Graft copolymers of para-alkylstyrene/isoolefin copolymers

• US 5,548,029 A
• Filed: 03/15/1995
• Issued: 08/20/1996
• Est. Priority Date: 05/27/1988
• Status: Expired due to Term

• Current Assignee: Exxon Chemical Patents Inc. (Exxon Mobil Corporation)
• Original Assignee: Exxon Chemical Patents Inc. (Exxon Mobil Corporation)
• Inventors: Dias, Anthony J., Wang, Hsien-Chang, Powers, Kenneth W., Chung, T-C., Olkusz, Joseph A.
• Primary Examiner(s): TESKIN, FRED M
• Application Number:
  US08/404,803
• Time in Patent Office: 524 Days
• Field of Search: 525/69, 525/70, 525/72, 525/73, 525/74, 525/77, 525/78, 525/80, 525/86, 525/241, 525/333.3, 525/333.4, 525/356, 525/357, 525/192, 525/194, 525/195, 525/203, 525/205, 525/206 , 525/207, 525/208, 525/210, 525/212, 525/217, 525/218, 525/219, 525/227, 525/231, 525/233, 525/238, 525/240
• US Class Current: 525/195
• CPC Class Codes: C08F 210/10 Isobutene
• CPC Class Codes: C08F 212/12 Monomers containing a branched unsaturated aliphatic radical or a ring substituted by an alkyl radical
• CPC Class Codes: C08F 8/00 Chemical modification by after-treatment graft polymers, block polymers, crosslinking with unsaturated monomers or with polymers C08F251/00 - C08F299/00; of conjugated diene rubbers C08C
• CPC Class Codes: C08F 8/20 Halogenation
• CPC Class Codes: C08G 81/021 Block or graft polymers containing only sequences of polymers of C08C or C08F
• CPC Class Codes: C08L 23/02 not modified by chemical after-treatment
• CPC Class Codes: C08L 23/22 Copolymers of isobutene; Butyl rubber ; Homo- or copolymers of other iso-olefins
• CPC Class Codes: C08L 2666/24 Graft or block copolymers according to groups C08L51/00, C08L53/00 or C08L55/02; Derivatives thereof
• CPC Class Codes: Y02P 20/582 Recycling of unreacted starting or intermediate materials

Abstract

Graft copolymers which are isoolefin/para-alkylstyrene copolymer represented by the formula ##STR1## in which R and R'"'"' can be hydrogen, alkyl, and the primary and secondary alkyl halides, "a" ranges from about 14 to about 70,000, "b" ranges from 0 to about 70,000, "c" ranges from 0 to about 70,000, "d" ranges from about 1 to about 70,000, X is a halogen, and Nu is a nucleophilic residue provided by a polymeric nucleophile.

Claims

1. A graft copolymer comprising ##STR77## wherein R and R'"'"' are independently selected from the group consisting of hydrogen, alkyl, and the primary and secondary alkyl halides, a ranges from about 14 to 70,000, b ranges from 0 to about 70,000, c ranges from 0 to about 70,000, d ranges from 1 to 70,000, X comprises a halogen, and Nu comprises a nucleophilic residue provided by a thermoplastic polymeric nucleophile having a molecular weight of at least 1,000 and being sufficiently nucleophilic such that said nucleophile is capable of donating electrons to benzyl halides.

2. The graft copolymer of claim 1 where Nu is y-P, wherein y comprises a linked nucleophilic residue and P comprises a thermoplastic polymer.

3. The graft copolymer of claim 2 wherein said thermoplastic polymer is selected from the group consisting of the polymers and copolymers of the anionically polymerizable monomers, the anionically and cationically ring-openable monomers, oxidatively coupleable monomers, and the polyolefins.

4. The graft copolymer of claim 3 wherein said anionically polymerizable monomers are selected from the group consisting of vinyl aromatic compounds, vinyl unsaturated amides, acenaphthylene, 9-acrylcarbazole;

acrylonitrile, methacrylonitrile, organic isocyanates, alkyl acrylates, alkyl methacrylates, vinyl pyridines, and mixtures thereof.

5. The graft copolymer of claim 3 wherein said anionically and cationically ring-openable monomers are selected from the group consisting of the cyclic ethers, sulfides, lactones, lactams, N-carboxyanhydrides.

