离子液体及聚离子液体复合材料的制备及其萃取和吸附分离性能研究

发布时间：2018-04-17 14:18

本文选题：离子液体 + 双水相萃取体系　；参考：《浙江工商大学》2015年硕士论文

【摘要】：离子液体是一种“绿色”溶剂,是新兴的功能材料,可代替大量传统使用的挥发性有机溶剂,广泛应用于在萃取分离、吸附分离等领域。聚离子液体有着离子液体相同的官能团,不仅保留了离子液体本身的可设计性与易调控性,而且其在常温下为高分子固体聚合物而非液体,具有离子液体所不具备的可加工性,使得聚离子液体有望成为新型分离材料。建立了亲水性离子液体双水相超声辅助萃取-高效液相色谱质谱联用法测定尿液中溴鼠灵的方法。采用亲水性离子液体1-丁基-3-甲基咪唑四氟硼酸盐和磷酸二氢钠[C4mim]BF4/NaH2PO4组成的双水相体系进行萃取,考察了分相无机盐种类和浓度、离子液体用量、样品浓度和pH等对萃取效率的影响,在XDB C18色谱柱上,以甲醇/0.2%乙酸(85+15,V/V)为流动相,采用电喷雾(ESI)电离负离子多反应监测模式(MRM)测定。结果尿液中溴鼠灵在0.02 μg·L-1～2.0 μg·L-1范围内具有良好的线性,相关系数0.999,回收率在86.8%～92.5%范围,日内相对标准偏差(RSDs)在3.3%～8.1%之间,日间RSDs在6.2%～9.7%之间,定量检出限为0.015μg·L-1。建立的方法简便、干扰少、特异性强,应用此法测定尿液中的溴鼠灵取得了满意的结果。制备的PILS膜结合了含亲水性溴阴离子的单体1-丁基-3-乙烯基咪唑溴化物(BVImBr)和含有疏水性羰基的具有氢结合能力的单体甲基丙烯酸甲酯(MMA),应用扫描电镜和红外光谱对其进行表征。通过对NaCl添加量、pH、提取温度等因素的研究,建立了膜固相微萃取苯胺的最佳萃取条件,膜对苯胺的吸附量可达0.76 μg·μg-1。在最优条件下,用LC-MS/MS方法对超声处理的OG样品进行测定,成功检测出微量苯胺。结果苯胺在0.5μg·L-1～10.0 μg·L-1范围内拥有良好的线性,相关系数为0.9998,苯胺的定量检出限为0.50 μg·L-1,加标回收率在90.6%～96.1%范围,日内相对标准偏差在4.6%～8.3%之间,日间相对标准偏差在8.6%～10.9%之间,表明新建立的SPMM-LC-MS/MS方法是可靠的,并且适用于苯胺的预富集和定量检测。采用溶剂热法制备了球形Fe3O4纳米粒子,对反应时间和六水合氯化铁的用量进行控制,研究这两个因素对纳米粒子合成的影响,对其进行SEM、TEM、FT-IR、VSM表征分析。建立了一种磁性聚离子液体的合成方法,主要是对Fe3O4纳米粒子进行SiO2包覆,使其表面带有羟基,然后对其进行硅烷化反应,使其表面带有氨基,最后与离子液体反应生成磁性聚离子液体复合物。所制得的磁性复合材料有a-Fe3O4-poly-BVIm-Br、 b-Fe3O4-poly-BVIm-Br、 a-Fe3O4-poly-MEBIm-Br和b-Fe3O4-poly-MEBIm-Br四种,采用SEM、TEM、FT-IR、XRD、VSM表征手段对其进行分析,表明磁性颗粒和离子液体成功的聚合在一起。通过橙黄G初始浓度、pH和反应温度这三因素对吸附率的影响研究,建立了最佳吸附条件。通过不同磁性聚离子液体对OG吸附效果的影响实验,表明吸附率均随着OG初始浓度的增加而下降,而b-Fe3O4-poly-MEBIm-Br的吸附率略高于b-Fe3O4-poly-BVIm-Br的吸附率,且稳定性更好。复合材料经甲醇解吸之后,萃取回收率可达90%,经过多次吸附解吸,萃取回收率无明显变化,稳定性好。提出了一种制备石墨烯聚离子液体的方法,主要通过氧化石墨烯上的含氧官能团与离子液体咪唑环上的双键进行化学聚合反应,在合成过程中加入水合肼这种强还原剂来还原氧化石墨烯,从而得到石墨烯聚离子液体复合材料。通过SEM、TEM、FT-IR, XRD等表征手段对两种聚合物进行分析,表明石墨烯和离子液体通过共价键键合在一起。在最优吸附条件下,考察了不同石墨烯聚离子液体对OG吸附效果的影响,均表明吸附率随着OG初始浓度的增加而下降。通过对比可知,rGO-poly-MEBIm-Br的吸附率略高于rGO-poly-BVIm-Br的吸附率,归因于前者的双键离咪唑环较远,化学结构较稳定,有利于吸附。
[Abstract]:Ionic liquid is a kind of "green" solvent, is new functional materials, can replace the traditional use of volatile organic solvents, widely used in extraction and separation, adsorption separation and other fields. Poly ionic liquids have the same functional groups with ionic liquids, not only retains the ionic liquid itself can be designed and easy to control. And at room temperature for polymer polymer solid rather than a liquid, with ionic liquids do not have the machinability, makes poly ionic liquid is expected to become the new separation materials. The mass spectrometry of hydrophilic ionic liquid aqueous two-phase ultrasonic assisted extraction and HPLC determination of brodifacoum in urine by hydrophilic method. Ionic liquid 1- butyl -3- methylimidazolium tetrafluoroborate and sodium dihydrogen phosphate aqueous two-phase system composed of [C4mim]BF4/NaH2PO4 extraction, investigated the phase of inorganic salt type and concentration, The amount of ionic liquids, effect of sample concentration and pH on extraction efficiency, in the XDB C18 column, methanol /0.2% acetic acid (85+15, V/V) as mobile phase, using electrospray ionization (ESI) ion multiple reaction monitoring mode (MRM). The results of urine determination of brodifacoum in 0.02 mu g. L-1 ~ 2 G - L-1 range with good linearity, the correlation coefficient is 0.999, the rate of recovery was 86.8% ~ 92.5% days, the relative standard deviation (RSDs) in 3.3% ~ 8.1%, 6.2% ~ 9.7% RSDs in the daytime, the quantitative detection limit of 0.015 G - L-1. method established is simple, interference less specific, application of this method in the urine of brodifacoum and satisfactory results were obtained. The PILS film prepared with bromine containing hydrophilic anionic monomer 1- -3- butyl vinyl