US 5,557,023 AGranted

Olefin oligomerization in the presence of novel complexes

AssigneeThe Governors of the University of Alberta

InventorsArpad F. Somogyvari, Beth L. Creed, Antonio P. Nicola, Alan R. Sanger, David J. Law, Ronald G. Cavell

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Abstract

The present invention relates to the oligomerization of lower alpha olefins, and particularly ethylene, to higher olefins in the presence of a catalyst precursor having either or both of a dithiophosphinate complex and a heterobifunctional ligand having a phosphine center and an imine or similar center, in the presence of an activator. The catalysts have a high reactivity and a good selectivity.

Claims40

Dependent claims

A process for the oligomerization of one or more C.sub.2-4 olefins to one or more higher olefins comprising;

a) forming a solution of a catalyst comprising an activator and a catalyst precursor in a mole ratio from 1:1 to 500:1 in a solvent selected from the group consisting of C.sub.6-12 cyclic aliphatic and aromatic compounds which are unsubstituted or substituted by a C.sub.1-4 alkyl radical wherein said catalyst precursor is selected from the group consisting of:
##STR23## wherein:
M is selected from the group consisting of Ni, Cr, Ti, V, Zr, Hf, W;
and Mo;
t, u, and v are integers, the sum of 2t+u+v is the coordination number of M, t is an integer from 1 to half the coordination number of M, u and v may be 0 or integers and the sum of u+v is from 0 to two less than the coordination number of M;
R.sub.1, and R.sub.2, are independently selected from the group consisting of C.sub.1-10 straight chained, branched or cyclic alkyl radicals, C.sub.6-8 monoaromatic aryl radicals which are unsubstituted or substituted by up to three substituents selected from the group consisting of C.sub.1-8 alkyl radicals, C.sub.1-6 alkoxy or thioalkyl radicals, C.sub.6-12 aryloxy radicals, C.sub.6-12 arylthio radicals, CF.sub.3 ;
and fluorine;
or
if taken together R.sub.1 and R.sub.2 form a diradical of the formula:
##STR24## wherein each n is independently 0 or 1;
m is an integer from 1 to 10;
each B is independently selected from the group consisting of O or S;
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(R.sub.3).sub.3 wherein R.sub.3 may independently be selected from the group of radicals consisting of C.sub.1-10 straight chained, branched or cyclic alkyl radicals;
C.sub.6-8 monoaromatic aryl radicals which are unsubstituted or substituted by up to three substituents selected from the group consisting of C.sub.1-8 alkyl radicals;
and
ii) ligands of the formula:
##STR25## wherein R.sub.4 may be a radical selected from the group of radicals from which R.sub.3 is selected;
and
R.sub.5 and R.sub.6 may independently be a hydrogen atom or a radical selected from the group consisting of C.sub.1-10 straight chained or branched alkyl radicals, C.sub.5-8 cyclic alkyl radicals, and C.sub.6-8 monoaromatic aryl radicals which are unsubstituted or substituted by up to three, substituents selected from the group consisting of C.sub.1-8 alkyl radicals;
(2) complexes of a heterobifunctional ligand having a phosphine center and an imine center of the formula:
##STR26## wherein:
M is as defined above;
