温控相分离催化的高碳烯烃氢甲酰化反应研究  

Hydroformylation of Higher Olefins Catalyzed by Thermoregulated Phase-separation

作　　者：吴小伟[1] 王艳华[1] 程昉[1] 金子林[1] 

机构地区：[1]大连理工大学精细化工国家重点实验室,大连116012

出　　处：《高等学校化学学报》2002年第10期1939-1943,共5页Chemical Journal of Chinese Universities

基　　金：国家自然科学基金(批准号 :2 990 60 0 1);中国石油化工集团公司石油化工科学研究院资助

摘　　要：考察了非离子表面活性膦配体 P[p-C6 H4 O(CH2 CH2 O) n H]3(PETPP,n=6～ 1 2 ,N=3 n)在有机溶剂中的溶解度 -温度关系 ,发现其在甲苯中具有临界溶解温度 (CST)现象 .基于 PETPP在甲苯中低温分相、高温互溶的 CST特性 ,提出了温控相分离催化的新概念 .并将其应用于癸烯氢甲酰化反应 ,转化率及醛收率分别达到 98.7%和 96.0 % .催化剂循环使用 1 0次 。The solubility of nonionic tension-active phosphine ligand P[p-C 6H 4O(CH 2CH 2O) nH] 3(PETPP, n=6-12, N=3n) in different solvents was investigated. It was found that PETPP(N=18-36) possesses a distinct critical solution temperature(CST) in toluene. A novel concept(Thermoregulated Phase-separable Catalysis, TPSC) based on CST of PETPP for separating a catalyst from the reaction mixture is presented. TPSC system involves only the organic phase, while no water was added. At room temperature(t<CST), the catalyst(PETPP/Rh complex) is insoluble in organic solvent. When being heated to t>CST, the catalyst is soluble in organic solvent. At the reaction temperature(t>CST), the reaction proceeds homogeneously. After the completion of the reaction, on cooling to room temperature(t<CST), the catalyst precipitates from the organic phase. Thus, by decantation, the products could be easily separated from the catalyst. The concept is introduced in the hydroformylation of higher olefins catalyzed by PETPP/Rh complex. The temperature, total pressure, molar ratio of PETPP to rhodium, different N values of PETPP and recycling efficiency of the catalyst on the hydroformylation of 1-decene were investigated. Under the condition: t=130 ℃, p=6.0 MPa[V(H 2)/V(CO)=1/1], the conversion of 1-decene and yield of aldehyde reached up to 98 6% and 96 0%, respectively. After recycling use of the catalyst for 10 times, the conversion of 1-decene was still more than 94.9%.

关 键 词：温控相分离催化 氢甲酰化反应 临界溶解温度 非离子表面活性膦配体 高碳烯烃 

分 类 号：O623.12[理学—有机化学] O643.32[理学—化学]