Process for producing electrically conductive composites and composites produced therein

Abstract

Production of electrically conductive composites comprising a dielectric porous substance, e.g., fiberglass fabric, and a pyrrole polymer in the pores of such substance, by treating the porous substance with a liquid pyrrole, and then treating the resulting porous substance with a solution of a strong oxidant in the presence of a non-nucleophilic anion, such as ferric chloride. The pyrrole monomer is oxidized to a pyrrole polymer, which precipitates in the interstices of the porous material. Alternatively, the dielectric porous material can first be treated with a solution of strong oxidant and non-nucleophilic anion followed by treatment with liquid pyrrole, to precipitate an electrically conductive polypyrrole in the pores of the material. The resulting composite of porous material, e.g., fiberglass fabric, containing polypyrrole is electrically conductive while the other properties of such impregnated conductive porous material are substantially unaffected. Several treatments of the porous substance with the pyrrole and oxidant solutions can be carried out to increase the electrical conductivity of the composite.

What is claimed is: 
     
       1. A process for producing an electrically conductive composite which comprises the steps of: (a) contacting a dielectric porous substance with a liquid pyrrole,   (b) contacting said porous substance with a solution of a strong oxidant capable of oxidizing pyrrole to a pyrrole polymer, .Iadd.said strong oxidant being a cation selected from the group consisting of Ce 4+ , NO +   and (C 6  H 5 ) 3  C +   cations, .Iaddend.and   (c) oxidizing said pyrrole by said strong oxidant in the presence of a substantially non-nucleophilic anion, and precipitating a conductive pyrrole polymer in the pores of said substance.Iadd., said non-nucleophilic anion being selected from the group consisting of sulfate, bisulfate, fluoroborate, PF 6   - , AsF 6   - , and SbF 6   -   anions.Iaddend..   
     
     
       2. The process of claim 1, wherein step (a) is carried out prior to step (b). 
     
     
       3. The process of claim 1, wherein step (b) is carried out prior to step (a). 
     
     
       4. The process of claim 1, said contacting steps (a) and (b) being carried out by applying said liquid pyrrole and said oxidant solution to said porous substance or by immersion of said porous substance in said liquid pyrrole and said oxidant solution. 
     
     
       5. The process of claim 1, including carrying out a plurality of treatments of said porous substance with said liquid pyrrole and said oxidant solution. 
     
     
       6. The process of claim 1, said pyrrole monomer selected from the group consisting of pyrrole, a 3- and 3,4-alkyl and aryl C-substituted pyrrole, an N-alkylpyrrole and an N-arylpyrrole. .[.7. The process of claim 1, said strong oxidant being a cation selected from the group consisting of Fe 3+ , Cu 2+ , Ce 4+ , NO +   and (C 6  H 5 ) 3   
     
     
        C +   cations..].  8. The process of claim 1, said strong oxidant being 
     
     
        an anion. 9. The process of claim 8, said oxidant anion being the persulfate anion. .[.10. The process of claim 1, said non-nucleophilic anion being selected from the group consisting of sulfate, bisulfate, perchlorate, chloride, fluoborate, PF 6   - , AsF 6   - , and 
     
     
        SbF 6   -   anions..].  11. .[.The process of claim 1,.]. .Iadd.A process for producing an electrically conductive composite which comprises the steps of: (a) contacting a dielectric porous substance with a liquid pyrrole,   (a) contacting said porous substance with a solution of a strong oxidant capable of oxidizing pyrrole to a pyrrole polymer, said strong oxidant being a cation selected from the group consisting of Fe 3+ , Cu 2+ , Ce 4+ , NO +   and (C 6  H 5 ) 3  C+ cations, and   (c) oxidizing said pyrrole by said strong oxidant in the presence of a substantially non-nucleophilic anion, and precipitating a conductive pyrrole polymer in the pores of said substance, .Iaddend.said non-nucleophilic anion being selected from the group consisting of p-toluenesulfonate, polystyrenesulfonate, polyvinylsulfonate, the   
     
