室温离子液体1-丁基-3-甲基咪唑磷酸二丁酯的电导率研究

利用磷酸三丁酯与N-甲基咪唑在恒温150℃下一步合成了离子液体1-丁基-3-甲基咪唑磷酸二丁酯,考察了其在丙酮,水,DMF,乙酸溶剂中的电导率及摩尔电导率。实验发现该离子液体在不同溶剂中的电导率(κ)相差很大,其顺序为κa(水)>κb(DMF)>κc(丙酮)>κd(乙酸)。在相同温度下,电导率及摩尔电导率随浓度的增大而增大;在相同浓度下,电导率及摩尔电导率随温度的升高而增大。     

1-乙基-3-甲基咪唑硫酸乙酯离子液体的合成工艺

以N-甲基咪唑和硫酸二乙酯为原料,采用一步法合成1-乙基-3-甲基咪唑硫酸乙酯离子液体(EMIES)。研究了反应温度、投料比以及溶剂对产率的影响,并用高效液相色谱法(HPLC)检查了产品的纯度,优化了EMIES的合成工艺。实验结果表明:在温度50℃,无溶剂,N-甲基咪唑和硫酸二乙酯投料比为1∶1.2,反应2h的反应条件下,收率可达97%,且产品纯度可达99%。     

室温离子液体1-丁基-3-甲基咪唑六氟磷酸盐的合成研究

由1-甲基咪唑和溴代正丁烷合成了中间体溴化1-丁基-3-甲基咪唑,讨论了温度和反应自身放热对此步反应的影响。中间体再经过阴离子交换,得到了标题化合物,收率为92％。产物的结构经IR和^1HNMR确认。     

系列室温离子液体1-烷基-3-甲基咪唑四氟硼酸盐性质的研究

合成了系列1-烷基-3-甲基咪唑四氟硼酸盐([C2-7mim]BF4)室温离子液体,并通过核磁氢谱、红外光谱、质谱等手段对其进行了结构表征。采用Wilhelmy白金板法在室温(25℃)测定了离子液体的表面张力,测试结果显示,随着1位氮上取代基碳链的增长,其表面张力γ呈现出下降的趋势,且变化范围较宽,如从[C2mim]BF4的表面张力值50.4 mJ/m2到[C7mim]BF4的36.1 mJ/m2。吸水性能测试结果表明,随着氮取代基碳链的增长,其饱和吸水量逐渐减少。     

多烷基咪唑离子液体的合成及性能比较

以咪唑或1,2-二甲基咪唑和卤代烷为原料,合成了4种多烷基咪唑类离子液体,以及6种1,3-二丁基咪唑和1-丁基-3-乙基咪唑类离子液体,产率较高。产物结构经核磁共振氢谱进行了确认。测定了产物水溶液的pH和不同浓度下的电导率,研究了烷基对离子液体酸性的影响,以及不同阴离子或烷基链长度对电导率的影响。测定了产物的吸湿性,结果表明,多烷基咪唑六氟磷酸盐离子液体具有较低的吸湿性。     

溴化1-乙烯基-3-烷基咪唑离子液体的电化学性能

合成了溴化1-乙烯基-3-烷基咪唑([VAIM]Br)离子液体,采用FTIR、¹H NMR、TG及DSC进行了表征,并系统研究了[VAIM]Br的电化学性能。结果表明:在298.15～323.15 K内,[VAIM]Br的电导率(σ)与温度符合Arrhenius方程,电导活化能随[VAIM]⁺上烷基链的增长而降低。分别以水、甲醇和乙醇为溶剂的[VAIM]Br溶液的电导率均随浓度的增大而显著增大,且σ(水)>σ(甲醇)>σ(乙醇)。通过电导法确定了[VAIM]Br在水、甲醇、乙醇中的临界胶束浓度,分别约为6.8×10^-6、1.5×10^-5、2.0×10^-5 mol·L^-1,表面活性优异。[VAIM]Br的电化学窗口在1.6～2.5 V,其电化学稳定性随[VAIM]⁺上烷基链的增长而逐渐降低。     

1-丁基-3-甲基咪唑四氟硼酸盐离子液体的合成研究

由N-甲基咪唑和溴代正丁烷合成了中间体溴化1-正丁基-3-甲基咪唑,讨论了反应时间和反应温度对反应的影响,最佳的反应条件是:80℃反应18 h。中间体再经过离子交换,得到标题化合物。又采用微波法完成了上述反应,原料配比和微波功率对反应有影响。反应物的摩尔比应在1.1∶1为好,微波功率采用240 W。产物的结构经IR和1H NMR确认。     

