功能化酸性离子液体催化合成氯乙酸异丙酯的研究

研究了功能化酸性离子液体催化合成氯乙酸异丙酯的反应,考察了不同离子液体、反应温度、反应时间和离子液体与反应物物质的量比［n(离子液体)∶n（反应物）］等对反应的影响。结果表明,以离子液体N-(4-磺酸基丁基)吡啶硫酸氢盐｛［(CH2)4SO3HPy］HSO4｝为催化剂,在60 ℃、n(离子液体)∶n（反应物）=1∶5,反应4 h后,反应的转化率和选择性分别为91%和100%。催化剂循环使用5次,催化活性不变。     

质子酸离子液体催化合成乙酸乙酯的研究

以质子酸离子液体为催化剂研究了乙醇和乙酸酯化反应生成乙酸乙酯。结果表明,离子液体的用量为催化剂量,在60 ℃、4 h、n(乙醇)∶n(乙酸)=1∶1的条件下,乙醇转化率92.3%,乙酸乙酯的选择性为100%。反应结束后,产物和离子液体分层,通过简单的倾倒即可分离产物。分离后的离子液体经真空干燥脱水后重复使用5次,催化活性不变。     

功能化离子液体在室温下催化醛(酮)与二元醇的缩合反应

采用功能化离子液体1-甲基-3-丙磺酸基咪唑盐作为溶剂/催化剂双功能体系,通过探针反应,固定原料环己酮与离子液体催化剂的摩尔比为50∶1进行工艺参数的优化,得到优化工艺条件为:n(环己酮)∶n(1,2-丙二醇)=1∶1.5,在20℃条件下反应0.1 h可以得到缩合产物,转化率大于97%.研究了该催化剂对其他醛(酮)与二元醇的缩合反应的催化性能,结果表明,该工艺无需有机溶剂及脱水剂,反应结束产物与催化体系分层,通过倾析便可得到产物,简化了分离过程且离子液体可以循环使用.     

功能化酸性离子液体催化合成丙酸异戊酯

研究了功能化酸性离子液体催化合成丙酸异戊酯的反应,考察了不同离子液体、反应温度、反应时间、离子液体与反应物物质的量比及催化剂重复使用次数等因素的影响。以功能化酸性离子液体［(CH₂)₄SO₃HMIm］HSO₄为催化剂,在60 ℃、n（丙酸）∶n（异戊醇）∶n（离子液体）=5∶5∶1和反应时间2 h的条件下,异戊醇转化率99.43%,丙酸异戊酯选择性100%。催化剂循环使用5次,催化活性基本不变。     

甲苯/酸性离子液体两相中顺酐选择性加氢生成四氢呋喃的研究

在甲苯/离子液体两相催化体系中,以三苯基膦和三氯化钌活化生成的配合物为催化剂,研究了顺酐选择性加氢生成四氢呋喃的反应,考察了离子液体、反应时间、反应温度、反应压力、顺酐与催化剂物质的量比以及离子液体用量对加氢反应的影响,同时考察了离子液体的循环使用。在453 K、12 h、4 MPa和n(PPh₃)∶n(RuCl₃)＝3∶1的条件下,反应的转化率和选择性分别为100%和962%。由于催化剂“负载”于离子液体中且产物不溶于离子液体,通过简单的相分离即可分离催化剂和产物。离子液体催化体系重复使用5次后,其催化活性基本不变。     

酸功能化离子液体催化合成马来酸二异辛酯

合成了4种酸功能化离子液体,由IR、1HNMR对其结构进行了确证,并将其用于催化合成马来酸二异辛酯。结果表明,以离子液体[HSO3-pMIM]HSO4为催化剂,n(马来酸酐)∶n(异辛醇)=1∶2.2,马来酸酐0.1 mol,催化剂用量2.3 g,回流反应2.0 h条件下,马来酸酐酯化率达98.5%。且该离子液体与反应产物易于分离。反应后的离子液体[HSO3-pMIM]HSO4未经处理可重复使用7次,酯化率仍高于97.5%,第7次使用后用水萃取,其回收率为68.5%,补加至第一次用量再次进行实验,得酯化率为98.5%。     

微波辐射下磺酸基功能化离子液体无溶剂催化合成4-甲基香豆素及其衍生物

研究了3种磺酸基功能化离子液体催化香豆素及其衍生物的合成,取代酚与乙酰乙酸乙酯在无溶剂微波辐射条件下,通过Pechmann缩合反应,合成了一系列4-甲基香豆素衍生物,探讨了反应时间、反应温度、催化剂用量、离子液体重复使用性能诸因素对产品产率的影响。结果表明,离子液体[C3SO3Hmim]HSO4是合成目标产物的良好催化剂,微波辐射时间10 min,反应温度100℃,n(酚)∶n(乙酰乙酸乙酯)=1∶1,催化剂用量x([C3SO3Hmim]HSO4)=20%时,最高产率可达94%。该法反应条件温和,操作简便,产物易分离,产率高,环境友好,离子液体可重复使用4次。     

