Processable Main-chain Benzoxazine Resin Derived from Daidzein with Intrinsic Flame Retardancy

Chao-Fan Hu; Jin-Yue Dai; Jing-Kai Liu; Shuai-Peng Wang; Li Jia; Hui Zhang; Xiao-Qing Liu

doi:10.1007/s10118-026-3676-8

Your Location：

Home >

Browse articles >

Processable Main-chain Benzoxazine Resin Derived from Daidzein with Intrinsic Flame Retardancy

RESEARCH ARTICLE | Updated：2026-06-09

- Processable Main-chain Benzoxazine Resin Derived from Daidzein with Intrinsic Flame Retardancy
- Chinese Journal of Polymer Science Vol. 44, Pages: 1-11(2026)
- Affiliations：
  
  a.School of Materials Science and Engineering, Shenyang University of Chemical Technology, Shenyang 110142, China
  b.Ningbo Institute of Materials Technology and Engineering, Chinese Academy of Sciences, Ningbo 315201, China
  c.State Key Laboratory of Advanced Marine Materials, Ningbo Institute of Materials Technology and Engineering, Chinese Academy of Sciences, Ningbo 315201, China
- Author bio：
  
  daijinyue@nimte.ac.cn (J.Y.D.)
  krista9150@sina.com (H.Z.)
- Funds：
- DOI：10.1007/s10118-026-3676-8
  CLC：
- Received：13 February 2026，
  
  Accepted：18 March 2026，
  
  Online First：09 June 2026，
  
  Published：2026-05
- Accepted：
Scan QR Code
Hu, C. F.; Dai, J. Y.; Liu, J. K.; Wang, S. P.; Jia, L.; Zhang, H.; Liu, X. Q. Processable main-chain benzoxazine resin derived from daidzein with intrinsic flame retardancy. Chinese J. Polym. Sci. https://doi.org/10.1007/s10118-026-3676-8

Chao-Fan Hu, Jin-Yue Dai, Jing-Kai Liu, et al. Processable Main-chain Benzoxazine Resin Derived from Daidzein with Intrinsic Flame Retardancy[J/OL]. Chinese Journal of Polymer Science, 2026, 441-11.
Hu, C. F.; Dai, J. Y.; Liu, J. K.; Wang, S. P.; Jia, L.; Zhang, H.; Liu, X. Q. Processable main-chain benzoxazine resin derived from daidzein with intrinsic flame retardancy. Chinese J. Polym. Sci. https://doi.org/10.1007/s10118-026-3676-8 DOI：

Chao-Fan Hu, Jin-Yue Dai, Jing-Kai Liu, et al. Processable Main-chain Benzoxazine Resin Derived from Daidzein with Intrinsic Flame Retardancy[J/OL]. Chinese Journal of Polymer Science, 2026, 441-11. DOI： 10.1007/s10118-026-3676-8.

摘要

Abstract

The development of intrinsically flame-retardant

low-smoke

low-toxicity

and halogen-free polymers represents a critical challenge. In this study

bio-based daidzein was employed as a partial phenolic source

and a series of main-chain benzoxazine resins (Dz-Ph-ddm) was synthesized

via

Mannich condensation with phenol

4′-diaminodiphenylmethane

and paraformaldehyde. The effects of daidzein content on the thermal stability

flame retardancy

mechanical properties

and char-forming behavior of cured resins were investigated. The results indicate that the rigid aromatic structure and benzopyranone unit of daidzein significantly promoted the formation of a dense and continuous char layer

achieving gas- and condensed-phase synergistic flame retardancy. With 20 mol% of daidzein addition

the resin exhibited a glass transition temperature (

) of 259.6 °C

the char yield at 800 °C increased by 42.5% compared to the control group

a UL-94 V-0 rating

and a 30.9% reduction in total heat release (THR) in cone calorimetry tests. The glass fiber-reinforced composite prepared using this resin as the matrix showed a 100.6% improvement in impact strength

with flexural and compressive strengths reaching 748.4 and 340.8 MPa

respectively. Moreover

it demonstrated good fire safety performance even in an 80 kPa low-pressure combustion environment. This work provides a facile strategy for the preparation of high-performance eco-friendly flame-retardant composites.

