Catalysis and Separation Using Supported Liquid Phase Catalyst with Organometallic Complexes

以Pd-TPPTS（三苯基膦三磺酸钠盐）为活性组分，乙二醇为载体膜，高比表面积硅胶为载体，制备了负载型液相催化剂。将所制备的催化剂用于甲苯中碘苯与丙烯酸丁酯的Heck偶联反应。考察了催化剂制备变量对Heck反应总速率的影响。结果表明，反应速率随Pd-TPPTS用量的增加或乙二醇用量的减少而加快。这些影响在大量使用时变得不那么明显。当Pd-TPPTS在乙二醇膜中的浓度一定时，反应速率受乙二醇用量的影响不大。因此，可以说，高的Pd-TPPTS浓度和薄的乙二醇膜厚度更适合于实际应用。乙二醇膜与甲苯溶剂之间的界面面积可能随乙二醇的用量变化不大。在反应后，催化剂易于从液体反应混合物中分离。有趣的是，相同的催化剂在第二次运行中显示出比第一次运行更高的活性;在四次循环运行期间观察到活性增加。乙二醇膜在分离、甲苯洗涤和反应过程中会发生状态变化。该催化剂在超临界二氧化碳介质中也是有效的。

Supported liquid phase catalysts were prepared using palladium-TPPTS (triphenylphosphine trisulfonate sodium salt) as an active component, ethylene glycol as a supporting film, and high-surface area silica gel as a supporting material. The catalysts prepared were used for Heck coupling reaction of iodobenzene and butyl acrylate in toluene. The influence of catalyst preparation variables on the overall rate of Heck reaction was examined. It was found that the rate of reaction was enhanced as the quantity of palladium-TPPTS was increased or the quantity of ethylene glycol was decreased. These effects become less marked at larger quantities of them. When the concentration of Pd-TPPTS in the ethylene glycol film was constant, the rate of reaction was little influenced by the quantity of ethylene glycol used. So, it can be said that high Pd-TPPTS concentration and thin ethylene glycol film thickness are better for practical application Probably the interfacial area between ethylene glycol film and toluene solvent little changed with the quantity of ethylene glycol used. It was easy to separate the catalyst from the liquid reaction mixture after reaction. It is interesting that the same catalyst showed higher activity for the second run than for the first one ; the activity was observed to increase during four recycled runs. The state of ethylene glycol film might be changed during separation, washing with toluene, and reaction. The catalyst was also effective in a medium of supercritical carbon dioxide.