载体对负载型水溶性铑膦配合物结构和氢甲酰化性能的影响

Abstract

[中文摘要]以丙烯、 1-己烯氢甲酰化为目标反应 ,研究了载体表面酸碱性、比表面积及孔径等对负载型水溶性铑膦配合物结构和催化性能的影响 .31 P(1 H) - NMR结果显示 ,水溶性铑膦配合物 HRh(CO) (TPPTS) 3负载到未经处理的 Si O2 表面后 ,配合物主要以 { Rh(CO) (TPPTS) 2 }物种形式存在 .负载型催化剂的活性和选择性与载体表面的酸碱性、比表面积、孔径密切相关 .载体孔径应足够大 ,以利于活性物种的负载及反应物 /产物的进出。[英文摘要]In this article influences of supports on the structure and catalysis of supported aqueous-phase catalysts(SAPC) for hydroformylation of propene and 1-hexene were studied. According to the results of 31 P(1H)-NMR it was found that when water- soluble phosphine rhodium complex of HRh(CO)(TPPTS)3 was brought to SiO2, the decomplexation of part of phosphine ligands in the complex occurs due to the strong interaction of basic ligand TPPTS with acidic surface of silica-gel carrier, forming a surface complex.containing two phosphine ligands,i.e.,{Rh(CO)(TPPTS)2}.How ever, when using Na2CO3-pretreated SiO2,the twin signals at D= 44.8 for HRh(CO)(TPPTS)3 in the 31P(1H)2NMR was observed as dominant species in the supported catalyst under identical conditions. The hydroformylarion performance of SAPC is also affected by surface area and pore size of the supports.