6. The graft copolymer of claim 3 wherein said oxidatively coupleable monomers comprises the alkyl substituted phenols.

7. The graft copolymer of claim 3 wherein said polyolefin is selected from the group consisting of polypropylene and the copolymers of propylene.

8. The graft copolymer of claim 2 wherein said linked nucleophilic residue is selected from the group consisting of ##STR78## wherein R₁, R₂, R₁, and R₂, are independently selected from the group consisting of hydrogen, aryl, and alkyl.

9. The graft copolymer of claim 1 wherein R and R'"'"' comprise hydrogen.

10. The graft copolymer of claim 1 wherein R and R'"'"' are independently selected from the group consisting of hydrogen, C₁ to C₅ alkyls, and C₁ to C₅ primary and secondary alkyl halides.

11. The graft copolymer of claim 1 wherein X comprises bromine.

12. A graft copolymer of

(a) an electrophile comprising a copolymer of an isoolefin having from 4 to 7 carbon atoms and a para-alkylstyrene having the formula ##STR79## wherein X is a halogen and R and R'"'"' are independently selected from the group consisting of hydrogen, alkyl and primary and secondary alkyl halides, and

(b) a thermoplastic polymeric nucleophile having a molecular weight of at least 1,000 and being sufficiently nucleophilic such that said nucleophile is capable of donating electrons to benzyl halides.

13. The graft copolymer of claim 12 where Nu is y-P, wherein y comprises a linked nucleophilic residue and P comprises a thermoplastic polymer.

14. The graft copolymer of claim 13 wherein said thermoplastic polymer is selected from the group consisting of the polymers and copolymers of the anionicatly polymerizable monomers, the anionically and cationically ring-openable monomers, oxidatively coupleable monomers, and the polyolefins.

15. The graft copolymer of claim 14 wherein said anionically polymerizable monomers are selected from the group consisting of vinyl aromatic compounds, vinyl unsaturated amides, acenaphthylene, 9-acrylcarbazole;

acrylonitrile, methacrylonitrile, organic isocyanantes, alkyl acrylates, alkyl methacrylates, vinyl pyridines, and mixtures thereof.

16. The graft copolymer of claim 14 wherein said anionically and cationically ring-opening monomers are selected from the group consisting of the cyclic ethers, sulfides, lactones, lactams, N-carboxyanhydrides.

17. The graft copolymer of claim 14 wherein said oxidatively coupleable monomers comprise the alkyl substituted phenols.

18. The graft copolymer of claim 14 wherein said polyolefin is selected from the group consisting of polypropylene and the copolymers of propylene.

19. The graft copolymer of claim 13 wherein said linked nucleophilic residue is selected from the group consisting of ##STR80## wherein R₁, R₂, R_1'"'"', and R₂, are independently selected from the group consisting of hydrogen, aryl, and alkyl.

20. The graft copolymer of claim 12 wherein said isoolefin comprises isobutylene.

21. The graft copolymer of claim 13 wherein X is selected from the group consisting of chlorine, bromine and iodine.

22. A graft copolymer comprising ##STR81## wherein R and R'"'"' are independently selected from the group consisting of hydrogen, alkyl, and the primary and secondary alkyl halides, a ranges from about 14 to 70,000, b ranges from 0 to about 70,000, c ranges from 0 to about 70,000, d ranges from 1 to 70,000, X comprises a halogen, and Nu comprises a nucleophilic residue provided by a polymeric nucleophile having a molecular weight of at least 1,000 and being sufficiently nucleophilic such that said nucleophile is capable of donating electrons to benzyl halides, wherein Nu comprises ##STR82## wherein R₂ and R₃ comprise a component selected from the group consisting of aryl, diaryl, polyaryl, and the alkyl, aryl, alkaryl, alkoxy, cycloalkyl, aryloxy and dialkylamino derivatives of the aryl, diaryl, or polyaryls, wherein R₄ through R₁₁ are independently selected from the group consisting of hydrogen, alkyl, and substituted alkyl, f ranges from 0 to about 20,000, g ranges from 0 to about 20,000, and h ranges from 0 to about 10,000, with the further proviso that the sum of f+g+h ranges from about 20 to about 20,000, y comprises a linked nucleophilic residue, and furthermore, wherein either (a) R₁ is (CH₂)_m, wherein m is a positive integer, and e is 0 or 1, or (b) R₁ is (CH₂)_m, wherein m is 0, and e ranges from 0 to about 1,000.

