Electrochromic composition

Patent metadata

Field	Value
Publication number	US-9841652-B2
Application number	US-201415022821-A
Country	US
Kind code	B2
Filing date	Sep 16, 2014
Priority date	Sep 17, 2013
Publication date	Dec 12, 2017
Grant date	Dec 12, 2017

Abstract

The present invention relates to an electrochromic composition comprising at least one reducing compound, at least one oxidizing compound which is selected from specific viologen derivatives, and at least one dye. Said composition can be used as a variable transmittance medium for the manufacture of an optical article, such as an ophthalmic lens.

First claim

The invention claimed is:

1. An electrochromic composition comprising:
at least one reducing compound;
at least one dye;
at least one electrochromic oxidizing compound selected from viologen derivatives of formula (I)

at least one least one electrochromic oxidizing compound selected from viologen derivatives of formula (II)

wherein
R 1 and R 2 are each independently selected from optionally substituted phenyl groups;
R 3 , R 4 , R 5 and R 6 are each independently selected from H, alkyl, alkoxy, alkylthio, haloalkyl, haloalkoxy, haloalkythio, polyakylenoxy, alkoxycarbonyl, aryl, substituted aryl, heteroaryl and substituted heteroaryl, wherein the alkyl group may be substituted by one or more substituents independently selected from alkoxy, cycloalkyl, aryl, substituted aryl, heteroaryl and substituted heteroaryl;
n, p, q and r are each independently an integer from 0 to 4, wherein when n, p, q or r are two or more, each of the R 3 , each of the R 4 , each of the R 5 or each of the R 6 may be identical or different;
A and B are respectively selected from nitrogen and —N + (R 7a )—, and from nitrogen and —N + (R 7b )—, wherein R 7a and R 7b are independently selected from:
alkyl which may be substituted by one or more groups independently selected from halogen, alkoxy, cycloalkyl, vinyl, allyl, aryl, substituted aryl, heteroaryl and substituted heteroaryl;
aryl and heteroaryl which may be both substituted by one or more groups independently selected from:
halogen, cyano, nitro, alkyl, haloalkyl, arylalkyl, cycloalkyl, cycloalkylalkyl and heterocycloalkylalkyl, alkenyl, alkynyl, allyl, vinyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, —N(aryl) 2 , —N(aryl)CO(aryl), —CO-aryl and —CO-substituted aryl;
—OR 8 , —SR 8 , —S(O)R 8 , —S(O 2 )R 8 , —S(O 2 )NR 8 R 9 , —NR 8 R 9 , —NR 8 COR 9 , —NR 8 CO(aryl), —NR 8 aryl, —CH 2 OR 8 , —CH 2 SR 8 , —CH 2 R 8 , —CO—R 8 and —CO 2 R 8 wherein R 8 and R 9 are independently selected from H, alkyl, haloalkyl, arylalkyl, cycloalkyl, cycloalkylalkyl and heterocycloalkylalkyl;
—S(O 2 )NR 10 R 11 and —NR 10 R 11 , wherein R 10 and R 11 form together with the nitrogen atom to which they are linked a saturated 5 to 7 membered heterocycloalkyl which may comprise in addition to the nitrogen atom one further heteroatom selected from oxygen, nitrogen and sulphur, and which may be optionally substituted by one or two groups independently selected from halogen, —R 8 , —OR 8 , and —NR 8 R 9 , wherein R 8 and R 9 are as defined above;
—V—W—R 12 wherein:
V is selected from oxygen, —N(R 8 )—, sulphur, —S(O)— and —S(O 2 )— wherein R 8 is as defined above;
W is alkylene, which may be substituted by one or more groups independently selected from halogen and alkoxy; and
R 12 is selected from —OR 8 , —NR 8 (alkyl) and —SR 8 wherein R 8 is as defined above; and

—OC(O)—R 13 wherein R 13 is selected from alkyl, haloalkyl, alkenyl, —W—R 12 , and aryl group which may be substituted by 1 to 4 groups selected from halogen, —R 8 , —OR 8 , —SR 8 , —NR 8 R 9 , —NR 10 R 11 , —CO—R 8 , —C(O)OR 8 , wherein R 8 , R 9 , R 10 , R 11 , R 12 and W are as defined above;