酸性离子液体中苯甲醇催化氧化合成苯甲醛

在没有任何有机溶剂和卤素的条件下，以30%H₂O₂为氧化剂，Na₂WO₄·2H₂O为催化剂，在酸性离子液体[(CH₂)₄SO₃HMIm]TSO中，研究了苯甲醇选择性氧化合成苯甲醛。在n(苯甲醇)∶n（H₂O₂）∶n(离子液体)∶n(Na₂WO₄·2H₂O)=40∶48∶1∶1、90 ℃和3 h条件下，催化效果最好，此时苯甲醇转化率为90.1%，苯甲醛选择性为92.1%。反应结束后，产物和离子液体分层，通过简单的倾倒即可分离产物。分离后的离子液体经真空干燥脱水后重复使用4次，催化活性基本不变。     

酸性离子液体[N_4H_4(CH_2)_6]·4HSO_4催化合成氯乙酸乙酯

以六次甲基四胺和浓硫酸为原料,制备了酸性离子液体[N_4H_4(CH_2)_6]·4HSO_4,并将其作为催化剂应用到氯乙酸乙酯的合成中,对酯化反应涉及的工艺参数进行了优化,采用1HNMR对产物进行了表征。结果表明:当n(氯乙酸)∶n(乙醇)=1∶1.8、离子液体质量为氯乙酸质量的30%、反应温度100℃、反应时间3.5 h时,氯乙酸乙酯收率最高,为93.27%。催化剂重复使用6次,氯乙酸乙酯收率为90.16%。     

功能化酸性离子液体催化缩醛(酮)的合成

研究了以功能化酸性离子液体1-甲基-3-(4-磺酸基)丁基咪唑硫酸氢盐为催化剂,在无任何有机溶剂的条件下醛(酮)与二元醇的缩合反应,同时考察了催化剂用量、反应时间和反应温度等因素对缩醛(酮)收率的影响。得出最佳反应条件为:反应温度353 K,醛(酮)∶IL(摩尔比)=5∶1,此时缩醛(酮)收率最高可达到93.8%。反应体系无需脱水,产物易于分离,催化剂重复使用5次,其催化活性基本不变。     

Biocatalytic ester synthesis in ionic liquid media

Ionic liquids have shown potential as green reaction media compared with organic solvents, mainly due to their lack of vapour pressure. In non‐aqueous enzymology, ionic liquids are opening up new fields. The advantages of using ionic liquids over the use of organic solvents as reaction medium for biocatalysis include enhancement of enzyme activity, stability and selectivity. In this work, the enzymatic synthesis of esters in ionic liquids has been extensively reviewed. Numerous examples of the application of ionic liquids as reaction medium for the enzymatic production of esters have been included. The effect of the nature of the ionic liquid on activity, selectivity and stability of enzymes which catalyze esters synthesis has been carefully analysed. Innovative reaction methodologies for the biosynthesis of esters, including ionic liquid/supercritical carbon dioxide biphasic systems and the integrated reaction/separation processes using supported liquid membranes based on ionic liquids have been revised. Copyright © 2010 Society of Chemical Industry     

Brφnsted酸性离子液体中苯甲酸酯、苄酯的无溶剂微波合成

该文以1-甲基咪唑、吡啶、苄基氯、硫酸、磷酸为原料,合成了4种B r nsted酸性离子液体:1-甲基-3-苄基咪唑硫酸氢根盐(a),1-甲基-3-苄基咪唑磷酸二氢根盐(b),N-苄基吡啶硫酸氢根盐(c),N-苄基吡啶磷酸二氢根盐(d),以它们作为催化剂和反应介质,考察了苯甲酸与系列脂肪醇、苄醇与系列脂肪酸、苯甲酸在无溶剂和微波辐射反应条件下的F ischer酯化反应,结果表明,当苯甲酸或苄醇与离子液体的摩尔比为1∶0.5时,无需外加催化剂,反应即可在化学计量条件下进行,12~20 m in完成反应,苯甲酸酯与苄酯的收率分别为77%~98%和78%~98.5%,气相色谱纯度≥95%。离子液体循环使用3次,催化活性仅下降1.8%~3.4%。     

