Insights into biobased epoxidized fatty acid isobutyl esters from biodiesel: Preparation and application as plasticizer

doi:10.1016/j.cjche.2021.03.048

Abstract

Abstract: Biodiesel was used to prepare epoxidized fatty acid isobutyl esters (Ep-FABEs) as a biobased plasticizer in this work. Transesterification of biodiesel with isobutanol catalyzed by tetrabutyl titanate was carried out in a gas-liquid tower reactor. The conversion achieved nearly 100% within 5 h under the reaction temperature, the mass ratio of catalyst to fatty acid methyl esters (FAMEs), and isobutanol to FAMEs total molar ratio of 180 ℃, 0.4 %(mass), and 5.4:1, respectively. In addition, kinetic model of the transesterification reaction was developed at 150–190 ℃. The calculated activation energy was 48.93 kJ·mol^-1. Then, the epoxidation of obtained fatty acid isobutyl esters (FABEs) was conducted in the presence of formic acid and hydrogen peroxide. The Ep-FABEs was further analyzed for its plasticizing effectiveness to replace dioctyl phthalate (DOP) and compared with conventional epoxy plasticizer epoxidized fatty acid methyl esters (Ep-FAMEs). The results indicated that the thermal stability and mechanical properties of PVC films with Ep-FABEs plasticizer were significantly improved compared with those plasticized with DOP. In addition, the extraction resistance and migration stability of Ep-FABEs were better than those of Ep-FAMEs. Overall, the prepared Ep-FABEs via structural modification of biodiesel proved to be a promising biobased plasticizer.

Key words: Biodiesel, Transesterification, Isobutyl esters, Epoxidized isobutyl esters, Biobased plasticizer

摘要： Biodiesel was used to prepare epoxidized fatty acid isobutyl esters (Ep-FABEs) as a biobased plasticizer in this work. Transesterification of biodiesel with isobutanol catalyzed by tetrabutyl titanate was carried out in a gas-liquid tower reactor. The conversion achieved nearly 100% within 5 h under the reaction temperature, the mass ratio of catalyst to fatty acid methyl esters (FAMEs), and isobutanol to FAMEs total molar ratio of 180 ℃, 0.4 %(mass), and 5.4:1, respectively. In addition, kinetic model of the transesterification reaction was developed at 150–190 ℃. The calculated activation energy was 48.93 kJ·mol^-1. Then, the epoxidation of obtained fatty acid isobutyl esters (FABEs) was conducted in the presence of formic acid and hydrogen peroxide. The Ep-FABEs was further analyzed for its plasticizing effectiveness to replace dioctyl phthalate (DOP) and compared with conventional epoxy plasticizer epoxidized fatty acid methyl esters (Ep-FAMEs). The results indicated that the thermal stability and mechanical properties of PVC films with Ep-FABEs plasticizer were significantly improved compared with those plasticized with DOP. In addition, the extraction resistance and migration stability of Ep-FABEs were better than those of Ep-FAMEs. Overall, the prepared Ep-FABEs via structural modification of biodiesel proved to be a promising biobased plasticizer.

关键词: Biodiesel, Transesterification, Isobutyl esters, Epoxidized isobutyl esters, Biobased plasticizer

Xiaojiang Liang, Fengjiao Wu, Qinglong Xie, Zhenyu Wu, Jinjin Cai, Congwen Zheng, Junhong Fu, Yong Nie. Insights into biobased epoxidized fatty acid isobutyl esters from biodiesel: Preparation and application as plasticizer[J]. Chinese Journal of Chemical Engineering, 2022, 44(4): 41-50.

