Method for preparing dioxyheterocycle-based electrochromic polymers
A method for preparing a conjugated polymer involves a DHAP polymerization of a 3,4-dioxythiophene, 3,4-dioxyfuran, or 3,4-dioxypyrrole and, optionally, at least one second conjugated monomer in the presence of a Pd or Ni comprising catalyst, an aprotic solvent, a carboxylic acid at a temperature in excess of 120° C. At least one of the monomers is substituted with hydrogen reactive functionalities and at least one of the monomers is substituted with a Cl, Br, and/or I. The polymerization can be carried out at temperature of 140° C. or more, and the DHAP polymerization can be carried out without a phosphine ligand or a phase transfer agent. The resulting polymer can display dispersity less than 2 and have a degree of polymerization in excess of 10.
1. A method for preparing a conjugated polymer, comprising
providing at least one first monomer comprising a 3,4-dioxythiophene, 3,4-dioxyselenophene, 3,4-dioxytellurophene 3,4-dioxyfuran, or 3,4-dioxypyrrole;
optionally providing at least one second monomer comprising a conjugated unit;
providing a Pd or Ni comprising catalyst;
providing an aprotic solvent;
providing a carboxylic acid;
combining the first monomer, second monomer, catalyst, solvent and carboxylic acid as a polymerization mixture; and
heating the polymerization mixture in excess of 120° C. but below the boiling point of the aprotic solvent, wherein at least one of the first monomers or second monomers is substituted with hydrogen reactive functionalities and at least one of the first or second monomers is substituted with non-hydrogen reactive functionalities, wherein the non-hydrogen reactive functionalities are Cl, Br, I, OTs, OTf, CN, OCN, SCN, wherein the polymerization mixture is free of a phosphine ligand, and wherein the ratio of the hydrogen reactive functionalities and the non-hydrogen reactive functionalities permits a degree of polymerization in excess of four.
2. The method of claim 1 , wherein the first monomer comprises the structure:
where x is 0 to 3; L is independently H, Cl, Br, I, OTs, OTf, CN, OCN, SCN, or other pseudohalide, X is S, Se, Te, 0, or NR; R is independently H, alkyl, aryl, substituted alkyl, or substituted aryl, oligoether, aminoalkyl, hydroxyalkyl, alkoxyalkyl, acyloxyalkyl, HOS(O) 2 alkyl, HOC(O)alkyl, (HO) 2 P(O)alkyl, aminoaryl, hydroxyaryl, alkoxyaryl, acyloxyaryl, HOS(O) 2 aryl, HOC(O)aryl or (HO) 2 P(O)aryl, —(CH 2 ) m —YC(O)R 2 , —(CH 2 ) m —C(O)YR 2 , —(CH 2 ) m —O—(CH 2 ) v YC(O)R 2 , —(CH 2 ) m —O—(CH 2 ) v C(O)YR 2 , —(CH 2 ) m —OCH z (CH 3 ) y [(CH 2 ) w YC(O)R 2 ] 3-z , —(CH 2 ) m —OCH z (CH 3 ) y [(CH 2 ) w C(O)YR 2 ] 3-z , or two R groups on adjacent carbons in combination are alkylene, arylene, substituted alkylene, or substituted arylene; m is 1 to 8; y is 0 to 2; z is 0 to 2; y+z is 0 to 2; w is 1 to 8; v is 2 to 8; Y is O, S, or NR 3 , R 2 is a straight chained, branched chain, cyclic or substituted cyclic alkyl group of 1 to 12 carbons; and R 3 is a straight chained, branched chain, cyclic or substituted cyclic alkyl group of 1 to 6 carbons.
