Investigation of the radical polymerization of vinyl acetate and its telomerization with carbon tetrachloride at high pressures

Abstract

1. The average molecular weight of polyvinyl acetate in radical polymerization increases only 50% when the pressure is raised from atmospheric to 4000 kg/cm2. The rate constant of chain propagation increases with increasing pressure only slightly more rapidly than the rate constant of chain transfer through the monomer. 2. The composition of telomers of vinyl acetate and carbon tetrachloride is practically unchanged when the pressure is raised from atmospheric to 3000 kg/cm2. The rate constant of chain transfer to carbon tetrachloride (during telomerization) and the rate constant of chain propagation (in polymerization of vinyl acetate) increase to approximately the same degree with increasing pressure. 3. The rate of radical telomerization of vinyl acetate with carbon tetrachloride triples when the pressure is raised from atmospheric to 3000 kg/cm2. Chain termination in the process studied evidently is accelerated with increasing pressure.