离子液体催化合成阻燃剂3-羟基苯膦酰丙酸

采用两步法合成3-羟基苯膦酰丙酸(CEPPA),即以三氯化磷与苯为原料,在离子液体三乙基苄基氯化铵氯化铝([BnEt3N]Cl-xAlCl3)催化下,合成苯膦二氯(DCPP),再用DCPP与丙烯酸合成3-羟基苯膦酰丙酸(CEPPA).确定第一步最佳反应条件为:n(三氯化磷)∶n(苯)∶n([BnEt3N]Cl-xAlCl3)=3∶1∶0.025,回流温度为72℃～76℃,反应时间为6 h,产率达81.1%;第二步通过改变反应物滴加顺序及调整反应温度,得到最佳反应条件为:n(丙烯酸)∶n(DCPP)=1.30∶1.00;滴加反应阶段,控制在70℃～80℃,反应1.5～2 h后,在90℃保温反应1 h;水解反应阶段,控制在92℃～95℃反应4 h,CEPPA的产率可达91%,并解决了反应中易结块问题.     

在离子液体中合成淀粉基絮凝剂的研究

以淀粉和丙烯酰胺为原料,在离子液体氯化1-烯丙基-3-甲基咪唑中通过接枝共聚反应合成了丙烯酰胺-淀粉絮凝剂.研究了淀粉在离子液体和水中溶解情况的差异.通过傅立叶变换红外光谱证实了丙烯酰胺与淀粉分子发生了接枝共聚反应.考察了丙烯酰胺与淀粉的质量之比、引发剂用量、反应温度和时间对接枝共聚反应的影响.比较了在离子液体和水中合成得到的絮凝剂在高岭土悬浊液中的絮凝能力.     

基于1-丁基-3-甲基咪唑十二烷基硫酸盐为活性物质的PVC膜电极的性能及其应用

以离子液体1-丁基-3-甲基咪唑六氟磷酸盐（BmimPF6）为活性物质制得离子选择性电极,该电极对离子液体BmimCl有较好的电位响应,线性响应浓度范围为1×10^-5mol/L～1×10^-2mol/L.用十二烷基硫酸钠（SDS）与BmimPF6进行阴离子交换制得的1-丁基-3-甲基咪唑十二烷基硫酸盐（BmimDS）作为活性物质,能降低电极的检测下限,线性响应浓度范围拓展为1×10^-6～1×10^-2mol/L.该电极显示出良好的稳定性和重现性.此外,该电极可作为电位滴定法的指示电极用于对四丁基氯化铵（TBACl）、十二烷基硫酸钠（SDS）的滴定分析.     

Pulse radiolysis studies of functionally substituted imidazolium-based ionic liquids

The reactions of imidazolium-based ionic liquids having different substituent groups on the ring with hydrated electrons (eaq-),hydroxyl radicals (·OH),and sulfate anion radicals (SO4·-) were investigated using nanosecond pulse radiolysis techniques.The spectra of these ionic liquids on reaction with eaq-all exhibited a similar peak at about 320 nm,and a typical peak for eaq-in aqueous ionic liquid solutions.The reaction rate constants for 1,3-disubstituted imidazolium-based ionic liquid hexafluorophosphates (BMIPF 6) with eaq-were deduced to be 10 10 L mol-1s-1,however the values were lower for trisubstituted ionic liquids.For example,the rate constant for 1-butyl-2,3-dimethylimidazolium tetrafluoroborate (BMMIBF 4) was 5.5×10 9 L mol-1s-1.Imidazolium-based ionic liquids reacted with hydroxyl radicals via adducts to produce a mixture of isomeric OH adducts,and the pk a value of the OH adducts was deduced to be 8.4±0.4 for 1-butyl-3-methylimdazolium tetrafluoroborate (BMIBF 4).Moreover,imidazolium cations were also oxidized by SO4·-to produce bivalent cation radicals,which exhibit a peak at 320 nm,and these rate constants are of the same order of magnitude,i.e.,10 9 L mol-1s-1,except that for 1-(2-hydroxyethyl)-3-methylimdazolium tetrafluoroborate with SO4·-(k=2.8×10 8 L mol-1 s-1).Theoretical calculations were carried out to estimate the structures of the products of reduction by eaq- and the results were related to the experimental data.     

