Kinetic subtleties of nitroxide mediated polymerization

Due to the academic and industrial interest of Nitroxide Mediated Polymerization (NMP), a lot of investigations have focused on the kinetics of this process. During the last decade, although the simplified kinetic scheme--equilibrium reactions between dormant species (alkoxyamine) and active species (alkyl radicals and nitroxides), propagation reaction of the macro-alkyl radical, and termination reactions--was suitable to predict the main trends at the macromolecular level, it has become obvious that it was not sufficient to describe all the kinetic effects involved in the NMP process. Indeed, like the conventional radical polymerization, NMP should be described as a 3 stage process including initiation, propagation, and self- and cross-termination. These two types of radical polymerization differ by the occurrence during NMP of an activation/deactivation process involving the dormant species in both the initiation and propagation stages. Evidence is provided of the importance of the rate of homolysis of the initiator (alkoxyamines) and of the rate of the first alkyl radical addition onto the monomer for the success of NMP. Thus, the fundamental kinetics of the main reactions involved in NMP as well as side-reactions are also discussed in this tutorial review.