关键词

Keywords

references

Cai, W.; Wen, H.; Wang, Z.; Lu, H.; Liu, H.; Wang, Y.; Liu, W.; Wang, J.; Qiu, J. Design, synthesis, flame retardancy and dielectric properties of novel aromatic hyperbranched benzoxazine. React. Funct. Polym. 2022 , 170 , 105098..

Wang, X.; Niu, H.; Huang, J.; Song, L.; Hu, Y. A desoxyanisoin- and furfurylamine-derived high-performance benzoxazine thermoset with high glass transition temperature and excellent anti-flammability. Polym. Degrad. Stabil. 2021 , 189 , 109604..

Chang, C. W.; Lin, C. H.; Lin, H. T.; Huang, H. J.; Hwang, K. Y.; Tu, A. P. Development of an aromatic triamine-based flame-retardant benzoxazine and its high-performance copolybenzoxazines. Eur. Polym. J. 2009 , 45 , 680−689..

Cao, J.; Duan, H.; Zou, J.; Zhang, J.; Wan, C.; Zhang, C.; Ma, H. Bio-based phosphorus-containing benzoxazine towards high fire safety, heat resistance and mechanical properties of anhydride-cured epoxy resin. Polym. Degrad. Stabil. 2022 , 198 , 109878..

Yang, X.-Z.; Yan, Z.; Yang, Z.; Qian, B.; Liu, Z.; Lv, R.; Fei, Z.; Sha, X.-L. Acetal-derived biomass benzoxazine resins: excellent heat resistance, mechanical properties and flame retardant properties. Chem. Eng. J. 2025 , 513 , 162617..

Machado, I.; Rachita, E.; Fuller, E.; Calado, V. M. A.; Ishida, H. Very high-char-yielding elastomers based on the copolymers of a catechol/furfurylamine benzoxazine and polydimethylsiloxane oligomers. ACS Sustain. Chem. Eng. 2021 , 9 , 16637−16650..

Liu, J.; Zhang, L.; Shun, W.; Dai, J.; Peng, Y.; Liu, X. Recent development on bio-based thermosetting resins. J. Polym. Sci. 2021 , 59 , 1474−1490..

Manikandan, B.; Chakraborty, S.; Selva Ganesan, S. Concise review on n aturally derived flame-retardants for cotton fabrics. Cellulose. 2024 , 31 , 7189−7206..

Qi, Y.; Weng, Z.; Kou, Y.; Song, L.; Li, J.; Wang, J.; Zhang, S.; Liu, C.; Jian, X. Synthesize and introduce bio-based aromatic s-triazine in epoxy resin: enabling extremely high thermal stability, mechanical properties, and flame retardancy to achieve high-performance sustainable polymers. Chem. Eng. J. 2021 , 406 , 126881..

Machado, I.; Shaer, C.; Hurdle, K.; Calado, V.; Ishida, H. Towards the development of green flame retardancy by polybenzoxazines. Prog. Polym. Sci. 2021 , 121 , 101435..

Spontón, M.; Lligadas, G.; Ronda, J. C.; Galià, M.; Cádiz, V. Development of a DOPO-containing benzoxazine and its high-performance flame retardant copolybenzoxazines. Polym. Degrad. Stabil. 2009 , 94 , 1693−1699..

Zheng, P.; Zhao, H.; Liu, Q. P/N synergistic integrated flame retardants with instant cross-linking at high-temperature for flame retardancy and impact resistance of epoxy resins. Polym. Degrad. Stabil. 2024 , 225 , 110817..

Yang, Y.; Yang, R.; Liu, Y.; Yao, Z.; Chen, Q.; Zhang, K. Synthesis of phosphaphenanthrene-functional monobenzoxazine for enhancing thermal properties of polybenzoxazine thermosets. React. Funct. Polym. 2023 , 191 , 105680..

Liu, J.; Dai, J.; Wang, S.; Peng, Y.; Cao, L.; Liu, X. Facile synthesis of bio-based reactive flame retardant from vanillin and guaiacol for epoxy resin. Compos. Part B: Eng. 2020 , 190 , 107926..

