温控PEG两相体系催化三聚丙烯氢甲酰化  

Hydroformylation of Tripropene in Thermoregulated PEG Biphasic Catalytic System

作　　者：杨玉川[1] 蒋景阳[1] 王艳华[1] 刘春[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,辽宁大连116012

出　　处：《催化学报》2007年第6期557-560,共4页

基　　金：国家自然科学基金(20376013);霍英东教育基金会基金(91071).

摘　　要：将具有“高温混溶、室温分相”特征的温控PEG(聚乙二醇)两相催化体系用于三聚丙烯氢甲酰化反应.系统研究了以Rh(acac)(CO)2/TMPGP(TMPGP:P[O(CH2CH2O)nCH3]3,n=8)为催化剂时各种反应条件对三聚丙烯氢甲酰化反应的影响,并考察了催化剂的循环使用效果.在合成气压力6MPa(CO/H2体积比为1)及温度为130℃的反应条件下,三聚丙烯氢甲酰化反应的转化率和醛收率可分别达77%和75%.室温下分离得到的含催化剂的PEG相循环使用11次,催化剂活性基本保持不变,第一次循环的铑流失率为1.5%(质量分数),11次循环的平均铑流失率为0.69%.于-20℃下分相得到的催化剂相可循环使用15次,其催化活性保持不变,第一次循环的铑流失率可降至0.16%.The thermoregulated PEG （polyethylene glycol） biphasic catalytic system, which has a characteristic of ＂being homogeneous at high temperature and biphasic at room temperature＂, was applied for the hydroformylation of tripropene catalyzed by Rh （acac） （CO） 2/TMPGP （ TMPGP ： P [ O （ CH2 CH20） n CH3 ] 3, n = 8 ）. The effects of reaction conditions on the reaction and the catalyst recycling efficiency were studied systematically. Under the optimized reaction conditions （V（CO） / V（H2） = 1, 6 MPa, and 130 ℃ ）, tripropene conversion and aldehyde yield reached 77% and 75 %, respectively. The PEG phase containing the catalyst was separated at room temperature and recycled 11 times without significant loss of catalytic activity. The Rh leaching into the product phase in the first run was 1.5 % （mass fraction）, and the average Rh loss for each run of the 11 cycles was 0.69 %. Further studies showed that the catalyst phase could be recycled 15 times without loss of catalytic activity when the whole catalytic system was cooled to - 20 ℃, and the Rh leaching into the product phase was only 0.16 % in the first run.

关 键 词：聚乙二醇 温控PEG两相催化 铑 三聚丙烯 氢甲酰化 

分 类 号：O643.32[理学—物理化学]