polymerization reaction components, particularly with solvent,
monomer and catalyst feed; and can adversely affect catalyst activity and
stability. It can result in decreasing or even elimination of catalytic
activity,
particularly when an activator capable of ionizing the Group 8, 9 or 10
metal complex is also present.
The term "an inert functional group" means a functional group on a
ligand or substituent which does not participate or react in the
polymerization reaction. For example, in the polymerization aspect of the
present invention an inert functional group would not react with any of the
monomers, the activator or the scavenger of the present invention.
Similarly for the alkylation of the metal complex or the formation of the
metal complex the inert functional group would not interfere with the
alkylation reaction or the formation of the metal complex respectively.
The phrase "a neutral monodenate ligand" means a ligand which is
only loosely bound to the metal by a coordinative bond. These may
include water (HZO) or tetrahydrofuran (THF).
As used in this specification, an activatable ligand is a ligand
removed or transformed by an activator. These include anionic
substituents and/or bound ligands. Exemplary activatable ligands are
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CA 02285523 2008-05-20
independently selected from the group consisting of a hydrogen atom, a
halogen atom, a C1_10 hydrocarbyl radical, a CI_10 alkoxy radical, a C5_10
aryl oxide radical; each of which said hydrocarbyl, alkoxy, and aryl oxide
radicals may be unsubstituted by or further substituted by a halogen atom,
a C1_8 alkyl radical, a Cl_8 alkoxy radical, a Cr1-I aryl or aryl oxy
radical, an
amido radical which is unsubstituted or substituted by up to two C1_8 alkyl
radicals, and a phosphido radical which is unsubstituted or substituted by
up to two CI_a alkyl radicals.
In the above compounds formula I - III, Rz, R3, R4 and R5 are
independently selected from the group consisting of a hydrocarbyl radical
and an inert functional group. Preferably R2, R3, R4 and R5 are selected
from the group consisting of C1_10 alkyl or aryl radicals, most preferably
Ci-4radicals such as a bulky t-butyl radical and phenyl radicals. In the
above compounds, R8, R9 and R10 are independently selected from the
group consisting of a hydrogen atom, a hydrocarbyl radical which is
unsubstituted or further substituted and an inert functional group,
preferably a hydrogen atom and a C1_10, most preferably a CI.4alkyl
radical. In the above formula, R 6 and R7 are independently selected from
the group consisting of a hydrocarbyl radical, preferably a phenyl radical
which is unsubstituted or substituted by up to five hydrocarbyl radicals, or
a C1_10 alkyl radical, or two hydrocarbyl radicals taken together may form a
ring, or a trialkyl, preferably C1_6, most preferably C1-4silyl radical. In
the
complex of formula I{I, R2 through R10 are as defined above and L' is a
neutral monodenate ligand easily displaced by one or more of a
scavenger, activator or monomer, preferably water or tetrahydrofuran. L2
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CA 02285523 2008-05-20
is an activatable ligand, preferably a halogen or a C1_6alkyl or alkoxide
radical, most preferably a chloride, bromide, or a CI-4alkyl or alkoxide
radical; x is from 0 to 12, preferably from 0 to 6; and y is the oxidation
state
of the metal M, preferably 2 or 3.
In the compound of formula I and III, preferably R8, R9 and R10 are
independently selected from the group consisting of a hydrogen atom or a
hydrocarbyl radical, preferably a hydrogen atom and a C1-4alkyl radical;
R4, R5, R2 and R3 are independently selected from the group consisting of
a hydrocarbyl radical which is unsubstituted or further substituted and an
inert functional group; and R6 and R7 are independently selected from the
group consisting of trimethyl silyl and an aryl radical, preferably from 6 to
14 carbon atoms which is unsubstituted or substituted by one or more
radicals selected from the group consisting of C1-6hydrocarbyl radicals,
most preferably 2,6-di-isopropyl phenyl radicals. In a particularly preferred
aspect of the present invention R8, R9 and R10 are the same; R2, R3, R4
and R5 are the same; and R6 and R' are the same.
In the compound of formula II, preferred substituents for R2, R3, R4,
R5, Rs, R', R8, R9 and R10 are as defined immediately above.
The metal complexes of the present invention may be prepared by
reacting the ligand with a compound of MXn = A(H20) X, wherein X may
be selected from the group consisting of halogen, C1.s alkoxide, nitrate or
sulfate, preferably halide and most preferably chloride or bromide; and A is
0 or an integer from 1-6.
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CA 02285523 2008-05-20
The reaction of the ligand of formula I with the compound of the
formula MX, = A (H20) may be conducted in a hydrocarbyl solvent at
temperature from -50 to 250 C, preferably from 20 to 120 C.
The resulting compound may then be alkylated (either partially or
fully). Some alkylating agents are Grignard agents of the formula RMgX
and organolithium reagents LiR wherein R is a Cl_lo alkyl radical and X is a
halogen and alkyl aluminum reagents. Alkyl aluminum reagents include
trialkyl aluminum, alkyl aluminum halides (i.e. (R)XALX3_X wherein R is a
Cl_lo alkyl radical, X is a halogen, x is 1 or 2 and MAO as described
below).
Solution polymerization processes are fairly well known in the art.
