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Effect of Dicarboxylic Acids’ Aliphatic Chain on the Curing of Epoxidized Soybean Oil (ESO) Resins

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Abstract

This work highlights the importance of renewable materials, specifically polymers derived from epoxidized oils, in promoting sustainable development and reducing the environmental impact of various industries. The use of carboxylic acids as hardeners for biobased resins from epoxidized oils is also discussed as a promising development in this field. However, there is a lack of research in this area, and finding the right combination of carboxylic acids and epoxidized oils remains a challenge. The present work aimed to address this gap by synthesizing biobased resins using epoxidized soybean oil (ESO) and dicarboxylic acids with specific aliphatic chain lengths, such as oxalic, succinic, adipic and sebacic acids with 0, 2, 4 and 8 carbons in aliphatic chain. The curing and properties of the resulting biopolymers were investigated using DSC, FTIR, TGA, and swelling ratio assessments. FTIR spectra evidenced that the reaction between epoxy and carboxylic groups occurred by the presence of ester groups, as verified after the disappearance of the epoxy bands at ~ 829 cm−1 and the appearance of related bands to hydroxyl (-OH) at ~ 3500 and ester at 1685–1742 cm−1, respectively. DSC scans presented exothermic peaks related to the curing reactions associated to an increasing enthalpy (ΔH) as the aliphatic chain size increases. The activation energy, Eac, estimated using Friedman and Vyazovkin approaches, is highly influenced by the chain size and pKa of the acids. Furthermore, the thermal and hydrocatalytic degradation increase with the decrease of aliphatic chain. The study also introduces oxalic acid as a biobased cross linker for ESO, which has not been so far combined without any synthetic modifications in its structure.

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References

  1. Abdelwahab MA, Misra M, Mohanty AK (2015) Epoxidized pine oil-siloxane: crosslinking kinetic study and thermomechanical properties. J Appl Polym Sci 132:1–12. https://doi.org/10.1002/app.42451

    Article  CAS  Google Scholar 

  2. Alarcon RT, Lamb KJ, Bannach G, North M (2021) Opportunities for the use of brazilian biomass to produce renewable chemicals and materials. Chemsuschem 14:169–188. https://doi.org/10.1002/cssc.202001726

    Article  CAS  PubMed  Google Scholar 

  3. Altuna FI, Hoppe CE, Williams RJJ (2018) Epoxy vitrimers: The effect of transesterification reactions on the network structure. Polymers (Basel). https://doi.org/10.3390/polym10010043

    Article  PubMed  Google Scholar 

  4. Bechthold I, Bretz K, Kabasci S, Kopitzky R, Springer A (2008) Succinic acid: a new platform chemical for biobased polymers from renewable resources. Chem Eng Technol. https://doi.org/10.1002/ceat.200800063

    Article  Google Scholar 

  5. Boyer A, Cloutet E, Tassaing T, Gadenne B, Alfos C, Cramail H (2010) Solubility in CO2 and carbonation studies of epoxidized fatty acid diesters: Towards novel precursors for polyurethane synthesis. Green Chem 12:2205–2213. https://doi.org/10.1039/c0gc00371a

    Article  CAS  Google Scholar 

  6. Chen X, Chen S, Xu Z, Zhang J, Miao M, Zhang D (2020) Degradable and recyclable bio-based thermoset epoxy resins. Green Chem 22:4187–4198. https://doi.org/10.1039/d0gc01250e

    Article  CAS  Google Scholar 

  7. Chrissafis K, Paraskevopoulos KM, Bikiaris DN (2006) Thermal degradation kinetics of the biodegradable aliphatic polyester, poly(propylene succinate). Polym Degrad Stab 91:60–68. https://doi.org/10.1016/j.polymdegradstab.2005.04.028

    Article  CAS  Google Scholar 

  8. Ciannamea EM, Ruseckaite RA (2018) Pressure sensitive adhesives based on epoxidized soybean oil: correlation between curing conditions and rheological properties. J Am Oil Chem Soc 95:525–532. https://doi.org/10.1002/AOCS.12046

    Article  CAS  Google Scholar 

  9. Di Mauro C, Malburet S, Genua A, Graillot A, Mija A (2020) Sustainable series of new epoxidized vegetable oil-based thermosets with chemical recycling properties. Biomacromol 21:3923–3935. https://doi.org/10.1021/acs.biomac.0c01059

