Cationic Addition Polymerization of 1,4-Dioxene Using GaCl3 as Lewis Acid Catalyst: Long-Lived Species-Mediated Polymerization
Cationic Addition Polymerization of 1,4-Dioxene Using GaCl3 as Lewis Acid Catalyst: Long-Lived Species-Mediated Polymerization
复制标题
使用 GaCl3 作为路易斯酸催化剂进行 1,4-二恶烯的阳离子加成聚合：长寿命物种介导的聚合
DOI：
10.1002/pola.26271
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发表时间：
2012
期刊：
影响因子：
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通讯作者：
Kyohei Uchigami
中科院分区：
文献类型：
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作者：
R. Motokawa;S. Koizumi;T. Hashimoto;M. Annaka and T. Nakahira;H. Amii;竹下 尚貴・橋本 剛・早下 隆士;笹井宏明;Kyohei Uchigami
使用简单的金属卤化物催化剂体系在二氯甲烷中进行1，4-二氧杂环烯（具有两个邻近双键的氧原子的六元环烯烃）的有效阳离子加成聚合。当使用GaCl 3与异丁基乙烯基醚-HCl加合物作为阳离子原在-78 ° C下进行反应时，控制聚合，得到具有预定分子量和相对窄的分子量分布的聚合物。通过单体加成实验和产物聚合物的1H NMR和MALDI-TOF-MS分析进一步证实了增长物种的长寿命性质。虽然进行了高度清洁的增长，但在1，4-二氧杂环戊二烯的受控阳离子聚合期间，表观速率常数发生了变化。根据不同条件下的聚合结果，讨论了变化的原因。所得聚（1，4-二氧杂环戊烯）具有217°C的极高玻璃化转变温度（Tg）和独特的溶解度。© 2012 Wiley Periodicals，Inc. J Polym Sci Part A：Polym Chem，2012
Effective cationic addition polymerization of 1,4‐dioxene, a six‐membered cyclic olefin with two oxygen atoms adjacent to the double bond, was performed using a simple metal halide catalyst system in dichloromethane. The polymerization was controlled when the reaction was conducted using GaCl3in conjunction with an isobutyl vinyl ether–HCl adduct as a cationogen at –78°C to give polymers with predetermined molecular weights and relatively narrow molecular weight distributions. The long‐lived properties of the propagating species were further confirmed by a monomer addition experiment and the analyses of the product polymers by1H NMR and MALDI–TOF–MS. Although highly clean propagation proceeded, the apparent rate constant changed during the controlled cationic polymerization of 1,4‐dioxene. The reason for the change was discussed based on polymerization results under various conditions. The obtained poly(1,4‐dioxene) exhibited a very high glass transition temperature (Tg) of 217°C and unique solubility. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012