李艳飞.固载化N,N-双齿席夫碱型氧钒(Ⅳ) 配合物的制备 及其在分子氧氧化乙苯中的催化作用[J].分子催化编辑部,2013,(3):271-278
固载化N,N-双齿席夫碱型氧钒(Ⅳ) 配合物的制备 及其在分子氧氧化乙苯中的催化作用
Preparation of N,N-Bidentate Schiff Base-Type Oxovanadium(IV) Complex Immobilized on CPS Microspheres and Catalytic Property in Oxidation of Ethylbenzene by Molecular Oxygen
投稿时间:2013-05-04  修订日期:2013-06-05
DOI:
中文关键词:  螯合树脂  Schiff碱  交联聚苯乙烯  甘氨酸  单分子亲核取代反应
英文关键词:Crosslinked polystyrene microspheres  Oxovanadium(IV) complex  Heterogeneous catalysis  Ethylbenzen  Dioxygen
基金项目:
作者单位E-mail
李艳飞 中北大学化工系 957477011@qq.com 
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中文摘要:
      以交联聚苯乙烯(CPS)微球为出发物质, 通过大分子反应, 制备了键合有苯甲醛(BA)的聚合物微球BA-CPS, 又以3-氨基吡啶(AP)为试剂, 使微球BA-CPS与之发生席夫碱反应, 制得了键合有N,N-双齿席夫碱配基的微球BAAP-CPS; 然后使微球BAAP-CPS与硫酸氧钒发生配位螯合反应, 成功制备了固载有N,N-双齿席夫碱型氧钒(Ⅳ) 配合物的微球CPS-[VO(BAAP)2], 即获得了非均相的氧钒(Ⅳ)配合物催化剂. 用红外光谱(FTIR)和紫外吸收光谱等手段对微球CPS-[VO(BAAP)2]的化学结构进行了表征. 将微球CPS-[VO(BAAP)2]用于乙苯的分子氧催化氧化过程, 考察了其催化活性及主要因素对乙苯催化氧化反应的影响, 探索研究了催化反应机理. 实验结果表明, 在分子氧氧化乙苯的反应中, 微球CPS-[VO(BAAP)2]具有很高的催化活性和优良的催化选择性, 可将乙苯高效地(45%的转化率)转化为单一产物苯乙酮. 氧化反应可能遵循自由基反应历程, 乙苯侧烷基氢过氧化物可能是关键的中间物. 乙苯催化氧化反应适宜的反应温度为110 ℃, 且体系中催化剂有一适宜用量. 催化剂CPS-[VO(BAAP)2]具有优良的循环使用性能.
英文摘要:
      With crosslinked polystyrene (CPS) microspheres as starting substance, the polymer microspheres BA-CPS, on which benzaldehyde (BA) was bonded, via polymer reaction. Then the microspheres BA-CPS were allowed to produce Schiff reaction with 3-aminopyridine (AP) as reagent, preparing BAAP-CPS microspheres, on which N,N-bidentate Schiff base ligand was bonded. Finally, the coordination reaction between BAAP-CPS microspheres and vanadyl sulfate was performed, obtaining N,N-bidentate Schiff base-tape oxovanadium(IV) complex-immobilized microspheres CPS-[VO(BAAP)2], namely successfully achieving the heterogeneous oxovanadium(IV) complex catalyst. The microspheres CPS-[VO(BAAP)2]were fully characterized by FTIR and solid ultraviolet spectrum. The microspheres CPS-[VO(BAAP)2] were used in the oxidation reaction of ethylbenzene by molecular oxygen, and their catalytic activity was examined. The experimental results show that in the oxidation reaction of ethylbenzene by molecular oxygen, the heterogeneous oxovanadium(IV) complex catalyst CPS-[VO(BAAP)2] have very high catalytic activity and excellent catalytic selectivity. At ordinary pressure of dioxygen, ethylbenzene can be transformed to acetophenoneas a single product with a yield of 45%. The oxidation reaction of ethylbenzen is carried according to a radical reaction pathway possibly, and the side alkyl hydroperoxide C6H5-ROOH is possibly the key intermediate. The suitable reaction temperature is 110℃, and there is an appropriate used amount of the catalyst. The catalyst CPS-[VO(BAAP)2] has excellent cycle and reuse property.
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