Effects of Salts of Metals on Vinyl Polymerization: Part 8. Polymerization of Vinyl Chloride in the presence of Ferric Chloride

Abstract

The polymerization of vinyl chloride in dimethylformamide, initiated with l,l'-azobisisobutyro- nitrile, and retarded with ferric chloride, has been investigated at temperatures from 40 to 70°C. A 6.65 M monomer concentration was used for most of the work, but some polymerizations were carried out using 2.66 M vinyl chloride. At ferric chloride concentrations of >10~3 M termination proceeded entirely by reaction with ferric chloride, but at lower concentrations some mutual termination of growing polymer radicals occurred. Rates of initiation, the activation energy for the initiation reaction, and values of the ratio Kp/Kx, where kx is the rate constant for the reaction between polyvinyl chloride) radicals and ferric chloride, were measured at 40, 50, 60, and 70°C.