Kinetic studies of the free cationic polymerization of ethyl vinyl ether and isobutyl vinyl ether initiated by triphenylmethyl hexachloroantimonate

The absolute rate constants for the cationic polymerization of ethyl and isobutyl vinyl ethers have been determined in methylene chloride solution. Under the conditions used, the polymerization proceeded by ‘free ions’. Extremely rigorous drying procedures were used and the values obtained were somewhat higher than those reported in the literature. The values were in reasonable agreement with the ‘free cation’ values obtained by a combination of rate and conductivity measurements of bulk polymerizations, initiated with gamma radiation under ‘super dry’ conditions. The activation energies were also in good agreement.