碱性离子液体催化甘油合成1,2-甘油碳酸酯(英)

以离子液体为催化剂,在无溶剂体系中,考察了生物质平台化合物甘油转化1,2-甘油碳酸酯的反应.与酸性离子液体和常用无机碱性催化剂相比,碱性离子液体咪唑基1-丁基-3-甲基咪唑([Bmim]Im)、氢氧化1-丁基-3-甲基咪唑([Bmim]OH)、咪唑基1-烯丙基-3-甲基咪唑([Amim]Im)、氢氧化1-烯丙基-3-甲基咪唑([Amim]OH)在甘油与碳酸二甲酯的酯交换反应中表现出优异的活性.其中,以[Bmim]Im离子液体为催化剂时甘油转化率为98.4%和甘油碳酸酯选择性接近100%.另外,该离子液体可以回收重复利用3次后甘油转化率仍可达92%,甘油碳酸酯选择性可近100%.此碱性离子液体催化方法具有反应结果较好、产物分离简单、条件温和以及环境友好等特点.     

碱性离子液体催化合成碳酸甲乙酯

以碱性离子液体为催化剂,对碳酸二甲酯(DMC)和碳酸二乙酯(DEC)酯交换反应合成碳酸甲乙酯进行了研究.筛选出高催化活性的碱性离子液体1-丁基-3甲基咪唑丁酸盐([C4mim][CH3(CH2)2COO])为催化剂,详细考察了反应时间、温度、催化剂用量、原料配比等因素对酯交换反应的影响.实验结果表明,在反应温度为90℃,催化剂用量为6%(占反应物总质量百分数),n(DMC)∶n(DEC)=1.5∶1,反应时间为5h时,DEC的转化率高达48%.[C4mim][CH3(CH2)2COO]重复利用5次后仍保持较高的催化活性.     

甘油碳酸酯合成方法概述

甘油碳酸酯（glycerol carbonate、4-hydroxymethyl-1,3-dioxolan-2-one）,又称为碳酸甘油酯、4-羟甲基-2-羰基-1,3-二氧戊环,主要用作反应中间体和溶剂,或与异氰酸盐、丙烯酸酯类产品反应生产聚合物用于涂料、胶黏剂和润滑剂等领域.尤其值得指出的是,甘油碳酸酯还是一种新型的多功能合成分子,由于分子内同时含有羟基和羰基官能团,     

离子液体催化CO2与环氧化物合成环状碳酸酯

综述了离子液体催化CO2与环氧化物的环加成反应制备环状碳酸酯的研究进展。目前报道的离子液体主要包括咪唑盐、季铵盐、季鏻盐等。对比了传统离子液体与功能化离子液体对CO2环加成反应的催化活性、选择性以及催化作用机制。与传统的离子液体相比,功能化离子液体的羟基或羧基等官能团与卤素离子等Lewis碱之间存在协同效应,使得其对CO2与环氧化物的环加成反应具有更好的催化活性;将功能化离子液体固载于无机材料(SiO2,SBA-15,MCM-41等)或聚合物所得的多相催化剂不仅保持了官能团与阴离子之间的协同效应,而且载体与离子液体活性组分之间也显示出协同效应,使得该类催化剂具有很好的催化活性,稳定性好,可以多次重复使用,具有较好的工业化前景,是值得深入研发的一类催化材料。此外,离子液体对于手性环状碳酸酯的合成也具有较好的催化活性和立体选择性。     

溴化锌-离子液体复合催化体系高效催化合成环状碳酸酯

随着全球“温室效应”和能源危机的加剧,用CO2作为某些化学品的Cl起始原料,既经济、安全,又能降低CO2对环境的危害,由于CO2的性质极不活泼,在固定CO2的反应中最典型的一个催化过程就是利用CO2和环氧化合物通过环加成反应合成环状碳酸酯：     

离子液体催化甘油和尿素合成甘油碳酸酯（英文）

将一系列酸性、碱性和中性的功能化离子液体用于催化甘油和尿素合成甘油碳酸酯.结果表明,中性离子液体表现出更高的催化活性.离子液体阳离子和阴离子的协同效应促进了反应的进行,离子液体阳离子的正电性活化尿素,阴离子的负电性活化甘油,并且催化剂酸碱位点的平衡对催化反应过程也有一定的影响.此外,离子液体可以实现回收利用至少五次,且催化活性基本不变.采用功能化离子液体替代传统金属催化剂,减少了不可再生资源的利用,且所用原料为廉价易得的生物基原料,过程中也不使用有机溶剂,环境友好.     

