硅胶表面3-甲基噻吩分子印迹聚合物的制备及吸附特性研究
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摘要
采用γ-氨丙基三乙氧基硅烷对硅胶微球表面进行接枝修饰,然后以甲基丙烯酸为功能单体,二甲基丙烯酸乙二醇酯为交联剂,甲苯为溶剂,3-甲基噻吩为模板分子,在硅胶微球表面聚合,得到3-甲基噻吩的硅胶微球表面分子印迹聚合物,用红外光谱进行结构表征。通过考察模板分子、功能单体、交联剂、溶剂的用量等对吸附容量的影响,得到3-甲基噻吩、甲基丙烯酸、二甲基丙烯酸乙二醇酯、甲苯适宜的摩尔聚合比,以此配比合成了3-甲基噻吩表面印迹聚合物,在模拟汽油中,研究了该聚合物对3-甲基噻吩的吸附动力学、吸附选择性、竞争性及再生性能。结果表明,分子印迹聚合物对3-甲基噻吩具有良好的吸附选择性和再生性能,最大吸附容量可达85mg/g,有望将其用于汽油中噻吩类硫的深度脱除,从而弥补加氢脱硫缺陷。
Based on grafting modification of silica microsphere surface with γ-aminopro-pyltriethoxysilane, surface molecularly imprinted polymers for 3-methyl thiophene were prepared with methacrylic acid as functional monomer, ethylene glycol dimethacrylate as cross-linker, toluene as solvent, and 3-methyl thiophene as template molecule. The final products were characterized with FT-IR. The effect of dosages of template molecule, functional monomer, cross-linker and solvent on adsorption capacity was investigated to determine the suitable molar ratio of template molecule, functional monomer, cross-linker and solvent for polymerization. Adsorption kinetics, static adsorption selectivity, competive adsorption and regenerability were also studied in simulated gasoline. The results showed that the molecularly imprinted polymer had good selectivity for 3-methyl thiophene with adsorption capacity of 85mg/g, which may provide an alternative for removing thiophenic sulfur compounds from gasoline and improving the methodology of gasoline deep hydrodesulfurization.
Based on grafting modification of silica microsphere surface with γ-aminopro-pyltriethoxysilane, surface molecularly imprinted polymers for 3-methyl thiophene were prepared with methacrylic acid as functional monomer, ethylene glycol dimethacrylate as cross-linker, toluene as solvent, and 3-methyl thiophene as template molecule. The final products were characterized with FT-IR. The effect of dosages of template molecule, functional monomer, cross-linker and solvent on adsorption capacity was investigated to determine the suitable molar ratio of template molecule, functional monomer, cross-linker and solvent for polymerization. Adsorption kinetics, static adsorption selectivity, competive adsorption and regenerability were also studied in simulated gasoline. The results showed that the molecularly imprinted polymer had good selectivity for 3-methyl thiophene with adsorption capacity of 85mg/g, which may provide an alternative for removing thiophenic sulfur compounds from gasoline and improving the methodology of gasoline deep hydrodesulfurization.
引文
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[18]李永,杨黄浩,庄峙厦,王小如.表面分子印迹聚合物纳米线用于蛋白质的特异识别.高等学校化学学报[J].2005,16(9):1634-1636.
[2]殷长宏,夏道宏.催化裂化汽油中类型硫含量分布.燃料化学学报[J].2001,29(3):256-258.
[3]孙志娟,余谟鑫,张心亚,陈焕新.油品中噻吩硫化物脱除技术研究进展.化工进展[J].2005,24(9):1002-1005.
[4]黎俊波,刘习文,曹灿灿,郭嘉,潘志权.Cu Y型分子筛制备及吸附脱硫影响因素研究.离子交换与吸附[J].2012,28(1):18-25.
[5]杨宝康,张继军,傅军,何鸣元.汽油中含硫化合物脱除新技术.石油炼制与化工[J].2000,31(7):36-39.
[6]李铁森,刘瑞萍,王佩瑜,王国旗.生产超低硫清洁汽油的挑战及对策.炼油技术与工程[J].2014,44(6):8-12.
[7]单国彬,刘会洲,邢建明.汽油吸附脱硫的研究进展.现代化工[J].2003,23(6):18-20.
[8]徐伟箭,项伟中,周晓,徐丰.基于硅胶表面修饰的分子印迹技术研究进展.应用化学[J].2003,20(10):226-229.
[9]仰云峰,车爱馥,吴健,徐志康.表面分子印迹研究进展.化学通报[J].2007,(5):324-330.
[10]冀峰,赵利霞,冯钦忠,严炜,林金明.硅胶表面扑灭津分子印迹材料的制备及性能表征.分析化学研究报告[J].2008,36(7):920-924.
[11]徐志祥,王硕,方国臻.内分泌干扰物雌酮分子印迹新型吸附功能材料的制备及其选择性能研究.离子交换与吸附[J].2008,24(6):489-495.
[12]Sulitzky C,Hall A G,Lanzaf.Grafting of molecularly imprinted polymer films on silica supports containing surface-bound free radical initiators.Macromolecules[J].2002,35:79-91.
[13]Carter S R,Rimmer S.Surface molecularly imprinted polymer core-shell particles.Advanced Functional Materials[J].2004,14(6):553-561.
[14]Peter A G Cormack,Klaus Mosbach.Molecular imprinting:Recent developments and the road ahead.Reactive&Functional Polymers[J].1999,41:115-124.
[15]Mark E Byrne,Vishal Salian.Molecular imprinting within hydorgels II:Progress and analysis of the field.International Journal of Pharmaceuticals[J].2008,364:188-212.
[16]Taher Alizadeh.Development of a molecularly imprinted polymer for pyridoxine using an ion-pair as template.Analytica Chimica Acta[J].2008,623:101-108.
[17]常勇慧,刘波,应汉杰,何明芳.分子印迹技术制备石油有机硫组分固相萃取剂的研究.离子交换与吸附[J].2003,19(5):450-456.
[18]李永,杨黄浩,庄峙厦,王小如.表面分子印迹聚合物纳米线用于蛋白质的特异识别.高等学校化学学报[J].2005,16(9):1634-1636.