Note: Descriptions are shown in the official language in which they were submitted.
CA 02357805 2002-04-26
OLIGOMERIZATION CATALYST PRECURSOR
This application is a division of Canadian Patent
Application Serial Number 2,177,008 filed on May 21, 1996.
The claims of the present application are directed to a
catalyst precursor. However, for a ready understanding of
the overall invention including all features which are
inextricably bound up in one and the same inventive concept,
the teachings of those features are all retained in the
present application.
The parent application describes and claims a
process for the oiigomerization of lower olefins to one or
more higher olefins, preferably alpha olefins. The
oligomerization is carried out in the presence of a
homogeneous catalyst comprising:
a) a catalyst precursor selected from the group
consisting of:
1) dithiophosphinate (sometimes also called
dithiophosphonates, typically when the P is substituted by
an alkoxy radical) complexes of Ni, Cr, Ti, Zr, Hf, V, W, and
Mo; and
_ l _
CA 02357805 2001-10-02
2) complexes of Ni, Cr, Ti, Ni, Zr, Hf, V, W, and
Mo with a heterobifunctional ligand having a phosphine center
and an imine or similar center; and
3) complexes of Cr, Ti, Ni, Zr, Hf, V, W, and Mo
having one or more ligands selected from the group consisting
of dithiophosphinate ligands and hetero-bifunctional ligands
having a phosphine center and an imine or similar center; and
b) an activator.
The oligomerization has a high conversion and a
high degree of selectivity to the target product.
The oligomerization of lower alpha olefins is of
industrial concern as many polymers of alpha olefins such as
ethylene and propylene comprise a higher alpha olefin such
as butene, hexene or octene. If ethylene could be
selectively oligomerized at relatively high conversion to a
higher alpha olefin such as butene, hexene or octene it would
mean that a plant need only have one monomer, such as
ethylene, from which co-monomers could be produced.
There have been a number of attempts to oligomerize
alpha olefins into higher alpha olefins.
There are a number of papers and patents in which
Kingsley John Cavell and/or Anthony J. Masters is/are named
as an authors) (e. g. WO 8302907) in which square planar
complexes of Ni2+ are used to oligomerize alpha olefins . The
complexes contain triphenyl phosphine and 2,4-pentane-
- 2 -
CA 02357805 2001-10-02
dithione (sacsac) or 4-thioxo-2-pentanone. These compounds
are not the dithiophosphinate precursors of the present
invention.
United States Patent 4,533,651 issued Aug. 6, 1985
assigned to Commonwealth Scientific and Industrial Research
Organization, Australia, also discloses oligomerization of
ethylene with a nickel complex which contains a phosphine.
The patent does not suggest the use of a ligand which
contains both a phosphine and an imine or a dithio-
phosphinate ligand of the present invention. Related United
States Patent 5,286,696 issued Feb. 14, 1994 and 5,210,360
issued May 11, 1993 both assigned to Phillips disclose the
oligomerization of ethylene using a nickel complex which
contains a phosphine. The patents do not disclose the
presence of both a phosphine and an imine group or a
dithiophosphinate in the ligand.
United States Patent 5,334,791 issued Aug. 2, 1994
to Ligands, Inc. discloses that some of the catalyst
precursors of the present invention may be used to
hydrogenate non-aromatic unsaturated hydrocarbons. United
States Patent 5, 352, 813 issued Oct . 4, 1994 to the University
of Alberta discloses that some of the catalyst precursors of
the present invention may be used to carbonylate methanol.
However, these patents do not disclose that such compounds
in conjunction with an activator of a compound such as
aluminum or boron could be used to oligomerize alpha olefins .
- 3 -
CA 02357805 2001-10-02
Further these references do not teach or suggest that such
an oligomerization if possible would have a high conversion
and a controllable selectivity.
