Initiators for anionic polymerization: Old and new developments

Abstract

Anionic polymerization techniques offer powerful methods for the controlled manipulation of macromolecular architecture, and are still today unique for the synthesis of a wide variety of model polymeric materials. The high–vacuum technique employed in classical anionic polymerization methodology requires highly developed and specialized skills, since the polymer scientist must possess both an adept glassblowing ability and a thorough understanding of the behavior of compounds (volatile and non volatile) in a vacuum environment. In addition, high–vacuum techniques are time consuming and usually lead to the synthesis of only a few grams of model polymeric materials. However, these ―limitations‖ are a small price to pay given their potential for generating homogeneous macromolecular polymers. Complex macromolecular architectures such as linear multiblocks, branched or cyclic homo and block polymers, stars with different number of branches, u stars, and more complex structures, like dumbbell, model elastomeric networks or comb copolymers, can be obtained by using this powerful method if appropriate initiators and experimental conditions are chosen. In this work, we present an up-to-date review of the literature regarding initiation for anionic polymerization.