Mechanisms and kinetics of living radical polymerizations

The polymerization rates and activation processes of several variants of living radical polymerization (LRP) are discussed on the basis of recent experimental and theoretical results. Because of bimolecular termination, which is inevitable in LRP as well as in conventional radical polymerization, the time‐conversion curves of LRP have several characteristic features depending on the experimental conditions, such as the presence or absence of conventional initiation. Despite the presence of termination (and initiation, in some cases), polymers obtained by LRP can have a low polydispersity, provided that the number of terminated chains is small compared to the number of potentially active chains. A large rate constant of activation, k_act, is another fundamental requisite for low polydispersities. Systematic experimental investigation into k_act has clarified the exact mechanisms of activation in several LRP systems. The magnitudes of k_act was found to largely differ from system to system.