碱性离子液体催化合成三羟甲基丙烷

doi:10.3866/PKU.WHXB201412101

物理化学学报 >> 2015, Vol. 31 >> Issue (2): 337-343.doi: 10.3866/PKU.WHXB201412101

碱性离子液体催化合成三羟甲基丙烷

龙金星¹, 袁正求¹, 马浩², 舒日洋¹, 李雪辉²

1. 中国科学院广州能源研究所, 中国科学院可再生能源重点实验室, 广州 510640;
2. 华南理工大学化学与化工学院, 广州 510640

收稿日期:2014-09-30 修回日期:2014-12-10 发布日期:2015-01-26
通讯作者: 龙金星, 李雪辉 E-mail:longjx@ms.giec.ac.cn;cexhli@scut.edu.cn
基金资助:
国家自然科学基金(51306191, 21336002)及教育部博士点基金(20130172110043)资助项目

Catalytic Synthesis of Trimethylolpropane in the Presence of Basic Ionic Liquid

LONG Jin-Xing¹, YUAN Zheng-Qiu¹, MA Hao², SHU Ri-Yang¹, LI Xue-Hui²

1. Key Laboratory of Renewable Energy, Guangzhou Institute of Energy Conversion, Chinese Academy of Sciences, Guangzhou 510640, P. R. China;
2. School of Chemistry and Chemical Engineering, South China University of Technology, Guangzhou 510640, P. R. China

Received:2014-09-30 Revised:2014-12-10 Published:2015-01-26
Contact: LONG Jin-Xing, LI Xue-Hui E-mail:longjx@ms.giec.ac.cn;cexhli@scut.edu.cn
Supported by:
The project was supported by the National Natural Science Foundation of China (51306191, 21336002) and Doctoral Fund of Ministry of Education of China (20130172110043).

摘要/Abstract

摘要：

以碱性离子液体为催化剂, 构建了一种新型、高效的合成三羟甲基丙烷(TMP)的方法. 系统考察了催化剂类型、催化剂用量、反应温度、反应时间、甲醛与正丁醛用量比等因素对三羟甲基丙烷分离收率的影响. 研究结果表明: 碱性离子液体的催化性能与其碱强度息息相关, 碱性越强、催化活性越高. 最优条件下, 经离子液体[bmim]OH催化后, 可得到84%的TMP分离收率, 这一结果优于传统的有机无机碱催化体系且成功规避了传统碱催化合成TMP过程中繁琐的除盐过程、降低了过程能耗. 此外, 离子液体催化剂和未反应的丁醛均表现了良好的重复使用性能.

关键词: 三羟甲基丙烷, 离子液体, 碱性强度, Cannizzaro缩合, 重复使用性

Abstract:

Ionic liquid (IL) catalyst attracts increasing attention during last few decades due to its excellent advantages of both homogeneous and heterogeneous catalyst. Here, a novel and efficient strategy for the production of trimethylolpropane (TMP) is proposed with basic IL catalysts. The catalytic activities of the IL catalysts are investigated. The effects of catalyst dosage, reaction temperature, time, and the molar ratio of the reactants are also studied. The results show that the basicity of the IL catalyst has a significant effect on the catalytic activity, where stronger basicity indicates higher catalytic activity. The IL 1-butyl-3-methyl imidazolium hydroxyl ([bmim]OH) is proven to be the most efficient catalyst where more than 84% isolated yield of TMP was obtained under optimized conditions. Furthermore, both the IL catalyst and butyraldehyde show excellent recyclability. Moreover, this IL catalytic system avoids the inevitable desalination encountered by current processes utilizing inorganic alkali catalysts.

Key words: Trimethylolpropane, Ionic liquid, Basic strength, Cannizzaro condensation, Recyclability

龙金星, 袁正求, 马浩, 舒日洋, 李雪辉. 碱性离子液体催化合成三羟甲基丙烷[J]. 物理化学学报, 2015, 31(2), 337-343. doi: 10.3866/PKU.WHXB201412101

LONG Jin-Xing, YUAN Zheng-Qiu, MA Hao, SHU Ri-Yang, LI Xue-Hui. Catalytic Synthesis of Trimethylolpropane in the Presence of Basic Ionic Liquid[J]. Acta Phys. -Chim. Sin. 2015, 31(2), 337-343. doi: 10.3866/PKU.WHXB201412101

