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金属离子印迹聚合物微球的研究

Study on the Metal Ion Imprinted Polymeric Microspheres

【作者】 裴广玲

【导师】 成国祥;

【作者基本信息】 天津大学 , 材料学, 2003, 博士

【摘要】 分子印迹聚合物已在分子层析、酶模拟、抗体/受体结合模拟、生物传感器、临床药物分析、膜分离技术等领域显示出广泛的应用前景。本文以Cu2+为印迹离子,以MAA为功能单体,TRIM为聚合物母体,以SDBS为分散剂,利用反相乳液-悬浮聚合法制备了Cu2+印迹聚合物微球。并对影响微球形态的工艺条件,如外水相中分散剂的种类、用量、功能单体的用量、内水相中金属离子的浓度、外水相的整体组成等进行了详细的研究。对制备的聚合物进行动力学和热力学研究,同时对不同工艺条件制备的聚合物对Cu2+、Ni2+的吸附选择行为进行测试。试验结果表明,利用反相乳液-悬浮聚合法可得到分散的聚合物微球,Cu2+印迹聚合物微球对Cu2+和Ni2+具有一定的选择性,其分离系数达到1.54。在上述研究的基础上,利用反相乳液悬浮聚合法,以2-丙烯酰胺-2-甲基丙磺酸(AMPS)为功能单体,制备了Cu2+和Ni2+印迹聚合物微球。对不同用量AMPS制备的聚合物形态及其吸附选择性能进行详细地研究。实验表明,随着功能单体含量的增加,聚合物微球的粒径和溶胀率都随之增大。与未印迹聚合物微球相比,印迹聚合物对印迹离子的吸附量明显增加,随着功能单体与印迹离子摩尔比的增大,印迹聚合物对印迹离子的相对吸附量也增加,相对分离因子(先增加后降低,在6:1时达到最大值1.70。此外,还采用反相乳液悬浮聚合法,改变外水相的组成,以PVA分散剂,制备了Cu2+印迹聚合物微球,并对所得聚合物的吸附选择性行为进行了研究。最后,以Ni2+为印迹离子,以TRIM为聚合物母体,MAA为功能单体,甲苯为致孔剂,采用悬浮聚合法制备Ni2+印迹聚合物微球。考察了分散剂的用量、功能单体的含量、引发剂的加入方式、油相与水相的比例、甲苯的含量等对微球形态的影响,同时研究了所得聚合物对印迹离子与竞争离子的选择性。在Ni2+和Cu2+、Ni2+和Zn2+的混合溶液中的吸附表明,Ni2+印迹聚合物对Ni2+选择性均高于未印迹聚合物的选择性,印迹聚合物的分离因子(分别为1.53和1.89,相对分离因子(分别为1.56和1.82。

【Abstract】 Molecular imprinted polymers(MIPs), as molecular recognition materials with high selectivity to imprinting molecules, have extensive potential application in separation, purification, enzyme mimic, biomimic sensors, membrane separation and other fields.This paper aimed to study the preparion technique of metal ion imprinted polymer in aqueous system, the surface morphology of polymer obtained and their selective properties to metal ions.In this paper, Cu2+ imprinted polymer microspheres were prepared by reverse-emulsion suspension polymerization. The methacrylic acid (MAA), TRIM and SDBS were used as functional monomer, polymeric matrix and dispersant respectively. The process affecting the polymer morphology, such as the kind and amount of dispersant, the amount of functional monomer, the Cu2+ concentration and the composition of external aqueous phase, were investigated in detail. At the same time , the selective adsorption to Cu2+ and Ni2+, including the dynamics and thermodynamics, was performed. The results indicated that the polymer obtained exhibited good selectivity to Cu2+ and Ni2+ and the separation factor up to 1.54.Cu2+ and Ni2+ imprinted polymers were prepared with the optimal recipe obtained by previous studies and 2-acrylanido-2-methyl-propanesulfonic acid(AMPs) as functional monomer. It was showed that the particle size and swelling rate of imprinted polymers increased with the increase of functional monomer. The adsorption capacity to imprinted metal ion enhanced with the increase of mol ratio between functional monomer and imprinted metal ions. However the relative separation factor ( firstly increased and then decreased.Moreover, in order to avoid the bad effect of other metal ions on the Cu2+ imprinted polymer, the polymers were performed by inverse emulsion suspension polymerization and PVA as dispersant. The process of preparing was studied and selective adsorptions were carried lastly, the suspension polymerization method was applied to manufacture Ni2+ imprinted polymer and MAA as functional monomer. Those factors affected the polymer morphology, for instance the amount of functional monomer, the added order of AIBN, the ratio of oil and water, the amount of toluene, were investigated detailed. A further research on the selectivity of polymers to the imprinted metal ion and <WP=4>competitive ion was performed. The results showed the resulting polymer appeared regular sphericity and existed good recognition property to imprinted ion in mixture of imprinted ion and competitive ion.

  • 【网络出版投稿人】 天津大学
  • 【网络出版年期】2004年 04期
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