Rh-TPPTS／CTAB-MMT催化剂的制备及其催化长链烯烃氢甲酰化反应性能研究

Preparation of Rh-TPPTS/CTAB-MMT Catalysts and Their Catalytic Performance of Long Chain Olefin Hydroformylation

通过浸渍法将水溶性铑膦配合物(Rh-TPPTS)负载到由十六烷基三甲基溴化铵(CTAB)修饰的蒙脱土(MMT)上,制备出Rh-TPPTS/CTAB-MMT负载型催化剂.采用XRD,FTIR,TG,BET,31P CP-MAS NMR和分散性实验对催化剂进行了表征.结果表明:水溶性铑膦配合物成功地负载到有机MMT上,并且该催化剂在有机溶剂中具有很好的分散性.该催化剂对于1-癸烯的氢甲酰化反应具有好的催化活性.在100℃、4 MPa、甲苯为溶剂的条件下,催化1-癸烯氢甲酰化可获得93.0%的转化率,95.8%的醛的选择性,2.1的正异比,137 h-1的TOF值.并对不同链长烯烃底物进行了考察.随着烯烃碳链的增加,醛的选择性下降,但是正异比有所增加.

A supported Rh-TPPTS/CTAB-MMT catalyst was prepared by impregnating water-soluble rhodium phosphine complex（Rh-TPPTS） with montmorillonite（MMT） modified with cetyltrimethylammonium bromide（CTAB）.The as-prepared catalyst was characterized by XRD,FTIR,TG,BET,31P CP-MAS NMR,and disper-sibility measurement.The results show that the water-soluble rhodium phosphine complex has been supported on the organic MMT successfully and this catalyst can be well dispersed in organic solvents.Moreover,this catalyst exhi-bits high activity in the hydroformylation of 1-decene.In the optimal reaction conditions（100 ℃,4 MPa syngas and toluene as solvent）,the conversion of 1-decene was 93.0%,the selectivity and TOF（turnover frequency defined as the moles of aldehyde per mole Rh per hour） was 137 h-1.Olefins with different chain length were also investigated.With the increasing of chain length,the selectivity of aldehyde decreases,but the n/i（molar ratio of linear to branched aldehyde） increases.