3-(2-氰基乙氧基)甲基-和3-[甲氧基(三乙氧基)]甲基-3'-甲基氧杂环丁烷的合成及其共聚体研究

以三羟甲基乙烷为原料, 通过脱水反应首先制得3-羟甲基-3'-甲基氧杂环丁烷(HMO). HMO再分别与丙烯腈和二缩三乙二醇单甲醚反应得到两个取代氧杂环丁烷单体3-(2-氰基乙氧基)甲基-和3-[甲氧基(三乙氧基)]甲基-3'-甲基氧杂环丁烷(HMOAN和HMOPEO). 再用阳离子开环聚合方法, 以BF 3\5乙醚作催化剂, 丁二醇为引发剂, 将两类单体共聚即可得到一系列不同组成的共聚物(PAP). 利用 1H NMR谱图计算了该共聚物中两种不同结构单元的比, 结果表明, 其与投料比基本吻合. GPC测得该共聚物的数均分子量范围为2 756～5 342, 分子量分布为1.26～1.83. DSC测试结果发现, 除在225～246 K之间有一个玻璃化转变温度之外, 在305～348 K之间还存在一个热转变温度. TGA测得共聚物的分解温度为573 K, 远高于目前广泛使用的液体电解质. 电导率测试结果表明, AN20的室温电导率可达到1.07×10 -5 S/cm, 353 K时电导率可达到2.79×10 -4 S/cm, 接近实用要求.     

3-(2-氰基乙氧基)甲基-和3-[甲氧基(三乙氧基)]甲基-3′-甲基氧杂环丁烷的合成及其共聚体研究

以三羟甲基乙烷为原料,通过脱水反应首先制得3-羟甲基-3′-甲基氧杂环丁烷(HMO).HMO再分别与丙烯腈和二缩三乙二醇单甲醚反应得到两个取代氧杂环丁烷单体3-(2-氰基乙氧基)甲基-和3-[甲氧基(三乙氧基)]甲基-3′-甲基氧杂环丁烷(HMOAN和HMOPEO).再用阳离子开环聚合方法,以BF3.乙醚作催化剂,丁二醇为引发剂,将两类单体共聚即可得到一系列不同组成的共聚物(PAP).利用1H NMR谱图计算了该共聚物中两种不同结构单元的比,结果表明,其与投料比基本吻合.GPC测得该共聚物的数均分子量范围为2 756~5 342,分子量分布为1.26~1.83.DSC测试结果发现,除在225~246 K之间有一个玻璃化转变温度之外,在305~348 K之间还存在一个热转变温度.TGA测得共聚物的分解温度为573 K,远高于目前广泛使用的液体电解质.电导率测试结果表明,AN20的室温电导率可达到1.07×10-5S/cm,353 K时电导率可达到2.79×10-4S/cm,接近实用要求.     

离子液体-分子溶剂混合体系中电导率的测量与关联

在298.15K下测定了1-正丁基-3-甲基咪唑四氟硼酸盐([Bmim][BF₄])和1-正丁基-3-甲基咪唑六氟磷酸盐([Bmim][PF₆])与不同分子溶剂混合体系的电导率。结果表明, 随着分子溶剂浓度的增大，离子液体的摩尔电导率逐渐增大，离子液体在溶液中的摩尔电导率可以用纯离子液体的摩尔电导率、分子溶剂的介电常数和摩尔体积进行关联。     

