Solution decomposition of poly(vinylidene chloride): Effect of solvent and evolved HCl

The effect of HCl on the rate of thermal decomposition of poly(vinylidene chloride) (PVDC) in nitrobenzene solution was measured with the object of determining the catalytic activity of HCl. Unlike those reports dealing with PVC decompositions, this study shows that in the absence of a cocatalyst, molecular HCl does not catalyze the decomposition of PVDC. In the presence of metals which can react with HCl to form Lewis acids (e.g., Fe0), a strong accelerating effect was observed. The uncatalyzed reaction shows a large rate increase with increasing polarity of the solvent, suggesting that in nitrobenzene the decomposition is mainly heterolytic in nature.