Process for producing functionalized polymers

Patent metadata

Field	Value
Publication number	US-8981020-B2
Application number	US-201213693534-A
Country	US
Kind code	B2
Filing date	Dec 4, 2012
Priority date	Aug 7, 2007
Publication date	Mar 17, 2015
Grant date	Mar 17, 2015

Abstract

A method for preparing a functionalized polymer, the method comprising the steps of (a) polymerizing monomer in the presence of a coordination catalyst to form a polymer, (b) inhibiting said step of polymerizing with a Lewis base, and (c) reacting the polymer with a functionalizing agent.

First claim

What is claimed is:

1. A continuous polymerization method for preparing a functionalized polymer, the method comprising the steps of:
(a) continuously introducing a monomer and a coordination catalyst to form a polymerization mixture;
(b) allowing at least a portion of the monomer to polymerize into a reactive polymer within a first zone;
(c) continuously removing the polymerization mixture containing the reactive polymer from the first zone and transferring the mixture to a second zone;
(d) continuously introducing a Lewis base to the polymerization mixture after removal from the first zone;
(e) continuously introducing a functionalizing agent to the polymerization mixture after said step of continuously introducing a Lewis base.

2. The method of claim 1 , polymerization mixture includes less than about 20% by weight solvent.

3. The method of claim 1 , where said step of introducing a Lewis base includes introducing the Lewis base in a sufficient amount to substantially cease the polymerization of monomer.

4. The method of claim 1 , after said step of continuously introducing a Lewis base, further comprising continuously removing the polymerization mixture from the second zone and transferring the mixture to a third zone.

5. The method of claim 1 , where the reactive polymer has an active terminus.

6. The method of claim 5 , where the functionalizing agent reacts with the reactive polymer at its active terminus.

7. The method of claim 1 , where the polymerization mixture includes less than about 5% by weight solvent.

8. The method of claim 1 , where said steps of continuously introducing monomer and said step of allowing at least a portion of the monomer to polymerize take place within an elongated reactor.

9. The method of claim 1 , where said step of allowing at least a portion of the monomer to polymerize takes place at a temperature of from about 20° C. to about 100° C.

10. The method of claim 1 , where said step of continuously introducing a Lewis base takes place prior to a monomer conversion of 50%.

11. The method of claim 10 , where said step of continuously introducing a Lewis base takes place prior to a monomer conversion of 20%.

12. The method of claim 1 , where the first zone is a reactor and the second zone is a downstream reactor.

13. The method of claim 1 , where the coordination catalyst is a lanthanide-based catalyst system.

14. The method of claim 1 , where the Lewis base contains no protic hydrogen atoms.

15. The method of claim 14 , where the Lewis base is a monodentate Lewis base selected from the group consisting of tetrahydrofuran, furan, N-methylpyrrole, N-methylimidazole, pyridine, thiophene, ethers, thioethers, amines, phosphines, phosphites, arsines, stibines, bismuthines, nitriles, isocyanides, cyanates, isocyanates, thiocyanates, and isothiocyanates.

16. The method of claim 14 , where the Lewis base is a bidentate Lewis base selected from the group consisting of N,N,N′,N′-tetramethylethylenediamine, 2,2-bis(2′-tetrahydrofuranyl)propane, 1,2-bis(piperidino)ethane, dipiperidinomethane, 2,2′-dipyridyl (also called 2,2′-bipyridine), 1,10-phenanthroline, 1,2-dimethoxyethane, bis(2-pyridyl)methane, β-diketones, bis(diphenylphosphino)methane, 1,2-bis(diphenylphosphino)ethane, 1,3-bis(diphenylphosphino)propane, 1,4-bis(diphenylphosphino)butane, cis-1,2-bis(diphenylphosphino)ethylene, 1,2-bis(diphenylphosphino)benzene, 1,1′-bis(diphenylphosphino)ferrocene, bis(dimethylphosphino)methane, 1,2-bis(dimethylphosphino)ethane, 1,3-bis(dimethylphosphino)propane, 1,4-bis(dimethylphosphino)butane, cis-1,2-bis(dimethylphosphino)ethylene, 1,2-bis(dimethylphosphino)benzene, 1,1′-bis(dimethylphosphino)ferrocene, and 1,2-bis(dimethylarsino)benzene.

