A Phosphorus/Nitrogen-containing Phosphaphenanthrene Derivative as Flame Retardant for Poly(lactic acid)

Shan Lin; Hong-Yan Zhu; Chun-Meng You; Da-Ming Ban

doi:10.1007/s10118-026-3634-5

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A Phosphorus/Nitrogen-containing Phosphaphenanthrene Derivative as Flame Retardant for Poly(lactic acid)

RESEARCH ARTICLE | Updated：2026-07-01

- A Phosphorus/Nitrogen-containing Phosphaphenanthrene Derivative as Flame Retardant for Poly(lactic acid)
- A Phosphorus/Nitrogen-containing Phosphaphenanthrene Derivative as Flame Retardant for Poly(lactic acid)
- Chinese Journal of Polymer Science 2026年44卷第7期页码：2282-2293
- Affiliations：
  
  School of Chemistry and Materials Science, Guizhou Normal University, Guiyang 550025, China
- Author bio：
  
  bdaming@gznu.edu.cn
- Funds：
  
  The authors gratefully acknowledge the financial support of the Guizhou Normal University. This work was financially supported by the National Natural Science Foundation of China (No. 51763005).;The authors declare no interest conflict.The data supporting the findings of this study are available from the corresponding author upon reasonable request.
- DOI：10.1007/s10118-026-3634-5
  中图分类号：
- 收稿：2026-01-04，
  
  录用：2026-02-25，
  
  网络首发：2026-05-14，
  
  纸质出版：2026-07-05
- Accepted：
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Lin, S.; Zhu, H. Y.; You, C. M.; Ban, D. M. A phosphorus/nitrogen-containing phosphaphenanthrene derivative as flame retardant for poly(lactic acid). Chinese J. Polym. Sci. 2026, 44, 2282–2293

Shan Lin, Hong-Yan Zhu, Chun-Meng You, et al. A Phosphorus/Nitrogen-containing Phosphaphenanthrene Derivative as Flame Retardant for Poly(lactic acid)[J]. Chinese Journal of Polymer Science, 2026, 44(7): 2282-2293.
Lin, S.; Zhu, H. Y.; You, C. M.; Ban, D. M. A phosphorus/nitrogen-containing phosphaphenanthrene derivative as flame retardant for poly(lactic acid). Chinese J. Polym. Sci. 2026, 44, 2282–2293 DOI： 10.1007/s10118-026-3634-5.

Shan Lin, Hong-Yan Zhu, Chun-Meng You, et al. A Phosphorus/Nitrogen-containing Phosphaphenanthrene Derivative as Flame Retardant for Poly(lactic acid)[J]. Chinese Journal of Polymer Science, 2026, 44(7): 2282-2293. DOI： 10.1007/s10118-026-3634-5.

摘要

A phosphorus-nitrogen flame retardant (FMPO) was synthesized

which endows poly(lactic acid) with high flame retardancy at a low loading

exhibiting synergistic gas-phase and condensed-phase flame-retardant effects.

Abstract

As a bio-based and biodegradable aliphatic polyester

poly(lactic acid) (PLA) holds great promise as a sustainable alternative to conventional petroleum-derived plastics. However

its inherent flammability remains a critical barrier to its use in advanced polymer composites requiring stringent fire-safety standards. In this work

a phosphorus/nitrogen-containing flame retardant (FMPO) was synthesized from melamine (MEL)

formaldehyde (FA) and 9

10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) at a 1:1 molar ratio to serve as a flame-retardant modifier for PLA. The results demonstrated that with only 1 wt% FMPO loading

the PLA composite achieved a UL-94 V-0 rating

and the limiting oxygen index (LOI) increased significantly to 33.2% by 5 wt%. At the same flame retardant content

PLA/5MEL only showed a LOI of 26.8% and a UL-94 V-2 rating. Meanwhile

the mechanical strength of PLA/5FMPO was significantly improved

exhibiting 136% and 41% higher impact strength and tensile strength than PLA/5MEL. The analysis of char residue and incomplete combustion products revealed that FMPO exhibits a bi-phase flame-retardant effect

characterized by gaseous-phase inert-gas dilution and radical quenching

along with a condensed-phase thermal barrier from the carbon layer. This study demonstrates an efficient and sustainable strategy for fabricating high-performance

flame-retardant PLA materials through P/N synergistic fire resistance.