Amarnath, N.; Appavoo, D.; Lochab, B. Eco-Friendly Halogen-Free Flame Retardant Cardanol Polyphosphazene Polybenzoxazine Networks. ACS Sustain. Chem. Eng. 2017 , 6 , 389−402..

Yu, M.; Chu, Y.; Xie, W.; Fang, L.; Zhang, O.; Ren, M.; Sun, J. Phosphorus-containing reactive compounds to prepare fire-resistant vinyl resin for composites: Effects of flame retardant structures on properties and mechanisms. Chem. Eng. J. 2024 , 480 , 148167..

G, A.; M, S.; S, D.; A, K.; M, A. Triazine cored Schiff base multifunctional polybenzoxazine/bio-silica hybrid composites for enhanced flame and corrosion resistance. React. Funct. Polym. 2025 , 217 , 106465..

Qiu, X.; Wan, X.; Wang, Z.; Li, Z.; Li, J.; Li, X.; Zhang, Z. A simple and universal strategy for construction and application of silica-based flame-retardant nanostructure. Compos. Part B: Eng. 2022 , 238 , 109887..

Chen, K.; Wu, X.; Yao, J.; Liao, H.; Ran, Q. An aldehyde and silicon contained flame retardant enhanced polybenzoxazine. Chem. Eng. J. 2025 , 518 , 164613..

Liu, Y.; Yuan, L.; Liang, G.; Gu, A. Developing intrinsic halogen-free and phosphorus-free flame retardant biobased benzoxazine resins with superior thermal stability and high strength. Eur. Polym. J. 2022 , 180 , 111581..

Xie, L.; Yang, R.; Li, N.; Froimowicz, P.; Zhang, K. Competitive study of novel triptycene-containing benzoxazine monomers and a thermoresponsive linear main chain-type benzoxazine copolymer: synthesis, polymerization, and thermal properties of their thermosets. Macromolecules. 2022 , 55 , 6973−6981..

Lu, Y.; Liu, J.; Zhao, W.; Zhang, K. Bio-benzoxazine structural design strategy toward highly thermally stable and intrinsically flame-retardant thermosets. Chem. Eng. J. 2023 , 457 , 141232..

Chen, L.; Zhao, D.; Wang, X. L.; Wang, Y. Z. Durable macromolecular firefighting for unsaturated polyester via integrating synergistic charring and hydrogen bond. Chem. Eng. J. 2022 , 443 , 136365..

Liu, Y.; Yuan, L.; Liang, G.; Gu, A. Preparation of thermally resistant and mechanically strong biomass benzoxazine resins via green strategy. ACS Sustain. Chem. Eng. 2024 , 12 , 1247−1254..

Lu, Y.; Zhang, Y.; Zhang, K. Renewable biomass resources to access halogen- and phosphorus-free flame retardant thermosets with ultra-low heat release capacity. Chem. Eng. J. 2022 , 448 , 137670..

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 , 168 , 8−15..

Zhang, K.; Han, M.; Han, L.; Ishida, H. Resveratrol-based tri-functional benzoxazines: synthesis, characterization, polymerization, and thermal and flame retardant pro perties. Eur. Polym. J. 2019 , 116 , 526−533..

Hao, B.; Wang, J.; Zhang, Y.; Sheng, W.; Zhang, K. Chrysin-based bio-benzoxazine: a copolymerizable green additive for lowering curing temperatures and improving thermal properties of various thermosetting resins. ACS Appl. Polym. Mater. 2022 , 4 , 1286−1297..

Teng, N.; Yang, S.; Dai, J.; Wang, S.; Zhao, J.; Zhu, J.; Liu, X. Making benzoxazine greener and stronger: renewable resource, microwave irradiation, green solvent, and excellent thermal properties. ACS Sustain. Chem. Eng. 2019 , 7 , 8715−8723..

Zhang, K.; Yu, X.; Wang, Y.; Liu, Y. Thermally activated structural changes of a norbornene–benzoxazine–phthalonitrile thermosetting system: simple synthesis, self-catalyzed polymerization, and outstanding flame retardancy. ACS Appl. Polym. Mater. 2019 , 1 , 2713−2722..

