铑-三苯基膦配合物功能化的聚合物@介孔氧化硅复合材料在1-辛烯氢甲酰化反应中的应用(英文)

通过在介孔氧化硅材料中原位聚合的方法制备了三苯基膦功能化的有机聚合物@介孔氧化硅复合材料PPh3polymer@FDU-12.采用X射线衍射、氮气吸附脱附、透射电镜和热重等手段对其结构和组成进行了表征.该复合材料与金属前驱体Rh(acac)(CO)2配位后得到的固体催化剂,在长链烯烃1-辛烯的氢甲酰化反应中,醛选择性可达92%–96%,并表现出高于聚合物的活性(99%转化率).这主要归因于介孔氧化硅材料的高比表面积和有序的孔结构更有利于反应物和催化活性中心的接触.研究发现,调变复合材料中聚合物的含量或使用不同孔道结构的氧化硅载体(SBA-15,MCM-41和FDU-12)都会影响固体催化剂的反应活性和选择性.该方法得到的多相催化剂具有较好的循环使用性能,在循环使用15次后仍能保持较好的反应活性,但醛选择性有所降低.

Rh-PPh3-polymer@mesosilica composite catalyst for the hydroformylation of 1-octene

Rh‐PPh3‐polymer@mesosilica composites were prepared by the polymerization of mixtures of divinylbenzene (DVB) and 4‐vinyl‐triphenylphosphine monomer in the nanopores of mesoporous silicas followed by coordination with Rh(acac)(CO)2 (acac=acetylacetonate). These catalysts were characterized by XRD, N2 sorption, TEM, FT‐IR, and TG, and could efficiently catalyze the hydro‐formylation of 1‐octene with higher activity than a pure polymer catalyst because of their high sur‐face area and large pore volume, which were beneficial for the exposure of active sites and mass transport. Through the control of pore size and pore connectivity by using different mesoporous silica (MCM‐41, SBA‐15, and FDU‐12), the activity and selectivity can be controlled. Rh‐PPh3‐polymer@FDU‐12 with a cage‐like mesostrucuture showed lower activity but slightly higher selectivity than the catalyst with a 2‐D hexagonal mesostructure (Rh‐PPh3‐polymer@SBA‐15 or Rh‐PPh3‐polymer@MCM‐41). By varying the polymer content in the nanopores of the mesosilica, the activity and selectivity (92%–96%) can also be tuned. The solid composite catalyst can be recy‐cled without loss of activity, but a decrease in selectivity was observed.