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- W2110542418 abstract "The study of electrically conducting polypyrrole, polythiophene and related compounds has attracted great interest because of the many possible applications of these materials. This work details the mechanistic studies of the electropolymerization of various heterocyclic monomers to form conducting polymers. A study of the kinetic order dependence of the polymerization of 2,2'-bithiophene (BT) and of pyrrole was performed. his was measured by stepped potential experiments on glassy carbon and on Pt electrodes, and by monomer consumption experiments as measured by gas chromatographic analysis. The major conclusion from this work is that the reaction follows a first order dependence on monomer concentration. This is true except for the first 100 msec where background or transient current (non-faradaic) is significant. However, the results were not completely reproducible because of possible side-reactions and variable reaction conditions in heterogeneous systems. Pyrrole-d5 was used in a deuterium isotope effect study in the polymerization. No primary effect was found at any applied potential (above and below the potential where the reaction becomes diffusion-limited) thus indicating that proton loss is not rate-limiting. A radical trap experiment revealed that polymer formation is completely inhibited by the presence of a radical scavenger, and thus a reaction with the scavenger is more favourable than coupling with another radical cation. These studies are consistent with a radical coupling mechanism of polymerization. A kinetic and molecular weight study of soluble poly(3methoxythiophene) demonstrated nearly ideal first order dependence on monomer concentration, 50 to 70% faradaic efficiencies, and a remarkably narrow, low molecular weight distribution. The molecular weight is constant at all monomer conversions from 10% to 90%, and the molecular weight and its distribution are independent of the applied potential. This behaviour is unexpected for a polymerization proceeding by radical propagation, ionic propagation or a condensation-type mechanism, and thus the mechanism of polymerization is unique in polymer science. The limiting effect of the molecular weight is discussed in terms of the polaron / bipolaron theory for conduction in aromatic heterocyclic polymers. A kinetic and mechanistic model consistent with the data is presented." @default.
- W2110542418 created "2016-06-24" @default.
- W2110542418 creator A5008455923 @default.
- W2110542418 date "1988-01-01" @default.
- W2110542418 modified "2023-09-27" @default.
- W2110542418 title "Mechanistic aspects of the electropolymerization of heterocyclic aromatics to form conducting polymers" @default.
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- W2110542418 hasPublicationYear "1988" @default.
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