Chain transfer in vinyl acetate polymerization

Abstract Chain transfer constants in the free‐radical polymerization of vinyl acetate have been determined for nearly 100 substances at 60°C. A few measurements at other temperatures or with other monomers are also reported. The transfer constants for vinyl acetate show the expected strong correlation with those for styrene, which has similar polarity. It is emphasized that accurate transfer constants cannot be obtained in strongly retarded systems without knowledge of the relative frequencies of the several termination processes, which in general would demand extensive kinetic data as well as molecular weight measurements. Polymerization rates of vinyl acetate have been determined in a few solvents and used to estimate relative rates of addition of solvent radicals to monomer.