迁移插入聚合法合成主链含金属聚合物及其电化学性能研究

Migration insertion polymerization and electrochemical properties of main chain metal-containing polymer

考察了迁移插入聚合技术在含金属主链聚合物上的合成。将易于获得的通过烷基间隔基相连的两个茂基二羰基铁(Fp)配合物AA和通过烷基间隔基相连的两个膦配体BB通过迁移插入进行聚合,得到稳定的含金属主链聚合物。在优化条件下,聚合物Mn高达13 950。所得聚合物通过NMR、IR、GPC、DLS、TEM、CV等进行了表征,所获得的含金属主链聚合物可溶于多种有机溶剂,并展现出可逆的氧化还原性质,氧化还原特性可随聚合物链在不同溶液中而变化,有机金属聚合物的氧化还原特性变化与聚合物链在溶液中的构型变化所引起的铁-羰基络合物的状态密切相关。含金属主链聚合物在H2O-THF溶液中的自组装呈现规则的平均直径为142nm的聚集体。

The migration insertion polymerization(MIP)technique on the main chain metal-containing polymer(MCP)synthesis was optimized.The readily available A-A(two Fp groups into one molecule via an alkyl spacer and capable of migration insertion reaction)and B-B(two neutral phosphine ligands into one molecule via an alkyl spacer)type monomers were employed to polymerization via MIP,resulting in stable MCPs.Under optimized conditions,the polymer Mn could reach as high as 13 950.The polymer was well characterized by NMR,IR,GPC,DLS,TEM and CV.The obtained MCP was soluble in various organic solvents and exhibited reversible redox properties.The redox characteristics could vary with polymer chains in different solutions,the redox characteristic change of the MCP should be closely related to the state of the iron-carbonyl complex caused by the change of the conformation of the polymer chain in solution.The self-assembly behavior of MCP in solution was also preliminarily tested and the self-assembly of the MCP in H 2O-THF solution exhibited a regular aggregates with average diameter of 142 nm.