Synthesis of functionalized polymers by means of anionic living polymerization. 1. Synthesis of functionalized polymers with α-methylstyryl groups by anionic reactions with use of 1-{4-[3-(4-isopropenylphenyl)propyl]phenyl}-1-phenylethylene

摘要

Well-defined end-functionalized poly(methyl methacrylate), poly(tert-butyl methacrylate), poly[(2-perfluorobutyl)ethyl methacrylate), and poly(2-hydroxyethyl methacrylate) with α-methylstyryl groups were synthesized by the anionic living polymerization of the corresponding methacrylate monomers (or the trimethylsilyl-protected monomer in the case of poly(2-hydroxyethyl methacrylate)) with the adduct prepared from s-BuLi and 1-{4[3-(4-isopropenylphenyl)propyl]phenyl}-1-phenylethylene (1). Well-defined end-functionalized polystyrene and polyisoprene with α-methylstyryl groups were also synthesized by directly reacting their anionic living polymers with 1 in THF at -78 °C. Furthermore, the polystyrene end-functionalized with two α-methylstyryl groups, the poly(styrene-b-MMA) functionalized with the α-methylstyryl group between the block segments, and the polystyrene functionalized with the α-methylstyryl group within the polymer chain were successfully synthesized by the anionic reactions of polystyryllithium with 1 followed by treating with 4-(3-bromopropyl)-α-methylstyrene, MMA, or the polystyrene with the terminal bromobutyl functionality.