Conducting substituted polyisothianaphthenes

• US 4,795,242 A
• Filed: 12/18/1986
• Issued: 01/03/1989
• Est. Priority Date: 05/22/1985
• Status: Expired due to Term

• Current Assignee: Regents of the University of California (University of California)
• Original Assignee: University of California
• Inventors: Ikenoue, Yoshiaki, Wudl: Fred, Kobayashi, Masao, Heeger, Alan
• Primary Examiner(s): Niebling, John F.
• Assistant Examiner(s): Marquis, Steven P.
• Application Number:
  US06/944,138
• Time in Patent Office: 747 Days
• Field of Search: 204/59 R, 204/72, 549/58, 549/43, 528/377, 528/405, 350/357
• US Class Current: 359/265
• CPC Class Codes: C08G 61/123 derived from five-membered heterocyclic compounds
• CPC Class Codes: C09K 9/02 Organic tenebrescent materials
• CPC Class Codes: G02F 1/15165 Polymers
• 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

Polyisothianaphthene substituted in the 5 and/or 6 positions so as to have an oxygen atom adjacent to C₅ or C₆. Substituents include alkoxys, hydroxys and dioxyalkylenes. The polymers are conducting and useful in electrochromic displays and as electrode materials.

Claims

1. A polymer having a structural formula selected from the group consisting of Ia and Ib wherein:

##STR16## R₁ is hydrogen or --OR₃ ;

R₂ and R₃ are selected independently from the group consisting of hydrogen and C₁ to C₈ hydrocarbons, with the proviso that R₂ and R₃ may be linked together to form, with both oxygens, a dioxyalkylene substituent on the benzene ring with the formula;

##STR17## wherein R₄ and R₅ are selected independently from the group consisting of hydrogen and C₁ to C₄ hydrocarbons;

X is selected from the group consisting of sulfur, selenium and tellurium;

Y^- represents an anion of an electrolyte;

z represents a number from 0.01 to 1 showing a ratio of the anion per mol of a monomer; and

n represents a number of from 5 to 500 showing the degree of polymerization.

2. The polymer of claim 1 wherein R₁ is --OR₃ ;

R₂ and R₃ are either (i) selected from the group consisting of methyl and ethyl, or (ii) together with the oxygens form said dioxyalkylene where R₄ and R₅ are selected from the group consisting of hydrogen, methyl and ethyl; and

X is sulfur.

3. The polymer of claim 2 wherein R₂ and R₃ are methyl or ethyl, and R₂ =R₃.

4. The polymer of claim 2 wherein R₂ and R₃ are methyl.

5. The polymer of claim 2 wherein R₂ and R₃ together from said dioxyalkylene, R₄ and R₅ are hydrogen or methyl, and R₄ =R₅.

6. The polymer of claim 5 wherein R₄ and R₅ are hydrogen.

7. The polymer of claim 2 wherein said structural formula is Ia.

8. The polymer of claim 3 wherein said structural formula is Ia.

9. The polymer of claim 4 wherein said structural formula is Ia.

10. The polymer of claim 5 wherein said structural formula is Ia.

11. The polymer of claim 6 wherein said structural formula is Ia.

12. The polymer of claim 2 wherein said structural formula is Ib.

13. The polymer of claim 3 wherein said structural formula is Ib.

14. The polymer of claim 4 wherein said structural formula is Ib.

15. The polymer of claim 5 wherein said structural formula is Ib.

16. The polymer of claim 6 wherein said structural formula is Ib.

17. The polymer of claim 12 wherein Y^- is selected from the group consisting of Cl^-, Br^-, I^-, ClO₄^-, BF₄^-, PF₆^-, AsF₆^-, SbF₆^-, AlCl₄^-, AlBr₄^-, FeCl₄^-, and CF₃ SO₃^-.

18. The polymer of claim 13 wherein Y^- is selected from the group consisting of Cl^-, Br^-, I^-, ClO₄^-, BF₄^-, PF₆^-, AsF₆^-, SbF₆^-, AlCl₄^-, AlBr₄^-, FeCl₄^-, and CF₃ SO₃^-.

19. The polymer of claim 14 wherein Y^- is selected from the group consisting of Cl^-, Br^-, I^-, ClO₄^-, BF₄^-, PF₆^-, AsF₆^-, SbF₆^-, AlCl₄^-, AlBr₄^-, FeCl₄^-, and CF₃ SO₃^-.

