The Preparation And Its Catalytic Performance Of Anchored Heterogenized Rhodium Phosphino Carbonyl Complex Catalyst

In the thesis, the anchored heterogenized complex catalysts were prepared by the combinative method of sol-gel and anchoring, and the catalytic properties of the catalysts for hydroformylation and hydrogenation were studied.First,2-diphenylphosphine methylene succinic acid and diphenylphosphine propionic acid were prepared from Ph3P by using the usual Schlenk technique and were characterized by NMR and FI-IR. The two compounds reacted with 3-Aminopropyltriethoxysilane to give the ligands with function group -Si(OEt)3, which reacted with [Rh(CO)2Cl]2 to give the correspondent homogeneous complexes. Finally, the anchored heterogenized complex catalysts( I , II) were obtained from thecopolymerization of the above ligand with TEOS by sol-gel method.The catalytic property of the catalyst( I) for hydroformylation was studied. The effects on the catalytic activity and selectivity of reaction temperature, pressure, quantities of catalyst,and time were observed. In the opimized conditions ,the conversion of 1-hexene could go up to 98.5%, selectivity is 92.4% and n/i is 1.43.The catalyst was run for 7 times without deduction of activity at the above conditions. From the result of ICP, XPS and N₂ absorption analysis, we could found that the catalyst( I ) had better recyclability . The catalyst( I ) was also applied to the hydroformylation of other olefins. It was found that the conversion decreased with the order of 1-hexene, l-octylene,l-dodecene,styrene. The n/i of aldehydes decreased with the order of styrene, 1 -dodecene, 1 -octylene, 1 -hexene.The catalysis of the catalyst (II) for the hydrogenation of 1 -hexene was also studied.The effects on the conversion and selectivity of quantities of catalyst, reaction temperature, pressure and time were observed and the optimal reaction conditions were also obtained. Under these conditions the conversion of 1-hexene could go up to 99.0% and the selectivity is 98.8%. The conversion could still go up to 98.9% when the catalyst(II) was run for 9 times. The analysisresults of ICP and XPS showed that the catalyst had better recyclablity. The reaction mechanism for hydrogenation of 1 -hexene with the catalyst( II) was concluded by comparing the FT-IR and XPS spectra of the fresh catalyst and after it was run for 9 times.The catalyst( II) was also applied to the hydrogenation of other olefins. It was found the conversion of it for the hydrogenation of olefins was decreased with increase of the number of carbon atom of olefins.