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

Well-defined end-functionalized poly(methyl methacrylate), poly(tert-butyl methacrylate), poly[(2-perfluorobutyl)ethyl methacrylate), and poly(2-hydroxyethyl methacrylate) with alpha-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 alpha-methylstyryl groups were also synthesized by directly reacting their anionic living polymers with 1 in THF at -78 degrees C. Furthermore, the polystyrene end-functionalized with two alpha-methylstyryl groups, the poly(styrene-b-MMA) functionalized with the alpha-methylstyryl group between the block segments, and the polystyrene functionalized with the alpha-methylstyryl group within the polymer chain were successfully synthesized by the anionic reactions of polystyryllithium with 1 followed by treating with 4-(3-bromopropyl)-alpha-methylstyrene, MMA, or the polystyrene with the terminal bromobutyl functionality.