UV stabilized compositions with improved solubility

• US 5,770,114 A
• Filed: 08/06/1997
• Issued: 06/23/1998
• Est. Priority Date: 08/06/1997
• Status: Expired due to Term

• Current Assignee: Gentex Corporation
• Original Assignee: Gentex Corporation
• Inventors: Byker, Harlan J., Srinivasa, Ramanujan
• Primary Examiner(s): HARRELL, ROBERT B
• Application Number:
  US08/906,750
• Time in Patent Office: 321 Days
• Field of Search: 252/583, 252/586, 252/589, 359/265, 359/272, 359/275
• US Class Current: 252/583
• CPC Class Codes: G02F 1/1503 caused by oxidation-reduction reactions in organic liquid solutions, e.g. viologen solutions

Abstract

The present invention concerns compositions, which comprise an aprotic polar solvent, at least one electrochromic compound, and a compound of the formula I ##STR1## wherein R₁ is, for example, tert-butyl, and R₂ is, for example, --CH₂ --CH₂ --COO--R₇ --, where R₇ is n-butyl or n-pentyl. Among embodiments of the invention are compositions used as media of variable transmittance in electrochromic devices, especially single-compartment, self-erasing, solution-phase electrochromic devices. The compounds of Formula I have increased solubility in aprotic polar solvents used in electrochromic devices and are effective in stabilizing compositions, which comprise at least one electrochromic compound and are useful as media of variable transmittance in electrochromic devices, against degradation due to exposure to UV-radiation. The compounds of Formula I further significantly assist in controlling the gel formation time of cross-linked polymer matrices, which comprise at least one electrochromic compound and are useful as media of variable transmittance in electrochromic devices.

Claims

1. A UV-stabilized composition which comprises (a) an aprotic polar solvent, (b) at least one electrochromic compound, and (c) a compound of the formula I ##STR4## wherein R₁ is H, a straight or branched alkyl group containing 1 to 18 carbons, or R₃ --COO--R₄, where R₃ is a single bond, or is a straight or branched alkylene group containing 1-6 carbons and R₄ is a straight or branched alkyl group containing 1-18 carbons, and if R₁ is H or a straight or branched alkyl group containing 1 to 18 carbons, then R₂ is R₃ --COO--R₄, and if R₁ is R₃ --COO--R₄, then R₂ is H, a straight or branched alkyl group containing 1 to 18 carbons, or R₅ --COO--R₆, where R₅ is a single bond, or is a straight or branched alkylene group containing 1 to 6 carbons, and R₆ is a straight or branched alkyl group containing 1-18 carbons.

2. The UV-stabilized composition according to claim 1 wherein the solvent is a liquid at room temperature and is selected from the group consisting of propylene carbonate, gamma-butyrolactone, gamma-valerolactone, and any homogeneous mixture that is liquid at room temperature of any two or more of said solvents or any one or more of said solvents with ethylene carbonate.

3. The UV-stabilized composition according to claim 2, wherein said at least one electrochromic compound comprises an anodic and a cathodic electrochromic compound.

4. The UV-stabilized composition according to claim 3 where said anodic compound is 5,10-dihydro-5,10-dimethylphenazine and where said cathodic compound is 1,1'"'"'-bis(3-phenyl(n-propyl))-4,4'"'"'-dipyridinium bis(tetrafluoroborate).

5. The UV-stabilized composition according to claim 2 wherein, in the compound of Formula I, R₁ is tert-butyl and R₂ is CH₂ --CH₂ --COO--R₇, where R₇ is n-butyl or n-pentyl.

6. The UV-stabilized composition according to claim 5 which comprises additionally an anodic and a cathodic electrochromic compound.

7. The UV-stabilized composition according to claim 6 where said anodic compound is 5,10-dihydro-5,10-dimethylphenazine and where said cathodic compound is 1,1'"'"'-bis(3-phenyl(n-propyl))-4,4'"'"'-dipyridinium bis(tetrafluoroborate).

8. The UV-stabilized composition according to claim 5 wherein the concentration at room temperature in the propylene carbonate of the compound of Formula I is between about 10 mM and about 250 mM.

