Evaluation of the Effect of Oil Types Used in Alkyd Resin Synthesis on Application Potentials Using the DFT Approach

Year 2025, Volume: 11 Issue: 4, 382 - 394, 31.12.2025

Nurullah Kartaloğlu , Okan Uçar

https://doi.org/10.28979/jarnas.1775806

Abstract

Alkyd resins are one of the most widely used classes of film-forming polymers, such as paints and coatings. The degree of unsaturation, fatty acid composition, and molecular structure of the oil used in resin synthesis determine the film formation rate, hardness, yellowing resistance, and overall performance of the resin. Tall Oil Fatty Acid (TOFA) contains a high percentage of oleic/linoleic acid, while hemp seed oil is rich in linoleic/linolenic acid. This study investigates the thermodynamic stability and potential performance differences of alkyd resins based on these two oil sources using density functional theory (DFT)-based theoretical calculations. The calculated quantum and thermodynamic parameters provide comprehensive information on the resins' electronic structures and potential reactivity properties, providing valuable preliminary information into the application potential of bio-based alkyd resins. The findings provide a crucial foundation for the design and development of sustainable materials.

Keywords

DFT calculation , alkyd , resin , quantum chemistry , thermodynamics

Ethical Statement

No approval from the Board of Ethics is required.

References

• S. Pathan, S. Ahmad, Green and sustainable anticorrosive coating derived from waterborne linseed alkyd using organic-inorganic hybrid cross linker, Progress in Organic Coatings 122 (2018) 189–198.
• A. Hadzich, G. A. Gross, M. Leimbach, A. Ispas, A. Bund, S. Flores, Effect of polyalcohols on the anticorrosive behaviour of alkyd coatings prepared with drying oils, Progress in Organic Coatings 145 (2020) 105671.
• H. Wang, G. Hu, X. Liu, L. Guo, X. Li, R. Guo, Y. Li, Concurrent alkylation and crosslinking of polyaniline for enhanced anticorrosive performance of waterborne alkyd coating, Progress in Organic Coatings 168 (2022) 106865.
• M. Alam, D. Akram, E. Sharmin, F. Zafar, S. Ahmad, Vegetable oil based eco-friendly coating materials: A review article, Arabian Journal of Chemistry 7 (4) (2014) 469–479.
• H. Nosal, J. Nowicki, M. Warzała, E. Nowakowska-Bogdan, M. Zarębska, Synthesis and characterization of alkyd resins based on Camelina sativa oil and polyglycerol, Progress in Organic Coatings 86 (2015) 59–70.
• N. Kartaloğlu, S. E. Akçin, M. Eren, A. Delibaş, Waterborne hybrid (alkyd/styrene acrylic) emulsion polymers and exterior paint applications, Journal of Coatings Technology and Research 20 (5) (2023) 1621–1637.
• A. S. Chukwuebuka, E. O. Samuel, C. O. Asadu, O. E. Onoghwarite, O. Celestine, C. A. Ezema, Optimal analysis of the effects of process conditions on the yield of alkyd resins from castor and soybean seed oils using response surface methodology, Chemical Engineering Journal Advances 9 (2022) 100217.
• R. Antonelli, G. R. P. Malpass, M. G. C. da Silva, M. G. A. Vieira, Fixed-bed adsorption of ciprofloxacin onto bentonite clay: characterization, mathematical modeling, and DFT-based calculations, Industrial & Engineering Chemistry Research 60 (10) (2021) 4030–4040.
• Y. Yang, H. Gao, Theoretical structure and vibrational spectra of ciprofloxacin: Density functional theory study, Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 102 (2013) 134–141.
• J. Grijalva, T. Y. Huang, J. Yu, P. Buzzini, D. Williams, J. T. Davidson, G. Monjardez, Analysis of major cannabinoids using Raman microscopy, density functional theory, chemometrics and a novel artificial intelligence approach, Talanta Open 10 (2024) 100337.
• O. A. Abu Ali, M. M. Elsawy, A. A. El-Henawy, New eco-friendly succinimide linseed oil resin: Synthesis, characterization, DFT and docking studies for surface coating, Pigment & Resin Technology 54 (6) (2024) 875-884.
• I. Mironi-Harpaz, D. Alperstein, D. Knani, M. Narkis, Curing of styrene-free unsaturated polyester alkyd: synthesis, characterization and simulation, Polymer International 59 (6) (2010) 836–841.
• W. Cheng, T. Qiao, C. Xue, H. Yang, Y. Huang, Y. Ma, H. Lin, Computation of binding energy of MCS and GO-Grafted MCS with waterborne epoxy resin using density functional theory method: Investigating the corrosion resistance of the composite coatings, ACS Omega 7 (44) (2022) 40374–40386.
• T. E. Odetoye, D. S. Ogunniyi, G. A. Olatunji, Preparation and evaluation of Jatropha curcas Linneaus seed oil alkyd resins, Industrial Crops and Products 32 (3) (2010) 225–230.