Z is selected from:
alkylene;
cycloalkylene; and
a bivalent groups of formula —R 14 —Y—R 15 —, wherein
R 14 and R 15 are each independently selected from single bond, alkylene and cycloalkylene; and
Y is selected from arylene, cycloalkylene, heteroarylene, arylene-arylene or arylene-CR′R″-arylene wherein R′ and R″ form together with the carbon to which they are linked a carbocyclic group;

wherein said alkylene, cycloalkylene, arylene, heteroarylene and carbocyclic groups may be substituted by one or more substituents selected from halogen, alkyl, alkoxy, alkylthio, hydroxyalkyl, acyloxy, cycloalkyl, aryl, substituted aryl, aryloxy heteroaryl and substituted heteroaryl;

m is 2 if A and B are nitrogen, 3 if one of A and B is nitrogen and the other is not nitrogen, and 4 if both A and B are not nitrogen; and
X″ is a counterion.

2. The electrochromic composition according to claim 1 , wherein Z is selected from C 1 -C 12 alkylene, aryl substituted C 1 -C 12 alkylene, phenylene, naphthylene, (C 1 -C 4 alkylene)-phenylene-(C 1 -C 4 alkylene), (C 1 -C 4 alkylene)-naphthylene-(C 1 -C 4 alkylene), quinoxaline-2,3-diyl, (C 1 -C 4 alkylene)-quinoxaline-2,3-diyl-(C 1 -C 4 alkylene), phenylene-phenylene, (C 1 -C 4 alkylene)-phenylene-phenylene-(C 1 -C 4 alkylene) and phenylene-fluorenylene-phenylene, preferably Z is selected from —CH 2 —, —(CH 2 ) 2 —, —(CH 2 ) 3 —, —(CH 2 ) 4 —, —(CH 2 ) 5 —, —CH 2 —CH(CH 3 )—CH 2 —, —CH 2 —CH(CH 2 Phenyl)-CH 2 —, —(CH 2 ) 2 —CH(CH 3 )—CH 2 —, —(CH 2 ) 3 —CH(CH 3 )—CH 2 —, —(CH 2 ) 2 —CH(CH 3 )—(CH 2 ) 2 —,

3. The electrochromic composition according to claim 1 , wherein R 3 , R 4 , R 5 and R 6 are each independently selected from C 1 -C 4 alkyl, C 1 -C 4 alkoxycarbonyl, alkanoyl, aroyl, aryl and heteroaryl, wherein the aryl and heteroaryl may be substituted by one or more substituents selected from C 1 -C 4 alkyl and C 1 -C 4 haloalkyl, preferably, R 3 , R 4 , R 5 and R 6 are each independently selected from methyl, ethoxycarbonyl, phenyl, p-methylphenyl and p-trifluoromethylphenyl.

4. The electrochromic composition according to claim 1 , wherein the counterion X − is selected from halide, tetrafluoroborate, tetraphenylborate, hexafluorophosphate, nitrate, methanesulfonate, trifluoromethane sulfonate, toluene sulfonate, hexachloroantimonate, bis(trifluoromethanesulfonyl)imide, perchlorate, acetate and sulfate.

5. The electrochromic composition according to claim 1 , wherein at least one of the viologen derivatives is selected from compounds of formula (III):

wherein Z, and X − are as defined in formula (II), and R 16 and R 17 are selected from alkyl and optionally substituted phenyl groups.

6. The electrochromic composition according to claim 1 , wherein at least one of the viologen derivatives is selected from compounds of formula (IV):

wherein R 4 , R 5 , Z, A, B, m and X − are as defined in formula (II) and at least one of R 4 and R 5 is not H.

7. The electrochromic composition according to claim 1 , wherein said viologen derivatives are selected from compounds I-1 to 1-50, III-1 to 111-18 and IV-1 and IV-14:

Compound
Formula

I-1

I-2

I-3

Assignees

• Essilor Int

Inventors

• Biver Claudine
• Archambeau Samuel
• Berit-Debat Fabien

Classifications

• G02C7/101

  having an electro-optical light valve (electro-optical elements per se G02F) · CPC title

• G02F2001/1502

  complementary cell · CPC title

• G02F1/15165

  Polymers · CPC title

• C09K9/02

  Organic tenebrescent materials · CPC title

• C09K2211/1007

  Non-condensed systems · CPC title