在CPS微球表面固载氨基酚型双齿席夫碱氧钒(Ⅳ)配合物及其催化氧化性能  

Immobilizing Aminophenol Type Bidentate Schiff Base Oxovanadium(Ⅳ)Complex on Surfaces of CPS Microspheres and Its Catalytic Oxidation Property

作　　者：孟素青 崔坤俐 高保娇[1] 

机构地区：[1]中北大学化工系,太原030051

出　　处：《功能高分子学报》2016年第3期305-312,共8页Journal of Functional Polymers

基　　金：山西省青年基金(2014021015-1)

摘　　要：使乙醛酸(GA)与氯甲基化交联聚苯乙烯(CMCPS)微球发生酯化反应,将醛基(AG)引入交联聚苯乙烯(CPS)微球表面,得到改性微球CPS-AG;再以间氨基苯酚(MAP)为试剂,使微球CPS-AG表面的AG发生席夫碱反应,制得了表面键合有氨基酚型双齿席夫碱配基的功能微球CPS-AGAP;最后,使微球CPS-AGAP与硫酸氧钒发生配位螯合反应,获得了表面固载有氨基酚型双齿席夫碱氧钒(Ⅳ)配合物的固体催化剂微球CPS-[VO(AGAP)2]。重点考察了主要因素对GA与CMCPS微球的酯化反应的影响。采用红外光谱(FT-IR)、固体紫外(UV)及扫描电子显微镜(SEM)对催化剂微球进行了充分表征。分别将微球CPS-[VO(AGAP)2]用于环己醇和乙苯的分子氧氧化过程,考察其催化活性。实验结果表明,溶剂的极性有利于GA与CMCPS微球之间的酯化反应,极性较强的N,N-二甲基乙酰胺为适宜的反应溶剂,90℃为适宜的反应温度。在适宜的反应条件下,CMCPS微球的氯甲基转化率可以达到82%。在分子氧氧化环己醇和乙苯的过程中,非均相催化剂CPS-[VO(AGAP)2]微球均表现出良好的催化活性。Esterification reaction between glyoxylic acid （GA） and chloromethylated crosslinked polystyrene （CMCPS） microspheres was made to be carried out,and the aldehyde group （AG） was introduced onto the surfaces of crosslinked polystyrene （CPS） microspheres,resulting in the modified microspheres CPS-AG.Subsequently,the Schiff base reaction of the AG on CPS-AG microspheres was conducted using m-aminophenol as reagent,obtaining the functional microspheres CPS-AGAP,on which aminophenol type bidentate Schiff base ligands were bonded.Finally,the chelating coordination reaction between CPS-AGAP microspheres and vanadyl sulfate was performed,and microspheres CPS-[VO（AGAP）2],on which aminophenol type bidentate Schiff base oxovanadium（Ⅳ） complex was immobilized,were successfully prepared.The effects of the main factors on the esterification reaction between GA and CMCPS microspheres were studied and the reaction conditions were optimized.The microspheres CPS-[VO（AGAP）2] were fully characterized by Fourier Transform Infrared spectroscopy （FT-IR）,Ultra-Violet spectrum （UV） and Scanning Electron Microscope （SEM）.The microspheres CPS-[VO（AGAP）2] were used in the oxidations of cyclohexanol and ethylbenzene with molecular oxygen as oxidant,respectively,and their catalytic activity was examined.Results showed that the polarity of the solvents was advantageous to the esterification reaction between GA and CMCPS microspheres,and the suitable solvent was N,N-dimethylacetamide with strong polarity.The appropriate reaction temperature was 90℃.Under the optimum reaction conditions,the conversion of the chloromethyl group of CMCPS microspheres could reach 82%.In the aerobic oxidations of cyclohexanol and ethylbenzene,CPS-[VO（AGAP）2] microspheres exhibited fine catalytic activity.

关 键 词：交联聚苯乙烯微球 双齿席夫碱配基 氧钒(Ⅳ)配合物 固载 催化氧化 

分 类 号：O631[理学—高分子化学]