    Article  CAS  Google Scholar 

  10. Ding C, Matharu AS (2014) Recent developments on biobased curing agents: a review of their preparation and use. ACS Sustain Chem Eng 2:2217–2236. https://doi.org/10.1021/sc500478f

    Article  CAS  Google Scholar 

  11. Ding C, Shuttleworth PS, Makin S, Clark JH, Matharu AS (2015) New insights into the curing of epoxidized linseed oil with dicarboxylic acids. Green Chem 17:4000–4008. https://doi.org/10.1039/c5gc00912j

    Article  CAS  Google Scholar 

  12. Falco G, Sbirrazzuoli N, Mija A (2019) Biomass derived epoxy systems: From reactivity to final properties. Mater. Today Commun. 21:100683. https://doi.org/10.1016/j.mtcomm.2019.100683

    Article  CAS  Google Scholar 

  13. Flory PJ (1953) Principles of polymer chemistry. Cornell University Press

    Google Scholar 

  14. Frias CF, Serra AC, Ramalho A, Coelho JFJ, Fonseca AC (2017) Preparation of fully biobased epoxy resins from soybean oil based amine hardeners. Ind Crops Prod 109:434–444. https://doi.org/10.1016/j.indcrop.2017.08.041

    Article  CAS  Google Scholar 

  15. Friedman HL (1967) Kinetics and Gaseous Products of Thermal Decomposition of Polymers. J Macromol Sci Part A - Chem 1:57–79. https://doi.org/10.1080/10601326708053917

    Article  CAS  Google Scholar 

  16. Gobin M, Loulergue P, Audic JL, Lemiègre L (2015) Synthesis and characterisation of bio-based polyester materials from vegetable oil and short to long chain dicarboxylic acids. Ind Crops Prod 70:213–220. https://doi.org/10.1016/j.indcrop.2015.03.041

    Article  CAS  Google Scholar 

  17. Gogoi P, Horo H, Khannam M, Dolui SK (2015) In situ synthesis of green bionanocomposites based on aqueous citric acid cured epoxidized soybean oil-carboxylic acid functionalized multiwalled carbon nanotubes. Ind Crops Prod 76:346–354. https://doi.org/10.1016/j.indcrop.2015.06.057

    Article  CAS  Google Scholar 

  18. Hu F, La Scala JJ, Yadav SK, Throckmorton J, Palmese GR (2021) Epoxidized soybean oil modified using fatty acids as tougheners for thermosetting epoxy resins: part 2—effect of curing agent and epoxy molecular weight. J Appl Polym Sci 138:50579. https://doi.org/10.1002/app.50579

    Article  CAS  Google Scholar 

  19. Hu F, La Scala JJ, Yadav SK, Throckmorton J, Palmese GR, La Scala JJ, Throckmorton J, Palmese GR (2021) Epoxidized soybean oil modified using fatty acids as tougheners for thermosetting epoxy resins: part 2—effect of curing agent and epoxy molecular weight. J Appl Polym Sci 138:50570. https://doi.org/10.1002/app.50579

    Article  CAS  Google Scholar 

  20. Jansen MLA, van Gulik WM (2014) Towards large scale fermentative production of succinic acid. Curr Opin Biotechnol. https://doi.org/10.1016/j.copbio.2014.07.003

    Article  PubMed  Google Scholar 

  21. Kulkarni MV, Viswanath AK (2004) Comparative studies of chemically synthesized polyaniline and poly(o-toluidine) doped with p-toluene sulphonic acid. Eur Polym J 40:379–384. https://doi.org/10.1016/j.eurpolymj.2003.10.007

    Article  CAS  Google Scholar 

  22. Kumar S, Krishnan S, Samal SK, Mohanty S, Nayak SK (2018) Toughening of petroleum based (DGEBA) epoxy resins with various renewable resources based flexible chains for high performance applications: a review. Ind Eng Chem Res 57:2711–2726. https://doi.org/10.1021/acs.iecr.7b04495