References

[1] I.J. Stojković, O.S. Stamenković, D.S. Povrenović, V.B. Veljković, Purification technologies for crude biodiesel obtained by alkali-catalyzed transesterification, Renew. Sustain. Energy Rev. 32 (2014) 1-15
[2] Y. Feng, T. Qiu, J. Yang, L. Li, X. Wang, H. Wang,. Transesterification of palm oil to biodiesel using Brønsted acidic ionic liquid as high-efficient and eco-friendly catalyst. Chinese Journal of Chemical Engineering (2017) 25(9)1222-1229
[3] M.B. Navas, J.F. Ruggera, I.D. Lick, M.L. Casella, A sustainable process for biodiesel production using Zn/Mg oxidic species as active, selective and reusable heterogeneous catalysts, Bioresour. Bioprocess. 7 (1) (2020) 4
[4] A.B. Chhetri, M.S. Tango, S.M. Budge, K.C. Watts, M.R. Islam, Non-edible plant oils as new sources for biodiesel production, Int J Mol Sci 9 (2) (2008) 169-180
[5] E. Modiba, C. Enweremadu, H. Rutto, Production of biodiesel from waste vegetable oil using impregnated diatomite as heterogenous catalyst, Chin. J. Chem. Eng. (2015) 23(1)281-289
[6] V.G. Gude, G.E. Grant, Biodiesel from waste cooking oils via direct sonication, Appl. Energy 109 (2013) 135-144
[7] H.M. Khan, C.H. Ali, T. Iqbal, S. Yasin, M. Sulaiman, H. Mahmood, M. Raashid, M. Pasha, B.Z. Mu, Current scenario and potential of biodiesel production from waste cooking oil in Pakistan:An overview, Chin. J. Chem. Eng. 27 (10) (2019) 2238-2250
[8] A. Campanella, C. Fontanini, M.A. Baltanás, High yield epoxidation of fatty acid methyl esters with performic acid generated in situ, Chem. Eng. J. 144 (3) (2008) 466-475
[9] S.W. Liu, C.X. Xie, R. Jiang, S.T. Yu, F.S. Liu, Hydrogenation of biodiesel using thermoregulated phase-transfer catalyst for production of fatty alcohols, Bioresour Technol 101 (15) (2010) 6278-6280
[10] T. Zheng, Z.Y. Wu, Q.L. Xie, M.Z. Lu, F. Xia, G.Q. Wang, Y. Nie, J.B. Ji, Biolubricant production of 2-ethylhexyl palmitate by transesterification over unsupported potassium carbonate, J. Am. Oil Chem. Soc. 95 (1) (2018) 79-88
[11] P.Y. Jia, H.Y. Xia, K.H. Tang, Y.H. Zhou, Plasticizers derived from biomass resources:A short review, Polymers (Basel) 10 (12) (2018) E1303
[12] F. Song, H.Y. Xia, P.Y. Jia, M. Zhang, L.H. Hu, Y.H. Zhou, The effects of epoxidized acrylated castor oil (EACO) on soft poly (vinyl chloride) films as a main plasticizer, Pol. J. Chem. Technol. 20 (4) (2018) 13-19
[13] J.Y. Wang, X.B. Zhao, D.H. Liu, Preparation of epoxidized fatty acid methyl ester with in situ auto-catalyzed generation of performic acid and the influence of impurities on epoxidation, Waste Biomass Valorization 9 (10) (2018) 1881-1891
[14] L.P. Xu, S. Yan, J.Y. Fu, J.K. Li, J.X. Xie, Study on plasticization and flame retardancy of phosphorus-containing branched polybutylene adipate in poly (vinyl chloride), J. Appl. Polym. Sci. 137 (1) (2020) 48335
[15] K.H. Chung, S. Jeong, H. Kim, S.J. Kim, Y.K. Park, S.C. Jung, Highly selective catalytic properties of HZSM-5 zeolite in the synthesis of acetyl triethyl citrate by the acetylation of triethyl citrate with acetic anhydride, Catalysts 7 (11) (2017) 321
[16] Y.C. Bai, J.Y. Wang, D.H. Liu, X.B. Zhao, Conversion of fatty acid methyl ester to epoxy plasticizer by auto-catalyzed in situ formation of performic acid:Kinetic modeling and application of the model, J. Clean. Prod. 259 (2020) 120791
[17] A.F. Aguilera, P. Tolvanen, J. Wärnå, S. Leveneur, T. Salmi, Kinetics and reactor modelling of fatty acid epoxidation in the presence of heterogeneous catalyst, Chem. Eng. J. 375 (2019) 121936
[18] J.V. de Quadros Jr, R. Giudici, Epoxidation of soybean oil at maximum heat removal and single addition of all reactants, Chem. Eng. Process.:Process. Intensif. 100 (2016) 87-93
[19] Z.Y. Wu, J.J. Cai, Z.H. Liu, L.H. Wu, X.J. Liang, Q.L. Xie, M.Z. Lu, F.W. Yu, Y. Nie, J.B. Ji, Modeling of an industrial scale hydrodynamic cavitation multiphase reactor for Prileschajew epoxidation, AIChE J. 66 (5) (2020) DOI:10.1002/aic.16914
