Living anionic polymerization

For about 40 years living anionic polymerization has been the premier technique for the synthesis of model polymers of controlled architecture and narrow molecular weight distribution (MWD). Nowadays, despite the continuing development of new strategies for the synthesis of well-defined polymers and copolymers (e.g. group transfer polymerization, living radical polymerization, etc.), anionic polymerization continues to be the most reliable and versatile method for the synthesis of a wide variety of model polymers. The main reason for the broad utility of living anionic polymerization is that the conditions necessary for the efficient generation of polyanions that do not undergo termination or chain transfer reactions are well established for many monomers [Hsieh HL, Quirk RP. Anionic polymerization: principles and practical applications, New York: Marcel Dekker, 1996]. Despite these successes, significant challenges remain in the field of anionic polymerization. These challenges include extension of the strategies for anionic synthesis of polymers with controlled architectures (such as star and graft copolymers), further development of strategies for chain end functionalization, and mastering control over polymerization of (meth)acrylates. Recent advances in these areas are summarized in this article.