Water-soluble electrically conducting polymers, their synthesis and use

• US 6,010,645 A
• Filed: 09/15/1994
• Issued: 01/04/2000
• Est. Priority Date: 03/03/1993
• Status: Expired due to Term

• Current Assignee: International Business Machines Corporation
• Original Assignee: International Business Machines Corporation
• Inventors: Angelopoulos, Marie, Gelorme, Jeffrey Donald, Patel, Niranjan Mohanlal, Newman, Thomas Harold, Seeger, David Earle
• Primary Examiner(s): Kopec, Mark
• Application Number:
  US08/306,654
• Time in Patent Office: 1,937 Days
• Field of Search: 252/500, 528/423, 528/422, 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 process for forming a water-soluble, electrically conductive composition of matter capable of forming a stable 5 wt. % solution in water, comprising a polyacid and a conjugated polymer composed of repeating units which contain a conjugated basic atom, the process comprising forming an aqueous solution of one or more monomers which contain a conjugated basic atom, and a polyacid, 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, said one or more monomers are selected from the group consisting of substituted and unsubstituted aniline, thiophene, pyrrole, p-phenytene sulfide and mercaptophenol, said polyacid is selected from the group consisting of poly (acrylic acid), poly (methacrlic acid), poly (styrenesulfonic acid), poly (vinylsulfonic acid), poly (styrene boric acid), poly (vinyl boric acid), poly (viny sulfuric acid), poly (styrene phosphoric acid), poly (vinyl phosphoric acid), poly (styrene phosphonic acid) and poly (vinyl phosphonic acid).

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

3. A process according to claim 1 wherein said one or more monomers are selected from the group consisting of substituted and unsubstituted aniline, thiophene, pyrrole, and mercaptophenol.

4. A process according to claim 3 wherein said substituted monomers are substituted with one or more radicals selected from the group consisting of alkyl, alkoxyalkyl, and alkoxy groups containing 1 to 30 carbon atoms.

66. A process according to claims 1, 2, 5, 6-46 or 60 further including disposing said composition of matter on a surface.

5. A process for forming an electrically conductive composition of matter capable of forming a stable 5 wt. % solution in water, comprising a polyacid, and a conjugated polymer composed of repeating units which contain a conjugated atom, the process comprising forming a solution of one or more monomers which contain said conjugated atom, and said polyacid, wherein the number of functional groups on said polyacid exceeds the number of said conjugated 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, said one or more monomers are selected from the group consisting of substituted and unsubstituted aniline, thiophene, pyrrole, p-phenylene sulfide and mercaptophenol, said polyacid is selected from the group consisting of poly(acrylic acid), poly(methacrylic acid), poly (styrenesulfonic 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).

6. A process according to claim 5 wherein said polyacid is poly(styrene sulfonic acid).

7. A process according to claim 5 wherein said one or more monomers are selected from the group consisting of substituted and unsubstituted aniline, thiophene, pyrrole, and mercaptophenol.

8. A process according to claim 7, wherein said substituted monomers are substituted with one or more radicals selected from the group consisting of alkyl, alkoxyalkyl, and alkoxy groups containing 1 to 30 carbon atoms.

34. A process according to claim 8, wherein said polyacid is vinylic.

9. A process for forming a water-soluble, electrically conductive composition of matter comprising a polyacid and a conjugated polymer composed of repeating units which contain a conjugated basic atom, said conjugated polymer is selected from the group consisting of substituted and unsubstituted homopolymers and copolymers of aniline, thiophene, pyrrole and p-phenylene sulfide, said process comprising forming a solution of one or more monomers which contain a conjugated basic atom, and a polyacid, 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.

10. A process according to claim 9 wherein said composition is formed in a solution containing water.

11. A process according to claim 9 wherein said composition forms a stable 5 wt. % solution in water.

12. A process according to claim 9 wherein said polyacid is water soluble.

13. A process according to claim 9 wherein said composition is dried to a dried composition which is soluble in an aqueous solution.

14. A process according to claim 9 wherein said polyacid comprises an organic polymer at least a part of whose repeating units include an acidic moiety.