    Article  CAS  Google Scholar 

  23. Lei YF, Wang XL, Liu BW, Ding XM, Chen L, Wang YZ (2020) Fully bio-based pressure-sensitive adhesives with high adhesivity derived from epoxidized soybean oil and rosin acid. ACS Sustain Chem Eng 8:13261–13270. https://doi.org/10.1021/acssuschemeng.0c03451

    Article  CAS  Google Scholar 

  24. Li YD, Jian XY, Zhu J, Du AK, Zeng JB (2018) Fully biobased and high performance epoxy thermosets from epoxidized soybean oil and diamino terminated polyamide 1010 oligomers. Polym Test 72:140–146. https://doi.org/10.1016/j.polymertesting.2018.10.010

    Article  CAS  Google Scholar 

  25. Liu J, Zhang L, Shun W, Dai J, Peng Y, Liu X (2021) Recent development on bio-based thermosetting resins. J Polym Sci. https://doi.org/10.1002/pol.20210328

    Article  Google Scholar 

  26. Manthey NW (2013). Development of hemp oil based bioresins for biocomposites. Fac. Eng. Surv. Doctor of.

  27. Mashouf Roudsari G, Mohanty AK, Misra M (2014) Study of the curing kinetics of epoxy resins with biobased hardener and epoxidized soybean oil. ACS Sustain Chem Eng 2:2111–2116. https://doi.org/10.1021/SC500176Z/ASSET/IMAGES/LARGE/SC-2014-00176Z_0008.JPEG

    Article  CAS  Google Scholar 

  28. Omonov TS, Curtis JM (2015) Plant Oil-Based Epoxy Intermediates for Polymers, Bio-based Plant Oil Polymers and Composites. Elsevier Inc., Netherlands. https://doi.org/10.1016/B978-0-323-35833-0.00007-4

    Book  Google Scholar 

  29. PANSUMDAENG, J., Kuntharin, S., Harnchana, V., Supanchaiyamat, N., (2020) Fully bio-based epoxidized soybean oil thermosets for high performance triboelectric nanogenerators. Green Chem 22:6912–6921. https://doi.org/10.1039/d0gc01738h

    Article  CAS  Google Scholar 

  30. Parada Hernandez NL, Bahú JO, Schiavon MIRB, Bonon AJ, Benites CI, Jardini AL, Maciel Filho R, Wolf Maciel MRW (2019) (Epoxidized castor oil – citric acid) copolyester as a candidate polymer for biomedical applications. J Polym Res. https://doi.org/10.1007/s10965-019-1814-5

    Article  Google Scholar 

  31. Poutrel QA, Blaker JJ, Soutis C, Tournilhac F, Gresil M (2020) Dicarboxylic acid-epoxy vitrimers: Influence of the off-stoichiometric acid content on cure reactions and thermo-mechanical properties. Polym Chem 11:5327–5338. https://doi.org/10.1039/d0py00342e

    Article  CAS  Google Scholar 

  32. Qi M, Xu YJ, Rao WH, Luo X, Chen L, Wang YZ (2018) Epoxidized soybean oil cured with tannic acid for fully bio-based epoxy resin. RSC Adv 8:26948–26958. https://doi.org/10.1039/c8ra03874k

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  33. Sahoo SK (2018) Development of completely bio - based epoxy networks derived from epoxidized linseed and castor oil cured with citric acid. Polym Adv Technol. https://doi.org/10.1002/pat.4316

    Article  Google Scholar 

  34. Sivanesan D, Seo BK, Lim CS, Kim S, Kim HG (2021) Trifunctional cycloaliphatic epoxy-based thermoset polymers: Synthesis, polymerization, and characterization. Polymer (Guildf). 220:123568. https://doi.org/10.1016/j.polymer.2021.123568

    Article  CAS  Google Scholar 

  35. Song H, Lee SY (2006) Production of succinic acid by bacterial fermentation. Enzyme Microb Technol. https://doi.org/10.1016/j.enzmictec.2005.11.043

    Article  Google Scholar 

  36. Tan SG, Chow WS (2010) Biobased epoxidized vegetable oils and its greener epoxy blends: a review. Polym - Plast Technol Eng. https://doi.org/10.1080/03602559.2010.512338