固相萃取-高效液相色谱法测定焦糖色素中副产物2-甲基咪唑、4-甲基咪唑和2-乙酰基-4-(1,2,3,4-四羟基丁基)咪唑

建立了固相萃取法结合高效液相色谱同时检测焦糖色素中2-甲基咪唑(2-Methylimidazole,2-MEI)、4-甲基咪唑(4-Methylimidazole,4-MEI)和2-乙酰基-4-(1,2,3,4-四羟基丁基)咪唑(2-Acetyl-4-(1,2,3,4-tetrahydroxybutyl) imidazole,THI)的方法.样品经加水涡旋提取后,经混合型强阳离子交换固相萃取小柱富集净化,以乙腈-0.05％氨水(10∶90,V/V)为流动相,流速为0.6 mL/min,用反向色谱柱Polaris C18-A(250 mm×4.6 mm,5μm)柱分离,分别在二极管阵列检测器215 nm波长条件下检测焦糖色素中的2-甲基咪唑、4-甲基咪唑和287 nm波长条件下检测2-乙酰基4.(1,2,3,4-四羟基丁基)咪唑的含量.2-甲基咪唑、4-甲基咪唑和2-乙酰基-4-(1,2,3,4-四羟基丁基)咪唑在0.2～ 20 mg/L之间线性关系良好(r＞0.9996),在10,25和100 mg/kg添加浓度的回收率范围为75.3％ ～93.4％,相对标准偏差均小于10％,检出限分别为为2.6,3.0和1.5 mg/kg,定量限分别为8.5,10.0和5.0 mg/kg.     

离子液体在番茄红素提取中的应用研究

以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)、1-乙基-3-甲基咪唑四氟硼酸盐([Emim]BF4)、1-乙基-3-甲基溴盐([Emim]Br)、1-丁基-3-甲基咪唑硫酸一氢盐([Bmim]HSO4)离子液体为萃取剂,并用超声波辅助萃取新鲜番茄中的番茄红素.对离子液体超声波辅助萃取新鲜番茄中的番茄红素的条件进行了优化,优化后的提取条件为:以[Bmim]BF4为萃取溶剂,离子液体浓度:V乙醇/V[Bmim]BF4=3,在固定超声温度为40℃,超声萃取时间10min,超声波功率380W,料液比1:5 (g/mL)时,效果最佳.     

高氯酸锂与1,3-氮氧杂环-戊-2-酮形成的二元熔盐电解质

制备了高氯酸锂(LiClO4)与1,3-氮氧杂环-戊-2-酮(OZO)形成的二元熔盐电解质, 虽然先导物具有较高的熔点, 但二者可形成均一、稳定的共熔体系, 测试结果表明该熔盐体系具有低的共熔温度(-50 益). 红外光谱分析表明OZO 通过Li—O 键与LiClO4中Li+配位而破坏了LiClO4的离子键,形成很大的配位阳离子,削弱了阴阳离子间的库伦作用力; 同时Li—O 配位也导致OZO 分子间的氢键断裂, 因而体系的共熔温度较之纯物质熔点显著降低, 部分样品室温下以液体状态稳定存在. 采用交流阻抗法和循环伏安法对其电化学性质进行研究, 结果显示, 配比n(LiClO4):n(OZO)=1:4.5 的样品室温(25 ℃)电导率为0.66×10^-3 S·cm^-1, 80 ℃电导率为7.33×10^-3 S·cm^-1; 其电化学稳定电位窗口约为3.5 V.     

氯化烷基咪唑系列离子液体标准摩尔燃烧焓和生成焓

用精密氧弹热量计测定了4种离子液体: 氯化1-甲基-3-乙基咪唑(C2MIC), 氯化1-甲基-3-丁基咪唑(C4MIC), 氯化1-甲基-3-戊基咪唑(C5MIC)和氯化1-甲基-3-己基咪唑(C6MIC)的燃烧热, 计算了它们的标准摩尔燃烧焓 和标准摩尔生成焓 , 结合文献中的标准摩尔溶解焓, 估算了烷基咪唑阳离子在水溶液中的标准摩尔生成焓, 以及亚甲基对标准摩尔燃烧焓和标准摩尔生成焓的贡献.     