3. The method of claim 1 , wherein the second monomer comprises ethene, carbazole, fluorene, benzothiadiazole, thiadiazoloquinoxaline, quinoline, quinoxaline, thienothiadiazole, thienopyrazine, pyrazinoquinoxaline, benzobisthiadiazole, thiadiazolothienopyrazine, thiophene, pyrrole, furan, selenophene, telurophene, thieno[3,2-b]thiophene, dithieno[3,2-b:2′,3′-d]thiophene, benzo[c][1,2,5]thiadiazole, benzo[c][1,2,5]-oxadiazole, benzo[d][1,2,3]triazole, pyrido[3,4-b]pyrazine, cyanovinylene, thiazolo[5,4-d]thiazole, 1,3,4-oxadiazole, 1,3,4-thiadiazole, 1,3,4-triazole, pyrrolo[3,4-c]pyrrole-1,4-dione, 2,2′-bithiazole, [1,2,5]thiadiazole-[3,4-c]pyridine, thieno[3,4-b]pyrazine, [1,2,5]oxadiazolo[3,4-c]pyridine, dicyanovinylene, benzo[1,2-c;4,5-c′]bis[1,2,5]thiadiazole, [1,2,5]thiadiazolo[3,4-g]quinoxaline, cyclopentadi-thiophene-4-one, 4-dicyano-methylenecyclopentadithiolene, benzo[c]thiophene, isoindigo, indigo, 4,4′-bis(alkyl)-[6,6′-bithieno[3,2-b]pyrrolylidene]-5,5′(4H,4′H)-dione, phenanthrene, phenanthrene-9,10-dione, benzo[1,2-b:6,5-b′]dithiophene-4,5-dione, napthalenediimide, perylenediimide, any aromatic of the structure:
or any oligomers thereof,
where: L is independently H, Cl, Br, I, OTs, OTf, CN, OCN, SCN, or other pseudohalide; X is NR′, PR′, S, O, Se, Te, CR 2 , SiR′ 2 , GeR′ 2 , BR′, or SO X where x=1 or 2; Z is NR′, PR′, S, O, Se, or Te; 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 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 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; 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, 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.
4. The method of claim 1 , wherein the aprotic solvent comprises dimethylformamide (DMF), DMAc, N-methylpyrolidone (NMP), hexamethylphosporamide (HMPA), dimethylsulfoxide (DMSO), or propylene carbonate.
5. The method of claim 1 , wherein the catalyst is palladium diacetate, palladium di-trifluoroacetate, or Bis(dibenzylideneacetone)palladium(0).
6. The method of claim 1 , wherein the carboxylic acid is pivalic acid or other aliphatic carboxylic acid.
7. The method of claim 1 , wherein the temperature is at least 130° C.
8. The method of claim 1 , wherein the temperature is at least 140° C.
9. The method of claim 1 , wherein the polymerization mixture is free of a phase transfer agent.
10. The method of claim 1 , wherein first monomer is 3,3-bis((2-ethylhexyloxy)methyl)-3,4-dihydro-2H-thieno[3,4-b][1,4]dioxepine, 6,8-dibromo-3,3-bis((2-ethylhexyloxy)methyl)-3,4-dihydro-2H-thieno[3,4-b][1,4]dioxepine, and/or 6-bromo-3,3-bis((2-ethylhexyloxy)methyl)-3,4-dihydro-2H-thieno[3,4-b][1,4]dioxepine.
11. The method of claim 10 , wherein the second monomer is 1,4-dibromobenzene or 4,7-dibromo-2,1,3-benzothiadiazole.
12. A method for preparing a conjugated polymer, comprising
providing at least one first monomer comprising a 3,4-dioxythiophene, 3,4-dioxyselenophene, 3,4-dioxytellurophene 3,4-dioxyfuran, or 3,4-dioxypyrrole;
optionally providing at least one second monomer comprising a conjugated unit;
providing a Pd or Ni comprising catalyst;
providing an aprotic solvent;
providing a carboxylic acid;
combining the first monomer, second monomer, catalyst, solvent and carboxylic acid as a polymerization mixture; and
heating the polymerization mixture in excess of 120° C., wherein at least one of the first monomers or second monomers is substituted with hydrogen reactive functionalities and at least one of the first or second monomers is substituted with non-hydrogen reactive functionalities, wherein the non-hydrogen reactive functionalities are Cl, Br, I, OTs, OTf, CN, OCN, SCN, wherein the polymerization mixture is free of a phosphine ligand, and wherein the ratio of the hydrogen reactive functionalities and the non-hydrogen reactive functionalities permits a degree of polymerization in excess of four.
