Radiation curable isoolefin copolymers

• US 5,459,174 A
• Filed: 06/24/1994
• Issued: 10/17/1995
• 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., Merrill, Natalie A., Wang, Hsian-Chang
• Primary Examiner(s): TESKIN, FRED M
• Application Number:
  US08/211,899
• Time in Patent Office: 480 Days
• Field of Search: 525/63, 525/70, 525/71, 525/72, 525/73, 525/76, 525/87, 525/301, 525/301.5, 525/333.4, 525/355, 525/356, 525/383, 525/384, 522/35, 522/33, 522/46, 522/120, 522/121, 522/132, 522/149, 522/904, 522/905, 524/576, 427/35, 427/42, 427/54.1, 427/208.4
• US Class Current: 522/35
• CPC Class Codes: C08F 210/08 Butenes
• CPC Class Codes: C08F 210/10 Isobutene
• CPC Class Codes: C08F 210/14 Monomers containing five or more carbon atoms
• CPC Class Codes: C08F 212/04 containing one ring
• 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 212/21 Bromine
• CPC Class Codes: C08F 2500/03 Narrow molecular weight distribution, i.e. Mw/Mn < 3
• CPC Class Codes: C08F 2800/20 as weight or mass percentages
• CPC Class Codes: C08F 2810/30 leading to the formation or introduction of aliphatic or alicyclic unsaturated groups
• CPC Class Codes: C08F 2810/50 wherein the polymer is a copolymer and the modification is taking place only on one or more of the monomers present in minority
• CPC Class Codes: C08F 8/14 Esterification
• CPC Class Codes: C08F 8/20 Halogenation
• CPC Class Codes: C08F 8/22 by reaction with free halogens
• 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 23/283 Halogenated homo- or copolymers of iso-olefins
• CPC Class Codes: C08L 2666/02 Organic macromolecular compounds, natural resins, waxes or and bituminous materials
• CPC Class Codes: C08L 2666/04 Macromolecular compounds according to groups C08L7/00 - C08L49/00, or C08L55/00 - C08L57/00; Derivatives thereof
• 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: C08L 71/123 : not modified by chemical after-treatment
• CPC Class Codes: C09D 123/22 : Copolymers of isobutene; Butyl rubber ; Homo- or copolymers of other iso-olefines
• CPC Class Codes: C09D 125/16 : Homopolymers or copolymers of alkyl-substituted styrenes
• CPC Class Codes: C09J 7/381 : based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
• CPC Class Codes: G03F 7/038 : Macromolecular compounds which are rendered insoluble or differentially wettable G03F7/075 takes precedence; macromolecular azides G03F7/012; macromolecular diazonium compounds G03F7/021
• CPC Class Codes: G03F 7/0388 : with ethylenic or acetylenic bands in the side chains of the photopolymer
• CPC Class Codes: Y10S 522/904 : Monomer or polymer contains initiating group
• CPC Class Codes: Y10S 522/905 : Benzophenone group

Abstract

A radiation curable functionalized polymer is disclosed. The functionalized polymer is a copolymer of an isoolefin of 4 to 7 carbon atoms and para-alkylstyrene, wherein the para-alkylstyrene is functionalized with an acrylate or a mixture of acrylates and/or a photosensitizer and/or other functional groups at the para-alkyl groups of the para-alkylstyrene.

Claims

1. A radiation curable functionalized copolymer comprising:

an isoolefin of 4 to 7 carbon atoms and a para-alkylstyrene comonomer said copolymer having acrylate functionality grafted randomly onto at least 0.5 to 55 mole % of the para-alkyl groups of the copolymer and

said copolymer has 1 ppm to 3 wt.%, based upon the weight of the copolymer, of photosensitive functionality randomly grafted onto a portion of the para-alkyl groups of the copolymer.

2. The polymer of claim 1, wherein the acrylate functionality is derived from an alpha, beta ethylenically unsaturated carboxylic acid from 3 to 8 carbon atoms.

3. The polymer of claim 1 wherein the acrylate is represented by the formula:

##STR29## wherein R¹ and R² are independently hydrogen or a C₁ to C₂₀ alkyl, R³ is hydrogen or a C₁ to C₂₀ alkyl or an unsaturated C₁ to C.sub.°

alkyl.

4. The polymer of claim 1, wherein the acrylate is reepresented by the formula:

##STR30## wherein R¹ and R² are independently hydrogen or a C₁ to C₁₀ alkyl; and

R³ is hydrogen or a C₁ to C₁₀ alkyl or an unsaturated C₁ to C₁₀ alkyl.

