Water-soluble electrically conducting polymers, their synthesis and use

• US 5,370,825 A
• Filed: 03/03/1993
• Issued: 12/06/1994
• Est. Priority Date: 03/03/1993
• Status: Expired due to Term

• Current Assignee: International Business Machines Corporation
• Original Assignee: International Business Machines Corporation
• Inventors: Newman, Thomas H., Seeger, David E., Angelopoulos, Marie, Gelorme, Jeffrey D., Patel, Niranjan M.
• Primary Examiner(s): Lieberman, Paul
• Assistant Examiner(s): KOPEC, MARK T
• Application Number:
  US08/025,490
• Time in Patent Office: 643 Days
• Field of Search: 252/500, 528/422, 528/423, 528/424, 528/377, 528/378, 528/210, 528/212, 528/214
• US Class Current: 252/500
• 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 7/093 characterised by antistatic means, e.g. for charge depletion
• CPC Class Codes: H01B 1/128 comprising six-membered aromatic rings in the main chain, e.g. polyanilines, polyphenylenes

Abstract

Disclosed is a novel composition of matter comprising a polyacid and a polymer containing repeating units which contain one or more basic atoms. The complex is water-soluble and electrically conductive. The complex is useful in providing organic discharge layers for use in electronic applications and fabrications.

Claims

1. A water-soluble, electrically conductive composition of matter capable of forming a stable 5 wt. % solution in water, comprising a polyacid wherein said polyacid is selected from the group consisting of poly(acrylic acid), poly(methacrylic acid), poly(styrene sulfonic acid), poly(vinylsulfonic acid), poly(styrene boric acid), poly(vinyl boric acid), poly(vinyl sulfuric acid), poly(styrene phosphonic acid), poly(vinyl phosphoric acid), poly(styrene phosphonic acid) and poly(vinyl phosphonic acid), and a polymer comprising at least one conjugated region composed of repeating units which contain a conjugated basic atom wherein said polymer is selected from the group consisting of substituted and unsubstituted homopolymers and copolymers of aniline, thiophene, pyrrole, and p-phenylene sulfide,

wherein the number of acidic groups in said polyacid exceeds the number of protonatable basic atoms in said polymer.

2. A composition of matter according to claim 1 wherein said polyacid is poly(styrene sulfonic acid).

3. A composition of matter according to claim 1 wherein said polyacid is poly(vinyl sulfonic acid).

4. A composition of matter according to claim 1 wherein said polyacid is poly(acrylic acid).

5. A composition of matter according to claim 1 wherein said polyacid is poly(methacrylic acid).

6. A composition of matter according to claim 1 wherein said polyacid is poly(vinyl phosphonic acid).

7. A composition of matter according to claim 1 wherein said polyacid is poly(styrene phosphonic acid).

8. A composition of matter according to claim 1 wherein said polymer is polyaniline.

9. A composition of matter according to claim 8 wherein said polyacid is poly(styrene sulfonic acid).

10. A composition of matter according to claim 1 wherein said polymer is polythiophene.

11. A composition of matter according to claim 1 wherein said polymer is polypyrrole.

12. A composition of matter according to claim 1 wherein said polymer is poly(p-phenylene sulfide).

13. A composition of matter according to claim 1 wherein said aniline is substituted with one or more substituents selected from the group consisting of alkyl, alkoxyalkyl, and alkoxy groups containing 1 to 30 carbon atoms.

14. A composition of matter according to claim 1 wherein said thiophene is substituted with one or more substituents selected from the group consisting of alkyl, alkoxyalkyl, and alkoxy groups containing 1 to 30 carbon atoms.

15. A composition of matter according to claim 1 wherein said pyrrole is substituted with one or more substituents selected from the group consisting of alkyl, alkoxyalkyl, and alkoxy groups containing 1 to 30 carbon atoms.

16. A composition of matter according to claim 1 wherein said p-phenylene sulfide is substituted with one or more substituents selected from the group consisting of alkyl, alkoxyalkyl, and alkoxy groups containing 1 to 30 carbon atoms.

17. A composition of matter according to claim 1 wherein said polymer is cross-linkable.

18. An aqueous solution comprising a composition of matter according to claim 1.

19. An aqueous solution according to claim 18 comprising dissolved therein at least about 5 wt. % of said composition of matter.

20. An aqueous solution according to claim 18 comprising dissolved therein about 5 wt. % to about 10 wt. % of said composition of matter.

21. An aqueous solution according to claim 18 comprising dissolved therein about 5 wt. % of said composition of matter.

22. A solution according to claim 18 wherein said polyacid is poly(styrene sulfonic acid).

23. A solution according to claim 18 wherein said polyacid is poly(vinyl sulfonic acid).

24. A solution according to claim 18 wherein said polyacid is poly(acrylic acid).

25. A solution according to claim 18 wherein said polyacid is poly(methacrylic acid).

26. A solution according to claim 18 wherein said polyacid is poly(vinyl phosphonic acid).

27. A solution according to claim 18 wherein said polyacid is poly(styrene phosphonic acid).

28. A solution according to claim 18 wherein said polymer is polyaniline.

29. A solution according to claim 18 wherein said polyacid is poly(styrene sulfonic acid).

30. A solution according to claim 18 wherein said polymer is polythiophene.

31. A solution according to claim 18 wherein said polymer is polypyrrole.

32. A solution according to claim 18 wherein said polymer is poly(p-phenylene sulfide).

33. A solution according to claim 18 wherein said aniline is substituted with one or more substituents selected from the group consisting of alkyl, alkoxyalkyl, and alkoxy groups containing 1 to 30 carbon atoms.

