Kinetics of polymer degradation involving the splitting off of small molecules: Part 3—Treatment of experimental data for dehydrochlorination of PVC in an inert atmosphere

Abstract

High conversion kinetic runs of PVC dehydrochlorination in a nitrogen atmosphere have been measured. Our data, as well as those available from the literature, have been treated employing the theory developed previously. Excellent agreement has been obtained between theory and experiment. Kinetic parameters obtained by the non-linear least-squares method show that the activation energy and the pre-exponential factor for random elimination of HCl from PVC chains are E α = 170 kJ mol −1 and log ( A s −1 ) = 12·7 independently of the type of polymer. The length of the kinetic chain in the zip propagation varies with PVC type and decreases with increasing temperature. The polymers contain up to 9 mole per cent of structures which do not split off HCl; the content of structural irregularities causing premature zip termination is small.