Page Header

Optimization of Partial Epoxidation on Jatropha curcas Oil Based Methyl Linoleate Using Urea-hydrogen Peroxide and Methyltrioxorhenium Catalyst

Yan-Ni Lye, Nadia Salih, Jumat Salimon


Natural epoxy fatty acids such as Coronaric acid (9,10-epoxy-12Z-octadecenoic acid) and vernolic acid (12,13-epoxy-9Z-octadecenoic acid) are rich in of Vernolia galamensis, Vernolia anthelmintica and Chrysanthemums coronanium. The two fatty acids each contains an oxirana ring and a double bond C = C. The oil or its derivatives are suitable for industrial usage as reactive diffluent of alkyd resins, plasticizers and stabilizers, surface coatings, surfactants and lubricants, as intermediates in chemical reactions for making linear epoxides of composite materials and polymers. However, the use of such oils on an industrial scale is impossible due to limited resources. Therefore, epoxidation reactions need to be carried out to overcome the demand for partial epoxide fatty acids. Partially epoxidation of methyl linoleate at room temperature (30°C) in the presence of pyridine, methyltrioxorhenium (MTO) as catalyst and urea-hydrogen peroxide (UHP) as oxidant was studied by using response surface methodology (RSM). A five-level-four-factors central composite rotatable design (CCRD) was used to optimize the partially epoxidation conditions and study the effect of MTO, UHP, pyridine and reaction time on relative conversion to oxirane (RCO). Quadratic polynomial model was employed to generate response surface plots for RCO. At optimal condition, 79.05% monoepoxide was formed at the RCO of 58.15% under condition of 0.75 mol% mole ratio of MTO, 300 mol% mole ratio of UHP and 9 mol% of pyridine at 120 min reaction time. It can be concluded that the effect of UHP mole ratios was the dominant factor to control the degree of partial epoxidation of methyl linoleate followed by mole ratio of MTO, reaction time and mole ratio of pyridine to formed methyl 12,13-epoxy-9Z-octadecenoate or/and methyl 9,10-epoxy-12Z-octadecenoate.


[1] L. H. Gan, K. S. Ooi, S. H. Goh, L. M. Gan, and Y. C. Leong, “Epoxidized esters of palm olein as plasticizers for poly(vinyl chloride),” European Polymer Journal, vol. 31, pp. 719–724, Aug. 1995.

[2] X. Wu, X. Zhang, S. Yang, H. Chen, and D. Wang, “The study of epoxidized rapeseed oil used as a potential biodegradable lubricant,” Journal of the American Oil Chemists’ Society, vol. 77, pp. 561–563, May 2000.

[3] G. H. Hutchinson, “Traditional and new uses for vegetable oils in the surface coatings and allied industries,” Surface Coatings International Part B: Coatings Transactions, vol. 85, pp. 1–8, Mar. 2002.

[4] J. Salimon, N. Salih, and E. Yousif, “Chemically modified biolubricant basestocks from epoxidized oleic acid: Improved low temperature properties and oxidative stability,” Journal of Saudi Chemical Society, vol. 15, pp. 195–201, Jul. 2011.

[5] M. R. Klaas and S. Warwel, “Complete and partial epoxidation of plant oils by lipase-catalyzed perhydrolysis,” Industrial Crops and Products, vol. 9, pp. 125–132, Jan. 1999.

[6] A. E.Gerbase, J. R. Gregório, M. Martinelli, M. C. Brasil, and N. F. Mendes, “Epoxidation of soybean oil by methyltrioxorhenium-CH2Cl2/ H2O2 catalytic biphasic system,” Journal of the American Oil Chemists’ Society, vol. 79, pp. 179–181, Feb. 2002.

[7] W. A. Herrmann, R. W. Fischer, and D. W. Marz, “Methyltroxorhenium as catalyst for olefin oxidation,” Angewandte Chemie, vol. 30, pp. 1638–1641, Dec. 1991.

[8] J. Yang, M. D. Morton, D. W. Hill, and D. F. Grant, “NMR and HPLC-MS-MS analysis of synthetically prepared linoleic acid diol glucuronides,” Chemistry and Physics of Lipid, vol. 140, pp. 75–87, Apr. 2006.

[9] W. Wang and J. H. Espenson, “Effects of pyridine and its derivatives on the equilibria and kinetics pertaining to epoxidation reactions catalyzed by methyltrioxorhenium,” Journal of the American Chemical Society, vol. 120, pp. 11335–11341, Oct. 1998.

[10] T. R. Boehlow and C. D. Spilling, “The regionand stereo- selective epoxidation of alkenes with methyl trioxorhenium and urea-hydrogen peroxide adduct,” Tetrahedron Letters, vol. 37, pp. 2717–2720, Apr. 1996.

