ELECTROCHROMIC ELECTROLYTE BLENDS

• US 20090078917A1
• Filed: 06/23/2006
• Published: 03/26/2009
• Est. Priority Date: 06/23/2006
• Status: Active Grant

• Current Assignee: E. I. du Pont de Nemours and Company (Corteva, Inc.)
• Original Assignee: E. I. du Pont de Nemours and Company (Corteva, Inc.)
• Inventors: Percec, Simona, Tilford, Susan H.
• Granted Patent: US 7,988,885 B2
• Time in Patent Office: Days
• US Class Current: 252/583
• CPC Class Codes: C09K 2211/1007 Non-condensed systems
• CPC Class Codes: C09K 2211/1011 Condensed systems
• CPC Class Codes: C09K 2211/1029 containing one nitrogen atom as the heteroatom
• 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 2001/164 the electrolyte is made of polymers

Abstract

The present invention is directed to electrochromic electrolyte polymer blends. These blends comprise an amorphous polymer and an electrochromophore component. The electrochromophore component comprises a polyalkylene polymer copolymerized with an electrochromic moiety. The blends can be used to make elastomeric films and coatings that can be used in laminates, which can be used to form manufactured articles such as architectural and vehicular glazing, eyewear, displays and signage.

Claims

1. A composition comprising:

a. an amorphous (co)polymer comprising one or more repeat units, (I),

wherein

p and q are independently selected from integers from 0 to 10,000, provided that at least one of p and q is greater than 0;

R¹ is selected from the group consisting of H, and substituted and unsubstituted alkyl;

R² is selected from the group consisting of H, OH, R¹, OR¹, OC(O)R⁴, COOR¹, and COOR³;

R³ is selected from the group consisting of H, Na, and K;

R⁴ is substituted or unsubstituted alkyl; and

b. an electrochromophore component comprising polyalkyleneoxide and an electrochromic moiety; and

c. an ion source; and

d. an electron mediator.

3. The composition of claim 1, wherein the electron mediator is selected from the group consisting of metallocenes and phenazines.

4. The composition of claim 1, further comprising a plasticizer.

5. The composition of claim 4, wherein the plasticizer is selected from the group consisting of polyethylene glycol and its derivatives;

adipates;

phosphates;

phthalates;

triaryl phosphate ester blends;

sebacates; and

sulfonamides.

6. The composition of claim 4, wherein the plasticizer is selected from the group consisting of tetraethylene glycol diheptanoate;

triethylene glycol-di-2-ethyl hexanoate;

2-ethyl-1-hexanol;

dihexyl adipate;

dioctyl adipate;

2-ethylhexyl diphenyl phosphate;

isodecyl diphenyl phosphate;

tert-butylphenyl diphenyl phosphate;

tricresyl phosphate;

triphenyl phosphate;

alkyl benzyl phthalate;

butylbenzyl phthalate;

dibutyl phthalate;

dioctyl phthalate;

dibutyl sebacate;

toluene sulfonamide and n-ethyl sulfonamide.

7. The composition of claim 1, further comprising conductive particles.

8. The composition of claim 7, wherein the conductive particles comprise materials selected from the group consisting of metals, ITO, carbon nanotubes, TiO₂, polyanilines, polypyrroles, polythiophenes and polythiophene copolymers.

9. The composition of claim 8, wherein the particle size is 10 nm-100 □

m.

10. The composition of claim 1, wherein the amorphous (co)polymer comprises at least one repeat unit of —

(CH₂CHOH)— and

at least one repeat unit having the structure;

11. The composition of claim 1, wherein the amorphous (co)polymer comprises repeat units derived from ethylene, methacrylic acid and salt forms of methacrylic acid.

12. The composition of claim 1, wherein the polyalkylene oxide is selected from the group consisting of polyethylene oxide, poly(propylene oxide), copolymers of poly(ethylene oxide), poly(propylene oxide and blends thereof.

13. The composition of claim 1, wherein the electrochromic moiety is covalently attached to the polyalkylene oxide.

14. The composition of claim 1, wherein the electrochromic moiety is selected from the group consisting of polyanilines, polypyrroles, polythiophenes, polythiophene copolymers, polycarbazole, carbazoles, methoxybiphenyl compounds, quinones, diphenylamines, phenylene diamines, pyrazolines, tetracyanoquinodimethane, and tetrathiafulvalene.

15. The composition of claim 1, wherein the electrochromic moiety comprises a substituted or unsubstituted aromatic or heteroaromatic group corresponding to a structure selected from the group consisting of structures IV-IX:

16. The composition of claim 1, wherein the electrochromic group is a derivative of 4,4′

-dipyridyl.

17. The composition of claim 1, wherein the electrochromic moiety comprises a functional group selected from the group consisting of —

SO₃K and —

ClO₃Li.

2. (canceled)

18. A laminate comprising:

a. a first electrically conductive substrate; and

b. an electrochromic layer in contact with the substrate, comprising;

i. an amorphous (co)polymer comprising one or more repeat units, (I),

wherein

p and q are independently selected from integers from 0 to 10,000, provided that at least one of p and q is greater than 0;

R¹ is selected from the group consisting of H, and substituted and unsubstituted alkyl;

R² is selected from the group consisting of H, OH, R¹, OR¹, OC(O)R⁴, COOR¹, and COOR³;

R³ is selected from the group consisting of H, Na, and K;

R⁴ is substituted or unsubstituted alkyl; and

ii. an electrochromophore component comprising polyalkyleneoxide and an electrochromic moiety;

iii. an ion source; and

iv. an electron mediator.

19. The laminate of claim 18, further comprising a second electrically conductive substrate in contact with the electrochromic layer.

20. The laminate of claim 19, wherein at least one electrically conductive substrate comprises a transparent, non-conductive substrate and an electrically conductive layer in contact with the electrochromic layer.

21. The laminate of claim 20 wherein the non-conductive substrate comprises a polymer selected from the group consisting of polyesters, polyimides, polyamides, polycarbonate, polyphenylene oxide, polysulfones, cellulosics, and polystyrene/polyphenylene oxide.

22. The laminate of claim 20, wherein the electrically conductive layer comprises material selected from the group consisting of ITO, titanium oxide, copper, aluminum, gold, platinum, silver, cobalt, palladium, iridium, and rhodium.

23. A manufactured article comprising the laminate of claim 19.

24. An article of claim 23, selected from the group consisting of:

architectural glazing, automotive glazing, mirrors, signage, and displays.