     
        corresponding free sulfonic acids, and dodecylsulfate. 12. The process of claim 11, said non-nucleophilic anion being derived from the free acids or the soluble salts of said acids. .[.13. The process of claim 1, said oxidant and said non-nucleophilic anion being provided by a compound selected from the group consisting of ferric perchlorate, ferric chloride, 
     
     
        cupric fluoborate and cupric perchlorate..].  14. The process of claim 1, said oxidant and said non-nucleophilic anion being provided by a compound selected from the group consisting of triphenylmethyl fluoborate and 
     
     
        nitrosyl hexafluorophosphate. 15. The process of claim 1, said pyrrole being present in aqueous or organic solvent medium in which said pyrrole and said oxidant are soluble and which does not interfere with the 
     
     
        oxidation reaction. 16. The process of claim 1, including an organic solvent for said oxidant, said solvent being inert with respect to said 
     
     
        oxidant and permitting said oxidant to oxidize said pyrrole. 17. The process of claim 1, said oxidant and said non-nucleophilic anion being 
     
     
        present in aqueous solution. 18. The process of claim 1, said pyrrole being present in a concentration in the range from about 0.03 to about 2 molar, said oxidant being present in the range of about 0.001 to about 2 molar, and said non-nucleophilic anion being present in a concentration in 
     
     
        the range from about 0.001 to about 2 molar. 19. The process of claim 1, said dielectric porous substance selected from the group consisting of a 
     
     
        porous ceramic, porous glass, a porous organic foam, and a fabric. 20. The process of claim 19, said porous substance being a fabric selected from the group consisting of fiberglass fabric, mixed oxide fabric and a 
     
     
        synthetic organic fabric. 21. The process of claim 20, said porous 
     
     
        substance being fiberglass fabric. 22. A process for producing an electrically conductive composite which comprises contacting .[.the.]. .Iadd.a .Iaddend.dielectric porous substance with a liquid pyrrole,   contacting the resulting substance containing liquid pyrrole in the pores thereof with a solution of a strong oxidant capable of oxidizing pyrrole to a pyrrole polymer and a substantially non-nucleophilic anion, .Iadd.said strong oxidant being a cation selected from the group consisting of Fe 3+ , Cu 2+ , Ce 4+ , NO +   and (C 6  H 5 ) 3  C +   cations, .Iaddend.and   oxidizing said pyrrole by said strong oxidant and precipitating a conductive pyrrole polymer comprising a pyrrole polymer cation and a substantially non-nucleophilic anion in the pores of said substance.Iadd., said non-nucleophilic anion being selected from the group consisting of p-toluenesulfonate, polystyrenesulfonate, polyvinylsulfonate, the corresponding free sulfonic acids, and dodecylsulfate.Iaddend.. .[.23. A process for producing an electrically conductive composite which comprises   contacting the dielectric porous substance with a solution of a strong oxidant capable of oxidizing pyrrole to a pyrrole polymer, and a substantially non-nucleophilic anion,   contacting the resulting substance containing said solution of strong oxidant and substantially non-nucleophilic anion in the pores thereof, with a liquid pyrrole, and   oxidizing said pyrrole by said strong oxidant and precipitating a conductive pyrrole polymer in the pores of said substance, and pyrrole polymer comprising a pyrrole polymer cation and a substantially non-nucleophilic anion..].  .[.24. The process of claim 22, said pyrrole monomer selected from the group consisting of pyrrole, a 3- and 3,4-alkyl and aryl C-substituted pyrrole, an N-alkylpyrrole and an N-arylpyrrole, said strong oxidant being a cation selected from the group consisting of Fe 3+ , Cu 2+ , Ce 4+ , NO +   and (C 6  H 5 ) 3  C +   cations, and said non-nucleophilic anion being selected from the group consisting of sulfate, bisulfate, perchlorate, chloride, fluoborate, PF 6   - , AsF 6   - , and SbF 6   -   anions..].  .[.25. The process of claim 24, said oxidant and said non-nucleophilic anion being provided by a compound selected from the group consisting of ferric perchlorate, ferric chloride, cupric fluoborate and cupric perchlorate..].   
     