These processes are conducted in the presence of an inert hydrocarbon
solvent typically a C5_72 hydrocarbon which may be unsubstituted or
substituted by CI-4 alkyl group such as pentane, hexane, heptane, octane,
cyclohexane, methylcyclohexane or hydrogenated naphtha. An additional
solvent is Isopar E(C8-1Z aliphatic solvent, Exxon Chemical Co.).
The polymerization may be conducted at temperatures from about
to about 250 C. Depending on the product being made, this
temperature may be relatively low such as from 20 to about 180 C. The
20 pressure of the reaction may be as high as about 15,000 psig for the older
high pressure processes or may range from about 15 to 4,500 psig.
Suitable olefin monomers may be ethylene and C3_20 mono- and di-
olefins. Preferred monomers include ethylene and C3_12 alpha olefins
which are unsubstituted or substituted by up to two CI.6 alkyl radicals.
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CA 02285523 2008-05-20
Illustrative non-limiting examples of such alpha-olefins are one or more of
propylene, 1-butene, 1-pentene, 1-hexene, 1-octene and 1-decene.
The reaction product of the present invention, in the presence of a
single alpha olefin, may be an oligomer having a molecular weight (Mw)
less than about 1500. The reaction product of the present invention may
also be a co- or homopolymer of one or more alpha olefins. The polymers
prepared in accordance with the present invention have a good molecular
weight. That is, weight average molecular weight (Mw) will preferably be
greater than about 50,000 ranging up to 107, preferably 105 to 107
.
The polyethylene polymers which may be prepared in accordance
with the present invention typically comprise not less than 60, preferably
not less than 70, most preferably not less than 80 weight % of ethylene
and the balance of one or more C410 alpha olefins, preferably selected
from the group consisting of 1-butene, 1-hexene and 1-octene. The
polyethylene prepared in accordance with the present invention may
contain branching (e.g. one or more branches per 1000 carbon atoms,
preferably 1-30 branches per 1000 carbon atoms, typical 1-20 branches
per 1000 carbon atoms and most preferably 1-10 branches per 1000
carbon atoms).
The activator may be selected from the group consisting of:
(i) an aluminoxane; and
(ii) an activator capable of ionizing the Group 8, 9 or 10 metal
complex (which may be used in combination with an alkylating activator).
The aluminoxane activator may be of the formula
(R20)2A10(R20AIO)R,AI(R20)2 wherein each R20 is independently selected
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CA 02285523 2008-05-20
from the group consisting of C7_20 hydrocarbyl radicals, m is from 0 to 50,
and preferably R20 is a Cl-4 alkyl radical and m is from 5 to 30. The
aluminoxane activator may be used prior to the reaction but preferably in
situ alkylation is typical (e.g. alkyl groups replacing leaving ligands,
hydrogen or halide groups).
If the Group 8, 9 or 10 metal complex is activated only with
aluminoxane, the amount of aluminoxane will depend on the reactivity of
the alkylating agent. Activation with aluminoxane generally requires a
molar ratio of aluminum in the activator to the Group 8, 9 or 10 metal in the
complex from 20:1 to 1000:1. MAO may be the higher end of the above
noted range.
The activator of the present invention may be a combination of an
alkylating activator which also serves as a scavenger other than
aluminoxane in combination with an activator capable of ionizing the
Group 8, 9 or 10 complex.
The alkylating activator (which may also serve as a scavenger) may
be selected from the group consisting of: (R)pMgX2_p wherein X is a
halide, each R is independently selected from the group consisting of Cl_,o
alkyl radicals, preferably CI_8 alkyl radicals and p is 1 or 2; RLi wherein R
is as defined above; (R)qZnX2-q wherein R is as defined above, X is
halogen and q is 1 or 2; (R)SAIX3_1 wherein R is as defined above, X is
halogen and s is an integer from 1 to 3. Preferably, in the above
compounds R is a C1.4 alkyl radical and X is chlorine. Commercially
available compounds include triethyl aluminum (TEAL), diethyl aluminum
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CA 02285523 2008-05-20
chloride (DEAC), dibutyl magnesium ((Bu)2Mg) and butyl ethyl magnesium
(BuEtMg or BuMgEt).
The activator capable of ionizing the Group 8, 9 or 10 metal
complex may be selected from the group consisting of:
(i) compounds of the formula [R15]+ [B(R18)4]" wherein B is a
boron atom, R15 is a cyclic C5-7aromatic cation or a triphenyl methyl cation
and each R18 is independently selected from the group consisting of
phenyl radicals which are unsubstituted or substituted with from 3 to 5
substituents selected from the group consisting of a fluorine atom, a Cl-4
alkyl or alkoxy radical which is unsubstituted or substituted by a fluorine
atom, and a silyl radical of the formula -Si-(R19)3 wherein each R19 is
independently selected from the group consisting of a hydrogen atom and
a C1-4alkyl radical; and
(ii) compounds of the formula [(R16)tZH]+[B(R'$)4]" wherein B is
a boron atom, H is a hydrogen atom, Z is a nitrogen atom or phosphorus
atom, t is 2 or 3 and R's is selected from the group consisting of C1_$ alkyl
radicals, a phenyl radical which is unsubstituted or substituted by up to
three CI-4afkyl radicals, or one R16 taken together with the nitrogen atom
to form an anilinium radical and R18 is as defined above; and
(iii) compounds (activators) of the formula B(R'$)3 wherein R18 is
as defined above.