[20] C. Bueno-Ferrer, M.C. Garrigós, A. Jiménez, Characterization and thermal stability of poly(vinyl chloride) plasticized with epoxidized soybean oil for food packaging, Polym. Degrad. Stab. 95 (11) (2010) 2207-2212
[21] J. Chen, X.Y. Li, Y.G. Wang, K. Li, J.R. Huang, J.C. Jiang, X.A. Nie, Synthesis and application of a novel environmental plasticizer based on cardanol for poly(vinyl chloride), J. Taiwan Inst. Chem. Eng. 65 (2016) 488-497
[22] O. Fenollar, D. García, L. Sánchez, J. López, R. Balart, Optimization of the curing conditions of PVC plastisols based on the use of an epoxidized fatty acid ester plasticizer. Eur. Polym. J. (2009) 45(9)2674-2684
[23] K.W. Lee, J.W. Chung, S.Y. Kwak, Synthesis and characterization of bio-based alkyl terminal hyperbranched polyglycerols:A detailed study of their plasticization effect and migration resistance, Green Chem., 18 (2016) 999-1009. https://doi.org/10.1039/c5gc02402a
[24] G. Feng, L. Hu, Y. Ma, P. Jia, Y. Hu, M. Zhang, C. Liu, Y. Zhou, An efficient bio-based plasticizer for poly (vinyl chloride) from waste cooking oil and citric acid:Synthesis and evaluation in PVC films, J. Clean. Prod., 189 (2018) 334-343. https://doi.org/10.1016/j.jclepro.2018.04.085
[25] P. Yang, H.Z. Sun, H.J. Fan, B. Shi, Novel environmentally sustainable cardanol-based plasticizers:Synthesis and properties, Polym. Int. 65 (4) (2016) n/a. DOI:10.1002/pi.5083
[26] S. Pan, D. Hou, J. Chang, Z. Xu, S. Wang, S. Yan, Q. Zeng, Z. Wang, Y. Chen, A potentially general approach to aliphatic ester-derived PVC plasticizers with suppressed migration as sustainable alternatives to DEHP, Green Chem., 21 (2019) 6430-6440. https://doi.org/10.1039/c9gc03077h
[27] T. Zheng, Z.Y. Wu, Q.L. Xie, J.J. Fang, Y.C. Hu, M.Z. Lu, F. Xia, Y. Nie, J.B. Ji, Structural modification of waste cooking oil methyl esters as cleaner plasticizer to substitute toxic dioctyl phthalate, J. Clean. Prod. 186 (2018) 1021-1030
[28] L.W. Chen, J.M. Xu, W.L. Xue, Z.X. Zeng, Mechanism and kinetics of esterification of adipic acid and ethylene glycol by tetrabutyl titanate catalyst, Korean J. Chem. Eng. 35 (1) (2018) 82-88
[29] W. Tian, Z.X. Zeng, W.L. Xue, Y.B. Li, T. Zhang, Kinetics of the mono-esterification between terephthalic acid and 1, 4-butanediol, Chin. J. Chem. Eng. 18 (3) (2010) 391-396
[30] W.Z. Sun, J.Q. Shao, Z.H. Xi, L. Zhao, Thermodynamics and kinetics of transesterification reactions to produce diphenyl carbonate from dimethyl carbonate catalyzed by tetrabutyl titanate and dibutyltin oxide, Can. J. Chem. Eng. 95 (2) (2017) 353-358
[31] L.N. Silva, C.C. Cardoso, V.M.D. Pasa, Production of cold-flow quality biodiesel from high-acidity on-edible oils:-esterification and transesterification of macauba (acrocomia aculeata) oil using various alcohols, Bioenergy Res. 9 (3) (2016) 864-873
[32] Y. Nie, X. Liang, Z. Wu, J. Fu, Q. Xie, Z. Tan, F. Wu, M. Lu, J. Ji, Tower type reaction device and process for preparing fatty acid butyl ester, CN Pat., 110787766A (2020).
[33] Z.Y. Wu, T. Zheng, L.H. Wu, H.F. Lou, Q.L. Xie, M.Z. Lu, L.Z. Zhang, Y. Nie, J.B. Ji, Novel reactor for exothermic heterogeneous reaction systems:Intensification of mass and heat transfer and application to vegetable oil epoxidation, Ind. Eng. Chem. Res. 56 (18) (2017) 5231-5238
[34] L.P. Zhang, B.Y. Sheng, Z. Xin, Q. Liu, S.Z. Sun, Kinetics of transesterification of palm oil and dimethyl carbonate for biodiesel production at the catalysis of heterogeneous base catalyst, Bioresour Technol 101 (21) (2010) 8144-8150
[35] G.D. Feng, Y. Hu, P.Y. Jia, M. Yan, Y.H. Zhou, Influence of a nitrogen-containing oil-based plasticizer on mechanical, thermal stability and fire performance of plasticized poly(vinyl chloride) and study of its mechanism of flame retardancy with Py-GC/MS, Ind. Crop. Prod. 77 (2015) 883-894