Ionic liquids as green reaction media for synthesis of poly(aryl ether ketone)s

Poly(aryl ether ketone)s (PAEKs) were successfully synthesized via nucleophilic aromatic substitution (SNAR) mechanism, using ionic liquids as green reaction media. The influence of various reaction parameters including monomer concentration, dehydration time, polymerization temperature and duration, IL’s cations and anions nature, upon PAEKs molecular weight was investigated. In addition, the peculiarities of hydrogen-bonding ability of ILs were investigated. The interaction of 2,2-bis(4-hydroxyphenyl) propane (bisphenol A) with ILs has a strong influence on PAEKs synthesis. Various moderate molecular weight PAEKs have been obtained in high yields with molecular weights ranging from 10000 to 18000g mol-1.     

离子液体在水、乙醇及其混合物中的电导率测定

用电导率仪测定了298.15 K条件下多种离子液体,即1-甲基-3-乙基咪唑溴([Emim]Br)、1-甲基-3-丁基咪唑溴([Bmim]Br)、1-甲基-3-丁基咪唑氯([Bmim]Cl)、1-甲基-3-丁基咪唑氟硼酸盐([Bmim][BF4])、1-甲基-3-甲基咪唑磷酸二甲酯([Mmim][DMP])、1-甲基-3-乙基咪唑磷酸二乙酯([Emim][DEP])、1-甲基-3-丁基咪唑磷酸二丁酯([Bmim][DBP])以及醋酸钾(KAc)在水、乙醇及其混合溶剂中的电导率数据。结果表明,室温离子液体的电导率顺序为：[Bmim][BF4]>[Mmim][DMP]> [Emim][DEP]> [Bmim][DBP],该顺序与离子液体的黏度成反比。离子液体在水中的电导率的次序大致为[Emim]Br>[Bmim]Cl[Bmim]Br[Bmim][BF4]>[Mmim][DMP]>[Emim][DEP]> [Bmim][DBP]。离子液体在水中的电导率高于在乙醇中的电导率,且电导率随浓度的增加均先升高后降低。与醋酸钾相比,溶剂变化对离子液体电导率的影响要小得多。离子液体[Mmim][DMP]和[Emim][DEP]能显著提高乙醇水溶液中乙醇的相对挥发度,且盐析作用[Mmim][DMP]> [Emim][DEP],这与在混合溶剂中电导率的大小次序是一致的。     

咪唑类离子液体的亲疏水性对电润湿器件性能的影响

文中研究离子液体应用于电润湿显示器件的导电流体性能. 选取极性较大的乙基咪唑为离子液体的阳离子,改变阴离子的亲疏水性,对比了几种离子液体的温度窗口、粘度等物理性质,并重点研究了离子液体亲疏水性对电润湿特性、油墨萃取、器件响应等方面的影响. 同时,在1-乙基-3-甲基咪唑四氟硼酸盐离子液体的阳离子上添加羟基基团,得到具有更强亲水性的离子液体. 结果表明:亲水性高的离子液体在介电材料含氟聚合物表面的初始接触角比较大,对油墨中染料的萃取程度比疏水性离子液体弱,证明了电润湿器件更适合选取亲水性高的离子液体作为导电流体. 最后,以1-乙基-3-甲基咪唑二腈胺盐离子液体作为导电流体制备的电润湿器件得到了较佳的电学和光学响应性能.     

PEG1000-DIL/甲苯温控两相体系催化四氢-β-咔啉类化合物的合成研究

一种有效的离子液体PEG1000-DAIL/甲苯温控两相体系催化Pictet-Spengler反应体系,能够有效的将一系列醛类化合物与色胺反应转化为相应的四氢-β-咔啉类化合物,产品收率都在88%以上。当色胺用量为5 mmol,醛用量为5 mmol,PEG1000-DAIL用量为10 mL,甲苯用量为10 mL时,收率可达88%~93%。催化剂可以方便的回收循环使用,PEG1000-DAIL重复使用5次而催化活性基本保持不变。反应条件温和,收率较高,操作方便,后处理简单,该工艺符合绿色化学的发展方向,具有良好的应用前景。     

HSO3-functionalized Brønsted acidic ionic liquids promote esterification of aromatic acid

Esterification of aromatic acid can be promoted via HSO3-functionalized Br nsted acidic ionic liquids (ILs). Under the optimum conditions, using 1-(3-sulfonic acid) propyl-3-methylimidazolium hydrogen sulfate ([MimC3SO3H][HSO4]) and 1-(4-sulfonic acid) butyl-3-methylimidazolium hydrogen sulfate ([MimC 4 SO 3 H][HSO4 ]) as dual solvent-catalysts, the conversion of esterification of aromatic acid was determined to be more than 90%, indicating that HSO3-functionalized ILs show much better catalytic ability than those of non-functionalized ionic liquids. The separation of desired product was easily performed by extraction with diethyl ether and these HSO3-functionalized ILs could be reused 7 times after vacuum drying. Our data represent an environmentally friendly method for the preparation of aromatic esters.     

