Abstract
High conversion kinetic runs of the thermal dehydrochlorination of PVC in an atmosphere of HCl have been treated employing a theory developed previously. Excellent agreement between theory and experiment has been reached for the immediate zip growth model. The kinetic parameters obtained by the non-linear least-squares method show that the activation energy and the pre-exponential factor of random elimination of HCl from PVC are identical with those for the inert atmosphere. In its interaction with degraded parts of the polymer chain, HCl catalyzes the initiation step of the zip reaction. HCl also causes the elongation of polyene sequences, mainly for temperatures below 220°C. The results suggest that the elongation occurs even for low concentrations of HCl in the polymer. The content of structural irregularities causing premature zip termination is small.
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