[11] G. S. Owens a n d M. M. Abu-Omar, “Methyltrioxorhenium-catalyzed epoxidations in ionic liquids,” Chemical Communications, vol. 13, pp. 1165–1166, Jun. 2000.

[12] H. Rudler, J. R. Gregorio, B. Denise, J. M. Brégeault, and A. Deloffre, “Assessment of MTO as a catalyst for the synthesis of acid sensitive epoxides. Use of the biphasic system H2O2/ CH2Cl2 with and without bipyridine and influence of the substituents on the double bonds,” Journal of Molecular Catalysis A: Chemical, vol. 133, pp. 255–265, Aug. 1998.

[13] H. Adolfsson, A. Converso, and K. B. Sharpless, “Comparison of amine additives most effective in the new methyltrioxorhenium-catalyzed epoxidation process,” Tetrahedron Letters, vol. 40, pp. 3991–3994, May 1999.

[14] H. Baş and İ. H. Boyacı, “Modeling and optimization I: Usability of response surface methodology,” Journal of Food Engineering, vol. 78, pp. 836–845, Feb. 2007.

[15] U. N. Wanasundara and F. Shahidi, “Concentration of omega 3-polyunsaturated fatty acids of seal blubber oil by urea complexation: Optimization of reaction conditions,” Food Chemistry, vol. 65, pp. 41–49, Apr. 1999.

[16] S. Akkaravathasinp, P. Narataruksa, and C. Prapainainar, “Optimization of semi-batch reactive distillation using response surface method: Case study of esterification of acetic acid with methanol in a process simulation,” Applied Science and Engineering Progress, vol. 12, pp. 209–215, Aug. 2019.

[17] P. Amunaycheewa, W. Rodiahwati, P. Sanvarinda, K. Cheenkachorn, A. Tawai, and M. Sriariyanun, “Effect of organic acid pretreatment on Napier grass (Pennisetum purpureum) straw biomass conversion,” KMUTNB International Journal of Applied Science and Tecchnology, vol.10, pp. 107–117, Jun. 2017.

[18] N. Junnienkul, M. Siariyanum, T. Douzou, P. Yasurin, and S. Asavasanti, “Optimization of alkyl imidazolium chloride pretreatment on rice straw biomass conversion,” KMUTNB International Journal of Applied Science and Technology, vol.11, pp. 199–207, Jun. 2018.

[19] A. Can and B. Ӧzçelik, “Enrichment of hazelnut oil with long-chain n-3 PUFA by lipase-catalyzed acidolysis: Optimization by response surface methodology,” Journal of the American Oil Chemists’ Society, vol. 82, pp. 27–32, Jan. 2005.

[20] E. R.Gunawan, M. Basri, M. B. A. Rahman, A. B. Salleh, and R. N. Z. A. Rahman, “Study on response surface methodology (RSM) of lipasecatalyzed synthesis of palm-based wax ester,” Enzyme and Microbial Technology, vol. 37, pp. 739–744, Dec. 2005.

[21] E. A. Cepeda and B. Calvo, “Sunflower oil hydrogenation: Study using response surface methodology,” Journal of Food Engineering, vol. 89, pp. 370–374, Dec. 2008.

[22] S. Sun, X. Ke, L. Cui, G. Yang, Y. Bi, F. Song, and X. Xu, “Enzymatic epoxidation of Sapindus mukorosso seed oil by perstearic acid optimized using response surface methodology,” Industrial Crops and Products, vol. 33, pp. 676–682, May 2011.

[23] Official and Recommended Practices of the American Oil Chemists’ Society, Oxirane Oxygen. 5th ed., Champaign: AOCS Press, 1968.

[24] R. Carlson, Design and Optimization in Organic Synthesis. Amsterdam: Elsevier Science Publishers B.V, 1992
[25] Z. S. Petrovic, A. Zlatanic, C. C. Lava, and S. Sinadinovic-Fiser, “Epoxidation of soybean oil in toluene with peroxyacetic and peroxyformic acids- kinetics and side reactions,” European Journal of Lipid Science and Technology, vol. 104, pp. 293–299, May 2002.

[26] R. H. Myers and D. C. Montgomery, Response Surface Methodology: Process and Product Optimization Using Designed Experiments. 2nd ed., Canada: John Wiley & Sons, Inc, 2002.
[27] R. L. Anderson, Practical Statistics for Analytical Chemists. New York: Van Nostrand Reinhold Company, 1987.

Full Text: PDF

DOI: 10.14416/j.asep.2020.12.006


  • There are currently no refbacks.