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实现共轭双烯烃的高选择性聚合向来是配位聚合领域重要的研究课题.近十五年来,含茂基配体或多齿非茂配体的稀土金属有机配合物作为一种新兴的均相催化剂逐渐引起了人们的关注.根据1999~2014年间的文献报道,以催化剂的顺-1,4,反-1,4和3,4-选择性为分类标志,介绍了多种可高选择性催化共轭双烯烃聚合的稀土金属有机配合物以及人们对聚合活性种的探索,着重阐述中心金属的电子效应和离子半径、配体的几何构型、助催化剂的种类及溶剂、温度等聚合条件对催化剂活性和选择性的影响.通过归纳这些影响因素与聚合机理之间的联系,期望能为科研工作者在研究配位聚合与设计催化剂方面有所帮助.
Achieving the highly selective polymerization of conjugated dienes has always been an important research topic in the field of coordination polymerization.In recent fifteen years, rare earth metal complexes containing cyclopentadienyl ligands or polydentate ligands as a new homogeneous The catalyst has gradually attracted people’s attention.According to the literature reports from 1999 to 2014, based on the cis-1,4, trans-1,4 and 3,4-selectivity of the catalyst as a classification marker, introduced a variety of high selectivity Catalytic conjugated diene polymerization of rare earth metal organic complexes and the exploration of polymerization active species, focusing on the central metal electronic effects and ionic radius, the geometry of the ligand, the type of cocatalyst and solvent, temperature and other polymerization conditions On the activity and selectivity of the catalyst.By summarizing the relationship between these influencing factors and the polymerization mechanism, it is hoped that it will be of great help to researchers in the study of coordination polymerization and catalyst design.