基于功能化离子液体的苯丙氨酸双水相萃取性能研究

系统研究1-(N,N-二乙基氨甲酰基甲基)-3-甲基咪唑氯盐([MDCBmim]Cl),1-(N,N-二乙基氨甲酰基甲基)-3-甲基咪唑氟硼酸盐([MDCBmim]BF4)、1-丁基-3-甲基咪唑氟硼酸盐([Bmim]BF4)3种离子液体的双水相体系对苯丙氨酸的萃取性能.考察了影响萃取过程的主要因素如pH、离子液体和磷酸盐的用量、体系温度.研究结果表明,功能化离子液体双水相体系对苯丙氨酸的萃取性能远好于常规离子液体.当pH=13时,在[MDCBmim]Cl/K2HPO4双水相体系中,苯丙氨酸的分配系数最高可达130,对其分配系数顺序为:[MDCBmim]Cl>[MDCBmim]BF4>[Bmim]BF4.     

甲醇-碳酸二甲酯-离子液体等压汽液平衡数据测定

在101.32 kPa下,用改进的Othmer釜测定了含离子液体1-乙基-3-甲基咪唑四氟硼酸(BF₄)的甲醇-碳酸二甲酯的等压汽液平衡数据,和含离子液体1-辛基-3-甲基咪唑四氟硼酸盐(BF₄)的甲醇-碳酸二甲酯的等压汽液平衡数据。结果表明：加入[EMIM]BF₄和[OMIM]BF₄,汽液平衡线偏离甲醇-碳酸二甲酯物系的汽液平衡线;离子液体摩尔分数越大,偏离程度越大[EMIM]BF₄与[OMIM]BF₄表现出明显盐效应,使甲醇对碳酸二甲酯的相对挥发度发生改变,均消除了甲醇-碳酸二甲酯物系的共沸点。离子液体对甲醇的盐析效应顺序为：[EMIM]BF₄>[OMIM]BF₄。因此,[EMIM]BF₄和[OMIM]BF₄可以作为甲醇-碳酸二甲酯物系萃取精馏的溶剂,汽液平衡数据的测定可为分离过程优化设计提供依据。     

Electrochemical properties of room temperature ionic liquids incorporating BF4^- and TFSI^- anions as green electrolytes

Two series of room temperature ionic liquids, 1-alkyl-3-methylimidazolium tetrafluoroborate and 1-alkyl- 3-methylimidazolium bis（trifluoromethylsulfonyl）imide （n = 2--4） as electrolytes were prepared and fundamental electrochemical properties of the neat ionic liquids and those mixed with an organic solvent （EC-DMC-DEC, 1 ： 1 ： 1, mass ratio） were investigated. It was found that the Arrhenius equation is approximately fit for the relationship between conductivity and temperature for neat ionic liquids within lower temperature range （298--323 K）. The VTF interpretation describes the conductivity temperature dependence for the ionic liquids containing tetrafluoroborate anion more accurately than those containing bis（trifluoromethylsulfonyl）imide anion within wider temperature range. The potential windows are approximately 4.0 V for all these ionic liquids. Conductivities of the mixed electrolytes show a maximum value as the solution concentrations increase.     

