Catalyst selection and optimization of curing process for benzoxazine binders
https://doi.org/10.26907/2542-064X.2025.4.713-727
Abstract
The process of benzoxazine resin curing in the presence of various catalysts was investigated. The catalytic activities were compared to identify the catalyst that most effectively reduced the benzoxazine curing temperature. The effect of the catalyst content on the curing of benzoxazine was assessed. The activation energies for the curing process were determined. The curing kinetics parameters were calculated from differential scanning calorimetry (DSC) data using Thermokinetics3 software. The possibility to control the temperature front and conversion of the binder through layer-by-layer changing of its composition (by varying the content of the catalyst in the benzoxazine system) across the thickness of the product, and thus altering the binder reactivity, was demonstrated. Based on the results obtained, a single-stage curing mode of benzoxazine binder that shortens the curing cycle through composite molding under dynamic heating conditions was singled out.
Supporting agencies: This study was supported by the Kazan Federal University Strategic Academic Leadership Program (PRIORITY-2030).
About the Authors
V. S. Nikitin
Kazan National Research Technical University named after A.N. Tupolev – KAI
Россия
Competing Interests:
Россия
Vadim S. Nikitin, Postgraduate Student, Department of Aircraft Production
Kazan
Competing Interests:
The authors declare no conflicts of interest
L. M. Amirova
Kazan National Research Technical University named after A.N. Tupolev – KAI
Россия
Competing Interests:
Россия
Liliya M. Amirova, Dr. Sci. (Chemistry), Full Professor, Department of Aircraft Production
Kazan
Competing Interests:
The authors declare no conflicts of interest
K. A. Andrianova
Kazan National Research Technical University named after A.N. Tupolev – KAI
Россия
Competing Interests:
Россия
Kristina A. Andrianova, Cand. Sci. (Engineering), Associate Professor, Department of Aircraft Production
Kazan
Competing Interests:
The authors declare no conflicts of interest
R. R. Amirov
Kazan Federal University
Россия
Competing Interests:
Россия
Rustem R. Amirov, Dr. Sci. (Chemistry), Full Professor, Head of Department of Inorganic Chemistry
Kazan
Competing Interests:
The authors declare no conflicts of interest
References
1. Li X.K., Zhang A.P., Bian J., Ni K.Y., Zhao W., Yang K.C., Lin H.L., Chen D.Q. Progress on the simulation, synthesis, processing and application of high performance thermosetting polybenzoxazine resin and its composites: A review. Prog. Org. Coat., 2024, vol. 192, art. 108506. https://doi.org/10.1016/j.porgcoat.2024.108506.
2. Lochab B., Monisha M., Amarnath N., Sharma P., Mukherjee S., Ishida H. Review on the accelerated and low-temperature polymerization of benzoxazine resins: Addition polymerizable sustainable polymers. Polymers, 2021, vol. 13, no. 8, art. 1260. https://doi.org/10.3390/polym13081260.
3. Zhang S., Yang A., He P., Wang Y., Liu Y., Li G., Ren J., Han R. How does prepolymerization affect the curing and properties of the thermosetting resins–benzoxazine resin as an example. Prog. Org. Coat., 2024, vol. 189, art. 108291. https://doi.org/10.1016/j.porgcoat.2024.108291.
4. Ye J., Fan Z., Zhang S., Liu X. Improved curing reactivity, thermal resistance and mechanical properties of furylamine-based benzoxazine using melamine as an amine source. Polym. Adv. Technol., 2023, vol. 34, no. 4, pp. 1253–1264. https://doi.org/10.1002/pat.5967.
5. Yang X., Zhu Z., Wang P., Lei W., Zhong F., Li Y., Feng W. Low-temperature gelling phenomenon for a class of slow-curing phthalonitrile-benzoxazine resin. J. Appl. Polym. Sci., 2024, vol. 141, no. 6, art. e54917. https://doi.org/10.1002/app.54917.
6. Kaya G., Kiskan B., Yagci Y. Phenolic naphthoxazines as curing promoters for benzoxazines. Macromolecules, 2018, vol. 51, no. 5, pp. 1688–1695. https://doi.org/10.1021/acs.macromol.8b00218.
7. Zhang K., Tan X., Wang Y., Ishida H. Unique self-catalyzed cationic ring-opening polymerization of a high performance deoxybenzoin-based 1,3-benzoxazine monomer. Polymer, 2019, vol. 168, pp. 8–15. https://doi.org/10.1016/j.polymer.2019.01.089.
8. Martos A., Sebastían R.M., Marquet J. Studies on the ring-opening polymerization of benzoxazines: Understanding the effect of the substituents. Eur. Polym. J., 2018, vol. 108, pp. 20–27. https://doi.org/10.1016/j.eurpolymj.2018.08.025.
9. Ren S., Tian F., Xiao F., Peng Z., Du Y. Polymerization behaviors and properties of benzoxazine resins based-on meta-substituted anilines. Thermochim. Acta, 2024, vol. 736, art. 179743. https://doi.org/10.1016/j.tca.2024.179743.
10. Liu C., Shen D., Sebastián R.M., Marquet J., Schönfeld R. Catalyst effects on the ring-opening polymerization of 1,3-benzoxazine and on the polymer structure. Polymer, 2013, vol. 54, no. 12, pp. 2873–2878. https://doi.org/10.1016/j.polymer.2013.03.063.
11. Zhang S., Ran Q., Fu Q., Gu Y. Controlled polymerization of 3,4-dihydro-2H-1,3-benzoxazine and its properties tailored by Lewis acids. React. Funct. Polym., 2019, vol. 139, pp. 75–84. https://doi.org/10.1016/j.reactfunctpolym.2019.03.016.
