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 . Quantum chemical calculation results show that it is more difficult to sulfonation with the increase of sulfonation depth during the sulfonation of triphenylphosphine.A new process of continuously introducing gaseous sulfur trioxide to prepare triphenylphosphine trisulfonate is proposed, With tributyl phosphate as extractant, the molar ratio of SO3 / TPP was 12, reaction time was 66-69h at 20 ~ 24 ℃, yield of trisulfonated product was 97.6% The use of triphenylphosphine for the rhodium / phosphine catalyst ligands in two-phase and multi-phase hydroformylation increases the normal / iso ratio of the product and effectively controls the loss of rhodium.