Kinetics of living radical polymerization of styrene with macromolecular initiator

Kinetics of living radical polymerization of styrene in emulsion initiated by polypropylene hydroperoxide with triethylenetetramine is proposed on the basis of a two stage mechanism. In the first stage fast initiation and propagation occur on the surface of polypropylene. In the second stage continuous chain propagation without termination proceeds in polymer particles in the emulsion. Dependence of rate and degree of polymerization on reaction time, initiator and activator concentrations predicted by the kinetics are ascertained by experimental results. Each polymer particle in the emulsion is suggested to consist of one polymer molecule with a living chain end. Main requisites for the living nature of this system are probably fast and/or limited decomposition and heterogeneity of the initiator in the emulsion polymerization.