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温控离子液体两相中烯烃的氢甲酰化和环丙烷化

Hydroformylation and Cyclopropanation of Alkenes in the Thermoregulated Ionic Liquid Biphasic System

【作者】 谭波

【导师】 金子林; 蒋景阳;

【作者基本信息】 大连理工大学 , 应用化学, 2008, 博士

【摘要】 在本课题组提出的温控离子液体液/液两相催化基础上,深入研究了离子液体IL350,IL550和IL750与甲苯-正庚烷组成的三组分体系的相图,并从中筛选出两相区宽、温控功能明显的IL750-甲苯-正庚烷温控离子液体两相体系。考察在该体系中以TPPTS为配体的Rh/P催化剂对1-十二烯氢甲酰化反应的催化性能及分离回收效果。结果表明,在组成为IL750:甲苯:正庚烷:1-十二烯=0.5:4.23:0.5:1.0,混溶温度为108℃的温控两相体系中,在优化反应条件(S/Rh=1500(molar ratio),TPPTS/Rh=8(molar ratio),P=5.0MPa(H2/CO=1:1),T=110℃,t=5h)下,1-十二烯的转化率和醛收率分别达到98%和96%,催化剂可以循环使用8次而催化活性无明显的降低,铑在有机相中的平均流失率为0.64%(wt)。成功地将IL750-甲苯-正庚烷温控体系应用于烯烃的环丙烷化反应。通过在离子液体IL750均相体系中烯烃环丙烷化的模型反应——苯乙烯与重氮乙酸乙酯的环丙烷化,筛选出环丙烷化的合适催化剂Pd/TPPTS。进而研究在温控离子液体两相体系中Pd/TPPTS在1-辛烯环丙烷化反应中的催化活性和循环使用效果。结果表明,在优化条件(1-辛烯:重氮乙酸乙酯=5:1,TPPTS/Na2PdCl4·3H2O=1(molar ratio),重氮乙酸乙酯:Na2PdCl4·3H2O=100,温度50℃,反应时间=7h)下,产率可达65%,催化剂经循环使用5次活性未见降低。基于含PEG链的离子液体IL750既能溶于PEG又能溶解TPPTS的特性,构想通过IL750为媒介,实现Rh/TPPTS催化剂在温控PEG两相氢甲酰化反应中的首次应用。结果表明,在具有“高温混溶,低温分相”特性的PEG200-甲苯温控体系中,在优化反应条件下,1-十二烯的转化率和醛收率分别达到96%和94%,催化剂可以循环使用8次而催化活性无明显的降低,铑的平均流失率为0.63%(wt)。

【Abstract】 Based on the thermoregulated ionic liquid biphasic system proposed by our research group,the phase diagrames of IL350-toluene-n-heptane,IL550-toluene-n-heptane and IL750-toluene-n-heptane are studied in detail.IL750-toluene-n-heptane biphasic system is selected to be the best system for its good thermoregulated character.In this thermoregulated ionic liquid biphasic system,the ligand TPPTS for the Rh/P-catalyzed hydroforrnylation of 1-dodecene is studied.It is found that when the composition is IL750:toluene: n-heptane:1-dodecene=0.5:4.23:0.5:1.0 and the miscible temperaute is 108℃,under optimum reaction conditions(S/Rh=1500(molar ratio),TPPTS/Rh =8(molar ratio),P=5.0 MPa(H2/CO=1:1),T=110℃,t=5h) the conversion of 1-dodecene and the yield of aldehydes reach up to 98%and 96%,respectively.The catalyst can be recycled 8 times without evident loss of catalytic activity and the average Rh loss in the product phase is 0.64%.The IL750-toluene-n-heptane thermoregulated ionic biphasic system is succesfully applied in the cyclopropanation of alkenes.After studing the model reaction-cyclopropanation of styrene with ethyl diazoacetate(EDA)-in IL750,the Pd/TPPTS is selected.The activity and recycling efficiency of this catalyst for the cyclopropanation of 1-octene in the thermoregulated ionic liquid biphasic system is further studied.Under the optimized reaction conditions(1-octene:EDA=5:1(molar ratio),TPPTS/Na2PdCl4·3H2O =1(molar ratio),EDA:Na2PdCl4·3H2O=100,T=50℃,t=7h),the yield reaches up to 65%, the catalyst can be recycled five runs without obvious decrease of activity.Based on the character that IL750 can both be dissolved in the PEG and dissolve TPPTS, IL750 is conceived to be media to realize the application of Rh/TPPTS complex for the hydroformylation of higher olefins in the thermoregulated PEG biphasic system.It is found that in the PEG200-toluene thermoregulated biphasic system,under optimum conditions,the conversion of 1-dodecene and the yield of aldehyde reach up to 96%and 94%,respectively. The catalyst,after being recycled 8 times,showes no appreciable loss of catalyst activity.The average loss of Rh loss is 0.63%.

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