The invention described and claimed inthe parent
application provides a process for the oligomerization of one
or more C2_9 olefins to one or more higher olefins comprising;
i) forming a dissolved catalyst system comprising:
a) a dissolved catalyst precursor selected from
the group consisting of:
1) dithiophosphinate complexes of Cr, Ti, Ni,
Zr, Hf, V, W, and Mo;
2) complexes of Cr, Ti, Ni, Zr, Hf, V, W, and
Mo with a heterobifunctional ligand having a phosphine center
and an imine or similar center; and
3) complexes of Cr, Ti, Ni, Zr, Hf, V, W, and
Mo having one or more ligands selected from the group
consisting of dithiophosphinate ligands and hetero-
bifunctional ligands having a phosphine center and an imine
or similar center; and
b) a soluble activator selected from the group
consisting of activators of the formula A1R3-nXn in which R is
a C1-a alkyl radical, X is a halogen atom and n is 0, l, or
2; alkyl aluminoxane compounds in which the alkyl group has
from 1 to 8 carbon atoms and boron trihalide, tetraphenyl-
borate and tri- or tetra(penta fluorophenyl) boron compounds
or complexes, in a mole ratio of activator to catalyst
- 4 -
CA 02357805 2001-10-02
precursor from 1:2 to 500:1 in a solvent selected from the
group comprising Co_lz cyclic aliphatic and aromatic compounds
which are unsubsfituted or substituted with a C1_9 alkyl
radical; and
ii) contacting said olefin in liquid form with the
solution of the catalyst at a temperature from -15°C to
250°C; and at a pressure from 15 to 1500 psi.
The catalyst precursor includes a source of a
transition metal selected from the group consisting of Cr,
Ti, Ni, Zr, Hf, V, W, and Mo, most preferably Ni, Cr, and Ti
and either a dithiophosphinate ligand or a heterobifunctional
ligand having a phosphine center and an imine center, or
both. Preferred transition metals are nickel (Ni) and
chromium (Cr).
The catalyst precursor may be a dithiophosphinate
complex (i.e. a) 1).
The dithiophosphinate catalyst precursor according
to an aspect of the present invention has the formula:
R ~ ~ S Xu
P M COMPLEX I
R2 S t Av
- 5 -
CA 02357805 2001-10-02
wherein:
M is selected from the group consisting of the
above noted metals, preferably Ni, Cr, Ti, V, and Zr, t, u,
and v are integers and the sum of 2t+u+v is the coordination
number of M and t is an integer from 1 to half the
coordination number of and a and v may be 0 integers,
M or
and the sum of a+v is from 0 to two less than the
coordination number of M, Rl,and Rz, are independently
selected from the group consisting of C1_lo straight chained,
branched or cyclic alkyl radicals; C6_8 monoaromatic aryl
radicals which are unsubstituted or substituted by up to
three substituents selected from the group consisting of C1_8
alkyl radicals; Cl_6 alkoxy or thioalkyl radicals; C6_12
aryloxy radicals; C6_lz arylthio radicals; CF3; and fluorine;
or if taken together R1 and Rz form a cyclic diradical (e. g.
a divalent radical) of the formula:
/(B)n
(CH~m
($)n
wherein n may independently be 0 or 1, m is an
integer from 1 to 10, preferably 2 to 10, and each B may be
independently selected from the group consisting of O or S;
- 6 -
CA 02357805 2001-10-02
X is selected from the group consisting of Cl, Br,
I, and H; and
A is a ligand selected from the group consisting
of
i) ligands of the formula P (R3) 3 wherein R, may
be independently selected from the group of radicals
consisting of C1_lo straight chained, branched or cyclic alkyl
radicals; C6_8 monoaromatic aryl radicals which are
unsubstituted or substituted by up to three, preferably one,
substituents selected from the group consisting of C1_e alkyl
radicals; and
ii) ligands of the formula
R5
~R ~ P-N=C/
42 \R
6
wherein R4 may be a radical selected from the group
of radicals from which R3 is selected and RS and R6 may
independently be a hydrogen atom or a radical selected from
the group consisting of C1_lo straight chained, or branched
alkyl radicals; CS_6 cyclic alkyl radicals, C6_e monoaromatic
aryl radicals which are unsubstituted or substituted by up
to three, substituents selected from the group consisting of
C1_e alkyl radicals .
CA 02357805 2001-10-02
In the above catalyst precursors, preferably X is
C1 or Br.
I f R1 and R2 are taken together to form a diradical
of the formula:
/'tB)n
~CH~m
~B)n
to
wherein n may independently be 0 or 1, m is an
integer from 1 to 10, preferably 2 to 10 and each B may be
independently selected from the group consisting of O or S,
preferably R1 and Rz are independently selected from the
group consisting of C1_8 straight chained, branched or cyclic
alkyl radicals; C6_8 monoaromatic aryl radicals which are
unsubstituted or substituted by a C1_4 alkyl radical; C1_6
alkoxy or thioalkyl radicals; CF3; and fluorine.
