甲酸自催化制备环氧脂肪酸甲酯的研究
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摘要
以大豆油脂肪酸甲酯为原料,在有机酸自催化体系中进行环氧化反应制备环氧脂肪酸甲酯。研究了有机酸种类及用量、H2O2用量、反应温度、反应时间和助剂(表面活性剂和相转移催化剂)等因素对环氧化反应的影响。有机酸的环氧化活性依次为:甲酸>乙酸>乙二酸=柠檬酸。反应中加入表面活性剂(吐温40、聚氧乙烯月桂醚、十六烷基三甲基溴化铵)和相转移催化剂(四丁基溴化铵、聚乙二醇400)会不同程度地降低环氧化产品的环氧值。通过单因素优化试验,得到脂肪酸甲酯环氧化的最佳反应条件为:脂肪酸甲酯10 g,甲酸∶H2O2∶碳-碳双键=0.6∶2∶1(mol/mol/mol),反应温度50℃,反应时间6 h,不添加任何助剂。在此条件下所制备的环氧脂肪酸甲酯的环氧值为5.91%。产品经1H-NMR分析表明,在化学位移5.4 ppm处的原料碳-碳双键的氢吸收峰消失,而在化学位移3.0 ppm处呈现出环氧键的氢特征吸收峰。
In this paper,using fatty acid methyl esters of soybean oil as a raw material,the preparation of epoxidized fatty acid methyl esters in the presence of organic acid autocatalytic system was studied. The effect of organic acids,the amount of hydrogen peroxide(H2 O2),reaction temperature,reaction time and auxiliaries(surfactants and phase transfer catalysts)on the synthesis of epoxidized fatty acid methyl esters were investigated.The epoxidation activity of organic acids was followed by formic acid > acetic acid > oxalic acid = citric acid,in which the formic acid showed the best efficiency. The addition of phase transfer catalysts(tetrabutylammonium bromide,polyethylene glycol 400) and surfactants(Tween 40,polyoxyethylene lauryl ether,cetyltrimethylammonium bromide) could reduce the epoxidation reaction in varying degrees. The results showed that the optimized epoxidation reaction parameters were as follows: fatty acid methyl esters 10 g,formic acid/H2 O2/C=C bonds at the molar ratio of 0.6 ∶2 ∶1,reaction temperature of 50 ℃,reaction time of 6 h and no auxiliaries. Under these conditions,the epoxy value of the epoxidized fatty acid methyl esters was 5.91%. The product was characterized by1 H-NMR and the result showed that the hydrogen absorption peaks of C=C bonds disappeared at the chemical shift of 5.4 ppm,while the hydrogen characteristic absorption peaks of epoxy bond appeared at the chemical shift of 3.0 ppm.
In this paper,using fatty acid methyl esters of soybean oil as a raw material,the preparation of epoxidized fatty acid methyl esters in the presence of organic acid autocatalytic system was studied. The effect of organic acids,the amount of hydrogen peroxide(H2 O2),reaction temperature,reaction time and auxiliaries(surfactants and phase transfer catalysts)on the synthesis of epoxidized fatty acid methyl esters were investigated.The epoxidation activity of organic acids was followed by formic acid > acetic acid > oxalic acid = citric acid,in which the formic acid showed the best efficiency. The addition of phase transfer catalysts(tetrabutylammonium bromide,polyethylene glycol 400) and surfactants(Tween 40,polyoxyethylene lauryl ether,cetyltrimethylammonium bromide) could reduce the epoxidation reaction in varying degrees. The results showed that the optimized epoxidation reaction parameters were as follows: fatty acid methyl esters 10 g,formic acid/H2 O2/C=C bonds at the molar ratio of 0.6 ∶2 ∶1,reaction temperature of 50 ℃,reaction time of 6 h and no auxiliaries. Under these conditions,the epoxy value of the epoxidized fatty acid methyl esters was 5.91%. The product was characterized by1 H-NMR and the result showed that the hydrogen absorption peaks of C=C bonds disappeared at the chemical shift of 5.4 ppm,while the hydrogen characteristic absorption peaks of epoxy bond appeared at the chemical shift of 3.0 ppm.