关键词

Keywords

references

Xu, Y.; Zhang, W.; Qiu, Y.; Xu, M.; Li, B.; Liu, L. Preparation and mechanism study of a high efficiency bio-based flame retardant for simultaneously enhancing flame retardancy, toughness and crystallization rate of poly(lactic acid). Compos. Part B Eng. 2022 , 238 , 109913..

Ling, M.; Yin, N.; Chen, Y.; Zhou, Z.; Chen, H.; Dai, C.; Huang, J.; Zhang, W. Construction of polylactic acid-based flame retardant composites by zinc oxide and bamboo carbon. Carbon Lett. 2024 , 34 , 665−675..

Wu, N.; Fu, G.; Yang, Y.; Xia, M.; Yun, H.; Wang, Q. Fire safety enhancement of a highly efficient flame retardant poly(phenylphosphoryl phenylenediamine) in biodegradable poly(lactic acid). J. Hazard. Mater. 2019 , 363 , 1−9..

Zhu, G.; Gao, J.; Zhu, Z. Rational design of across-linked fully biobased flame retardant for high-efficiency fire safety and multifunctional enhancement in polylactic acid composites. ACS Sustainable Chem. Eng. 2025 , 13 , 7318−7331..

Nisar, M.; Santos, L. M. D.; Ullah, H.; Galland, G. B.; Geshev, J.; Bergmann, C.; Quijada, R. Poly(lactide) and Ni nanoparticles supported thermally reduced graphene oxide nanoarchitecture for magnetic stimuli-responsive material. Polym. Compos. 2025 , 46 , 11509−11525..

Russo, S.; Ferrentino, N.; Santulli, F.; Paul, G.; Lamberti, M.; Mazzeo, M.; Venditto, V.; Marchese, L.; Pappalardo, D. Circular strategies for polylactic acid waste: a pathway to advanced thermosets. ACS Sustainable Chem. Eng. 2025 , 13 , 15331−15341..

Gong, W.; Fan, M.; Luo, J.; Liang, J.; Meng, X. Effect of nickel phytate on flame retardancy of intumescent flame retardant polylactic acid. Polym. Adv. Technol. 2020 , 32 , 1548−1559..

Ma, M.; Jiang, Z.; Liu, Z.; Huang, B.; Sun, N.; Chen, S.; Shi, Y.; He, H.; Zhu, Y.; Wang, X. Toward flame retardancy, antimelt dripping, an d UV resistance properties of polylactic acid based on eco-friendly core-shell flame retardant. ACS Appl. Polym. Mater. 2024 , 6 , 3814−3825..

Ozah, R.; Kumar, J. V. S. P.; Anand, S. H.; Kumar, C. R. Experimental investigation on mechanical, flammability, wear and thermal properties of 3D printed polylactic acid composite contain rice husk ash Si 3 N 4 nanoparticle. J. Aust. Ceram. Soc. 2025 , 61 , 1211−1222..

Pasha, H. Y.; Mohtasebi, S. S.; Taherimehr, M.; Tabatabaeekoloor, R.; Firouz, M. S.; Javadi, A. New poly(lactic acid)-based nanocomposite films for food packaging applications. Iran. Polym. J. 2023 , 32 , 855−871..

Zhong, W.; Xu, P.; Niu, D.; Wang, Q.; Yang, W.; Zhang, X.; Liu, T.; Ma, P. Enhanced flame retardancy, ultraviolet shielding, and preserved mechanical properties of polylactic acid with fully biobased multifunctional additives by a green method. ACS Sustain. Chem. Eng. 2024 , 12 , 4017−4027..

Jia, L.; Zhang, W. C.; Tong, B.; Yang, R. J. Crystallization, mechanical and flame-retardant properties of poly(lactic acid) composites with DOPO and DOPO-POSS. Chinese J. Polym. Sci. 2018 , 36 , 871−879..

