离子液体[C_6mim]PF_6的微波辅助合成及光谱表征

在微波辐射下,1-甲基咪唑与1-溴己烷通过季铵化反应,合成[C6mim]Br,通过正交实验设计,得到了最佳工艺条件,即1-甲基咪唑与1-溴己烷的摩尔比为1∶1.1,温度70℃,反应时间10 min,产率可达97%。进一步与HPF6反应,可制得离子液体[C6mim]PF6,产率70%。并对其结构用核磁共振氢谱,红外光谱和紫外光谱进行了表征。     

(NH4)2C2O4·H2O和NH4HC2O4·0.5H2O 单晶的培养研究

利用六次甲基四胺缓慢水解产生的NH3和草酸反应,扩散法培养出(NH4)2C2O4·H2O和NH4HC2O4·0.5H2O两种单晶.     

超声波辅助法合成离子液体[C2OHmim]BF4及其双水相体系的研究

采用超声波辅助法合成了N-(2-羟乙基)-3-甲基咪唑四氟硼酸盐([C2OHmim]BF4),产率达57.69%,并建立了[C2OHmim]BF4和无机盐形成的离子液体双水相体系。结果表明,盐的种类和浓度对体系的形成影响很大,(NH4)2SO4能与[C2OHmim]BF4水溶液形成双水相体系。在2 mL[C2OHmim]BF4与3 mL水的混合溶液中加入0.750 0 g(NH4)2SO4后,能形成稳定的双水相且相比达0.923,接近于1;在pH=6～9时,溶液酸度对体系相比的影响较小;在不同温度下体系的热稳定性较好,受温度影响不大;离子液体可再利用。     

[60]富勒烯[2+1]环加成反应研究进展

对[60]富勒烯的[2 1]环加成反应、主要试剂及反应机理进行了综述。     

稳定同位素标记[2H4]-β-紫罗兰酮的合成及表征

以柠檬醛为原料,以D6-丙酮为稳定同位素标记前体物,经碱催化羟醛缩合及酸催化关环反应合成了[2H4]-β-紫罗兰酮,考察了碱和酸的种类、用量及温度对反应的影响,确定了最优路线:先在20%NaOH重水溶液中于55℃反应2 h合成假性紫罗兰酮,再经浓硫酸于-10℃反应10 min合成目标产物,两步总收率为60%。目标化合物结构通过质谱、核磁共振氢谱、核磁共振碳谱、红外光谱进行表征,经高效液相色谱确认化学纯度>99%,经计算同位素丰度为98.1%。该方法所得目标产物可作为稳定同位素稀释分析法中的对照物质。     

甲基咪唑盐酸盐/草酸型低共熔溶剂的制备及其在模拟油中氧化脱硫中的应用

通过简单加热并搅拌甲基咪唑盐酸盐和草酸的混合物合成了甲基咪唑盐酸盐/草酸（[HMIM]Cl/H₂C₂O₄）型酸性低共熔溶剂,以[HMIM]Cl/H₂C₂O₄为萃取剂和催化剂、H₂O₂为氧化剂催化氧化法脱除模拟油中的二苯并噻吩,考察不同的脱硫体系、反应温度、催化剂加入量、氧硫比、模拟油中含硫化合物类型对脱硫率的影响。实验表明,在反应温度为40℃、模拟油量为5 ml、[HMIM]Cl/H₂C₂O₄加入量为1.25 ml、O/S 12、反应时间为140 min的最佳反应条件下二苯并噻吩的脱除率可以达到92.2%。动力学分析表明,该氧化脱硫体系符合一级反应动力学方程。循环使用7次后催化剂的活性没有明显降低。     

聚丙烯酰胺对AS—C4H9OH—H2O体系相图的影响

本考察了含有和不含有无机盐时，ＰＡＭ和ＨＰＡＭ对ＡＳ－Ｃ４Ｈ９ＯＨ－Ｈ２Ｏ三元相图的影响。结果表明，ＡＳ－Ｃ４Ｈ９ＯＨ－Ｈ２Ｏ体系的相图中由两相区，液晶区，胶束区和乳状液区组成，ＰＡＭ的加入对体系相太怃明显影响，ＨＰＡＭ相对行为的影响与电解质类似，但其作用远小于电解质；ＮａＣｌ和ＣａＣｌ２的存在有利于液晶形成，且乳状液区面积明显增大，盐的浓度越大，反离子价数越高，乳状液区面积越大，无机盐－聚丙烯     

离子液体[BMIm]BF_4在神华煤溶胀预处理中的应用

采用离子液体1-丁基-3-甲基咪唑四氟硼酸盐([BMIm]BF4)对中国神华煤进行直接液化前的溶胀处理,通过对溶胀度的测定及不同条件下溶胀煤样的直接液化实验,探讨了离子液体[BMIm]BF4在煤溶胀预处理方面的应用.结果表明,离子液体[BMIm]BF4溶胀预处理能破坏煤结构中的弱共价键,使煤的溶胀度获得了显著提高,进而改善了其液化性能,提高了煤的直接液化转化率和油气产率.在溶胀条件方面,随溶胀时间的增加,煤溶胀度和液化转化率提高;而温度对煤溶胀度和液化转化率的影响较复杂,存在一个合适的溶胀温度范围,在此温度之上,溶胀度和液化转化率随温度的升高而降低.而且使用过的[BMIm]BF4可以回收循环使用.     

