Highly conductive polymer composition and process for producing the same

• US 4,933,106 A
• Filed: 11/25/1987
• Issued: 06/12/1990
• Est. Priority Date: 11/27/1986
• Status: Expired due to Term

• Current Assignee: Showa Denko KK (Resonac Holdings Corp.)
• Original Assignee: Showa Denko KK (Resonac Holdings Corp.)
• Inventors: Sakai, Toshiyuki, Kobayashi, Masao
• Primary Examiner(s): Barr, Josephine
• Application Number:
  US07/125,416
• Time in Patent Office: 930 Days
• Field of Search: 252/500, 524/80, 525/279, 204/59 R, 204/59 F
• US Class Current: 252/500
• CPC Class Codes: C08G 61/00 Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule C08G2/00 - C08G16/00 take precedence
• CPC Class Codes: C08G 61/123 derived from five-membered heterocyclic compounds
• CPC Class Codes: H01B 1/127 comprising five-membered aromatic rings in the main chain, e.g. polypyrroles, polythiophenes
• CPC Class Codes: H01M 4/60 of organic compounds
• CPC Class Codes: Y02E 60/10 Energy storage using batteries

Abstract

A highly conductive polymer composition can be obtained by doping a neutralized conductive polymer having a π-electron conjugated structure with an anionic polymer electrolyte. The conductive polymer composition is stable for a long period of time, and the content of the dopant in the polymer composition can be freely controlled. A process for producing the polymer composition is also disclosed.

Claims

1. A highly conductive polymer composition comprising:

(A) a neutralized conductive polymer having a π

-electron conjugated structure, wherein said neutralized conductive polymer is polyisothianaphthene or a polymer of an isothianaphthene derivative, and

(B) a dopant which is an anionic polymer electrolyte, wherein said anionic polymer electrolyte is selected from the group consisting of polyacrylic acid, polymethacrylic acid, polyvinylsulfuric acid, polyvinylsulfonic acid, polystyrenesulfonic acid, poly-α

-methylsulfuric acid, polyethylenesulfonic acid, polyglutamic acid, polyaspartic acid, polyphosphoric acid, alginic acid, pectinic acid, and a fluorine-based polymer containing a sulfonic acid group(s) or a carboxylic acid group(s), wherein said fluorine-based polymer containing a sulfonic acid group(s) or carboxylic acid group(s) is obtained by polymerizing a fluorinated alkene of 2 to 20 carbon atoms with a perfluorinated alkene containing a sulfonic acid group(s) or a carboxylic acid group(s), wherein said anionic polymer electrolyte is contained in said polymer composition in an amount of from 0.05 to 0.20 mol per mol of monomer unit of said neutralized conductive polymer.

2. A highly conductive polymer composition as claimed in claim 1, wherein said neutralized conductive polymer is polyisothianaphthene.

3. A highly conductive polymer composition as claimed in claim 2, wherein said anionic polymer electrolyte is polyphosphoric acid.

7. A polymer composition according to claim 1, wherein said neutralized conductive polymer has an anion content of not more than 0.03 mols per mol of monomer unit constituting said neutralized conductive polymer prior to doping with said anionic polymer electrolyte.

13. A polymer composition according to claim 1, wherein said derivative is selected from the group consisting of 5-methylisothianaphthene and 5,6-dimethylisothianaphthene.

15. A polymer composition according to claim 1, wherein said neutralized conductive polymer is prepared by electrochemical polymerization.

4. A process for producing a highly conductive polymer composition comprising the steps of:

(A) neutralizing a conductive polymer having a π

-electron conjugated structure, wherein said neutralized conductive polymer is polyisothianaphthene or a polymer of an isothianaphthene derivative,

(B) subjecting the resulting neutralized conductive polymer to electrochemical doping with an anionic polymer electrolyte, wherein said anionic polymer electrolyte is selected from the group consisting of polyacrylic acid, polymethacrylic acid, polyvinylsulfuric acid, polyvinylsulfonic acid, polystyrenesulfonic acid, poly-α

-methylsulfuric acid, polyethylenesulfonic acid, polyglutamic acid, polyaspartic acid, polyphosphoric acid, alginic acid, pectinic acid, and a fluorine-based polymer containing a sulfonic acid group(s) or a carboxylic acid group(s), wherein said fluorine-based polymer containing a sulfonic acid group(s) or carboxylic acid group(s) is obtained by polymerizing a fluorinated alkene of 2 to 20 carbon atoms with a perfluorinated alkene containing a sulfonic acid group(s) or a carboxylic acid group(s), wherein said anionic polymer electrolyte is contained in said polymer composition in an amount of from 0.05 to 0.20 mol per mol of monomer unit of said neutralized conductive polymer.

5. A process as claimed in claim 4, wherein said neutralized conductive polymer is polyisothianaphthene.

6. A process as claimed in claim 5, wherein said anionic polymer electrolyte is polyphosphoric acid.

8. A process according to claim 6, wherein said neutralized conductive polymer has an anion content of not more than 0.03 mols per mol of monomer unit constituting said neutralized conductive polymer prior to doping with said anionic polymer electrolyte.

9. A process as claimed in claim 4, wherein said electrochemical doping is carried out by using said neutralized conductive polymer as a work electrode of an electrolytic cell, adding to said cell an electrolytic solution prepared by dissolving said anionic polymer electrolyte in a solvent, and applying to said work electrode an electric potential of from -2.5 to +3.0 V against an Ag/Ag⁺ reference electrode.

10. A process as claimed in claim 9, wherein said electric potential is from -1.5 to +3.0 V against an Ag/Ag⁺ reference electrode.

11. A process as claimed in claim 9, wherein said solvent is selected from the group consisting of acetonitrile, propylene carbonate, nitromethane, sulfolane, acetone, 2-methyl-2-pentanone, benzonitrile, tetrahydrofuran, dimethylsulfoxide, dimethylformamide, N-methylpyrrolidone, hexamethylphosphoramide, pyridine and water.

12. A process as claimed in claim 9, wherein said anionic polymer electrolyte is present in said electrolytic solution at a concentration of from 1×

1-^-4 to 10 mol/l.

14. A process according to claim 4, wherein said derivative is selected from the group consisting of 5-methylisothianaphthene and 5,6-dimethylisothianaphthene.

16. A process according to claim 4, wherein said neutralized conductive polymer is prepared by electrochemical polymerization.