Yellow to transmissive electrochromic polymers

Patent metadata

Field	Value
Publication number	US-10294416-B2
Application number	US-201515309993-A
Country	US
Kind code	B2
Filing date	May 28, 2015
Priority date	May 28, 2014
Publication date	May 21, 2019
Grant date	May 21, 2019

Abstract

Yellow electrochromic polymers (ECPs) are prepared that display a yellow neutral state and a highly transmissive oxidized state. The ECPs are copolymers where a dyad of dioxyhetereocyclic repeating unis alternate with a monad of an aromatic repeating unit. An alternate yellow ECP has an oxidation potential of 450 mV or less and is an alternating copolymer of an acyclic dioxythiophene (AcDOT) or a propylene dioxythiophene (ProDOT) with an aromatic repeating unit that has an electron donating substituent. The yellow ECPs can be processed from solution for electrochromic devices.

First claim

We claim:

1. A yellow electrochromic polymer (ECP), comprising a copolymer with a dyad of a dioxy heterocyclic repeating units alternating with an aromatic repeating unit of the structure:

where n is 2 to 200,000; X is S, Se, O, or NR; R is independently H, C 1 -C 30 alkyl, C 2 -C 30 alkenyl, C 2 -C 30 alkynyl, C 6 -C 14 aryl, C 7 -C 30 arylalkyl, C 8 -C 30 arylalkenyl, C 8 -C 30 arylalkynyl, C 2 -C 30 alkylester, C 7 -C 15 arylester, C 8 -C 30 alkylarylester, C 3 -C 30 alkenylester, C 3 -C 30 alkynylester, NH 2 , C 1 -C 30 alkylamino, C 6 -C 14 arylamino, C 7 -C 30 (arylalkyl)amino, C 2 -C 30 alkenyl amino, C 2 -C 30 alkynylamino, C 8 -C 30 (arylalkenyl)amino, C 8 -C 30 (arylalkynyl)amino, C 2 -C 30 dialkylamino, C 12 -C 28 diarylamino, C 4 -C 30 dialkenylamino, C 4 -C 30 dialkynylamino, C 7 -C 30 aryl(alkyl)amino, C 7 -C 30 di(arylalkyl)amino, C 8 -C 30 alkyl(arylalkyl)amino, C 15 -C 30 aryl(arylalkyl)amino, C 8 -C 30 alkenyl(aryl)amino, C 8 -C 30 alkynyl(aryl)amino C(O)NH 2 (amido), C 2 -C 30 alkylamido, C 7 -C 14 arylamido, C 8 -C 30 (arylalkyl)amido, C 2 -C 30 dialkylamido, C 12 -C 28 diarylamido, C 8 -C 30 aryl(alkyl)amido, C 15 -C 30 di(arylalkyl)amido, C 9 -C 30 alkyl(arylalkyl)amido, C 16 -C 30 aryl(arylalkyl)amido, thiol, C 1 -C 30 alkylhydroxy, C 6 -C 14 arylhydroxy, C 7 -C 30 arylalkylhydroxy, C 3 -C 30 alkenylhydroxy, C 3 -C 30 alkynylhydroxy, C 8 -C 30 arylalkenylhydroxy, C 8 -C 30 aryl alkynylhydroxy, C 3 -C 30 polyether, C 3 -C 30 polyetherester, C 3 -C 30 polyester C 3 -C 30 polyamino, C 3 -C 30 polyaminoamido, C 3 -C 30 polyaminoether, C 3 -C 30 polyaminoester, C 3 -C 30 polyamidoester, C 3 -C 30 alkylsulfonic acid, C 3 -C 30 alkylsulfonate salt, C 1 -C 30 carboxylate salt, C 1 -C 30 thiocarboxylate salt, C 1 -C 30 dithiocarboxylate salt, or C 3 -C 30 alkyl C 1 -C 4 trialkyammonium salt, and wherein Ar has the structure:

