Well‐Controlled Living Polymerization of N‐Propargylamides and Their Derivatives by Rhodium Catalysis
Well‐Controlled Living Polymerization of N‐Propargylamides and Their Derivatives by Rhodium Catalysis
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铑催化下 N-炔丙酰胺及其衍生物的可控活性聚合
DOI：
10.1002/anie.202117234
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发表时间：
2022
期刊：
影响因子：
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通讯作者：
Maeda Katsuhiro
中科院分区：
文献类型：
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作者：
Ito Kosuke;Taniguchi Tsuyoshi;Nishimura Tatsuya;Maeda Katsuhiro
已经开发出一种显着改进的 N-炔丙基酰胺及其衍生物的活性聚合方法。带有芳基取代的1,3,5-己三烯链的铑(I)络合物可以作为此类非共轭末端炔烃聚合的优异引发剂，从而得到具有窄分子量分布的相应顺式立构聚合物。通过研究单体与引发剂的初始进料比对所得聚合物的分子量以及多级聚合的影响，已经证实了典型的活性性质。此外，我们证明，本方法能够实现聚合物链端的官能化，并合成由聚（N-炔丙酰胺）和聚（苯乙炔）嵌段组成的具有窄分子量分布的新型嵌段共聚物。
A substantially improved method for living polymerization ofN‐propargylamides and their derivatives has been developed. Rhodium(I) complexes bearing an aryl‐substituted 1,3,5‐hexatriene chain can work as excellent initiators of the polymerization of such non‐conjugated terminal alkynes to give the correspondingcis‐stereoregular polymers having a narrow molecular weight distribution. The typical living nature has been confirmed by investigating the effects of initial feed ratios of the monomer to the initiator on the molecular weight of the resulting polymers as well as multistage polymerization. Moreover, we demonstrated that the present method enables functionalization of both polymer chain ends and synthesis of novel block copolymers consisting of poly(N‐propargylamide) and poly(phenylacetylene) blocks with a narrow molecular weight distribution.