In the above compounds, preferably R18 is a pentafluorophenyl
radical, R15 is a triphenylmethyl cation, Z is a nitrogen atom and R16 is a
CI-4alkyl radical or R16 taken together with the nitrogen atom to form an
anilinium radical which is substituted by two C1-4alkyl radicals.
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CA 02285523 2008-05-20
The activator capable of ionizing the Group 8, 9 or 10 metal
complex abstract one or more L' ligands so as to ionize the Group 8, 9 or
metal center into a cation, but not to covalently bond with the Group 8,
9 or 10 metal; and to provide sufficient distance between the ionized
5 Group 8, 9 or 10 metal and the ionizing activator to permit a polymerizable
olefin to enter the resulting active site.
Examples of compounds capable of ionizing the Group 8, 9 or 10
metal complex include the following compounds:
triethylammonium tetra(phenyl)boron,
10 tripropylammonium tetra(phenyl)boron,
tri(n-butyl)ammonium tetra(phenyl)boron,
trimethylammonium tetra(p-tolyl)boron,
trimethylammonium tetra(o-tolyl)boron,
tributylammonium tetra(pentafluorophenyl)boron,
tributylammonium tetra(pentafluorophenyl)boron,
tri(n-butyl)ammonium tetra(o-tolyl)boron,
N,N-dimethylanilinium tetra(phenyl)boron,
N,N-diethylanilinium tetra(phenyl)boron,
N,N-diethylanilinium tetra(phenyl)n-butylboron,
N,N-2,4,6-pentamethylanilinium tetra(phenyl) boron
di-(isopropyl)ammonium tetra(pentafluorophenyl)boron,
dicyclohexylammonium tetra(phenyl)boron,
triphenylphosphonium tetra(phenyl)boron,
tri(methylphenyl)phosphonium tetra(phenyl)boron,
tri(dimethylphenyl)phosphonium tetra(phenyl)boron,
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CA 02285523 2008-05-20
tropillium tetrakispentafluorophenyl borate,
triphenylmethylium tetrakispentafluorophenyl borate,
benzene (diazonium) tetrakispentafluorophenyl borate,
tropillium phenyltrispentafluorophenyl borate,
triphenylmethylium phenyltrispentafluorophenyl borate,
benzene (diazonium) phenyltrispentafluorophenyl borate,
tropillium tetrakis (2,3,5,6-tetrafluorophenyl) borate,
triphenylmethylium tetrakis (2,3,5,6-tetrafluorophenyl) borate,
benzene (diazonium) tetrakis (3,4,5-trifluorophenyl) borate,
tropillium tetrakis (3,4,5-trifluorophenyl) borate,
benzene (diazonium) tetrakis (3,4,5-trifluorophenyl) borate,
tropillinum tetrakis (1,2,2-trifluoroethenyl) borate,
triphenylmethylium tetrakis (1,2,2-trifluoroethenyl) borate,
benzene (diazonium) tetrakis (1,2,2-trifluoroethenyl) borate,
tropillium tetrakis (2,3,4,5-tetrafluorophenyl) borate,
triphenylmethylium tetrakis (2,3,4,5-tetrafluorophenyl) borate, and
benzene (diazonium) tetrakis (2,3,4,5-tetrafluorophenyl) borate.
Readily commercially available activators which are capable of
ionizing the Group 8, 9 or 10 metal complexes include:
N,N- dimethylaniliniumtetrakispentafluorophenyl borate,
triphenylmethylium tetrakispentafluorophenyl borate, and
trispentafluorophenyl boron.
If the Group 8, 9 or 10 metal complex is activated with a
combination of an aluminum alkyl compound (generally other than
aluminoxane), and a compound capable of ionizing the Group 8, 9 or 10
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CA 02285523 2008-05-20
metal complex; the molar ratios of Group 8, 9 or 10 metal:metal in the
alkylating agent (e.g. Al): metalloid (e.g. boron or phosphorus) in the
activator capable of ionizing the Group 8, 9 or 10 metal complex (e.g.
boron) may range from 1:1:1 to 1:100:5. Preferably, the alkylating
activator is premixed/reacted with the Group 8, 9 or 10 metal complex and
the resulting alkylated species is then reacted with the activator capable of
ionizing the Group 8, 9 or 10 metal complex.
In a solution polymerization, the monomers are dissolved/dispersed
in the solvent either prior to being fed to the reactor or for gaseous
monomers, the monomer may be fed to the reactor so that it will dissolve
in the reaction mixture. Prior to mixing, the solvent and monomers are
generally purified to remove polar moieties. The polar moieties or catalyst
poisons include water, oxygen, metal impurities, etc. Preferably steps are
taken before provision of such into the reaction vessel, for example by
chemical treatment or careful separation techniques after or during the
synthesis or preparation of the various components. The feedstock
purification prior to introduction into the reaction solvent follows standard
practices in the art (e.g. molecular sieves, alumina beds and oxygen
removal catalysts) are used for the purification of ethylene, alpha-olefin
and optional diene. The solvent itself as well (e.g. cyclohexane and
toluene) is similarly treated. In some instances, out of an abundance of
caution, excess scavenging activators may be used in the polymerization
process.
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The feedstock may be heated prior to feeding into the reactor.
However, in many instances it is desired to remove heat from the reactor
so the feedstock may be at ambient temperature to help cool the reactor.