链接本文: https://www.whxb.pku.edu.cn/CN/10.3866/PKU.WHXB201412101

https://www.whxb.pku.edu.cn/CN/Y2015/V31/I2/337

参考文献

(1) Werle, P.; Morawietz, M.; Lundmark, S.; Sörensen, K.; Karvinen, E.; Lehtonen, J. Alcohols, Polyhydric. In Ullmann's Encyclopedia of Industrial Chemistry;Wiley-VCH Verlag GmbH & Co. KGaA:Weinheim, Germany, 2008.
(2) Serra-Holm, V.; Salmi, T.; Multamäki, J.; Reinik, J.; Mäki-Arvela, P.; Sjöholm, R.; Lindfors, L. P. Appl. Catal. A: Gen. 2000, 198 (1-2), 207.
(3) Rantakylä, T. K.; Salmi, T.; Aumo, J.; Mäki-Arvela, P.; Sjöholm, R.; Ollonqvist, T.; Väyrynen, J.; Lindfors, L. P. Ind. Eng. Chem. Res. 2000, 39 (8), 2876. doi: 10.1021/ie990745h
(4) Rantakylä, T. K.; Salmi, T.; Kuusisto, J.; Mäki-Arvela, P.; Ollonqvist, T.; Väyrynen, J.; Lindfors, L. P. Ind. Eng. Chem. Res. 2002, 41 (3), 524. doi: 10.1021/ie001000a
(5) Zhang, Q.; Zhang, S.; Deng, Y. Green Chem. 2011, 13 (10), 2619. doi: 10.1039/c1gc15334j
(6) Ning, H.; Hou, M. Q.; Yang, D. Z.; Kang, X. C.; Han, B. X. Acta Phys. -Chim. Sin. 2013, 29 (10), 2107. [宁汇, 侯民强, 杨德重, 康欣晨, 韩布兴. 物理化学学报, 2013, 29 (10), 2107.] doi: 10.3866/PKU.WHXB201304172
(7) Yuan, X.; Lou, S. J.; Kou Y. Acta Phys. -Chim. Sin. 2010, 26 (4), 908. [苑晓, 娄舒杰, 寇元. 物理化学学报, 2010, 26 (4), 908.] doi: 10.3866/PKU.WHXB20100433
(8) Pinkert, A.; Marsh, K. N.; Pang, S. S.; Staiger, M. P. Chem. Rev. 2009, 109 (12), 6712. doi: 10.1021/cr9001947
(9) Gong, Y. Y.; Liu, M.; Jia, S. Y.; Feng, J. P.; Song, C. S.; Guo, X. W. Acta Phys. -Chim. Sin. 2012, 28 (3), 686. [公艳艳,刘民, 贾松岩, 冯建萍, 宋春山, 郭新闻. 物理化学学报, 2012, 28 (3), 686.] doi: 10.3866/PKU.WHXB201112292
(10) Zakrzewska, M. E.; Bogel-Lukasik, E.; Bogel-Lukasik, R. Chem. Rev. 2011, 111 (2), 397. doi: 10.1021/cr100171a
(11) Parvulescu, V. I.; Hardacre, C. Chem. Rev. 2007, 107 (6), 2615. doi: 10.1021/cr050948h
(12) Long, J.; Li, X.;Wang, L.; Zhang, N. Sci. Chin. Chem. 2012, 55 (8), 1500. doi: 10.1007/s11426-012-4633-7
(13) Li, Z.; Zhao, Y.W.; Han, F.; Yang, L.; Song, H. Y.; Chen, J.; Xia, G. C. Sci. Sin. Chim. 2012, 42 (4), 502. [李臻, 赵应伟,韩峰, 杨磊, 宋河远, 陈静, 夏春谷. 中国科学: 化学, 2012, 42 (4), 502.] doi: 10.1360/032011-727
(14) Zhu, Y. H.; Zeng, H. Y.; Li, S. S.; Lu, Z. X.; Ma, C. A. Acta Phys. -Chim. Sin. 2012, 28 (2), 421. [朱英红, 曾红燕, 李珊珊, 陆在祥, 马淳安. 物理化学学报, 2012, 28 (2), 421.] doi:10.3866/PKU.WHXB201112122
(15) Hallett, J. P.;Welton, T. Chem. Rev. 2011, 111 (5), 3508. doi: 10.1021/cr1003248
(16) Ranu, B. C.; Banerjee, S. Org. Lett. 2005, 7, 3049. doi: 10.1021/ol051004h
(17) Moreira, D. N.; Longhi, K.; Frizzo, C. P.; Bonacorso, G. H.; Zanatta, N.; Martins, A. M. Catal. Commun. 2010, 11, 476. doi: 10.1016/j.catcom.2009.12.001
