Bio-derived Flame-retardant Curing Agents Enable One-step, Ambient Synthesis of Ultra-tough, Smoke-suppressed Epoxy

Hang-Tian Hu; Dan Xie; Zheng-Hong Guo; Feng-Qing Chen; Xing-Wei He; Gao-Bo Lou; Jin-Feng Dai; Li-Na Liu

doi:10.1007/s10118-025-3471-y

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Bio-derived Flame-retardant Curing Agents Enable One-step, Ambient Synthesis of Ultra-tough, Smoke-suppressed Epoxy

RESEARCH ARTICLE | Updated：2026-01-13

- Bio-derived Flame-retardant Curing Agents Enable One-step, Ambient Synthesis of Ultra-tough, Smoke-suppressed Epoxy
- Bio-derived Flame-retardant Curing Agents Enable One-step, Ambient Synthesis of Ultra-tough, Smoke-suppressed Epoxy
- Chinese Journal of Polymer Science 2026年44卷第1期页码：209-222
- Affiliations：
  
  a.School of Chemistry and Materials Engineering, Zhejiang A & F University, Hangzhou 311300, China
  b.Key Laboratory of Wood Science and Technology of Zhejiang Province, Zhejiang A & F University, Hangzhou 311300, China
  c.Institute of Fire Safety Materials, School of Materials Science and Engineering, Ningbo Tech University, Ningbo 315100, China
- Author bio：
  
  20230195@zafu.edu.cn (D.X.)
  liulina198310@126.com (L.N.L.)
- Funds：
  
  This work was financially supported by Zhejiang Provincial "Leading Force" and "Leading Bird" R&D Key Project (No. 2022C03128), Basic Public Welfare Research Plan of Zhejiang Province (No. LY21C160003), National Natural Science Foundation (No. 51991355) and Zhejiang A&F University Scientific Research Start-up Fund (No. 2023LFR134).;Electronic supplementary information (ESI) is available free of charge in the online version of this article at http://doi.org/10.1007/s10118-025-3471-y.
- DOI：10.1007/s10118-025-3471-y
  中图分类号：
- 收稿：2025-09-13，
  
  录用：2025-10-08，
  
  网络首发：2025-12-18，
  
  纸质出版：2026-01-15
- Accepted：
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Hu, H. T.; Xie, D.; Guo, Z. H.; Chen, F. Q.; He, X. W.; Lou, G. B.; Dai, J. F.; Liu, L. N. Bio-derived flame-retardant curing agents enable one-step, ambient synthesis of ultra-tough, smoke-suppressed epoxy. Chinese J. Polym. Sci. 2026, 44, 209–222

Hang-Tian Hu, Dan Xie, Zheng-Hong Guo, et al. Bio-derived Flame-retardant Curing Agents Enable One-step, Ambient Synthesis of Ultra-tough, Smoke-suppressed Epoxy[J]. Chinese Journal of Polymer Science, 2026, 44(1): 209-222.
Hu, H. T.; Xie, D.; Guo, Z. H.; Chen, F. Q.; He, X. W.; Lou, G. B.; Dai, J. F.; Liu, L. N. Bio-derived flame-retardant curing agents enable one-step, ambient synthesis of ultra-tough, smoke-suppressed epoxy. Chinese J. Polym. Sci. 2026, 44, 209–222 DOI： 10.1007/s10118-025-3471-y.

Hang-Tian Hu, Dan Xie, Zheng-Hong Guo, et al. Bio-derived Flame-retardant Curing Agents Enable One-step, Ambient Synthesis of Ultra-tough, Smoke-suppressed Epoxy[J]. Chinese Journal of Polymer Science, 2026, 44(1): 209-222. DOI： 10.1007/s10118-025-3471-y.

摘要

Bio-based toughening flame retardant (PA-DAO) synthesized by a one-step neutralization method using phytic acid (PA) and 1

8-diaminooctane (DAO) at room temperature. Incorporation of 25 wt% PA-DAO increased the limiting oxygen index from 20.5% to 28.1% and achieved a UL-94 V-0 rating

concomitant with a 71% reduction in PHRR and 53% suppression of total smoke production (TSP).

