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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 interface characteristics of RhC (CO) (TPPTS) 2-CTAB-catalyzed 1-dodecene hydroformylation in water / organic two-phase system were studied from the perspective of interfacial chemistry. The results showed that the addition of catalyst and excess ligand decreased the CMC of CTAB. Light scattering and micrographs of the samples showed that there was a balance between CTAB monomer-micellar-O / W emulsions in the CTAB range of 2-7-6 m mol / dm3, O / W microemulsion may be formed at CTAB concentration; the interface of micelles and O / W emulsion droplet is negatively charged, which confirms the interfacial adsorption of high-valent organic counterions; excess ligands maintain equilibrium of rhodium-phosphine complex and make rhodium ( Ⅰ) is stable in the aqueous phase. The micellar interface is the main area where catalysis occurs. The oil / water interface of emulsion droplets is the main channel for the mass transfer of reactive species between water and oil phase.