Green Polyols from Tamanu Seed Oil: Reaction Kinetics and Process Optimization
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Keywords:
hydroxylation, mole ratio, polyol concentration, oxirane number, temperature
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Abstract
Using methanol, this study examined the hydroxylation process of epoxidized tamanu seed oil (ETSO), with an oxirane number of 3.92 to 4.04 mmol/g, under the catalyzation of sulfuric acid (H2SO4). The objectives of this study were, first, to synthesize polyol from ETSO, and, second, determine how temperature and catalyst concentration play a role in the hydroxylation process. During the experiment, a second-order reaction kinetic model was used for analysis. The hydroxylation process was conducted in a batch reactor for 4 hours under constant temperatures and stirring speed. During the experiment, the samples were taken every 30 minutes. The oxirane number of ETSO and the concentration of polyols were used to the reaction rates. The optimal conditions were found at a temperature of 65°C, with a methanol-to-epoxide mole ratio of 4:1 and a catalyst concentration of 3%. The pre-exponential factor (A) and the calculated activation energy (Ea) were found to be 59,041.74 g.mmol-1.min-1 and 44.69 kJ/mol, respectively. This research, therefore, has successfully identified the optimal conditions for the synthesis of bio-based polyols from tamanu oil.
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Budiyati, E., Habibburohman, M. S., Fauzi, N. A., Wasi, M. A., Musthofa, M., & Ur rahmah, A. (2025). Green Polyols from Tamanu Seed Oil: Reaction Kinetics and Process Optimization. Communications in Science and Technology, 10(2), 336–342. https://doi.org/10.21924/cst.10.2.2025.1749
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References
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34. J.C. de Haro, I. Izarra, J.F. Rodríguez, Á. Pérez, M. Carmona, Modelling the epoxidation reaction of grape seed oil by peracetic acid, J. Clean. Prod. 138 (2016) 70–76.
35. A.B. Kousaalya, S.D. Beyene, V. Gopal, B. Ayalew, S. Pilla, Green epoxy synthesized from Perilla frutescens: A study on epoxidation and oxirane cleavage kinetics of high-linolenic oil, Ind. Crops Prod. 123 (2018) 25–34.
36. E. Budiyati, H.M. Sofyan, N. Irsyad, A. Salsyabila, M. Musthofa, Mass transfer and reaction rate parameters for the in-situ epoxidation of tamanu oil, Chem. Pap. 78 (2024) 4131–4141.
37. E. Budiyati, Budhijanto, A. Budiman, Rochmadi, Kinetic study of epoxidation of Tung oil (Reutealis trisperma (Blanco) Airy Shaw) by peroxyacetic acid, IOP Conf. Ser. Mater. Sci. Eng. 778 (2020).
38. E. Budiyati, R. Rochmadi, A. Budiman, B. Budhijanto, Effects of the Molar Ratio of Acetic Acid to UFA and Stirring Velocity in the Tung Oil Epoxidation, Key Eng. Mater. 884 (2021) 117–124.
39. C. Paquot, Determination of Epoxy-Group Oxygen, Stand. Methods Anal. Oils, Fats Deriv. (1979) 92–93.
40. S. Dinda, V. Ravisankar, P. Puri, Development of Bio-epoxide from Nahor (Mesua ferrea Linn) Oil, J. Taiwan Inst. Chem. Eng. 65 (2016) 399–404.
41. M. Mirza-Aghayan, M. Alizadeh, M. Molaee Tavana, R. Boukherroub, Graphite oxide: A simple and efficient solid acid catalyst for the ring-opening of epoxides by alcohols, Tetrahedron Lett. 55 (2014) 6694–6697.
42. H. Dai, L. Yang, B. Lin, C. Wang, G. Shi, Synthesis and characterization of the different soy-based polyols by ring opening of epoxidized soybean oil with methanol, 1,2-ethanediol and 1,2-propanediol, JAOCS, J. Am. Oil Chem. Soc. 86 (2009) 261–267.
43. V. Pantone, A.G. Laurenza, C. Annese, F. Fracassi, C. Fusco, A. Nacci, A. Russo, L. D’Accolti, Methanolysis of epoxidized soybean oil in continuous flow conditions, Ind. Crops Prod. 109 (2017) 1–7.
