Kinetics and Mechanism of the Polyene Formation during Dehydrochlorination of Poly(Vinyl Chloride) in the Solid State

In investigating the thermal, photolytical and chemical dehydrochlorination of poly(vinyl chloride) (PVC) it is shown that the formation of polyenes proceeds independently of the kind of initiation in a fast zip reaction and by the same mechanism. The sequence length distribution of the formed polyenes depends mainly on the conformation of the PVC chains. A strong correlation between this distribution and the conformation equilibrium of the polymer chains as well as the physical structure of the polymer solid is demonstrated.