15. A process according to claim 14 wherein said acidic moiety is selected from the group consisting of a carboxylic acid group, a phosphonic acid group, a phosphoric acid group, a boric acid group, a sulfuric acid group and a sulfonic acid group.

16. A process according to claim 14 wherein said acid moiety is selected from the group consisting of one pendant from a back bone of said polyacid and a substituent on a group which is pendant from said back bone.

17. A process according to claim 9 wherein said polyacid is vinylic.

18. A process according to claim 9 wherein said polyacid comprise copolymers having repeat units at least a part of which contain an acidic moiety.

19. A process according to claim 9 wherein said polyacid comprises repeat units having formula --(CH₂ CHX)--, wherein X is selected from the group consisting of an acid group and a substituent which is substituted with an acid group.

20. A process according to claim 9 wherein said polyacid comprises copolymers having repeat units some of which containing pendant acidic groups and other repeat units which do not.

21. A process according to claim 20 wherein said copolymers are selected from the group consisting of block copolymers and copolymers in which acidic and non-acidic repeat units are interspersed.

22. A process according to claim 9 wherein said conjugated polymer further comprises ethylenically unsaturated units.

23. A process according to claim 22 wherein said ethylenically unsaturated units are selected from the group consisting of ethylene, propylene, vinyl chloride, strene, vinyl alcohol and vinyl acetate.

24. A process according to claim 9 wherein said composition is dissolved in an alkanol.

25. A process according to claim 9 wherein said polyacid comprises an acidic moiety selected from the group consisting of a carboxylic acid group, a phosphonic acid group, a phosphoric acid group, a boric acid group, a sulfuric acid group and a sulfonic acid group.

26. A process according to claim 9 wherein said composition is a powder.

27. A process according to claim 26 wherein said powder is soluble in an aqueous solution.

58. A process according to claim 9 further including forming crosslinks between molecules of said composition of matter to form a crosslinked composition which is substantially water insoluble.

28. A process for forming an electrically conductive composition of matter comprising a polyacid, and a conjugated polymer composed of repeating units which contain a conjugated atom, said conjugated polymer is selected from the group consisting of substituted and unsubstituted homopolymers and copolymers of aniline, thiopherine, pyrrole and p-phenylene sulfide, said process comprising forming a solution of one or more monomers which contain said conjugated atom, wherein the number of functional groups on said polyacid exceeds the number of said conjugated 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.

29. A process according to claim 28 wherein said composition is formed in a solution containing water.

30. A process according to claim 28 wherein said composition forms a stable 5 wt % solution in water.

31. A process according to claim 28 wherein said polyacid comprises an organic polymer at least a part of whose repeating units include an acidic moiety.

32. A process according to claim 31 wherein said acidic moiety is selected from the group consisting of a carboxylic acid group, a phosphonic acid group, a phosphoric acid group, a boric acid group, a sulfuric acid group and a sulfonic acid group.

33. A process according to claim 31 wherein said acid moiety is selected from the group consisting of one pendant from a back bone of said polyacid and a substituent on a group which is pendant from said back bone.

35. A process according to claim 28 wherein said polyacid comprise copolymers having repeat units at least a part of which contain an acidic moiety.

36. A process according to claim 28 wherein said polyacid comprises repeat units having formula --(CH₂ CHX)--, wherein X is selected from the group consisting of an acid group and a substituent which is substituted with an acid group.

37. A process according to claim 28 wherein said polyacid comprises copolymers having repeat units some of which containing pendant acidic groups and other repeat units which do not.

38. A process according to claim 31 wherein said copolymers are selected from the group consisting of block copolymers and copolymers in which acidic and non-acidic repeat units are interspersed.

39. A process according to claim 28 wherein said conjugated polymer further comprises ethylenically unsaturated units.

40. A process according to claim 39 wherein said ethylenically unsaturated units are selected from the group consisting of ethylene, propylene, vinyl chloride, styrene, vinyl alcohol and vinyl acetate to form a crosslinked composition which is substantially water insoluble.

41. A process according to claim 28 wherein said composition is dissolved in an alkanol.

42. A process according to claim 28 wherein said polymer and said polyacid form a doped polymer further including forming crosslinks between said doped polymers.