9. The UV-stabilized composition according to claim 8 wherein the concentration at room temperature in the propylene carbonate of the 5,10-dihydro-5,10-dimethylphenazine is between about 1 mM and about 100 mM, and the concentration at room temperature in the propylene carbonate of the 1,1'"'"'-bis(3-phenyl(n-propyl))-4,4'"'"'-dipyridinium bis(tetrafluoroborate) is between about 1 mM and about 100 mM.

10. The UV-stabilized composition according to claim 1 wherein the solvent is propylene carbonate.

11. The UV-stabilized composition according to claim 10, wherein said at least one electrochromic compound comprises an anodic and a cathodic electrochromic compound.

12. The UV-stabilized composition according to claim 11 where said anodic compound is 5,10-dihydro-5,10-dimethylphenazine and where said cathodic compound is 1,1'"'"'- bis(3-phenyl(n-propyl))-4,4'"'"'-dipyridinium bis(tetrafluoroborate).

13. The UV-stabilized composition according to claim 12 wherein the concentration at room temperature in the propylene carbonate of the 5,10-dihydro-5,10-dimethylphenazine is between about 1 mM and about 100 mM, and the concentration at room temperature in the propylene carbonate of the 1,1'"'"'-bis(3-phenyl(n-propyl))-4,4'"'"'-dipyridinium bis(tetrafluoroborate) is between about 1 mM and about 100 mM.

14. The UV-stabilized composition according to claim 11 wherein, in the compound of Formula I, R₁ is tert-butyl and R₂ is CH₂ --CH₂ --COO--R₇, where R₇ is n-butyl or n-pentyl.

15. The UV-stabilized composition according to claim 10 wherein the concentration at room temperature in the propylene carbonate of the compound of Formula I is between about 10 mM and about 250 mM.

16. The UV-stabilized composition according to claim 1 wherein Formula I is at a concentration at room temperature between about 10 mM and about 250 mM in propylene carbonate, and where said composition further comprises 5,10-dihydro-5,10-dimethylphenazine at a concentration at room temperature in the propylene carbonate of between about 1 mM and about 100 mM, and 1,1'"'"'-bis(3-phenyl(n-propyl))-4,4'"'"'-dipyridinium bis(tetrafluoroborate) at a concentration at room temperature in the propylene carbonate of between about 1 mM and about 100 mM.

17. An electrochromic device comprising a UV-stabilized composition which comprises (a) an aprotic polar solvent, (b) at least one electrochromic compound, and (c) a compound of the formula I ##STR5## wherein R₁ is H, a straight or branched alkyl group containing 1 to 18 carbons, or R₃ --COO--R₄, where R₃ is a single bond, or is a straight or branched alkylene group containing 1-6 carbons and R₄ is a straight or branched alkyl group containing 1-18 carbons, and if R₁ is H or a straight or branched alkyl group containing 1 to 18 carbons, then R₂ is R₅ --COO--R₆, where R₅ is a single bond, or is a straight or branched alkylene group containing 1 to 6 carbons, and R₆ is a straight or branched alkyl group containing 1-18 carbons, and if R₁ is R₃ --COO--R₄, then R₂ is H, a straight or branched alkyl group containing 1 to 18 carbons, or R₅ --COO--R₆.

18. The electrochromic device according to claim 17 wherein the solvent is a liquid at room temperature and is selected from the group consisting of propylene carbonate, gamma-butyrolactone, gamma-valerolactone, and any homogeneous mixture that is liquid at room temperature of any two or more of said solvents or any one or more of said solvents with ethylene carbonate.

19. The electrochromic device according to claim 18, wherein said at least one electrochromic compound comprises an anodic and a cathodic electrochromic compound.

20. The electrochromic device according to claim 19 where said anodic compound is 5,10-dihydro-5,10-dimethylphenazine and where said cathodic compound is 1,1'"'"'-bis(3-phenyl(n-propyl))-4,4'"'"'-dipyridinium bis(tetrafluoroborate).

21. The electrochromic device according to claim 17 wherein, in the compound of Formula I, R₁ is tert-butyl and R₂ is CH₂ --CH₂ --COO--R₇, where R₇ is n-butyl or n-pentyl.

