アダマンタン骨格を有する高分子の精密合成

抄録

The coupling polymerization of 3,3'-dibromo-1,1'-biadamantane with magnesium gave the poly(1,3-adamantane) in good yield. The similar poly(1,3-adamantane)s could be obtained by the ring-opening polymerizations of 1,3-dehydroadamantanes (DHA) with trifluoromethanesulfonic acid. In the case of non-substituted DHA, the resulting polymer was not soluble in the various organic solvents. By contrast, the polymerization of butyl-substituted DHA gave the soluble poly(1,3-adamantane) in quantitative yield. DHA also underwent the spontaneous copolymerization with electron-deficient monomers such as acrylonitrile and methyl acrylate without catalyst to afford the alternating copolymers. The anionic polymerizations of 3-(methacryloyloxy)-1,1'-biadamantane, 4-(1-adamantyl)styrene, and 2-(1-adamantyl)-1,3-butadiene provided the stable living polymers possessing the predicted molecular weights and the narrow molecular weight distributions (Mw/Mn=1.1) in quantitative yields. The syntheses of polymers containing adamantyl groups in the main chain or the side chain are attained. All the polymers containing adamantyl skeletons showed high glass transition temperatures and high thermal properties, indicating the drastic effect of introduced adamantane moieties.