Na_2B_4O_7在NaCl-KCl-NaF熔盐体系中的溶解度及溶解机理

采用等温饱和法研究了Na_2B_4O_7在NaCl-KCl-NaF熔盐体系中的溶解度。通过热力学及X射线衍射分析,确定了Na_2B_4O_7的溶解机理。结果表明:随温度的升高Na_2B_4O_7在NaCl-KCl-NaF熔盐体系中的溶解度增大,温度达到750℃时溶解度显著增大;Na_2B_4O_7在熔盐体系中的溶解平衡时间随温度的升高而缩短,温度达到750℃后在3.5h溶解均能达到平衡;Na_2B_4O_7在NaCl-KCl-NaF熔盐体系中的溶解机理为物理溶解。     

[omim]BF4离子液体萃取酚类化合物的研究

采用水浴微波法合成离子液体萃取剂[omim]BF4.研究[omim]BF4对苯酚、邻甲酚等7种酚类化合物的萃取,考察了萃取时间、温度、相比及pH值对萃取效果的影响.实验结果表明:萃取10 min就可以达到平衡;随着温度升高或[omim]BF4与含酚水溶液相比的降低,分配系数降低;酚溶液在pH< pKa时,即酚类化合物主要以分子状态存在时,萃取效率较高.与萃取剂[bmim]PF6及传统有机溶剂相比,[omim]BF4萃取酚类化合物的分配系数处在同一数量级.同时对[omim]BF4萃取酚类化合物的机理进行了探讨,离子液体中的氟与酚类化合物的羟基形成了氢键.     

Highly selective synthesis for 4,4′-bisphenol F from phenol and formaldehyde catalyzed with [C_4mim][HSO_4] ionic liquid

The effects of N-methylimidazole cation [Cnmim] with different alkyl chain lengths, the types of cations and anions of ionic liquids and the reaction parameters on the catalytic activity and the selectivity for 4,4′-bisphenol F were investigated. The hydrogen bonding between the hydroxyl of phenol and the C2-position hydrogen of imidazole moiety in hydrophilic imidazole-based ionic liquid has important influence on the selectivity for 4,4′-bisphenol F, and under the conditions of the molar ratio of phenol/[C4mim][HSO4] 1:1, reaction temperature65 °C and the theoretical molar ratio of phenol/formaldehyde 2:1, the selectivity for 4,4′-bisphenol F reached69.1%. Compared with the high phenol/formaldehyde ratio reported in literatures, the low molar ratio of phenol/formaldehyde and the low reaction temperature can greatly reduce energy consumption, and has important significance for industrial application.     

Thermodynamic and Surface Properties of Aqueous 1-Dodecyl-3-Methylimidazolium Chloride [C12mim][Cl] Solution in the Presence of a Series of Inorganic Salts

The micellization behavior of amphiphiles is a well-analyzed physicochemical phenomenon, which can be easily influenced by various parameters such as pressure, temperature, and the presence of different additives. Inorganic salts are able to affect the thermodynamic and surface properties of amphiphiles significantly. The effect of a series of salts as additives namely lithium chloride (LiCl), potassium chloride (KCl), sodium chloride (NaCl), sodium bromide (NaBr), and sodium iodide (NaI) on interfacial chemical characteristics of the surface-active ionic liquid (SAIL) 1-dodecyl-3-methylimidazolium chloride [C₁₂mim][Cl] in aqueous solution were examined through conductance, surface tension, fluorescence, ¹H NMR, and dynamic light scattering measurements. The interfacial and thermodynamic parameters of all investigated SAIL-salt systems were evaluated from surface tension and conductance measurements, respectively. A detailed analysis of the microenvironment of the micelles and the size of the micelles was done using ¹H NMR and dynamic light scattering measurements.     

Anodic behavior of gold in 1-butyl-3-methylimidazolium methanesulfonate ionic liquid with chloride anion

The anodic behavior of gold has been investigated in presence of chloride and/or water in 1-butyl-3-methylimidazolium methanesulfonate (BMI CH₃SO₃) ionic liquid (IL). The cyclic voltammetry (CVs) in presence of chloride ions shows two waves attributed to the oxidation of the gold electrode which occurs under two steps: the first one is attributed to the electrochemical dissolution of gold into to gold(I), while the second one is attributed to an overlap of the chloride oxidation step as well as the oxidation of Au(I) to Au(III). Furthermore the determination of water and chloride content in IL allowed observing that the passive layer induced by water could be removed under chloride. Thanks to those results we were able to clarify the conditions of gold recovering in this kind of electrolyte.     

