Poly(3‐chlorothiophene) films prepared by the direct electrochemical oxidation of 3‐chlorothiophene in mixed electrolytes of boron trifluoride diethyl etherate and sulfuric acid

3‐Chlorothiophene (CT) was electrochemically polymerized in mixed electrolytes of a boron trifluoride diethyl etherate solution containing 0–20% (by volume) sulfuric acid. The oxidation potentials of the monomer in these media were measured to be only 1.06–1.31 V (vs Ag/AgCl). These values were much lower than that of CT in acetonitrile and 0.1 mol/L (Bu)₄NBF₄ (1.92 V vs Ag/AgCl). Poly(3‐chlorothiophene) (PCT) films with conductivities of 0.1–2 S cm^?1 were obtained. The structure, morphology, and electrochemical behavior of the PCT films also were investigated. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 502–509, 2003