• F. Siano, S. Moccia, G. Picariello, G. L. Russo, G. Sorrentino, M. Di Stasio, M. G. Volpe, Comparative study of chemical, biochemical characteristics and ATR-FTIR analysis of seeds, oil and flour of the edible Fedora cultivar hemp (Cannabis sativa L.), Molecules 24 (1) (2018) 83.
• R. L. Logan, Tall oil fatty acids, Journal of the American Oil Chemists' Society 56 (11) (1979) 777A–779A.
• Y. Z. Aygün, M. M. E. Mert, Changes of oil and fatty acid ratios during germination of industrial hemp (Cannabis sativa L.) seeds, Changes 16 (1) (2023) 56–62.
• N. Kartaloğlu, A. Delibaş, Investigation of the effect of fluorine and silane-containing monomers on waterborne hybrid (alkyd/styrene acrylic) latexes, Journal of Coatings Technology and Research 21 (3) (2024) 1067–1084.
• C. Lee, W. Yang, R. G. Parr, Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density, Physical Review B 37 (2) (1988) 785.
• W. Guerrab, I. M. Chung, S. Kansiz, J. T. Mague, N. Dege, J. Taoufik, R. Salghi, I. H. Ali, M. I. Khan, H. Lgaz, Y. Ramli, Synthesis, structural and molecular characterization of 2,2-diphenyl-2H,3H,5H,6H,7H-imidazo[2,1-b][1,3]thiazin-3-one, Journal of Molecular Structure 1197 (2019) 369–376.
• M. Bursch, J. M. Mewes, A. Hansen, S. Grimme, Best-practice DFT protocols for basic molecular computational chemistry, Angewandte Chemie International Edition 61 (42) (2022) e202205735.
• P. Winget, T. Clark, Enthalpies of formation from B3LYP calculations, Journal of Computational Chemistry 25 (2004) 725–733.
• M. R. Islam, M. D. H. Beg, S. S. Jamari, Alkyd based resin from non-drying oil, Procedia Engineering 90 (2014) 78–88.
• A. O. Mustapha, S. G. Oladele, S. F. Adisa, Y. T. Afolabi, A response surface methodology to optimize the vield of alkyd resin from Jatropha (Jatropha Curcas) and Sesame (Sesamum Indicum) seed oils using CaCO3 as catalyst, Turkish Journal of Science and Technology 17 (2) (2022) 475-488.
• M. Wang, D. Wang, N. Wang, L. Wang, T. Wang, D. Yu, Comparison of reactive sites of different conjugated linoleic acid molecules by quantum chemical calculations, European Journal of Lipid Science and Technology 125 (12) (2023) 2300089.
• B. Mazouin, A. A. Schöpfer, von O. A. Lilienfeld, Selected machine learning of HOMO–LUMO gaps with improved data-efficiency, Materials Advances 3 (22) (2022) 8306-8316.
• H. Rahmania, S. Kato, K. Sawada, C. Hayashi, H. Hashimoto, S. Nakajima, Y. Otoki, J. Ito, K. Nakagawa, Revealing the thermal oxidation stability and its mechanism of rice bran oil, Scientific Reports 10 (1) (2020) 14091.
• M. A. Ali, S. Chew, F. A. Majid, Contribution of endogenous minor components in the oxidative stability of rice bran oil, Food Measurement and Characterization 17 (2023) 187–210.
• L. Dubrulle, R. Lebeuf, M. Fressancourt-Collinet, V. Nardello-Rataj, Optimization of the vegetable oil composition in alkyd resins: A kinetic approach based on FAMEs autoxidation, Progress in Organic Coatings 112 (2017) 288-294.
• J. C. Hubert, R. A. M. Venderbosch, W. J. Muizebelt, R. P. Klaasen, K. H. Zabel, Singlet oxygen drying of alkyd resins and model compounds, Journal of Coatings Technology 69 (1997) 59–64.
• M. Goikoetxea, Y. Reyes, C. M. de las Heras Alarcón, R. J. Minari, I. Beristain, M. Paulis, M. J. Barandiaran, J. L. Keddie, J. M. Asua, Transformation of waterborne hybrid polymer particles into films: Morphology development and modeling, Polymer 53 (5) (2012) 1098–1108.
• E. Limousin, E. González, D. E. Martínez-Tong, N. Ballard, J. M. Asua, Modelling the dynamic development of the curing process and film morphology of films cast from waterborne acrylic-alkyd hybrids, Chemical Engineering Journal 400 (2020) 125891.
• T. Lu, F. Chen, Multiwfn: A multifunctional wavefunction analyzer, Journal of computational chemistry 33 (5) (2012) 580-592.
• S. Lin, C. Xu, L. Xu, Z. L. Wang, The overlapped electron‐cloud model for electron transfer in contact electrification, Advanced Functional Materials 30 (11) (2020) 1909724.
• J. Zhang, T. Lu, Efficient evaluation of electrostatic potential with computerized optimized code, Physical Chemistry Chemical Physics 23 (36) (2021) 20323-20328.
• M. Lapuerta, J. Rodríguez-Fernández, F. Oliva, Determination of enthalpy of formation of methyl and ethyl esters of fatty acids. Chemistry and Physics of Lipids 163 (2) (2010) 172-181.
• A. Osmont, L. Catoire, I. Gökalp, Thermochemistry of methyl and ethyl esters from vegetable oils, International Journal of Chemical Kinetics 39 (9) (2007) 481-491.