The Cutthroat Competition Between Termination and Transfer to Shape the Kinetics of Radical Polymerization

There is a fascinating interplay between termination and transfer that shapes the kinetics of radical polymerization (RP). In one limit all dead‐chain formation is by termination, in the other by transfer. Because of chain‐length‐dependent termination (CLDT), the rate law for RP takes a different form in each limit. However, common behavior is observed if one instead considers how the average termination rate coefficient varies with average degree of polymerization. Examples are given of using these principles to understand trends in actual RP data, and it is also demonstrated how to extract quantitative information on CLDT from simple steady‐state experiments.