烯丙基,3-甲基咪唑室温离子液体制备方法及应用

正本发明涉及1-烯丙基,3-甲基咪唑室温离子液体的制备方法及应用,制备方法包括如下步骤:(1)将质量份比例为1:1~1.15的N-甲基咪唑和烯丙基氯加入到100mL的三口烧瓶中,充N2保护,油浴加热回流;(2)回流至只产生少量液滴,为反应基本完全;     

1- 基-3-苄基咪唑盐类室温离子液体的微波合成及表征

以1 -甲基咪唑和溴化苄为原料,微波辐射下无溶剂合成了溴化1-甲基-3-苄基咪唑([Bzmim]Br),并以它为母体,合成了4种新型的1 -甲基-3-苄基咪唑盐室温离子液体.整个操作具有操作简便、产率高和反应时间短等优点.产物结构经IR和1HNMR确证.     

1-丁基-3-甲基咪唑六氟磷酸盐离子液体合成

按照两步法合成了离子液体1-丁基-3-甲基咪唑六氟磷酸盐([Bmim]PF6),探讨了时间、温度、溶剂、反应物配比等对中间体1-丁基-3-甲基咪唑溴盐([Bmim]Br)以及离子液体[Bmim]PF6产率的影响。结果表明,反应物配比为(1∶1.1)~(1∶2),温度70℃,反应30 h,中间体产率为95.91%;中间体中加入等摩尔KPF6,25℃下反应10 h后,离子液体产率为97.26%。     

Enhancement of Electrical Conductivity of Polyethylene Terephthalate (PET) Fabrics via Ionic Liquids

In this study, polyethylene terephtalate (PET) fabrics were treated with two types of ionic liquids, 1-ethyl-2,3-dimethylimidazolium ethyl sulfate (EIL) and methyl-tri-n-butylammonium methyl sulfate (BIL), resulting in noticeably better long-term electrical conductivity of treated PET fabrics. Thermal conductivity, thermal stability, surface morphology and chemical structure were also explored. The effects of concentration of EIL (2, 6, 10 w/v %) and BIL (10, 15, 20 w/v %) ionic liquids were discussed. With the given set up, surface resistivities of the PET fabrics decreased with treatment application of the ionic liquids. Besides, BIL treatment provided higher electrical conductivity as compared with EIL. Moreover, surface resistivity presented diminishing tendency with increasing the concentration. It is also found that thermal degradation temperatures of the PET fabrics decreased with ionic liquids treatment. A coating layer was observable on surface of the fabric and in the gaps of the yarns with the ionic liquids treatment. This work provided a novel method for obtaining enhanced electrically conductive PET fabrics for textile industry.     

离子液体催化剂及其催化作用

概述了离子液体的类型、特性及其合成方法。对功能化离子液体在Fischer酯化反应、Mannich反应、Friedel-Crafts烷基化反应、醇脱水反应中的应用进行了详细的评述。此外,探索了离子液体催化三聚甲醛和甲缩醛反应合成聚甲氧基二甲醚(CH3-O-(CH2O)n-CH3)低聚物的可行性。研究结果表明,功能化的离子液体表现出较好的催化活性和选择性,获得的产物分子量分布达80～320。     

Dielectric Study of Tetraalkylammonium and Tetraalkylphosphonium Levulinate Ionic Liquids

Broadband dielectric spectroscopy in a broad temperature range was employed to study ionic conductivity and dynamics in tetraalkylammonium- and tetraalkylphosphonium-based ionic liquids (ILs) having levulinate as a common anion. Combining data for ionic conductivity with data obtained for viscosity in a Walden plot, we show that ionic conductivity is controlled by viscosity while a strong association of ions takes place. Higher values for ionic conductivities in a broad temperature range were found for the tetraalkylphosphonium-based IL compared to its ammonium homolog in accordance with its lower viscosity. Levulinate used in the present study as anion was found to interact and associate stronger with the cations forming ion-pairs or other complexes compared to the NTf₂ anion studied in literature. In order to analyze dielectric data, different fitting approaches were employed. The original random barrier model cannot well describe the conductivity especially at the higher frequencies region. In electric modulus representation, two overlapping mechanisms contribute to the broad low frequencies peak. The slower process is related to the conduction mechanism and the faster to the main polarization process of the complex dielectric permittivity representation. The correlation of the characteristic time scales of the previous relaxation processes was discussed in terms of ionic interactions.     

