# US 7,410,927 B2 · Catalysts for olefin polymerization

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- Number: US 7,410,927 B2
- Document ID: US7410927B2
- Status: Granted
- Kind: B2
- Application number: 11/105,683
- Filed: 2005-04-13
- Published: 2006-10-19
- Granted: 2008-08-12
- Earliest claimed: 2005-04-13
- Assignees: Chevron Phillips Chemical Company LP
- Inventors: Albert P. Masino
- Web page: https://patentgrep.com/patent/US7410927B2

## CPC

- C08F 10/00: Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- B01J 31/0272: {containing elements other than those covered by B01J31/0201 - B01J31/0255}
- B01J 2531/62: Chromium
- C08F 210/16: Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
- C08F 2410/07: Catalyst support treated by an anion, e.g. Cl-, F-, SO42-
- C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS

## Abstract

This invention relates to the field of olefin polymerization catalyst compositions, and methods for the polymerization and copolymerization of olefins, including polymerization methods using a catalyst composition. One aspect of this invention is the formation and use of a catalyst composition comprising a transition metal compound and an activator for olefin polymerization processes.

## Claims

### Claim 1

A catalyst composition comprising:
a) a transition metal compound with the following formula:
wherein:
M is chromium or vanadium;
R, R1, R2, R3, and R4 are independently an alkyl, aryl, alkaryl or arylaryl group, anyone of which has 1-20 carbon atoms;
a is 1, 2 or 3;
Z is a monovalent anionic group;
Z′ is a monovalent anionic group;
b is 0, 1 or 2, and c is 0, 1 or 2;
L is a neutral donor ligand;
d is 0, 1 or 2; and
b) a chemically-treated solid oxide comprising a solid oxide treated with an electron withdrawing anion;
wherein:
the solid oxide comprises silica, alumina, silica-alumina, or mixtures thereof; and
the electron withdrawing anion comprises fluoride, chloride, bromide, sulfate, or any combination thereof.

### Claim 2 (depends on 1)

The catalyst composition of claim 1, wherein (Z) and (Z′) are independently an aliphatic group, an aromatic group, a cyclic group, a combination of aliphatic and cyclic groups, an oxygen group, a sulfur group, a nitrogen group, a phosphorus group, an arsenic group, a carbon group, a silicon group, a germanium group, a tin group, a lead group, a boron group, an aluminum group, an inorganic group, an organometallic group, or a substituted derivative thereof, any one of which having from 1 to about 20 carbon atoms; or a halide.

### Claim 3 (depends on 1)

The catalyst composition of claim 1, wherein L is an ether, furan or nitrile.

### Claim 4 (depends on 1)

The catalyst composition of claim 1, further comprising aluminoxanes, organoborates, or ionic ionizing compounds.

### Claim 5 (depends on 1)

The catalyst composition of claim 1, further comprising an organoaluminum compound with the following formula:
Al(X5)n(X6)3-n;
wherein (X5) is a hydrocarbyl having from 1 to about 20 carbon atoms; (X6) is an alkoxide or aryloxide, any one of which having from 1 to about 20 carbon atoms, a halide, or a hydride; and n is a number from 1 to 3, inclusive.

### Claim 6 (depends on 5)

The catalyst composition of claim 5, wherein the chemically treated solid oxide is fluorided alumina, chlorided alumina, bromided alumina, fluorided silica-alumina chlorided silica-alumina, sulfated alumina, sulfated silica-alumina, or a combination thereof.

### Claim 7 (depends on 1)

The catalyst composition of claim 1, wherein the chemically-treated solid oxide further comprises a metal or metal ion.

### Claim 8 (depends on 7)

The catalyst composition of claim 7, wherein the metal or metal ion comprises zinc, nickel, vanadium, silver, copper, gallium, tin, tungsten, molybdenum, or any combination thereof.