In the above complexes the ligand A is preferably
selected from the group of ligands consisting of:
i) ligands of the formula P (R3) 3 where in R3 may
be independently selected from the group of radicals
consisting of C1_8 straight chained, branched or cyclic alkyl
radicals; C6_e monoaromatic aryl radicals which are
unsubstituted or substituted by a C1_4 alkyl radical;
ii) ligands of the formula:
_ g _
CA 02357805 2001-10-02
R~
(R ) P-N=C/
42
R6
wherein R~ may be a radical selected from the group
consisting of radicals from the group consisting of .C1_e
straight chained, branched or cyclic alkyl radicals; C6_e
monoaromatic aryl radicals which are unsubstituted or
substituted by a C1_4 alkyl radical and RS and R6 may
independently be a hydrogen atom or a radical selected from
the group consisting of C1_e straight chained, branched or
cyclic alkyl radicals; C6_e monoaromatic aryl radicals which
are unsubstituted or substituted by a C1_4 alkyl radical.
The catalyst precursor may contain a hetero-
bifunctional ligand (i.e. i) a) 2).
The catalyst precursor having a heterobifunctional
ligand having a phosphine center or an arsenic and an imine
center has the general formula:
ao
% 10
F
COMPLEX It \M~
R P\ ~ 'G
11 ~ N
R12 ~R )
$p
_ g _
CA 02357805 2001-10-02
wherein M, is as defined above; R9, Rlo, R11, and R1z
are independently selected from the group consisting of Clmc
straight chained,. branched or cyclic alkyl radicals; C6_e
monoaromatic aryl radicals which are unsubstituted or
substituted by up to three substituents, preferably one,
selected from the group consisting of C1_8 preferably C1_4
alkyl radicals; F and G are independently selected from the
group consisting of Cl, Br, I, and H, and ligands selected
from the group consisting of:
i) ligands of the formula P(R3)3 wherein R3 is
independently selected from the group of radicals consisting
of C1_lo straight chained, branched or cyclic alkyl radicals;
C6_8 monoaromatic aryl radicals which are unsubstituted or
substituted by up to three preferably one, substituents
selected from the group consisting of C1_e preferably C1_4
alkyl radicals; and
ii) ligands of the formula
R5
(R ) P-N=C/
42 \
R6
- 10 -
CA 02357805 2001-10-02
wherein R4 may be a radical selected from the group of
radicals from which R3 is selected and RS and R6 are
independently a hydrogen atom or a radical selected from the
group consisting of C1_~o Preferably C1_4 straight chained, or
branched alkyl radicals; C5_a cyclic alkyl radicals, Co_a
monoaromatic aryl radicals which are unsubstituted or
substituted by a up to three, preferably only one,
substituents selected from the group consisting of C1_a
preferably C1_4 alkyl radicals;
Y is P or As (preferably P) , Q is selected from
the group consisting of (CH2)n wherein n is 1, 2, or 3, a CZ_4
alkyl radical, a disubstituted C6 aryl radical, and R7N
wherein R7 is selected from the group consisting of C1_s
straight chained or branched alkyl radicals, C6_lo aryl
radicals which are either unsubst~ituted or substituted by a
C1_9 alkyl radical, and p is 0 or 1. If present, Ra is
selected from the group consisting of:
i) a radical of the formula
A' B'
E
C D
- 11 -
CA 02357805 2001-10-02
wherein A', B', C, D, are independently selected
from the group consisting of F, H, NOZ, a C1_6 alkyl radical,
and a CB_1z aryl radical, and E is an endocyclic nitrogen atom
or a C-CN radical or isomers thereof,
ii) SiR1R2R3 wherein R1, R2, and R3 are
independently selected from the group consisting of C1_4 alkyl
radicals; and
iii) a group of the formula
CI
- Ti CI
Cp
in which Cp is a cyclopentadienyl radical.
In the above ligands/complexes preferably M is Cr,
Ti and Ni.
Suitable ligands include those of the formula
Ph2PCH2CH2PPhz=NSiMe3 (i . a . Y is P, Q is -CHzCH2-, and RB is
trimethyl silyl); and
/CH2
Ph P/ ~ PPh
2 2
2 5 ~ 8)v
- 12 -
CA 02357805 2001-10-02
. t
wherein p is 0 or 1, Q is CHZ and if present RB is selected
from the group as defined above.
