化学学报 ›› 2013, Vol. 71 ›› Issue (10): 1411-1420.DOI: 10.6023/A13040434 上一篇    下一篇

研究论文

氯化1-乙基-3-甲基咪唑离子液体表面印迹聚合物的合成及其特异吸附和固相萃取性能研究

高霞a,b, 樊静a, 王小龙a, 张艳树a   

  1. a 河南师范大学环境学院 黄淮水环境与污染防治省部共建教育部重点实验室 河南省环境污染控制重点实验室 新乡 453007;
    b 新乡医学院公共卫生学院 新乡 453003
  • 投稿日期:2013-04-22 发布日期:2013-08-06
  • 通讯作者: 樊静,E-mail:fanjing@htu.cn E-mail:fanjing@htu.cn
  • 基金资助:

    项目受国家自然科学基金(No. 20977025)和河南省软科学研究项目(No. 102400440069)资助

Synthesis of a Novel 1-Ethyl-3-methylimidazolium Chloride Ionic Liquid Molecularly Imprinted Polymer and Its Properties of Specific Adsorption and Solid Phase Extraction

Gao Xiaa,b, Fan Jinga, Wang Xiaolonga, Zhang Yanshu a   

  1. a School of Environment, Henan Key Laboratory for Environmental Pollution Control, Key Laboratory for Yellow and Huai River Water Environmental and Pollution Control, Ministry of Education, Henan Normal University, Xinxiang, Henan 453007, China;
    b School of Public Health, Xinxiang Medical University, Xinxiang, Henan 453003, China
  • Received:2013-04-22 Published:2013-08-06
  • Supported by:

    Project supported by the National Natural Science Foundation of China (No. 20977025) and the Soft Science Research Project of Henan Province (No. 102400440069).

以氯化1-乙基-3-甲基咪唑(C2mimCl)离子液体为模板分子, 甲基丙烯酸和乙二醇二甲基丙烯酸酯为双功能单体, 聚苯乙烯-二乙烯苯为载体, 制备了C2mimCl表面印迹聚合物(C2mimClMIP/PS-DVB). 采用红外、扫描电镜和Brunauer-Emmett-Teller分析技术对C2mimClMIP/PS-DVB进行了表征. 通过静态吸附实验研究了C2mimClMIP/PS-DVB对模板分子及其结构类似物的吸附行为和选择性识别特性. 结果表明, 聚合物对C2mimCl和氯化1-丁基-3-甲基咪唑(C4mimCl)两种离子液体有高度的选择性识别作用. 将C2mimClMIP/PS-DVB作为固相萃取(SPE)剂制备成SPE柱, 并与高效液相色谱联用, 考察了C2mimClMIP/PS-DVB的动态吸附性能. 结果表明, 在选定的参数条件下, SPE柱能够从结构类似物中选择性分离富集C2mimCl和C4mimCl, 且具备很好的稳定性和可再生性能. 将SPE柱用于地下水中C2mimCl的分离富集, 显示出良好的实用性能.

关键词: 氯化1-乙基-3-甲基咪唑离子液体, 聚苯乙烯-二乙烯苯, 表面印迹, 特异吸附, 固相萃取

1-Ethyl-3-methylimidazolium chloride (C2mimCl) ionic liquid molecularly imprinted polymer (C2mimClMIP/PS-DVB) was prepared on the surface of poly(styrene-divinylbenzene) (PS-DVB) by using C2mimCl as the template molecule, methacrylic acid (MAA) and ethyleneglycol dimethacrylate (EGDMA) as the bifunctional monomer. The preparation conditions were optimized and the molar ratio of 1:4:14 for C2mimCl:MAA:EGDMA was selected as the optimal polymerization molar ratio. Then infrared spectra (IR) spectrophotometer, scanning electron microscopy (SEM) and Brunauer-Emmett-Teller (BET) surface area and pore size analyzer were used to characterize the molecularly imprinted polymer, it was shown that C2mimClMIP/PS-DVB was successfully prepared on the surface of PS-DVB. The static adsorption experiments were performed in acetonitrile to investigate the adsorption properties and selective recognition characteristics of the polymer for C2mimCl and its structural analogues. Selective adsorption experiments showed that C2mimClMIP/PS-DVB has high selectivity for C2mimCl and C4mimCl. Adsorption isotherm experiments suggested that the maximum adsorption capacity of C2mimClMIP/PS-DVB and C2mimClNIP/PS-DVB for C2mimCl was 144.71 μmol/g and 22.56 μmol/g, respectively, and for C4mimCl was 124.53 μmol/g and 21.42 μmol/g. While the total number of binding sites Nt, mean association constant K0 and the heterogeneity index m of C2mimClMIP/PS-DVB were 130.9 μmol/g, 0.37 L/mmol and 0.8, respectively. C2mimClMIP/PS-DVB solid phase extraction column was prepared to investigate the solid phase extraction properties of C2mimClMIP/PS-DVB. Various parameters, such as the loading volume, flow rate and eluent solvent, were optimized for the C2mimClMIP/PS-DVB solid phase extraction column experiments. Then the dynamic adsorption experiments were carried out by coupling C2mimClMIP/PS-DVB solid phase extraction column with high performance liquid chromatography (HPLC), it was shown that C2mimClMIP/PS-DVB solid phase extraction column could separate and enrich C2mimCl and C4mimCl selectively in the presence of their structural analogues, which also exhibited inherent stability and good reusability. The C2mimClMIP/PS-DVB solid phase extraction column was finally applied to separate and enrich C2mimCl in the ground water samples and exhibited good practicability.

Key words: 1-ethyl-3-methylimidazolium chloride ionic liquid, poly(styrene-divinylbenzene), surface molecularly imprinted polymer, specific adsorption, solid phase extraction