Stabilized electrochromic media

• US 7,718,096 B2
• Filed: 06/27/2006
• Issued: 05/18/2010
• Est. Priority Date: 06/30/2005
• Status: Active Grant

• Current Assignee: CIBA Specialty Chemicals
• Original Assignee: CIBA Specialty Chemicals
• Inventors: Yale, David, Cliff, Nancy, Kanouni, Mouhcine
• Primary Examiner(s): Kopec; Mark
• Assistant Examiner(s): Nguyen; Khanh Tuan
• Application Number:
  US11/475,699
• Publication Number:
  US 20070002423A1
• Time in Patent Office: 1,421 Days
• Field of Search: 252/500, 252/583, 252/586, 359/265, 359/275, 359/241, 359/245, 525/391, 544/209, 544/198, 546/207, 546/14, 524/110, 524/94, 524/100, 526/256, 526/258, 106/31.43
• US Class Current: 252/583
• CPC Class Codes: C07D 211/94 Oxygen atom, e.g. piperidine N-oxide
• CPC Class Codes: C08K 5/3435 Piperidines
• CPC Class Codes: C09K 2211/1029 containing one nitrogen atom as the heteroatom
• CPC Class Codes: C09K 2211/1033 with oxygen
• CPC Class Codes: C09K 2211/1044 containing two nitrogen atoms as heteroatoms
• CPC Class Codes: C09K 9/02 Organic tenebrescent materials
• CPC Class Codes: G02F 1/167 by electrophoresis
• CPC Class Codes: G02F 2201/086 UV absorbing

Abstract

Disclosed are compositions, which are stabilized against degradation and yellowing during exposure to ultraviolet light by the presence of certain nitroxyl, hydroxyl amine and hydroxyl amine salt additives, a method of stabilizing the compositions by the addition of said additives, to the use of such compositions as media in electroactive devices such as electrochromic and electrophoteric devices, and the electroactive devices comprised of these media.

Claims

1. An electroactive device which device comprises a medium in the electroactive device, which medium composition comprises

i) one or more solvents suitable as a medium in the electroactive device,

ii) an effective amount of one or more additive compounds selected from the group consisting of ultraviolet light absorbers, and

iii) an effective amount of one or more additive compounds selected from the group consisting of nitroxyls, hydroxyl amines and hydroxyl amine salts,

wherein at least one of the one or more nitroxyls, hydroxyl amines and hydroxyl amine salts of component (iii) is a compound of formula I, II or III

2. The device according to claim 1, wherein at least one of the one or more solvents is selected from the group consisting of sulfones, amides, sulfoxides, ethers, polyethers, alcohols, polyols, nitriles, ketones, aldehydes, carboxylic acids, cyclic esters, cyclic carbonates, glycidyl ether carbonates and silicon/polyol co-polymers.

3. The device according to claim 2, wherein at least one of the one or more solvents is selected from the group consisting of 3-methylsulfolane, tetramethylene sulfone, N,N-dimethylformamide, dimethyl sulfoxide, tetraglyme, methanol, ethanol, ethoxyethanol, acetonitrile, glutaronitrile, 3-hydroxypropionitrile, methoxypropionitrile, 3-ethoxypropionitrile 2-methylglutaronitrile, cyanoethyl sucrose, acetone, methyl ethyl ketone, methyl amyl ketone, cyclopentanone, cyclohexanone, benzoyl acetone, 4-hydroxy-4-methyl-2-pentanone, acetophenone, acetic acid, beta-propiolactone, 2-acetylbutyrolactone, gamma-butyrolactone, gamma-valerolactone, 4-ethenyl-1,3-dioxalane-2-one, propylene carbonate, ethylene carbonate and 1,2-butylene carbonate.

4. The device according to claim 3, wherein at least one of the one or more solvents is selected from the group consisting of 3-methylsulfolane, tetramethylene sulfone, tetraglyme, acetonitrile, glutaronitrile, 3-hydroxypropionitrile, methoxypropionitrile, 3-ethoxypropionitrile, 2-methylglutaronitrile, acetone, methyl ethyl ketone, methyl amyl ketone, cyclopentanone, cyclohexanone, 4-ethenyl-1,3-dioxalane-2-one, propylene carbonate, ethylene carbonate and 1,2-butylene carbonate.