    Article  Google Scholar 

  37. Tellers J, Jamali M, Willems P, Tjeerdsma B, Sbirrazzuoli N, Guigo N (2021) Cross-linking behavior of eutectic hardeners from natural acid mixtures. Green Chem 23:536–545. https://doi.org/10.1039/d0gc03172k

    Article  CAS  Google Scholar 

  38. Tran TN, Di Mauro C, Graillot A, Mija A (2020) Chemical reactivity and the influence of initiators on the Epoxidized Vegetable Oil/Dicarboxylic acid system. Macromolecules 53:2526–2538. https://doi.org/10.1021/acs.macromol.9b02700

    Article  CAS  Google Scholar 

  39. Treloar LRG (1975) The physics of rubber elasticity.

  40. Vidil T, Tournilhac F, Musso S, Robisson A, Leibler L (2016) Control of reactions and network structures of epoxy thermosets. Prog Polym Sci 62:126–179. https://doi.org/10.1016/j.progpolymsci.2016.06.003

    Article  CAS  Google Scholar 

  41. Vyazovkin S, Burnham AK, Criado JM, Pérez-Maqueda LA, Popescu C, Sbirrazzuoli N (2011) ICTAC Kinetics Committee recommendations for performing kinetic computations on thermal analysis data. Thermochim Acta. https://doi.org/10.1016/j.tca.2011.03.034

    Article  Google Scholar 

  42. Waig Fang S, De Caro P, Pennarun PY, Vaca-Garcia C, Thiebaud-Roux S (2013) Synthesis and characterization of new polyesters based on renewable resources. Ind Crops Prod 43:398–404. https://doi.org/10.1016/j.indcrop.2012.07.027

    Article  CAS  Google Scholar 

  43. Wu J, Zhao C, Li Y, Li H, Xiang D, Sun Z, Li X (2021) Properties of bio-based thermosetting composites synthesized from epoxidized soybean oil and azo-cardanol benzoxazine. J Polym Res. https://doi.org/10.1007/s10965-021-02442-z

    Article  Google Scholar 

  44. Yadav GG, David A, Favaloro T, Yang H, Shakouri A, Caruthers J, Wu Y (2013) Synthesis and investigation of thermoelectric and electrochemical properties of porous Ca9Co12O28 nanowires. J Mater Chem A 1:11901–11908. https://doi.org/10.1039/c3ta12096a

    Article  CAS  Google Scholar 

  45. Zeng R, Wu Y, Li Y, Wang M, Zeng J (2017) Curing behavior of epoxidized soybean oil with biobased dicarboxylic acids. Polym Test 57:281–287. https://doi.org/10.1016/j.polymertesting.2016.12.007

    Article  CAS  Google Scholar 

  46. Zhang C, Li Y, Chen R, Kessler MR (2014) Polyurethanes from solvent-free vegetable oil-based polyols. ACS Sustain Chem Eng 2:2465–2476. https://doi.org/10.1021/SC500509H/ASSET/IMAGES/MEDIUM/SC-2014-00509H_0007.GIF

    Article  CAS  Google Scholar 

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Acknowledgements

The author would thank BBC Química – São Paulo, Brazil for kindly providing the epoxidized soybean oil (ESO). Authors are gratefully to CERTBIO (Northeast Biomaterials Evaluation and Development Laboratory—Brazil) for the supported infrastructure.

Funding

The authors are grateful to CNPq (National Council for Scientific and Technological Development, Brasilia/DF, Brazil) for the financial support. Fundação de Apoio à Pesquisa do Estado da Paraíba (FAPESQ) (Concession term: 022/2023). Professor Renate Wellen is CNPq fellow (Number: 303426/2021-7).

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  1. Academic Unit of Materials Engineering, Federal University of Campina Grande, Campina Grande, 58249-140, Brazil

    N. C. Nepomuceno & R. M. R. Wellen

  2. Materials Engineering Department, Federal University of Paraiba, João Pessoa, 58051-900, Brazil

    Vinicius Barreto & R. M. R. Wellen

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  1. N. C. Nepomuceno
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Nepomuceno, N.C., Barreto, V. & Wellen, R.M.R. Effect of Dicarboxylic Acids’ Aliphatic Chain on the Curing of Epoxidized Soybean Oil (ESO) Resins. J Polym Environ 32, 45–56 (2024). https://doi.org/10.1007/s10924-023-02958-z

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