氯化1-(4-氨基丁基)-3-甲基咪唑离子液体电子结构性质研究

采用密度泛函理论方法 B3LYP/6-311++G(d,p)计算了氯化1-(4-氨基丁基)-3-甲基咪唑离子液体气相下几何构型、离子对结合能和二阶微扰稳定化能等。得到了8种不同的稳定结构,不同结构所具有的能量差异最大为11.1 kcal·mol~(-1)。能量最小稳定构型的氯化1-(4-氨基丁基)-3-甲基咪唑自然价键前线轨道分析结果表明:超共轭作用主要发生在咪唑环内,LP(1)N1→BD*(2)N4-C5电子离域引起的稳定化能达73.54 Kcal·mol~(-1)。氯阴离子和1-(4-氨基丁基)-3-甲基咪唑阳离子作用生成氯化1-(4-氨基丁基)-3-甲基咪唑时,轨道对称性匹配占主导作用,阴离子的HOMO轨道与阳离子具有更高能量的非占据σ*轨道相互作用,形成了σ型的C-H…Cl氢键。     

氯化烷基眯唑系列离子液体标准摩尔燃烧焓和生成焓

用精密氧弹热量计测定了4种离子液体：氯化1-甲基-3-乙基咪唑（C2MIC）,氯化1-甲基-3-丁基咪唑（c4MIC）,氯化1-甲基-3-戊基咪唑（C5MIC）和氯化1-甲基-3-己基咪唑（C6MIC）的燃烧热,计算了它们的标准摩尔燃烧焓△cHm^ 和标准摩尔生成焓△fHm^ ,结合文献中的标准摩尔溶解焓,估算了烷基咪唑阳离子在水溶液中的标准摩尔生成焓,以及亚甲基对标准摩尔燃烧焓和标准摩尔生成焓的贡献．     

离子液体表面活性剂烷基硫酸1-丁基-3-甲基咪唑鎓盐的合成及其在水溶液中的聚集行为

采用离子交换法,由氯化1-丁基-3-甲基咪唑鎓(C_4mimCl)和烷基硫酸钠合成了一系列无卤素的阴离子表面活性离子液体—烷基硫酸1-丁基-3-甲基咪唑鎓盐[C_4mim][C_nH_(2n+1)SO_4](n=8,12,16),利用表面张力仪、稳态荧光光谱等手段考察了表面活性离子液体在水溶液表面及体相中的聚集行为。结果表明,与传统无机反离子相比,有机咪唑阳离子[C_4mim]~+作为反离子的离子液体型表面活性剂具有较高的表面活性,[C_4mim]~+产生的氢键引起的抑制分子规则排列的作用小于其促进分子有序排列的疏水作用。长烷基链的阴离子是界面膜及胶束的主要组成成分,阴离子疏水烷基碳链的增长虽然可促进胶束的形成,但却在一定程度上抑制[C_4mim]~+参与界面或胶束的形成;阴离子所带烷基链越长,越不利于阳离子[C_4mim]~+参与界面膜或胶束的形成,界面膜或胶束中表面活性剂排布越松散,即界面张力越大,体系中胶束聚集数较小。     

Partial molar volumes of ionic liquid 1-butyl-3-methylimidazolium tetrafluoroborate in n-donor solvents

The values of partial molar volume (PMV) of ionic liquid, 1-butyl-3-methylimidazolium tetrafluoroborate were determined in twelve n-donor solvents and compared with the known values of PMVs of lithium and magnesium perchlorates in the same solvents. The proportionality in the change in the molar volumes of these salts and the predominant contribution of anion solvation were observed. The values of PMVs of the 1-butyl-3-methylimidazolium cation were calculated.     

高分子固体电解质LiNO_3-LiOOCCH_3/聚丙烯酸锂的合成与性能研究

以丙烯酸和氢氧化锂为原料用反相乳液聚合法合成聚丙烯酸锂 (PAALi) ,将其熔于低共熔盐 (一定比例的LiNO3 LiOOCCH3混合物 )中得到新型高分子固体电解质 (SPE) ,用XRD、IR、DTA、TG DTG等技术进行了表征 ,讨论了影响合成PAALi工艺及新型固体电解质电阻率的主要因素 ,在LiNO3 LiOOCCH3摩尔比为 1∶1时 ,将其按质量百分比 80∶2 0与聚丙烯酸锂混合均匀并熔融 ,得到的电解质其室温离子电导率可达 2× 10 - 5S·cm- 1 ,大量低共熔盐的加入可明显提高SPE的离子导电率 .XRD、DTA及TG DTG结果表明低共熔盐与聚丙烯酸锂形成了新的配合物     

