Bipyridinium salt solutions

• US 5,294,376 A
• Filed: 06/25/1991
• Issued: 03/15/1994
• Est. Priority Date: 06/25/1991
• Status: Expired due to Fees

• Current Assignee: Gentex Corporation
• Original Assignee: Gentex Corporation
• Inventors: Byker, Harlan J.
• Primary Examiner(s): Higel, Floyd D.
• Application Number:
  US07/720,170
• Time in Patent Office: 994 Days
• Field of Search: 359/265, 359/839, 546/257, 252/600
• US Class Current: 252/600
• CPC Class Codes: C07D 213/22 containing two or more pyridine rings directly linked together, e.g. bipyridyl
• CPC Class Codes: C09K 9/02 Organic tenebrescent materials
• CPC Class Codes: G02F 1/1503 caused by oxidation-reduction reactions in organic liquid solutions, e.g. viologen solutions
• CPC Class Codes: G02F 2001/1502 complementary cell
• CPC Class Codes: G02F 2001/15145 the electrochromic layer comprises a mixture of anodic and cathodic compounds

Abstract

The present invention provides solutions of certain 4,4'"'"'-bipyridinium salts, such as salts of 1,1'"'"'- dibenzyl-2,2'"'"',6,6'"'"'-tetraalkyl-4,4'"'"'-bipyridinium cations. The solutions of the invention are employed as solutions of variable transmittance in solution-phase electrochromic devices, including such devices that are single-compartment and self-erasing. In the solutions of the invention in such devices, the bipyridinium salts are cathodic electrochromic compounds, as reduction of a cation of such a salt causes its molar extinction coefficient at at least one wavelength in the visible range to increase markedly. Electrochromic devices, in which solutions of the invention provide variable transmittance, are, in turn, components of variable transmittance in display devices, windows and other types of light filters, and variable reflectance mirrors, such as those that can be used as dimmable rearview mirrors in motor vehicles.

Claims

1. A solution which comprises a solvent;

an anodic electrochromic compound which, upon oxidation of its zero-potential equilibrium state, undergoes an increase in molar extinction coefficient at at least one wavelength in the visible range; and

a cathodic electrochromic compound which is a salt of a cation of the formula ##STR11## wherein R₇ and R₈ are independently selected from the group consisting of an alkyl group with 1-20 carbon atoms and benzyl; and

R₉, R₁₀, R₁₁, and R₁₂ are independently selected from the group consisting of hydrogen and an alkyl group with 1-4 carbon atoms, provided that at least three of R₉, R₁₀, R₁₁, and R₁₂ are alkyl groups.

2. A solution according to claim 1 wherein the solvent is liquid at room temperature and consists essentially of a polar organic solvent or a mixture of polar organic solvents.

3. A solution according to claim 2 wherein the solvent consists essentially of propylene carbonate, gamma-butyrolactone, gamma-valerolactone, or an homogeneous mixture of any two or more of said solvents or any one or more of said solvents with ethylene carbonate.

4. A solution according to claim 3 wherein the solvent consists essentially of propylene carbonate.

5. A solution according to claim 1 wherein the anodic compound in the solution is selected from the group consisting of 5,10-dihydro-5,10-dimethylphenazine, N,N,N'"'"',N'"'"'-tetramethyl-p-phenylenediamine, N,N,N'"'"',N'"'"'-tetraphenyl-p-phenylenediamine, and bis-3,3'"'"'-diethyl-2,2'"'"'-benzothiazole azine.

6. A solution according to claim 2 wherein the anodic compound in the solution is selected from the group consisting of 5,10-dihydro-5,10-dimethylphenazine, N,N,N'"'"',N'"'"'-tetramethyl-p-phenylenediamine, N,N,N'"'"',N'"'"'-tetraphenyl-p-phenylenediamine, and bis-3,3'"'"'-diethyl-2,2'"'"'-benzothiazole azine.

7. A solution according to claim 3 wherein the anodic compound in the solution is selected from the group consisting of 5,10-dihydro-5,10-dimethylphenazine, N,N,N'"'"',N'"'"'-tetramethyl-p-phenylenediamine, N,N,N'"'"',N'"'"'-tetraphenyl-p-phenylenediamine, and bis-3,3'"'"'-diethyl-2,2'"'"'-benzothiazole azine.

8. A solution according to claim 4 wherein the anodic compound in the solution is selected from the group consisting of 5,10-dihydro-5,10-dimethylphenazine, N,N,N'"'"',N'"'"'-tetramethyl-p-phenylenediamine, N,N,N'"'"',N'"'"'-tetraphenyl-p-phenylenediamine, and bis-3,3'"'"'-diethyl-2,2'"'"'-benzothiazole azine.

