Star-shaped cyclopolymers were first synthesized on the basis of living cationic cyclopolymerization of divinyl ethers bearing a variety of bulky substituents, including cyclohexene, norbornene, norbornane, cyclic acetal, and adamantane groups. All the obtained cyclopolymers exhibited a high degree of cyclization, as high as ~97%, judging from the contents of residual pendant vinyl ether double bonds in the polymers. The glass transition temperatures (Tgs) of both the linear and star-shaped cyclopolymers were in the range of 145−229 °C depending on the pendant substituents. Methacrylate-terminated end-functionalized star-shaped cyclopolymers were synthesized by the functionalized initiator-based living cationic cyclopolymerization of divinyl ethers. The subsequent cross-linked core formation occurred via the reaction of the growing tail termini, whereas the methacrylate head terminals remained intact. The obtained end-functionalized star-shaped cyclopolymers were subjected to a thermal cross-linking reaction to yield star-shaped cyclopolymer networks with film-forming ability.Controlled cationic cyclopolymerizations of divinyl ethers with cyclohexene, norbornene, norbornane, cyclic acetal, or adamantane moiety were carried out. High-molecular-weight star-shaped cyclopolymers were synthesized by the reaction of the formed living cyclopolymers with a small amount of divinyl ether crosslinking agent. Glass transition temperatures (Tg’s) of both the cyclopolymers and star-shaped cyclopolymers were as high as 145−229 oC. Methacrylate-terminated end-functionalized star-shaped cyclopolymers were synthesized by the functionalized initiator-based living cationic cyclopolymerization of divinyl ethers followed by the chain linking reactions among the formed living cyclopolymers with divinyl ether crosslinker. The obtained end-functionalized star-shaped cyclopolymers were subjected to thermal crosslinking reaction to give star-shaped cyclopolymer networks with film-forming ability.

中文翻译：

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通过受控阳离子环聚合合成高分子量二乙烯基醚星形环聚合物及其网络膜

星形环聚合物首先是基于带有各种庞大取代基的二乙烯基醚的活性阳离子环聚合反应合成的，这些取代基包括环己烯、降冰片烯、降冰片烷、环状缩醛和金刚烷基团。从聚合物中残余乙烯基醚双键的含量来看，所有获得的环聚合物都表现出高环化程度，高达~97%。取决于悬垂取代基，线性和星形环聚合物的玻璃化转变温度（Tgs）都在 145-229°C 的范围内。甲基丙烯酸酯封端的末端官能化星形环聚合物是通过二乙烯基醚的官能化引发剂活性阳离子环聚合反应合成的。随后的交联核心形成通过不断增长的尾部末端的反应发生，而甲基丙烯酸酯头部端子保持完整。将得到的末端官能化星形环聚合物进行热交联反应，得到具有成膜能力的星形环聚合物网络。 二乙烯基醚与环己烯、降冰片烯、降冰片烷、环状缩醛或金刚烷部分的受控阳离子环聚合进行了。通过形成的活性环聚合物与少量二乙烯基醚交联剂反应合成高分子量星形环聚合物。环聚合物和星形环聚合物的玻璃化转变温度 (Tg) 均高达 145-229 oC。甲基丙烯酸酯封端的末端官能化星形环聚合物是通过二乙烯基醚的官能化引发剂活性阳离子环聚合反应合成的，随后形成的活性环聚合物与二乙烯基醚交联剂发生链联反应。将得到的末端官能化的星形环聚合物进行热交联反应，得到具有成膜能力的星形环聚合物网络。