where: X is NR′, PR′, S, O, Se, SO x , CR 2 , SiR′ 2 , GeR′ 2 , or BR′, where x=1 or 2; X′ is NR′, O, Se, or S; where R′ is H, C 1 -C 30 alkyl, C 2 -C 30 alkenyl, C 2 -C 30 alkynyl, C 6 -C 14 aryl, C 7 -C 30 arylalkyl, C 8 -C 30 arylalkenyl, C 8 -C 30 arylalkynyl, C 1 -C 30 hydroxyalkyl, C 6 -C 14 hydroxyaryl, C 7 -C 30 hydroxyarylalkyl, C 3 -C 30 hydroxyalkenyl, C 3 -C 30 hydroxyalkynyl, C 8 -C 30 hydroxyarylalkenyl, C 8 -C 30 hydroxyarylalkenyl, C 3 -C 30 polyether, C 3 -C 30 polyetherester, C 3 -C 30 polyester, C 3 -C 30 polyamino, C 3 -C 30 polyaminoamido, C 3 -C 30 polyaminoether, C 3 -C 30 polyaminoester, C 3 -C 30 polyamidoester, C 3 -C 30 alkylsulfonic acid, C 3 -C 30 alkylsulfonate salt, C 1 -C 30 alkylcarboxylate salt, C 1 -C 30 alkylthiocarboxylate salt, C 1 -C 30 alkyldithiocarboxylate salt or C 3 -C 30 alkyl C 1 -C 4 trialkyammonium salt R″ is independently H, C 1 -C 30 alkyl, C 3 -C 30 alkenyl, C 2 -C 30 alkynyl, C 6 -C 14 aryl, C 7 -C 30 arylalkyl, C 8 -C 30 arylalkenyl, C 8 -C 30 arylalkynyl; and R is independently H, C 1 -C 30 alkyl, C 2 -C 30 alkenyl, C 2 -C 30 alkynyl, C 6 -C 14 aryl, C 7 -C 30 arylalkyl, C 8 -C 30 arylalkenyl, C 8 -C 30 arylalkynyl, hydroxy, C 1 -C 30 alkoxy, C 6 -C 14 aryloxy, C 7 -C 30 arylalkyloxy, C 2 -C 30 alkenyloxy, C 2 -C 30 alkenyloxy, C 8 -C 30 arylalkenyloxy, C 8 -C 30 arylalkynyloxy, CO 2 H, C 2 -C 30 alkylester, C 7 -C 15 arylester, C 8 -C 30 alkylarylester, C 3 -C 30 alkenylester, C 3 -C 30 alkynylester, NH 2 , C 1 -C 30 alkylamino, C 6 -C 14 arylamino, C 7 -C 30 (arylalkyl)amino, C 2 -C 30 alkenylamino, C 2 -C 30 alkynylamino, C 8 -C 30 (arylalkenyl)amino, C 8 -C 30 (arylalkynyl)amino, C 2 -C 30 dialkylamino, C 12 -C 28 diarylamino, C 4 -C 30 dialkenylamino, C 4 -C 30 dialkynylamino, C 7 -C 30 aryl(alkyl)amino, C 7 -C 30 di(arylalkyl)amino, C 8 -C 30 alkyl(arylalkyl)amino, C 15 -C 30 aryl(arylalkyl)amino, C 8 -C 30 alkenyl(aryl)amino, C 8 -C 30 alkynyl(aryl)amino C(O)NH 2 (amido), C 2 -C 30 alkylamido, C 7 -C 14 arylamido, C 8 -C 30 (arylalkyl)amido, C 2 -C 30 dialkylamido, C 12 -C 28 diarylamido, C 8 -C 30 aryl(alkyl)amido, C 15 -C 30 di(arylalkyl)amido, C 9 -C 30 alkyl(arylalkyl)amido, C 16 -C 30 aryl(arylalkyl)amido, thiol, C 1 -C 30 hydroxyalkyl, C 6 -C 14 hydroxyaryl, C 7 -C 30 hydroxyarylalkyl, C 3 -C 30 hydroxyalkenyl, C 3 -C 30 hydroxyalkynyl, C 8 -C 30 hydroxyarylalkenyl, C 8 -C 30 hydroxyarylalkynyl, C 3 -C 30 polyether, C 3 -C 30 polyetherester, C 3 -C 30 polyester, C 3 -C 30 polyamino, C 3 -C 30 polyaminoamido, C 3 -C 30 polyaminoether, C 3 -C 30 polyaminoester, C 3 -C 30 polyamidoester, C 3 -C 30 alkylsulfonic acid, C 3 -C 30 alkylsulfonate salt, C 1 -C 30 carboxylate salt, C 1 -C 30 thiocarboxylate salt, C 1 -C 30 dithiocarboxylate salt, or C 3 -C 30 alkylC 1 -C 4 trialkyammonium salt.

2. The yellow electrochromic polymer (ECP) according to claim 1 , wherein Ar has the structure:

3. The yellow electrochromic polymer (ECP) according to claim 1 , wherein the copolymer has the structure:

4. The yellow electrochromic polymer (ECP) according to claim 1 , wherein the copolymer is soluble in at least one organic solvent.

5. A yellow electrochromic polymer (ECP), comprising an alternating copolymer with a propylene dioxythiophene (ProDOT) or an acyclic dioxythiophene (ACDOT) repeating unit alternating with one or more aromatic repeating units wherein the oxidation potential is 450 mV or less, and wherein at least one of the aromatic repeating units comprises an electron donating substituent.

6. The yellow electrochromic polymer (ECP) according to claim 5 , wherein the copolymer has the structure: ProDOT-Cbz; R-ProDOT-Ph/Ph(MeO) 2 ; or ProDOT-Ph(MeO) 2 .

7. A yellow electrochromic polymer (ECP), comprising an alternating copolymer with a propylene dioxythiophene (ProDOT) or an acyclic dioxythiophene (ACDOT) repeating unit alternating with a pyrene repeating unit, wherein the pyrene repeating unit has the following structure:

Assignees

• Georgia Tech Res Inst

Inventors

• Kerszulis Justin Adam
• Reynolds John Robert
• Dyer Aubrey Lynn

Classifications

• C08G61/126

  with a five-membered ring containing one sulfur atom in the ring · CPC title

• C08G2261/411

  Suzuki reactions · CPC title

• C08G2261/3142

  fluorene-based, e.g. fluorene, indenofluorene, or spirobifluorene · CPC title

• C08G2261/3243

  containing one or more sulfur atoms as the only heteroatom, e.g. benzothiophene · CPC title

• C08G2261/64

  Solubility · CPC title