AbstractThis 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 α-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 (Mw/Mn = 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.This review deals with the synthesis of various polymers carrying bulky and rigid adamantyl substituents in the side chain. The synthetic methods of those polymers include the typical polymer reaction by introducing adamantyl groups to the present polymers and the polymerization of the monomers bearing the adamantyl pendant groups. A variety of vinyl monomers, such as styrenes, 1,3-butadiene, and (meth)acrylates, are capable of the living anionic polymerization to afford the polymers having predictable molecular weights and narrow molecular weight distributions (Mw/Mn =1.1). 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.

中文翻译：

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侧链带金刚烷基取代基聚合物的合成

摘要这篇综述讨论了在侧链上带有庞大而刚性的金刚烷基取代基的各种聚合物的合成。这些聚合物的合成方法包括将金刚烷基引入现有聚合物的典型聚合物反应和带有侧基金刚烷基的单体的聚合反应。特别地，对于后一种合成方法，α-烯烃、乙炔、(甲基)丙烯酸酯、(甲基)丙烯酰胺、乙烯基醚、1,3-二烯、苯乙烯等含金刚烷基的乙烯基单体的加成聚合是描述。多种乙烯基单体能够进行活性阴离子聚合，以提供具有可预测分子量和窄分子量分布 (Mw/Mn = 1.1) 的聚合物。在几种情况下，引入的金刚烷基提供空间位阻以防止副反应并控制聚合的加成模式。一般来说，与相应的母体聚合物相比，所得金刚烷基取代的聚合物显示出极高的玻璃化转变温度和高热稳定性，这源于刚性金刚烷基取代基。 本综述涉及在侧边带有庞大和刚性金刚烷基取代基的各种聚合物的合成链。这些聚合物的合成方法包括通过将金刚烷基引入本聚合物的典型聚合物反应和带有金刚烷基侧基的单体的聚合。各种乙烯基单体，如苯乙烯、1,3-丁二烯和（甲基）丙烯酸酯，能够进行活性阴离子聚合以提供具有可预测分子量和窄分子量分布的聚合物（Mw/Mn = 1.1）。与相应的母体聚合物相比，所得金刚烷基取代的聚合物显示出极高的玻璃化转变温度和源自刚性金刚烷基取代基的高热稳定性。