43. A process according to claim 28 wherein said polyacid comprises an acidic moiety selected from the group consisting of a carboxylic acid group, a phosphonic acid group, a phosphoric acid group, a boric acid group, a sulfuric acid group and a sulfonic acid group.

44. A process according to claim 28 wherein said polyacid is water-soluble.

45. A process according to claim 28 wherein said composition is a powder.

46. A process according to claim 45 further including dissolving said powder in a solution containing water.

47. A process for forming a electrically conductive composition of matter comprising a polyacid and a conjugated polymer composed of repeating units which contain a conjugated basic atom, said conjugated polymer is selected from the group consisting of substituted and unsubstituted homopolymers and copolymers of aniline, thiophene, pyrrole and p-phenylene sulfide, said process comprising forming a solution of one or more monomers which contain a conjugated basic atom, and a polyacid, 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, said polymer comprises ethylenically unsaturated units, and after forming said composition of matter cross-linking said composition of matter.

48. A process for forming an electrically conductive composition of matter comprising a polyacid dopant, and a conjugated polymer composed of repeating units which contain a conjugated atom, said conjugated polymer is selected from the group consisting of substituted and unsubstituted homopolymers and copolymers of aniline, thiophene, pyrrole and p-phenylene sulfide, said process comprising forming a solution of one or more monomers which contain said conjugated atom, and a polyfunctional dopant, wherein the number of functional groups on said polyfunctional dopant exceeds the number of said conjugated atoms, said 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, said polymer comprises ethylenically unsaturated units, and after forming said composition of matter cross-linking said composition of matter.

49. A process for forming a electrically conductive composition of matter comprising a polyacid and a conjugated polymer composed of repeating units which contain a conjugated basic atom, said conjugated polymer is selected from the group consisting of substituted and unsubstituted homopolymers and copolymers of aniline, thiophene, pyrrole and p-phenylene sulfide, said process comprising forming a solution of one or more monomers which contain a conjugated basic atom, and a polyacid, 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 forming crosslinks between said doped polymers to form a crosslinked composition which is substantially water insoluble.

50. A method of forming a composition of matter, said composition of matter comprising a polymer having at least one conjugated region composed of repeating units which contain a number of conjugated basic atoms, wherein said polymer is selected from the group consisting of substituted and unsubstituted homopolymers and copolymers of aniline, thiopherine, pyrrole and p-phenylene sulfide, said process comprising:

forming a solution of one or more monomers which contain said conjugated atom and a polyacid having a number of functional sites, said solution comprising a polar solvent;

polymerizing said 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;

said functional sites of said polyacid dope said polymer to be electrically conductive;

said number of functional sites of said polyacid exceeds said number of conjugated basic atoms, there being excess functional sites of said polyacid;

said excess functional sites of said polyacid are capable of interacting with said polar solvent thereby permitting said composition to be soluble in said polar solvent.

51. A process according to claim 50 when in said polar solvent contains an --OH group.

52. A process according to claim 51 wherein said polar solvent is selected from the group consisting of water and an alkanol.

53. A process according to claim 50 wherein said polar solvent comprises solvents selected from the group consisting of water, an alkanol and combinations thereof.

54. A process according to claims 50 wherein said excess functional sites are acidic groups permitting said composition to be soluble in said polar solvent.

55. A method according to claim 50 further including removing said polar solvent to result in a residue of said composition.

56. A process according to claim 55 further including re-dissolving said residue in another polar solvent.

57. A process according to claim 55 wherein said residue is re-dissolved in a solvent comprising water.

59. A process for forming an electrically conductive composition of matter comprising a polyacid dopant, and a conjugated polymer composed of repeating units which contain a conjugated atom, said conjugated polymer is selected from the group consisting of substituted and unsubstituted homopolymers and copolymers of aniline, thiopherine, pyrrole and p-phenylene sulfide, said process comprising forming a solution of one or more monomers which contain said conjugated atom, and a polyfunctional dopant, wherein the number of functional groups on said polyfunctional dopant exceeds the number of said conjugated 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, and after forming said composition of matter forming crosslinks between molecules of said composition of matter.

