1964 Volume 37 Issue 12 Pages 1849-1854
The fact that a polymer containing C=N double bonds is formed from saturated nitrile complexes with metal chlorides is supported by the infrared absorption at about 1600 cm−1 and the characteristic addition of silver nitrate. The polyacetonitrile has an electric conductivity from 10−10 to 10−5Ω−1 cm−1 and an energy gap from 0.4 to 1.2 eV., indicating that the polymer is an organic semiconductor.
The electric conductivity increases and the energy gap decreases with increases in the heating time and temperature, suggesting a more extensive formation of a conjugated system, including also C=C double bonds among polymer chains at a higher temperature. This theory is supported by the evolution of ammonia, resulting in simultaneous decreases of the H and N contents of the polymer, the appearance of the absorption at 840 cm−1, by oxidation by potassium permanganate, by analyses of ESR line shapes, and by viscometric measurements. This structual change may bring about a noncrystalline pattern in X-ray diffraction. Therefore, it is indicated that polyacetonitrile does not have a complete C=N conjugated sequence because of some pyrolysis, accompanied by the extension of a conjugated sustem such as cross-linking at a higher temperature and a longer heating.
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