Suitable-ligands also include:
CH3
H \
\PPh2
Ph2P
F ~ F
F F
CN
1-(N-4-cyanotetrafluorophenyl-diphenylphosphoranimine)-1-
(diphenylphosphino)ethane (i.e. Q is CH-CH3, p is 1 and Re is
tetrafluorocyanophenyl);
ph2p PPh2
N
F F
2o F ~ F
CN
1-(N-4-cyanotetrafluorophenyldiphenylphosphoranimine)-2-
(diphenylphosphino)benzene (i.e. p is 1, Q is a
disubstituted (divalent) phenyl radical, and Re is
tetrafluorocyanophenyl);
- 13 -
CA 02357805 2001-10-02
t
Ph2P PPh2
CHZ
0
1-(N-benzyldiphenylphosphoranimine)-2-(diphenylphosphino)-
benzene (i.e. p is 1, Q is a disubstituted (divalent) phenyl
radical, and Ra is benzyl);
H2 CH~
Ph2P Ii Ph2
N
F F
F, ~ F
CN
1-(N-4-cyanotetrafluorophenyldiphenylphosphoranimine)-2-
(diphenylphosphino)ethane (i.e. p is 1, Q is -CHzCHz- (e. g.
an ethylene diradical), and Re is tetrafluorocyanophenyl);
/CH2 CH2
Ph2P ~ IPh2
N
SiMe3
- 14 -
CA 02357805 2001-10-02
c
1-diphenylphosphino-2-(N-trimethylsilyldiphenylphosphor-
animine)ethane (i.e. Q is -CH2CH2-, p is 1 and Re is trimethyl
silyl);
CH2
Ph2 ~ \PPh2
N
O2
0
N02
N-2,4-di(nitro)phenyl(diphenylphosphoranimine)-methylene-
diphenylphosphine (i.e. Q is -CHZ-, p is 1 and Re is
2,4-dinitrophenyl)
20
~CH2~
Ph2P ~ Ph2
N
SiMe3
1-diphenylphosphino-1-(N-trimethylsilyldiphenylphosphor-
animine)methane (i.e. Q is -CHZ-, p is 1 and RB is trimethyl
silyl) (in the above specific formulae R9, Rlo, R11, and R12 are
all phenyl radicals); and
- 15 -
CA 02357805 2001-10-02
r
'Ph
Ph2PN= /C
'H
N-diphenylphosphinobenzylimine.
The catalyst precursor according to another aspect
of the invention may be of the formula
R~ i 10
P
M ' Q . COMPLEX III
~N=P--R11
::.
wherein M and Q are as defined above; j is 2 or 3
depending on the coordination number of M; and R9, Rlo, R11.
and R12 are independently selected from the group consisting
of C1_lo straight chained, branched or cyclic alkyl radicals;
C6_8 monoaromatic aryl radicals which are unsubstituted or
substituted by up to three substituents, preferably one,
selected from the group consisting of C1_8, preferably C1_a.
alkyl radicals.
- 16 -
CA 02357805 2001-10-02
The catalyst precursor may be of the formula
L L
/ 2
COMPLEX !V
s
L3 L4
wherein M is as defined above and L1, Lz, L3, and
L4 are independently selected from the group consisting of
i) ligands of the formula
RS
(R ) P-N=C/
42
. R6
wherein R4 may be a radical selected from the group
of radicals from which R3 is selected and RS and R6 may
independently be a hydrogen atom or a radical selected from
the group consisting of C1_~o, straight chained, or branched
alkyl radicals; CS_e cyclic alkyl radicals, C6_8 monoaromatic
aryl radicals which are unsubstituted or substituted by up
to three, preferably one, substituents selected from the
group consisting of C1_8, preferably C1_4 alkyl radicals;
- 17 -
CA 02357805 2001-10-02
i i ) or L1 and L2 , or L3 and L4 , or both, may be
taken together to form a ligand of the formula
R R10
Q~ Y~
I
R11
R12 (R )
8p
wherein Y, Q, Ra, R9, Rlo, R11, and R12, and p are as
defined above:
iii) ligands of the formula P (R3) 3 where in R3 may
be independently selected from the group of radicals
consisting of C1_lo straight chained, branched or cyclic alkyl
radicals; C6_e monoaromatic aryl radicals which are
unsubstituted or substituted by up to three, preferably one,
substituents selected from the group consisting of C1_a, alkyl
radicals; and provided at least one of L1, Lz, L3, and L4 is
a ligand of formulas i) or ii) above;
iv) olefins selected from the group consisting of
CZ_4 olefins, and C6_s cyclic, nonconjugated diolefins; and
provided at least one of L1, L2, L3, and L4 is a ligand of
formulas i) or ii) above.
Suitable olefins include ethylene, 1,5-cyclo-
octadiene (cod); and norbornadiene (nbd).
