Abstract
The tacticity of different samples of PVC suspension has been measured by 13C NMR spectroscopy. The dehydrochlorination of PVC samples under vacuum with continuous removal of HCl by freezing has been studied at 200 °. The values of the effective constants of dehydrochlorination rates of unstable fragments and normal units of PVC, the values of the initial and the stationary rates of degradation and the total concentrations of unstable groups in PVC samples have been obtained. It has been shown that only the contents of isotactic nonads may be compared with the values of the concentrations of unstable fragments in the samples. There is no correlation between the initial rate of PVC degradation and the content of isotactic triads or nonads. A correlation exists between the total concentration of unstable fragments and the initial rate of degradation of PVC samples. The obtained results give evidence that the tacticity of macromolecules has no significant influence on the initial stage of the thermal degradation of PVC and that the branching groups with the chlorine atom near the tertiary carbon atom and the internal chloroallylic fragments may be the main unstable groups of PVC macromolecules.
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