基于氮,膦配体多孔有机聚合物材料的设计合成及其催化应用

Design and Synthesis of N,P-Ligands Based POPs (Porous Organic Polymers) and Their Applications in Heterougeneous Catalysis

多孔有机聚合物(porous organic polymers,POPs)是近年来涌现出的由纯粹的有机分子砌块,通过共价键连接而成的一类具有高比表面积、丰富的孔结构、低骨架密度和良好热稳定性的新型材料。而N,P配体在均相过渡金属络合物催化的氢甲酰化反应、偶联反应、加氢反应、硅氢加成反应,CO2环加成等反应中具有重要的应用,通过合理的设计和修饰N,P配体的电子效应和立体结构,可有效地调控目标产物的收率和选择性。得益于有机合成策略的多样性,POPs材料也具有合成路径及构建方式多样,可较为方便地在聚合物骨架中定点引入特定功能位点的特点,这为基于N,P配体均相过渡金属催化剂的多相化提供了全新的思路与契机。本文将对国内国外相关课题组及本课题组在基于N,P配体POPs材料的设计合成及其催化应用方面所做的工作进行简要的总结归纳,并对该方向进行相应的工业应用前景展望。

Porous organic polymers （POPs）, which were constructed by covalently bonded pure organic molecular building blocks, were a newly-emerging class of material with high surface area, abundant pore structure, low framework density and good heat stability in recent years. On the other hand, N, P-based ligands have widely applications in homogeneous transition metal complexes catalyzed reactions such as hydroformylation reaction, coupling reaction, hydrogenation reaction, hydrosilylation reaction and COz cycloaddition reaction. The yield and selectivity of target products can be effectively controlled by appropriate design and modification of N, P-based ligands with specific electronic and steric effects. Thanks to the diversity of organic synthesis strategies, POPs possess abundant synthesis and construction routes and the specific functional sites can be conveniently introduced into the skeleton of POPs, which provide great perspectives and opportunities for heterogenisation of N, P ligands based homogeneous transition metal complexes catalysts. This paper briefly summarizes the contributions on ＂design and synthesis of N, P-based POPs and their applications in heterougeneous catalysis＂ made by domestic and foreign research colleagues and our group, and provides a future prospect of industrial application of N, P-based POPs.