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›› 2010, Vol. 10 ›› Issue (2): 361-366.

• 材料工程专栏 • 上一篇    下一篇

有机官能化介孔催化剂制备及其在正丁醛自缩合制辛烯醛反应中的应用

苏博 郎万中 曾群英 刘训稳 杨春基 郭亚军   

  1. 上海师范大学化学系 上海师范大学化学系 中国石油研究院大庆化工研究中心 上海师范大学化学系 中国石油研究院大庆化工研究中心 上海师范大学化学系
  • 收稿日期:2009-12-18 修回日期:2010-03-23 出版日期:2010-04-20 发布日期:2010-04-20
  • 通讯作者: 郎万中

Preparation of Organic Functionalized Mesoporous Catalysts and Their Applications to the Self-condensation Reaction of n-Butanal to 2-Ethylhexenal

SU Bo, LANG Wan-zhong, ZENG Qun-ying, LIU Xun-wen YANG Chun-ji, GUO Ya-jun,   

  1. Department of Chemistry, Shanghai Normal University Department of Chemistry, Shanghai Normal University Daqing Chemical Engineering Center, Institute of PetroChina Company Department of Chemistry, Shanghai Normal University Daqing Chemical Engineering Center, Institute of PetroChina Company Department of Chemistry, Shanghai Normal University
  • Received:2009-12-18 Revised:2010-03-23 Online:2010-04-20 Published:2010-04-20
  • Contact: LANG Wan-zhong,

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摘要： 通过表面接枝法将3-氨丙基三甲氧基硅烷、N-氨乙基-g-氨丙基三甲氧基硅烷和N,N-二乙基氨丙基三甲氧基硅烷嫁接在MCM-41介孔分子筛表面，制得3种相应有机胺官能介孔固体碱催化剂NH2-MCM, NH2NH-MCM及NR2-MCM，并利用2-氰乙基三甲氧基硅烷对NH2-MCM进行了修饰，制得NH2-MCM-COOH酸碱双功能催化剂，对所制催化剂进行了性能表征，将其用于正丁醛自缩合制辛烯醛反应，研究了催化剂的催化性能. 结果表明，相同反应条件下，3种催化剂中NH2-MCM的催化效果最好，在用量为0.3 mmol胺时反应10 h，辛烯醛产率达70%以上；NH2-MCM-COOH用量为0.15 mmol胺时反应10 h，辛烯醛产率约为NH2-MCM的2倍，表明催化剂表面碱性有机胺基团和酸性基团具有明显的酸碱协同效应，可显著促进正丁醛缩合反应.

关键词: 介孔分子筛, MCM-41, 固体碱, 有机胺, 正丁醛, 辛烯醛

Abstract: Three organic amine functionalized MCM-41 solid base catalysts, NH2-MCM, NH2NH-MCM and NR2-MCM, using 3-aminepropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, and N,N-diethyl-3-aminopropyltriethoxysilane as precursors, were prepared by surface grafting. Anchoring 2-cyanoethyltrimethoxysilane on the surface of NH2-MCM, the acid-base amphoteric bifunctionalized catalyst NH2-MCM-COOH was prepared. The properties of as-synthesized catalysts were analyzed. The as-synthesized catalysts were applied to self-condensation reaction of n-butanal to investigate the catalytic activity. It is shown that NH2-MCM has the best catalytic activity among the three catalysts under the same conditions. With 0.3 mmol amine, the yield of 2-ethylhexenal attains above 70% after 10 h of reaction. Compared with NH2-MCM, NH2-MCM-COOH exhibits excellent catalytic activity, after 10 h of reaction with 0.15 mmol amine，the yield of 2-ethylhexenal nearly doubles that for NH2-MCM. The results reveal that the alkaline organic amine groups and acid groups on the surface of catalysts have obvious synergic effect to promote the self-condensation reaction of n-butanal.

Key words: mesoporous zeolite, MCM-41, solid base, organic amine, n-butanal, 2-ethylhexenal