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. Our recent studies on the polymerization of diazocarbonyl compounds to afford functional polymers are reviewed. In the first part of this article, Pd-mediated polymerization of various functionalized diazoacetates and unique properties of the resulting polymers due to the effects of the dense packing of the functional groups in the polymers are described. The second part of this report summarizes our recent results on the polycondensation of bifunctional diazocarbonyl compounds as monomers.

中文翻译：

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通过 Pd 介导的重氮乙酸酯聚合和双（重氮羰基）化合物缩聚合成功能聚合物

我们最近对重氮羰基化合物聚合以提供功能性聚合物的研究进行了综述。在本文的第一部分中，描述了 Pd 介导的重氮乙酸酯聚合。制备了具有酯取代基的各种官能化重氮乙酸酯，并与基于 Pd 的引发体系聚合以产生聚（取代亚甲基）（PSM），其在主链的每个碳原子上具有官能团。相对于在每个其他碳原子上具有相同官能团的乙烯基聚合物对应物 [聚（取代乙烯）] 的物理和化学性质，检查了所得官能化 PSM 的物理和化学性质，并且由于密集堆积的影响而增强了性能在一些实施例中观察到 PSM 中官能团的变化。本报告的第二部分总结了我们最近关于双官能重氮羰基化合物作为单体的缩聚的结果。三个成功的例子，即（1）通过过渡金属催化的双（重氮乙酸酯）单组分缩聚反应合成定义明确的不饱和聚酯，（2）通过缩聚反应制备新型芳香族多胺描述了双（重氮乙酸酯）与芳族二胺的合成，以及（3）双（重氮羰基）化合物的多组分缩聚反应，提供了前所未有的酸可降解聚合物聚（β-酮烯醇醚）。我们最近对重氮羰基化合物聚合以提供功能性聚合物的研究进行了综述。在本文的第一部分，描述了各种官能化重氮乙酸酯的 Pd 介导聚合，以及由于聚合物中官能团密集堆积的影响，所得聚合物的独特性质。本报告的第二部分总结了我们最近关于双官能重氮羰基化合物作为单体的缩聚的结果。