R.sub.9, R.sub.10, R.sub.11, and R.sub.12 are independently selected from the group consisting of C.sub.1-10 straight chained, branched or cyclic alkyl radicals, C.sub.6-8 monoaromatic aryl radicals which are unsubstituted or substituted by up to three substituents selected from the group consisting of C.sub.1-8 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(R.sub.3).sub.3 where in R.sub.3 is as defined above;
and ii) ligands of the formula:
##STR27## wherein R.sub.4 , R.sub.5 and R.sub.6 are as defined above;
Y is P or As;
Q is selected from the group consisting of (CH.sub.2).sub.n wherein n is 1, 2, or 3, a C.sub.2-4 alkyl radical, a disubstituted C.sub.6 aryl radical, R.sub.7 N wherein R.sub.7 is selected from the group consisting of C.sub.1-6 straight chained or branched alkyl radicals, C.sub.6-10 aryl radicals which are unsubstituted or substituted by a C.sub.1-4 alkyl radical;
p is 0 or 1;
and if present R.sub.8 is selected from the group consisting of:
i) a radical of the formula:
##STR28## wherein A, B, C, D, are independently selected from the group consisting of F, H, NO.sub.2, a C.sub.1-6 alkyl radical, and a C.sub.8-12 aryl radical, and E is an endocyclic nitrogen atom or a C--CN radical or isomers thereof;
ii( SiR.sup.1 R.sup.2 R.sup.3 where in R.sup.1, R.sup.2, and R.sup.3 are independently selected from the group consisting of C.sub.1-4 alkyl radicals;
and
iii) a group of the formula:
##STR29## in which Cp is a cyclopentadienyl radical;
(3) complexes of the formula:
##STR30## wherein M, X, and Q are as defined above;
j is 2 or 3 depending on the coordination number of M;
and R.sub.9, R.sub.10, R.sub.11, and R.sub.12 are independently selected from the group consisting of C.sub.1-10 straight chained, branched or cyclic alkyl radicals;
and C.sub.6-8 monoaromatic aryl radicals which are unsubstituted or substituted by up to three substituents selected from the group consisting of C.sub.1-8 alkyl radicals;
and
(4) complexes of the formula:
##STR31## wherein M is as defined above, and L.sub.1, L.sub.2, L.sub.3, and L.sub.4 are independently selected from the group of consisting of:
i) ligands of the formula:
##STR32## wherein R4, R.sub.5 and R.sub.6 are as defined above L.sub.1 and L.sub.2, or L.sub.3 and L.sub.4, or both, may be taken together to form a ligand of the formula:
##STR33## wherein Y, Q, R8, R.sub.9, R.sub.10, R.sub.11, and R.sub.12, and p are as defined above:
iii) ligands of the formula P(R.sub.3).sub.3 where in R.sub.3 is as defined above provided at least one of L.sub.1, L.sub.2, L.sub.3, and L.sub.4 is a ligand of formulas i) or ii) above;
and
iv) olefins selected from the group consisting of C.sub.2-4 olefins, and C.sub.6-8 cyclic, nonconjugated diolefins provided at least one of L.sub.1, L.sub.2, L.sub.3, and L.sub.4 is a ligand of formulas i) or ii) above;
and said activator selected from the group consisting of aluminum alkyl compounds of the formula AiR.sub.(3-n) X.sub.n in which R is a C.sub.1-8 alkyl radical, X is a halogen atom and n is 0, 1, or 2, alkyl aluminoxane compounds in which the alkyl group has from 1 to 8 carbon atoms, boron trihalide, tetraphenylborate, and tri- or tetra(penta fluorophenyl) boron compounds or complexes;
and
b) contacting said olefin in liquid form with the solution of the catalyst at a temperature from -15.degree. C. to 250.degree. C.;
and at a pressure from 15 to 1500 psi.

