Synthesis of glycerol monolaurate using functionalized ionic liquids catalysts

doi:10.11949/j.issn.0438-1157.20141423

Abstract

Abstract:

Six ionic liquids based on pyridine (Py), 1-methylimidazole (MIM), N-methyl-2-pyrrolidinone(NMP) cations were prepared by coupling corresponding SO₃H-functionalized zwitterion ionic complex with different counterpart anions including H₃PW₁₂O₄₀ and p-toluenesulfonic acid (PTSA). The obtained ionic liquids were well characterized by FT-IR, TG, ¹H NMR, ¹³C NMR methods and then these ionic liquids were deployed in the esterification reaction of glycerol with lauric acid under the condition without organic solvent. The effects of various key reaction parameters including reaction temperature, glycerol/lauric acid molar ratio, molar ratio of ionic liquid to lauric acid and the type of catalysts on the acid conversion and yield of glycerol monolaurate were discussed. The results indicated that all the ionic liquids exhibit good thermal stability and compared with other ionic liquids, [MIMBS]₃PW₁₂O₄₀ ionic liquid has the best thermal stability. When [MIMBS][PTSA] ionic liquid was used to optimize esterification reaction parameters, the optimum reaction conditions were established as follows: glycerol/lauric acid ratio of 4, amount of catalyst of 1% molar to lauric acid, reaction time of 3 h at 130℃. When used under the optimized reaction condition, all the ionic liquids exhibit excellent catalytic activity, the acid conversions are all above 92% and the highest yield of glycerol monolaurate of 64.6% has been achieved. In addition, comparing the structure of the investigated ionic liquids, it can be found that under the condition of lauric acid being catalyzed by the ionic liquids with PTSA anion, the conversion is higher than that when lauric acid was catalyzed by ionic liquids with H₃PW₁₂O₄₀ anion. With respect to the yield of glycerol monolaurate, when the reaction was catalyzed by ionic liquids, [MIMBS][PTSA] gives the highest yield. As to the reusability behavior of these ionic liquids, the results indicated that all these catalysts can be reused up to five times without noticeable loss of catalytic activity.

Key words: glycerol monolaurate, ionic liquids, functionalization, esterification, catalyst

摘要：

合成了由吡啶、N-甲基咪唑、N-甲基-2-吡咯烷酮提供有机阳离子, 磷钨酸、对甲苯磺酸提供阴离子的6种离子液体。使用NMR、FT-IR和TG对离子液体表征, 并考察它们催化甘油与月桂酸酯化的催化效果。结果表明, 这些离子液体都具有较好的热稳定性, 以1-(丁基-4-磺酸基)-3-甲基咪唑磷钨酸盐离子液体的热稳定性最好。在最佳条件使用离子液体催化甘油与月桂酸反应时, 阴离子的种类对月桂酸的转化率影响较大, 以对甲苯磺酸为阴离子的离子液体催化反应时, 月桂酸转化率较以磷钨酸为阴离子的离子液体的高;1-(丁基-4-磺酸基)-3-甲基咪唑对甲苯磺酸盐离子液体做催化剂时甘油单月桂酸酯的产率最高。催化剂重复使用性方面, 离子液体重复使用5次催化活性没有明显变化。

关键词: 甘油单月桂酸酯, 离子液体, 功能化, 酯化, 催化剂

CLC Number:

O643.3

WANG Song, ZHANG Zhengyan, CHANG Qianqian, LI Sanxi, ZHANG Linnan. Synthesis of glycerol monolaurate using functionalized ionic liquids catalysts[J]. CIESC Journal, 2015, 66(S1): 209-215.

王松, 张争艳, 常欠欠, 李三喜, 张林楠. 功能化离子液体催化合成甘油单月桂酸酯[J]. 化工学报, 2015, 66(S1): 209-215.