9. A solution according to claim 7 wherein the anodic compound is 5,10-dihydro-5,10-dimethylphenazine.

10. A solution according to claim 8 wherein the anodic compound is 5,10-dihydro-5,10-dimethylphenazine.

11. A solution according to claim 5 wherein, in the cathodic electrochromic compound, R₉, R₁₀, R₁₁, and R₁₂ of the cation are alkyl groups, and the anions are selected from the group consisting of BF₄^-, PF₆^- and ClO₄^-.

12. A solution according to claim 6 wherein, in the cathodic electrochromic compound, R₉, R₁₀, R₁₁, and R₁₂ of the cation are alkyl groups, and the anions are selected from the group consisting of BF₄^-, PF₆^- and ClO₄^-.

13. A solution according to claim 7 wherein, in the cathodic electrochromic compound, R₉, R₁₀, R₁₁, and R₁₂ of the cation are alkyl groups, and the anions are selected from the group consisting of BF₄^-, PF₆^- and ClO₄^-.

14. A solution according to claim 8 wherein, in the cathodic electrochromic compound, R₉, R₁₀, R₁₁, and R₁₂ of the cation are alkyl groups, and the anions are selected from the group consisting of BF₄^-, PF₆^- and ClO₄^-.

15. A solution according to claim 9 wherein, in the cathodic electrochromic compound, R₉, R₁₀, R₁₁, and R₁₂ of the cation are alkyl groups, and the anions are selected from the group consisting of BF₄^-, PF₆^- and ClO₄^-.

16. A solution according to claim 10 wherein, in the cathodic electrochromic compound, R₉, R₁₀, R₁₁, and R₁₂ of the cation are alkyl groups, and the anions are selected from the group consisting of BF₄^-, PF₆^- and ClO₄^-.

17. A solution according to claim 11 wherein, in the cation of the cathodic electrochromic compound, both R₇ and R₈ are benzyl.

18. A solution according to claim 17 wherein, in the cathodic electrochromic compound, R₉, R₁₀, R₁₁, and R₁₂ of the cation are methyl and the anions are BF₄^-.

19. A solution according to claim 12 wherein, in the cation of the cathodic electrochromic compound, both R₇ and R₈ are benzyl.

20. A solution according to claim 19 wherein, in the cathodic electrochromic compound, R₉, R₁₀, R₁₁, and R₁₂ of the cation are methyl and the anions are BF₄^-.

21. A solution according to claim 13 wherein, in the cation of the cathodic electrochromic compound, both R₇ and R₈ are benzyl.

22. A solution according to claim 21 wherein, in the cathodic electrochromic compound, R₉, R₁₀, R₁₁, and R₁₂ of the cation are methyl and the anions are BF₄^-.

23. A solution according to claim 14 wherein, in the cation of the cathodic electrochromic compound, both R₇ and R₈ are benzyl.

24. A solution according to claim 23 wherein, in the cathodic electrochromic compound, R₉, R₁₀, R₁₁, and R₁₂ of the cation are methyl and the anions are BF₄^-.

25. A solution according to claim 15 wherein, in the cation of the cathodic electrochromic compound, both R₇ and R₈ are benzyl.

26. A solution according to claim 25 wherein, in the cathodic electrochromic compound, R₉, R₁₀, R₁₁, and R₁₂ of the cation are methyl and the anions are BF₄^-.

27. A solution according to claim 16 wherein, in the cation of the cathodic electrochromic compound, both R₇ and R₈ are benzyl.

28. A solution according to claim 27 wherein, in the cathodic electrochromic compound, R₉, R₁₀, R₁₁, and R₁₂ of the cation are methyl and the anions are BF₄^-.

29. A solution according to any one of claims 1, 8, 10, 14, 16, 23, 24, 27 and 28 wherein the concentrations of the cathodic electrochromic compound and the anodic electrochromic compound are from 0.001M to 0.1M.

30. A solution according to claim 29 which is thickened with 1 wt. %-10 wt. T polymethymethacrylate.

31. A solution according to any one of claims 1, 8, 10, 14, 16, 23, 24, 27 and 28 which comprises a UV-stabilizing compound.

32. A solution according to claim 29 which comprises, at a concentration from 0.1M to 0.6M, an alkyl ester of 2-cyano-3,3-diphenyl acrylate, wherein the alkyl group has 1-10 carbon atoms.

33. A solution according to claim 32 wherein the alkyl ester is ethyl 2-cyano-3,3-diphenyl acrylate.

34. A solution according to claim 30 which comprises, at a concentration from 0.1M to 0.6M, an alkyl ester of 2-cyano-3,3-diphenyl acrylate, wherein the alkyl group has 1-10 carbon atoms.

