聚苯乙烯固载过渡金属催化剂在硅氢加成和加氢反应中的应用

Application of Polystyrene Immobilized Transition Metals as Catalysts for Hydrosilylation and Hydrogenation

聚苯乙烯树脂具有优良的物理化学性能,其与过渡金属的络合物在硅氢加成和催化加氢反应中得到了广泛应用,表现出良好的催化活性、反应选择性和重复使用性能,具有均相催化剂和其他固载型催化剂不具备的优势。利用含配位基团的化合物对聚苯乙烯改性后,可显著提高对金属的配位能力以及催化剂的稳定性,也往往表现出更好的催化性能。鉴于近年来聚苯乙烯固载的过渡金属催化剂在硅氢加成和催化加氢反应中的研究较为引人注目,本文对该类催化剂的制备方法、催化性能及相关机理进行了总结和分析。首先介绍了经胺、膦、巯基、不饱和烃等改性的聚苯乙烯固载的过渡金属催化剂在硅氢加成反应中的应用,其次介绍了聚苯乙烯固载的铂、钯、铑、钌、纳米金、铬、双金属胶体等在催化加氢反应中的应用,重点介绍了聚苯乙烯树脂与金属钯、铑的固载型催化剂,最后对该类催化剂的发展方向进行了分析和展望。

Polystyrene resin has been widely employed as carriers of transition metals due to its excellent physical and chemical properties. The obtained polystyrene-immobilized transition metal complexes generally exhibit high catalytic activity, enhanced reaction selectivity and good reusability, and thus have been attracting great attention for improving the efficiency of hydrosilylation and hydrogenation reactions in recent years. In addition, modifying polystyrene by coordinating-group-containing compounds could significantly enhance the coordination ability to metal ions. Consequently, the resultant catalysts usually provide better catalytic performance. In view of this, the current review summarizes the novel progress for the synthesis and application of polystyrene-immobilized transition metal complexes as catalysts in hydrosilylation and hydrogenation. The preparation method, catalytic performance and the related mechanism are introduced. Firstly, the amine-, phosphine-, mercapto groups-, and unsaturated hydrocarbon-modified polystyrene immobilized transition metals for catalytic hydrosilylation are described. Secondly, polystyrene immobilized transition metals （including Pt, Pd, Rh, Ru, Au nanoparticles, Cr, etc. ） for catalytic hydrogenation are described, with the emphasis on the complexes of Pd and Rh. At last, the development trend of this kind of catalysts is suggested.