Inter- and intra-molecular interactions in anionic polymerization of polar vinyl monomers

This review article presents the results on the nature of the active centers of propagation (AC) in anionic polymerization of polar vinyl monomers such as acrylates, methacrylates, vinyl nitrites and vinyl ketones and especially their interactions with donor-acceptor ligands, carried out in the Laboratory of Polymerization Processes of the Institute of Polymers, Bulgarian Academy of Sciences. Particular attention to the interactions involving AC with lithium and magnesium counter-ions was paid due to their strong tendency of interacting with a variety of ligands, as well as in reactions of self-association resulting in numerous possibilities of controlling the structure of the polymers as well as the composition of copolymers. The model compounds or "living"oligomers of polar vinyl monomers were studied intensively by using IR spectroscopy and conductometry. Their physicochemical characteristics in solution, before and after adding of ligands, were investigated. A typical feature is the use of lithium picrate as a model in studying the interactions with monomers, compounds with polar groups, and most typical additives: alkoxide, LiCl, tetraalkylammonium salts and trialkylaluminum compounds.