Carbonylative Polymerization of Epoxides Mediated by Tri-metallic Complexes: A Dual Catalysis Strategy for Synthesis of Biodegradable Polyhydroxyalkanoates.
Carbonylative Polymerization of Epoxides Mediated by Tri-metallic Complexes: A Dual Catalysis Strategy for Synthesis of Biodegradable Polyhydroxyalkanoates.
复制标题
三金属配合物介导的环氧化物的羰基化聚合：合成可生物降解的聚羟基脂肪酸酯的双重催化策略。
作者：
Jinchao Yang;J. Yang;Wen;Xiao‐Bing Lu;Ye Liu
聚羟基烷酸酯（PHA）是一类独特的商业化生产的生物降解聚酯，其性能适合部分替代石油基塑料。本研究以三元金属配合物为催化剂，采用双催化策略，合成了17种Mn值高达38.2kg/mol的新型多羟基脂肪酸.聚合以顺序方式进行，这需要环氧化物到β -内酯的羰基化扩环及其随后的开环聚合，其通过羧酸酯物质在O-烷基键处选择性地发生。环氧化物单体的广泛可用性和结构多样性为PHA提供了各种结构、优异的功能和可调的性质。这项研究代表了一个罕见的例子，使用环氧化物和一氧化碳为原料的PHA的制备。
Polyhydroxyalkanoates (PHAs) are a unique class of commercially manufactured biodegradable polyesters with properties suitable for partially substituting petroleum-based plastics. However, high costs and low volumes of production have restricted their application as commodity materials. In this study, tri-metallic complexes were developed for carbonylative polymerization of epoxides via a dual catalysis strategy, affording 17 products of novel PHAs with up to 38.2 kg/mol M n values. The polymerization proceeds in a sequential fashion, which entails the carbonylative ring expansion of epoxide to β -lactone and its subsequent ring-opening polymerization that occurs selectively at the O- alkyl bond via carboxylate species. The wide availability and structural diversity of epoxide monomers provide PHAs with various structures, excellent functionalities, and tunable properties. This study represents a rare example of the preparation of PHAs using epoxides and carbon monoxide as raw materials.