含离子液体的复配表面活性剂微乳液的电导性质

研究了CTAB和TritionX-100复配表面活性剂在氯仿作为溶剂时,增溶离子液体bmimBF(IL)时所形成非水微乳液的电导性质,并且与含水体系的微乳液作了比较,发现两者存在较大的差别.在非水微乳液中,随着离子液体质量分数的增加,体系经历了IL/O型微乳液、双连续相、O/IL微乳液三种状态,并且采用循环伏安法对此结论进行了验证.两种表面活性剂复配后,在IL/O型微乳液阶段电导率随着CTAB的摩尔分数(α)增大而增大,在双连续相和O/IL微乳液阶段,体系的电导率随着α增大而减小.在含水微乳液中,只出现O/W型微乳液,而且随着增溶水质量分数的增加电导率下降.增溶水量一定的情况下,电导率随着α值增大而增大.     

咪唑型室温离子液体介质中甲苯氯甲基化反应的研究

在溴化N,N-二烷基咪唑型室温离子液体反应介质中,尝试了甲苯、多聚甲醛和氯化氢气体的氯甲基化反应。以[C5mim]Br为催化剂,考察了反应温度、反应时间和离子液体用量对反应转化率的影响,获得的较佳反应条件为:反应温度65℃,反应时间10h,离子液体催化剂用量为甲苯物质的量的4%,在此条件下甲苯的转化率为82.6%,单氯甲基化选择性为100%。随着溴化N,N-二烷基咪唑型室温离子液体烷基链的增长,甲苯转化率有所提高;以溴化N-十二烷基-3-甲基咪唑离子液体为催化剂时,甲苯转化率可达90%,单氯甲基化选择性为100%。反应结束后产物与离子液体自动分层,便于分离。离子液体催化剂重复使用6次,甲苯转化率保持恒定。     

磁性离子液体1-甲基-3-烷基咪唑四卤化铁盐的合成及其物性表征

合成了4种1-甲基-3-烷基咪唑四氯化铁盐[Cnmim]FeCl4(n=2, 4, 6, 8)及3种1-甲基-3-丁基咪唑四卤化铁([C4mim]FeX4, X=Cl, Br)磁性离子液体,光谱结果表明,[Cnmim]FeCl4及[C4mim]FeBr4中阴离子单一,而[C4mim]FeClBr3及[C4mim]FeCl3Br中的阴离子为FeBr4-, FeBr3Cl-, FeCl2Br2-, FeCl3Br-, FeCl4-的混合物. 测定了其密度、粘度、电导率,磁性离子液体密度较大,25℃时为1.25~1.94 g/cm3;粘度较小,25℃时为21~65 mPa×s;电导率较大,30℃时为0.23~1.37 S/m. 并研究了其物性随温度及结构的变化规律.     

普通离子液体和功能化离子液体的合成研究进展

离子液体是在室温下为液体、具有离子特性的新型绿色溶剂,作为一类环境友好型的反应介质,在诸多领域有其独特的性质.综述了普通离子液体和功能化离子液体的合成研究进展,并对其前景进行了展望.     

Investigation on Aggregate Formation of Ionic Liquids

Understanding the behavior of ionic liquids on the molecular level is essential for explaining solubilizing or reaction processes, including catalytic reactions in ionic liquids or with ionic liquids as co‐solvent. Using mass spectrometry techniques it is possible to characterize their aggregate formation behavior, which depends on the used solvent. With increasing polarity of the solvent and decreasing ionic liquid concentration, the size of the formed aggregates decreases. From conductivity measurement curves “critical aggregate concentrations” were calculated, which confirm the results of mass spectrometry measurements. Addition of ionic liquids increases the solubility of acetophenone in water. This effect can be explained by the aggregate formation ability of ionic liquids. The findings can be used to explain the outstanding solubility and solvation properties of ionic liquids.     

Fabrication,Physicochemical Characterizations and Electrical Conductivity Studies of Modified Carbon Nanofiber-Reinforced Epoxy Composites: Effect of 1-Butyl-3-Methylimidazolium Tetrafluoroborate Ionic Liquid

This study presents the fabrication of carbon nanofiber-reinforced epoxy nanocomposites using 1-butyl-3-methylimidazolium tetrafluoroborate ionic liquid as filler dispersant. FTIR and XRD measurements were utilized to assess structural attributes and crystallographic change in the composites. In addition, morphological studies were performed by field emission scanning electron microscope while the extent of miscibility between epoxy and IL was computed by Accelrys Materials Studio Software. The conductivity measurement was performed by two point impedance analyzer and result demonstrated increase in the electrical conductivity from ～10^?7 to ～10^?5?S?cm^?1 compared to pristine epoxy composite.