Advances in Living Anionic Polymerization: From Functional Monomers, Polymerization Systems, to Macromolecular Architectures

This Perspective presents the development in living anionic polymerization since 1990. The main subjects involve the following concerns of living anionic polymerization: functional styrene derivatives, new monomers and promising additives, the regio- and stereoselective polymerization, special polymers having rigid-rod-like or helical conformations, the synthesis of complex branched polymers composed of comblike segments via living anionic poly(macromonomer)s, and the precise synthesis of macromolecular architectures including multiblock polymers, exact graft polymers, multicomponent μ-star polymers, dendrimer-like star-branched polymers, and hyperbranched polymers by the recently developed methodologies and a new all-around iterative methodology. Throughout the Perspective, attention has focused on recent advances both in the precisely controlled functional polymer syntheses and in various structurally elaborate complex macromolecular architectures. Such advances have significantly expanded the range of available well-defined specialty functional polymers, which have been difficult to synthesize until recently. The future perspectives based on the present situation will also be described.