三磺化三苯基膦(TPPTS)制备方法的改进

Improvement of Synthesis Method of TPPTS

量子化学计算结果表明 ,在三苯基膦磺化过程中 ,随磺化深度的增加 ,磺化难度加大 .提出了连续通入气态三氧化硫制备三磺化三苯基膦的新工艺 ,以磷酸三丁酯为萃取剂 ,SO3/TPP摩尔比为 1 2 ,在 2 0～ 2 4℃温度下反应 66～ 69h,三磺化产物收率可达 97.6% .将制得的三磺化三苯基膦用于两相和多相氢甲酰化反应的铑 /膦催化剂配体 ,提高了产物的正 /异比 ,有效地控制了铑的流失 .

The results of semiempirical AM1 calculation of quantum chemistry indicate that in the course of TPP sulfonating, the difficulty of sulfonation increases with the increase of sulfonation reaction. An improved process for synthesis of TPPTS was suggested by introducing fresh SO 3 gas into the reactor. The tributylphosphate was employed as an extractant. With a SO 3/TPP molar ratio 12, temperature 20~24 ℃ and reaction time 66~69 h, the yield of TPPTS reaches 97.6%. TPPTS was employed as the ligand of rhodium/phosphine catalysts, which were applied to the biphase and supported aqueous phase (SAP) hydroformylation reactions. The result shows that the n/i ratio can be increased significantly, and the lose of Rh can be controlled effectively.