Generally, the catalyst components may be premixed in the solvent
for the reaction or fed as separate streams to the reactor. In some
instances premixing is desirable to provide a reaction time for the catalyst
components prior to entering the reaction. Such an "in line mixing"
technique is described in a number of patents in the name of DuPont
Canada Inc. For example it is described in U.S. patent 5,589,555 issued
December 31, 1996.
The reactor may comprise a tube or serpentine reactor used in the
"high pressure" polymerizations or it may comprise one or more reactors
or autoclaves. It is well known that the use in series of two such reactors
each of which may be operated so as to achieve different polymer
molecular weight characteristics. The residence time in the reactor system
will depend on the design and the capacity of the reactor. Generally, the
reactors should be operated under conditions to achieve a thorough
mixing of the reactants. On leaving the reactor system, the solvent is
removed and the resulting polymer is finished in a conventional manner.
The present invention will now be illustrated by the following
examples in which unless otherwise specified weight means weight % and
parts means parts by weight (e.g. grams).
Materials: 2,6-dibromopyridine, diethylphosphine (Et2PH),
diphenylphosphine (Ph2PH), di-tert-butylphosphine chloride (t-Bu2PCI),
iron (II) chloride (FeCl2), iron (II) chloride tetrahydrates (FeCI2.4(H20)),
iron
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CA 02285523 2008-05-20
(II) tetrafluoroborate hexahydrate (Fe(BF4)2.4H20), iron (III) bromide
(FeBr3), iron (III) chloride (FeC13.6H20), cobalt chloride (CoCI2), bis
(benzonitrile) dichloropalladium (II) (PdCI2(PhCN)2), nickel (II) bromide
(NiBr2), n-Butyl lithium (BuLi, 1.6M in hexane), and trimethylsilyl azide
(TMSN3) were purchased from Aldrich Chemical Company, Inc. and Strem
Chemical Inc. Solvents were prepared by passing through molecular
sieves, de-oxo catalysts and alumina columns prior to use.
Methylaluminoxane (PMAO-IP) (13.5 weight % of Al) was purchased from
AKZO-NOBEL and used as supplied. 2,6-bis (diphenylphosphino)pyridine
(Ic) was prepared using the method described in the literature (G. R.
Newkome and D. C. Hager, J. Org. Chem., 43(5), 947, 1978). Diimine-
Nickel complex (VIII) was synthesized as described in the literature (L.K.
Johnson, C.M. Killiam, M. Brookhart, J. Am. Chem. Soc., 117, 6414,
1995). The anhydrous toluene was purchased from Aldrich and purified
over molecular sieves prior to use. B(C6F5)3 was purchased from Boulder
Scientific Inc. and used without further purification.
Measurements: NMR spectra were recorded using a Bruker 200MHz
spectrometer. 'H NMR chemical shifts were reported with reference to
tetramethylsilane. Polymer molecular weights and molecular weight
distributions were measured by GPC (Waters 150-C) at 140 C in 1,2,4-
trichlorobenzene calibrated using polyethylene standards. DSC was
conducted on a DSC 220 C from Seiko Instruments. The heating rate is
10 C/minute from 0 to 200 C. FT-IR was conducted on a Nicolet Model
750 Magna IR spectrometer. MI was measured on an automatic MI
machine with model number of MP993 at 190 C.
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CA 02285523 2008-05-20
Operation: All synthesis and catalyst preparations were performed under
nitrogen or argon using standard Schienk techniques or in a dry-box.
EXAMPLES
Example 1
Synthesis of 2.6-(t-Bu2P)2,pyridine (la)
To a THF (100 mL) solution of 2,6-dibromopyridine (2.37 g, 10
mmol) at -78 C was added slowly a THF (30 mL) solution of BuLi (6.25
mL, 1.6M in hexane, 10 mmol). The resulting yellow solution was allowed
to warm to -25 C. A THF (30 mL) solution of t-Bu2PCI (1.81 g, 10 mmol)
was added to the reaction mixture slowly. The brown solution was allowed
to warm to room temperature and was stirred for 1 hour. The reaction
mixture was cooled to -78 C and a THF (30 mL) solution of BuLi (6.25 mL,
1.6M in hexane, 10 mmol) was slowly added. The reaction mixture was
warmed to -25 C and a THF (30 mL) solution of t-Bu2PCI (1.81 g, 10
mmol) was added. The reaction mixture was warmed to room temperature
and stirred for another 1 hour. All volatiles were then removed under
vacuum. The resulting residue was dissolved in heptane (50 mL) and LiBr
was removed by filtration. When the heptane was evaporated, a brown
oily residue was obtained. The pure product was obtained by vacuum
distillation of the residue (122 C / 0.5 mmHg). 'H NMR (toluene-ds, S):
1.29 (d, J = 11.4Hz, 36H), 6.95 (m, 1 H), 7.45 (rn, 2H). The purity and
molecular formula (M+=367 (30%)) were confirmed by GC-MS.
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CA 02285523 2008-05-20
p N
P"r
Example 2
Synthesis of 2.6-(Et2P)2eyridine (Ib)
A THF (100 mL) solution of diethyl phosphine (4.61 g, 51.2 mmol)
was treated with n-BuLi (32 mL, 1.6 M, 51.2 mmol) using a drop-wise
addition. The reaction mixture was allowed to stir 20 minutes and was
then added to a solution of 2,6-dibromopyridine (6.04 g, 25.5 mmol) at
50 C resulting in a darkening of the solution to a brown/black color. The
reaction was then further heated at 50 C for 5 hours. The product (1.52 g,
yield: 50%) was purified by a short path distillation (76-78 C / 0.3 mmHg).