离子液体催化吲哚羟烷基化反应

报道了咪唑类离子液体催化吲哚和环状碳酸酯反应合成羟烷基吲哚,系统考察了反应时间、催化剂用量、反应温度和反应物比例对离子液体催化反应性能的影响.在优化的反应条件下,吲哚与碳酸乙烯酯或碳酸丙烯酯反应可高效地生成1-(2-羟乙基)吲哚、1-(2-羟丙基)吲哚及其相应的衍生物.离子液体的催化活性与离子液体中的阴离子有关,其催化活性顺序为BF₄^-﹤Br^-﹤Cl^-﹤OAc^-,与阴离子的碱度顺序一致.     

室温离子液体中催化合成肉桂酸苄酯

研究离子液体中肉桂酸钾和氯化苄经缩合合成肉桂酸苄酯的新方法,并对多种离子液体的作用性能进行了考察.研究结果表明,离子液体中BMImBF4的催化性能最佳,但是肉桂酸苄酯的收率仍不高,只有当相转移催化剂四丁基氯化铵存在时,肉桂酸钾与溶于离子液体中的氯化苄在温和的反应条件下才可高效率地得到肉桂酸苄酯,收率可达96.5%.产物分离简单,离子液体和相转移催化剂形成的双催化体系可以稳定地循环使用5次以上.     

功能化离子液体室温催化合成乙酸苄酯

制备了N-甲基-N′-磺酸烷基-咪唑阴离子型功能化室温离子液体,研究了功能化室温离子液体(TSILs)于室温下催化乙酸和苯甲醇反应合成乙酸苄酯的新方法,考察了多种TSILs的催化性能。结果表明,所合成的TSILs具有很高的催化活性,乙酸和苯甲醇的摩尔比为1:1．3,在室温下反应2．5 h,乙酸苄酯的产率可达92％,选择性超过99％。由于生成的乙酸苄酯不溶于催化体系,反应产物与催化体系分层,通过简单的倾析便可实现产物分离,简化了分离过程。离子液体可以循环使用,而其催化活性没有明显降低。     

离子液体中CO_2与炔醇在温和条件下高效合成-亚甲基环状碳酸酯

本文研究了离子液体1-乙基-3-甲基咪唑二乙基磷酸酯([EMIM][(EtO)2PO2])中醋酸银(AgOAc)对CO2与炔醇反应生成-亚甲基环状碳酸酯的催化性能,发现该反应可以在温和的条件下进行.在AgOAc/[EMIM][(EtO)2PO2]催化体系中,30℃、4 MPa CO2压力下,反应6h时-亚甲基环状碳酸酯的产率为97%;当压力降到0.5 MPa时,反应24 h产物产率为65.8%.[EMIM][(EtO)2PO2]在反应中起到了溶剂和碱的双重作用.AgOAc/[EMIM][(EtO)2PO2]体系重复利用3次活性仅略有下降.另外,该体系也可用于催化CO2与其他炔醇(3-甲基-1-戊炔-3-醇、3,5-二甲基-1-己炔-3-醇和2-苯基-3-丁炔-2-醇)的反应.     

尿素醇解合成碳酸二甲酯过程中离子液体催化剂的含量分析

提出了尿素醇解合成碳酸二甲酯体系中1-甲基-3-丁基咪唑氯化锌离子液体催化剂的含量分析方法。采用紫外光谱法测定了离子液体催化剂的最大吸收波长,并建立了标准工作曲线,其线性相关系数为0.9986,方法的相对标准偏差RSD为2.5%,回收率为98.7%～102.4%。     

Converting wastes into added value products: from glycerol to glycerol carbonate, glycidol and epichlorohydrin using environmentally friendly synthetic routes

Glycerol carbonate, synthesised via a non-phosgene route using glycerol and CO₂ or urea in presence of a heterogeneous catalyst, was efficiently converted into a series of derivatives through the functionalization of the -OH moiety, using high yield, high selectivity synthetic routes not affecting the carbonate functionality. So, for example, glycerol carbonate was converted into epichlorohydrin, a product that has a large industrial application, under very mild conditions, using a two-step reaction with a 98% yield and 100% selectivity. The high yield and mild reaction conditions (very often close to the ambient conditions) make the environmentally friendly synthetic approach described in this work of potential applicative interest. All compounds prepared were fully characterized.     

Dimethyl carbonate synthesis catalyzed by DABCO-derived basic ionic liquids via transesterification of ethylene carbonate with methanol

Easily prepared DABCO-derived (1,4-diazobicyclo[2.2.2]octane) basic ionic liquids were developed for an efficient synthesis of dimethyl carbonate (DMC) via the transesterification of ethylene carbonate (EC) with methanol. 1-Butyl-4-azo-1-azoniabicyclo[2.2.2]octane hydroxide ([C₄DABCO]OH) exhibited high catalytic activity and 81% DMC yield together with 90% EC conversion was obtained under mild reaction conditions. Notably, the catalyst could be recycled for four times without loss of catalytic activity. Moreover, a possible mechanism was also discussed.     

