Synthesis Of Zirconium Phosphonate-Supported Palladium Catalysts And Application In The Catalytic Hydrogenation Reaction

In this thesis, using phenylglycine and phenylalanine as raw materials, the aminoalcohol functional group was covalently linked to the backbone of zirconium phosphonates by the several synthetic steps: esterification, nucleophillic addition, Mannich and precipitation, and the hydroxyl group in the internal and external surface was partially modified by ClPPh2. PtCl2(COD) and Na2PdCl4 particles were anchored into the backbone of zirconium phosphonate by the complexing reaction with oxygen and phosphorus atom and organosoluble zirconium phosphonate-supported palladium and platinum catalysts in THF and CHC13 had been obtained.This type of zirconium phosphonate-supported palladium and platinum catalysts were all soluble in THF with the good solubility (0.26-0.32 g/mL). Furthermore, supported platinum catalysts were also soluble in CHCl3 with the solubilities (0.18-0.21 g/mL). While the second solvent (twice volume) such as n-hexane, petroleum ether, cyclohexane and other nonpolar solvent was added, the supported catalysts quantitatively precipitated out from the homogeneous phase and recycled. The N2 adsorption-desorption isotherms and TEM showed that the catalysts 7a, b and 8a, b possessed the layered, mesoporous and filiform structure.The zirconium phosphonate-supported palladium catalysts 7a, b can smoothly catalyze the hydroge-nation of acetophenone and its derivatives in the homogeneous phase. The 95.9% conversion of acetophenone and 87.2% yield of 1-phenyl-l-ethanol were obtained. The optimum catalytic conditions were shown as follows:CH3OH/THF (v/v=3:1),1 mol%Pd and 7 h with stirring at 30℃. After the reaction was completed, the second solvent (twice volume) such as n-hexane, petroleum ether, cyclo-hexane and other nonpolar solvent was added, and zirconium phosphonate-supported palladium catalysts 7a, b precipitated out and recovered by the centrifugation and filtration. The zirconium phosphonate-supported palladium catalysts 8a, b had no activity in catalytic hydrogenation of pyruvate ethyl ester and acetophenone.