22. The electrochromic device according to claim 17 wherein said solvent is propylene carbonate and Formula I is at a concentration at room temperature between about 30 mM and about 150 mM in propylene carbonate, and where said composition further comprises 5,10-dihydro-5,10-dimethylphenazine at a concentration at room temperature in the propylene carbonate of between about 1 mM and about 100 mM, and 1,1'"'"'-bis(3-phenyl(n-propyl))-4,4'"'"'-dipyridinium bis(tetrafluoroborate) at a concentration at room temperature in the propylene carbonate of between about 1 mM and about 100 mM.

23. An electrochromic medium of reversibly variable transmittance to light which comprises:

(a) a solvent

(b) a cross-linked polymer matrix resulting from crosslinking polymer chains that are formed by polymerizing at least one monomer;

(c) at least one electrochromic compound in solution in said solvent and interspersed in said polymer matrix; and

(d) a compound of the formula I ##STR6## wherein R₁ is H, a straight or branched alkyl group containing 1 to 18 carbons, or R₃ --COO--R₄, where R₃ is a single bond, or is a straight or branched alkylene group containing 1-6 carbons and R₄ is a straight or branched alkyl group containing 1-18 carbons, and if R₁ is H or a straight or branched alkyl group containing 1 to 18 carbons, then R₂ is R₅ --COO--R₆, where R₅ is a single bond, or is a straight or branched alkylene group containing 1 to 6 carbons, and R₆ is a straight or branched alkyl group containing 1-18 carbons, and if R₁ is R₃ --COO--R₄, then R₂ is H, a straight or branched alkyl group containing 1 to 18 carbons, or R₅ --COO--R₆.

24. The electrochromic medium according to claim 23, where said at least one monomer is selected from the group consisting of:

2-isocyanatoethyl methacrylate;

2-isocyanatoethyl acrylate;

vinyl ether n-butyl methyl methacrylate;

tetraethylene glycol vinyl ether;

glycidyl methacrylate;

acetoacetoxyethyl methacrylate and acetoacetoxyethyl acrylate.

25. The electrochromic medium according to claim 24 further including a crosslinker which is selected from the group consisting of:

4,4'"'"'-isopropylidenediphenol;

4,4'"'"'-(1,4 phenylenediisopropylidene) bisphenol;

4,4'"'"'-(1,3 phenylenediisopropylidene) bisphenol;

4,4'"'"'-sulfonyldiphenol;

4'"'"',5,7-trihydroxyflavanone;

4,4'"'"'-(1-phenylethylidene) bisphenol;

4,4'"'"'-cyclohexylidene bisphenol;

4,4'"'"'-(-9-fluorenylidene)diphenol;

4,4'"'"'-(hexafluroisopropylidene) diphenol;

1,3-dihydroxy benzene;

2,2'"'"'-bis(4-hydroxy-3-methylphenyl) propane; and

4,4'"'"'-isopropylidene bis(2,6-dimethyl phenyl).

26. The electrochromic medium according to claim 23 where said polymer chains results from the polymerization of at least two distinct monomers.

27. The electrochromic medium according to claim 26 where said at least two monomers are selected from the group consisting of:

methyl methacrylate;

methyl acrylate;

2-isocyanatoethyl methacrylate;

2-isocyanatoethyl acrylate;

vinyl ether n-butyl methyl methacrylate;

tetraethylene glycol divinyl ether;

glycidyl methacrylate;

acetoacetoxyethyl methacrylate and acetoacetoxyethyl acrylate.

28. The electrochromic medium according to claim 27 where said at least two monomers comprise isocyanatoethyl methacrylate and methyl methacrylate in a ratio from about 1:

3 to about 1;

50.

29. The electrochromic medium according to claim 28 where the ratio of isocyanatoethyl methacrylate to methyl methacrylate is about 1:

10.

30. The electrochromic medium according to claim 28 where said polymer chains formed from at least isocyanato methacrylate and methyl methacrylate are crosslinked by a compound having more than one functional group that contains an active hydrogen.