Mechanism and Kinetics of Nitroxide-Controlled Free Radical Polymerization (ORGANIC MATERIALS CHEMISTRY-Polymeric Materials)

Abstract

In the nitroxide-mediated free radical polymerization, the rate of polymerization is determined by the balance of the rates of thermal initiation and bialkyl termination, just like in the conventional system, while the polydispersity is determined by the dissociation-combination frequency of the polymer-nitroxyl adduct and the rate of decomposition of the adduct. These mechanisms were quantitatively confirmed by both experiments and computer simulations.