5. The polymer of claim 1, wherein the acrylate functionality comprises acryloyl or methacryloyl.

6. The polymer of claim 1, wherein the acrylate functionality is methacrylate.

7. The polymer of claim 1 wherein the photosensitive functionality is an aromatic ketone.

8. The polymer of claim 1, wherein the photosensitive functionality is 4-hydroxybenzophenone.

9. The polymer of claim 1, wherein the isoolefin is isobutylene.

10. A composition comprising the polymer of claim 1.

11. The composition of claim 10 further comprising one or more tackifiers.

12. The polymer of claim 1, wherein the para-alkylstyrene is para-methylstyrene.

13. The composition of claim 11, formed into a hot melt pressure-sensitive adhesive.

14. The composition of claim 10 formed into a sealant, a barrier, a coating, a negative resist, a film, a molded article or a membrane.

15. The polymer of claim 1 wherein said comonomer is represented by the formula:

##STR31## wherein R and R'"'"' are independently hydrogen, alkyl, primary alkyl halides, or secondary alkyl halides; and

each W is independently a functional group selected from the group consisting of crosslinking functionality and photosensitive functionality, wherein the comonomer can be present at up to 50 mole %.

16. The polymer of claim 15 wherein W comprises up to about 95% acrylate and up to about 10% benzophenone.

17. The polymer of claim 15 wherein the photosensitive group is present at about 1 ppm to about 0.3 weight % based upon the copolymer and the acrylate is present at about 0.5 to about 55 mole %.

18. The polymer of claim 1 wherein the copolymer is thermally stable between about 80°

and about 170°

C.

19. The polymer of claim 1 further comprising a third functionality randomly grafted onto at least a portion of the para-alkyl groups.

20. A process for. coating a copolymer onto a substrate surface comprising:

coating a substrate surface with a composition comprising a copolymer of claim 1; and

exposing the coating to a radiation to crosslink the copolymer.

21. The process of claim 20 wherein the composition contains one or more tackifiers.

22. A composition comprising:

(a) the copolymer of claim 1;

(b) one or more elastomers; and

(c) optionally, carbon black.

23. The composition of claim 22, wherein the elastomer(s) is selected form the group consisting of natural rubber, ethylene propylene rubber, ethylene propylene diene terpolymer, neoprene rubber nitrile rubber, butadiene rubber, Butyl rubber, chlorobutyl rubber, bromobutyl rubber, polyisobutylene rubber, isoprene rubber, acrylonitrile butadiene rubber, acrylonitrile chloroprene rubber, acrylonitrile isoprene rubber, styrene butadiene rubber, vinyl pyridene styrene butadiene rubber, styrene butadiene styrene block copolymer, styrene chloroprene rubber and styrene isoprene rubber.

24. The composition of claim 22 wherein the copolymer of claim 1 is present at up to about 15 phr.

25. The composition of claim 22 formed into an article.

26. A composition comprising:

(a) the copolymer of claim 1;

(b) one or more elastomers; and

(c) one or more plastic polymers selected from the group consisting of homopolymers and copolymers of ethylene, propylene and styrene;

wherein the comonomer is present in the plastic polymer at up to about 10 weight percent, based upon the weight of the composition.

27. The composition of claim 26 wherein the copolymer of claim 1 is present up to about 15 phr.

28. The composition of claim 26 formed into an article.

29. The composition of claim 25 or 28 further cured by radiation.

30. A process for curing elastomers and elastomer blends comprising:

(a) blending the copolymer of claim 1;

with

(b) one or more elastomers; and

(c) subsequently exposing the blend to radiation.

31. The process of claim 30, wherein the blend is formed into an article.

32. The process of claim 30, wherein the blend is exposed to ultraviolet or electron beam radiation.

33. The composition of claim 26, wherein the plastic polymer is present at less than about 20 weight percent, based upon the weight of the composition.

34. The copolymer of claim 19, wherein the third functionality is an amine.

35. A composition comprising two or more copolymers as defined by claim 1, wherein each copolymer has an acrylate or photosensitive functional group that differs from the other copolymers.

36. A radiation curable functionalized blend, comprising:

a copolymer of an isoolefin of 4 to 7 carbon atoms and a para-alkylstyrene comonomer said copolymer having acrylate functionality grafted randomly onto at least 0.5 to 55 mole% of the para-alkyl groups of the copolymer, and wherein the acrylate is represented by the formula;

##STR32## wherein R¹ and R² are independently hydrogen or a C₁ to C₂₀ alkyl, R³ is hydrogen or a C₁ to C₂₀ alkyl or an unsaturated C₁ to C₂₀ alkyl; and

blended with 1 ppm to 3 wt. %, based upon the weight of the copolymer, of photosensitive functionality.