[1,2-bisPyEt]Cl2-XAlCl3离子液体催化合成苯基二氯化膦方法研究

以[1,2-bisPyEt]Cl2-XAlCl3（1,2-bisPyEt=1,2-二吡啶基乙烷阳离子）离子液体催化苯与PCl3反应合成苯基二氯化膦（DCPP）,对催化剂的催化活性、分离方法、催化剂的可回收性、反应物组成和反应时间对反应的影响进行了研究与探讨。研究表明,用该离子液体催化时具有催化剂用量少、产品可直接分离,反应时间短等特点。提出了一种催化机理,对反应过程中催化剂可重复利用以及催化剂重复使用时失活等现象作了解释。     

离子液1－丁基-3-甲基咪唑六氟磷酸盐修饰碳糊电极的制备与表征

以离子液1－丁基－3－甲基咪唑六氟磷酸盐（[BMIM]PF6）代替传统液体石蜡为黏合剂与石墨粉相混合制备了一种新型的离子液修饰碳糊电极（IL－CPE）。采用扫描电子显微镜对电极的表面形貌进行了表征，以铁氰化钾为电化学探针对该离子液修饰电极的电化学行为进行了研究，并与传统碳糊电极进行了比较。结果表明，由于[BMIM]PF6具有较高的导电性，使这种新型离子液修饰电极比传统碳糊电极具有更高的导电效率，电流响应明显增加；同时由于[BMIM^-]PF6具有一定的黏度和较强的疏水性，使制备的电极具有一定的机械强度和较好的稳定性。     

含氮手性离子液体的合成及应用研究进展

综述咪唑鎓盐、季铵盐和吡啶鎓盐等含氮手性离子液体的合成及其在不对称催化反应中的应用研究进展.研究成果表明,手性离子液体的制备既可以直接使用手性源(如氨基酸、氨基醇、或生物碱等),也可以利用不对称合成.含氮手性离子液体手性中心的构建、固载化方法以及构效关系将是今后研究工作的重点.     

Atom Transfer Radical Polymerization of Acrylonitrile in Ionic Liquids

The controllable molecular weight and polydispersity of polyacrylonitriles(PANs) were synthesized in ionic liquids(ILs) by atom transfer radical polymerization(ATRP) using ethyl-2 bromopropionate(EPN-Br) as initiator and CuBr/pentamethyldiethylenetria-mine(PMDETA) as catalyst.The polydispersity index(PDI) in the ATRP of acrylonitriel(AN) in ILs is lower than 1.3.From the polymerization kinetics,plots of ln([M]0/[M]) with time show a linear dependence at the early stage of polymerization while the deviation ...     

Excited-state solvation dynamics of meso-tetrakis(4-sulfonatophenyl) porphyrin in solid imidazolium-sulfonate-based ionic liquids

The steady-state absorption and fluorescence emission positions of diprotonated meso-tetrakis(4-sulfonatophenyl) porphyrin (H₄TPPS^2?) are dependent on the polarity of the selected two solid ionic liquids (ILs) and are red-shifted with the increase of cation size. The solvation dynamics process of H₄TPPS^2? in these ILs occurs on two well-separated time scales. The short components with 121.2–128.6 ps arise from the local motion of the ion-pairs in close proximity to the porphine core, and the long components with 1056.6–1261.8 ps are due to the collective translation motions of the ion-pairs. The dynamic Stokes shifts and the relaxation times increase with the increasing cation size of the ILs.     

双核碱性功能化离子液体催化Knoevenagel缩合反应

采用咪唑与二溴烷烃为原料,两步法合成了5种新型咪唑类碱性双核功能化离子液体催化剂,考察了在醛与氰基化合物的Knoevenagel缩合反应中的催化性能。结果表明:咪唑类碱性双核功能化离子液体在Knoevenagel反应中具有很好的催化性能,在其中以双-(3-甲基-1-咪唑)亚丁基双氢氧化物离子液体的催化糠醛与丙二氰Knoevenagel缩合反应的活性最好,其产物的收率高达93.2%,而双-(3-甲基-1-咪唑)亚己基双氢氧化物离子液体对研究中的类醛与氰基化合物的Knoevenagel缩合反应都有较好的催化效果。     

离子液体萃取锝和铼的研究

系统地研究离子液体对ReO_4~-和TcO_4~-的萃取。结果发现,咪唑类和季铵盐类离子液体可通过阴离子交换机理高效萃取ReO_4~-和TcO_4~-。其中,PF_6~-类离子液体对ReO_4~-和TcO_4~-的萃取效率明显高于NTf_2~-类离子液体。当阴离子相同时,离子液体阳离子侧链增长,萃取效率增大。增加水相HNO_3浓度或在水相中加入相应离子液体的阴离子可以抑制ReO_4~-和TcO_4~-的萃取。水相中加入相应离子液体的阳离子则可以促进萃取反应进行。在低酸度下,己基三丁基铵双三氟甲烷磺酰亚胺[N_(6,444)][NTf2]和1-辛基-3-甲基咪唑六氟磷酸盐[C_8mim][PF_6]对模拟废液中的ReO_4~-均具有很好的萃取选择性。LiNTf_2和KPF_6水溶液可以分别实现对[N_(6,444)][NTf_2]和[C_8mim][PF6]中ReO_4~-的有效反萃。     

