Synthesis of polymers carrying adamantyl substituents in side chain

This review addresses the synthesis of various polymers carrying bulky and rigid adamantyl substituents in their side chains. Synthetic methods for these polymers include typical polymer reactions of introducing adamantyl groups into existing polymers and the polymerization of monomers bearing pendant adamantyl groups. In particular, with regard to the latter synthetic method, the addition polymerization of adamantyl-containing vinyl monomers such as alpha-olefins, acetylenes, (meth) acrylates, (meth) acrylamides, vinyl ethers, 1,3-dienes, and styrenes is described. A variety of vinyl monomers are capable of undergoing living anionic polymerization to afford polymers with predictable molecular weights and narrow molecular weight distributions (M-w/M-n = 1.1). In several cases, the introduced adamantyl groups afford steric hindrance to prevent side reactions and control the addition modes of the polymerization. In general, the resulting adamantyl-substituted polymers show extremely high glass transition temperatures and high thermal stability derived from the stiff adamantyl substituents compared with the corresponding parent polymers.