引文
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[7] PETROVI'C Z S,ZLATANI'C A,LAVA C C,et al.Epoxidation of soybean oil in toluene with peroxoacetic and peroxoformic acids-kinetics and side reactions[J]. European Journal of Lipid Science and Technology,2002,104(5):293-299.
[8] AGUILERA A F,TOLVANEN P,ER魧NEN K,et al. Epoxidation of oleic acid under conventional heating and microwave radiation[J]. Chemical Engineering and Processing,2016,102:70-87.
[9]施赛泉,蒋平平,史润萍,等.无硫酸环境环氧化大豆油合成条件优化[J].化工进展,2008,27(5):753-756.
[10] SAURABH T,PATNAIK M,BHAGT S L,et al. Epoxidation of vegetable oils:A review[J]. International Journal of Advanced Engineering Technology,2011,2(4):491-501.
[11]吴亚,魏俊发,张敏,等.过氧钨配合物催化过氧化氢制备环氧大豆油的研究[J].应用化工,2005,34(2):119-120.
[12] CAMPANELLA A,FONTANINI C,BALTANAS M A. High yield epoxidation of fatty acid methyl esters with performic acid generated in situ[J]. Chemical Engineering Journal,2008,144(3):466-475.
[13]冯树波,杨华,郑二丽,等.不同催化体系中脂肪酸甲酯环氧化反应研究[J].中国油脂,2011,36(10):49-53.
[2]杨坤于,英瑜,盖世伟,等.环氧脂肪酸甲酯合成研究[J].四川化工,2009,12(1):10-13.
[3]余磊,聂勇,陈卫,等.脂肪酸甲酯在甲酸自催化体系中的环氧化和开环反应动力学研究[J].化工时刊,2013,27(3):11-16.
[4] NOOR ARMYLISAS A H,SITI HAZIRAH M F,YEONG S K,et al. Modification of olefinic double bonds of unsaturated fatty acids and other vegetable oil derivatives via epoxidation:A review[J]. Grasas Y Aceites,2017,68(1):e174.
[5] BHALERAO M S,KULKARNI V M,PATWARDHAN A V. Ultrasound-assisted chemoenzymatic epoxidation of soybean oil by using lipase as biocatalyst[J]. Ultrasonics Sonochemistry,2018,40:912-920.
[6] YAO M Y,HUANG Y B,NIU X,et al. Highly efficient silica-supported peroxycarboxylic acid for the epoxidation of unsaturated fatty acid methyl esters and vegetable oils[J]. ACS Sustainable Chemistry&Engineering,2016,4(7):3840-3849.
[7] PETROVI'C Z S,ZLATANI'C A,LAVA C C,et al.Epoxidation of soybean oil in toluene with peroxoacetic and peroxoformic acids-kinetics and side reactions[J]. European Journal of Lipid Science and Technology,2002,104(5):293-299.
[8] AGUILERA A F,TOLVANEN P,ER魧NEN K,et al. Epoxidation of oleic acid under conventional heating and microwave radiation[J]. Chemical Engineering and Processing,2016,102:70-87.
[9]施赛泉,蒋平平,史润萍,等.无硫酸环境环氧化大豆油合成条件优化[J].化工进展,2008,27(5):753-756.
[10] SAURABH T,PATNAIK M,BHAGT S L,et al. Epoxidation of vegetable oils:A review[J]. International Journal of Advanced Engineering Technology,2011,2(4):491-501.
[11]吴亚,魏俊发,张敏,等.过氧钨配合物催化过氧化氢制备环氧大豆油的研究[J].应用化工,2005,34(2):119-120.
[12] CAMPANELLA A,FONTANINI C,BALTANAS M A. High yield epoxidation of fatty acid methyl esters with performic acid generated in situ[J]. Chemical Engineering Journal,2008,144(3):466-475.
[13]冯树波,杨华,郑二丽,等.不同催化体系中脂肪酸甲酯环氧化反应研究[J].中国油脂,2011,36(10):49-53.
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