### Claim 9 (depends on 1)

The catalyst composition of claim 1, wherein the chemically-treated solid oxide further comprises a metal or metal ion, and wherein the chemically-treated solid oxide comprises zinc-impregnated chlorided alumina, zinc-impregnated fluorided alumina, zinc-impregnated chlorided silica-alumina, zinc-impregnated fluorided silica-alumina, zinc-impregnated sulfated alumina, or any combination thereof.

### Claim 10

A catalyst composition comprising:
a) a transition metal compound with the following formula:
wherein:
M is chromium or vanadium;
R1, R2, and R3 are independently an alkyl, aryl, alkaryl or arylaryl group, anyone of which has 1-20 carbon atoms;
Z is an alkyl, aryl, or halogen;
Z′ is an alkyl, aryl, or halogen;
L is an ether, furan or nitrile; and
b) a chemically-treated solid oxide comprising a solid oxide treated with an electron-withdrawing anion, wherein:
the solid oxide comprises silica, alumina, silica-alumina, or mixtures thereof;
the electron-withdrawing anion comprises fluoride, chloride, bromide, sulfate, or combinations thereof; and
c) an organoaluminum compound with the following formula:
Al(X5)n(X6)3-n;
wherein (X5) is a hydrocarbyl having from 1 to about 20 carbon atoms; (X6) is an alkoxide or aryloxide, any one of which having from 1 to about 20 carbon atoms, a halide, or a hydride; and n is a number from 1 to 3, inclusive.

### Claim 11 (depends on 10)

The catalyst composition of claim 10, wherein the organoaluminum compound comprises trimethylaluminum, triethylaluminum, tripropylaluminum, diethylaluminum ethoxide, tributylaluminum, diisobutylaluminum hydride, triisobutylaluminum, diethylaluminum chloride, or any combination thereof.

### Claim 12 (depends on 10)

The catalyst composition of claim 10, wherein the weight ratio of the organoaluminum compound to the chemically-treated solid oxide is from about 5:1 to about 1:1000.

### Claim 13 (depends on 10)

The catalyst composition of claim 10, wherein the weight ratio of the chemically-treated solid oxide to the transition metal compound is from about 10,000:1 to about 1:1.

### Claim 14 (depends on 10)

The catalyst composition of claim 10, wherein the chemically-treated solid oxide comprises fluorided alumina, chlorided alumina, bromided alumina, fluorided silica-alumina, chlorided silica-alumina, sulfated alumina, sulfated silica-alumina, or a combination thereof.

### Claim 15

A process to produce a catalyst composition comprising contacting a transition metal compound and an activator, wherein:
a) the transition metal compound has the following formula:
wherein:
M is chromium or vanadium;
R, R1, R2, R3, and R4 are independently an alkyl, aryl, alkaryl or arylaryl group, anyone of which has 1-20 carbon atoms;
a is 1, 2 or 3;
Z is a monovalent anionic group;
Z′ is a monovalent anionic group;
b is 0, 1 or 2, and c is 0, 1 or 2;
L is an ether, furan or nitrile;
d is 0, 1 or 2; and
b) the activator comprises a chemically-treated solid oxide combined with an organoaluminum compound, wherein the chemically-treated solid oxide comprises a solid oxide treated with an electron withdrawing anion;
wherein:
the solid oxide comprises silica, alumina, silica-alumina, or mixtures thereof; and
the electron withdrawing anion comprises fluoride, chloride, bromide, sulfate, or any combination thereof.

### Claim 16 (depends on 1)

The catalyst composition of claim 1, wherein the chemically treated solid oxide is chlorided alumina, fluorided silica-alumina, sulfated alumina, or a combination thereof.

### Claim 17 (depends on 10)

The catalyst composition of claim 10, wherein the chemically treated solid oxide is chlorided alumina, fluorided silica-alumina, sulfated alumina, or a combination thereof.

### Claim 18 (depends on 1, 10)

A process for polymerizing olefins comprising contacting the catalyst composition of claims 1 or 10 with at least one olefin monomer under polymerization conditions suitable to produce a polymer.

### Claim 19 (depends on 18)

The process of claim 18 wherein the olefin monomer is ethylene.