44. J.M. Yelwa, S. Abdullahi, Epoxidation and Hydroxylation of Sunflower Seed Oil, Int. J. Sci. Res. Chem. 4 (2019) 1–7.
45. E. Santacesaria, R. Turco, V. Russo, R. Tesser, M. Di, Soybean oil epoxidation: Kinetics of the epoxide ring opening reactions, Processes 8 (2020).
46. G.D. Yadav, S. Singh, Ring opening of epoxides with alcohols using Fe(Cp)2BF 4 as catalyst, Tetrahedron Lett. 55 (2014) 3979–3983.
47. G. Acik, M. Kamaci, C. Altinkok, H.R.F. Karabulut, M.A. Tasdelen, Synthesis and properties of soybean oil-based biodegradable polyurethane films, Prog. Org. Coatings 123 (2018) 261–266.
48. A.B. Kousaalya, S.D. Beyene, V. Gopal, B. Ayalew, S. Pilla, Green epoxy synthesized from Perilla frutescens: A study on epoxidation and oxirane cleavage kinetics of high-linolenic oil, Ind. Crops Prod. 123 (2018) 25–34.
2. H. Górska-Warsewicz, K. Rejman, W. Laskowski, M. Czeczotko, Milk and dairy products and their nutritional contribution to the average polish diet, Nutrients 11 (2019).
3. C. Vergallo, Nutraceutical vegetable oil nanoformulations for prevention and management of diseases, Nanomaterials 10 (2020) 1–30.
4. U. Pasqual Laverdura, L. Rossi, C. Courson, A. Zarli, K. Gallucci, Selective Catalytic Hydrogenation of Vegetable Oils over Copper-Based Catalysts Supported on Amorphous Silica, Energies 16 (2023).
5. A. Kumar, A. Sharma, K. C. Upadhyaya, Vegetable Oil: Nutritional and Industrial Perspective, Curr. Genomics 17 (2016) 230–240.
6. X. Zhao, X. Xiang, J. Huang, Y. Ma, J. Sun, D. Zhu, Studying the Evaluation Model of the Nutritional Quality of Edible Vegetable Oil Based on Dietary Nutrient Reference Intake, ACS Omega 6 (2021) 6691–6698.
7. A. Chafidz, Enhancing thermal and mechanical properties of polypropylene using masterbatches of nanoclay and nano-CaCO3: A review, Commun. Sci. Technol. 3 (2018) 19–26.
8. F.T.R. Silalahi, T.M. Simatupang, M.P. Siallagan, Biodiesel produced from palm oil in Indonesia: Current status and opportunities, AIMS Energy 8 (2020) 81–101.
9. A. Demirbas, A. Bafail, W. Ahmad, M. Sheikh, Biodiesel production from non-edible plant oils, Energy Explor. Exploit. 34 (2016) 290–318.
10. D.A. Ramdhani, W. Trisunaryanti, Triyono, Study of green and sustainable heterogeneous catalyst produced from Javanese Moringa oleifera leaf ash for the transesterification of Calophyllum inophyllum seed oil, Commun. Sci. Technol. 8 (2023) 124–133.
11. M. Górecki, M. Sosada, B. Pasker, M. Pająk, P. Fraś, Preparation of ibuprofen emulsions with rapeseed phospholipids and vegetable oils, Indian J. Pharm. Educ. Res. 50 (2016) 271–276.
12. C.L. Burnett, M.M. Fiume, W.F. Bergfeld, D. V. Belsito, R.A. Hill, C.D. Klaassen, D. Liebler, J.G. Marks, R.C. Shank, T.J. Slaga, P.W. Snyder, F. Alan Andersen, Safety Assessment of Plant-Derived Fatty Acid Oils, Int. J. Toxicol. 36 (2017) 51S-129S.
13. M. Yang, M. Zhou, L. Song, A review of fatty acids influencing skin condition, J. Cosmet. Dermatol. 19 (2020) 3199–3204.
14. U. Biermann, U.T. Bornscheuer, I. Feussner, M.A.R. Meier, J.O. Metzger, Fatty Acids and their Derivatives as Renewable Platform Molecules for the Chemical Industry, Angew. Chemie - Int. Ed. 60 (2021) 20144–20165.
15. M. Temkov, V. Mureșan, Tailoring the structure of lipids, oleogels and fat replacers by different approaches for solving the trans-fat issue—a review, Foods 10 (2021).