5. The device according to claim 1, wherein at least one of the one or more ultraviolet light absorbers is selected from the group consisting of hydroxyphenylbenzotriazoles, benzophenones, and tris-aryl-s-triazines.

6. The device according to claim 1, wherein at least one component that is selected from nitroxyls, hydroxyl amines and hydroxyl amines salts is a nitroxyl.

7. The device according to claim 1, wherein at least one component that is selected from nitroxyls, hydroxyl amines and hydroxyl amine salts is a hydroxyl amine.

8. The device according to claim 1, wherein at least one component that is selected from nitroxyls, hydroxyl amines and hydroxyl amine salts is a hydroxyl amine salt.

9. The device according to claim 1 wherein X is phosphate, phosphonate, carbonate, bicarbonate, nitrate, chloride, bromide, bisulfite, sulfite, bisulfate, sulfate, borate, formate, acetate, benzoate, citrate, oxalate, tartrate, acrylate, polyacrylate, fumarate, maleate, itaconate, glycolate, gluconate, malate, mandelate, tiglate, ascorbate, polymethacrylate, a carboxylate of nitrilotriacetic acid, hydroxyethylethylenediaminetriacetic acid, ethylenediaminetetraacetic acid or of diethylenetriaminepentaacetic acid, a diethylenetriaminepentamethylenephosphonate, an alkylsulfonate or an arylsulfonate.

10. A The device according to claim 1 wherein at least one of the one or more nitroxyls, hydroxyl amines and hydroxyl amine salts of component (iii) is selected from the group consisting of

bis(1-oxyl-2,2-6-6-tetramethylpiperidin-4-yl) sebacate;

bis(1-hydroxy-2,2-6-6-tetramethylpiperidin-4-yl) sebacate;

1-hydroxy-2,2-6-6-tetramethyl-4-acetoxypiperidinium citrate;

1-oxyl-2,2,6,6-tetramethyl-4-acetamidopiperidine;

1-hydroxy-2,2,6,6-tetramethyl-4-acetamidopiperidine;

1-hydroxy-2,2,6,6-tetramethyl-4-acetamidopiperidinium bisulfate;

1-oxyl-2,2,6,6-tetramethyl-4-oxo-piperidine;

1-hydroxy-2,2,6,6-tetramethyl-4-oxo-piperidine;

1-hydroxy-2,2,6,6-tetramethyl-4-oxo-piperidinium acetate;

1-oxyl-2,2,6,6-tetramethyl-4-methoxy-piperidine;

1-hydroxy-2,2,6,6-tetramethyl-4-methoxy-piperidine;

1-hydroxyl-2,2,6,6-tetramethyl-4-methoxy-piperidinium acetate;

1-oxyl-2,2,6,6-tetramethyl-4-acetoxypiperidine;

1-hydroxy-2,2,6,6-tetramethyl-4-acetoxypiperidine;

1-oxyl-2,2,6,6-tetramethyl-4-propoxy-piperidine;

1-hydroxy-2,2,6,6-tetramethyl-4-propoxy-piperidinium acetate;

1-hydroxy-2,2,6,6-tetramethyl-4-propoxy-piperidine;

1-oxyl-2,2,6,6-tetramethyl-4-(2-hydroxy-4-oxapentoxy) piperidine;

1-hydroxy-2,2,6,6-tetramethyl-4-(2-hydroxy-4-oxapentoxy) piperidinium acetate;

1-oxyl-2,2,6,6-tetramethyl-4-hydroxypiperidine;

1-hydroxy-2,2,6,6-tetramethyl-4-hydroxypiperidine;

1-hydroxy-2,2,6,6-tetramethyl-4-hydroxypiperidinium chloride;

1-hydroxy-2,2,6,6-tetramethyl-4-hydroxypiperidinium acetate;