Qi, Y.; Weng, Z.; Zhang, K.; Wang, J.; Zhang, S.; Liu, C.; Jian, X. Magnolol-based bio-epoxy resin with acceptable glass transition temperature, processability and flame retardancy. Chem. Eng. J. 2020 , 387 , 124115..

Thirukumaran, P.; Shakila Parveen, A.; Sarojadevi, M. Synthesis and copolymerization of fully biobased benzoxazines from renewable resources. ACS Sustain. Chem. Eng. 2014 , 2 , 2790−2801..

Sheng, W.; Yin, R.; Chen, J.; Zhang, K. High-performance highly cross-linked networks based on ortho-imide functional mono-benzoxazines containing benzocyclobutene group. React. Funct. Polym. 2022 , 171 , 105154..

Zhang, W.; Li, G.; Yi, C.; Zhou, H.; Huang, B.; Meng, J.; Zou, Y.; Ma, C.; Liu, Y. Developing biobased benzoxazine resins with excellent processability, thermal stability, flame retardancy and dielectric properties. Eur. Polym. J. 2026 , 242 , 114436..

Ma, C.; Li, J. Synthesis of an organophosphorus flame retardant derived from daidzein and its application in epoxy resin. Compos. Part B: Eng. 2019 , 178 , 107471..

Dai, J.; Teng, N.; Peng, Y.; Liu, Y.; Cao, L.; Zhu, J.; Liu, X. Biobased benzoxazine derived from daidzein and furfurylamine: microwave-assisted synthesis and thermal properties investigation. ChemSusChem 2018 , 11 , 3175−3183..

Liu, J.; Safronava, N.; Lyon, R. E.; Maia, J.; Ishida, H. Enhanced thermal property and flame retardancy via intramolecular 5-membered ring hydrogen bond-forming amide functional benzoxazine resins. Macromolecules 2018 , 51 , 9982−9991..

Han, M.; You, S.; Wang, Y.; Zhang, K.; Yang, S. Synthesis of highly thermally stable daidzein-based main-chain-type benzoxazine resins. Polymers 2019 , 11 , 1341..

Zhu, Z.; Zhang, X.; Jiang, Y. Rational design and synthesis of novel benzoxazine resins with excellent thermal and flame―retardant properties. React. Funct. Polym. 2025 , 217 , 106491..

Sang, C.; Yang, W.; Chang, W.; Jiang, B.; Wang, C.; Sheng, Y.; Peng, S.; Zhang, J.; Brown, S. A.; Wang, C. H.; Sha, Z. Synergistic crosslinking of phenolic-epoxy for denser networks with enhanced thermal-mechanical properties. Adv. Compos. Hybrid Mater. 2026 , 9 , 41..

Wu, M.; Cao, G.; Xiao, Z. Polyimide-modified epoxy coatings reinforced with functional fillers for enhanced thermal stability and corrosion resistance. Adv. Compos. Hybrid Mater. 2025 , 8 , 172..

Zhou, Y.; Chu, F.; Qiu, S.; Guo, W.; Zhang, S.; Xu, Z.; Hu, W.; Hu, Y. Construction of graphite oxide modified black phosphorus through covalent linkage: an efficient strategy for smoke toxicity and fire hazard suppression of epoxy resin. J. Hazard. Mater. 2020 , 399 , 123015..

Hua, Y.; Liu, J.; Zhang, J.; Liu, Z.; Hu, G.; Yang, Y.; Sui, Y.; Sun, J.; Gu, X.; Zhang, S. A compound with boron and phosphorus towards epoxy resin with excellent flame retardancy, smoke suppression, transparency, and dielectric properties. Chem. Eng. J. 2024 , 483 , 149212..

Liu, Y.; Ran, Q.; Gu, Y. Preparation and properties of benzoxazine blends with intumescent flame retardancy. Polym. Degrad. Stabil. 2019 , 163 , 15−24..

