Abstract
Kinetic features and the mechanism of proton-transfer anionic polymerization of vinyl monomers (2-hydroxyethylacrylate (HEA) and l-hydroxyethylmethacrylate (HEMA) bearing groups with mobile hydrogen atom are discussed. It is established that polymerization combines features of chain growth and step growth polymerization. The living chain polymerization mechanism dominates at heterogeneous proceeding of the reaction. The peculiarities of the HEA and HEMA polymerization mechanism under the action of alkaline metals and their alcoholates are established. Polymerization initiated by tert-BuOLi is accompanied by a transesterification reaction with formation, along with macromonomer as main target product, of polyester di(met)acrylates, polyester diols and macrocycles. In addition to the transesterification reaction at HEMA polymerization initiated by potassium, formation of carbon chain fragments caused by interaction of enolate anion with double bond is revealed.
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