Abstract

Anionic initiators for chain-reaction polymerization are described. The general relationship between monomer structure, pK_a, and appropriate initiating species is discussed. The scope and limitations of the use of alkali metals, aromatic radical anions, nuclides, alkyllithium, and other organoalkali compounds, organomagnesium and organobarium compounds, diphenylmethyl carbanions, fluorenyl carbanions, enolate anions, metal free compounds, and alkoxides as initiators are presented. The uniqueness of alkyllithium initiators in hydrocarbon solvents for controlled, living, anionic polymerization is discussed.