Synthesis of functional polymers by the Pd-mediated polymerization of diazoacetates and polycondensation of bis(diazocarbonyl) compounds
Synthesis of functional polymers by the Pd-mediated polymerization of diazoacetates and polycondensation of bis(diazocarbonyl) compounds
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DOI：
10.1038/s41428-019-0271-7
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发表时间：
2020-03
期刊：
影响因子：
2.8
通讯作者：
Hiroaki Shimomoto
中科院分区：
文献类型：
--
作者：
Hiroaki Shimomoto
综述了近年来我们在重氮羰基化合物聚合制备功能聚合物方面的研究进展。本文第一部分介绍了钯催化的重氮乙酸酯聚合反应。合成了各种含酯取代基的官能化重氮乙酸酯，并用钯引发体系进行聚合，合成了主链上每个碳原子都带有官能团的多取代亚甲基S(PSMS)。与具有相同官能团的乙烯基聚合物[聚(取代乙烯)S]相比，所得到的官能化PSM的物理和化学性质与其他碳原子上具有相同官能团的聚合物相比，在一些例子中观察到由于官能团的致密堆积效应而提高了性能。本报告的第二部分总结了我们在双官能团重氮羰基化合物单体缩聚方面的最新研究成果。介绍了三个成功的例子，即(1)过渡金属催化重氮乙酸酯S的单组分缩聚合成了结构明确的不饱和聚酯；(2)重氮乙酸酯S与芳香族二胺缩聚合成了新型的芳香族多胺；(3)双(重氮羰基)化合物的多组分缩聚得到了一种前所未有的酸降解聚合物--聚β-酮烯醇醚。
Our recent studies on the polymerization of diazocarbonyl compounds to afford functional polymers are reviewed. In the first part of this article, the Pd-mediated polymerization of diazoacetates is described. Various functionalized diazoacetates with ester substituents were prepared and polymerized with Pd-based initiating systems to yield poly(substituted methylene)s (PSMs) with functional groups on each carbon atom in the main chain. The physical and chemical properties of the resulting functionalized PSMs were examined relative to those of their vinyl polymer counterparts [poly(substituted ethylene)s] possessing the same functional groups on every other carbon atom, and enhanced properties due to the effects of the dense packing of the functional groups in the PSMs were observed in some examples. The second part of this report summarizes our recent results on the polycondensation of bifunctional diazocarbonyl compounds as monomers. Three successful examples, namely, (1) the synthesis of well-defined unsaturated polyesters by the transition metal-catalyzed, single-component polycondensation of bis(diazoacetate)s, (2) the preparation of a new type of aromatic polyamine by the polycondensation of bis(diazoacetate)s with aromatic diamines, and (3) the multicomponent polycondensation of bis(diazocarbonyl) compounds affording an unprecedented acid-degradable polymer, poly(β-keto enol ether), are described.