Kinetics of "living" free radical polymerization

Living free-radical polymerization (LFRP) of styrene is usually performed following two different reaction procedures: by TEMPO-mediated LFRP or by atom transfer radical polymerization. The main difference between the previous two processes is related to how the exchange between the active and the dormant state of the polymer chains is performed. A mathematical model suitable for handling both processes is presented. Its validation has been performed by comparison with experimental data taken both from the literature and from our laboratory. These comparisons are intended to cover the most significant reaction conditions a LFRP of styrene can offer. In spite of a limited parameter fitting, the general reliability of the model has been confirmed. Thus, the model is thought to have a potential in designing the proper conditions to improve the LFRP. (C) 1999 Elsevier Science Ltd. All rights reserved.