CHAPTER 3: Controlled/Living Radical Polymerization in the Presence of Iniferters

Conventional free radical polymerization is limited in its inability to control polymer properties such as average molecular weight, molecular weight distribution and end-group functionality. New processes are being developed, in which the free radical propagating chain is reversibly terminated, allowing the free radical polymerization to behave in a controlled fashion. The first step in the development of controlled/living radical polymerization (C/LRP) dates back to the early 1980s when it was found that the use of iniferter (namely, agents that initiate, transfer, and terminate) systems exhibited a degree of livingness. Iniferter methodology can be used to polymerize most vinyl monomers under mild reaction conditions via thermal, redox and photochemical activations. The present chapter reviews recent advances in the use of iniferters in the C/LRP, their benefits, and current limitations. Applications of iniferters for the synthesis of telechelic polymers, complex macromolecular architectures and modification of surfaces are also discussed.