60. A process to make an electrically conductive molecular complex made by a template-guided chemical polymerization process, the molecular complex comprising a polymeric polyelectrolyte and a conductive polymer selected from the group consisting of polypyrrole, polythiophene, poly(phenylene sulfide) and substitutions thereof, said template-guided chemical polymerization process comprises the addition of conducting monomers to an aqueous or nonaqueous solution of a polyelectrolyte to form a monomer/polyelectrolyte solution, followed by the subsequent addition of an oxidant to the monomer/polyelectrolyte solution to polymerize the monomer to form a molecular complex comprising a polyelectrolyte and a conducting polymer wherein the ratio of the conducting polymer to the polyelectrolyte is in the range of 1:

1 to greater than 1;

1.

61. The process according to claim 60 wherein said polyelectrolyte is a polymer with anionic functional group selected from the groups consisting of carboxylic acid, sulfonic acid, phosphoric acid, boric acid.

62. The process according to claim 60 wherein said polyelectrolyte is selected from the group consisting of poly(styrenesulfonic acid), poly(acrylic acid), poly(methacrylic acid), salt forms thereof and copolymers thereof.

63. The process according to claim 60 wherein said polyelectrolyte is poly(styrenesulfonic acid).

64. The process according to claim 60 wherein said polyelectrolyte is poly(2-acrylamido-2-methyl-1-propenesulfonic acid).

65. The process according to claim 60 wherein said polyelectrolyte is poly(acrylic acid).

94. A process according to claims 60 to 92 or 93 further including disposing said electrically conductive molecular complex on a surface.

67. A process to make an electrically conductive molecular complex made by a template-guided chemical polymerization process, the molecular complex comprising a polymeric polyelectrolyte and a conductive polymer, said template-guided chemical polymerization process comprises the addition of conducting monomers to an agueous or nonaqueous solution of a polyelectrolyte to form a monomer/polyelectrolyte solution, followed by the subsequent addition of an oxidant to the monomer/polyelectrolyte solution to polymerize the monomer to form a molecular complex comprising a polyelectrolyte and a conducting polymer wherein the ratio of the conducting polymer to the polyelectrolite is in the range of 1:

1 to greater than 1;

1;

said polyelectrolyte is poly(styrenesulfonic acid) and said conductive polymer is polypyrrole.

68. A process to make an electrically conductive molecular complex made by a template-guided chemical polymerization process, the molecular complex comprising a polymeric polyelectrolyte and a conductive polymer, said template-guided chemical polymerization process comprises the addition of conducting monomers to an aqueous or nonaqueous solution of a polyelectrolyte to form a monomer/polyelectrolyte solution, followed by the subsequent addition of an oxidant to the monomer/polyelectrolyte solution to polymerize the monomer to form a molecular complex comprising a polyelectrolyte and a conducting polymer wherein the ratio of the conducting polymer to the polyelectrolyte is in the range of 1:

1 to greater than 1;

1;

said polyelectrolyte is poly(acrylic acid) and said conductive polymer is polypyrrole.

69. A process to make an electrically conductive molecular complex made by a template guided polymerization process, the molecular complex comprising at least two polymeric polyelectrolytes and a conductive polymer, said process comprising the addition of monomers to an aqueous or nonaqueous solution of at least two polyelectrolytes selected from the group consisting of poly(styrenesulfonic acid), poly(acrylic acid), poly(methacrylic acid), and one type of conducting polymer is selected from the group consisting of polypyrrole, polythiophene, poly(phenylenesulfide) and substituted versions thereof to form a monomer/polyelectrolyte/polyelectrolyte solution followed by the addition of an oxidant to the monomer/polyelectrolyte/polyelectrolyte solution to polymerize the monomer to form a molecular complex comprising at least two polymeric polyelectrolytes and a conductive polymer wherein the ratio of the conductive polymer to the polyelectrolyte is in the range of 1:

1 to greater than 1;

1.

70. The process according to claim 69 wherein said two types of polyelectrolyte are poly(acrylic acid) and poly(styrenesulfonic acid).

71. The process according to claim 69 wherein said two types of polyelectrolyte are poly(acrylic acid) and poly(2-acrylamido-2-methyl-1-propenesulfonic acid).