Heck Reaction of Iodoarenes with Methyl Acrylate Catalyzed by Cyclopalladated Complexes of Tertiary Arylamines Immobilized in Ionic Liquid [Bmim]~+BF_4~-

IntroductionAsoneofthemostimportantC—Cformationreactionsandone stepmethodforthearylationofolefins ,Heckre actionhasattractedmuchinterest.1However ,thereactionusuallyneedsarelativelylargeamountofpalladiumcata lyst (>1mol%)forsatisfactoryconversions .Recently ,avarietyofpalladacyclesincorporatingcyclometallatedphos phine ,2 phosphite ,3 carbene ,4 imine5andoxime6havebeenreported .Theuseofcatalystswithnitrogen basedligandswasdemonstratedtopossessveryhighactivity .Wehavereportedthecyclopalladat…     

电极/离子液体界面电容

用电化学阻抗方法研究了铂片电极在BMIMPF6,BMIMBF4,BMIMClO4,BMIMTf2N,BMIMCl,BMIMBr,C3OHMIMBF4,C3OHMIMClO4和BMMIMPF6(BMIM:1-butyl-3-methylimidazolium;C3OHMIM:1-(3-hydroxypropyl)-3-methylimidazolium;BMMIM:1-butyl-2-methyl-3-methylimidazolium;Tf2N:bis(trifluoromethylsulfonyl)amide)等离子液体中的界面电容及结构.结果表明:当阴、阳离子半径相差不大且不存在特性吸附时,在零电荷电势附近,电极/离子液体界面的电容-电势曲线将出现电容单峰或者双峰.电极的零电荷电势对应于单峰的峰电势或者双峰之间的谷电势.当电极电势远离零电荷电势时,电极/离子液体界面成紧密层结构,可由紧密层理论来描述.如果存在离子的特性吸附,相应的电容峰可能不再出现,而表现为双层电容随电极电势对零电荷电势的偏离而单调增加.还研究了添加小的Li+离子对电极/离子液体界面电容的影响.通过向BMIMTf2N中加入LiTf2N,发现Li+离子可以改变电极/离子液体界面的双层结构,但无助于界面电容的提高,甚至可能引起电容的降低.最后探讨了不同条件下,尤其考虑阴阳离子特性吸附时,电极/离子液体的界面结构.     

Extraction of Lithium from Salt Lake Brine with Triisobutyl Phosphate in Ionic Liquid and Kerosene

Three ionic liquids(ILs), namely, 1-butyl-3-methylimidazolium hexafluorophosphate, 1-butyl-3-me- thylimidazolium bis[(trifluoromethyl)sulfonyl]imide and 1-ethyl-3-methylimidazolium bis[(trifluoromethyl)sul- fonyl]imide with the triisobutyl phosphate(TIBP) and kerosene system were respectively used to extract lithium ion from salt lake brine with a high concentration ratio of magnesium and lithium experimentally. Results indicate that the highest extraction selectivity for lithium was obtained with IL 1-ethyl-3-methylimidazolium bis[(trifluoromethyl)- sulfonyl]imide. The effects of solution pH and phase ratio R(O/A) on the extractive step and the influence of acid concentration of the stripping solution and R(O/A) on the back extraction step were also investigated systematically. The single-step extraction efficiency of lithium ion was 83.71% under the optimal extraction conditions, and the single-step back extraction efficiency was 85.61% with a 1.0 mol/L HCl in 1.0 mol/L NaCl medium as stripping agent at R(O/A)=2. The liquid-liquid extraction mechanism and the complex of the ligand with lithium were proposed.     

