负载水溶性铑－膦配合物催化1－己烯氢甲酰化反应的研究

将水溶性铑－膦配合物Ｒｈｃｉ（ＣＯ）（ＴＰＰＴＳ）＿２（ＴＰＰＴＳ：Ｐ－（ｍ－Ｃ＿６Ｈ＿４ＳＯ＿３Ｎａ）＿３）负载于扩孔硅胶上，制成负载水相催化剂（ＳＡＰＣ），在高压反应釜中研究其催化１－己烯氢甲酰化的性能。结果表明，催化剂的水含量对其活性影响很大，在一较窄的水含量范围内（２５—３５ｗｔ％），催化剂活性急剧增大，且存在一极大值，表现出水膜催化剂的特性。反应温度、总压和ＣＯ／Ｈ＿２分压、Ｒｈ／Ｐ比的影响，与使用烃溶性能。三苯膦络合催化剂时有类似规律，溶剂的影响不明显，实验证明，ＳＡＰＣ具有良好催化活性，ＳｉＯ＿２上负载的铑配合物不会被原料和产物洗提而造成流失，有利于催化剂的稳定和重复使用。

1-Hexene Hydroformylation on Supported Aqueous-Phase Catalyst of Rhodium Complex

The supported aqueous-phase catalyst(SAPC) has been prepared by impregnating water-soluble organometallic complex RhCl(CO)(TPPTS)_2 (TPPTS is the trisodium salt of tri(m-sulfophenyl)phosphine)onto a hydrophilic SiO_2 with high surface area and narrow pore volume distribution.The 1-hexene hydroformylation on SAPC has been carried out in an autoclave. The effects of the process, parameters such as the Rh/phosphine ratio, temperature, total and partial pressure of H_2/CO,solvent as well as the rhodium and water content of SAPC are studied. The results indicate that the water content of the catalyst can strongly influence the catalytic activity. A maximum of activity is observed when the water content of SAPC is in the range of about25-3 5 wt%. The formation of the water film with a suitable depth on the SiO_2 surface is the key factor for the molecular dispersion and migration of the rhodium complexes in the water film. The hydroformylation of olefin occurs on the inter face of two immiscible phases consisted of water and organic layers. The SAPC is an active immobilized homogeneous catalyst. The rhodium complexes do not leach into the product.