Electrochemical polymerization of poly(thiophene-3-acetic acid), poly(thiophene-co-thiophene-3-acetic acid) and determination of their molar mass

Abstract

The electrochemical preparation and molar mass characterization of conducting polymers, poly(thiophene-3-acetic acid) (poly(TPAA)), and poly(thiophene-co-thiophene-3-acetic acid) (poly(TP/TPAA)) are reported. RRDE results revealed that, unlike other conducting polymers, current efficiency during the deposition of poly(TPAA) is by far less than 1 due to significant solubility of the polymer. Up to 48% of the oxidation products of the disc electrode can dissipate into the bulk solution. These dissipated species are polymers in oxidized form and reactive towards reductant originally present in the coating solution. The low current efficiency necessitates the use of relatively high monomer concentration and high polymerization potential to obtain a conducting poly(TPAA) film. Characterization with gel permeation chromatography (GPC) of molar mass and its distribution has been carried out. The results show that up to 65% to 85% of the whole polymers are comprised of big molecules containing over 2000 monomer units, which indicates the possibility of cross-linking of polymer chains. The remaining parts of the polymers are relatively short chains containing several to dozens of monomers. Increase of TPAA content in the copolymers leads to better solubility and higher molar mass. The latter is accompanied by greater electronic conjugation in the polymer chains.