Solubility of light alkanes and alkenes in ionic liquids

The solubility of light hydrocarbons in a variety of ionic liquids was studied, and it was found that ionic liquids containing Cu(Ⅰ) had higher solubility for hydrocarbons and alkene/alkane solubility selectivity, and Et₃NHCl-2.1CuCl ionic liquid was preferred. The effects of temperature and pressure on the solubility of light hydrocarbons were investigated for the selected ionic liquid. It was found that low temperature and high pressure were favorable for the dissolution of light hydrocarbons, and the alkene/alkane solubility selectivity decreased with the increase of temperature and pressure. The alkene/alkane solubility selectivity was above 8.3 at the temperature of 30℃ and the pressure of 0.2 MPa. The initial dissolution rate of hydrocarbons in ionic liquid was large, but it decreased rapidly with prolonging time, and the dissolution rate of alkenes was higher than that of alkanes at the same conditions. The alkene/alkane separation selectivity increased with decreasing content of alkenes in the mixture of alkenes and alkanes. Light hydrocarbons dissolved in ionic liquids could be desorbed by means of increasing temperature, restoring the dissolution capability of ionic liquids to hydrocarbons. Alkanes were easier to be desorbed than alkenes, and small-molecule hydrocarbons were easier to be desorbed than large-molecule hydrocarbons. The desorption percentage exceeded 92% under optimal conditions. Ionic liquid had a good reusable performance in the absorption and separation of light alkanes and alkenes. The solubility only decreased by less than 5% when it was reused five times, and the alkane/alkane solubility selectivity was basically not affected by reusing times. Software Gaussian 09 was used to study the interaction between anions of ionic liquids and light alkanes and alkanes, and the solubility difference of light alkenes and alkanes in different ionic liquids was well explained.     

小分子烷烃与烯烃在离子液体中的溶解性能

研究了多种离子液体对小分子烃类的溶解性能,发现含有Cu(Ⅰ)的离子液体对烃类具有较高的溶解度和烯烃/烷烃溶解选择性,优选出了Et₃NHCl-2.1CuCl离子液体。考察了温度和压力对小分子烃类溶解性能的影响规律,发现低温和高压有利烃类的溶解,烯烃/烷烃溶解选择性随温度和压力的升高而减小;在30℃和0.2 MPa的条件下,烯烃/烷烃溶解选择性均在8.3以上。烃类在离子液体中的初始溶解速率较大,但随时间的延长快速降低,相同条件下烯烃的溶解速率高于烷烃的溶解速率。烯烃/烷烃分离选择性随混合气中烯烃含量的减小而增大。升温可以解吸出离子液体中的烃类,烷烃比烯烃容易解吸,优化条件下的解吸率可达92%以上。离子液体对小分子烷烃和烯烃的吸收分离具有良好的重复使用性能。利用Gaussian 09软件对离子液体的阴离子与烯烃、烷烃的作用进行了计算分析,解释了烯烃和烷烃在不同离子液体中溶解性能差异的原因。     

离子液体支撑液膜技术及其在气体分离中的研究进展

分析离子液体支撑液膜的气体分离机理,总结目前离子液体支撑液膜的制备方法以及不同膜材料、不同离子液体及其亲疏水性对离子液体支撑液膜稳定性的影响。介绍离子液体支撑液膜在气体分离中的应用,对离子液体支撑液膜的工业化前景进行了展望。     

Simple three parameter equations for correlating liquid phase compositions in subcritical and supercritical systems

Two Chrastil type expressions have been developed to model the solubility of supercritical fluids/gases in liquids. The three parameter expressions proposed correlates the solubility as a function of temperature, pressure and density. The equation can also be used to check the self-consistency of the experimental data of liquid phase compositions for supercritical fluid–liquid equilibria. Fifty three different binary systems (carbon-dioxide + liquid) with around 2700 data points encompassing a wide range of compounds like esters, alcohols, carboxylic acids and ionic liquids were successfully modeled for a wide range of temperatures and pressures. Besides the test for self-consistency, based on the data at one temperature, the model can be used to predict the solubility of supercritical fluids in liquids at different temperatures.     

[Cnmim]Br/FeCl3型离子液体萃取脱除二苯并噻吩

合成了6种咪唑型离子液体[C_3-8mim]Br/FeCl₃,采用红外光谱和拉曼光谱对其进行表征,并考察了离子液体对二苯并噻吩的萃取脱除效果。结果发现,[C₃mim]Br/FeCl₃的萃取脱硫效果最佳,升高温度和增大剂油比均有利于脱硫率的提高,剂油比1:1(体积比)时,萃取时间达到12 min就可使脱硫率高达92%。且萃取反应完成后,离子液体不做处理继续重复使用,重复使用5次,脱硫率可以达到60%。