- 18 -
CA 02357805 2001-10-02
t
Preferably the catalyst precursor is a complex of
the transition metal, preferably Ni, Cr, Ti, V, and Zr, most
preferably Ni.
The catalyst precursor is dissolved in a solvent
in which the co-catalyst and the alpha olefin are also
soluble or a solvent which is miscible with solvents for the
co-catalyst and alpha olefin. Typically the solvent is a
C6_12 cyclic aliphatic or aromatic compound which is
unsubstituted or substituted by up to six substituents
selected from the group consisting of C1_4 alkyl radicals and
halogen atoms. Suitable solvents include cyclohexane,
toluene and chlorobenzene.
The activator for the catalyst is typically an
aluminum alkyl compound such as are used in Ziegler-Natta
catalysts. The activator may be selected from the group of
activators consisting of:
i) activators of~ the formula A1R3_nXn wherein R is
a C1_8, preferably C1_4, alkyl radical, most preferably an
ethyl radical, X is halogen, preferably chlorine, and n is
0, 1 or 2;
ii) C1_8, preferably C1_4 alkyl, most preferably
methyl aluminoxane compounds; and
iii) boron trifluoride.
The activator is advantageously selected from the
group consisting of triethyl aluminum, diethyl aluminum
chloride (DEAC), ethyl aluminum dichloride (EADC), methyl
- 19 -
CA 02357805 2001-10-02
s
aluminoxane (MAO), boron trifluoride, tetraphenylborate and
tri- or tetra(penta fluorophenyl) boron compounds and
complexes.
Commercially available activators include DEAC,
EADC, MAO and boron trifluoride.
The degree of oligomerization is controlled by the
mole ratio of activator to catalyst precursor which may
range from 1:2 to 500:1, preferably from 5:1 to 250:1.
The olefin may be used in the form of a condensed
liquid depending on the pressure and temperature (i.e. for
ethylene the temperature must be below 9°C for the monomer
to be a liquid) of the process or more generally in the form
of a solution of olefin in a solvent as noted above.
Ethylene and propylene are preferred olefins.
The solution of catalyst precursor, activator and
olefin are then reacted in a pressurized vessel (a Parr
bomb, autoclave or a reactor (CSTR)) at a temperature from
-15°C to 250°C, preferably from 0 to 250°C, and for the
nickel complexes most preferably from 0 to 30°C. The
pressure in the reactor may be from 15 to 1500 psi,
preferably from 60 to 1200 psi. If the pressure and
temperature are such to maintain the olefin in a liquid form
then the olefin need not be dissolved in a solvent.
Typically the residence time in the reactor will
be at least a half an hour. The reactants are all liquids
and the process is homogeneous. On exiting the reactor the
- 20 -
CA 02357805 2001-10-02
s
liquid phase may be subjected to conventional separation
techniques such as distillation to separate the oligomerized
olefin from the feed olefin.
One particular advantage of the process of the
present invention is "high reactivity". The activity is
typically not less than 1500 g of olefin per gram of
catalyst per hour of residence time in the reactor. Further
by selecting the catalyst precursor and activator it is
possible to control the product distribution. For example,
starting with ethylene the product may be 90+~ of 1-butene.
The invention will be illustrated by the
following non-limiting examples. In the examples unless
otherwise indicated parts means parts by weight (e. g.
grams). In the examples Ph is phenyl, Me is methyl, OEt is
ethoxide, and Bu is butyl.
Catalyst Precursors
Dithiophosphinate Complexes:
[NiCl ( PPh3 ) ( SzPPhz ) ] (A)
NiCl2 (PPh3) 2 (1 .645 g, 2 . 5 mmol) in ethanol (150 cm3) was
stirred under argon with NH4[SzPPhz] (0.672 g, 2.5 mmol) for
0.5 hours. Fifty cm3 of diethyl ether was added to the
resulting solution which was then stirred for a further 10
minutes, after which the solution was filtered and washed
with degassed diethyl ether (3 X 20cm') . One hundred and
fifty cm3 of CHzClz was added to the filtrate and the
- 21 -
CA 02357805 2001-10-02
t
resulting mixture was further filtered to remove any
inorganic salts. The compound was then recrystallized using
a mixture of CHZC12/hexane. The yield was 1.18 g (76%).
