AMORPHOUS POLYMERS WITH PENDANT CHROMOGENIC GROUPS

• US 20090279160A1
• Filed: 06/23/2006
• Published: 11/12/2009
• Est. Priority Date: 06/23/2006
• Status: Active Grant

• Current Assignee: DuPont Safety & Construction, Inc. (DuPont de Nemours, Inc.)
• Original Assignee: E. I. du Pont de Nemours and Company (Corteva, Inc.)
• Inventors: Percec, Simona, Tilford, Susan H.
• Granted Patent: US 8,287,767 B2
• Time in Patent Office: Days
• US Class Current: 359/265
• CPC Class Codes: C09K 2211/14 Macromolecular compounds
• CPC Class Codes: C09K 2211/145 containing oxygen as the only heteroatom
• CPC Class Codes: C09K 2211/1466 containing nitrogen as the only heteroatom
• CPC Class Codes: C09K 9/02 Organic tenebrescent materials
• CPC Class Codes: G02F 1/15165 Polymers
• CPC Class Codes: G02F 2202/022 polymeric
• CPC Class Codes: Y10T 428/31529 Next to metal

Abstract

Amorphous polymers with chromogenic pendant groups are provided. The amorphous polymers can be used to make elastomeric films and coatings that can be incorporated into laminates and used to make articles such as architectural and vehicular glazing, and in applications such as eyewear, displays and signage.

Claims

1. A composition comprising an amorphous (co)polymer comprising one or more repeat units,

wherein

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

R is selected from the group consisting of H and R³;

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

R² is selected from a group consisting of H, OH, R³, OR³, COOR³, and COOR⁴;

R³ comprises an electrochromic group;

at least one of R and R² in at least one repeat unit per polymer chain is OR³, R³ or COOR³;

R⁴ is selected from a group consisting of H, Na, and K;

A is selected from a group consisting of O and NR′

; and

R′

is selected from a group consisting of H and substituted and unsubstituted alkyl.

2. The composition of claim 1, wherein at least one R³ further comprises a linker selected from the group consisting of ester groups, amide groups, ether groups, thioether groups, —

(CH₂)_n—

, —

(CH₂O)_m—

, —

(CH₂CH₂O)_m—

, —

CH₂—

OC(O)(CH₂)_r—

, and —

(CH₂CH₂NH)—

where n, m and r are integers from 1 to 1000.

3. The composition of claim 1, wherein at least one R³ further comprises a linker with a branched structure:

where each n is an integer from 0 to 1000.

4. The composition of claim 1, wherein A is O.

5. The composition of claim 1, wherein R¹═

H, R²═

OH and the (co)polymer further comprises a repeat unit of structure XI

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

7. The composition of claim 1, wherein the electrochromic group is selected from a group consisting of substituted and unsubstituted aryl and heteroaryl compounds represented by structures IV-IX:

8. The composition of claim 7, wherein the substituent is selected from a group consisting of —

SH, —

CN, —

NH₂, —

COOH and —

P(O)(OR)₂.

9. The composition of claim 1, wherein the amorphous (co)polymer further comprises a functional group selected from the group of —

SO₃K and —

ClO₃Li.

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

(CH₂CH₂)—

repeat unit and at least one —

(CH₂C(CH₃)(CO₂H))—

repeat unit.

11. The composition of claim 1, further comprising one or more additives selected from a group consisting of salts, plasticizers, electron mediators, and conductive particles.

12. The composition of claim 1, wherein the Tg of the polymer is less than 100°

C.

21. A manufactured article comprising the laminate of claim 12.

22. An article of claim 21, selected from the group consisting of:

eyewear, automotive glazing, architectural glazing, mirrors, signs, and displays.

13. A laminate comprising:

a. a first electrically conductive substrate; and

b. an electrochromic layer in contact with the substrate, wherein the electrochromic layer comprises an amorphous (co)polymer comprising one or more repeat units,

wherein

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

R is selected from a group consisting of H and R³;

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

R² is selected from a group consisting of H, OH, R³, OR³, COOR³, and COOR⁴;

R³ comprises an electrochromic group;

at least one of R and R² in at least one repeat unit per polymer chain is OR³, R³ or COOR³;

R⁴ is selected from a group consisting of H, Na, and K;

A is selected from a group consisting of O and NR′

; and

R′

is selected from a group consisting of H and substituted and unsubstituted alkyl.

14. The laminate of claim 13, wherein the first electrically conducting substrate comprises a glass substrate coated with a conductive material.

15. The laminate of claim 14, wherein the conductive layer comprises at least one material selected from a group consisting of ITO, titanium oxide, copper, aluminum, gold, platinum, silver, cobalt, palladium, iridium, and rhodium.

16. The laminate of claim 13 wherein the first electrically conductive substrate comprises a conductive layer coated on a polymer substrate, wherein the polymer is selected from a group consisting of polyesters, polyimides, polyamides, polycarbonate;

polyphenylene oxide;

polysulfones;

polyester-amides, polyester-imides, polyester ethers, polyether sulfone, polyetherether ketone (PEK), polyetherimide, cellulosics; and

polystyrene/polyphenylene oxide.

17. The laminate of claim 16, wherein the conductive layer comprises material selected from a group consisting of ITO, titanium oxide, copper, aluminum, gold, platinum, silver, cobalt, palladium, iriduim, and rhodium.

18. The laminate of claim 13, further comprising a second electrically conductive substrate.

19. The laminate of claim 18, wherein the second electrically conductive substrate comprises a conductive layer coated on a glass substrate or on a polymer substrate, wherein the polymer is selected from a group consisting of polyesters, polyimides, polyamides, polycarbonate;

polyphenylene oxide;

polysulfones;

polyester-amides, polyester-imides, polyester ethers, polyether sulfone, polyetherether ketone (PEK), polyetherimide, cellulosics; and

polystyrene/polyphenylene oxide.

20. The laminate of claim 19, wherein the amorphous polymer comprises:

a. a polyvinyl butyral;

or

b. poly(ethylene oxide-co-epichlorohydrin);

or

c. a copolymer comprising repeat units derived from ethylene, methacrylic acid and salt forms of methacrylic acid.