On the Critical Role of RAFT Agent Design in Reversible Addition-Fragmentation Chain Transfer (RAFT) Polymerization

Abstract

There are a certain number of precautions a polymer chemist should take before undertaking a reversible addition-fragmentation chain transfer (RAFT) polymerization with a view of obtaining a polymer with controlled macromolecular characteristics (, PDI) and little or no change of rate of polymerization in comparison with conventional radical polymerization. Among them, a proper selection of the so-called R and Z groups borne by the thiocarbonyl thio skeleton of the RAFT agent is essential and is strongly dependent on the considered monomer. In this review, we introduce the basic concepts associated with the RAFT process like its mechanism and kinetics, and how the RAFT agent structure can strongly influence its reactivity and sometimes lead to undesired kinetic behaviors.

Keywords:

• Reversible Addition-Fragmentation Chain Transfer (RAFT)
• reversible-deactivation radical polymerization (RDRP)
• polymerization
• mechanism
• kinetics

Acknowledgements

Sections 2 and 3 dealing with the mechanism and kinetics of RAFT polymerization were inspired from parts of the following chapter that was recently submitted for publication: Barner-Kowollik, C.; Blinco, J. P.; Destarac, M.; Thurecht, K.J.; Perrier^, S.; Zard, S.Z. “Reversible Addition Fragmentation Chain Transfer (RAFT) polymerization: Mechanism, process, and applications”, In Encyclopedia of Radicals in Chemistry, Biology and Materials, Studer, A., Ed.; Wiley-VCH (In preparation). The author would like to thank Aymeric Guinaudeau for help in the preparation of Tables 1 to 3.