POLYPHOSPHAZENES BEARING POLYMERIZABLE PYRROLE, THIOPHENE, AND FURAN SIDE GROUPS - SYNTHESIS AND CHEMICAL OXIDATION

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 -CH2CCHSCHCH, -CH2CH2CCHSCHCH, -CH2CH2CSCHCHCH, -CH2CH2CH2NCHCHCHCH, -CH2CCHOCHCH, -(CH2)11NCHCHCHCH, or -(CH2CH2O)2CH2CH2NCHCHCHCH, and [NP(NHR)2]n, where R is -CH2CH2CH2NCHCHCHCH or -CH2CH2CCHSCHCH. 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 H-1, C-13, and P-31 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-degrees-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.