Abstract

A simultaneous boost in toughness and fire safety of epoxy (EP) is achieved through solvent-free one-step neutralization of phytic acid with 1

8-diaminooctane to yield a multifunctional bio-based curing agent

PA-DAO. When used as the sole hardener

5 wt% PA-DAO increased the tensile

flexural

and impact strengths by 165%

81%

and 455%

respectively

over the parent amine system

whereas the tensile and flexural toughness increased by 1387% and 775%

respectively. At 25 wt% loading

the resin attained a UL-94 V-0 rating and a limiting oxygen index of 28.1%

accompanied by a 71% reduction in the peak heat-release rate and a 53% suppression of total smoke production. This facile

green protocol provides scalable access to ultra-tough

intrinsically flame-retardant epoxy networks without external plasticizers or additives.

关键词

Keywords

references

Jin, F. L.; Li X.; PARK S. J. Synthesis and application of epoxy resins: a review. J. Ind. Eng. Chem. 2015 , 29 , 1−11..

Zhang, J. H.; Mi, X. Q.; Chen, S. Y.; Xu, Z. J.; Zhang, D. H.; Miao, M. H.; Wang, J. S. A bio-based hyperbranched flame retardant for epoxy resins. Chem. Eng. J. 2020 , 381 , 1 22719..

Li, G. M.; Zhang, P.; Huo, S. Q.; Fu, Y. K.; Chen, L.; Wu, Y. P.; Zhang, Y. Y.; Chen, M.; Zhao, X. L.; Song, P. A. Mechanically strong, thermally healable, and recyclable epoxy vitrimers enabled by ZnAl-layer double hydroxides. ACS Sustainable Chem. Eng. 2021 , 9 , 2580−2590..

Huo, S. Q.; Song, P.A.; Yu, B.; Ran, S. Y.; Chevali, V. S.; Liu, L.; Fang, Z. P.; Wang, H. Phosphorus-containing flame retardant epoxy thermosets: Recent advances and future perspectives. Prog. Polym. Sci. 2021 , 114 , 101366..

Mi, X. Q.; Liang, N.; Xu, H. F.; Wu, J.; Jiang, Y.; Nie, B.; Zhang, D. H. Toughness and its mechanisms in epoxy resins. Prog. Mater. Sci. 2022 , 130 , 100977..

Lee, M.; Kwon, W.; Kwon, D.; Lee, E.; Jeong, E. Fracture toughness of the novel in-situ polytriazolesulfone modified epoxy resin for carbon fiber/epoxy composites. J. Ind. Eng. Chem. 2019 , 77 , 461−469..

Xu, Z. G; Song, P. A.; Zhang, J.; Guo, Q. P.; Mai, Y. W. Epoxy nanocomposites simultaneously strengthened and toughened by hybridization with graphene oxide and block ionomer. Compos. Sci. Technol. 2018 , 168 , 363−370..

Fang, F. Song, P. A.; Ran, S. Y.; Guo, Z. H.; Wang, H.; Fang, Z. P. A facile way to prepare phosphorus-nitrogen-functionalized graphene oxide for enhancing the flame retardancy of epoxy resin. Compos. Commun. 2018 , 10 , 97−102..

Ren, J. X.; Chen, S.; Hou, Y. D.; Deng, X. C.; Tian, L.; Ma, C.; Huang, S. C.; Lu, C. F. Biobased reactive flame retardant with the phenylethylamine structure for enhancing flame retardancy and mechanical properties of epoxy resins. J. Appl. Polym. Sci. 2025 , 142 , e56547..

Xu, Y.; Yang, W. J.; Zhou, Q. K.; Gao, T. Y.; Xu, G. M.; Tai, Q. L.; Zhu, S. E.; Lu, H. D.; Yuen, R. K.K.; Yang, W.; Wei, C. X. Highly thermo-stable resveratrol-based flame retardant for enhancing mechanical and fire safety properties of epoxy resins. Chem. Eng. J. 2022 , 450 , 138475..

