Anionic Polymerizations of 1-Adamantyl Methacrylate and 3-Methacryloyloxy-1,1′-biadamantane

Anionic polymerizations of 1‐adamantyl methacrylate (1) and 3‐methacryloyloxy‐1,1′‐biadamantane (2) were carried out in THF at −50 to −78 °C for 24 h. The initiator employed was either [1,1‐bis(4′‐trimethylsilylphenyl)‐3‐methylpentyl]lithium (3)/lithium chloride, or diphenylmethylpotassium. The polymerizations of 1 and 2 proceeded quantitatively to afford the polymers having the predicted molecular weights based on the molar ratios of monomers and initiators and the narrow molecular weight distributions (Mw/Mn = 1.05–1.18), indicating the living character of the polymerization systems of 1 and 2. Novel well‐defined block copolymers, poly[2‐block‐(tert‐butyl methacrylate)], poly(2‐block‐isoprene‐block‐2), and poly[[(2,2‐dimethyl‐1,3‐dioxolan‐4‐yl)methyl methacrylate]‐block‐2], were anionically synthesized by the sequential copolymerization of 2 and comonomers. The poly(2) had the significantly higher glass transition temperature (Tg) of 236 °C and decomposed over 370 °C, while poly(1) started to decompose at around 320 °C before its Tg was reached. This thermal stability can be explained by the substituent effects of the bulky adamantyl and 1,1′‐biadamantyl moieties.