Polymerization of diazoacetates: New synthetic strategy for C-C main chain polymers
Polymerization of diazoacetates: New synthetic strategy for C-C main chain polymers
复制标题
DOI：
10.1016/j.polymer.2018.11.049
复制
发表时间：
2019-06
期刊：
影响因子：
4.6
通讯作者：
E. Ihara;Hiroaki Shimomoto
中科院分区：
文献类型：
--
作者：
E. Ihara;Hiroaki Shimomoto
介绍了重氮乙酸酯聚合的最新进展。重氮乙酸酯聚合是一种有效的C1聚合方法，可以从一个碳单元构建C-C主链，因而受到广泛关注。由Cu、Pd、B和微波活化组成的各种引发体系已被揭示可以从相对低分子量的重氮乙酸酯得到聚合物。铑引发的重氮乙酸酯聚合以其以立体定向方式提供高分子量聚合物的能力而引人注目。通过实验和理论研究的结合，阐明了铑引发聚合反应的活性物种和机理细节的本质。重氮基乙酸酯与（CH 2）n-提供单体的共聚产生了独特的聚合物结构的乙烯-丙烯酸酯共聚物。对铑引发聚合得到的聚合物进行了一系列的聚合后改性研究。一些钯基引发体系已被证明是有效的重氮乙酸酯的聚合。引入了多种取代基作为重氮乙酸酯的酯基，并在钯系引发体系下进行聚合。与它们的乙烯基聚合物对应物相比，检查了取代基的密集堆积对所得聚合物的性质的影响，并且在许多实施例中确实观察到聚（取代的亚甲基）中的增强的性质。
Recent progress on polymerization of diazoacetates is described. Polymerization of diazoacetates has attracted much attention as an efficient method for C1 polymerization, which constructs C-C main chains fromone carbon units. A variety of initiating systems consisting of Cu, Pd, B, and microwave activation have been revealed to afford polymers from diazoacetates with relatively low molecular weight. Rh-initiated polymerization of diazoacetates is remarkable for its ability of affording high molecular weight polymers in a stereospecific manner. The essence of the active species and mechanistic details for the Rh-initiated polymerization have been clarified by a combination of experimental and theoretical investigations. Copolymerization of diazoacetate with (CH2)n-affording monomers yielded unique polymer structures comparable to those of ethylene-acrylate copolymers. A series of postpolymerization modification approaches have been examined for the polymers obtained by the Rh-initiated polymerization. Some Pd-based initiating systems have been revealed to be effective for the polymerization of diazoacetates. A variety of substituents were introduced as ester substituents of diazoacetates, and they were polymerized by the Pd-based initiating systems. The effect of dense packing of the substituents on properties of the resulting polymers were examined in comparison to their vinyl polymer counterparts, and the enhanced properties in poly(substituted methylene)s were indeed observed in a number of examples.