Nonsolvent application of ionic liquids: organo-catalysis by 1-alkyl-3-methylimidazolium cation based room-temperature ionic liquids for chemoselective N-tert-butyloxycarbonylation of amines and the influence of the C-2 hydrogen on catalytic efficiency

1-Alkyl-3-methylimidazolium cation based ionic liquids efficiently catalyze N-tert-butyloxycarbonylation of amines with excellent chemoselectivity. The catalytic role of the ionic liquid is envisaged as "electrophilic activation" of di-tert-butyl dicarbonate (Boc(2)O) through bifurcated hydrogen bond formation with the C-2 hydrogen of the 1-alkyl-3-methylimidazolium cation and has been supported by a downfield shift of the imidazolium C-2 hydrogen of 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([bmim][NTf(2)]) from δ 8.39 to 8.66 in the presence of Boc(2)O in the (1)H NMR and a drastic reduction of the catalytic efficiency with 1-butyl-2,3-dimethylimidazolium ionic liquids that are devoid of the C-2 hydrogen. The differential time required for reaction with aromatic and aliphatic amines has offered means for selective N-t-Boc formation during inter and intramolecular competitions. Preferential N-t-Boc formation with secondary aliphatic amine has been achieved in the presence of primary aliphatic amine. Comparison of the catalytic efficiency for N-t-Boc formation with a common substrate revealed that [bmim][NTf(2)] is superior to the reported Lewis acid catalysts.     

Structure and conformation properties of 1-alkyl-3-methylimidazolium halide ionic liquids: a density-functional theory study

The structures and conformational properties of 1-alkyl-3-methylimidazolium halide ionic liquids have been studied with a Becke's 3 Parameter functional method. The interaction mechanisms between the cation and the anion in 1-ethyl-3-methylimidazolium (Emim+) halide and 1-butyl-3-methylimidazolium (Bmim+) halide ionic liquids were investigated using 6-31G*, 6-31++G**, and 6-311++G** basis sets. Forty structures of different ion pairs were optimized and geometrical parameters of them have been discussed in details. Halide ions (Cl- or Br-) have been gradually placed in different regions around imidazolium cation and the interaction energies between the anion and the cation have been calculated. Theoretical results indicate that there are four activity regions in the vicinity of the imidazolium cations, in these regions the imidazolium cations and the halide anions formed stable ion pairs. Imidazolium cations can form hydrogen bond interactions with one, two or three but no more than three nearest halide anions. The halide ions are situated in hydrogen bond positions rather than at random.     

Ionic Liquid Solvent Based on Cyclic Guanidinium Cation for Nucleophilic Displacement Reactions

The nucleophilic displacement reaction of n-bromooctane and potassium iodide in ionic liquid based on cyclic guanidinium cation(2) was investigated. The kinetic reasuh shows that the rate of the reaction is enhanced in ionic liquid (2). The same reaction in [bmim][PF6] (1)(where bmim=1-butyl-3-methylimidazolium) was also studied. It was found that as a reaction medium ionic liquid (2) is better than (1) for nucelophilic displacement reactions.     

离子液体［bmim］HSO4中合成的苯胺与环氧丙烷共聚物的电催化性能

 采用恒电流电解法,在1-丁基-3-甲基咪唑硫酸氢盐(［bmim］HSO4)离子液体中合成了苯胺与环氧丙烷共聚物(PAN-PPO). 扫描电镜观察表明, PAN-PPO由直径小于80 nm的纳米纤维组成. PAN-PPO对草酸氧化具有较好的电催化活性. 采用电化学原位红外光谱技术对草酸的电催化氧化进行了简单的分析.     

Interaction of 1-butyl-3-methylimidazolium bromides and silver(I) or tantalum(V) salts in binary systems: Spectral and thermochemical studies

Systems based on an ionic liquid of 1-butyl-3-methylimidazolium bromide and like silver(I) or tantalum(V) salts were studied, depending on their composition, by differential scanning calorimetry and FT-IR spectroscopy. The role of hydrogen bonding of the cation and complex metal-containing anion was discussed.