72. A process to make an electrically conductive molecular complex made by a template-guided chemical polymerization process, the molecular complex comprising a polyacid and a conductive polymer selected from the group consisting of polypyrrole, polythiophene, poly(phenylene sulfide) and substitutions thereof, said template-guided chemical polymerization process comprises the addition of conducting monomers to an aqueous or nonaqueous solution of a polyacid to form a monomer/polyacid solution, followed by the subsequent addition of an oxidant to the monomer/polyacid solution to polymerize the monomer to form a molecular complex comprising a polyacid and a conducting polymer wherein the ratio of the conducting polymer to the polyacid is in the range of 1:

1 to greater that 1;

1.

73. The process according to claim 72 wherein said polyacid is a polymer with anionic functional group selected from the groups consisting of carboxylic acid, sulfonic acid, phosphoric acid, boric acid.

74. The process according to claim 72 wherein said polyacid is selected from the group consisting of poly(styrenesulfonic acid), poly(acrylic acid), poly(methacrylic acid), salt forms thereof and copolymers thereof.

75. The process according to claim 72 wherein said polyacid is poly(styrenesulfonic acid).

76. The process according to claim 72 wherein said polyacid is poly(2-acrylamido-2-methyl-1-propenesulfonic acid).

77. The process according to claim 72 wherein said polyacid is poly(acrylic acid).

78. A process to make an electrically conductive molecular complex made by a template-guided chemical polymerization process, the molecular complex comprising a polyacid and a conductive polymer, said template-guided chemical polymerization process comprises the addition of conducting monomers to an aueous or nonaqueous solution of a polyacid to form a monomer/polyacid solution, followed by the subsequent addition of an oxidant to the monomer/polyacid solution to polymerize the monomer to form a molecular complex comprising a polyacid and a conducting polymer wherein the ratio of the conducting polymer to the polyacid is in the range of 1:

1 to greater than 1;

1;

said polyacid is poly(styrenesulfonic acid) and said conductive polymer is polypyrrole.

79. A process to make an electrically conductive molecular complex made by a template-guided chemical polymerization process, the molecular complex comprising a polyacid and a conductive polymer, said template-guided chemical polymerization process comprises the addition of conducting monomers to an aqueous or nonaqueous solution of a polyacid to form a monomer/polyacid solution, followed by the subsequent addition of an oxidant to the monomer/polyacid solution to polymerize the monomer to form a molecular complex comprising a polyacid and a conducting polymer wherein the ratio of the conducting polymer to the polyacid is in the range of 1:

1 to greater than 1;

1;

said polyacid is poly(acrylic acid) and said conductive polymer is polypyrrole.

80. A process to make an electrically conductive molecular complex made by a template guided polymerization process, the molecular complex comprising at least two polymeric polyacid and a conductive polymer, said process comprising the addition of monomers to an aqueous or nonaqueous solution of at least two polyacids selected from the group consisting of poly(styrenesulfonic acid), poly(acrylic acid), poly(methacrylic acid), and one type of conducting polymer is selected from the group consisting of polypyrrole, polythiophene, poly(phenylenesulfide) and substituted versions thereof to form a monomer/polyacid/polyacid solution followed by the addition of an oxidant to the monomer/polyacid/polyacid solution to polymerize the monomer to form a molecular complex comprising at least two polymeric polyacid and a conductive polymer wherein the ratio of the conductive polymer to the polyacid is in the range of 1:

1 to greater than 1;

1.

81. The process according to claim 80 wherein said two types of polyacid are poly(acrylic acid) and poly(styrenesulfonic acid).

82. The process according to claim 80 wherein said two types of polyacid are poly(acrylic acid) and poly(2-acrylamido-2-methyl-1-propenesulfonic acid) and said conducting polymer is polyaniline.