1-hydroxy-2,2,6,6-tetramethyl-4-hydroxypiperidinium bisulfate;

1-hydroxy-2,2,6,6-tetramethyl-4-hydroxypiperidinium citrate;

bis(1-hydroxy-2,2,6,6-tetramethyl-4-hydroxypiperidinium) citrate;

tris(1-hydroxy-2,2,6,6-tetramethyl-4-hydroxypiperidinium) citrate;

tetra(1-hydroxy-2,2,6,6-tetramethyl-4-hydroxypiperidinium) ethylenediaminetetraacetate;

tetra(1-hydroxy-2,2,6,6-tetramethyl-4-acetamidopiperidinium) ethylenediaminetetraacetate;

tetra(1-hydroxy-2,2,6,6-tetramethyl-4-oxopiperidinium) ethylenediaminetetraacetate;

penta(1-hydroxy-2,2,6,6-tetramethyl-4-hydroxypiperidinium) diethylenetriaminepentaacetate;

penta(1-hydroxy-2,2,6,6-tetramethyl-4-acetamidopiperidinium) diethylenetriaminepentaacetate;

penta(1-hydroxy-2,2,6,6-tetramethyl-4-oxopiperidinium) diethylenetriaminepentaacetate;

tri(1-hydroxy-2,2,6,6-tetramethyl-4-hydroxypiperidinium) nitrilotriacetate;

tri(1-hydroxy-2,2,6,6-tetramethyl-4-acetamidopiperidinium) nitrilotriacetate;

tri(1-hydroxy-2,2,6,6-tetramethyl-4-oxopiperidinium) nitrilotriacetate;

penta(1-hydroxy-2,2,6,6-tetramethyl-4-hydroxypiperidinium) diethylenetriaminepentamethylenephosphonate;

penta(1-hydroxy-2,2,6,6-tetramethyl-4-acetamidopiperidinium) diethylenetriaminepentamethylenephosphonate; and

penta(1-hydroxy-2,2,6,6-tetramethyl-4-oxopiperidinium) diethylenetriaminepentamethylenephosphonate.

11. The device according to claim 1 wherein at least one of the one or more nitroxyls, hydroxyl amines and hydroxyl amine salts of component (iii) is selected from the group consisting of

bis(1-oxyl-2,2-6-6-tetramethylpiperidin-4-yl) sebacate;

1-oxyl-2,2,6,6-tetramethyl-4-acetamidopiperidine;

1-oxyl-2,2,6,6-tetramethyl-4-oxo-piperidine;

1-oxyl-2,2,6,6-tetramethyl-4-methoxy-piperidine;

1-oxyl-2,2,6,6-tetramethyl-4-acetoxypiperidine;

1-oxyl-2,2,6,6-tetramethyl-4-propoxy-piperidine;

1-oxyl-2,2,6,6-tetramethyl-4-(2-hydroxy-4-oxapentoxy)piperidine;

1-oxyl-2,2,6,6-tetramethyl-4-hydroxypiperidine.

12. The electrochromic device according to claim 11, wherein the medium is an electrochromic medium which further comprises at least one anodic material;

at least one cathodic material, wherein either or both of the anodic and cathodic materials are electroactive and at least one of the anodic and cathodic materials is electrochromic.

13. A The device according to claim 1 wherein at least one of the one or more nitroxyls, hydroxyl amines and hydroxyl amine salts of component (iii) is selected from the group consisting of

bis(1-hydroxy-2,2-6-6-tetramethylpiperidin-4-yl) sebacate;

1-hydroxy-2,2,6,6-tetramethyl-4-acetamidopiperidine;

1-hydroxy-2,2,6,6-tetramethyl-4-oxo-piperidine;

1-hydroxy-2,2,6,6-tetramethyl-4-methoxy-piperidine;

1-hydroxy-2,2,6,6-tetramethyl-4-acetoxypiperidine;

1-hydroxy-2,2,6,6-tetramethyl-4-propoxy-piperidine;

1-hydroxy-2,2,6,6-tetramethyl-4-hydroxypiperidine.