\
E~
N ~ t
P
i
P
Et Et
Example 3
Synthesis of 2,6-(t-Bu2P=NTMS)2pyridine (Ila)
A 200 mL Schienk flask was fitted with a condenser, a nitrogen
inlet, a gas outlet bubbler and a TMSN3 (trimethyl silyl azide) addition line.
The flask was charged with 2,6-(t-Bu2P)2pyridine (Ia) (1.84 g, 5 mmol).
The TMSN3 line was charged with TMSN3 (7.3 mL, 5.5 mmol) through a
syringe. At room temperature, 3 mL of TMSN3 was injected into the flask
and the mixture was heated to 95 C. The remaining TMSN3 was added to
the reaction at 95 C. As the addition occurred, nitrogen was evolved.
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CA 02285523 2008-05-20
After the addition was completed, the reaction mixture was kept for an
additional 2 hours at 110 C. When the slight excess of TMSN3 was
removed under vacuum, a white solid (2.7 g, 100%) was obtained.
'H NMR (toluene-d8, S): 0.42 (s, 18H), 1.21 (d, J = 14.3Hz, 36H),
7.23 (m, 1 H), 8.36 (m, 2H).
~ I \
N
Y
/"
Example 4
Synthesis of 2,6-(Et;?P=NTMS)7eYridine (Ilb)
A 200 mL Schlenk flask was fitted with a condenser, a nitrogen
inlet, a gas outlet bubbler and a TMSN3 addition line. The flask was
charged with 2,6-(Et2P)2pyridine (Ib) (1.28 g, 5 mmol). The TMSN3 line
was charged with TMSN3 (7.3 mL, 5.5 mmol) through a syringe. At room
temperature, 3 mL of TMSN3 was injected into the flask and the mixture
was heated to 95 C. The remaining TMSN3 was added to the reaction at
95 C. As the addition occurred, nitrogen was evolved. After the addition
was completed, the reaction mixture was kept for an additional 2 hours at
110 C. When the slight excess of TMSN3 was removed under vacuum, an
oil (2.15 g, 100%) was obtained. 'H NMR (toluene-d8, 8): 0.38 (s, 18H),
0.84 (t, J = 7.6Hz, 6H), 0.92 (t, J = 7.7Hz, 6H), 1.66(m, 8H), 7.19 (m, 2H),
8.06 (m, 2H).
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CA 02285523 2008-05-20
\
E~ ~ /Et
Et N Et
~ N\
Example 5
Synthesis of 2,6-(Ph7P=NTMS)?pvridine (Ilc)
A 200 mL Schlenk flask was fitted with a condenser, a nitrogen
inlet, a gas outlet bubbler and a TMSN3 addition line. The flask was
charged with 2,6-(Ph2P)2pyridine (Ic) (2.24 g, 5 mmol). The TMSN3 line
was charged with TMSN3 (7.3 mL, 5.5 mmol) through a syringe. At room
temperature, 3 mL of TMSN3 was injected into the flask and the mixture
was heated to 95 C. The remaining TMSN3 was added to the reaction at
95 C. As the addition occurred, nitrogen was evolved. After the addition
was completed, the reaction mixture was kept for an additional 2 hours at
110 C. When the slight excess of TMSN3 was removed under vacuum, a
white solid (3.1 g, 100%) was obtained. 'H NMR (toluene-d8, 8): 0.30 (s,
18H), 7.03 (m, 4H), 6.97 (m, 8H), 7.16 (m, 1 H), 7.55 (m, 8H), 8.32 (m, 2H).
P~ /Ph
Ph N //P~'Ph
//N ~
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CA 02285523 2009-04-15
Examples 6-11
Synthesis of Catalyst Precursors
General Procedure: The ligand (2,6-(t-Bu2P=NTMS)2pyridine (Ila), 1 eq.)
and a metal salt (FeCI2, FeCI2.4H20, CoC12, FeBr3, FeCI3.6H20 or NiBr2)
were added together in a Schienk flask in a dry-box. Then the flask was
charged with THF (30 mL) or dichloromethane (CH2CI2, 30 mL). The
mixture was stirred for several hours until there were no detectable metal
salts left in the flask. The reaction solution was filtered to remove some
insoluble polymeric materials and was concentrated. Heptane (5 mL) was
added to precipitate the complex. The resultant solid was filtered and
washed with heptane and dried in vacuo.
Example 6
Fe(II) Complex (Illa) from FeC12
Isolated as a beige yellow solid (Yield: 80%). 'H NMR (THF-d8, all
peaks appear as singlets due to their broadness, 8): 0.13 (s, br), 1.29 (s,
br), 8.5 (s, br).
Example 7
Fe(II) Complex (IIIb) from FeC16.4H2O
Isolated as a white solid (Yield: 90%). 'H NMR (THF-d8, all peaks
appear as singlets due to their broadness, S): 0.01 (s, br), 1.21 (s, br), 8.5
(s, br), 10.2 (s, br).
23
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CA 02285523 2008-05-20
Example 8
Co(II) Complex (IV) from CoCI2
Isolated as a blue solid (Yield: 100%). 'H NMR (THF-d8, all peaks
appear as singlets due to their broadness, 8): -1.16 (s, br), 0.03 (s, br),
0.66 (s, br), 0.87 (s, br), 1.27 (s, br.), 7.13(s, br.), 7.46(s, br.).