Zhou, X.; Li, R. L.; Fu, F.; Shen, M. G.; Li, Q. G.; Liu, H.; Xu, X.; Song, Z. Q. 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..

Zhu, Z. M.; Shang, K.; Wang, L. X.; Wang, J. S. Synthesis of an effective bio-based flame-retardant curing agent and its application in epoxy resin: curing behavior, thermal stability and flame retardancy. Polym. Degrad. Stab. 2019 , 167 , 179−188..

Wu, Y.; Song, N. N.; Wang, W. C.; Zhao, Y. P. Synthesis of graphene/epoxy resin composite via 1,8-diaminooctane by ultrasonication approach for corrosion protection. Ultrason. Sonochem. 2018 , 42 , 464−470..

Wang, P. J.; Liao, D. J.; Hu, X. P.; Pan, N.; Li, W. X.; Wang, D. Y.; Yao, Y. Facile fabrication of biobased P-N-C-containing nano-layered hybrid: preparation, growth mechanism and its efficient fire retardancy in epoxy. Polym. Degrad. Stab. 2019 , 159 , 153−162..

Zhu, Z. M.; Wang, L. X.; Lin, X. B.; Dong, L. P. Synthesis of a novel phosphorus-nitrogen flame retardant and its application in epoxy resin. Polym. Degrad. Stab. 2019 , 169 , 108981..

Yang, Y. F.; Wang, X. G.; Fei, B.; Li, H. F.; Gu, X. Y.; Sun, J.; Zhang, S. Preparation of phytic acid-based green intumescent flame retardant and its application in PLA nonwovens. Polym. Adv. Technol. 2021 , 32 , 3039−3049..

Gao, Y. Y.; Deng, C.; Du, Y. Y.; Huang, S. C.; Wang, Y. A novel bio-based flame retardant for polypropylene from phytic acid. Polym. Degrad. Stab. 2019 , 161 , 298−308..

Chu, F. K.; Ma, C.; Zhang, T.; Xu, Z. M.; Mu, X. W.; Cai W.; Zhou, X.; Ma, S. C.; Zhou, Y. F.; Hu, W. Z.; Song, L. Renewable vanillin-based flame retardant toughening agent with ultra-low phosphorus loading for the fabrication of high-performance epoxy thermoset. Compos. Part B Eng. 2020 , 190 , 107925..

Butt, F. K; Cao, C. B; Ahmed, R.; Khan, W. S.; Cao, T.; Bidin, N.; Li, P.; Wan, Q.; Qu, X. H.; Tahir, M.; Idrees, F. Synthesis of novel ZnV 2 O 4 spinel oxide nanosheets and their hydrogen storage properties. CrystEngComm 2014 , 16 , 894−899..

Zhang, T. L.; Wu, M.; Kuga, S.; Ewulonu, C. M.; Huang, Y. Cellulose nanofibril-based flame retardant and its application to paper. ACS Sustain Chem. Eng. 2020 , 8 , 10222−10229..

Cui, X. F.; Li, Q. F.; Li, Y.; Wang, F. H .; Jin, G.; Ding, M. Microstructure and corrosion resistance of phytic acid conversion coatings for magnesium alloy. Appl. Surf. Sci. 2008 , 255 , 2098−2103..

Lakho, D. A.; Yao, D. G.; Cho, K.; Ishaq, M.; Wang, Y. J. Study of the curing kinetics toward development of fast-curing epoxy Resins. Polym.-Plast. Technol. Eng. 2017 , 56 , 161−170..

Zhu, Z. M.; Xu, Y. J.; Liao, W.; Xu, S. M.; Wang, Y. Z. Highly flame retardant expanded polystyrene foams from phosphorus-nitrogen-silicon synergistic adhesives. Ind. Eng. Chem. Res. 2017 , 56 , 4649−4658..