[NiCl (PPh3) (S2PMez) ] (B)
NiClz(PPh3)z (10.00 g, 15 mmol) in toluene (300 cm3) was
stirred under argon with NaSZPMez.2H20 (2.67 g, 15 mmol) for
2.5 hours. The solution was cooled to -20°C and filtered,
the solid residue was washed with degassed diethyl ether (3
X 20cm3) and dried under vacuum for 0.5 hours. One hundred
and fifty cm3 of CHZClz was added to the filtrate and the
resulting mixture was further filtered to remove any
inorganic salts. The compound was then recrystallized using
a mixture of CHzClz/hexane. The yield was 3.46 g (47%) .
[Ni (PPh3) (SzP (OEt) z) z] (C)
NiClz(PPh3)z (1.00 g, 1.5 mmol) in dichloromethane (150 cm3)
was stirred under argon with NH4 [SZP (OEt) z] (2 . 76 g, 1 . 5 mmol)
for 0.5 hours. The solution was filtered to remove
inorganic salts. The dichloromethane was removed under
vacuum and the resulting solid was redissolved in diethyl
ether (20 cm3). Slow evaporation of the solvent to
approximately 5 cm3 at room temperature resulted in the
precipitation of the desired product. The compound was
recrystallized using this method to remove any excess PPh3.
(Yield 0.69 g, 65%)
- 22 -
CA 02357805 2001-10-02
t
[Ni (S2P (OEt) 2) 2] (D)
NiClz. 6H20 (0.238 g, 1.0 mmol) in absolute ethanol (50 cm')
was stirred under ' argon with NH4 [S2P (OEt) 2] (0 .406 g, 2 . 0
mmol) for 1 hour. The resulting solution was filtered and
the precipitate was dissolved in dichloromethane. The
solution was washed with degassed water (3 X 20 cm3) to
remove inorganic salts. The organic layer was separated and
the solvent removed under vacuum and the resulting solid was
redissolved in hexane (20 cm3). Slow evaporation of the
solvent resulted in the precipitation of the desired
product. The compound was recrystallized from hexane
(cooling to -40°C). (Yield 0.25 g, 58%)
[Ni (PPh3) 2 SZPMe2] + BPh4- (E)
[NiCl2 (PPh3) 2] (1 g, 1 .53 mmol) NaS2PMe2 (0. 116 g, 1 . 53 mmol)
and NaBPh4 (0.523 g, 1.53 mmol) were stirred in an aceto-
nitrile solution (30 cm3) under argon for 1 hour. The
solution was filtered to remove NaCl and the solvent was
removed under vacuum. Vigorous stirring of the residue with
dry degassed hexane gave the product as a brown precipitate.
(Yield 0.96 g, 63%)
[NiCl (PBu3) (SZPPhz) ] (F)
[NiClz (PPh3) 2] (1 . 657 g, 3 mmol) in 150 cm3 of toluene was
stirred under argon with NH4 [S2PPh2] (0. 802 g, 3 mmol) for 0.5
- 23 -
CA 02357805 2001-10-02
hours. The solution was then filtered to remove inorganic
salts. The toluene was removed under reduced pressure to
yield a purple oil. The yield is nearly quantitative.
[NiCl (PBu3) (SZPMe2) ] (G)
[NiCl: (PBu~),] (1.657 g, 3 mmol) in 150 cm3 of toluene were
stirred under argon with NaS2PMez.2H20 (0.553 g, 3 mmol) for
2 hours. The solution was then filtered to remove inorganic
salts. The toluene was removed under reduced pressure to
give a high yield (80-90%) of a purple oil.
Phosphine Imine Complexes:
[Ni (PhzP-N=CHPh) 4] (H)
Bis(1,5-cyclooctadiene)nickel (0.48 g, 1.76 mmol) and
Ph2P-N=CHPh (2.023 g, 6.99 mmol) were stirred as a suspension
in hexane in a flask under an argon atmosphere at 0°C.
Dichloromethane was slowly added to the suspension until
solution occurred and immediately a brown precipitate
formed. After allowing the mixture to come to room
temperature the precipitate was filtered and dried under
vacuum to give a product sensitive to air and moisture:
[Ni (Ph2P-N=CHPh) 4] NMR 31P (1H} CDzCl2 b 74 . 0 ppm.
- 24 -
CA 02357805 2001-10-02
t
[Ni(cod)(Ph2P-N=CHPh)2] (cod = cyclooctadiene) (I)
Bis(1,5-cyclooctadiene)nickel (1.377 g, 5 mmol) and
Ph2P-N=CHPh (2.9 g,' 10 mmol) were stirred as a suspension in
hexane in a flask under an argon atmosphere at 0°C.
