Polymeric compositions comprising thieno[3,4-b]thiophene, method of making, and use thereof

• US 20040074779A1
• Filed: 07/11/2003
• Published: 04/22/2004
• Est. Priority Date: 07/11/2002
• Status: Active Grant

• Current Assignee: Samsung Electronics Co. Ltd.
• Original Assignee: University of Connecticut (State of Connecticut)
• Inventors: Sotzing, Gregory Allen
• Granted Patent: US 7,125,479 B2
• Time in Patent Office: Days
• US Class Current: 205/414
• CPC Class Codes: C08G 61/126 with a five-membered ring containing one sulfur atom in the ring
• CPC Class Codes: H01B 1/127 comprising five-membered aromatic rings in the main chain, e.g. polypyrroles, polythiophenes
• CPC Class Codes: H01G 11/48 Conductive polymers
• CPC Class Codes: H01G 11/56 Solid electrolytes, e.g. gels; Additives therein
• CPC Class Codes: Y02E 60/13 Energy storage using capacitors

Abstract

Polymers and copolymers comprising repeating units of 5 thieno[3,4-b]thiophene. Water-borne dispersions of such polymers and copolymers can be cast by conventional methods to provide uniform, thin films which possess utility in numerous electroactive applications including electrochromic displays, optically transparent electrodes and antistatic coatings. The compositions of this invention can be doped with conventional p-dopants or n-dopants. The invention also presents an aqueous process for preparing such polymeric compositions.

Claims

1. A process comprising electrochemical reaction of a monomeric composition comprising thieno[3,4-b]thiophene, to form a polymeric composition comprising units derived from thieno[3,4-b]thiophene.

2. The process of claim 1, wherein electrochemical reaction is in an electrochemical cell comprising an electrolyte, a working electrode, a counter electrode, and a reference electrode in operable communication.

3. The process of claim 2, wherein the working electrode is a platintum, gold, or vitreous carbon working electrode, and the counter electrode is platinum.

4. The process of claim 3, wherein the working electrode is a vitreous carbon electrode and the electrolyte is tetrabutylammonium perchlorate/acetonitrile.

5. The process of claim 1, wherein reaction provides the polymeric composition on an indium tin oxide substrate.

6. The process of claim 1, further comprising reducing the polymeric composition.

8. The process of claim 1, wherein the polymeric composition has a band gap of about 0.85 V.

9. The process of claim 8, wherein the polymeric composition is transparent.

10. The process of claim 1, wherein the polymeric composition has no observable color in the oxidized form.

11. The process of claim 1, wherein the monomeric composition further comprises a co-monomer reactive with the thieno[3,4-b]thiophene.

12. The process of claim 11, wherein the co-monomer is a thiophene, substituted thiophene, substituted thieno[3,4-b]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, C₆-C₃₆ aryl, C₃-C₆ cycloalkyl, C₁-C₁₂ alkyl, halogen (i.e., F, Cl, Br, I), C₁-C₁₂ alkoxy, C₁-C₁₂ alkylthio, C₁-C₁₂ perfluoroalkyl, C₆-C₃₆ perfluoroaryl, pyridyl, cyano, thiocyanato, nitro, amino, CI-C₁₂ alkylamino, C₁-C₁₂ aminoalkyl, acyl, sulfoxyl, sulfonyl, amido, and/or carbamoyl.

13. The process of claim 12, wherein the co-monomer is

14. The process of claim 12, wherein the co-monomer is

15. The process of claim 14, wherein X is C₁-C₁₂ alkyl- or C₆-C₁₂ phenyl-substituted ethylene, or a 1,2-cyclohexylene.

16. The process of claim 12, wherein the co-monomer is

17. The process of claim 1, wherein the monomeric composition further comprises a polyanion.

18. The process of claim 17, wherein the polyanion is a polycarboxylate or a polymeric sulfonate.