Ionic liquids for tetraarylporphyrin preparation

In place of widely used dichloromethane, a series of ionic liquids, ILs, was employed as a reaction medium for the one-flask preparation of tetraarylporphyrins. The porphyrin yield in the IL was comparable to that in the dichloromethane, as long as both the water content and the fluidity were conditioned to be in the optimum state. When acidic IL, [C₄-SAbim][CF₃SO₃] possessing a sulfonic acid moiety was used as the reaction medium, nothing but a black tarry by-product was obtained due to its strong acidity. However, using the acidic IL in a biphasic mode together with dichloromethane enabled porphyrins to form, even at a high reactant concentration. Furthermore, the phase-separated acidic IL was reusable for at least 10 times without any loss of catalytic activity.     

Biocatalytic designs for the conversion of renewable glycerol into glycerol carbonate as a value-added product

A comparative study of two different biocatalytic models, e.g. enzyme immobilized on magnetic particles (EIMP) and cross-linking enzyme aggregates onto magnetic particles (CLEMPA) was performed. The first model was designed as enzyme-immobilized on the magnetic particles surface (EIMP). The second model was constructed as a network structure with the enzyme aggregates and magnetic particles placed into the nodes and polyglutaraldehyde cross-linker as the network ledges. The design was called cross-linking enzyme aggregates onto magnetic particles (CLEMPA). The biocatalysts were prepared using lipase enzyme from Aspergillus niger for catalyzing the glycerol (Gly) conversion to glycerol carbonate (GlyC). The biocatalyst characteristics for both designs (EIMP and CLEMPA) were evaluated using scanning electron microscopy (SEM), laser light scattering (LLS) and UV-Vis techniques. The EIMP model was strongly influenced by the composition of the polymeric layer covering the particles surface, while the size of the magnetic particles affected mostly the CLEMPA design. Also, the biocatalytic capacity of the tested models was evaluated as maximum 52% Gly conversion with 90% GlyC selectivity for EIMP, and 73% Gly conversion with 77% GlyC selectivity for CLEMPA. Both biocatalytic models were successfully used to prepare GlyC from “crude” glycerol collected directly from the biodiesel process (e.g. 49% Gly conversion with 91% GlyC selectivity for EIMP and 70% Gly conversion with 80% GlyC selectivity for CLEMPA).      

Synthesis of propylene carbonate from urea and 1,2-propanediol

The production of propylene carbonate(PC)from urea and 1,2-propanediol(PG)was investigated in a batch process.The catalytic performances of zinc chloride and magnesium chloride were investigated for this reaction system.The influences of various operation conditions on the PC yield were explored.In this work,MgCl_2 and ZnCl_2 showed the excellent catalytic activity toward PC synthesis,and the yields of propylene carbonate reached 96.5%and 92.4%,respectively.The optimum reaction conditions were as follows...     

离子液体作高效液相色谱流动相添加剂分离测定芳香胺

建立了以离子液体作反相高效液相色谱流动相添加剂分离测定邻苯二胺、苯胺和对甲苯胺3种芳香胺的方法。实验以C18反相色谱柱为分离柱,采用紫外检测方法,考察了检测波长、甲醇含量、咪唑离子液体烷基链长度、离子液体溶液浓度等条件对分离和测定的影响,并与其它分离测定芳香胺的方法进行了比较。优化的色谱条件为:以甲醇/1-丁基-3-甲基咪唑四氟硼酸盐水溶液(3.0mmol/L,乙酸调节pH 3.5)=30/70(V/V)为流动相;检测波长254 nm;流速1.0mL/min;柱温30℃。在此条件下,3种芳香胺达到基线分离,在6.5 min之内分离完全;在1～40 mg/L范围内,线性回归方程的相关系数达到0.99以上;检出限为0.07～0.41 mg/L。将本方法应用于废水的测定,加标回收率在92.3%～96.7%之间,相对标准偏差小于3.5%。     

Ionic liquids as surfactants in micellar liquid chromatography

This paper is devoted to application of ionic liquids as surfactants in LC of organic compounds, derivatives of 1,4‐thiosemicarbazides. According to HPLC requirements the most advantageous conditions such as transparency for ultraviolet light, low CMC, additional inorganic salt additives, and appropriate organic solvent were established. The CMC was determined using conductivity measurements. Suitability of two different stationary phases: RP‐C18 and cyanopropyl bonded phase was examined under micellar conditions. Chosen ionic liquid surfactant was compared to common traditional amphiphilic reagent – SDS. Elaborated on chromatographic micellar conditions were tested as a pilot technique for prediction of distribution coefficients of organic analytes in ionic liquid‐based aqueous two‐phase system.