卤代咪唑盐类离子液体的合成、表征及其应用

以咪唑为起始原料,通过N-烷基化和季铵化反应合成了3种卤代1-苄基-3-甲基咪唑盐类离子液体:氯代1-苄基-3-甲基咪唑、溴代1-苄基-3-甲基咪唑、碘代1-苄基-3-甲基咪唑,以红外、核磁及热失重分析表征了它们的结构,并将它们应用于乙酸正丁酯的催化合成,取得满意的效果.     

[BF4]、[PF6]离子液体及其与DMF二元体系在293.15～353.15K下的密度和体积性质

为获得离子液体与有机物物理性质的数据,常压下,293.15～353.15K温度范围内,分别测定了1-丁基-3-甲基咪唑四氟硼酸盐([bmim][BF4])、1-丁基-3-甲基咪唑六氟磷酸盐([bmim][PF6])2种咪唑类离子液体以及它们和N,N-二甲基甲酰胺(DMF)构成的2个二元体系的密度。利用实验数据计算了溶液的超额摩尔体积(VE),结果均为负值,表明离子液体与DMF之间存在离子-偶极作用和填隙效应。分别用一次线性方程和二次多项式方程关联出密度随温度和DMF浓度的变化关系,结果比较满意。     

Electron transfer in N-butylpyridinium tetrafluoroborate ionic liquid by pulse radiolysis

The radiolysis behavior of neat pyridinium ionic liquids (ILs) and their aqueous solutions was investigated using nanosecond pulse radiolysis techniques. Radiolysis of the ionic liquids, such as N-butylpyridinium tetrafluoroborate (BuPyBF4 ), resulted in the formation of solvated electrons and organic radicals. Solvated electrons reacted with the pyridinium moiety to produce a pyridinyl radical, which can transfer electrons to various acceptors. The electron-transfer rate constants of the solvent-derived butylpyridinyl radicals in BuPyBF 4 and in several compounds (for example, duroquinone, 4,4′-pyridine, benzophenone, and 1,1′- dimethyl-4,4′-bypyridinium dichloride) (k of the order 10 8 L/(mol s) were lower than those measured in water and in i-PrOH but were significantly higher than the diffusion-controlled rate constants estimated based on viscosity. The electron-transfer rate constants in neat BuPyBF 4 were one order of magnitude faster than the diffusion-controlled values. This finding suggests that Bu- PyBF 4 acts not only as solvent but also as active solute, such as in solvent-mediated reactions. These reactions result in electrons reaching their final destinations via intervening pyridinium groups without requiring the diffusion of a specific radical.     

不同烃链长度咪唑类离子液体对日本三角涡虫的急性毒性

采用SPSS软件概率单位法研究了4种不同烃链长度的咪唑类离子液体对日本三角涡虫的急性毒性.结果表明:[C4mim]Br,[C6mim]Br,[C8mim]Br和[C10mim]Br对日本三角涡虫72h、96h的半数致死浓度(LC50)分别为2 079.46和1 744.38mg·L-1,919.35和725.00mg·L-1,312.79和238.50mg·L-1以及32.57和23.25mg·L-1.由LC50值的大小可知,4种不同烃链长度的咪唑类离子液体的毒性[C10mim]Br>[C8mim]Br>[C6mim]Br>[C4mim]Br.由此可见,咪唑类离子液体对涡虫的急性毒性大小与其烷基侧链长度密切相关,碳链越长毒性越大.此外,根据急性毒性试验涡虫的中毒症状,也就离子液体对涡虫可能的靶器官问题进行了初步探讨.     

新型有效的PEG1000-DAIL[BF4]/Fe2(SO4)3均相催化氯化苄水解反应

在离子液体PEG₁₀₀₀-DAIL[BF₄]、甲苯和Fe₂(SO₄)₃组成的温控两相催化体系作用下,氯化苄的均相催化水解反应能够高效地进行,在110 ℃搅拌反应40 min,产物苯甲醇收率高达96%.该新方法收率高,操作简单,催化体系可以较好地回收循环使用而且催化活性基本保持不变.同时,对水解反应的机理和温控两相催化的过程也进行了阐述.