大孔酚醛树脂表面配位催化中心的构建及其催化烯烃氢甲酰化反应研究

At present, the mobilized hydroformylation catalysts are not being used on an industrial scale for their poor linear selectivity and severe loss of the active component Rh. The way of building the catalytic center of P-Rh complex over the supporters is the direct reason for affecting the performance of the supported catalysts. Based on the excellent outcome of the homogeneous complexes of multidentate ligands and Rh in the hydroformylation reaction, a novel approach is proposed to study the heterogenization of the homogeneous hydroformylation catalyst via building the multidentate chelated catalytic center of P-Rh complex on the surface of the supporter. So the macroporous phenolic resin is selected as the supporter, and the approaches to realizing the multidentate chelated P-Rh catalytic center over the supports is to be explored. The effects of the P coordinated environment on the catalytic performance and the mobilization is to be investigated, so as to prepare the new mobilized P-Rh complex catalyst with high activity and selectivity as well as good stabilization. Additionally, base on this catalytic system, the continuous process of the biphasic hydroformylation of butene to pentanal is to be developed, which will lay the foundation for its industrial application.

目前 ，固载型氢甲酰化催化剂存在直链选择性差和活性组分铑流失严重的问题，很难实现工业化应用。磷-铑配合物催化中心在载体表面的构建方式是影响其催化性能的直接原因。本课题基于均相多齿磷配体与铑的配合物在氢甲酰化反应中表现出的优异性能，提出在载体表面构建多齿螯合磷-铑配合物催化中心的新方法来研究均相氢甲酰化催化剂多相化。拟采用大孔酚醛树脂为载体，通过研究表面羟基的调变和官能化方法，探究在载体表面构建多齿螯合磷-铑配位催化中心的方法和途径。考察磷配位环境对催化剂的催化性能和固载化效果的影响，制备出高活性和选择性，高稳定性的新型固载化磷-铑配合物催化剂。基于这一催化体系，开发连续化的气-固两相丁烯氢甲酰化制戊醛反应过程，为其工业应用奠定基础。

本项目以多孔酚醛树脂为催化剂载体，采用表面官能团修饰的方法制备了固载型铑-膦配合物催化剂，开发了一种均相氢甲酰化反应催化剂固载化的新方法。经过红外光谱、X射线光电子能谱等方法对所制得催化剂的表征，证实了二苯基膦结构配位中心的存在及铑膦配合物催化中心在酚醛树脂载体表面的形成。考察了固载型铑膦配合物催化剂在1-辛烯氢甲酰化反应中的催化性能，所制备的固载型铑膦配合物催化剂与均相催化剂的催化活性相当，且实现催化剂的方便分离与循环使用。