水溶性铑－膦配合物催化长链烯烃氢甲酰化反应研究──反应条件的影响

Olefin Hydroformylation Catalyzed by Water-Soluble Rhodium Complex Rhcl(CO)(TPPTS)_2──Effect of the Reaction Parameters

本文研究了两相催化体系中，在ＣＴＡＢ（Ｃ＿（１６）Ｈ＿（３３）ＮＭｅ＿３Ｂｒ）存在下，水溶性铑－膦配合物ＲｈＣｌ（ＣＯ）（ＴＰＰＴＳ）＿２对１－己烯氢甲酰化反应的催化性能，详细考察了反应温度、压力、膦／铑比等对催化活性的影响。结果表明，在１．０ＭＰａ恒压下，反应温度１００℃，膦／铑摩尔比为１６，Ｈ＿２：ＣＯ＝１：１的条件下，１－己烯氢甲酰化的转化频率（ＴＯＦ）可达到３９．８ｍｉｎ￣（－１）。在此反应条件下，有机相和水相容易分离，铑－膦配合物流失到有机相中的量极小。

The catalystic properties of water-soluble rhodium complex,RhCl(Co)(TPPTS)_2 [TPPTS:P(m-C_6H_4SO_3Na)_3],for hydroformylation of the long-chain olefin in the biphasic system and in the presence of CTAB (C_(16)H_(33)Nme_3Br)were studied.The influence of reaction parameters, such as temperature,total pressure,partial pressure ratio of CO to H_2 and molar ratio of TPPTS to Rh,was extensively investigated. The addition of CTAB into the biphasic catalytic system accelerated markedly the reaction rate.Under the reaction conditions: total pressure 1.0 MPa,CO:H_2=1:1,100℃,TPPTS/Rh=16,the turnover frequencies for hydroformylation of 1-hexene,1-octene and 1dodecene were 39.8,38.8 and 37.5 min￣(-1),respectively.The ratio of branched aldehyde to normal aldehyde was≥3.6.The organic products and the aqueous solution of catalyst could be easily seperated by decantution.The additive surfactant CTAB in a range of suitable concentration did not influence the seperation of two phases.