83. A process to make an electrically conductive molecular complex made by a template-guided chemical polymerization process, the molecular complex comprising a polyfunctional dopant and a conductive polymer selected from the group consisting of polypyrrole, polythiophene, poly(phenylene sulfide) and substitutions thereof, said template-guided chemical polymerization process comprises the addition of conducting monomers to an aqueous or nonaqueous solution of a polyfunctional dopant to form a monomer/polyfunctional dopant solution, followed by the subsequent addition of an oxidant to the monomer/polyfunctional dopant solution to polymerize the monomer to form a molecular complex comprising a polyfunctional dopant and a conducting polymer wherein the ratio of the conducting polymer to the polyfunctional dopant is in the range of 1:

1 to greater than 1;

1.

84. The process according to claim 83 wherein said polyacid is a polymer with anionic functional group selected from the groups consisting of carboxylic acid, sulfonic acid, phosphoric acid, boric acid.

85. The process according to claim 83 wherein said polyacid is selected from the group consisting of poly(styrenesulfonic acid), poly(acrylic acid), poly(methacrylic acid), salt forms thereof and copolymers thereof.

86. The process according to claim 83 wherein said polyfunctional dopant is poly(styrenesulfonic acid).

87. The process according to claim 83 wherein said polyfunctional dopant is poly(2-acrylamido-2-methyl-1-propenesulfonic acid).

88. The process according to claim 83 wherein said polyfunctional dopant is poly(acrylic acid).

89. A process to make an electrically conductive molecular complex made by a template-guided chemical polymerization process, the molecular complex comprising a polyfunctional dopant and a conductive polymer, said template-guided chemical polymerization process comprises the addition of conducting monomers to an aqueous or nonaqueous solution of a polyfunctional dopant to form a monomer/polyfunctional dopant solution, followed by the subsequent addition of an oxidant to the monomer/polyfunctional dopant solution to polymerize the monomer to form a molecular complex comprising a polyfunctional dopant and a conducting polymer wherein the ratio of the conducting polymer to the polyfunctional dopant is in the range of 1:

1 to greater than 1;

1

said polyfunctional dopant is poly(styrenesulfonic acid) and said conductive polymer is polypyrrole.

90. A process to make an electrically conductive molecular complex made by template-guided chemical polymerization process, the molecular complex comprising a polyfunctional dopant and a conductive polymer selected from the group consisting of polyaniline, polypyrrole, polythiophene, polyohenylene sulfide) and substitutions thereof, said template-guided chemical polymerization process comprises the addition of conducting monomers to an aqueous or nonaqueous solution of a polyfunctional dopant to form a monomer/polyfunctional dopant solution, followed by the subsequent addition of an oxidant to the monomer/polyfunctional dopant solution to polymerize the monomer to form a molecular complex comprising a polyfunctional dopant and a conducting polymer wherein the ratio of the conducting polymer to the polyfunctional dopant is in the range of 1:

1 to greater than 1;

1;

said polyfunctional dopant is poly(acrylic acid) and said condutye polymer is polypyrrole.

91. A process to make an electrically conductive molecular complex made by a template guided polymerization process, the molecular complex comprising at least two polymeric polyfunctional dopant and a conductive polymer, said process comprising the addition of monomers to an aqueous or nonaqueous solution of at least two polyfunctional dopants selected from the group consisting of poly(styrenesulfonic acid), poly(acrylic acid), poly(methacrylic acid), and one type of conducting polymer is selected from the group consisting of polypyrrole, polythiophene, poly(phenylenesulfide) and substituted versions thereof to form a monomer/polyfunctional dopant/polyfunctional dopant solution followed by the addition of an oxidant to the monomer/polyfunctional dopant/polyfunctional dopant solution to polymerize the monomer to form a molecular complex comprising at least two polymeric polyfunctional dopant and a conductive polymer wherein the ratio of the conductive polymer to the polyfunctional dopant is in the range of 1:

1 to greater than 1;

1.

92. The process according to claim 91 wherein said two types of polyfunctional dopant are poly(acrylic acid) and poly(styrenesulfonic acid).

93. The process according to claim 91 wherein said two types of polyfunctional dopant are poly(acrylic acid) and poly(2acrylamido-2-methyl-1-propenesulfonic acid).

95. A method comprising forming a water-soluble, electrically conductive composition of matter capable of forming a stable solution in water, comprising admixing a polyacid and units selected from the group consisting of monomers 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.