Tan, Y.; Shao, Z. B.; Yu, L. X.; Long, J. W.; Qi, M.; Chen, L.; Wang, Y. Z. Piperazine-modified ammonium polyphosphate as monocomponent flame-retardant hardener for epoxy resin: flame retardance, curing behavior and mechanical property. Polym. Chem. 2016 , 7 , 3003−3012..

Lou, G. B.; He, X. W.; Zhang, W. B.; Rao, Q. Q.; Fu, S. Y.; Liu, L. N.; Dai, J. F. Ultratough epoxy resin based on an ionic complex from phytic acid. Ind. Eng. Chem. Res. 2024 , 63 , 1875−1883..

Tan, Y.; Shao, Z. B.; Chen, X. F.; Long, J. W.; Chen, L.; Wang, Y. Z. Novel multifunctional organic-inorganic hybrid curing agent with high flame-retardant efficiency for epoxy resin. ACS Appl. Mater. Interfaces 2015 , 7 , 7919−17928..

Huo, S. Q.; Zhou, Z. X.; Jiang, J. W.; Sai, T.; Ran, S. Y.; Fang, Z. P.; Song, P. A.; Wang, H. Flame-retardant, transparent, mechanically-strong and tough epoxy resin enabled by high-efficiency multifunctional boron-based polyphosphonamide. Chem. Eng. J. 2022 , 427 , 131578..

Chen, W. X.; Liu, H. D.; Cai, H.; Zhou, X.; Huang, Y.; Zhou, Z. X.; Wu, L. X.; Wang, J. L. Bio-based phytic acid-modified nickel-ion-loaded polydopamine nanosheets as green flame retardants for epoxy resin composites. Constr. Build. Mater. 2025 , 484 , 141774..

[Ye, G. F.; Huo, S. Q.; Wang, C.; Song, P. A.; Fang, Z. P.; Wang, H.; Liu, Z. T. Durable flame-retardant, strong and tough epoxy resins with well-preserved thermal and optical properties via introducing a bio-based, phosphorus-phosphorus, hyperbranched oligomer. Polym. Degrad . Stab. 2023 , 207 , 110235..

Chen, X. W.; Wang, S. P.; Mahmud, S.; Wang, J.; Da i, J. Y.; Liu, X. Q. Biobased hyperbranched flame retardant for epoxy resin modification: simultaneously improved flame retardancy, toughness, and smoke toxicity suppression. Ind. Eng. Chem. Res. 2024 , 63 , 20047−20058..

He, X. B.; Zhou, J. X.; Huang, Y. L.; Zhang, Y. X.; Li, S. N.; Dai, J. F.; Jiang, B. Y. Facile synthesis of a bio-based macromolecule endowing epoxy resin with charming flame-retardant, transparent, and ultraviolet shielding properties. J. Appl. Polym. Sci. 2025 , 142 , e56971..

Fu, L. Y.; Liu, X.; Zhou, Y. B.; Wu, M. H.; Liu, S. M.; Zhao, J. Q.; Mo, Y. Q. Highly flame-retarded epoxy thermoset imparted by bio-based phosphorus/nitrogen-containing furan derivative with enhanced mechanical toughness. Macromol. Mater. Eng. 2022 , 307 , 2100981..

Wang, Y. D.; Liu, L. Y. Ma, L.; Yuan, J.; Wang, L. X.; Wang, H.; Xiao. F.; Zhu, Z. M. Transparent, flame retardant, mechanically strengthened and low dielectric EP composites enabled by a reactive bio-based P/N flame retardant. Polym. Degrad. Stab. 2022 , 204 , 110106..

Luo, Y.; Lan, Y. H.; Cai, J. Y.; Jiang, Q.; Wang, X. Y.; Zhang, H. W.; Hou, L. X.; Xiao, L. Q. Multi-functional bio-based DOPO derivative for enhanced flame retard ancy and mechanical strength in epoxy resin. Eur. Polym. J. 2025 , 222 , 113605..

