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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.
The mesoporous silica composite PPh3polymer @ FDU-12 was prepared by in-situ polymerization in mesoporous silica. X-ray diffraction, nitrogen adsorption and desorption, transmission electron microscopy Thermogravimetry and other means were used to characterize its structure and composition.The solid catalyst obtained from the coordination of the composite with the metal precursor Rh (acac) (CO) 2 catalyzed the hydroformylation of 1-octene , The aldehyde selectivity can reach 92% -96%, and show an activity higher than that of the polymer (> 99% conversion), mainly due to the high specific surface area and ordered pore structure of the mesoporous silica material More conducive to reactant and catalytic activity center contact.The study found that the content of the polymer in the modified composite or the use of different pore structure of the silica carrier (SBA-15, MCM-41 and FDU-12) will affect the solid catalyst Of the reactivity and selectivity of the heterogeneous catalyst obtained by the method has good recycle performance, after recycle for 15 times can still maintain a good reactivity, but the aldehyde selectivity decreased.