Dichloromethane was slowly added to the suspension until
solution occurred and immediately a brown precipitate
formed. After allowing the mixture to come to room
temperature the precipitate was filtered and dried under
vacuum to give a product sensitive to air and moisture:
[Ni (cod) (PhzP-N=CHPh) z] NMR 31P {1H} CD2C12 b 73 . 15 ppm.
[Ni (Ph2PCHzP (Ph) ZN-C6FQCN) 2] . CHzCl2 (J)
Bis(1,5-cyclooctadiene)nickel (0.387 g, 1.4 mmol) and
PhzPCH2P (Ph) 2=N-C6F4CN (1 . 53 g, 2 . 67 mmol) were stirred as a
suspension in hexane (15 cm3) in a flask under an argon
atmosphere at 0°C. Dichloromethane (5 cm3) was slowly added
to the suspension until a brown solution formed from which
there formed a red precipitate. After allowing the mixture
to come to room temperature the precipitate was filtered and
dried under vacuum to give an analytically pure product.
[Ni (cod) Ph2PCH2P (Ph2) =N-C6F4CN] . CHZClz (K)
Bis(1,5-cyclooctadiene)nickel (1.347 g, 4.9 mmol) and
PhzPCH2P (Ph2) =N-C6F4CN (2 . 8 g, 4 . 9 mmol) were stirred as a
suspension in hexane (15 cm3) in a flask under an argon
atmosphere at 0°C. Dichloromethane (15 cm3) was slowly added
- 25 -
CA 02357805 2001-10-02
t
to the suspension until the suspension changed from yellow
to red/brown. After allowing the mixture to come to room
temperature the precipitate was filtered and dried under
vacuum to give a pale red powder.
A series of oligomerizations was then carried out
with some of the above catalyst precursors and diethyl
aluminum chloride (DEAC) or ethyl aluminum dichloride (EADC)
as the activator. The oligomerizations were carried out
under a nitrogen containing olefin atmosphere. The yields
of C4, C6, Ce, Clo, C12, C14, Cls~ C18. and polymer C18, expressed
as percentages were measured. The results are set forth in
Table 1. In the table: PRE is the catalyst precursor; ACT
is the activator; PPE is ethylene partial pressure in pounds
per square inch gauge (PSIG); Temp is the reaction
temperature in °C; Ti is reaction time in hours; PPN is the
nitrogen partial pressure in PSIG; Rato is the mol/mol ratio
of activator to catalyst precursor; C followed by a number
is the wt% of that cut of carbon atoms in the product; and
C18+ is the "polymer cut" (which was filtered out of the
solution).
- 26 -
CA 02357805 2001-10-02
N t < ~ V1 ~ O N '4 N O
p a O O v p
p N N O M O N W t' ~ ~ ~ r~.O
O ~ tf1P r- O O '~ v v v O'
N
O = < ~ N N O N Y; M ~ N ~ ~ ~ N
N Y- ~ ~f C N1 " v v
P
t~ C7 1~
P S ,~ .p N ~ N ~ N ~ If1O ~; r ~ M
O O M N O O
V [ W f
O S W ~O N ~ N ~ M V O 1f1 N 1!1t!1N
O N O M .O N P O O
4 O tn O N '~ N ~ ~ N ~ ~ O
~' = 4J M ~ N O
O ~ a Q7 O O O O O O
C~
y p = ~ ~ 1!~~ N ~ ~ 1!1N V1 3~ ~ ~ O M
O P N O O O O O O
H
V1
W M ~ N ~ P ~ M P ~ ~ O
O ~f ~ CO wt O O O
~t < a ~O eN-~ N ~ N ~ O P ~ 0O CO N In
W ~ ~ M N N !w M N O O
O ~ ~O ~ ~ ~ O O O
M t 1~i7M N ~ N N . r
O ~ M O O O O O O O
N t W ~ ~ r- N ~ ~ YM1P N N ~ ~ O
O ~ O O O O O O O O
V
W M ~ " N ~ ~ O ~ M ~ M N N O
O ~ N ~ ~O ~ e~-Q ~ C
~
E
.J
d
z m r. m ~ - z ate. .o g
owea t a ~, ~- a ~ ci c~ e~ ~ c~ ci c~ c~ ci c
- 27 -
CA 02357805 2001-10-02
The initial activity of the catalyst system could
exceed 400,000 moles of C2 consumed per mole of catalyst per
hour. In some cases the Clo+ fraction may contain aromatic
components possibly from a reaction with the solvent.
