Polyphosphazenes Bearing Polymerizable Pyrrole, Thiophene, and Furan Side Groups: Synthesis and Chemical Oxidation

Harry R. Allcock, Jeffrey A. Dodge, Leon S. Van Dyke, Charles R. Martin

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Abstract

The synthesis and chemical oxidation of linear poly(organophosphazenes) that bear polymerizable, heterocyclic side groups are described. The polymers were prepared for use as precursors to electronically conductive materials. The polymers have the general structure [NP(OR)2]n, where R is -[formula omitted]. The cyclic trimer [NP(OCH2CCHSCHCH)2]3 was synthesized as a model compound and as a possible precursor to cyclomatrix conductive materials. Molecular structural characterization for the linear high polymers was achieved by the use of 1H, 13C, and 31P NMR spectroscopy, gel permeation chromatography, and elemental microanalysis. The glass transition temperatures of the polymers were determined using differential scanning calorimetric analysis and were found to be in the range -48 to +1 °C. Chemical oxidation of the materials was carried out in solution using Fe(ClO4)3 or FeCl3. The resultant dark, insoluble powders were compressed into pellets, and their electronic conductivities were measured. All the materials were found to be semiconductive with conductivities in the range 4 X 10-10-5 X 10-5 S cm-1. The results of attempted electrochemical oxidation and chemical oxidation using iodine are also described.

Original languageEnglish (US)
Pages (from-to)780-788
Number of pages9
JournalChemistry of Materials
Volume4
Issue number4
DOIs
StatePublished - Feb 1 1992

All Science Journal Classification (ASJC) codes

  • Chemistry(all)
  • Chemical Engineering(all)
  • Materials Chemistry

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