Anionic Ring-Opening Polymerization of Epoxides and Related Nucleophilic Polymerization Processes

The polymerizations of epoxides by anionic and related nucleophilic ring-opening reactions are reviewed and discussed in this chapter. The elementary mechanisms involved and the main synthetic strategies developed for the preparation of homopolymers and copolymers are described. The chapter is organized as follows. A brief introduction to the subject is provided in the first section. The second section deals with the anionic polymerization of ethylene oxide and substituted epoxides involving alkali metal derivatives as initiators. The use of organic derivatives as either counterion or catalyst is presented in the third section. The fourth section is devoted to the coordinated polymerizations of epoxides by mono- and bimetallic catalytic systems. Finally, the last section examines polymerizations involving monomer activation and the recent progress achieved by this approach in the control of the polymerization of an increasing number of epoxides, including functional ones.