# US 12,180,323 B2 · Polymerization catalyst composition and method of employing same

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- Number: US 12,180,323 B2
- Document ID: US12180323B2
- Status: Granted
- Kind: B2
- Application number: 18/111,759
- Filed: 2023-02-20
- Published: 2023-06-22
- Granted: 2024-12-31
- Earliest claimed: 2019-12-30
- Assignees: Bridgestone Corporation; Bridgestone Americas Tire Operations, LLC
- Applicants: Bridgestone Corporation; Bridgestone Americas Tire Operations, LLC
- Inventors: Steven M. Baldwin; James J. Kuhel, III
- Web page: https://patentgrep.com/patent/US12180323B2

## CPC

- C08F 4/545: {rare earths being present, e.g. triethylaluminium + neodymium octanoate}
- C08F 136/06: Butadiene
- C08F 2/06: Organic solvent
- C08F 36/06: Butadiene
- C08F 2410/01: Additive used together with the catalyst, excluding compounds containing Al or B
- C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS

## Abstract

Without significantly impacting monomer conversion, the cis-1,4 mer content of conjugated diene mer in polymers can be increased by adding one or more Lewis bases to a catalyst composition that includes a Group 3 metal atom-containing carboxylate. This effect can be seen even at above average monomer concentrations.

## Claims

### Claim 1

A process for providing a polymer from monomers that comprise at least one polyene, said process comprising:
contacting, in one or more organic liquids, said monomers with a catalyst composition and allowing them to polymerize in a reaction mixture,
wherein said catalyst composition comprises a compound that comprises a Group 3 metal atom-containing carboxylate, a catalyst activator, a compound that comprises a halogen atom, and a Lewis base, wherein a molar ratio of Lewis base to Group 3 metal atom is less than 1:1 to 1:30;
wherein the monomers are present in a weight percentage of 15% to 30% by weight of a reaction mixture at a beginning of polymerization.

### Claim 2 (depends on 1)

The process of claim 1 wherein said at least one polyene comprises one or more conjugated dienes.

### Claim 3 (depends on 2)

The process of claim 2 wherein said at least one polyene consists of one or more conjugated dienes.

### Claim 4 (depends on 1)

The process of claim 1 wherein said molar ratio is no more than 1:2.

### Claim 5 (depends on 4)

The process of claim 4 wherein said molar ratio is no more than 1:5.

### Claim 6 (depends on 5)

The process of claim 5 wherein said molar ratio is 5:1 to 1:10.

### Claim 7 (depends on 1)

The process of claim 1 wherein a concentration of said monomers in said one or more organic liquids is 20 to 25 weight percent.

### Claim 8 (depends on 1)

The process of claim 1 wherein said Group 3 metal atom is a lanthanide.

### Claim 9 (depends on 1)

The process of claim 1 wherein the metal is neodymium.

### Claim 10

A process for providing a polymer from conjugated diene monomers, said process comprising contacting, in one or more organic liquids, said monomers with a catalyst composition and allowing them to polymerize, wherein said catalyst composition comprises a compound that comprises a lanthanide carboxylate, a catalyst activator, a compound that comprises a halogen atom, and a Lewis base, wherein a molar ratio of Lewis base to lanthanide is no more than 5:2; and
wherein the Lewis base is selected from the group consisting of: 2,6-dialkylpyridine, oligomeric oxolanyl alkane, 2-ethylhexanoic acid (EHA), tri (nonylphenyl) phosphite, and combinations thereof.

### Claim 11 (depends on 10)

The process of claim 10 wherein said catalyst activator comprises at least one of a trihydrocarbylaluminum, a dihydrocarbylaluminum hydride, and a hydrocarbylaluminum dihydride.

### Claim 12 (depends on 10)

The process of claim 10 wherein said molar ratio is 1:1 to 1:30.

### Claim 13 (depends on 10)

The process of claim 10 wherein a concentration of said monomers in said one or more organic liquids is from 5 to 25 weight percent.

### Claim 14

A process for providing a polymer from 1,3-butadiene monomers, said process comprising:
contacting, in one or more organic liquids, said 1,3-butadiene monomers with a catalyst composition that comprises a compound that comprises a neodymium carboxylate, an alkylating agent that consists of a trihydrocarbyl-aluminum and a dihydrocarbylaluminum hydride, a compound that comprises a halogen atom, and a Lewis base,
wherein a molar ratio of Lewis base to neodymium is no more than 5:2; and
the Lewis base corresponds to formula (I):
wherein R represents a C1-C4 alkyl group and n is an integer of from 0 to 5;
wherein the 1,3 butadiene monomers are present in a weight percentage of 15% to 30% by weight of a reaction mixture at a beginning of polymerization;
a reactor temperature of −10° to 200° C. is maintained for polymerization;
and the polymer has a cis-1,4-linkage content of at least 95%.

### Claim 15 (depends on 14)

The process of claim 14 wherein a concentration of 1,3-butadiene in said one or more organic liquids is 20 to 30 weight percent.

### Claim 16 (depends on 14)

The process of claim 14, wherein an amount of the neodymium carboxylate is about 0.005 to about 2 mmol.

### Claim 17 (depends on 1)

The process of claim 1, wherein the Lewis base is added as a separate component after the Group 3 metal atom-containing carboxylate, the catalyst activator, and the compound that comprises a halogen atom is added.

### Claim 18 (depends on 1)

The process of claim 1, wherein the Lewis base is selected from the group consisting of: 2,6-dialkylpyridine, oligomeric oxolanyl alkane, 2-ethylhexa-noic acid (EHA), tri (nonylphenyl) phosphite, and combinations thereof.

### Claim 19 (depends on 1)

The process of claim 1, wherein the polymer has a cis-1,4-linkage content of at least 97%.

### Claim 20 (depends on 10)

The process of claim 10, wherein the polymer has a cis-1,4-linkage content of at least 97%.