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US 5,397,757 AGranted
Cocatalysts for metallocene-based olefin polymerization catalyst systems
AssigneeMobil Oil Corporation
InventorsRobert I. Mink, Yury V. Kissin
Life of this patent
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Abstract
The invention relates to a catalyst composition for ethylene polymerization which comprises (1) a metallocene complex, (2) carbon tetrachloride or carbon tetrabromide, (3) an organomagnesium compound, (4) trimethylaluminum.
Claims31
A process for preparing supported alpha olefin polymerization catalyst compositions which comprises the steps of:
- (i) forming a catalyst precursor by providing silica which is porous and has a particle size of 1 to 200 microns, having pores which have an average diameter of 50 to 500 Angstroms and having a pore volume of 0.5 to 5.0 cc/g;
- and impregnating said silica with at least one metallocene compound of the formula:
- Cp.sub.m MA.sub.n B.sub.p wherein
- Cp is cyclopentadienyl unsubstituted or substituted by at least one substituent group comprising 1 to 6 carbon atoms, wherein said substituent group is selected from the group consisting of alkyl, alkylene and silane;
- m is 1 or 2;
- M is zirconium or hafnium;
- and each of A and B is selected from the group consisting of a halogen atom, a hydrogen atom and an alkyl group, providing that m+n+p is equal to the valence of M;
- and
- ii) combining the catalyst precursor of (i) with a combination of:
- at least one organomagnesium compound having the formula R.sub.m MgR'.sub.n where R and R' are the same or different C.sub.4 -C.sub.12 alkyl groups, m and n are each 0, 1 or 2, provided that m+n is equal to the valence of Mg;
- at least one halogen-containing compound selected from the group consisting of carbon tetrachloride and carbon tetrabromide;
- and
- trimethylaluminum,
- wherein the organomagnesium compound is used in an amount sufficient to provide an organomagnesium compound:metallocene molar ratio of 10 to 500,
- wherein trimethylaluminum is used in an amount sufficient to provide a trimethylaluminum:metallocene molar ratio of 50 to 1000,
- wherein said carbon tetrachloride or carbon tetrabromide, is present in an amount to provide a molar ratio with the organomagnesium compound which ranges from 0.5 to 5.
13 more elements
Catalyst composition for producing ethylene polymers or copolymers comprising
- (1) a metallocene compound,
- (2) carbon tetrachloride or carbon tetrabromide,
- (3) an organomagnesium compound,
- (4) trimethylaluminum,
- wherein organomagnesium compound is used in an amount sufficient to provide an organomagnesium compound:metallocene molar ratio of 10 to 500, wherein trimethylaluminum is used in an amount sufficient to provide a trimethylaluminum:metallocene molar ratio of 50 to 1000,
- wherein said carbon tetrachloride or carbon tetrabromide, is present in an amount to provide a molar ratio with the organomagnesium compound which ranges from 0.5 to 5 wherein the metallocene compound has the formula:
- Cp.sub.m MA.sub.n B.sub.p wherein
- Cp is cyclopentadienyl unsubstituted or substituted by at least one substituent group comprising 1 to 6 carbon atoms, wherein said substituent group is selected from the group consisting of alkyl, alkylene and silane;
- m is 1 or 2;
- M is zirconium or hafnium;
- and each of A and B is selected from the group consisting of a halogen atom, a hydrogen atom and an alkyl group, providing that m+n+p is equal to the valence of M;
- and
- wherein the organomagnesium compound has the formula R.sub.m MgR'.sub.n where R and R' are the same or different C.sub.4 -C.sub.12 alkyl groups, m and n are each 0, 1 or 2, provided that m+n is equal to the valence of Mg.
10 more elements
A supported catalyst composition for producing ethylene polymers or copolymers comprising
- (1) a metallocene compound
- (2) carbon tetrachloride or carbon tetrabromide,
- (3) an organomagnesium compound,
- (4) trimethylaluminum,
- wherein organomagnesium compound is used in an amount sufficient to provide an organomagnesium compound:metallocene molar ratio of 10 to 500,
- wherein trimethylaluminum is used in an amount sufficient to provide a trimethylaluminum:metallocene molar ratio of 50 to =1000
- wherein said carbon tetrachloride or carbon tetrabromide, is present in an amount to provide a molar ratio with the organomagnesium compound which ranges from 0.5 to 5,
- wherein said metallocene compound is supported on silica, which is porous and has a particle size of 1 to 500 microns, having pores which have an average diameter of 50 to Angstroms and having a pore volume of 0.5 to 5.0 cc/g;
- wherein the metallocene compound has the formula:
- Cp.sub.m MA.sub.n B.sub.p wherein
- Cp is cyclopentadienyl unsubstituted or substituted by at least one substituent group comprising 1 to 6 carbon atoms, wherein said substituent group is selected from the group consisting of alkyl, alkylene and silane;
- m is 1 or 2;
- M is zirconium or hafnium;
- and each of A and B is selected from the group consisting of a halogen atom, a hydrogen atom and an alkyl group, providing that m+n+p is equal to the valence of wherein the organomagnesium compound has the formula M;
- and
- wherein the organomagnesium compound has the formula R.sub.m MgR'.sub.n where R and R' are the same or different C.sub.4 -C.sub.12 alkyl groups, m and n are each 0, 1 or 2, provided that m+n is equal to the valence of Mg.
13 more elements
Dependencies are inferred from the claim text.