含磷氮键的金属化合物催化环酯开环聚合  

Ring-Opening Polymerization of Cyclic Ester Catalyzed by Metal Complexes Containing Phosphorus and Nitrogen Bonds

作　　者：王行 薛小盼 蒋友淑 张文娟[1] 马艳平[2] 孙文华[2] Xing Wang;Xiaopan Xue;Youshu Jiang;Wenjuan Zhang;Yanping Ma;Wen-Hua Sun(Beijing Key Laboratory of Clothing Materials R&D and Assessment,School of Materials Design and Engineering,Beijing Institute of Fashion Technology,Beijing 100029,China;Institute of Chemistry,Chinese Academy of Sciences,Beijing 100190,China)

机构地区：[1]北京服装学院,材料设计与工程学院,北京市重点实验室服装材料研究开发与评价中心,北京100029 [2]中国科学院化学研究所,北京100190

出　　处：《化学进展》2024年第10期1425-1442,共18页Progress in Chemistry

基　　金：国家自然科学基金项目(No.51973005)资助。

摘　　要：脂肪族聚酯是重要的可降解材料,可基于生物质转化获得环酯单体进而聚合制备成的大宗树脂;环酯单体到聚酯转化的技术关键是催化剂,新型均相催化剂不仅可以高效地催化环酯开环聚合而且能够实现所得聚酯分子量及结构控制,提升树脂材料的性能。目前科研人员普遍关注席夫碱配位金属化合物,而含有磷氮键配体的多齿配位金属化合物在环酯开环聚合中展示了特异性和巨大价值。虽然氮与磷元素具有相似的电子结构,然而其电负性差异较大,所以含有磷氮键的多齿配体能够帮助调控金属的配位环境并提高环酯开环聚合的催化性能。磷氮键既可以是单键也可以是双键,作为配体与金属配位时总是氮原子优先配位,磷则帮助调控邻近配位氮原子上空间位阻与电子效应,其结果不仅提高了催化活性而且能够对所得聚酯结构实现剪裁。本文集中讨论近年来含磷氮键的金属配合物催化环酯的开环聚合,基于配体结构系统地总结了配体结构与催化性能以及所得聚酯产物微结构的关联,以求推进新型高效配合物催化剂的设计合成,引导产业界选出具有实用价值的催化剂,推动相关科学发展与实现产业化。Aliphatic polyesters are important biodegradable polymers and bulk materials,and their monomers of cyclic esters can come from biomass.The catalysts are the key for converting cyclic esters into polyesters,in which the new homogenous catalysts not only initiate the ring-opening polymerization(ROP)of cyclic esters with high activities but also finely tune the molecular weights and structures of the obtained polyesters and thus improve the polymer properties.Currently metal complexes ligated by Schiff-bases have attracted much attention in the ROP of cyclic esters,in contrast,metal complexes containing the phosphorus-nitrogen bond are very limited but display unique catalytic properties and show the potential for industry.The nitrogen and phosphorus possesssimilar electronic structure but with different electronegativity,which helps to adjust the coordination ability of ligand to metal and thus improve thecatalytic performance in the ROP of cyclic esters.The phosphorus-nitrogen bond can be a single bond or a double bond,and the corresponding metal complexes are commonly formed with nitrogen coordination than phosphine coordination,in which by regulating the steric and electronic of phosphine groups the environment around the adjacent coordinatingnitrogen could be adjusted with resulting in good activity but also in controllability to tailor the microstructure of the resultant polyesters.This review collects the recent progress of such multidentate metal complex catalysts containing phosphine nitrogen bond for ring-opening polymerization of cyclic esters,and summarizes the relationship between ligand structure,catalytic performance,and the microstructure of the resulting polyester,which favor the exploring the new efficient complex catalysts and guiding the industry to select the practical catalysts to promote the scientific development as well as industrialization of related technologies.

关 键 词：磷氮键 金属有机 均相催化 开环聚合 生物可降解聚酯 

分 类 号：O643.6[理学—物理化学]