(18) Xu, J.; Liu, B.;Wu,W.; Qian, C.;Wu, Q.; Lin, X. J. Org. Chem. 2006, 71, 3991. doi: 10.1021/jo0600914
(19) Yang, L.; Xu, L.; Zhou,W.; Li, L.; Xia, C. Tetrahedron Lett. 2006, 47, 7723. doi: 10.1016/j.tetlet.2006.08.103
(20) Siddiqui, I. R.; Srivastava, A.; Shamim, S.; Srivastava, A.; Rahila, M. A.W. S.; Abumhdi, A. A. H.; Srivastava, A.; Rai, P. J. Mol. Catal. A Chem. 2014, 382, 126. doi: 10.1016/j.molcata.2013.10.026
(21) Li, J.; Sun, H.; Cai, X. C.; Dai, L. Y. Chin. J. Org. Chem. 2007, 27, 1296. [李娟, 孙辉, 蔡晓晨, 戴立益. 有机化学, 2007, 27, 1296.
(22) Mamaghani, M.; Pourranjbar, M.; Nia, R. H. J. Sulf. Chem. 2014, 35 (1), 1. doi: 10.1080/17415993.2013.800061
(23) Mehnert, C. P.; Dispenziere, N. C.; Cok, R. A. Chem. Commun. 2002, 2, 1601.
(24) Li, X. H.; Duan, H. L.; Pan, T. J.;Wang, L. F. Chin. J. Anal. Chem. 2006, 34, S192. [李雪辉, 段红丽, 潘景添, 王乐夫. 分析化学, 2006, 34, S192.]
(25) Chen, X.W.; Song, H. B.; Chen, P.;Wang, F. R.; Qian, Y.; Li, X. H. Acta. Chim. Sin. 2012, 70, 770. [陈学伟, 宋红兵, 陈鹏, 王芙蓉, 钱宇, 李雪辉. 化学学报, 2012, 70, 770.] doi: 10.6023/A1108223
(26) Abd Hamid, H.; Yunus, R.; Rashid, U.; Choong, S. T.; Al-Muhtaseb, H. A. Chem. Eng. J. 2012, 200, 532.
(27) Smith, B. M.; March, J. March's Advanced Organic Chemistry; JohnWiley & Sons, 2009.
(28) Long, J.; Guo, B.; Teng, J.; Yu, Y.;Wang, L.; Li, X. Bioresour. Technol. 2011, 102, 10114. doi: 10.1016/j.biortech.2011.08.043
(29) Zhao, Y.; Long, J.; Deng, F.; Xia, C.; Peng, J. Catal. Commun. 2009, 10, 732. doi: 10.1016/j.catcom.2008.11.030
(30) Long, J. X.; Guo, B.; Li, X. H.;Wang, F. R.;Wang, L. F. Acta Phys. -Chim. Sin. 2011, 27 (5), 995. [龙金星, 郭斌, 李雪辉, 王芙蓉, 王乐夫. 物理化学学报, 2011, 27 (5), 995.] doi:10.3866/PKU.WHXB20110506
(31) Clayden, J.; Greeves, N.;Warren, S. Organic Chemistry, 2^nd ed.; Oxford University Press: London, 2012.
(32) Cornils, B.; Fischer, R.W.; Kohlpaintner, C. Butanals, In: Ullmann's Encyclopedia of Industrial Chemistry;Wiley-VCH Verlag GmbH & Co. KGaA:Weinheim, Germany, 2000.
(33) Long, J.; Zhang, Q.;Wang, T.; Zhang, X.; Xu, Y.; Ma, L. Bioresour Technol. 2014, 154, 10. doi: 10.1016/j.biortech.2013.12.020
(34) Mayo,W. D.; Miller, A. F.; Hannah,W. R. Course Notes on the Interpretation of Infrared and Raman Spectra; JohnWiley & Sons: New Jersey, 2004.
(35) Silverstein, R. M.;Webster, F. X.; Kiemle, J. D. Spectrometric Identification of Organic Compounds, 7th ed.; JohnWiley & Sons:Westford, USA, 2005.

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碱性离子液体催化合成三羟甲基丙烷

Catalytic Synthesis of Trimethylolpropane in the Presence of Basic Ionic Liquid

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