imidazole bromide (BVImBr) and containing a hydrophobic carbonyl with hydrogen bonding ability of single Tijia methacrylate (MMA), application The samples were characterized by means of scanning electron microscopy and infrared spectrum. By adding the amount of NaCl, pH, factors of extraction temperature, the optimum extraction conditions for the establishment of a membrane solid phase micro extraction of aniline, membrane of aniline adsorption capacity was 0.76 g / g-1. under the optimal conditions for ultrasonic treatment of OG samples using LC-MS/MS method, successfully detect trace aniline. The aniline in 0.5 ~ g ~ L-1 ~ 10 g - L-1 range has a good linear correlation coefficient is 0.9998, the detection of aniline quantitative limit was 0.50 G - L-1, the recovery was 90.6% ~ 96.1% days of standard addition, relative standard deviation 4.6% ~ 8.3% day, the relative standard deviation was 8.6% ~ 10.9%, SPMM-LC-MS/MS show that the new method is reliable, and is suitable for the preconcentration of aniline and quantitative detection. Fe3O4 nanoparticles were prepared by solvothermal method, the reaction time and six hydration To control the amount of ferric chloride, study the influence of two factors on the synthesis of nanoparticles, SEM, the TEM, FT-IR, VSM characterization. Establish a synthesis method of a magnetic poly ionic liquid, mainly on the Fe3O4 nanoparticles were coated with SiO2, so that the surface with hydroxyl groups, and then on the silylation reaction that made the surface with amino, finally and ionic liquid reaction of magnetic poly ionic liquid composites. The magnetic composites are a-Fe3O4-poly-BVIm-Br, b-Fe3O4-poly-BVIm-Br, a-Fe3O4-poly-MEBIm-Br and b-Fe3O4-poly-MEBIm-Br four, using SEM, TEM, FT-IR, XRD, VSM characterization methods to analyze it, show that the magnetic particles and ionic liquid successful polymerization together. Through the initial orange G concentration, pH and reaction temperature of the three factors on the influence of adsorption rate, we established the optimal adsorption conditions. Through different magnetic poly The influence of ionic liquids on OG adsorption effect, adsorption rate increased with the initial concentration of OG decreased, while the b-Fe3O4-poly-MEBIm-Br adsorption rate is slightly higher than the b-Fe3O4-poly-BVIm-Br adsorption rate and better stability. The composite by methanol desorption after extraction, the recovery was 90%, after several adsorption desorption, extraction recovery rate had no obvious change. Good stability. Provides a method for preparing graphene poly ionic liquids, the chemical polymerization mainly by oxygen functional groups and ionic liquids on the imidazole ring double bond containing graphene oxide, adding hydrazine hydrate in the synthesis process to the strong reduction of graphene oxide reducing agent to obtain graphene poly ionic liquids composite materials. Through SEM, TEM, FT-IR, XRD were characterized by means of analysis of two kinds of polymer, indicate that graphene and ionic liquids together by covalent bond. Under the optimal adsorption conditions, the effects of different graphene poly ionic liquid for the adsorption of OG, showed that the adsorption rate decreased with increasing initial concentration of OG. By contrast, the adsorption rate of rGO-poly-MEBIm-Br is slightly higher than the adsorption rate of rGO-poly-BVIm-Br, the former is attributed to the double bond is far away from the imidazole ring, chemical structure stable, conducive to the adsorption.

【学位授予单位】：浙江工商大学
【学位级别】：硕士
【学位授予年份】：2015
【分类号】：TB33

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