Production of cis-1,4-polydienes with multiple silane functional groups prepared by in-situ hydrosilylation of polymer cement

Patent metadata

Field	Value
Publication number	US-10975178-B2
Application number	US-201716329979-A
Country	US
Kind code	B2
Filing date	Sep 1, 2017
Priority date	Sep 2, 2016
Publication date	Apr 13, 2021
Grant date	Apr 13, 2021

Abstract

A method of preparing a silane-functionalized polymer, the method comprising: preparing a polymerization system including a cis-1,4-polydiene by introducing a lanthanide-based catalyst and a conjugated diene monomer; and adding a hydrosilane compound to the polymerization system including a cis-1,4-polydiene.

First claim

What is claimed is:

1. A method of preparing a silane-functionalized polymer, the method comprising
combining:
(i) a cis-1,4-polydiene,
(ii) a hydrosilane compound, and
(iii) a lanthanide-based catalyst; and

allowing the cis-1,4-polydiene to react with the hydrosilane compound to form the silane-functionalized polymer.

2. The method of claim 1 , wherein the step of combining includes:
(i) preparing a polymerization system including the cis-1,4-polydiene by introducing the lanthanide-based catalyst and a conjugated diene monomer; and
(ii) adding the hydrosilane compound to the polymerization system including the cis-1,4-polydiene.

3. The method of claim 2 , where the lanthanide-based catalyst includes (a) a lanthanide-containing compound, (b) an alkylating agent, and (c) a halogen source.

4. The method of claim 2 , further comprising the step of chain-end functionalizing the cis-1,4-polydiene by reacting a cis-1,4-polydiene having a reactive chain end with a secondary-functionalizing agent.

5. The method of claim 2 , where no additional catalyst is added prior to the step of adding the hydrosilane compound to the polymerization system including the cis-1,4-polydiene.

6. The method of claim 2 , where the hydrosilane compound is defined by the formula I
SiH x R 4-x

where x is an integer from 1 to 4, and each R is independently a halogen atom, or a monovalent organic group, or where two or more R groups may join to form a polyvalent organic group.

7. The method of claim 2 , where the hydrosilane compound is defined by the formula II
SiH x (OR) 4-x

where x is an integer from 1 to 4, and each R is individually a hydrocarbyl or silyl group, or where two or more R groups join to form a polyvalent organic group.

8. The method of claim 2 , where the hydrosilane compound is defined by the formula III

where n is an integer from 0 to 8, and each R is individually a hydrogen atom, halogen atom, or a hydrocarbyl group, or where two or more R groups join to form a polyvalent organic group, with the proviso that at least one R in the hydrosilane compound is a hydrogen atom.

9. The method of claim 2 , where the hydrosilane compound is defined by the formula IV

where R 1 and R 2 are each individually a hydrogen atom, halogen atom, or a monovalent organic group, with the proviso that the at least one R 1 or R 2 in the hydrosilane compound is a hydrogen atom, and y is from about 3 to about 6 units.

10. The method of claim 2 , where the hydrosilane compound is selected from the group consisting of trihydrocarbyloxy silane, hydrocarbyl dihydrocarbyloxy silane, dihydrocarbyl hydrocarbyloxy silane, trisilyloxy silane, hydrocarbyl disilyloxy silane, dihydrocarbyl silyloxy silane, and cyclic hydrosilane compounds.

11. The method of claim 2 , where the cis-1,4-polydiene has a 1,2-linkage content of from about 0.1 to about 7%, a cis-1,4-linkage content that is greater than 60%, and a number average molecular weight of from about 1,000 to about 1,000,000.

12. The method of claim 1 , further comprising combining the silane-functionalized polymer with a filler and a curative to thereby form a vulcanizable composition.

13. The method of claim 1 , where the hydrosilane compound is defined by the formula I
SiH x R 4-x

where x is an integer from 1 to 4, and each R is independently a halogen atom, or a monovalent organic group, or where two or more R groups may join to form a polyvalent organic group.

14. The method of claim 1 , where the hydrosilane compound is defined by the formula II
SiH x (OR) 4-x

where x is an integer from 1 to 4, and each R is individually a hydrocarbyl or silyl group, or where two or more R groups join to form a polyvalent organic group.

15. The method of claim 1 , where the hydrosilane compound is defined by the formula III

where n is an integer from 0 to 8, and each R is individually a hydrogen atom, halogen atom, or a monovalent organic group, or where two or more R groups join to form a polyvalent organic group, with the proviso that at least one R in the hydrosilane compound is a hydrogen atom.

16. The method of claim 1 , where the hydrosilane compound is defined by the formula IV

where R 1 and R 2 are each individually a hydrogen atom, halogen atom, or a monovalent organic group, with the proviso that the at least one R 1 or R 2 in the hydrosilane compound is a hydrogen atom, and y is from about 3 to about 6 units.

17. The method of claim 1 , where the cis-1,4-polydiene has a 1,2-linkage content of from about 0.1 to about 7%.

18. The method of claim 1 , where the cis-1,4-polydiene includes a secondary-functional group.

19. The method of claim 2 , further comprising combining the silane-functionalized polymer with a filler and a curative to thereby form a vulcanizable composition.

20. The method of claim 12 , further comprising vulcanizing the vulcanizable composition to thereby form a tire component.

Assignees

• Bridgestone Corp

Inventors

• Baldwin Steven M
• Salamant Walter A

Classifications

• B60C1/0016 Primary

  Compositions of the tread · CPC title

• C08F136/06

  Butadiene · CPC title

• C08F2410/01

  Additive used together with the catalyst, excluding compounds containing Al or B · CPC title

• B60C1/00

  Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition · CPC title

• C08L15/00

  Compositions of rubber derivatives (C08L11/00, C08L13/00 take precedence) · CPC title