Baochai, L.; Bakar, A. A.; Mohamad, Z. An overview of the recent advances in flame retarded poly(lactic acid). Polym. Adv. Technol. 2023 , 34 , 1435−1450..

Li, B.; Sun, H.; Zhang, L.; Zhao, X.; Bakar, A. A.; Mohamad, Z. Flame-retarded poly (lactic acid) containing phosphating chitosan. Fire Mater. 2024 , 49 , 173−183..

Liu, Y.; Liu, Y.; Yang, R. Polylactic acid flame-retarded by nano-compound of form II ammonium polyphosphate with montmorillonite. J. Fire Sci. 2021 , 39 , 495−511..

Yuqin, Z.; Di, W.; Zhongliang, G.; Huiying, W. Performance analysis and structure characterization of polylactic acid modified with three flame retardants. New J. Chem. 2024 , 48 , 7469−7479..

Zheng, R.; Chen, Y.; Sun, Z.; Zhang, J.; Deng, Y.; Xu, X. Jute woven fabric modified by phosphorus-containing organosilicon compound reinforced flame retardant polylactic acid composites with enhanced flame retardant and mechanical properties. Polym. Adv. Technol. 2023 , 34 , 3617−3630..

Ma, C.; Yu, B.; Hong, N.; Pan, Y.; Hu, W.; Hu, Y. Facile synthesis of a highly efficient, halogen-free, and intumescent flame retardant for epoxy resins: thermal properties, combustion behaviors, and flame-retardant mechanisms. Ind. Eng. Chem. Res. 2016 , 55 , 10868−10879..

Yemisci, F.; Yesil, S.; Aytac, A. Improvement of the flame retardancy of plasticized poly(lactic acid) by means of phosphorus-based flame retardant fillers. Fire Mater. 2017 , 41 , 964−972..

Long, L.; Nie, X.; Wang, X.; Shan, C.; Qin, S.; Gong, W.; Hai, F.; Yu, J. Properties and mechanism of flame retardant poly(lactic acid) composites containing phosphaphenanthrene-hydroxyl phenyl maleimide derivative. J. Polym Sci. 2025 , 63 , 1695−1706..

Gu, L.; Qiu, J.; Sakai, E. Effect of DOPO-containing flame retardants on poly(lactic acid): non-flammability, mechanical properties and thermal behaviors. Chem. Res. Chin. Univ. 2017 , 33 , 143−149..

Zhang, D.; Pei, M.; Wei, K.; Tan, F.; Gao, C.; Bao, D.; Qin, S. Flame-retardant properties and mechanism of polylactic acid-conjugated flame-retardant compos ites. Front. Chem. 2022 , 10 , 894112..

Pei, M.; Wei, K.; Zhang, D.; Qin, S. Polylactic acid flame-retardant composite preparation and investigation of flame-retardant characteristics. Polym. Eng. Sci. 2023 , 63 , 880−894..

Yang, X.-M.; Qiu, S.; Yusuf, A.; Sun, J.; Zhai, Z.; Zhao, J.; Yin, G.-Z. Recent advances in flame retardant and mechanical properties of polylactic acid: a review. Int. J. Biol. Macromol. 2023 , 243 , 125050..

Wang, X.; He, W.; Long, L.; Huang, S.; Qin, S.; Xu, G. A phosphorus- and nitrogen-containing DOPO derivative as flame retardant for polylactic acid (PLA). J. Therm. Anal. Calorim. 2020 , 145 , 331−343..

Vakili, M.; Alavi Nikje, M. M.; Hajibeygi, M.; Vahabi, H. A reactive melamine-DOPO based flame retardant for superior thermal stability and flame retardancy in rigid polyurethane foam. J. Elastomers Plast. 2024 , 57 , 58−79..

Rao, W.-H.; Hu, Z.-Y.; Xu, H.-X.; Xu, Y.-J.; Qi, M.; Liao, W.; Xu, S.; Wang, Y.-Z. Flame-retardant flexible polyurethane foams wit h highly efficient melamine salt. Ind. Eng. Chem. Res. 2017 , 56 , 7112−7119..

