Progress in the application of immobilized ionic liquids in esterification reactions

doi:10.16085/j.issn.1000-6613.2015.12.017

Abstract

Abstract: Immobilized ionic liquids have advantages of both high surface area to volume ratio of the carrier material and high catalytic activity of ionic liquids,which can improve not only the utilization efficiency of the ionic liquids,resulting reduced amount of ionic liquids,but also the catalytic reactivity of the ionic liquids in the esterification reaction. This article mainly reviews the application of immobilized ionic liquids in esterification reactions,and the catalytic performance of the immobilized ionic liquids,supported individually by silica gel,mesoporous molecular sieve,magnetic mesoporous silica nano-materials and high polymer,are introduced. Then the catalytic mechanism of the immobilized ionic liquid on the esterification reaction and the factors that affect the catalytic reactivity of the immobilized ionic liquids are discussed briefly. The unsolved problems of immobilized ionic liquids and the future development direction are proposed,including establishing systematic structure-activity relationship of carrier and ionic liquid and its long-term industrial performance evaluation.

Key words: ionic liquids, immobilized, supports, esterification, reactivity

摘要： 固载化离子液体兼具载体材料高比表面积与离子液体的高催化活性等优点,不仅提升了离子液体的利用率,大幅度降低了离子液体的用量,而且可以显著提高离子液体在酯化反应中的催化活性。本文主要综述了固载化离子液体在催化酯化反应方面的研究进展,分别介绍了以硅胶、介孔分子筛、磁性介孔二氧化硅纳米材料以及高分子等为载体的固载化离子液体在酯化反应中的催化性能,简要分析了固载化离子液体催化酯化反应的机理与影响固载化离子液体催化活性的因素,并对固载化离子液体目前存在的问题以及今后的发展方向进行了总结,建立系统的载体与离子液体的构效关系,并对其性能进行长期的工业评测是今后的主要努力方向。

关键词: 离子液体, 固载化, 载体, 酯化, 活性

CLC Number:

O643.36

DUAN Xiaolei, CHI Cheng, ZHU Lijun, ZHOU Yulu, XIANG Yuzhi, XIA Daohong. Progress in the application of immobilized ionic liquids in esterification reactions[J]. Chemical Industry and Engineering Progree, 2015, 34(12): 4238-4247.

段晓磊, 迟骋, 朱丽君, 周玉路, 项玉芝, 夏道宏. 固载化离子液体催化酯化反应研究进展[J]. 化工进展, 2015, 34(12): 4238-4247.