Xu, Y.; Li, Z.; Zhu, K.; Sun, X.; Liu, Y.; Xiong, S.; Wu, Y.; Yang, Y. Thermal degradation behavior and gas phase flame-retardant mechanism of diamine-based polybenzoxazine/polyhexahydrotriazine interpenetrating polymer network. Polym. Degrad. Stabil. 2022 , 204 , 110103..

Mao, Y.; Wang, W.; Huang, W.; Cai, H. Flame retardant, transparent, low dielectric and low smoke density EP composites implemented with reactive flame retardants containing P/N/B. Polym. Degrad. Stabil. 2024 , 230 , 111078..

Zhou, X.; Li, R.; Fu, F.; Shen, M.; Li, Q.; Liu, H.; Xu, X.; Song, Z. A novel efficient flame-retardant curing agent for epoxy resin based on P-N synergistic effect: bio-based benzoxazine phosphate ester. Chem. Eng. J. 2024 , 499 , 156441..

Yao, Z.; Lu, Y.; Song, J.; Zhang, K. Synthesis of daidzein and thiophene containing benzoxazine resin and its thermoset and carbon material. Molecules 2023 , 28 , 5077..

Jia, L.; Zhang, Y.; Dai, J.; Wu, Y.; Liu, J.; Liu, X. Flame-retardant polybenzoxazine nanocomposites with suppressed smoke and toxic gas emission enabled by copper-embedded laser-induced graphene. Compos. Commun. 2026 , 64 , 102776..

Mukhtar, M.; Klosterman, D.; Morgan, A. B. Preparation, cure, characterization, and mechanical properties of reactive flame-retardant cyanate ester/epoxy resin blends and their carbon fiber reinforced composites. Compos. Part B: Eng. 2024 , 282 , 111580..

Liu, T.; Xu, M.; Bai, Z.; Xu, X.; Ren, D.; Chen, W.; Liu, X. Toughening effect of poly(arylene ether nitrile) on phthalonitrile resin and fiber reinforced composites. J. Mater. Sci. 2022 , 57 , 18343−18355..

Wu, M.; Chen, C.; Peng, A.; Zeng, Z.; Zhang, Z.; Liu, X.; Huang, Y. Self-catalyzed bio-benzoxazines containing phthalonitrile with high thermal stability and intrinsic flame retardancy as well as its composite reinforced by aramid fiber. Polym. Degrad. Stabil. 2025 , 242 , 111705..

Zhang, W.; Yu, Z.; Hou, D.; Wang, Q.; Pan, L.; Chen, X.; Yue, D.; Feng, Y. Synergistic enhancing the flame-retardant and mechanical properties in epoxy/glass fiber composites. Compos. Part B: Eng. 2026 , 312 , 113277..

Luo, Y.; Hou, Y.; Zhang, P.; Xu, P.; Luo, Z. Z.; Zhang, L.; Zhang, P.; Liu, G.; Yan, Q. Dual-effect integration of thermal management and flame retardancy for 3d boron nitride/epoxy/benzoxazine composites. Advanced Functional Materials 2026 , 36, e26998..

Views

Downloads

CSCD

Alert me when the article has been cited

Submit

Tools

Publicity Resources

Facile Mechanochemical Preparation of Polyamide-derivatives via Solid-state Benzoxazine-isocyanide Chemistry

Designing a Phthalonitrile/Benzoxazine Blend for the Advanced GFRP Composite Materials

Polarity-regulated Nano-silica Steering Carbon Black Network Evolution and Reconfiguration in Conductive Silicone Elastomers: Experimental and Molecular Simulations

Anti-biofouling Hydrogels: Surface Hydration, Classification, and Biomedical Applications

High Energy Dissipation Polymer Gels by Regulating Relaxation of Confined Chains

Related Author

Xu Sun

Wei Shi

Xin-Yu Zhou

Sheng Ding

Xu-Lin Yang

Kui Li

Ming-Zhen Xu

Xiao-Bo Liu

Related Institution

Oil & Gas Field Applied Chemistry Key Laboratory of Sichuan Province, College of Chemistry and Chemical Engineering, Southwest Petroleum University

Research Branch of Functional Materials, Institute of Microelectronic & Solid State Electronic, University of Electronic Science and Technology of China

⁰