Protic-soluble organic electrochromic compounds

Patent metadata

Field	Value
Publication number	US-9939701-B2
Application number	US-201615065808-A
Country	US
Kind code	B2
Filing date	Mar 9, 2016
Priority date	Nov 20, 2015
Publication date	Apr 10, 2018
Grant date	Apr 10, 2018

Abstract

Protic-soluble electrochromic materials, ion-paired electrochromic materials including protic-soluble electrochromic materials, as well as electrochromic media and electrochromic devices incorporating such materials, are provided. The use of protic solvent mixtures, especially mixtures incorporating water, allows for the use of a wider variety of substrate materials. For example, plastics that may be soluble in organic aprotic solvent systems may be used in water-based devices.

First claim

What is claimed is:

1. An electrochromic medium comprising a cathodic material, an anodic material, and a liquid or gel that comprises a protic solvent; wherein the electrochromic medium comprises at least one of
a cathodic protic-soluble electrochromic material represented by Formula (I):

wherein
R 1 and R 2 are each independently —(CH 2 ) m —CO 2 − , —(CH n )—P(O)(OH)(O − ), —(CH 2 ) p —OP(O)(OH)(O − ), or —(CH 2 ) q —S(O) 2 O − ;
R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , and R 10 are each independently H, OH, O-alkyl, F, Cl, Br, I, CN, NO 2 , alkyl, or aryl;
n is 2, 3, 4, 5, 6, 7, 8, 9, or 10;
m, p, and q are each independently 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10;

a cathodic protic-soluble electrochromic material represented by Formula (II):

wherein
R 11 and R 12 are each independently an alkyl group substituted with a N + (R 21 ) 3 or P + (R 22 ) 3 ;
R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , and R 20 are each independently H, OH, O-alkyl, F, Cl, Br, I, CN, NO 2 , alkyl, or aryl;
R 21 and R 22 are independently at each occurrence be alkyl substituted with a carboxylate, phosphonate, phosphate, or sulfonate or phenyl substituted with a carboxylate, phosphonate, phosphate, or sulfonate; and
M 1 is independently at each occurrence an alkali metal, an alkali earth metal, or an ammonium compound;

an anodic protic-soluble electrochromic material of represented by Formula (III):

wherein
R 23 and R 28 are each independently alkyl or alkyl substituted with a carboxylate, phosphonate, phosphate, or sulfonate, provided that at least one is alkyl substituted with a carboxylate, phosphonate, phosphate, or sulfonate;
R 24 , R 25 , R 26 , R 27 , R 29 , R 30 , R 31 , and R 32 are each independently H or alkyl;
x is an integer corresponding to the number of carboxylate, phosphonate, phosphate, sulfonate groups; and

M 2 is independently at each occurrence an alkali metal, an alkali earth metal, or an ammonium compound; and
an anodic protic-soluble electrochromic material represented by Formula (V), (VI), or (VII)

wherein
E 1 , E 2 , E 3 , E 4 , and E 5 are each independently O, S, or NR 47 ;
R 38 , R 47 , R 65 , and R 66 are independently at each occurrence an alkyl group substituted with a carboxylate, phosphonate, phosphate, or sulfonate;
R 39 , R 40 , R 41 , R 42 , R 43 , R 44 , R 45 , R 46 , R 48 , R 49 , R 50 , R 51 , R 52 , R 53 , R 54 , R 55 , R 56 , R 57 , R 58 , R 59 , R 60 , R 61 , R 62 , R 63 , R 67 , R 68 , R 69 , R 70 , R 71 , R 72 , R 73 , R 74 , R 75 , and R 76 are each independently H, F, Cl, Br, I, CN, OH, O-alkyl, SH, S-alkyl, NO 2 , alkyl, aryl, or amino, or any two adjacent groups of join to form a monocyclic, polycyclic, or heterocyclic group;
R 64 is alkylene;
y, y′, and y″ are each independently an integer corresponding to the number of carboxylate, phosphonate, phosphate, sulfonate groups; and
M 4 , M 5 , and M 6 are independently at each occurrence an alkali metal, an alkali earth metal, or an ammonium compound.

2. The electrochromic medium of claim 1 , wherein in Formula (II)
R 12 and R 21 are each independently —(CH 2 ) s —CO 2 − , —(CH 2 ) t —P(O)(OH)(O − ), —(CH 2 ) u —OP(O)(OH)(O − ), or —(CH 2 ) w —S(O) 2 O − ; and
s, t, u, and w are each independently 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10.

3. The electrochromic medium of claim 1 , wherein in Formula (III)
R 23 and R 28 are each independently alkyl, —(CH 2 ) m′ —CO 2 − , —(CH 2 ) n′ —P(O)(OH)(O − ), —(CH 2 ) p′ —OP(O)(OH)(O − ), or —(CH 2 ) q′ —S(O) 2 O − ; and
m′, n′, p′, and q′ are each independently 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10.

4. The electrochromic medium of claim 1 , wherein the cathodic protic-soluble electrochromic material of Formula (I) is

or a mixture thereof.

5. The electrochromic medium of claim 1 , wherein the anodic protic-soluble electrochromic material of Formula (III) is

6. The electrochromic medium of claim 1 , wherein the anodic protic-soluble electrochromic material of Formula (V) is

or a mixture thereof.

7. The electrochromic medium of claim 1 , wherein the protic solvent comprises an alcohol, a carboxylic acid, a primary amino compound, a secondary amino compound, water, or a mixture of any two or more thereof.

8. The electrochromic medium of claim 1 , wherein the protic solvent comprises methanol, ethanol, isopropanol, trifluoroethanol, butanol, ethylene glycol, propylene glycol, water, or a mixture of any two or more thereof.

9. The electrochromic medium of claim 1 , wherein the protic solvent comprises a diol.

10. The electrochromic medium of claim 1 , wherein the amount of protic solvent in the liquid or gel is from about 40 wt % to about 100 wt %.

Assignees

• Gentex Corp

Inventors

• Baumann Kelvin L
• Lin Rongguang
• Giri Punam
• Franz Sue

Classifications

• C09K11/06

  containing organic luminescent materials · CPC title

• C09K2211/1029

  containing one nitrogen atom as the heteroatom · CPC title

• C07D213/22

  containing two or more pyridine rings directly linked together, e.g. bipyridyl · CPC title

• G02F1/15 Primary

  based on an electrochromic effect · CPC title

• G02F1/15165

  Polymers · CPC title