References 21

[1]	Machado M D S, Perez-Pariente J, Sastre E, Cardoso D, de Guerenu A M. Selective synthesis of glycerol monolaurate with zeolitic molecular sieves [J]. Applied Catalysis A: General, 2000, 203(2): 321-328.
[2]	Bergsson G, Steingrímsson Ó, Thormar H. Bactericidal effects of fatty acids and monoglycerides on Helicobacter pylori [J]. International Journal of Antimicrobial Agents, 2002, 20(4): 258-262.
[3]	Li Qingsheng, Estes J D, Schlievert P M, Duan Lijie. Glycerol monolaurate prevents mucosal SIV transmission [J]. Nature, 2009, 458(7241): 1034-1038.
[4]	Corma A, Iborra S, Miquel S, Primo J. Catalysts for the production of fine chemicals: production of food emulsifiers, monoglycerides, by glycerolysis of fats with solid base catalysts [J]. Journal of Catalysis, 1998, 173(2): 315-321.
[5]	Sonntag N O V. Glycerolysis of fats and methyl esters-status review and critique [J]. Journal of the American Oil Chemists' Society, 1982, 59(10): 795-802.
[6]	Tanawannapong Y, Kaewchada A, Jaree A. Biodiesel production from waste cooking oil in a microtube reactor [J]. Journal of Industrial and Engineering Chemistry, 2013, 19(1): 37-41.
[7]	Chung K H. Transesterification of Camellia japonica and Vernicia fordii seed oils on alkali catalysts for biodiesel production [J]. Journal of Industrial and Engineering Chemistry, 2010, 16(4): 506-509.
[8]	Carla C B Pereira, Mônica A P da Silva, Marta A P Langon.Enzymatic Synthesis of Monolaurin [J]. Appl. Biochem. Biotechnol., 2004, 114: 433-445.
[9]	Abdullah A Z, Wibowo T Y, Zakaria R. Effect of tetramethyl ammonium hydroxide on the activity of LiOH-intercalated montmorillonite catalyst in the transesterification of methyl laurate with glycerol [J]. Chem. Eng. J., 2011, 167: 328-334.
[10]	Nakamura R, Komura K, Sugi Y. The esterification of glycerine with lauric acid catalyzed by multi-valent metal salts. Selective formation of mono-and dilaurins [J]. Catalysis Communications, 2008, 9(4): 511-515.
[11]	Wee L H, Lescouet T, Fritsch J. Synthesis of monoglycerides by esterification of oleic acid with glycerol in heterogeneous catalytic process using tin-organic framework catalyst [J]. Catalysis Letters, 2013, 143(4): 356-363.
[12]	Bates E D, Mayton R D, Ntai I, Davis J H Jr. CO2 capture by a task-specific ionic liquid [J]. J. Am. Chem. Soc., 2002, 124: 926-927.
[13]	Visser A E, Holbrey J D, Rogers R D. Hydrophobic ionic liquids incorporating N-alkylisoquinolinium cations and their utilization in liquid-liquid separations [J]. Chemical Communications, 2001, 23: 2484-2485.
[14]	Leng Yan, Wang Jun, Zhu Dunru. Heteropolyanion-based ionic liquids: reaction-induced self-separation catalysts for esterification [J]. Angewandte Chemie, 2009, 121(1): 174-177.
[15]	Yunus R, Lye O T, Fakhru'l-Razi A. A simple capillary column GC method for analysis of palm oil-based polyol esters [J]. Journal of the American Oil Chemists' Society, 2002, 79(11): 1075-1080.
[16]	Hermida L, Abdullah A Z, Mohamed A R. Synthesis of monoglyceride through glycerol esterification with lauric acid over propyl sulfonic acid post-synthesis functionalized SBA-15 mesoporous catalyst [J]. Chemical Engineering Journal, 2011, 174(2): 668-676.
[17]	Huang Baohua(黄宝华), Li Zijin(黎子进), Wang Yanfei(汪艳飞), Zhang Kun(张焜), Fang Yanxiong(方岩雄), Zhou Beilei(周蓓蕾). Esterification catalyzed by brönsted acidic ionic liquids [J]. Acta Chim Sinica (化学学报), 2008, 66: 1837-1844.
[18]	Shih-Yuan Lee A, Yang Huichun, Su Fengyih. An unprecedented and highly chemoselective esterification method [J]. Tetrahedron Letters, 2001, 42(2): 301-303.
[19]	da Silva-Machado M, Cardoso D, Pérez-Pariente J, Sastre, E. Esterification of lauric acid with glycerol using modified zeolite beta as catalyst [J]. Studies in Surface Science and Catalysis, 2000, 130: 3417-3422.
[20]	Huang Baohua(黄宝华), Wang Yanfei(汪艳飞), Zhang Kun(张焜), Fang Yanxiong(方岩雄), Zhou Beilei(周蓓蕾). Synthesis of pyrrolidonium acidic ionic liquids and their catalytic activity for esterification of acetic acid and butanol [J]. Chin. J. Catal.(催化学报), 2007, 28: 743-748.
[21]	Perez-Pariente J, Diaz I, Mohino F, Satre E. Selective synthesis of fatty monoglycerides by using functionalised mesoporous catalysts [J]. Applied Catalysis A: General, 2003, 254(2): 173-188.