Synthesis and post-polymerization reaction of end-clickable stereoregular polymethacrylates via termination of stereospecific living anionic polymerization
Synthesis and post-polymerization reaction of end-clickable stereoregular polymethacrylates via termination of stereospecific living anionic polymerization
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通过终止立体定向活性阴离子聚合合成可末端点击的立构规整聚甲基丙烯酸酯的合成和后聚合反应
DOI：
10.1039/c4py01285b
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发表时间：
2015
期刊：
影响因子：
--
通讯作者：
Tatsuki Kitayama
中科院分区：
文献类型：
--
作者：
Yasuhiro Kohsaka;Takashi Kurata;Kazuki Yamamoto;Shoya Ishihara;Tatsuki Kitayama
采用活性阴离子聚合方法，通过与α-卤代甲基丙烯酸酯的封端反应，合成了具有高立构规整度和可点击端基的聚甲基丙烯酸甲酯。终止反应是有效的，并容忍的反应条件到这样的程度，几乎定量的末端官能化，在全同立构和间同立构特定的聚合体系中实现。在甲基丙烯酸乙烯酯和甲基丙烯酸三甲基硅酯的聚合反应中也实现了封端反应。然而，对于丙烯酸丁酯的聚合，终止效率被限制为小于69%。此外，在Et 3 N的催化下，不同的硫醇对ω-端的CC双键进行了定量的末端官能化.在碱催化下，带有ω-端CC双键的有规立构聚甲基丙烯酸乙烯酯发生硫醇-烯反应，选择性地保留了乙烯基酯官能团，随后水解得到ω-官能化的有规立构聚甲基丙烯酸。该封端剂与保护的氨基锂的组合提供了具有正交可点击的α-和ω-末端的立构规整的聚（甲基丙烯酸甲酯）。
Poly(methyl methacrylate)s with high stereoregularity and clickable end-groups were synthesized via terminating reactions with α-(halomethyl)acrylates in stereospecific living anionic polymerization. The terminating reaction was efficient and tolerant to the reaction conditions to such an extent that almost quantitative end-functionalization was achieved in isotactic- and syndiotactic-specific polymerization systems. The terminating reactions were also achieved in polymerizations of vinyl methacrylate and trimethylsilyl methacrylate. For the polymerization of butyl acrylate, however, the termination efficiency was limited to less than 69%. Furthermore, the quantitative end-functionalization of the incorporated CC double bond at ω-end was achieved with various thiols catalyzed by Et3N. The base-catalysed thiol–ene reaction of the stereoregular poly(vinyl methacrylate) with a ω-end CC double bond selectively proceeded to retain vinyl ester functions, and the subsequent hydrolysis afforded ω-functional stereoregular poly(methacrylic acid). A combination of the terminating agent with a protected lithium amide afforded stereoregular poly(methyl methacrylates) with orthogonally clickable α- and ω-ends.
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影响因子：
5.5
作者：
Grover GN;Alconcel SN;Matsumoto NM;Maynard HD
通讯作者：
Maynard HD
影响因子：
2.8
作者：
T. Nakano;A. Matsuda;Y. Okamoto
通讯作者：
T. Nakano;A. Matsuda;Y. Okamoto
丙烯酸伯烷基酯与叔丁基锂/大块铝路易斯酸的活性聚合
影响因子：
4.6
作者：
M. Tabuchi;T. Kawauchi;T. Kitayama;K. Hatada
通讯作者：
K. Hatada
影响因子：
5.5
作者：
Tao L;Kaddis CS;Loo RR;Grover GN;Loo JA;Maynard HD
通讯作者：
Maynard HD
(甲基)丙烯酸酯与三烷基甲硅烷基保护的N-苄基酰胺锂的阴离子聚合
影响因子：
2.8
作者：
Takehiro Kitaura;T. Kitayama
通讯作者：
T. Kitayama