Determination of trace heavy metals in milk using an ionic liquid and bismuth oxide nanoparticles modified carbon paste electrode

A novel carbon composite electrode modified with bismuth oxide nanoparticles and the ionic liquid n-octylpyridinium hexafluorophosphate was fabricated and used to simultaneously determine cadmium and lead levels using square wave anodic stripping voltammetry.This electrode combines the unique advantages of nanomaterials and ionic liquid with the low cost and easy fabrication of the carbon composite electrode.Compared with the traditional binder based composite electrode,our electrode exhibited well-defined and separate stripping voltammetric peaks for cadmium and lead.Furthermore,the antifouling capacity of the bismuth film electrode was significantly improved by the ionic liquid.Under optimized conditions,the linear range of the composite electrode was from 3.0 to 30.0 μg L-1 for both metal ions with a detection limit of 0.15 μg L-1 for cadmium and 0.21 μg L-1 for lead.Trial milk sample analyses showed that the modified electrode was sensitive,reliable and effective for the determination of trace heavy metals,holding great promise for routine analysis applications.     

Ionic liquids containing the urea moiety for recognition of halides and complex anions

A series of novel imidazolium based ionic liquids containing the urea moiety were designed and synthesized for anion recognition. 1-Ethylurea-3-methylimidazolium acetate ([Eumim]OAc) was used as the receptor for the halides and complex anions (BF4-, PF6-, BPh4-). 1H NMR spectra showed that the urea protons and imidazolium C(2) proton of the receptor ([Eumim]OAc) moved upfield on addition of various anions. A Job plot showed that the [Eumim]OAc receptor formed a 1:1 complex with BPh4-. X-ray diffraction analysis and the molecular modeling study revealed that the conformations of [Eumim]OAc and [Eumim]BPh4 were different. The conformational change of the cation was caused by anion exchange, and may provide an alternative to current methods for recognition of anions.     

NaY对(PEO)_(16)LiClO_4-EC组织和导电性能的影响

以纳米级NaY分子筛为填充剂,制备了(PEO)16LiClO4-EC-x%NaY(x=0,3,5,8,12,20,35)全固态复合聚合物电解质薄膜.通过扫描电镜、EDS能谱和交流阻抗方法研究了NaY对(PEO)16LiClO4-EC电解质体系显微组织特征与离子导电性能的影响.结果表明,适量NaY可使PEO的球晶生长受到抑制,表面形成有利于锂离子传输的超枝状和交联网络结构,离子传输的无定形区域增大;同时,适量EC有利于NaY在聚合物基体中的均匀分布,当NaY含量为12%(质量分数)时,复合聚合物电解质的室温离子电导率达到最大值,为1.890×10-4S.cm-1.     

[PECHBIm][PF_6]离子液体作为气相色谱固定相的性能研究

合成了一种聚合离子液体[PECHBIm][PF6],考察了其分解温度,确定了此离子液体作为气相色谱固定液的最高使用温度,测定了相对极性。以该离子液体作为固定液制作的气相色谱填充柱,对苯系混合物、烷烃混合物、醇系混合物均具有较好的分离效果。     

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。     

含手性交联剂的液晶弹性体液晶性能

把非液晶手性交联剂十一烯酸异山梨醇酯(M1)与向列型液晶单体4-戊氧基苯甲酸-4'-烯丙氧基联苯单酚酯(M2)接枝到聚甲基含氢硅氧烷链上,交联剂的摩尔分数从0至20%,得到系列液晶弹性体P1～P7·通过热分析、偏光显微分析等手段研究了手性交联剂对弹性体液晶性能的影响·结果表明P1～P7都有液晶性能,P1为向列型液晶聚合物,P2～P7为胆甾相液晶弹性体·系列液晶弹性体的tg和ti随交联剂含量的增加而降低,P1～P6具有较宽的液晶相范围·所合成的液晶弹性体热稳定性均较好,质量损失5%时的热失重温度均在300℃以上·