23. The graft copolymer of claim 22 wherein said linked nucleophilic residue y is selected from the group consisting of ##STR83## wherein R₁₂, R₁₃, R₁₄, and R₁₅ can be hydrogen, alkyl or aryl.

24. The graft copolymer of claim 23 wherein said residue is derived from yM wherein M is an alkali or alkaline earth metal, or an onium ion.

25. The graft copolymer of claim 24 wherein M is selected from the group consisting of sodium, potassium, magnesium and lithium and said onium ion comprises tetraalkylammonium.

26. The graft copolymer of claim 22 wherein R and R'"'"' comprises hydrogen.

27. The graft copolymer of claim 22 wherein R and R'"'"' are independently selected from the group consisting of hydrogen, C₁ to C₅ alkyls, and C₁ to C₅ primary and secondary alkyl halides.

28. The graft copolymer of claim 22 wherein X comprises bromine.

29. The graft copolymer of claim 22 wherein m is 1 and e is 0.

30. The graft copolymer of claim 22 wherein m is 0, R₃ is aryl, and e is 1.

31. The graft copolymer of claim 22 wherein R₄ and R₅ are hydrogen.

32. The graft copolymer of claim 22 wherein said polymeric nucleophile is polyisoprene.

33. The graft copolymer of claim 22 wherein said polymeric nucleophile is polybutadiene.

34. The graft copolymer of claim 22 wherein said polymeric nucleophile is dimethylbutadiene.

35. The graft copolymer of claim 22 wherein said polymeric nucleophile is styrene-butadiene copolymer.

36. The graft copolymer of claim 30 wherein R₂ is aryl, and R₄ and R₅ are hydrogen.

37. A graft copolymer of

(a) an electrophile comprising a copolymer of an isoolefin having from 4 to 7 carbon atoms and a para-alkylstyrene having the formula ##STR84## wherein X is a halogen and R and R'"'"' are independently selected from the group consisting of hydrogen, alkyl, and primary and secondary alkyl halides, and

(b) a polymeric nucleophile having a molecular weight of at least 1,000 and being sufficiently nucleophilic such that said nucleophile is capable of donating electrons to benzyl halides.

38. The graft copolymer of claim 37 wherein said polymeric nucleophile comprises ##STR85## wherein R₂ and R₃ comprise a component selected from the group consisting of aryl, diaryl, polyaryl, and the alkyl, aryl, alkaryl, alkoxy, cycloalkyl, aryloxy and dialkylamino derivatives of the aryl, diaryl, or polyaryls, wherein R₄ through R₁₁ are independently selected from the group consisting of hydrogen, alkyl, and substituted alkyl, f ranges from 0 to about 20,000, g ranges from 0 to about 20,000, and h ranges from 0 to about 10,000, with the further proviso that the sum of f+g+h ranges from about 20 to about 20,000, y comprises a linked nucleophilic residue, and furthermore, wherein either (a) R₁ is (CH₂)_m, wherein m is a positive integer, and e is 0 or 1, or (b) R₁ is (CH₂)_m, wherein m is 0, and e ranges from 0 to about 1,000.

39. The graft copolymer of claim 38 wherein said linked nucleophilic residue y is selected from the group consisting of ##STR86## wherein R₁₂, R₁₃, R₁₄ and R₁₅ can be hydrogen, alkyl or aryl.

40. The graft copolymer of claim 39 wherein said residue is derived from yM wherein M is an alkali or alkaline earth metal, or an onium ion.

41. The graft copolymer of claim 40 wherein M is selected from the group consisting of sodium, potassium, magnesium, and lithium and said onium ion comprises tetraalkylammonium.

42. The graft copolymer of claim 37 wherein said isoolefin comprises isobutylene.

43. The graft copolymer of claim 38 wherein X is selected from the group consisting of chlorine, bromine and iodine.

44. The graft copolymer of claim 38 wherein R₃ is aryl.

45. The graft copolymer of claim 44 wherein R₄ and R₅ are hydrogen.