Living cationic polymerization of a novel bicyclic conjugated diene monomer, tetrahydroindene, and its block copolymers with vinyl ether
Living cationic polymerization of a novel bicyclic conjugated diene monomer, tetrahydroindene, and its block copolymers with vinyl ether
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新型双环共轭二烯单体四氢茚及其与乙烯基醚嵌段共聚物的活性阳离子聚合
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发表时间：
2006
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通讯作者：
Y. Okamoto
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作者：
N. Mizuno;K. Satoh;M. Kamigaito;Y. Okamoto
使用基于 SnCl4 的引发体系实现了新型双环共轭二烯单体四氢茚 (THI)（双环[4.3.0]-2,9-壬二烯）的活性阳离子聚合，其中路易斯酸作为源自 2-氯乙基乙烯基醚氯化氢加合物的休眠 C−Cl 末端的活化剂作为引发剂 (1) 在亲核添加剂存在下如乙酸乙酯。所得聚合物的数均分子量与单体转化率成正比增加，并且在整个反应过程中MWD很窄（Mw/Mn~1.2）。通过1H NMR和MALDI-TOF MS分析证实了所得聚(THI)明确的末端结构，表明α端存在引发剂部分，而ω端存在氯。异丁基乙烯基醚 (IBVE) 与 THI 的活性阳离子嵌段共聚产生了由硬非极性 THI 和软极性 IBVE 链段组成的二嵌段和三嵌段共聚物...
The living cationic polymerization of a novel bicyclic conjugated diene monomer, tetrahydroindene (THI) (bicyclo[4.3.0]-2,9-nonadiene), was achieved using the SnCl4-based initiating system, in which the Lewis acid works as an activator for the dormant C−Cl terminal originating from the hydrogen chloride adduct of the 2-chloroethyl vinyl ether as an initiator (1) in the presence of a nucleophilic additive such as ethyl acetate. The number-average molecular weights of the obtained polymers increased in direct proportion to the monomer conversion, and the MWDs were narrow throughout the reactions (Mw/Mn ∼ 1.2). The well-defined terminal structure of the obtained poly(THI) was confirmed by the 1H NMR and MALDI-TOF MS analysis, which shows the presence of the initiator moiety at the α end and the chlorine at the ω end. The living cationic block copolymerization of isobutyl vinyl ether (IBVE) followed by THI led to the di- and triblock copolymers consisting of the hard nonpolar THI and soft polar IBVE segments ...