20. The polymer of claim 15 wherein Y^- is selected from the group consisting of Cl^-, Br^-, I^-, ClO₄^-, BF₄^-, PF₆^-, AsF₆^-, SbF₆^-, AlCl₄^-, AlBr₄^-, FeCl₄^-, and CF₃ SO₃^-.

21. The polymer of claim 16 wherein Y^- is selected from the group consisting of Cl^-, Br^-, I^-, ClO₄^-, BF₄^-, PF₆^-, AsF₆^-, SbF₆^-, AlCl₄^-, AlBr₄^-, FeCl₄^-, and CF₃ SO₃^-.

22. The polymer of claim 12 wherein Y^- is HSO₄^-.

23. The polymer of claim 13 wherein Y^- is HSO₄^-.

24. The polymer of claim 14 wherein Y^- is HSO₄^-.

25. The polymer of claim 15 wherein Y^- is HSO₄^-.

26. The polymer of claim 16 wherein Y^- is HSO₄^-.

32. An improved electrochromic display device comprising a display electrode, an opposing electrode, a liquid electrolyte therebetween, a housing for the display device which contains said opposing electrode and said liquid electrolyte, and a means for applying voltage across said two electrodes, wherein the improvement comprises a coating on said display electrode formed from the polymeric material of claim 1.

33. The device of claim 32, wherein the thickness of said coating of polymeric material is in the range of about 0.03 to about 30 microns.

34. The device of claim 33, wherein the thickness of said coating of polymeric material is in the range of about 0.05 to about 22 microns.

35. The device of claim 34, wherein the thickness of said coating of polymeric material is in the range of about 0.1 to about 10 microns.

36. The device of claim 32, wherein said liquid electrolyte comprises a support electrolyte dissolved or dispersed in a suitable solvent.

37. The device of claim 36, wherein the supporting electrolyte is selected from the group consisting of LiPF₆, LiSbF₆, LiAsF₆, LiClO₄, NaI, NaPF₆, NaSbF₆, NaAsF₆, NaClO₄, KI, KPF₆, KSbF₆, KAsF₆, KClO₄, [(n-Bu)₄ N]⁺ ·

ClO₄^-, LiAlCl₄, LiBF₄, (C₆ H₅)₄ P·

BF₄, (C₆ H₅)₄ P·

AsF₆ and (C₆ H₅)₄ P·

ClO₄.

38. The device of claim 36, wherein said solvent is an aprotic organic solvent.

39. The device of claim 38, wherein said solvent is selected from the group consisting of tetrahydrofuran, 2-methyltetrahydrofuran, 1,4-dioxane, acetonitrile, proprionitrile, 4-methyl-2-pentanone, butyronitrile, valeronitrile, benzonitrile, 1,2-dichloroethane, γ

-butyrolactone, valerolactone, dimethoxyethane, methylformate, propylene carbonate, ethylene carbonate, dimethylformamide, dimethyl sulfoxide, ethyl phosphate, methyl phosphate, ethyl phosphite, methyl phosphite and 3-methylsulfolane.

27. A method of preparing a poly(isothianaphthene) polymer by electrochemical polymerization comprising:

(a) providing a monomer having the formula;

##STR18## R₁ is hydrogen or --OR₃ ;

R₂ and R₃ are selected independently from the group consisting of hydrogen and C₁ to C₈ hydrocarbons, with the proviso that R₂ and R₃ can link together to form, with both oxygens, a dioxyalkylene substituent on the benzene ring with the formula;

##STR19## wherein R₄ and R₅ are selected independently from the group consisting of hydrogen and C₁ to C₄ hydrocarbons;

(b) dissolving said monomer in an aprotic solvent containing electrolyte to provide a monomer solution, said electrolyte being ionic and a source of nucleophilic anions; and

(c) electrochemically polymerizing said monomer solution to provide a poly(isothianaphthene).

28. The method of claim 27 wherein said monomer is 5,6-dioxymethylene-isothianaphthene.

29. The method of claim 27 wherein said monomer is 5,6-dimethoxy-isothianaphthene.

30. The method of claim 27 wherein said polymerization forms said poly(isothianaphthene) into a membrane on a transparent conductive base.

31. The method of claim 28 wherein said polymerization forms said poly(isothianaphthene) into a membrane on a transparent conductive base.