A further series of experiments was then run. The
results of these experiments are set out in Tables 2 and 3
in which the same abbreviations are used.
- 28 -
CA 02357805 2001-10-02
N O O If1~ O O M ~ lO~ ~ N
W M O ~ ~ O . O
O .O P ~t M O o
~O
~ O ~ O ~ O ~
W N ' N y t Y1
~O O
O a ~O O O O O O O O
~O ~p
O t 0 ~ ~ l ~ N ~ ~ N 0 0
4J V1 N M ; v
r-
O ~, ~O O O O O O O O
O ~ N O O O ~
_ t ~ ~ ~ N ~ P M N
41 y A O r- N r- r- O O
M N ~ ~
_ < O tf1 O ~O ~ N r O
4J M N N
O
O ~ P O O O C O O O
O
M ~ M 0 M ~ ~ O
I~ t W M N N ~ . N i M
0
O D O O O o O o O
P .O
_ P in
N _ O' ~ '~ O ~ P P N M
~
W ~O N ~ M M O CO M P vt O O
iii
H
P
h < O ~ O O V ~ N
O ~ O ; M ~O O
41 M N
~
O 0, IA O O O O O O
U ~ N M O ~ ~ O
t O 1A ~ O ~ M
M N N ~ ~ N ~ ~ j
N N O O
~
M = t O ~ ~ O N P N O N ~ ~ O N
O ~ O N ~ P N O O O O O O O
P
~ O 0 O N ~
N 4 a ~ N vt ~ 00 C . N
0
O N W ~
Y1 ~T LI1M N O O
P e- r-
P O ~ N ~ ~ V O M ~ ~-
O . t e M CJ
- n - C7
C!
C~
M N ~ Q _
_
_
_
~ , N !~ M vt O '- .C .a
~ ~
m ~
~
r r
r r
.r-
v-
v-
w
0 0
0 0
v a
a.
~
~l7r 41 y = 1~ 1 v0 4 C !'11 d n_C
~ d m V V V (~ V V V V V
CG a. ~ d r ~ L L
L L
/~ /~
I1
N M
vt
N
vvvv
- 29 -
CA 02357805 2001-10-02
i
Table 3
RUN 13 14 15 ~ 6 ~ 16
PRE A H H A
ACT EDAC EADC DEAL DEAL
PPE 30 60 60 30
Temp 15 15 25 15
Ti 0.5 0.5 1 0.5
PPN 20 20 20 20
Rato 134 144 146 157
C4 64.96 69.44 94.03 91.2
C6 2.82 3.41 5.01 7.90
C8 0.88 0.69 0.32 0.37
Clo 6.20 7.86 0.04 0.05
C12 16.37 8.62 ' 0.18 0.12
C14 4.84 2.69 0.08 0.05
C16 3.48 2.87 0.17 0.06
Cl8 0.04 0.00 0.00 0.00
Cle+ 0.39 4.42 0.17 0.19
(6) the amount of catalyst is double that of Table 1 #8.
In the examples of the subject matter of the
present invention it was observed that isomerization could
be controlled to some extent by pressure. That is at
- 30 -
CA 02357805 2001-10-02
i
ethylene pressures greater than 100 psig, typically from 100
to 400 psig, preferably from 100 to 200 psig, there tended
to be higher amounts of the 1- higher olefin. Typically in
the runs of oligomerization using the catalysts of the
present invention the lowest selectivity for the preparation
of 1-butene was from about 3 to 10% (runs l, 2, 3, 4, and 7
from Table 1, runs 2, 4, 7, 8, 9, and 10 from Table 2, and
run 13 and 16 from Table 3. The selectivity of the other
runs except for runs 10 and 11 of Table 1 ranged from 10 to
25%, while in runs 10 and 11 of Table 1 the selectivity of
1-butene was about 80% and 60%, respectively. For
comparative purposes the catalyst of example 1 of United
States Patent 4, 533, 651 was prepared and activated over a
comparable ratio of DEAC and EADC (105 to 199) and
oligomerization of ethylene was carried out under comparable
times, temperatures and pressures. In all of the
comparative runs using the catalyst of example 1 of United
States Patent 4,533,651, the selectivity for 1-butene was in
the 2 to 5% range.
The catalysts of the present invention can be
controlled by pressure and the ratio of the activator to the
catalysts to produce higher amounts of higher olefins and to
be more selective in producing 1- or alpha olefins.
- 31 -