References

[1] 邓友全. 离子液体-性质、制备与应用[M]. 北京:中国石化出版社,2006.
[2] Wasserscheid P,Waffenschmidt H. Ionic liquids in regioselective platinum-catalysed hydroformylation of methyl-3-pentenoate[J]. Journal of Catalysis,1999,186(2):481-484.
[3] Boxwell C J,Dyson P J,Ellis D J,et al. A highly selective arene hydrogenation catalyst that operates in ionic liquid[J]. Journal of the American Chemical Society,2002,124(32):9334-9335.
[4] Csihony S,Fischmeister C,Bruneau C,et al. First ring-opending metathesis polymerization in an ionic liquid. Efficient recycling of a catalyst generated from a cationic ruthenium allenylidene complex[J]. New Journal Chemistry,2002,26(11):1667-1670.
[5] Mehnert C P,Mozeleski E J,Cook R A. Supported ionic liquid catalysis investigated for hydrogenation reactions[J]. Chem. Commun.,2002(24):3010-3011.
[6] Kim D W,Chi D Y. Polymer-supported ionic liquids:Imidazolium salts as catalysts for nucleaphilic substitution reactions including fluorinations[J]. Angew. Chem. Int. Ed.,2004,43(4):483-485.
[7] Shi F,Deng Y Q,Sima T L,et al. Alternatives to phosgene and carbon monoxide:Synthesis of symmetric urea derivatives with carbon dioxide in ionic liquids[J]. Angewandte Chemie International Edition,2003,42(28):3257-3260.
[8] Valkenberg M H,DeCastro C,Holderich W F. Immobilisation of ionic liquids on solid supports[J]. Green Chem.,2002,4:88-93.
[9] Watanabe M,Yamada S I,Ogata N. Ionic conductivity of polymer electrolytes containing room temperature molten salts based on pyridinium halide and aluminium chloride[J]. Electxochim Acta,1995,40:2285-2288.
[10] Gu Yanlong,Ogawa Chikako,Kobayashi Shu. Silica-supported sodium sulfanate with ionic liquid; A neutral catalyst system for michael reactions of indoles in water[J]. Oiganic Letters,2007,9(2):175-178.
[11] Riisager A,Wasserscheid P,van Hal R,et al. Countinuous fixed-bed gas-phase hydroformylation using supported ionic liquid-phase(SILP)Rh catalysts[J]. Journal of Catalysis,2003,219(2):452-455.
[12] Virhanen Pasi,Kaihu Hannu,Geza Toth,et al Tavanls one-pot synthesis of menihols from citral Modifying supported ionic liquid catalysts(SILCAs) with Leis and Brønsted acids[J]. Journal of Catalysis,2009,263:209-219.
[13] Mehnert C P,Cook R A,Dispenziere N C,et al. Supported ionic liquid catalysis-a new concept for homogeneous hydroformylation catalysis[J]. Journal of the American Chemical Society,2002,124:12932-12933.
[14] Sahoo Stunan,Ktunar Pradeep,Lefebvre E,et al. Oxidative kinetic resolution of alcohols using chiralMn-salen canplex immobilized onm ionic liquid modified silica[J]. Applied Catalysis:General,2009,354:17-25.
[15] Chrobok Anna,Baj Stefan,Pudko Wojciech,et al. Supported hydrogensulfate ionic liquid catalysis in Baeyer-Villiger reactions[J]. Applied Catalysis A:General,2009,366:22-28.
[16] 蔡源,黄德英,万辉,等. 硅胶固载离子液体催化剂的制备及在酯化反应中的应用[J]. 精细化工,2007,24(12):1196-1199.
[17] 张继申,万辉,管国锋. 硅胶负载酸性离子液体催化剂的制备及性能[J]. 化学反应工程与工艺,2009,24(6):503-508.
[18] Miao J,Wan H,Guan G. Synthesis of immobilized Brønsted acidic ionic liquid on silica gel as heterogeneous catalyst for esterification[J]. Catalysis Communications,2011,12(5):353-356.
[19] 梁丽亚. 固载化酸性离子液体催化酯化反应研究[D]. 石家庄:河北科技大学,2013.
[20] 王颖,罗仕忠,文婕,等. 硅胶固载杂多酸离子液体催化剂 bmim-PW₁₂/SiO₂ 的制备及其在酯化反应中的应用[J]. 合成化学,2012,20(3):276-280.
[21] 施介华,潘高. 1-丁基-3-甲基咪唑磷钨酸盐的制备及其对酯化反应的催化性能[J]. 催化学报,2008,29(7):629-632.
[22] 劳锡寮. 固载离子液体的制备及其在催化酯化反应中的应用研究[D]. 广州:广东工业大学,2009.
[23] Qiao K,Hagiwara H,Yokoyam C. Acidic ionic liquid modified silica gel as novel solid catalysts for esterification and nitration reactions[J]. Journal of Molecular Catalysis A:Chemical,2006,246:65-69.
[24] 孙琳,刘春萍,马松梅,等. 硅胶固定化离子液体催化介成乙酸乙酯[J]. 广州化工,2007,35(3):18-20.
[25] 刘春萍,刘刚,温全武,等. 硅胶固定化咪唑酸性离子液体的合成及在酯化反应中的应用[J]. 精细化工,2009,26(3):213-217.
[26] 程丹丹. Brønsted 酸性离子液体催化酯化反应的研究[D]. 郑州:郑州大学,2009.
[27] 李斐瑾. Brønsted 酸性离子液体催化酯化反应的研究[D]. 杭州: 浙江大学,2008.
[28] 李艳,李斐瑾,陈传杰,等. 固定化 Brønsted 酸性离子液体催化酯化反应[J]. 化工学报,2009,60(6):1452-1458.
[29] Vafaeezadeh M,Hashemi M M. Efficient fatty acid esterification using silica supported Brønsted acidic ionic liquid catalyst:Experimental study and DFT modeling[J]. Chemical Engineering Journal,2014:35-41.
[30] Zhen B,Li H,Jiao Q,et al. SiW₁₂O₄₀-based ionic liquid catalysts: Catalytic esterification of oleic acid for biodiesel production[J]. Industrial & Engineering Chemistry Research,2012,51(31):10374-10380.
[31] Zhen B,Jiao Q,Zhang Y,et al. Acidic ionic liquid immobilized on magnetic mesoporous silica:Preparation and catalytic performance in esterification[J]. Applied Catalysis A:General,2012,445:239-245.
[32] Wu Z W,Li Z,Wu G M,et al. Brønsted acidic ionic liquid modified magnetic nanoparticle:An efficient and green catalyst for biodiesel production[J]. Industrial & Engineering Chemistry Research,2014,53(8):3040-3046.
[33] Jiang Y,Y Guo C,Xia H S,et al. Magnetic nanoparticles supported ionic liquids for lipase immobilization:Enzyme activity in catalyzing esterification[J]. Journal of Molecular Catalysis B:Enzymatic,2008,58:103-109.
[34] Karimi B,Vafaeezadeh M. SBA-15-Functionalized sulfonic acid confined acidic ionic liquid:A powerful and water-tolerant catalyst for solvent-free esterifications[J]. Chem Commun,2012,48(27):3327-3329.
[35] 吴悦彤. 新型固载化离子液体的制备、表征及应用研究[D]. 上海:华东师范大学理工学院,2013.
[36] Zhang L,Cui Y D,Zhang C P,et al. Biodiesel production by esterification of oleic acid over brønsted acidic ionic liquid supported onto Fe-incorporated SBA-15[J]. Ind. Eng. Chem. Res.,2012,51(51):16590-16596.
[37] 文毅. MCM-41固载酸功能化离子液体及其对酯化反应的催化[D]. 重庆:重庆大学,2013.
[38] Xu Z J,Wan H,Miao J M,et al. Reusable and effcient polystyrene-supported acidic ionic liquid catalyst for esterifications[J]. Journal of Molecular Catalysis A:Chemical,2010,332:152-157.
[39] Shao Y B,Wan H,Miao J M,et al. Synthesis of an immobilized Brønsted acidic ionic liquid catalyst on chloromethyl polystyrene grafted silica gel for esterification[J]. Reaction Kinetics,Mechanisms and Catalysis,2013,109:149-158.
[40] 职慧珍,罗军,马伟,等. PEG型酸性温控离子液体中芳香酸和醇的酯化反应[J]. 高等学校化学学报,2008,29(4):772-774.
[41] 滕俊江,张庆,林建明. 离子液体掺杂聚苯胺催化合成水杨酸异戊酯[J]. 日用化学工业,2012,42(2):126-128.
[42] 李靖,姜健,常卫星,等. 一种聚合物负载离子液体及其制法和在催化酯化中的用途:中国,201310488091. 3[P]. 2014-01-29.
[43] 张丽珍. 负载离子液体的合成及催化活性的研究[D]. 广州:暨南大学,2010.