14. The device according to claim 1 wherein at least one of the one or more nitroxyls, hydroxyl amines and hydroxyl amine salts of component (iii) is selected from the group consisting of

1-hydroxy-2,2-6-6-tetramethyl-4-acetoxypiperidinium citrate;

bis(1-hydroxy-2,2,6,6-tetramethyl-4-acetoxypiperidinium) citrate;

tris(1-hydroxy-2,2,6,6-tetramethyl-4-acetoxypiperidinium) citrate;

1-hydroxy-2,2,6,6-tetramethyl-4-acetamidopiperidinium bisulfate;

1-hydroxy-2,2,6,6-tetramethyl-4-oxo-piperidinium acetate;

1-hydroxy-2,2,6,6-tetramethyl-4-oxo-piperidinium citrate;

bis(1-hydroxy-2,2,6,6-tetramethyl-4-oxo-piperidinium) citrate;

tris(1-hydroxy-2,2,6,6-tetramethyl-4-oxo-piperidinium) citrate;

1-hydroxyl-2,2,6,6-tetramethyl-4-methoxy-piperidinium acetate;

1-hydroxy-2,2,6,6-tetramethyl-4-propoxy-piperidinium acetate;

1-hydroxy-2,2,6,6-tetramethyl-4-(2-hydroxy-4-oxapentoxy)piperidinium acetate;

1-hydroxy-2,2,6,6-tetramethyl-4-hydroxypiperidinium chloride;

1-hydroxy-2,2,6,6-tetramethyl-4-hydroxypiperidinium acetate;

1-hydroxy-2,2,6,6-tetramethyl-4-hydroxypiperidinium bisulfate;

1-hydroxy-2,2,6,6-tetramethyl-4-hydroxypiperidinium citrate;

bis(1-hydroxy-2,2,6,6-tetramethyl-4-hydroxypiperidinium) citrate;

tris(1-hydroxy-2,2,6,6-tetramethyl-4-hydroxypiperidinium) citrate;

1-hydroxy-2,2,6,6-tetramethyl-4-acetamidopiperidinium citrate;

bis(1-hydroxy-2,2,6,6-tetramethyl-4-acetamidopiperidinium) citrate;

tris(1-hydroxy-2,2,6,6-tetramethyl-4-acetamidopiperidinium) citrate;

tetra(1-hydroxy-2,2,6,6-tetramethyl-4-hydroxypiperidinium) ethylenediaminetetraacetate;

tetra(1-hydroxy-2,2,6,6-tetramethyl-4-acetamidopiperidinium) ethylenediaminetetraacetate;

tetra(1-hydroxy-2,2,6,6-tetramethyl-4-oxopiperidinium) ethylenediaminetetraacetate;

penta(1-hydroxy-2,2,6,6-tetramethyl-4-hydroxypiperidinium) diethylenetriaminepentaacetate;

penta(1-hydroxy-2,2,6,6-tetramethyl-4-acetamidopiperidinium) diethylenetriaminepentaacetate;

penta(1-hydroxy-2,2,6,6-tetramethyl-4-oxopiperidinium) diethylenetriaminepentaacetate;

tri(1-hydroxy-2,2,6,6-tetramethyl-4-hydroxypiperidinium) nitrilotriacetate;

tri(1-hydroxy-2,2,6,6-tetramethyl-4-acetamidopiperidinium) nitrilotriacetate;

tri(1-hydroxy-2,2,6,6-tetramethyl-4-oxopiperidinium) nitrilotriacetate;

penta(1-hydroxy-2,2,6,6-tetramethyl-4-hydroxypiperidinium) diethylenetriaminepentamethylenephosphonate;

penta(1-hydroxy-2,2,6,6-tetramethyl-4-acetamidopiperidinium) diethylenetriaminepentamethylenephosphonate; and

penta(1-hydroxy-2,2,6,6-tetramethyl-4-oxopiperidinium) diethylenetriaminepentamethylenephosphonate.

