双酚F分子印迹聚合物的制备及其固相萃取研究

发布时间：2019-06-06 19:15

【摘要】：随着科学技术的快速发展,我国取得了举世瞩目的成就,但同时面临着严重的环境污染,环境污染物的去除和复杂环境样品的预处理成为突出问题。本文摒弃了吸附效率有限、专一性差的传统吸附剂,利用分子印迹技术合成了对特定目标物具有特异性识别能力的分子印迹聚合物,并结合静态吸附实验研究了聚合物的吸附性能、识别性能和再生性能。同时将该聚合物作为固相萃取填料制备了分子印迹固相萃取小柱,讨论了MISPE柱的固相萃取性能。主要研究内容如下:(1)以4,4'-双酚F为模板分子、α-甲基丙烯酸为功能单体、乙二醇二甲基丙烯酸酯为交联剂,采用本体聚合法制备了一种4,4'-双酚F分子印迹聚合物(BPF-MIPS),并对聚合物制备条件进行优化,确定乙腈为致孔剂,模板分子与功能单体的适宜摩尔比为1:4,功能单体与交联剂的适宜摩尔比为1:5。利用傅里叶红外光谱、扫描电镜、比表面分析、热重分析等测试手段对聚合物的结构和形貌进行表征,结果表明在本实验条件下制备的BPF-MIPS是一种球状,形貌均一,多孔且孔道复杂的交联聚合物,比表面积和孔径分别为75.67 m2/g和1.69 nm,并具有热稳定性。(2)结合静态吸附实验对4,4'-BPF在BPF-MIPS上的吸附行为及识别性能进行了探究。等温吸附和动力学实验表明,BPF-MIPS对4,4'-BPF的吸附量大于NIPS,大约历时200 min达到吸附平衡,吸附平衡数据和动力学数据可分别用Freundlich模型和准二级动力学方程拟合。热力学实验表明该吸附过程是放热的、自发进行的,且低温有利于吸附。Scatchard方程分析表明:BPF-MIPS对水相中4,4'-BPF具有较强的吸附能力,吸附过程存在两种不同类型的结合位点,高亲和力结合位点的最大表观吸附量达到37.1 mg/g,平衡解离常数为2.03×10-5 mol/L。选择性实验表明,BPF-MIPS对4,4'-BPF较好的选择性,对双酚A及苯酚的选择性因子分别为2.07、11.7。聚合物重复使用8次后对4,4'-BPF的吸附量仍是初次使用时的94.9%,表现出良好的再生性能。(3)将BPF-MIPS作为填料制备了分子印迹固相萃取小柱(MISPE),MISPE柱以甲醇-水(7/3,v/v)为淋洗剂,甲醇-乙酸(9/1,v/v)为洗脱剂;MISPE柱的穿透体积为60 mL,穿透容量为5.98 mg/g,总传质系数0.0339 s-1,传质区长度为20.44 mm;MISPE柱对4,4'-BPF具有特异性,能将水环境中4,4'-BPF进行选择性分离富集。
[Abstract]:With the rapid development of science and technology, China has made remarkable achievements, but at the same time, it is facing serious environmental pollution. The removal of environmental pollutants and the pretreatment of complex environmental samples have become outstanding problems. In this paper, the traditional adsorbents with limited adsorption efficiency and poor specificity were abandoned, and the molecular imprinted polymers with specific recognition ability for specific targets were synthesized by molecular imprinting technique. The adsorption properties, recognition properties and regeneration properties of the polymers were studied by static adsorption experiments. At the same time, the polymer was used as solid phase extraction packing to prepare the molecularly imprinted solid phase extraction column, and the solid phase extraction performance of MISPE column was discussed. The main research contents are as follows: (1) using 4, 4 mol-bisphenol F as template molecule, 伪-methacrylic acid as functional monomer, ethylene glycol dimethacrylate as crosslinker, A kind of 4, 4 / bisphenol F molecular imprinted polymer (BPF-MIPS) was prepared by bulk polymerization. The preparation conditions of the polymer were optimized. The optimum molar ratio of template molecule to functional monomer was 1 脳 4. The suitable molar ratio of functional monomer to crosslinker is 1 鈮，

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