17. The method of claim 14 , where the Lewis base is a tridentate Lewis base selected from the group consisting of 2,2′:6′,2″-terpyridine, N,N,N′,N″,N″-pentamethyldiethylenetriamine, tris(2-pyridyl)methane, bis(2-diphenylphosphinoethyl)phenylamine, bis(2-diphenylphosphinoethyl)phenylphosphine, tris(diphenylphosphino)methane, 1,1,1-tris(diphenylphosphinomethyl)ethane, and bis(3-dimethylarsinopropyl)methylarsine.

18. The method of claim 14 , where the Lewis base is a quadridentate Lewis base selected from the group consisting of N,N,N′,N″,N′″,N′″-hexamethyltriethylenetetramine, tris(2-diphenylphosphinoethyl)phosphine, tris(2-diphenylphosphinoethyl)amine, tris(2-dimethylaminoethyl)amine, tris(2-diphenylphosphinophenyl)phosphine, tris(2-diphenylarsinophenyl) arsine, and tris(2-methylthioethyl)amine.

19. The method of claim 14 , where the Lewis base is a multidentate Lewis base selected from the group consisting of macrocyclic nitrogen-based Lewis bases, macrocyclic polyethers, macrocyclic polythioethers, macrobicyclic or macropolycyclic Lewis bases containing mixed oxygen and nitrogen donor atoms, and ethylenediaminetetraacetate.

20. The method of claim 1 , where said step of continuously introducing a Lewis base to the polymerization mixture takes place within the second zone.

21. The method of claim 1 , where said step of continuously introducing a functionalizing agent to the polymerization mixture takes place within the second zone.

22. The method of claim 1 , where the Lewis base is introduced to the polymerization mixture together with the functionalizing agent.

23. The method of claim 4 , further comprising the step of continuously removing the polymerization mixture from the third zone and transferring the mixture to a fourth zone, and introducing a quenching agent to the mixture within the fourth zone.

24. The method of claim 1 , where the functionalizing agent is introduced immediately prior to the introduction of the Lewis base.

25. The method of claim 1 , where the functionalizing agent is introduced after the introduction of the Lewis base.

26. The method of claim 1 , where said step of continuously introducing a Lewis base takes places within the second zone, further comprising the step of continuously removing the polymerization mixture from the second zone and transferring the mixture to a third zone, and where said step of continuously introducing a functionalizing agent to the polymerization mixture takes place within the third zone.

27. A continuous polymerization process for preparing a functionalized polymer, the process comprising the steps of:
(a) continuously polymerizing monomer at a temperature below 100° C. to a monomer conversion of less than 50%, to thereby produce an active polymerization mixture having a reactive polymer with an active terminus;
(b) continuously treating the active polymerization mixture with a Lewis base to thereby substantially cease polymerization of the monomer while substantially maintaining the ability to react the active terminus of the polymer with a functionalizing agent; and
(c) continuously introducing a functionalizing agent to the active polymerization mixture to thereby react the active terminus of the polymer with the functionalizing agent.

28. The process of claim 27 , where the monomer is conjugated diene monomer and said step of continuously polymerizing is effected with a lanthanide-based catalyst system.

29. The process of claim 27 , where said step of continuously introducing a functionalizing agent introduces the functionalizing agent to the active polymerization mixture treated with the Lewis base.

Assignees

• Bridgestone Corp

Inventors

• Luo Steven
• Mccauley Kevin M
• Tartamella Timothy L
• Smale Mark W
• Shetty Randhir

Classifications

• C08F36/00

  Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds (C08F32/00 takes precedence) · CPC title

• C08L19/006

  Rubber characterised by functional groups, e.g. telechelic diene polymers · CPC title

• C08F4/545

  rare earths being present, e.g. triethylaluminium + neodymium octanoate · CPC title

• C08F36/06

  Butadiene · CPC title

• C08C19/44 Primary

  of polymers containing metal atoms exclusively at one or both ends of the skeleton · CPC title