15. The device according to claim 1, wherein at least one of the one or more nitroxyls, hydroxyl amines and hydroxyl amine salts of component (iii) is a hydroxyl amine or hydroxyl amine salt of formula IV or V

R₁R₂N—

OH 

 

(IV)

(R₁R₂N—

OH)·

(HY) 

 

(V)

where

R₁ is alkyl of 1 to 36 carbon atoms, cycloalkyl of 5 to 12 carbon atoms or aralkyl of 7 to 9 carbon atoms;

or R₁ is said alkyl, cycloalkyl or aralkyl substituted by one to six alkyl of 1 to 12 carbon atoms, halogen, cyano, E₁O—

, E₁CO—

, E₁OCO—

, E₁COO—

, E₁S—

, E₁SO—

, E₁SO₂—

, —

NH₂, —

NHE₁, —

NE₁E₂, —

PO(OE₁)(OE₂) or —

OPO(OE₁)(OE₂) groups;

R₂ is hydrogen or independently has the same meaning as R₁, where at least one of R₁ and R₂contains a hydrogen alpha to the —

NOH moiety;

or

R₁ and R₂ together form a C_2-12heterocyclic ring which contains at least one carbon substituted hydrogen alpha to the —

NOH moiety, where said C_2-12heterocyclic ring is unsubstituted or is substituted by one to three alkyl of 1 to 12 carbon atoms, halogen, cyano, E₁O—

, E₁CO—

, E₁OCO—

, E₁COO—

, E₁S—

, E₁SO—

, E₁SO₂—

, —

NH₂, —

NHE₁, —

NE₁E₂,

—

PO(OE₁)(OE₂) or —

OPO(OE₁)(OE₂) groups;

or where said C_2-12heterocyclic ring is interrupted by one to three —

O—

, —

NE₁—

, —

CO—

, —

CONE₁-, —

S—

, —

SO—

, —

SO₂—

, —

COO—

, —

PO₃—

or —

PO₄E₁ groups;

or where said heterocyclic ring is both substituted and interrupted by said groups;

E₁ and E₂ independently are hydrogen, alkyl of 1 to 4 carbon atoms or alkyl of 1 to 4 carbon atoms substituted by one to three hydroxyl groups;

or E₁ and E₂ independently are an oligomer of poly(ethylene glycol) or poly(propylene glycol) terminated by hydroxyl, methoxy, acetate or propionate, where the oligomer has a molecular weight up to about 500, and

X is an inorganic or organic anion, and

where the total charge of cations h is equal to the total charge of anions j.

16. The device according to claim 15 wherein X is phosphate, phosphonate, carbonate, bicarbonate, nitrate, chloride, bromide, bisulfite, sulfite, bisulfate, sulfate, borate, formate, acetate, benzoate, citrate, oxalate, tartrate, acrylate, polyacrylate, fumarate, maleate, itaconate, glycolate, gluconate, malate, mandelate, tiglate, ascorbate, polymethacrylate, a carboxylate of nitrilotriacetic acid, hydroxyethylethylenediaminetriacetic acid, ethylenediaminetetraacetic acid or of diethylenetriaminepentaacetic acid, a diethylenetriaminepentamethylenephosphonate, an alkylsulfonate or an arylsulfonate.

17. The device according to claim 1 wherein the ultraviolet light absorbers and the additive selected from nitroxyls, hydroxyl amines and hydroxyl amine salts, in total, are present from about 0.05% to about 30% by weight, based on the weight of the solvent.

18. The device according to claim 1 wherein at least one of the one or more solvents is selected from the group consisting of esters, epoxides, vinyl ethers, aromatic hydrocarbons, halogenated organic solvents, saturated linear or branched hydrocarbons, silicone oils, and low molecular weight halogen-containing polymers.

19. An electroactive device according to claim 1, wherein the electroactive device is an electrochromic device.

20. A method of preparing a stabilized medium useful in electroactive devices, which method comprises adding an effective amount of one or more additive compounds selected from the group consisting of nitroxyls, hydroxyl amines and hydroxyl amine salts wherein at least one of the one or more nitroxyls, hydroxyl amines and hydroxyl amine salts is a compound of formula I, II or III