室温离子液体[BMIm]PF_6中纳米银的制备及结构表征

在微波条件下合成了1-丁基-3-甲基咪唑六氟磷酸盐([BMIm]PF6)离子液体,用红外光谱对其结构进行了表征。用该离子液体作为反应介质,采用硼氢化钠为还原剂制备了金属银纳米微粒,用X射线衍射、扫描电子显微镜、傅立叶红外光谱和热分析对纳米银的结构和形貌进行了表征。结果表明,所制备的纳米银具有立方相结构,粒径约为10 nm;离子液体不但作为反应的溶剂而且还作为修饰剂,包覆在银纳米微粒的表面,从而阻止了银纳米微粒的团聚。     

浆粕性质对纤维素/[Bmim]Cl纺丝原液性能的影响

选用棉浆和木浆3种纤维素浆粕为原料,以离子液体1-丁基-3-甲基咪唑氯盐([Bmim] Cl)为溶剂,探讨了浆粕的聚合度(DP)和α-纤维素含量对其在[Bmim] Cl中的溶解情况、纺丝液的流变行为及其纤维性能的影响.结果表明:浆粕的DP和α-纤维素含量越高,其在[Bmim] Cl中完全溶解所需时间就越长;相对于α-纤...     

Thermodynamic analysis on calcium dissolution in the system of Ca(II)-NH3-NH4Cl-H2O

Based on the principles of ionic balance, electro-neutrality and the existing thermodynamic data, the thermodynamics equilibrium on calcium dissolution in the system of Ca(II)-NH₃-NH₄Cl-H₂O was theoretically calculated. The results show that the equilibrium pH values in the system vary from 11.43 to 12.59, and the solubility of Ca(II) is significant in the system of NH₄Cl-NH₃-H₂O. The c(NH₄OH) has little influence on c(Ca²⁺)_T and when the ammonia concentration is kept constant, the total calcium concentration (c(Ca²⁺)_T) with a maximum concentration of 2.03 mol/L increases linearly with the increase of concentration of c(NH₄Cl). Calcium mainly presents in the form of calcium-bearing complexes instead of calcium ion in the system. The reaction degrees of Ca²⁺ with ammonium hydroxide and H₂O are less in the system. The absolute average error of calcium equilibrium concentration between the experimental and theoretical calculated values is 7.07% in confirmatory experiments. The results are helpful to clarify the leaching behaviour of calcium ions in the system of Ca(II)-NH₃-NH₄Cl-H₂O and provide the theoretical foundation to improve the calcium yield and remove impurities in the leaching stage of the indirect aqueous CO₂ sequestration process.     

铬矿在CaO-SiO2-MgO-Al2O3渣系中的熔解行为

研究了形状一定的致密铬矿在CaO-SiO2-MgO-Al2O3渣系中的熔解行为,系统考察了不同渣系组成对铬矿在渣中熔解量及熔解速度的影响,结合实验现象讨论了铬矿在渣中的熔解机理. 研究结果表明,在本实验条件下,炉渣碱度在0.8~1.5范围内,随渣碱度降低,铬矿熔解量及熔解速度均增大;铬矿熔解量和熔解速度随着Al2O3和MgO质量分数,尤其是Al2O3质量分数增大而减小,在炉渣中添加CaF2可明显加快铬矿熔解速度.     

纳米二氧化钛悬乳体系光催化降解愈创木酚机理的研究

采用溶胶-凝胶法(Sol-gel)制备的纳米TiO2作为催化剂,以造纸废水中木质素的模型物愈创木酚(G-M)为对象,在一定的降解条件下对G-M光催化降解动力学和机理进行了研究。结果表明,G-M的光催化降解过程包含吸附和降解两个过程,通过对G-M在TiO2表面吸附性能的研究,得到其吸附平衡常数;运用L-H方程,对G-M光催化降解动力学方程进行讨论,得到降解动力学方程:1/r=1.774/C+0.1034。同时,对TiO2光催化降解机理进行了探讨。     

氧化镁-氯化铵-水体系中氧化镁蒸氨机理

研究了MgO-NH4Cl-H2O体系中MgO蒸氨机理,考察了蒸氨效率与蒸氨时间的关系,用XRD分析了蒸氨过程体系中的固相组分,研究了MgO的水化及其作用,探讨了MgO蒸氨机理. 结果表明,MgO于蒸氨30 min内完全水化为Mg(OH)2;蒸氨机理可分为MgO水化完全前和水化完全后两阶段,水化完全前,MgO水化为体系提供了大量OH-,促进了蒸氨反应,此时OH-, MgO与Mg(OH)2共同起蒸氨作用;水化完全后,主要是Mg(OH)2起蒸氨作用.     

氯化1-丁基-3-甲基咪唑（[BMIM]Cl）的合成反应动力学研究

对N-甲基咪唑和氯代正丁烷合成氯化1-丁基-3-甲基咪唑（[BMIM]C1）的季铵化反应进行了动力学研究。通过莫尔法研究温度、投料比与搅拌速率等参数对转化率的影响,探索了不同实验条件对反应平衡的影响。此外,合成反应符合二级反应动力学模型,并且温度、投料比与搅拌速率等参数符合动力学理论规律。反应速率常数随温度的升高而增大,但并不随投料比而改变。搅拌速率在低于600r／min时,反应速率常数随着搅拌速率的提高而增大;搅拌速率高于600r／min时,则不随之而改变。