基于DES-RAFT反应技术的邻苯二甲酸二甲酯分子印迹聚合物制备及表征

Reparation and Characterization of Molecularly Imprinted Polymers of Dimethyl Phthalate Based on DES-RAFT Reaction Technique

本研究基于低共熔溶剂(DES)体系的基本性质,采用可逆加成-断裂链转移(RAFT)沉淀聚合法制备一种新型分子印迹聚合物,并对其进行结构表征和性能评价。结果表明:选择四丁基溴化铵-月桂酸作为低共熔溶剂(DES)体系,邻苯二甲酸二甲酯(DMP)为分子模板,α-甲基丙烯酸(MAA)为功能单体,乙二醇二甲基丙烯酸酯(EGDMA)为交联剂,偶氮二异丁腈(AIBN)为链引发剂,三硫代碳酸二苄基酯(DBTTC)为链转移剂,以模板∶功能单体∶交联剂摩尔比为1∶4∶16进行聚合反应,制备而成的邻苯二甲酸二甲酯分子印迹聚合物(DMP-MIPs)对目标物具有良好的特异选择性。同时,由于低共熔溶剂特有的氢键作用,不仅改善了聚合物微球的尺寸和形貌,而且增强了分子印迹聚合物对邻苯二甲酸二甲酯的吸附能力,印迹因子IF可达1.122。将DES-MIPs应用于实际水样检测,并进行3个浓度(0.05 mg/L、0.5 mg/L、1.0 mg/L)加标实验,平均回收率为86.8%~94.3%,相对标准偏差(RSD)在2.41%~3.21%之间。由此可见,基于DESRAFT反应技术制备的分子印迹聚合材料对水质中DMP有良好的选择性吸附,有望应用于环境等领域的有毒有害物质检测。

Based on the basic properties of eutectic solvent(DES)system,a novel molecular-imprinted polymer was prepared by reversible addition-fragmentation chain transfer(RAFT)precipitation polymerization,and its structure characterization and properties were evaluated.The results show that the prepared dimethyl phthalate molecularly imprinted polymer(DMP-MIPs)has good specific selectivity for the targets if it is prepared when tetrabutylammonium bromide lauric acid is selected as the eutectic solvent(DES)system,dimethyl phthalate(DMP)as the molecular template,α-methacrylic acid(MAA)as the functional monomer,ethylene glycol dimethacrylate(EGDMA)as the crosslinking agent,azodisobutyronitrile(AIBN)as the chain initiator,dibenzyl trithiocarbonate(DBTTC)as chain transfer agent,and with a ratio of the template and the functional monomer to the crosslinker molar being 1:4:16 under the polymerization.At the same time,due to the unique hydrogen bonding of the eutectic solvent,not only the size and morphology of the polymer microspheres are improved,but also the adsorption capacity of the molecularly imprinted polymer for dimethyl phthalate is enhanced,and the imprinting factor IF can reach 1.122.DES-MIPs was applied to the actual water sample detection,and three concentrations(0.05,0.5,1.0 mg/L)were added to the experiment.The average recovery rate was between 86.8%-94.3%,and the relative standard deviation(RSD)was between 2.41%and 3.21%.Thus it can be seen that the molecularly imprinted polymeric material prepared based on DES-RAFT reaction technology has good selective adsorption of DMP in water quality,and is expected to be applied to the environmental field for detection of toxic and harmful substances.