Modified diene polymer, method for producing same, rubber composition, and pneumatic tire

Patent metadata

Field	Value
Publication number	US-9725562-B2
Application number	US-201314758426-A
Country	US
Kind code	B2
Filing date	Dec 11, 2013
Priority date	Jan 9, 2013
Publication date	Aug 8, 2017
Grant date	Aug 8, 2017

Abstract

A modified diene polymer is obtained by decomposing a diene polymer having a carbon-carbon double bond in a main chain by oxidative cleavage of the carbon-carbon double bond to reduce a molecular weight, changing acido-basic properties of a system containing polymer fragments obtained such that the system is changed into a basic system when the system is acidic and the system is changed into an acidic system when the system is basic to combine the polymer fragments, thereby obtaining an intermediate polymer having an altered structure, and epoxidizing a carbon-carbon double bond moiety of a main chain of the intermediate polymer.

First claim

The invention claimed is:

1. A method for procuring a modified diene polymer, comprising:
decomposing a diene polymer having a carbon-carbon double bond in a main chain by oxidative cleavage of the carbon-carbon double bond, thereby obtaining polymer fragments having reduced molecular weight,
changing acido-basic properties of a system containing the polymer fragments such that the system is changed into a basic system when the system is acidic and the system is changed into an acidic system when the system is basic to combine the polymer fragments, thereby obtaining an intermediate polymer having an altered structure, and
epoxidizing a carbon-carbon double bond moiety in a main chain of the intermediate polymer.

2. The method for producing a modified diene polymer according to claim 1 , comprising hydroxylating at least a part of epoxy groups formed by the epoxidizing.

3. A method for producing a modified diene polymer, comprising:
using a diene polymer having a carbon-carbon double bond in a main chain and further having epoxy groups formed by oxidation of a double bond moiety of the main chain,
decomposing the diene polymer by oxidative cleavage of the carbon-carbon double bond to obtain polymer fragments having reduced molecular weight, and
changing acido-basic properties of a system containing the polymer fragments such that the system is changed into a basic system when the system is acidic and the system is changed into an acidic system when the system is basic to combine the polymer fragments, thereby obtaining a polymer having an altered structure.

4. The method for producing a modified diene polymer according to claim 3 , comprising hydroxylating at least a part of the epoxy groups.

5. The method for producing a modified diene polymer according to claim 1 , wherein the polymer fragments obtained by the oxidative cleavage contains a structure represented by the following formula (5) at a terminal:

wherein R 1 is hydrogen atom, an alkyl group having from 1 to 5 carbon atoms, or a halogen group.

6. The method for producing a modified diene polymer according to claim 1 , wherein the modified diene polymer has at least one linking group selected from the group consisting of linking groups represented by the following formulae (1) to (4) in the molecule and has a structure in which diene polymer chains containing epoxy groups formed by oxidation of a double bond moiety of a main chain and/or hydroxyl groups directly bonded to the main chain are linked through the linking group

7. A modified diene polymer obtained by the production method according to claim 1 .

8. A modified diene polymer having at least one linking group selected from the group consisting of linking groups represented by the following formulae (1) to (4) in the molecule and having a structure in which diene polymer chains containing epoxy groups formed by oxidation of a double bond moiety of a main chain and/or hydroxyl groups directly bonded to the main chain are linked through the linking group

9. The modified diene polymer according to claim 8 , wherein the diene polymer chain contains epoxy groups formed by oxidation of a double bond moiety of the main chain.

10. The modified diene polymer according to claim 9 , wherein the glass transition temperature is from −60° C. to −40° C.

11. The modified diene polymer according to claim 9 , wherein the content of the epoxy groups is from 5 to 25 mol %.

12. The modified diene polymer according to claim 8 , wherein the diene polymer chain is constituted of an isoprene unit represented by the following formula (8) and an epoxidized isoprene unit represented by the following formula (9)

13. The modified diene polymer according to claim 8 , wherein the diene polymer chain contains hydroxyl groups directly bonded to the main chain.

14. The modified diene polymer according to claim 13 , wherein the diene polymer chain contains epoxy groups formed by oxidation of a double bond moiety of the main chain together with the hydroxyl groups.

15. The modified diene polymer according to claim 8 , wherein the diene polymer chain has at least one of a constituting unit represented by the following formula (10) or a constituting unit represented by the following formula (11)

16. The modified diene polymer according to claim 15 , wherein the diene polymer chain further has a constituting unit represented by the following formula (9)

17. The modified diene polymer according to claim 13 wherein the content of the hydroxyl groups is from 1 to 15 mol %.

18. The modified diene polymer according to claim 14 , wherein the content of the hydroxyl groups is from 1 to 15 mol % and the content of the epoxy groups is from 1 to 20 mol %.

19. A rubber composition comprising a filler in an amount of from 5 to 150 parts by mass per 100 parts by mass of a rubber component comprising the modified diene polymer according to claim 8 .

20. A pneumatic tire using the rubber composition according to claim 19 .

21. A pneumatic tire using the rubber composition according to claim 19 in a tread.

22. The method for producing a modified diene polymer according to claim 3 , wherein the polymer fragments obtained by the oxidative cleavage contains a structure represented by the following formula (5) at a terminal:

wherein R 1 is hydrogen atom, an alkyl group having from 1 to 5 carbon atoms, or a halogen group.

23. The method for producing a modified diene polymer according to claim 3 , wherein the modified diene polymer has at least one linking group selected from the group consisting of linking groups represented by the following formulae (1) to (4) in the molecule and has a structure in which diene polymer chains containing epoxy groups formed by oxidation of a double bond moiety of a main chain and/or hydroxyl groups directly bonded to the main chain are linked through the linking group

Assignees

• Toyo Tire & Rubber Co

Inventors

• Kawai Nobutomo

Classifications

• C08C19/08

  Depolymerisation · CPC title

• C08K3/04

  Carbon · CPC title

• C08C19/06 Primary

  Epoxidation · CPC title

• B60C1/0016

  Compositions of the tread · CPC title

• C08J3/24 Primary

  Crosslinking, e.g. vulcanising, of macromolecules (mechanical aspects B29C35/00; crosslinking agents C08K) · CPC title