16. R.A. Nicholson, A.G. Marangoni, Lipase-catalyzed glycerolysis extended to the conversion of a variety of edible oils into structural fats, Curr. Res. Food Sci. 4 (2021) 163–174.
17. J.N.R. Ract, F.A.S.D.M. Soares, H.G. Rodrigues, J.R. Bortolon, G.M. Murata, M.I.A. Gonçalves, E. Hatanaka, R. Curi, L.A. Gioielli, Production of vegetable oil blends and structured lipids and their effect on wound healing, Brazilian J. Pharm. Sci. 51 (2015) 415–427.
18. D.K.T. Moreira, J.N.R. Ract, A.P.B. Ribeiro, G.A. Macedo, Production and characterization of structured lipids with antiobesity potential and as a source of essential fatty acids, Food Res. Int. 99 (2017) 713–719.
19. A. Pribowo, J. Girish, M. Gustiananda, R.G. Nandhira, P. Hartrianti, Potential of Tamanu (Calophyllum inophyllum) Oil for Atopic Dermatitis Treatment, Evidence-Based Complement. Altern. Med. 2021 (2021).
20. T. Léguillier, M. Lecsö-Bornet, C. Lémus, D. Rousseau-Ralliard, N. Lebouvier, E. Hnawia, M. Nour, W. Aalbersberg, K. Ghazi, P. Raharivelomanana, P. Rat, The wound healing and antibacterial activity of five ethnomedical Calophyllum inophyllum oils: An alternative therapeutic strategy to treat infected wounds, PLoS One 10 (2015) 1–20.
21. M. Borowicz, J. Paciorek-Sadowska, M. Isbrandt, Synthesis and application of new bio-polyols based on mustard oil for the production of selected polyurethane materials, Ind. Crops Prod. 155 (2020) 112831.
22. A.E. Coman, J. Peyrton, G. Hubca, A. Sarbu, A.R. Gabor, C.A. Nicolae, T.V. Iordache, L. Averous, Synthesis and characterization of renewable polyurethane foams using different biobased polyols from olive oil, Eur. Polym. J. 149 (2021) 110363.
23. Z. Chi, Z. Guo, Z. Xu, M. Zhang, M. Li, L. Shang, Y. Ao, A DOPO-based phosphorus-nitrogen flame retardant bio-based epoxy resin from diphenolic acid: Synthesis, flame-retardant behavior and mechanism, Polym. Degrad. Stab. 176 (2020) 109151.
24. J.M.R. Gallo, S. Teixeira, U. Schuchardt, Synthesis and characterization of niobium modified montmorillonite and its use in the acid-catalyzed synthesis of β-hydroxyethers, Appl. Catal. A Gen. 311 (2006) 199–203.
25. D. Bradley, G. Williams, M. Lawton, Aluminium triflate: A remarkable Lewis acid catalyst for the ring opening of epoxides by alcohols, Org. Biomol. Chem. 3 (2005) 3269–3272.
26. S. Zakavi, G.R. Karimipour, N.G. Gharab, Meso-tetraarylporphyrin catalyzed highly regioselective ring opening of epoxides with acetic acid, Catal. Commun. 10 (2009) 388–390.
27. H. Firouzabadi, N. Iranpoor, A.A. Jafari, S. Makarem, Aluminumdodecatungstophosphate (AlPW12O40) as a reusable Lewis acid catalyst. Facile regioselective ring opening of epoxides with alcohols, acetic acid and thiols, J. Mol. Catal. A Chem. 250 (2006) 237–242.
28. Z.S. Petrovic, I. Javni, A. Zlatanic, A. Guo, Modified vegetable oil-based polyol, United States Pat. (2010) US 7,786,239 B2.
29. A. Guo, Y. Cho, Z.S. Petrović, Structure and properties of halogenated and nonhalogenated soy-based polyols, J. Polym. Sci. Part A Polym. Chem. 38 (2000) 3900–3910.
30. Z.S. Petrović, A. Guo, W. Zhang, Structure and properties of polyurethanes based on halogenated and nonhalogenated soy-polyols, J. Polym. Sci. Part A Polym. Chem. 38 (2000) 4062–4069.
31. M. Ionescu, D. Radojčić, X. Wan, M.L. Shrestha, Z.S. Petrović, T.A. Upshaw, Highly functional polyols from castor oil for rigid polyurethanes, Eur. Polym. J. 84 (2016) 736–749.
