两相催化体系中长链烯烃氢甲酰化反应研究 反应初期的界面化学特征  

THE INTERFACIAL CHARACTERISTICS OF 1 DODECENE HYDROFORMYLATION IN BIPHASE CATALYTIC SYSTEM

作　　者：陈华[1] 何玉萼[1] 戴智耀 王良兵[1] 李贤均[1] 

机构地区：[1]四川大学化学学院,成都610064

出　　处：《催化学报》1999年第6期628-632,共5页

基　　金：国家自然科学基金;中国石化总公司联合资助

摘　　要：从界面化学的角度研究了水／ 有机物两相体系中ＲｈＣｌ（ＣＯ）（ＴＰＰＴＳ）２ＣＴＡＢ催化１十二碳烯氢甲酰化反应初期的界面特征． 结果表明，催化剂及过量配体的加入，使ＣＴＡＢ的ＣＭＣ降低．样品的光散射及显微照片表明，在ＣＴＡＢ 浓度为２－７ ～６ ｍ ｍｏｌ／ｄｍ３ 范围内，体系中存在着ＣＴＡＢ单体胶束Ｏ／ Ｗ 型乳状液间的平衡，在较高ＣＴＡＢ浓度下可能形成Ｏ／ Ｗ 型微乳； 胶束及Ｏ／ Ｗ 型乳状液滴界面呈负电性，证实高价有机反离子的界面吸附； 过量配体维持铑膦络合平衡并使铑（ Ⅰ） 稳定存在于水相； 胶束界面是发生催化反应的主要区域，乳状液滴的油／ 水界面则是反应物种在水油相间进行传质的主要通道．The initial interfacial characteristics of 1 dodecene hydroformylation catalyzed by water soluble rhodium phosphine complex RhCl(CO)[P( m C 6H 4SO 3Na) 3] 2 in CH 3(CH 2) 15 N(CH 3) 3 Br(CTAB) aqueous solution at 60 ℃ have been studied. The critical micelle concentration (CMC) of CTAB reduced to 0 3～0 4 mmol/dm 3 because of the addition of catalyst and excessive phosphine ligand. The light scattering and the microphotograph showed that there is dynamic balance among CTAB monomers, micelle and O/W emulsion in the CTAB concentration range of 2 7～6 0 mmol/dm 3, and that the microemulsion was probably formed at higher concentration of CTAB. The interface of micelle and emulsified oil drops appeared negative charge caused by the tight adsorption of organic multivalence counterions [P( m C 6H 4SO 3) 3] 3- and HRh(CO) x [P( m C 6H 4SO 3) 3] 3n- n . Excessive ligand keeps the stability of catalyst in water phase. The chief chemical steps of catalytic cycle take place mainly at the micelle interface, organic reactants and products are transported through the oil/water interface of emulsified oil drops.

关 键 词：十二碳烯 氢甲酰化 铑膦配合物 长链烯烃 催化剂 

分 类 号：O623.511[理学—有机化学] O643.36[理学—化学]