Substituted thieno[3,4-B]thiophene polymers, method of making, and use thereof
Substituted thieno[3,4-b] thiophene polymers and copolymers are disclosed. Adjusting the type and quantity of substitution allows for the intricate control of the resulting polymer's conductivity, optoelectronic properties, and/or solubility. A process for preparing such polymers and use thereof are also provided.
1. A composition, comprising:
a substituted polymer comprising units of substituted thieno[3,4-b]thiophene prepared by electrophilic substitution of a first polymer comprising thieno[3,4-b]thiophene units, wherein the electrophilic substitution reaction is sulfonation, nitration, halogenation, or a combination comprising at least one of the foregoing reactions.
2. The composition of claim 1 , wherein the electrophilic substitution reaction is sulfonation.
3. The composition of claim 1 , wherein the thieno[3,4-b]thiophene units of the substituted polymer are substituted with sulfonic acid (—SO 3 H), sulfonate (—SO 3 − ), halogen, nitro, or a combination comprising at least one of the foregoing substituents.
4. The composition of claim 3 , wherein the substitution is sulfonic acid (—SO 3 H), sulfonate (—SO 3 − ), or a combination comprising at least one of the foregoing substituents.
5. The composition of claim 1 , wherein about 1 to about 99 mole percent of the thieno[3,4-b]thiophene units are substituted.
6. The composition of claim 1 , wherein about 10 to about 80 mole percent of the thieno[3,4-b]thiophene units are substituted.
7. The composition of claim 1 , wherein about 30 to about 70 mole percent of the thieno[3,4-b]thiophene units are substituted.
8. The composition of claim 1 , wherein the substituted polymer comprises units of sulfonated thieno[3,4-b]thiophene and wherein the composition further comprises a base.
9. The composition of claim 8 , wherein the base is metal hydroxide, C 1 –C 24 primary amine, C 1 –C 24 secondary amine, C 1 –C 24 tertiary amine, polyamine, or a combination comprising at least one of the foregoing.
10. The composition of claim 1 , wherein the substituted polymer is soluble or dispersible in water or organic solvents.
11. The composition of claim 1 , wherein the substituted polymer is water soluble at greater than or equal to about 5 mg/ml.
12. The composition of claim 1 , wherein the first polymer is a copolymer comprising thieno[3,4-b]thiophene units and units derived from thiophene, substituted thiophene, dithieno[3,4-b:3′,4′-d]thiophene, bithiophene, pyrrole, substituted pyrrole, phenylene, substituted phenylene, naphthalene, substituted naphthalene, biphenyl, substituted biphenyl, terphenyl, substituted terphenyl, phenylene vinylene, substituted phenylene vinylene, or a combination comprising at least one of the foregoing co-monomers, wherein the substituents are one or more of —H, hydroxyl, C 6 –C 36 aryl, C 3 –C 6 cycloalkyl, C 1 –C 12 alkyl, halogen, C 1 –C 12 alkoxy, C 1 –C 12 alkylthio, C 1 –C 12 perfluoroalkyl, C 6 –C 36 perfluoroaryl, pyridyl, cyano, thiocyanato, nitro, amino, C 1 –C 12 alkylamino, C 1 –C 12 aminoalkyl, acyl, sulfoxyl, sulfonyl, amido, carbamoyl, or a combination comprising at least one of the foregoing substituents.
13. The composition of claim 1 , further comprising an additional conjugated polymer, insulating polymer, or a combination comprising at least one of the foregoing polymers to form a blend.
14. The composition of claim 1 , wherein the polymer is n-doped or p-doped.
15. An article comprising the substituted polymer of claim 1 .
16. The composition of claim 3 , wherein the nitro substituent is reduced to an amino substituent, and optionally futher protonated to an ammonium substituent.
17. A composition, comprising:
a substituted polymer comprising units of substituted thieno[3,4-b]thiophene prepared by electrophilic substitution of a first polymer comprising thieno[3,4-b]thiophene units, wherein the electrophilic substitution reaction is sulfonation, nitration, alkylation, acylation, halogenation, or a combination comprising at least one of the foregoing reactions; and wherein about 10 to about 80 mole percent of the thieno[3,4-b]thiophene units are substituted.
18. A method of preparing a polymer, comprising:
performing an electrophilic substitution reaction on a first polymer comprising thieno[3,4-b]thiophene units to form a substituted polymer comprising substituted thieno[3,4-b]thiophene units.
19. The method of claim 18 , wherein the electrophilic substitution reaction is sulfonation, nitration, alkylation, acylation, halogenation, or a combination comprising at least one of the foregoing reactions.
20. The method of claim 18 , wherein the electrophilic substitution reaction is sulfonation.
21. The method of claim 18 , wherein the substituted thieno[3,4-b]thiophene units comprise substituents, wherein the substituents are sulfonic acid (—SO 3 H), sulfonate (—SO 3 − ), halogen, nitro, acyl, alkyl, or a combination comprising at least one of the foregoing substituents.
22. The method of claim 21 , wherein the substituents are sulfonic acid (—SO 3 H), sulfonate (—SO 3 − ), or a combination comprising at least one of the foregoing substitutions.
23. The method of claim 18 , wherein about 1 to about 99 mole percent of the thieno[3,4-b]thiophene units are substituted.
24. The method of claim 18 , wherein about 10 to about 80 mole percent of the thieno[3,4-b]thiophene units are substituted.
25. The method of claim 18 , wherein about 30 to about 70 mole percent of the thieno[3,4-b]thiophene units are substituted.
26. The method of claim 18 , wherein the substituted polymer comprises units of sulfonated thieno[3,4-b]thiophene and wherein the method further comprises adding a base to the substituted polymer to form a complex.
27. The method of claim 26 , wherein the base is metal hydroxide, C 1 –C 24 primary amine, C 1 –C 24 secondary amine, C 1 –C 24 tertiary amine, polyamine, or a combination comprising at least one of the foregoing.
28. The method of claim 18 , wherein the substituted polymer is water soluble.
29. The method of claim 18 , wherein the substituted polymer is soluble in organic solvents.
30. The method of claim 18 , wherein the substituted polymer is dispersible in water or organic solvents.
31. The method of claim 18 , wherein the substituted polymer is n-doped or p-doped.
32. An article comprising the substituted polymer prepared by the method of claim 18 .
33. A film, comprising a layer of the substituted polymer prepared by the method of claim 18 , and a layer comprising a base, wherein the base is metal hydroxide, C 1 –C 24 primary amine, C 1 –C 24 secondary amine, C 1 –C 24 tertiary amine, polyamine, or a combination comprising at least one of the foregoing.
34. An article comprising the film of claim 33 .
35. The method of claim 21 , further comprising reducing the nitro substituent to an amino substituent;
or reducing the nitro substituent to an amino substituent, and protonating the amino substituent to form an ammonium substituent.