Kinetics of polymerization initiated by peroxides containing heterocyclic groups. I. Kinetics of bulk polymerization of styrene and vinyl acetate initiated by difuroyl peroxide

Abstract

AbstractThe rate and degree of bulk polymerization of styrene and vinyl acetate initiated by difuroyl peroxide and, for comparison, by dilauroyl and dibenzoyl peroxides were measured at several temperatures as a function of the initiator concentration. Also the rates of initiation were determined by the inhibition method with Banfield's radicals. The rate of polymerization initiated by difuroyl peroxide appears to be lower than could be expected from the rate of initiation determined by the inhibition method and from the decomposition of difuroyl peroxide. In the case of polymerization of vinyl acetate there are significant deviations from the proportionality between Rp and the square root of the initiator concentration, which follows from the conventional kinetic scheme. The degrees of polymerization are also low, and the plots of Pn−1 versus Rp are not linear. These deviations can be accounted for by postulating a retardation effect of the furan cycle and chain transfer to difuroyl peroxide.