Living anionic polymerization of vinyl monomers using benzyltrimethylsilane‐metal alkoxide initiator systems

Abstract Well controlled living anionic polymerization of vinyl monomers was achieved by using the initiator system composed of desilylation of benzyltrimethylsilane (BnTMS) by potassium tert ‐butoxide ( t ‐BuOK) in tetrahydrofuran and trapping the resulting benzyl anion with α‐methylstyrene or 1,1‐diphenylethylene in the initiator system in order to control the desilylation and polymerization reaction. This method led to high initiation efficiency and strict control of molecular weights of the obtained polymers. Furthermore, the initiator system could be applied to the synthesis of a block copolymer of PMMA‐ b ‐P t BMA. These results showed that living nature of the polymer obtained using BnTMS/ t ‐BuOK initiator system in the presence of the appropriate additives.