34. A solution according to claim 18 wherein said thiophene is substituted with one or more substituents selected from the group consisting of alkyl, alkoxyalkyl, and alkoxy groups containing 1 to 30 carbon atoms.

35. A solution according to claim 18 wherein said pyrrole is substituted with one or more substituents selected from the group consisting of alkyl, alkoxyalkyl, and alkoxy groups containing 1 to 30 carbon atoms.

36. A solution according to claim 18 wherein said p-phenylene sulfide is substituted with one or more substituents selected from the group consisting of alkyl, alkoxyalkyl, and alkoxy groups containing 1 to 30 carbon atoms.

37. A solution according to claim 18 wherein said polymer is cross-linkable.

38. A water-insoluble, electrically conductive composition of matter comprising a polyacid selected from the group consisting of poly(acrylic acid), (methacrylic acid), poly(styrene sulfonic acid), poly(vinylsulfonic acid), poly(styrene boric acid), poly(vinyl boric acid), poly(vinyl sulfuric acid), poly(styrene phosphoric acid), poly(vinyl phosphoric acid), poly(styrene phosphonic acid) and poly(vinyl phosphonic acid), and a polymer comprising at least one conjugated region composed of repeating units which contain a conjugated basic atom, wherein said polymer is selected from the group consisting of substituted and unsubstituted homopolymers and copolymers of aniline, thiophene, pyrrole, and p-phenylene sulfide,

wherein the number of acidic groups in said polyacid exceeds the number of protonatable basic atoms in said polymer,

wherein said composition of matter is capable of forming a stable 5 wt. % solution in water when said polymer is not cross-linked, wherein said polymer is cross-linked.

39. A composition of matter according to claim 38 wherein said polymer is selected from the group consisting of polymers of aniline, thiophene, pyrrole, and p-phenylene sulfide.

40. A composition of matter according to claim 39 wherein said polymer is polyaniline.

41. A composition of matter according to claim 38 wherein said polyacid is poly(styrene sulfonic acid).

42. A composition of matter according to claim 41 wherein said polymer is polyaniline.

43. A water-soluble, electrically conductive composition of matter capable of forming a stable 5 wt. % solution in water, and comprising a polyacid and a conjugated polymer composed of repeating units which contain a conjugated basic atom, wherein the number of acidic groups in said polyacid exceeds the number of protonatable basic atoms in said polymer, which composition of matter is the product of the process comprising forming an aqueous solution of one or more monomers selected from the group consisting of substituted and unsubstituted aniline, thiophene, pyrrole, and mercaptophenol, and a polyacid selected from the group consisting of poly(acrylic acid), poly(methacrylic acid), poly(styrene sulfonic acid), poly(vinylsulfonic acid), poly(styrene boric acid), poly(vinyl boric acid), poly(vinyl sulfuric acid), poly(styrene phosphoric acid), poly(vinyl phosphoric acid), poly(styrene phosphonic acid) and poly(vinyl phosphonic acid), wherein the number of acid groups on said polyacid exceeds the number of said basic atoms, and polymerizing the monomer while controlling the rate of initiation and the rate of propagation of said polymerization such that the polymerization forms said composition of matter in said solution.

44. A composition of matter according to claim 43 wherein said polyacid is poly(styrene sulfonic acid).

45. A composition of matter according to claim 43 wherein said polyacid is poly(vinyl sulfonic acid).

46. A composition of matter according to claim 43 wherein said polyacid is poly(acrylic acid).

47. A composition of matter according to claim 43 wherein said polyacid is poly(methacrylic acid).

48. A composition of matter according to claim 43 wherein said polyacid is poly(vinyl phosphonic acid).

49. A composition of matter according to claim 43 wherein said polyacid is poly(styrene phosphonic acid).

50. A composition of matter according to claim 43 wherein said polymer is polyaniline.

51. A composition of matter according to claim 43 wherein said polyacid is poly(styrene sulfonic acid).

52. A composition of matter according to claim 43 wherein said polymer is polythiophene.

53. A composition of matter according to claim 43 wherein said polymer is polypyrrole.

54. A composition of matter according to claim 43 wherein said polymer is poly(p-phenylene sulfide).

55. A composition of matter according to claim 43 wherein said aniline is substituted with one or more substituents selected from the group consisting of alkyl, alkoxyalkyl, and alkoxy groups containing 1 to 30 carbon atoms.

56. A composition of matter according to claim 43 wherein said thiophene is substituted with one or more substituents selected from the group consisting of alkyl, alkoxyalkyl, and alkoxy groups containing 1 to 30 carbon atoms.

57. A composition of matter according to claim 43 wherein said pyrrole is substituted with one or more substituents selected from the group consisting of alkyl, alkoxyalkyl, and alkoxy group containing 1 to 30 carbon atoms.

58. A composition of matter according to claim 43 wherein said p-phenylene sulfide is substituted with one or more substituents selected from the group consisting of alkyl, alkoxyalkyl, and alkoxy groups containing 1 to 30 carbon atoms.

59. A composition of matter according to claim 43 wherein said polymer is cross-linkable.