Polymers functionalized with protected hydrazone compounds containing an acyl group

• US 9,115,231 B2
• Filed: 07/26/2013
• Issued: 08/25/2015
• Est. Priority Date: 07/26/2012
• Status: Expired due to Fees

• Current Assignee: Bridgestone Corporation
• Original Assignee: Bridgestone Corporation
• Inventors: Luo, Steven, Dickstein, Joshua S.
• Primary Examiner(s): Boyle, Robert C
• Application Number:
  US13/951,753
• Publication Number:
  US 20140031488A1
• Time in Patent Office: 760 Days
• Field of Search: None
• US Class Current: 1/1
• CPC Class Codes: C08C 19/22 Incorporating nitrogen atoms into the molecule
• CPC Class Codes: C08C 19/44 of polymers containing metal atoms exclusively at one or both ends of the skeleton
• CPC Class Codes: C08F 136/06 Butadiene
• CPC Class Codes: C08F 2810/40 taking place solely at one end or both ends of the polymer backbone, i.e. not in the side or lateral chains
• CPC Class Codes: C08F 36/06 Butadiene
• CPC Class Codes: C08K 5/30 Hydrazones; Semicarbazones
• CPC Class Codes: C08L 15/00 Compositions of rubber derivatives C08L11/00, C08L13/00 take precedence

Abstract

A method for preparing a functionalized polymer, the method comprising the steps of: (i) polymerizing monomer to form a reactive polymer; and (ii) reacting the reactive polymer with a protected hydrazone compound containing an acyl group.

Claims

1. A method for preparing a functionalized polymer, the method comprising the steps of:

(i) polymerizing monomer to form a reactive polymer, wherein the monomers include conjugated diene monomers, and

(ii) reacting the reactive polymer with a protected hydrazone compound containing an acyl group.

2. The method of claim 1, where the protected hydrazone compound containing an acyl group contains one or more hydrazone groups selected from the group consisting of N,N-dihydrocarbylhydrazone groups, N,N-bis(trihydrocarbylsilyl)hydrazone groups, N,N-bis(dihydrocarbylhydrosilyl)hydrazone groups, N-hydrocarbyl-N-trihydrocarbylsilylhydrazone groups, N-hydrocarbyl-N-dihydrocarbylhydrosilylhydrazone groups, N,N-hydrocarbylenehydrazone groups, N,N-silahydrocarbylenehydrazone groups, and N,N-disilahydrocarbylenehydrazone groups.

3. The method of claim 1, where the protected hydrazone compound containing an acyl group is defined by the formula I:

4. The method of claim 3, where the protected hydrazone compound containing an acyl group is defined by the formula II:

5. The method of claim 3, where the protected hydrazone compound containing an acyl group is defined by the formula III:

6. The method of claim 3, where the protected hydrazone compound containing an acyl group is defined by the formula IV:

7. The method of claim 3, where the protected hydrazone compound containing an acyl group is defined by the formula V:

8. The method of claim 3, where the protected hydrazone compound containing an acyl group is defined by the formula VI:

9. The method of claim 3, where the protected hydrazone compound containing an acyl group is defined by the formula VII:

10. The method of claim 3, where the protected hydrazone compound containing an acyl group is defined by the formula VIII:

11. The method of claim 3, where the protected hydrazone compound containing an acyl group is defined by the formula IX:

12. The method of claim 3, where the protected hydrazone compound containing an acyl group is defined by the formula X:

13. The method of claim 3, where the protected hydrazone compound containing an acyl group is defined by the formula XI:

14. The method of claim 3, where the protected hydrazone compound containing an acyl group is defined by the formula XII:

15. The method of claim 3, where the protected hydrazone compound containing an acyl group is defined by the formula XIII:

16. The method of claim 3, where the protected hydrazone compound containing an acyl group is defined by the formula XIV:

17. The method of claim 3, where the protected hydrazone compound containing an acyl group is defined by the formula XV:

18. The method of claim 3, where the protected hydrazone compound containing an acyl group is defined by the formula XVI:

19. The method of claim 3, where the protected hydrazone compound containing an acyl group is defined by the formula XVII:

20. The method of claim 3, where the protected hydrazone compound containing an acyl group is defined by the formula XVIII:

21. The method of claim 3, where the protected hydrazone compound containing an acyl group is defined by the formula XIX:

22. The method of claim 3, where the protected hydrazone compound containing an acyl group is defined by the formula XX:

23. The method of claim 3, where the protected hydrazone compound containing an acyl group is defined by the formula XXI:

24. The method of claim 3, where the protected hydrazone compound containing an acyl group is defined by the formula XXII:

25. The method of claim 3, where the protected hydrazone compound containing an acyl group is defined by the formula XXIII:

26. The method of claim 3, where the protected hydrazone compound containing an acyl group is defined by the formula XXIV:

27. The method of claim 1, where the protected hydrazone compound containing an acyl group is an N,N-dihydrocarbylhydrazone containing an acyl group.

28. The method of claim 1, where the protected hydrazone compound containing an acyl group is an N,N-bis(trihydrocarbylsilyl)hydrazone containing an acyl group.

29. The method of claim 1, where the protected hydrazone compound containing an acyl group is an N,N-bis(dihydrocarbylhydrosilyl)hydrazone containing an acyl group.

30. The method of claim 1, where the protected hydrazone compound containing an acyl group is an N-hydrocarbyl-N-trihydrocarbylsilylhydrazone containing an acyl group.

31. The method of claim 1, where the protected hydrazone compound containing an acyl group is an N-hydrocarbyl-N-dihydrocarbylhydrosilylhydrazone containing an acyl group.

32. The method of claim 1, where the protected hydrazone compound containing an acyl group is an N,N-hydrocarbylenehydrazone containing an acyl group.

33. The method of claim 1, where the protected hydrazone compound containing an acyl group is an N,N-silahydrocarbylenehydrazone containing an acyl group.

34. The method of claim 1, where the protected hydrazone compound containing an acyl group is an N,N-disilahydrocarbylenehydrazone containing an acyl group.

35. The method of claim 1, where said step of polymerizing employs a coordination catalyst.

36. The method of claim 35, where the coordination catalyst is a lanthanide-based catalyst.

37. The method of claim 36, where the lanthanide-based catalyst includes (a) a lanthanide-containing compound, (b) an alkylating agent, and (c) a halogen source.

38. The method of claim 37, where the alkylating agent includes an aluminoxane and an organoaluminum compound represented by the formula AlR_nX₃₋

n, where each R, which may be the same or different, is a monovalent organic group that is attached to the aluminum atom via a carbon atom, where each X, which may be the same or different, is a hydrogen atom, a halogen atom, a carboxylate group, an alkoxide group, or an aryloxide group, and where n is an integer of 1 to 3.

39. The method of claim 35, where said step of polymerizing monomer takes place within a polymerization mixture including less than 20% by weight of organic solvent.

40. The method of claim 1, where said step of polymerizing employs an anionic initiator.

41. The method of claim 40, where the anionic initiator is an organolithium compound.

42. A method for preparing a functionalized polymer, the method comprising the steps of:

(i) polymerizing conjugated diene monomer, and optionally monomer copolymerizable therewith, to form a polymer having a reactive chain end; and

(ii) reacting the reactive chain end of the polymer with a protected hydrazone compound containing an acyl group.

43. The method of claim 42, where said step of polymerizing employs a coordination catalyst or an anionic initiator.

44. The method of claim 43, further comprising the step of protonating the polymer after said step of reacting.

45. A functionalized polymer prepared by the steps of:

(i) polymerizing conjugated diene monomer, and optionally monomer copolymerizable therewith, to form a polymer having a reactive chain end; and

(ii) reacting the reactive chain end of the polymer with a protected hydrazone compound containing an acyl group.

46. A tire component prepared by employing the functionalized polymer of claim 45.

47. A vulcanizable composition comprising:

the functionalized polymer of claim 45, a filler, and a curative.