Example 9
Fe(III) Complex (Va) from FeBr3
Isolated as a brown solid (Yield: 95%). 'H NMR (THF-d8, S): 0.09
(s, 18H), 1.24 (d, 36H), 8.4 (s, br, 2H), 7.97 (s, br., 1 H).
Example 10
Fe(III) Complex (Vb) from FeCI3.6H2O
Isolated as a THF insoluble yellow solid (Yield: 100%).
Example 11
Ni(II) Complex (VI) from NiBr2
Isolated as a greenish solid (Yield: 50%). 'H NMR (THF-d8, S):
0.09 (s,18H), 1.23 (d, 36H), 8.3 (s, br, 2H), 7.95 (s, br., 1 H).
Example 12
Pd(II) Complex (VII) from lic and Pd(PhCN)2Ci2
The ligand (2,6-(Ph2P=NTMS)2pyridine, IIc) (0.622g, 1 mmol) and
PdCI2(PhCN)2 (0.384 g, 1 mmol) were added together in a Schlenk flask in
a dry-box. The flask was charged with dichloromethane (CH2CI2, 30 mL).
The mixture was stirred for 12 hours. The reaction solution was filtered to
remove some insoluble polymeric materials and was concentrated.
Heptane (5 mL) was added to precipitate the complex. The resultant solid
was filtered, washed with heptane and dried in vacuo. The product was
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CA 02285523 2008-05-20
isolated as a yellow solid (Yield: 74%). 'H NMR (toluene-d8, S): 0.17 (s,
18H), 7.20 (m, 12H), 7.4 (m, 1 H), 7.85 (m, 8H), 8.45 (m, 2H).
P~ ~Ph
Ph N ~Ph
/N /Rd~-N\
-)S~CI CI Polymerizations
Examples 13-15
Low Pressure Slurrx Process
Ethylene polymerization experiments were carried out at room
temperature in a Schlenk flask (50 mL) equipped with magnetic stirring bar
with constant supply of neat gaseous ethylene at atmospheric pressure.
The catalysts were activated by PMAO-IP. In a typical experiment, the
flask was charged with a toluene (25 mL) solution of Illa (15 mg, 0.0224
mmol) and was purged with ethylene gas. Then a toluene (5 mL) solution
of PMAO-IP (13.5 Al weight %, 4.49 g, 22.4 mmol in toluene) was injected
via syringe. After 0.5 hours, the ethylene supply was closed and the
reaction mixture with polyethylene solid was pour into an acidified ethanol
(5 vol % HCI). The product was filtered off and dried under vacuum for 6
hours.
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CA 02285523 2008-05-20
TABLE I
Polymerization of Ethylene at Low Pressure and Room Temperature
Example Complex Activity Mol. Wt.*
No No. (gPE/mmol M. h) (polydispersity)
13 I I la 10.7 609,700 1.8
14 I l i b 9.43 782,100 2.4
15 Va 4.51 396,400 (1.7)
*Oligomers were observed in the GPC measurements with molecular weight less
than
1000. GC-MS analysis confirmed the presence of C18-C6 olefins.
Example 16-27
Hiah Pressure Slurry and Solution Polymerizations
In the examples, the pressures given are gauge pressures. The
following abbreviations and terms are used:
Branching: reported as the number of methyl groups per 1000
methylene groups in the polymer. It is determined by13C{'H}-NMR.
Polydispersity: weight average molecular weight (Mw) divided by
number average molecular weight (Mn).
DSC: differential scanning calorimetry.
GPC: gel permeation chromatography.
MeOH: methanol.
PMAO-IP: a type of polymethylaluminoxane.
All the polymerization experiments described below were conducted
using an Autoclave Engineers Zipperclave reactor (500 mL). All the
chemicals (solvent, catalyst and cocatalyst) were fed into the reactor
batchwise except ethylene which was fed on demand. No product was
removed during the polymerization reaction. As are known to those skilled
in the art, all the feed steams were purified prior to feeding into the
reactor
by contact with various absorption media to remove catalysts killing
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impurities such as water, oxygen, sulfur and polar materials. All
components were stored and manipulated under an atmosphere of purified
argon or nitrogen. The reactor uses a programmable logical control (PLC)
system with Wonderware 5.1 software for the process control. Ethylene
polymerizations were performed in the reactor equipped with an air driven
stirrer and an automatic temperature control system.
The catalyst was dissolved in toluene. Polymerization temperature
was 50 C for slurry polymerizations and 140 C for solution
polymerizations. The polymerization reaction time varied from 9 to 60
minutes for each experiment. The reaction was terminated by adding 5
mL of methanol to the reactor and the polymer was recovered by
evaporation of the solvent. The polymerization activities were calculated
based on the weight of the polymer produced.
Slurry Polymerizations
Example 16
The Iron Complex (Illa) with MAO Activation
Toluene (216 mL) was transferred into the reactor with 0.5 mL of
PMAO-IP (216.0 umol) in 10 mL of toluene as a scavenger. The solution
was heated to 50 C and saturated with 300 psig of ethylene. The catalyst
(Illa) (64.6 umol, 43.2 mg) was dissolved in toluene (12.2 mL) and then
injected into the reactor. After one minute, PMAO-IP (38.8 mmol, 8.6 mL)
was injected into the reactor. The polymerization happened immediately
and reaction temperature raised to 70 C. The reaction was terminated by
adding 5 mL of MeOH after 30 minutes. The polymer was dried. Yield =
22.2 g. Activity = 687.4gPE/mmolcat*hr. Mn = 943x103. Tm = 132.9 C.
