Abstract
The decisive initiating step of the thermal degradation of PVC is the random unimolecular elimination of hydrochloric acid from an arbitrary undegraded monomeric unit. Random initiation is associated with activated initiation occurring at structural defects of the polymer at the beginning of the process. The rate constants of initiation (for degradation in DIOA solution, under argon atmosphere) have been determined. The activation energies of random initiation and initiation at structural defects are about 22 and 19 kcal mol- 1, respectively. A temperature dependence with a characteristic trend has been established relating to the concentration of structural defects.
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