13. The method of claim 12 , wherein the first monomer comprises the structure:
where x is 0 to 3; L is independently H, Cl, Br, I, OTs, OTf, CN, OCN, SCN, or other pseudohalide, X is S, Se, Te, O, or NR; R is independently H, alkyl, aryl, substituted alkyl, or substituted aryl, oligoether, aminoalkyl, hydroxyalkyl, alkoxyalkyl, acyloxyalkyl, HOS(O) 2 alkyl, HOC(O)alkyl, (HO) 2 P(O)alkyl, aminoaryl, hydroxyaryl, alkoxyaryl, acyloxyaryl, HOS(O) 2 aryl, HOC(O)aryl or (HO) 2 P(O)aryl, —(CH 2 ) m —YC(O)R 2 , —(CH 2 ) m —C(O)YR 2 , —(CH 2 ) m —O—(CH 2 ) v YC(O)R 2 , —(CH 2 ) m —O—(CH 2 ) v C(O)YR 2 , —(CH 2 ) m —OCH z (CH 3 ) y [(CH 2 ) w YC(O)R 2 ] 3-z , —(CH 2 ) m —OCH z (CH 3 ) y [(CH 2 ) w C(O)YR 2 ] 3-z , or two R groups on adjacent carbons in combination are alkylene, arylene, substituted alkylene, or substituted arylene; m is 1 to 8; y is 0 to 2; z is 0 to 2; y+z is 0 to 2; w is 1 to 8; v is 2 to 8; Y is O, S, or NR 3 , R 2 is a straight chained, branched chain, cyclic or substituted cyclic alkyl group of 1 to 12 carbons; and R 3 is a straight chained, branched chain, cyclic or substituted cyclic alkyl group of 1 to 6 carbons.
14. The method of claim 12 , wherein the second monomer comprises ethene, carbazole, fluorene, benzothiadiazole, thiadiazoloquinoxaline, quinoline, quinoxaline, thienothiadiazole, thienopyrazine, pyrazinoquinoxaline, benzobisthiadiazole, thiadiazolothienopyrazine, thiophene, pyrrole, furan, selenophene, telurophene, thieno[3,2-b]thiophene, dithieno[3,2-b:2′,3′-d]thiophene, benzo[c][1,2,5]thiadiazole, benzo[c][1,2,5]-oxadiazole, benzo[d][1,2,3]triazole, pyrido[3,4-b]pyrazine, cyanovinylene, thiazolo[5,4-d]thiazole, 1,3,4-oxadiazole, 1,3,4-thiadiazole, 1,3,4-triazole, pyrrolo[3,4-c]pyrrole-1,4-dione, 2,2′-bithiazole, [1,2,5]thiadiazole-[3,4-c]pyridine, thieno[3,4-b]pyrazine, [1,2,5]oxadiazolo[3,4-c]pyridine, dicyanovinylene, benzo[1,2-c;4,5-c′]bis[1,2,5]thiadiazole, [1,2,5]thiadiazolo[3,4-g]quinoxaline, cyclopentadi-thiophene-4-one, 4-dicyano-methylenecyclopentadithiolene, benzo[c]thiophene, isoindigo, indigo, 4,4′-bis(alkyl)-[6,6′-bithieno[3,2-b]pyrrolylidene]-5,5′(4H,4′H)-dione, phenanthrene, phenanthrene-9,10-dione, benzo[1,2-b:6,5-b′]dithiophene-4,5-dione, napthalenediimide, perylenediimide, any aromatic of the structure:
or any oligomers thereof,
where: L is independently H, Cl, Br, I, OTs, OTf, CN, OCN, SCN, or other pseudohalide; X is NR′, PR′, S, O, Se, Te, CR 2 , SiR′ 2 , GeR′ 2 , BR′, or SO x where x=1 or 2; Z is NR′, PR′, S, O, Se, or Te; 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 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 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; 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, 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.
15. The method of claim 12 , wherein the aprotic solvent comprises dimethylformamide (DMF), DMAc, N-methylpyrolidone (NMP), hexamethylphosporamide (HMPA), dimethylsulfoxide (DMSO), or propylene carbonate.
16. The method of claim 12 wherein the catalyst is palladium diacetate, palladium di-trifluoroacetate, or Bis(dibenzylideneacetone)palladium(0).
17. The method of claim 12 , wherein the carboxylic acid is pivalic acid or other aliphatic carboxylic acid.
18. The method of claim 12 , wherein the polymerization mixture is free of a phase transfer agent.
19. The method of claim 12 , wherein first monomer is 3,3-bis((2-ethylhexyloxy)methyl)-3,4-dihydro-2H-thieno[3,4-b][1,4]dioxepine, 6,8-dibromo-3,3-bis((2-ethylhexyloxy)methyl)-3,4-dihydro-2H-thieno[3,4-b][1,4]dioxepine, and/or 6-bromo-3,3-bis((2-ethylhexyloxy)methyl)-3,4-dihydro-2H-thieno[3,4-b][1,4]dioxepine.
20. The method of claim 12 , wherein the second monomer is 1,4-dibromobenzene or 4,7-dibromo-2,1,3-benzothiadiazole.