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12, 15 and 121 were not measurable indicating the formation of a high
molecular weight polymer.
Example 17
The Iron Complex (Illa) with Borane Activation
Toluene (216 mL) was transferred into the reactor with 0.5 mL of
PMAO-IP (216.0 umol) in 10 mL of toluene as a scavenger. The solution
was heated to 50 C and saturated with 300 psig of ethylene. The catalyst
(Illa) (64.6 umol, 43.2 mg) was dissolved in toluene (11.8 mL) and
transferred into a catalyst injection bomb, and then mixed with PMAO-IP
(1.8 mmol, 0.4 mL). B(C6F5)3 (68.4 umol, 35 mg) was dissolved in toluene
(12.4 mL) and loaded into a cocatalyst injection bomb. The catalyst and
cocatalyst were injected into the reactor simultaneously. The
polymerization happened slowly at the beginning, then the polymerization
temperature climbed to 97 C. The polymerization reaction was terminated
by adding 5 mL of MeOH after 53 minutes. The polymer was dried. Yield
= 10.1 g. Activity = 178.7 gPE/mmolcat*hr. Mn = 687x103. Tm =
133.8 C. 12, 15 and 121 were not measurable indicating the formation of a
high molecular weight polymer.
Example 18
The Iron Complex in-situ Formation then with MAO Activation
Toluene (216 mL) and FeCI2 (64.6 umol, 8.2 mg) were transferred
into the reactor with 0.5 mL of PMAO-IP (216.0 umol) in 10 mL of toluene
as a scavenger. The solution was heated to 50 C and saturated with 300
psig of ethylene. The ligand (Ila) (67 umol, 36.2 mg) was dissolved in
toluene (12.2 mL) and then injected into the reactor. The reaction mixture
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CA 02285523 2008-05-20
was stirred for 5 minutes, then PMAO-IP (38.8 mmol, 8.6 mL) was injected
into the reactor. No reaction temperature increase was observed. The
reaction was terminated by adding 5 mL of MeOH after 36 minutes. The
polymer was dried. Yield = 3.3 g. Activity = 85.3 gPE/mmolcat"hr. Tm =
132.1 C. 12, 15 and 121 were not measurable indicating the formation of a
high molecular weight polymer.
Example 19
The Iron Complex (Illa) with MAO Activation for Ethylene and 1-Octene
Copolymerization
Toluene (216 mL) and 1-octene (30 mL) were transferred into the
reactor with 0.5 mL of PMAO-IP (216.0 umol) in 10 mL of toluene as a
scavenger. The solution was heated to 50 C and saturated with 100 psig
of ethylene. The catalyst (Illa) (64.8 umol, 43.3 mg) was dissolved in
toluene (12.2 mL) and then injected into the reactor. After one minute,
PMAO-IP (38.8 mmol, 8.6 mL) was injected into the reactor. The reaction
temperature reached 63 C at the beginning. The polymerization reaction
was terminated by adding 5 mL of MeOH after 9 minutes. The polymer
was dried. Yield = 5.4 g. Activity = 555.8 gPE/mmolcat*hr. Mn =
158.7x103. Tm = 105.9 C. 12.3 branches per 1000 carbon atoms was
determined by13C{'H] NMR. 12, 15 and 121 were not measurable
indicating the formation of a high molecular weight polymer.
Example 20
The Cobalt Complex (IV) with MAO Activation
Toluene (216 mL) was transferred into the reactor with 0.5 mL of
PMAO-IP (216.0 umol) in 10 mL of toluene as a scavenger. The solution
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was heated to 50 C and saturated with 300 psig of ethylene. The catalyst
(IV) (64.8 umol, 44.0 mg) was dissolved in toluene (12.2 mL) and then
injected into the reactor. After one minute, PMAO-IP (38.8 mmol, 8.6 mL)
was injected into the reactor. The polymerization happened immediately
and reaction temperature raised to 63 C. The reaction was terminated by
adding 5 mL of MeOH after 30 minutes. The polymer was dried. Yield =
6.2 g. Activity = 191.4 gPE/mmolcat*hr. Tm = 127.3 C. 12, 15 and 121
were not measurable indicating the formation of a high molecular weight
polymer.
Example 21
The Fe(III) Complex (Va) with MAO Activation
Toluene (216 mL) was transferred into the reactor with 0.5 mL of
PMAO-IP (216.0 umol) in 10 mL of toluene as a scavenger. The solution
was heated to 50 C and saturated with 300 psig of ethylene. PMAO-IP
(38.8 mmol, 8.6 mL) was injected into the reactor. After one minute, the
catalyst (Va) (64.6 umol, 50.3 mg) was dissolved in toluene and injected to
the reactor. The polymerization happened immediately and reaction
temperature raised to 137 C. The reaction was terminated by adding 5
mL of MeOH after 9.5 minutes. The polymer was dried. Yield = 20.4 g.
