Co基催化剂在氢甲酰化反应中的应用研究进展

Research progress on application of Co-based catalysts in hydroformylation reaction

氢甲酰化反应是工业中重要的合成醛的过程。目前,氢甲酰化反应中使用的催化剂以Rh和Co基催化剂为主,其中Rh基催化剂主要应用于短链烯烃的氢甲酰化,中长链烯烃的氢甲酰化仍采用Co基催化剂。以Co基催化剂为主线,重点综述了均相和多相负载型Co基催化剂的制备及在氢甲酰化反应中的应用研究进展。分析表明,在均相Co基催化剂中引入给电子能力强、空间位阻大的烷膦配体有助于提高产品醛区域选择性并使反应条件变得更温和。在多相负载型Co基催化剂中,载体种类及性质、贵金属助剂、金属前驱体、配体及制备条件等均能对氢甲酰化反应催化性能产生影响。今后可以设计合成给电子能力强、空间位阻大的烷膦配体,将其负载于具有高比表面积、多级孔道结构的载体上或通过官能团修饰将配体多相化负载金属Co以提高其氢甲酰化反应催化性能。

Hydroformylation reaction is an important process for aldehydes synthesis in industry.The catalysts used in hydroformylation reaction are mainly Rh and Co-based catalysts,among which Rh based catalysts are mainly applied for the hydroformylation of short-chain olefins,while Co-based catalysts are mainly empolyed in the hydroformylation of mid-and longchained olefins.With Co-based catalysts as the main line,the preparation of homogeneous and heterogeneous supported Co catalysts and their applications in hydroformylation were reviewed.The analysis reveals that the introduction of alkylphosphine ligands with high electron-donating and steric hindrance in homogeneous Co-based catalysts can improve the regioselectivity of product aldehydes and moderate the reaction conditions.In the heterogeneous supported Co-based catalysts,the type and properties of supports,nobal metal promoters,metal precursors,ligands and preparation conditions can affect the performance of hydroformylation reaction.In the future,alkylphosphine ligands with strong electron-donating ability and high steric hindrance can be designed and synthesized,which can be supported on the supports with high specific surface area and hierarchical pore structure,or the ligands can be heterogenized and supported with metal Co through functional group modification to improve its catalytic performance in hydroformylation reaction.