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Dependencies are inferred from the claim text.

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Abstract

A process for the oligomerization of one or more C.sub.2-4 olefins to one or more higher olefins comprising;

a) forming a solution of a catalyst comprising an activator and a catalyst precursor in a mole ratio from 1:1 to 500:1 in a solvent selected from the group consisting of C.sub.6-12 cyclic aliphatic and aromatic compounds which are unsubstituted or substituted by a C.sub.1-4 alkyl radical wherein said catalyst precursor is selected from the group consisting of:
##STR23## wherein:
M is selected from the group consisting of Ni, Cr, Ti, V, Zr, Hf, W;
and Mo;
t, u, and v are integers, the sum of 2t+u+v is the coordination number of M, t is an integer from 1 to half the coordination number of M, u and v may be 0 or integers and the sum of u+v is from 0 to two less than the coordination number of M;
R.sub.1, and R.sub.2, are independently selected from the group consisting of C.sub.1-10 straight chained, branched or cyclic alkyl radicals, C.sub.6-8 monoaromatic aryl radicals which are unsubstituted or substituted by up to three substituents selected from the group consisting of C.sub.1-8 alkyl radicals, C.sub.1-6 alkoxy or thioalkyl radicals, C.sub.6-12 aryloxy radicals, C.sub.6-12 arylthio radicals, CF.sub.3 ;
and fluorine;
or
if taken together R.sub.1 and R.sub.2 form a diradical of the formula:
##STR24## wherein each n is independently 0 or 1;
m is an integer from 1 to 10;
each B is independently selected from the group consisting of O or S;
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(R.sub.3).sub.3 wherein R.sub.3 may independently be selected from the group of radicals consisting of C.sub.1-10 straight chained, branched or cyclic alkyl radicals;
C.sub.6-8 monoaromatic aryl radicals which are unsubstituted or substituted by up to three substituents selected from the group consisting of C.sub.1-8 alkyl radicals;
and
ii) ligands of the formula:
##STR25## wherein R.sub.4 may be a radical selected from the group of radicals from which R.sub.3 is selected;
and
R.sub.5 and R.sub.6 may independently be a hydrogen atom or a radical selected from the group consisting of C.sub.1-10 straight chained or branched alkyl radicals, C.sub.5-8 cyclic alkyl radicals, and C.sub.6-8 monoaromatic aryl radicals which are unsubstituted or substituted by up to three, substituents selected from the group consisting of C.sub.1-8 alkyl radicals;
(2) complexes of a heterobifunctional ligand having a phosphine center and an imine center of the formula:
##STR26## wherein:
M is as defined above;
R.sub.9, R.sub.10, R.sub.11, and R.sub.12 are independently selected from the group consisting of C.sub.1-10 straight chained, branched or cyclic alkyl radicals, C.sub.6-8 monoaromatic aryl radicals which are unsubstituted or substituted by up to three substituents selected from the group consisting of C.sub.1-8 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(R.sub.3).sub.3 where in R.sub.3 is as defined above;
and ii) ligands of the formula:
##STR27## wherein R.sub.4 , R.sub.5 and R.sub.6 are as defined above;
Y is P or As;
Q is selected from the group consisting of (CH.sub.2).sub.n wherein n is 1, 2, or 3, a C.sub.2-4 alkyl radical, a disubstituted C.sub.6 aryl radical, R.sub.7 N wherein R.sub.7 is selected from the group consisting of C.sub.1-6 straight chained or branched alkyl radicals, C.sub.6-10 aryl radicals which are unsubstituted or substituted by a C.sub.1-4 alkyl radical;
p is 0 or 1;
and if present R.sub.8 is selected from the group consisting of:
i) a radical of the formula:
##STR28## wherein A, B, C, D, are independently selected from the group consisting of F, H, NO.sub.2, a C.sub.1-6 alkyl radical, and a C.sub.8-12 aryl radical, and E is an endocyclic nitrogen atom or a C--CN radical or isomers thereof;
ii( SiR.sup.1 R.sup.2 R.sup.3 where in R.sup.1, R.sup.2, and R.sup.3 are independently selected from the group consisting of C.sub.1-4 alkyl radicals;
and
iii) a group of the formula:
##STR29## in which Cp is a cyclopentadienyl radical;
(3) complexes of the formula:
##STR30## wherein M, X, and Q are as defined above;
j is 2 or 3 depending on the coordination number of M;
and R.sub.9, R.sub.10, R.sub.11, and R.sub.12 are independently selected from the group consisting of C.sub.1-10 straight chained, branched or cyclic alkyl radicals;
and C.sub.6-8 monoaromatic aryl radicals which are unsubstituted or substituted by up to three substituents selected from the group consisting of C.sub.1-8 alkyl radicals;
and
(4) complexes of the formula:
##STR31## wherein M is as defined above, and L.sub.1, L.sub.2, L.sub.3, and L.sub.4 are independently selected from the group of consisting of:
i) ligands of the formula:
##STR32## wherein R4, R.sub.5 and R.sub.6 are as defined above L.sub.1 and L.sub.2, or L.sub.3 and L.sub.4, or both, may be taken together to form a ligand of the formula:
##STR33## wherein Y, Q, R8, R.sub.9, R.sub.10, R.sub.11, and R.sub.12, and p are as defined above:
iii) ligands of the formula P(R.sub.3).sub.3 where in R.sub.3 is as defined above provided at least one of L.sub.1, L.sub.2, L.sub.3, and L.sub.4 is a ligand of formulas i) or ii) above;
and
iv) olefins selected from the group consisting of C.sub.2-4 olefins, and C.sub.6-8 cyclic, nonconjugated diolefins provided at least one of L.sub.1, L.sub.2, L.sub.3, and L.sub.4 is a ligand of formulas i) or ii) above;
and said activator selected from the group consisting of aluminum alkyl compounds of the formula AiR.sub.(3-n) X.sub.n in which R is a C.sub.1-8 alkyl radical, X is a halogen atom and n is 0, 1, or 2, alkyl aluminoxane compounds in which the alkyl group has from 1 to 8 carbon atoms, boron trihalide, tetraphenylborate, and tri- or tetra(penta fluorophenyl) boron compounds or complexes;
and
b) contacting said olefin in liquid form with the solution of the catalyst at a temperature from -15.degree. C. to 250.degree. C.;
and at a pressure from 15 to 1500 psi.

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