32. E. Budiyati, R. Rochmadi, A. Budiman, B. Budhijanto, Effects of the mole ratio of reactant on the methanolysis of epoxidized tung oil, AIP Conf. Proc. 2667 (2023).
33. E. Budiyati, Rochmadi, A. Budiman, Budhijanto, Hydroxylation kinetics of epoxidized Tung oil using methanol as nucleophilic agent, Int. J. Technol. 14 (2023) 1060–1071.
34. J.C. de Haro, I. Izarra, J.F. Rodríguez, Á. Pérez, M. Carmona, Modelling the epoxidation reaction of grape seed oil by peracetic acid, J. Clean. Prod. 138 (2016) 70–76.
35. A.B. Kousaalya, S.D. Beyene, V. Gopal, B. Ayalew, S. Pilla, Green epoxy synthesized from Perilla frutescens: A study on epoxidation and oxirane cleavage kinetics of high-linolenic oil, Ind. Crops Prod. 123 (2018) 25–34.
36. E. Budiyati, H.M. Sofyan, N. Irsyad, A. Salsyabila, M. Musthofa, Mass transfer and reaction rate parameters for the in-situ epoxidation of tamanu oil, Chem. Pap. 78 (2024) 4131–4141.
37. E. Budiyati, Budhijanto, A. Budiman, Rochmadi, Kinetic study of epoxidation of Tung oil (Reutealis trisperma (Blanco) Airy Shaw) by peroxyacetic acid, IOP Conf. Ser. Mater. Sci. Eng. 778 (2020).
38. E. Budiyati, R. Rochmadi, A. Budiman, B. Budhijanto, Effects of the Molar Ratio of Acetic Acid to UFA and Stirring Velocity in the Tung Oil Epoxidation, Key Eng. Mater. 884 (2021) 117–124.
39. C. Paquot, Determination of Epoxy-Group Oxygen, Stand. Methods Anal. Oils, Fats Deriv. (1979) 92–93.
40. S. Dinda, V. Ravisankar, P. Puri, Development of Bio-epoxide from Nahor (Mesua ferrea Linn) Oil, J. Taiwan Inst. Chem. Eng. 65 (2016) 399–404.
41. M. Mirza-Aghayan, M. Alizadeh, M. Molaee Tavana, R. Boukherroub, Graphite oxide: A simple and efficient solid acid catalyst for the ring-opening of epoxides by alcohols, Tetrahedron Lett. 55 (2014) 6694–6697.
42. H. Dai, L. Yang, B. Lin, C. Wang, G. Shi, Synthesis and characterization of the different soy-based polyols by ring opening of epoxidized soybean oil with methanol, 1,2-ethanediol and 1,2-propanediol, JAOCS, J. Am. Oil Chem. Soc. 86 (2009) 261–267.
43. V. Pantone, A.G. Laurenza, C. Annese, F. Fracassi, C. Fusco, A. Nacci, A. Russo, L. D’Accolti, Methanolysis of epoxidized soybean oil in continuous flow conditions, Ind. Crops Prod. 109 (2017) 1–7.
44. J.M. Yelwa, S. Abdullahi, Epoxidation and Hydroxylation of Sunflower Seed Oil, Int. J. Sci. Res. Chem. 4 (2019) 1–7.
45. E. Santacesaria, R. Turco, V. Russo, R. Tesser, M. Di, Soybean oil epoxidation: Kinetics of the epoxide ring opening reactions, Processes 8 (2020).
46. G.D. Yadav, S. Singh, Ring opening of epoxides with alcohols using Fe(Cp)2BF 4 as catalyst, Tetrahedron Lett. 55 (2014) 3979–3983.
47. G. Acik, M. Kamaci, C. Altinkok, H.R.F. Karabulut, M.A. Tasdelen, Synthesis and properties of soybean oil-based biodegradable polyurethane films, Prog. Org. Coatings 123 (2018) 261–266.
48. A.B. Kousaalya, S.D. Beyene, V. Gopal, B. Ayalew, S. Pilla, Green epoxy synthesized from Perilla frutescens: A study on epoxidation and oxirane cleavage kinetics of high-linolenic oil, Ind. Crops Prod. 123 (2018) 25–34.