12. Liu C., Shen D., Sebastián R.M., Marquet J., Schönfeld R. Mechanistic studies on ring-opening polymerization of benzoxazines: A mechanistically based catalyst design. Macromolecules, 2011, vol. 44, no. 12, pp. 4616–4622. https://doi.org/10.1021/ma2007893.
13. Zhang T., Bonnaud L., Raquez J.-M., Poorteman M., Olivier M., Dubois P. Cerium salts: An efficient curing catalyst for benzoxazine based coatings. Polymers, 2020, vol. 12, no. 2, art. 415. https://doi.org/10.3390/polym12020415.
14. Devaraju S., Eswar P., Gangadhar Reddy T., Ravi Kumar K. Metal salts used as an efficient catalyst to reduce the ring opening polymerization temperature of benzoxazines. J. Macromol. Sci., Part A: Pure Appl. Chem., 2022, vol. 59, no. 8, pp. 567–573. https://doi.org/10.1080/10601325.2022.2098144.
15. Yang W., Xie Y., Chen J., Huang C., Xu Y., Lin Y. Metal ion-catalyzed low-temperature curing of urushiol-based polybenzoxazine. Front. Chem., 2022, vol. 10, art. 879605. https://doi.org/10.3389/fchem.2022.879605.
16. Zhang X., Mohamed M.G., Xin Z., Kuo S.-W. A tetraphenylethylene-functionalized benzoxazine and copper(II) acetylacetonate form a high-performance polybenzoxazine. Polymer, 2020, vol. 201, art. 122552. https://doi.org/10.1016/j.polymer.2020.122552.
17. Zhang X., Hu W., Pei L., Zhao S., Zhang C., Wang Z. In(NO3)3 catalyzed curing reaction of benzoxazine. High Perform. Polym., 2020, vol. 32, no. 6, pp. 702–709. https://doi.org/10.1177/0954008319899128.
18. Akkus B., Kiskan B., Yagci Y. Counterion effect of amine salts on ring-opening polymerization of 1,3-benzoxazines. Macromol. Chem. Phys., 2019, vol. 220, no. 1, art. 1800268. https://doi.org/10.1002/macp.201800268.
19. Mahadik-Khanolkar S., Donthula S., Sotiriou-Leventis C., Leventis N. Polybenzoxazine aerogels. 1. High-yield room-temperature acid-catalyzed synthesis of robust monoliths, oxidative aromatization, and conversion to microporous carbons. Chem. Mater., 2014, vol. 26, no. 3, pp. 1303–1317. https://doi.org/10.1021/cm403483p.
20. Rodríguez R.B., Iguchi D., Erra-Balsells R., Salum M.L., Froimowicz P. Design and effects of the cinnamic acids chemical structures as organocatalyst on the polymerization of benzoxazines. Polymers, 2020, vol. 12, no. 7, art.1527. https://doi.org/10.3390/polym12071527.
21. Mydeen K.M., Ramachandran S., Krishanasamy B., Muthukaruppan A. Studies on catalyst assisted low-temperature curing of benzoxazines. React. Funct. Polym., 2024, vol. 198, art. 105880. https://doi.org/10.1016/j.reactfunctpolym.2024.105880.
22. Ribeiro F.W.M., Omari I., Thomas G.T., Paul M., Williams P.J.H., McIndoe J.S., Correra T.C. Microstructural analysis of benzoxazine cationic ring-opening polymerization pathways. Macromol. Rapid Commun., 2024, vol. 45, no. 2, art. 2300470. https://doi.org/10.1002/marc.202300470.
23. Amirov R.R., Andrianova K.A., Nikitin V.S., Antipin I.S., Amirova L.M. Epoxy-benzoxazine powder binders for producing reinforced composites with a matrix gradient. Uchenye Zapiski Kazanskogo Universiteta. Seriya Estestvennye Nauki, 2024, vol. 166, no. 4, pp. 590–607. https://doi.org/10.26907/2542-064X.2024.4.590-607. (In Russian)
24. Andrianova K.A., Nikitin V.S., Amirov R.R., Antipin I.S., Amirova L.M. Carbon fiber with a gradient of matrix composition based on benzoxazinephthalonitrile compositions. Vopr. Materialoved., 2024, vol. 120, no. 4, pp. 78–87. (In Russian)
25. Antipin I.S., Amirova L.M., Andrianova K.A., Madiyarova G.M., Shumilova T.A., Kazymova M.A., Amirov R.R. Solutionless synthesis of benzoxazine monomers of different structures and polymers based on them. Herald Technol. Univ., 2023, vol. 26, no. 9, pp. 17–25. https://doi.org/10.55421/1998-7072_2023_26_9_17. (In Russian)
26. ISO 11357-5:2013. Plastics — Differential scanning calorimetry (DSC) – Part 5: Determination of characteristic reaction-curve temperatures and times, enthalpy of reaction and degree of conversion. ISO TC 61/SC 5, 2013. 10 p.
27. Khamidullin O.L., Andrianova K.A., Nikitin V.S., Amirova L.M. The process of curing epoxy–amine resins with a composition gradient in thick-walled cylindrical products. J. Mater. Sci., 2025, vol. 60, no. 11, pp. 5267–5279. https://doi.org/10.1007/s10853-025-10748-2.
28. Thomas P.H. On the thermal conduction equation for self-heating materials with surface cooling. Trans. Faraday Soc., 1958, vol. 54, pp. 60–65. https://doi.org/10.1039/TF9585400060.
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For citations:
Nikitin V.S., Amirova L.M., Andrianova K.A., Amirov R.R. Catalyst selection and optimization of curing process for benzoxazine binders. Uchenye Zapiski Kazanskogo Universiteta Seriya Estestvennye Nauki. 2025;167(4):713-727. (In Russ.) https://doi.org/10.26907/2542-064X.2025.4.713-727
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