Macromolecular models for branched PVC. II. Reactivity of chlorine bound to a tertiary carbon atom in the copolymer vinyl chloride–isopropenyl chloride

The selectivity of the phenolysis reaction of a chlorine atom bound to a tertiary carbon ClT on a macromolecular model, i.e., the copolymer of vinyl chloride–isopropenyl chloride, was verified. The phenolysis reaction can be used as a chemical method to determine ClT in the copolymers. Phenolic polyelectrolytes are obtained as products. The increase of the ClT content leads to an appreciable decrease of the thermal stability of the polymer. The thermal decomposition by dehydrochlorination is a chain reaction. The γ and ultraviolet radiolysis processes did not reveal a remarkable influence of ClT; the samples with an increased ClT content showed a decreased stability towards sunlight. One concludes that when ClT is present in PVC it can initiate the decomposition reaction at lower temperatures than would be expected.