Poly(substituted Methylene) Synthesis: Construction of C―C Main Chain from One Carbon Unit
Poly(substituted Methylene) Synthesis: Construction of C―C Main Chain from One Carbon Unit
复制标题
DOI：
10.1007/12_2009_46
复制
发表时间：
2010
影响因子：
--
通讯作者：
E. Ihara
中科院分区：
文献类型：
--
作者：
E. Ihara
本文综述了由一个碳单元构成的C-C主链聚合物的制备方法。这种策略的第一个例子是重氮烷和芳基重氮甲烷的聚合，尽管单体的爆炸性很高，但在1950-1970年期间，这两种聚合物被广泛研究。金属表面催化重氮烷聚合是一种制备纳米级聚亚甲基薄膜的有效方法，可替代聚乙烯薄膜，近年来受到广泛关注。具有不同取代基的重氮羰基化合物如重氮乙酸酯、重氮酮和重氮乙酰胺已通过钯配合物聚合得到具有极性官能团的聚（取代亚甲基）。Rh（diene）配合物以立体定向的方式取代重氮乙酸乙酯，得到高分子量聚合物（Mn高达270，000）。有机硼烷引发的亚砜次甲基的活性聚合是制备具有可控链长和明确聚合物结构的聚亚甲基的非常有效的方法。还描述了与上述实施例相关的一些聚合。
This review describes recent progress in the preparation of C–C main chain polymers, where the main chain is constructed from one carbon unit. The first example for this strategy is polymerization of diazoalkanes and aryldiazomethanes, which were extensively explored in the period 1950–1970, despite the high explosiveness of the monomers. The metal surface-catalyzed polymerization of diazoalkanes has recently attracted much attention, as an efficient method for coating the surface with nanometer-scale polymethylene thin films, which can be regarded as a useful substitute for polyethylene films. Diazocarbonyl compounds such as diazoacetates, diazoketones, and diazoacetamides with a variety of substituents have been polymerized by Pd-complexes to give poly(substituted methylene)s with polar functional groups. Rh(diene) complexes polymerize ethyl diazoacetate in a stereospecific manner, giving high molecular weight polymers (Mnup to 270,000). Organoborane-initiated living polymerization of sulfoxonium methylides is remarkably effective as a method for preparing polymethylenes with a controlled chain length and a well-defined polymer architecture. Some polymerizations related to the above examples are also described.