Living Anionic Polymerization of 4-(1-Adamantyl)-α-Methylstyrene

摘要

Anionic polymerization of a novel α-methylstyrene derivative para-substituted with a bulky and rigid adamantyl group, 4-(1-adamantyl)-α-methylstyrene (AdαMS) is carried out with sec-butyllithium (sec-BuLi) in tetrahydrofuran (THF) at -78 °C. The polymerizations of AdαMS quantitatively proceed to afford the polymers possessing controlled molecular weights and narrow molecular weight distributions (M_w/M_n = 1.03-1.16). The propagating carbanion of poly(AdαMS) is stable and undergoes depolymerization at room temperature due to the low ceiling temperature. The resulting poly(AdαMS) has a significantly high glass transition temperature (T_g) at 274 °C. The T_g values of random copolymers of AdαMS and α-methylstyrene can be controlled by changing the feed molar ratio of the comonomers from 167 to 274 °C.