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

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 (Mw/Mn = 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 (Tg) at 274 °C. The Tg 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.