35. A solution according to claim 34 wherein the alkyl ester is ethyl 2-cyano-3,3-diphenyl acrylate.

36. A solution which is liquid at room temperature and comprises a solvent and a BF₄^-, PF₆^-, or ClO₄^- salt of a cation of Formula XVII ##STR12## wherein R₃₆ and R₃₇ independently selected from the group consisting of benzyl and alkyl of 1-20 carbon atoms;

and R₃₄, R₃₅, R₃₈ and R₃₉ are independently selected from the group consisting of hydrogen and alkyl groups of 1-4 carbon atoms, provided that at least three of R₃₄, R₃₅, R₃₈ and R₃₉ are alkyl.

37. A solution of claim 36 wherein the solvent consists essentially of propylene carbonate, gamma-butyrolactone, gamma-valerolactone, or an homogeneous mixture of any two or more of said solvents or any one or more of said solvents with ethylene carbonate.

38. A solution of claim 36 wherein, in the cation of Formula XVII, R₃₆ and R₃₇ are benzyl.

39. A solution of claim 37 wherein, in the cation of Formula XVII, R₃₆ and R₃₇ are benzyl.

40. A solution of claim 38 wherein the cation of Formula XVII is 1,1'"'"'-dibenzyl-2,2'"'"',6,6'"'"'-tetramethyl-4,4'"'"'-bipyridinium.

41. A solution of claim 39 wherein the cation of Formula XVII is 1,1'"'"'-dibenzyl-2,2'"'"',6,6'"'"'-tetramethyl-4,4'"'"'-bipyridinium.

42. A solution of claim 37 wherein the solvent consists essentially of propylene carbonate, the anion is BF₄^-, and the concentration of the salt at room temperature is from 0.001M to 0.1M.

43. A solution of claim 39 wherein the solvent consists essentially of propylene carbonate, the anion is BF₄^-, and the concentration of the salt at room temperature is from 0.001M to 0.1M.

44. A solution of claim 41 wherein the solvent consists essentially of propylene carbonate, the anion is BF₄^-, and the concentration of the salt at room temperature is from 0.001M to 0.1M.

45. A solution of any one of claims 36-41 which comprises a compound selected from the group consisting of 5,10-dihydro-5,10-dimethylphenazine, N,N,N'"'"',N'"'"'-tetramethyl-p-phenylenediamine, N,N,N'"'"',N'"'"'-tetraphenyl-p-phenylenediamine, and bis-3,3'"'"'-diethyl-2,2'"'"'-benzothiazole azine.

46. A solution of any one of claims 42-44 which comprises, at a concentration from 0.001M to 0.1M, a compound selected from the group consisting of 5,10-dihydro-5,10-dimethylphenazine, N,N,N'"'"',N'"'"'-tetramethyl-p-phenylenediamine, N,N,N'"'"',N'"'"'-tetraphenyl-p-phenylenediamine, and bis-3,3'"'"'-diethyl-2,2'"'"'-benzothiazole azine.

47. A solution of claim 45 which comprises 5,10-dihydro-5,10-dimethylphenazine.

48. A solution of claim 46 which comprises 5,10-dihydro-5,10-dimethylphenazine.

49. A solution of claim 45 which comprises a UV-stabilizing compound.

50. A solution of claim 49 wherein the UV-stabilizing compound is an alkyl ester of-2-cyano-3,3-diphenylacrylate, wherein the alkyl group is of 1-10 carbon atoms.

51. A solution of claim 50 wherein the UV-stabilizing compound is an ethyl 2-cyano-3,3-diphenyl-acrylate.

52. A solution of claim 46 which comprises, at a concentration at room temperature between 0.1M and 0.6M, an alkyl ester of 2-cyano-3,3-diphenyl-acrylate, wherein the alkyl group is of 1-10 carbon atoms.

53. A solution of claim 47 which comprises, at a concentration at room temperature between 0.1M and 0.6M, an alkyl ester of 2-cyano-3,3-diphenyl-acrylate, wherein the alkyl group is of 1-10 carbon atoms.

54. A solution of claim 52 wherein the alkyl ester is ethyl 2-cyano-3,3-diphenyl-acrylate.

55. A solution of claim 53 wherein the alkyl ester is ethyl 2-cyano-3,3-diphenyl-acrylate.

56. A solution of claim 54 which is thickened with 1 wt. %-10 wt % polymethylmethacrylate.

57. A solution of claim 55 which is thickened with 1 wt. %-10 wt. % polymethylmethacrylate.