Wang, C. C.; Ren, B.; Ma, R.; Li, X. Y. A bio-based reactive P/N synergistic flame retardant for improving the fire safety and mechanical properties of epoxy resin. Polym. Eng. Sci. 2024 , 64 , 4730−4745..

Zhu, Z. M.; Wang, L. X.; Dong, L. P. Influence of a novel P/N-containing oligomer on flame retardancy and thermal degradation of intumescent flame-retardant epoxy resin. Polym. Degrad. Stab. 2019 , 162 , 129−137..

Yan, L.; Xu, Z. S.; Wang, X. H.; Deng, N.; Chu, Z. Y. Preparation of a novel mono-component intumescent flame retardant for enhancing the flame retardancy and smoke suppression properties of epoxy resin. J. Therm. Anal. Calorim. 2018 , 134 , 1505−1519..

Yang, S.; Huo, S. Q.; Wang, J.; Zhang, B.; Wang, J. S.; Ran, S. Y.; Fang, Z. P.; Song, P. A. Wang, H. A highly fire-safeand smoke-suppressive single-component epoxy resin with switchable curing temperature and rapid curing rate. Compos. Part B Eng. 2021 , 217 , 108601..

Huo, S. Q.; Yang, S.; Wang, J.; Cheng, J. W.; Zhang, Q. Q.; Hu, Y. F.; Ding, G. P.; Zhang, Q. X.; Song, P. A. A liquid phosphorus-containing imidazole derivative as flame-retardant curing agent for epoxy resin with enhanced thermal latency, mechanical, and flame-retardant performances. J. Hazard. Mater. 2020 , 386 , 121984..

Fang, F.; Huo, S. Q.; Shen, H. F.; Ran, S. Y.; Wang, H.; Song, P. A.; Fang, Z. P. A bio-basedionic complex with different oxidation states of phosphorus for reducing flammability and smoke release of epoxy resins. Compos. Commun. 2020 , 17 , 104−8..

Zhang, T.; Yan, H. Q.; Shen, L.; Fang, Z. P.; Zhang, X. M.; Wang, J. J.; Zhang, B.Y. A phosphorus-, nitrogen- and carbon-containing polyelectrolyte complex: preparation, characterization and its flame retardant performance on polypropylene. RSC Adv. 2014 , 4 , 48285−92..

Xu, Y. J.; Shi, X. H.; Lu, J. H.; Qi, M.; Guo, D. M.; Chen, L.; Wang, Y. Z. Novel phosphorus-containing imidazolium as hardener for epoxy resin aiming at controllable latent curing behavior and flame retardancy. Compos. Part B Eng. 2020 , 184 , 107673..

Luo, H. Q.; Rao, W. H.; Zhao, P.; Wang, L.; Liu, Y. L.; Yu, C. B. An efficient organic/inorganic phosphorus-nitrogen-silicon flame retardant towards low-flammability epoxy resin. Polym. Degrad. Stab. 2020 , 178 , 109195..

Wang, Y.; Zhang, L.; Liu, J. H.; Xiao, Y. F.; Liu, C.; Wang, Y. Z.; Chen, L. Multi-functional flame-retardant epoxy resin featuring diverse crosslinking networks. Chem. Eng. J. 2024 , 499 , 156143..

Cai, D.; Li, Y. C.; Wang, W. S.; Ma, Y.; Cao, N.; Zhang, J. X.; Pan, D.; Naik, N.; Wei, S. Y.; Huang, M. N.; Guo, Z. H. Reinforcing and toughening blends of recycled acrylonitrile-butadiene-styrene/recycled high-impact polystyrene through ionic crosslinking. Surf. Interfaces 2022 , 28 , 101607..

Wang, X. H.; Peng, J. S.; Zhang, Y. Y.; Li, M. Z.; Saiz, E.; Tomsia, A. P.; Cheng, Q. F. Ultratough bioinspired graphene fiber via sequential toughening of hydrogen and ionic bonding. ACS Nano 2018 , 21 , 12638−12645..

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