     
         26. The process of claim .[.24,.]. .Iadd.22, .Iaddend.employing pyrrole, said pyrrole being present in a concentration in the range from about 0.03 to about 2 molar, said oxidant being present in the range of about 0.001 to about 2 molar, and said non-nucleophilic anion being present in a 
     
     
        concentration in the range from about 0.001 to about 2 molar. 27. The process of claim 26, said porous substance being a fabric selected from the group consisting of fiberglass fabric, mixed oxide fabric and a synthetic organic fabric. .[.28. The process of claim 23, said pyrrole monomer selected from the group consisting of pyrrole, a 3- and 3,4-alkyl and aryl C-substituted pyrrole, an N-alkypyrrole and an N-arylpyrrole, said strong oxidant being a cation selected from the group consisting of Fe 3+ , Cu 2+ , Ce 4+ , NO +   and (C 6  H 5 ) 3  C +   cations, and said non-nucleophilic anion being selected from the group consisting of sulfate, bisulfate, perchlorate, chloride, fluoborate, PF 6   - , AsF 6   - , and SbF 6   -   anions..].  .[.29. The process of claim 28, said pyrrole being present in a concentration in the range from about 0.03 to about 2 molar, said oxidant being present in the range of about 0.001 to about 2 molar, and said non-nucleophilic anion being present in a concentration in the range from about 0.001 to about 2 molar..].  .[.30. The process of claim 29, said porous substance being a fabric selected from the group consisting of fiberglass fabric, mixed 
     
     
        oxide fabric and a synthetic organic fabric..].  31. An electrically conductive composite produced by the process of claim 1. .[.32. An electrically conductive composite produced by the process of claim 7..]. 
     
     
         3. An electrically conductive composite produced by the process of claim 
     
     
        .[.10.]. .Iadd.11.Iaddend.. 34. An electrically conductive composite 
     
     
        produced by the process of claim 18. 35. An electrically conductive 
     
     
        composite produced by the process of claim 20. 36. An electrically conductive composite produced by the process of claim 22. .[.37. An electrically conductive composite produced by the process of claim 23..]. 
     
     
        .Iadd.38.  A process for producing an electrically conductive structural composite which comprises the steps of: (a) contacting a dielectric porous structural substance with a liquid pyrrole,   (b) contacting said porous substance with a solution of a strong oxidant capable of oxidizing pyrrole to a pyrrole polymer, said strong oxidant being a cation selected from the group consisting of Fe 3+ , Cu 2+ , Ce 4+ , NO +   and (C 6  H 5 ) 3  C +   cations, and   (c) oxidizing said pyrrole by said strong oxidant in the presence of a substantially non-nucleophilic anion, and precipitating a conductive pyrrole polymer in the pores of said substance, said non-nucleophilic anion being selected from the group consisting of p-toluenesulfonate, polystyrenesulfonate, polyvinylsulfonate, the corresponding free sulfonic   
     
     
        acids, and dodecylsulfate. .Iaddend..Iadd.39.  The process of claim 38, said pyrrole being present in aqueous medium in which said pyrrole and said oxidant are soluble and which does not interfere with the oxidation reaction. .Iaddend..Iadd.40. The process of claim 38, said dielectric porous substance selected from the group consisting of a porous glass, a porous organic foam, and a fabric. .Iaddend..Iadd.41. The process of claim 38, said porous substance being a fabric selected from the group consisting of fiberglass fabric, mixed oxide fabric and a synthetic 
     
     
        organic fabric. .Iaddend..Iadd.42.  The process of claim 38, said porous substance being fiberglass fabric. .Iaddend..Iadd.43. The process of claim 38, said oxidant and said non-nucleophilic anion being present in aqueous solution. .Iaddend..Iadd.44. An electrically conductive composite produced by the process of claim 38. .Iaddend..Iadd.45. An electrically conductive composite produced by the process of claim 44. .Iaddend.