高等学校化学学报

高等学校化学学报 ›› 2003, Vol. 24 ›› Issue (11): 2099.

• 论文 • 上一篇    下一篇

聚苯乙烯负载席夫碱Mo(Ⅵ)配合物合成、表征及其在环己烯环氧化反应中的催化活性

章亚东, 高晓蕾, 蒋登高, 陈霞, 王自健   

  1. 郑州大学化工学院, 郑州 450002
  • 收稿日期:2002-10-30 出版日期:2003-11-24 发布日期:2003-11-24
  • 通讯作者: 章亚东(1965年出生),男,博士,副教授,主要从事精细化工理论与工程技术研究.E-mail:zhangyadong@zzu.edu.cn E-mail:zhangyadong@zzu.edu.cn
  • 基金资助:

    河南省杰出人才创新基金项目(批准号:0121001900)资助

Synthesis and Characterization of Polystyrene-grafted Molybdenum (Ⅵ) Schiff Base Complex and Its Catalytic Activity in Epoxidation of Cyclohexene

ZHANG Ya-Dong, GAO Xiao-Lei, JIANG Deng-Gao, CHEN Xia, WANG Zi-Jian   

  1. College of Chemical Engineering, Zhengzhou University, Zhengzhou 450002, China
  • Received:2002-10-30 Online:2003-11-24 Published:2003-11-24

PDF (PC)

被引次数

52

摘要： 合成了聚苯乙烯负载乙二胺缩水杨醛席夫碱与Mo(Ⅵ)的配合物,并对其结构进行了表征.该配合物催化环己烯环氧化反应与小分子配合物MoO2(acac)2相比,具有更优良的催化活性和选择性;建立了催化剂中Mo分析和环氧环己烷气相色谱分析新方法;探讨了配合物及环氧环己烷合成过程诸因素的影响;优化了环氧环己烷合成条件,即以n(t-BuOOH)=0.1mol计,n(C6H10)∶n(t-BuOOH)=3∶1,溶剂5mL,反应温度80℃,时间60min.在该条件下,环氧环己烷收率(以t-BuOOH计)99.2%以上,质量分数约99.5%(GC检测).催化剂循环使用5次后,未见活性明显下降,环氧环己烷收率(以t-BuOOH计)仍接近99%.

关键词: Mo(Ⅵ)席夫碱配合物, 环己烯, 环氧环己烷, 聚苯乙烯

Abstract: Molybdenum(Ⅵ) Schiff base complex derived from salicylaldehyde and ethylenediamine grafted in polystyrene-divinyl benzene(PS) supporter, was synthesized and characterized by IRspectra.The macromolecule Schiff base acts as uninegative bidentate ligand and bonding occurs through the hydroxyl oxygen and nitrogen atoms.The Mo(Ⅵ) complex grafted in polystyrene as the catalyst has been used in epoxidation process of cyclohexene, and its catalytic activity and selectivity have also been investigated.The experimental results show that the complex possesses an excellent activity and selectivity for epoxidation of cyclohexene.The effects of many factors on the graft process of PSsupporter and synthesis of cyclohexene oxide have also been discussed.New analysis method of amount of Mo in the catalyst and gas chromatogram (GC) method of epoxycyclohexane analysis have been set up.The optimum reaction condition has been obtained by orthogonal experiment design, that is, according to n(t-BuOOH)=0.1 mol, n(C6H10)∶n(t-BuOOH)=3∶1, volume of solvent is about 5mL, reaction temperature 80 ℃, reaction time 60 min, and weight of molybdenum in the catalyst is 2.08×10-2g.Under this condition, based on amounts of t-BuOOH, the yield of epoxycyclohexane is more than 99.2%, purity of epoxycyclohexane is about 99.5% by GCanalysis.The catalyst after being used circularly for 5 times still possesses higher catalysis activity and selectivity, the yield of cyclohexene oxide approaches 99% under the above-mentioned reaction condition.

Key words: Molybdenum (Ⅵ) Schiff base complex, Cyclohexene, Epoxycyclohexane, Polystyrene

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