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 ( M w / M n = 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 ( T g ) of 236 °C and decomposed over 370 °C, while poly( 1 ) started to decompose at around 320 °C before its T g was reached. This thermal stability can be explained by the substituent effects of the bulky adamantyl and 1,1′‐biadamantyl moieties. magnified image