Living anionic polymerization of styrenes containing adamantyl skeletons

Anionic polymerizations of a series of para-substituted styrene derivatives containing adamantyl groups, 4-(1-adamantyl)styrene (1), 3-(4-vinylphenyl)-1, 1'-biadamantane (2), 4-(1-adamantyl)-α-methylstyrene (3), 4-(1-adamantyloxy)styrene (4), 1-adamantyl 4-vinylbenzoate (5), and N-(1-adamantyl)-N-(4-vinylbenzylidene)amine (6), were carried out in THF at -78 °C. The polymerizations of 1-6 quantitatively proceeded to afford the well-defined polymers possessing the predicted molecular weights and the narrow molecular weight distributions (M_w/M_n = 1.03-1.10). The stability of the propagating chain ends was confirmed by the sequential copolymerizations of 1-6 with various monomers. The resulting poly(1), poly(2), poly(3), poly(4), poly(5), and poly(6) showed remarkably high glass transition temperatures at 234, 232, 273, 184, 227, and 254 °C, respectively, indicating the drastic substituent effect of adamantyl groups.