Abstract
Living radical polymerization mechanisms offer polymers of controlled composition, architecture, and molecular weight distribution. They provide routes to narrow dispersity end-functional polymers, to high purity block copolymers, and to stars and other more complex architectures. The combination of a living mechanism with the scope and versatility of the radical process allows a wider selection of monomers and monomer combinations, and more freedom in choosing reaction conditions. This chapter focuses on the various approaches that have been developed in moving towards a living radical polymerization paying particular attention to the mechanism and the scope of each method. Tests for living radical polymerization are first described. Deactivation by reversible coupling and unimolecular activation is also discussed. The kinetics and mechanism of living radical polymerization are detailed. This chapter also discusses atom transfer radical polymerization, reversible chain transfer, living radical copolymerization, end-functional polymers, block polymers, star polymers and graft copolymers, and polymer brushes.
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