催化学报

催化学报 ›› 2010, Vol. 31 ›› Issue (11): 1405-1410.DOI: 10.3724/SP.J.1088.2010.00518

• 研究论文 • 上一篇    下一篇

环戊二烯掺杂乙烷桥联有序介孔材料的制备、表征及应用

周媛, 高鹏飞, 张铁明, 王永钊, 赵永祥   

  1. 山西大学化学化工学院精细化学品教育部工程研究中心, 山西太原 030006
  • 收稿日期:2010-05-19 出版日期:2010-11-12 发布日期:2014-03-28

Preparation, Characterization and Application of Cyclopentadiene-Containing Mesoporous Ethanesilica

ZHOU Yuan, GAO Pengfei, ZHANG Tieming, WANG Yongzhao, ZHAO Yongxiang*   

  1. Engineering Research Center of Ministry of Education for Fine Chemicals, School of Chemistry and Chemical Engineering, Shanxi University, Taiyuan 030006, Shanxi, China
  • Received:2010-05-19 Online:2010-11-12 Published:2014-03-28

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摘要： 以单硅酯 (2-(环戊基-1,3-二烯基) 乙基) 三乙氧基硅烷 (TEECp) 和含有亚乙基桥键的硅酯 1,2-二 (三乙氧基硅基) 乙烷为硅源, 以三嵌段共聚物 P123 为模板剂, 通过调节 TEECp 预水解时间, 采用共聚法合成了环戊二烯掺杂乙烷桥联材料 (Cp-PMO), 并采用小角 X 射线衍射、N2 物理吸附、透射电镜、红外光谱和热重等技术对样品进行了表征. 结果表明, 环戊二烯基被成功引入到乙烷桥联材料中, 所得 Cp-PMO 样品具有高度有序的二维六方介孔孔道, 热稳定性较高; 随着材料中环戊二烯含量的增加, 其有序性降低, 孔径、比表面积和孔体积均有所减小, 孔壁逐渐增厚. 在乙酸乙酯与正丁醇的酯交换反应中, Cp-PMO 样品表现出较高的催化活性. 当该样品中环戊二烯含量为 30% 时, 乙酸乙酯转化率和乙酸丁酯收率分别可达 19.3% 和 10.6%.

关键词: 共缩聚, 环戊二烯, 介孔材料, 乙酸乙酯, 丁醇, 酯交换, 乙酸丁酯

Abstract: By adjusting the prehydrolysis time of (2-(cyclopenta-1,3-dienyl)ethyl)triethoxysilane (TEECp), cyclopentadiene-containing mesoporous ethanesilica (Cp-PMO) was synthesized through the co-condensation of 1,2-bis(triethoxysilyl)ethane (BTEE) and TEECp using triblock PEO-PPO-PEO copolymer P123 as the structure-directing agent. The prepared material samples were characterized by X-ray diffraction, N2 adsorption-desorption, transmission electron microscopy, Fourier transform infrared spectroscopy, and thermogravimetric analysis. The results showed that cyclopentadiene was successfully incorporated into the material, which had highly ordered hexagonal mesostructure. With increasing cyclopentadiene loading, the mesostructure order, pore size, BET surface area, and pore volume of Cp-PMO decreased, while the pore wall widths increased. The Cp-PMO with 30% cyclopentadiene loading showed high activity in the transesterification of ethyl acetate and n-butanol to n-butyl acetate and its yield was 10.6%.

Key words: co-condensation, cyclopentadiene, mesoporous material, ethyl acetate, butanol, transesterification, butyl acetate