Activity = 1956.0 gPE/mmolcat*hr. Tm = 132.9 C. 12, 15 and 121 were not
measurable indicating the formation of a high molecular weight polymer.
Example 22
The Nickel Complex (VI) with MAO Activation
Toluene (216 mL) was transferred into the reactor with 0.5 mL of
PMAO-IP (216.0 umol) in 10 mL of toluene as a scavenger. The solution
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was heated to 50 C and saturated with 300 psig of ethylene. PMAO-IP
(38.8 mmol, 8.6 mL) was injected into the reactor. After one minute, the
catalyst (VI) (64.6 umol, 43.8 mg) was dissolved in toluene and injected to
the reactor. The polymerization happened immediately and reaction
temperature raised to 75 C. The reaction was terminated by adding 5 mL
of MeOH after 10 minutes. The polymer was dried. Yield = 9.9 g. Activity
= 913.9 gPE/mmolcat*hr. Tm = 1.29.3 C. 12, 15 and 121 were not
measurable indicating the formation of a high molecular weight polymer.
Example 23
The Palladium Complex (VII) with MAO Activation
Toluene (216 mL) was transferred into the reactor with 0.5 mL of
PMAO-IP (216.0 umol) in 10 mL of toluene as a scavenger. The solution
was heated to 50 C and saturated with 300 psig of ethylene. PMAO-IP
(38.8 mmol, 8.6 mL) was injected into the reactor. After one minute, the
catalyst (VII) (69.3 umol, 51.9 mg) was dissolved in toluene (12.2 mL) and
then injected into the reactor. Polymerization happened immediately and
reaction temperature raised to 55 C. The reaction was terminated by
adding 5 mL of MeOH after 20 minutes. The polymer was dried. Yield =
6.3 g. Activity = 272.8 gPE/mmolcat*hr. Tm = 135.4 C. 121 = 2.21; 12 and
15 were not measurable.
Solution Polymerizations
Example 24
The Iron Complex (Illa) with MAO Activation
Toluene (216 mL) was transferred into the reactor with 0.5 mL of
PMAO-IP (216.0 umol) in 10 mL of toluene as a scavenger. The solution
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was heated to 140 C and saturated with 240 psig of ethylene. PMAO-IP
(38.8 mmol, 8.6 mL) was injected into the reactor. After one minute, the
catalyst (Illa) (64.6 umol, 43.2 mg) was dissolved in toluene and injected
to the reactor. The polymerization happened immediately, reaction
temperature raised to 150 C and the catalyst deactivated within minutes.
The reaction was terminated by adding 5 mL of MeOH after 13 minutes.
The polymer was dried. Yield = 7.9 g. Activity = 564.8 gPE/mmolcat*hr.
Tm = 133.4 C. 12, 15 and 121 were not measurable indicating the formation
of a high molecular weight polymer.
Example 25
The Fe(II) Complex (Ilib) with MAO Activation
Toluene (216 mL) was transferred into the reactor with 0.5 mL of
PMAO-IP (216.0 umol) in 10 mL of toluene as a scavenger. The solution
was heated to 140 C and saturated with 286 psig of ethylene. PMAO-IP
(38.8 mmol, 8.6 mL) was injected into the reactor. After one minute, the
catalyst (Illb) (64.6 umol, 44.5 mg) was dissolved in toluene and injected
to the reactor. The polymerization happened immediately, reaction
temperature raised to 150 C and the catalyst deactivated within 1 minute.
The reaction was terminated by adding 5 mL of MeOH after 10 minutes.
The polymer was dried. Yield = 6.1 g. Activity = 564.3 gPE/mmolcat*hr.
Tm = 141.0 C. 12, 15 and 121 were not measurable indicating the formation
of a high molecular weight polymer.
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Example 26
The Fe(III) Complex (Va) with MAO Activation for Ethylene and 1-Octene
Copolymerization
Toluene (216 mL) and 40 mL of 1-octene were transferred into the
reactor with 0.5 mL of PMAO-IP (216.0 umol) in 10 mL of toluene as a
scavenger. The solution was heated to 140 C and saturated with 300 psig
of ethylene. PMAO-IP (38.8 mmol, 8.6 mL) was injected into the reactor.
After one minute, the catalyst (Va) (64.6 umol, 50.3 mg) was dissolved in
toluene and injected to the reactor. The polymerization happened
immediately with no temperature raise. The reaction was terminated by
adding 5 mL of MeOH after 10 minutes. The polymer was dried. Yield =
4.5 g. Activity = 409.7 gPE/mmolcat*hr. Tm = 130.2 C. 8.2 branches per
1000 carbon atoms was determined by 13C{'H] NMR. 12 and 15 were not
measurable and 121 = 0.3649.
Comparative Examples
Example 27
The Nickel Diimine Complex (VIII) with MAO Activation
Cyclohexane (216 mL) was transferred into the reactor. The
solvent was heated to 160 C and saturated with 306 psig of ethylene.
PMAO-IP (13.0 mmol, 3.25 mL) was injected into the reactor. After one
minute, the catalyst (VIII) (43.6 umol, 27.1 mg) was dissolved in toluene
and injected to the reactor. The polymerization happened immediately
with no temperature raise. The reaction was terminated by adding 5 mL of
MeOH after 10 minutes. The polymer was dried. Yield = 2.5 g. Activity =
347.2 gPE/mmolcat*hr. Mn = 2.2 x 103. Mw = 26 x 103.
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