三乙胺基SO_3H-功能化离子液体催化合成己二酸二丁酯.pdf

石油学报(石油加工)
2016年2月
ACTA PETROLEI SINICA (PETROLEUM PROCESSING SECTION)
第32卷第1期
文章编号:1001-8719(2016)01-0042-07
三乙胺基SO3H-功能化离子液体催化合成
己二酸二丁酯
高健',郜蕾,尹银',廉红蕾',雒廷亮
(1.郑州大学化工与能源学院,河南郑州450001;2.郑州大学国际学院,河南郑州45000
摘要:以三乙胺为主要原料合成了5种 Bronsted酸性离子液体,考察了不同结构离子液体对合成己二酸二丁酯的
催化活性,并将离子液体酸性强弱与酸催化活性进行关联,同时优化反应温度、原料配比、反应时间、催化剂用
量等反应条件。结果表明,以N-(4-磺酸基)丁基三乙胺硫酸氢盐离子液体为催化剂,添加带水剂环已烷,在反应
温度10℃、n(1- Butanol)/n( Adipic acid)=6、m( Catalyst)/m( Adipic acid)=0.01、m( Cyclohexane)/
m( Raw materials)=0.15、反应时间3h的条件下,已二酸转化率达到99%;经连续重复使用7次,该催化剂仍可
保持很高的催化活性。
关键词:三乙胺;离子液体;酸催化;己二酸二丁酯
中图分类号:O643文献标识码:Adoi:10.3969/j.issn.1001-8719.2016.01.007
Synthesis of Dibutyl Adipate Over tri-ethylammonium-based SO, H-functionalized Ionic Liquids
GAO Jian, GAO Lei, YIN Yin, LIAN Honglei, LUO Tingliang
(1. School of Chemical En gineering and Energy, Zhengzhou University, Zhengzhou 450001, China,
2. International College, Zhengzhou University, Zhengzhou 450000, Chine
Abstract: Several tri-ethylammonium-based acidic ionic liquids were synthesized. Esterification of
1-butanol with adipic acid was carried out by using the prepared Bronsted acidic ionic liquid as
catalyst. The relationship of Bronsted acidity-catalytic activity and the relative acidity of these
prepared catalysts were studied. Moreover, the reaction conditions of temperature, molar ratio of
reactants, time and ionic liquid amount were optimized. The results indicated that with cyclohexane
as water-carrying agent, [(CH; CH: ) N(CH2), SO, HILHSO acidic ionic liquid as the catalyst and
under the optimized reaction conditions of 110C, 3 h, n(1-butanol)/n(Adipic acid)=6
m(Catalyst)/m(Adipic acid)=0 01, m(Cyclohexane)/m(Raw materials)=0. 15, the conversion of
dipic acid could reach 99%, and the high catalytic activity of the catalyst could be also obtained
ter seven recycles.
Key words: tri-ethylamine; ionic liquid; acid catalysis; dibutyl adipate
己二酸二丁酯是一种重要有机合成中间体,可类及纤维素类树脂的增塑剂。与所有的酯化反应一
用作香精、香精控制剂、特种溶剂及常温下乙烯基样,传统方法合成己二酸二丁酯主要采用浓硫酸作
收稿日期:2014-08-29
基金项目:河南省自然科学基金项目(122300410076)及河南省教育厅科学技术研究重点项目(12A150023)资助
第一作者:高健,男,讲师,博士,从事功能化离子液体新材料的合成及其催化性能研究;E- mail: gaojian@zu.edu,cn
通讯联系人:廉红蕾,女,讲师,博士,从事酸性离子液体材料的合成及其催化性能研究;Tel:0371-67781713;E-mail: hongleilian
(a zzu. edu. cn