Yan, Y.; Liang, B. Flame-retardant behavior and mechanism of a DOPO-based phosphorus-nitrogen flame retardant in epoxy resin. High Perform. Polym. 2018 , 31 , 885−892..

Zhang, Q.; Yang, S.; Wang, J.; Cheng, J.; Zhang, Q.; Ding, G.; Hu, Y.; Huo, S. A DOPO based reactive flame retardant constructed by multiple heteroaromatic groups and its application on epoxy resin: curing behavior, thermal degradation and flame retardancy. Polym. Degrad. Stabil. 2019 , 167 , 10−20..

Wang, C.; Ren, B.; Ma, R.; Li, X. 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..

Chen, R.; Hu, K.; Tang, H.; Wang, J.; Zhu, F.; Zhou, H. A novel flame retardant derived from DOPO and piperazine and its application in epoxy resin: flame retardance, thermal stability and pyrolysis behavior. Polym. Degrad. Stabil. 2019 , 166 , 334−343..

Chen, R.; Dongmei, B.; Jiang, J.; Sun, C.; Chen, H.; Zhang, M. Effect of 3-methoxysalicylaldehyde on transparency and mechanical properties of EP modified with aminopyridine-based DOPO derivative. High Perform. Polym. 2022 , 35 , 401−411..

Xi, W.; Qian, L.; Qiu, Y.; Chen, Y. Flame-retardant behavior of bi-group molecule derived from phosphaphenanthrene and triazine groups on polylactic acid. Polym. Adv. Technol. 2016 , 27 , 781−788..

Ran, G.; Liu, X.; Guo, J.; Sun, J.; Li, H.; Gu, X.; Zhang, S. Improving the flame retardancy and water resistance of polylactic acid by introducing polyborosiloxane microencapsulated ammonium polyphosphate. Compos. Part B Eng. 2019 , 173 , 106772..

Hou, B. Y.; Wang, Y. N.; Gong, T. Y.; Wang, R.; Huang, L. P.; Li, B. J.; Li, J. C. Fabrication of highly efficient biodegradable oligomeric lactate flame-retardant plasticizers for ultra-flexible flame-retardant poly (lactic acid) composites. Chem. Eng. J. 2024 , 485 , 149932..

Liu, T.; Jing, J.; Zhang, Y.; Fang, Z. Synthesis of a novel polyphosphate and its application with APP in flame retardant PLA. RSC Adv. 2018 , 8 , 4483−4493..

Ran, S.; Fang, F.; Guo, Z.; Song, P.; Cai, Y.; Fang, Z.; Wang, H. Synthesis of decorated graphene with P, N-containing compounds and its flame retardancy and smoke suppression effects on polylactic acid. Compos. Part B Eng. 2019 , 170 , 41−50..

Yu, S.; Xiang, H.; Zhou, J.; Zhu, M. Enhanced flame-retardant performance of poly (lactic acid) (PLA) composite by using intrinsically phosphorus-containing PLA. Prog. Nat. Sci.: Mater. Int. 2018 , 28 , 590−597..

Gao, D.; Wen, X.; Guan, Y.; Czerwonko, W.; Li, Y.; Gao, Y.; Mijowska, E.; Tang, T. Flame retardant effect and mechanism of nanosized NiO as synergist in PLA/APP/CSi-MCA composites. Compos. Commun. 2020 , 17 , 170−176..

Meng, Q.; Liu, X.; Li, S.; Wang, K.; Chen, L.; Wu, B.; Han, S. Silane-grafted black phosphorus nanosheets via ball milling: simultaneously enhanced flame retardancy and mechanical properties in polyurea composites. React. Funct. Polym. 2026 , 218 , 106549..

Hou, B.; Shan, X.; Li, B.; Zhang, Y.; Xu, B.; Cui, Q.; Chen, Z.; Li, J. Constructing novel biobased p hosphorus-containing oligomeric lactates toward synchronously enhancing the toughness and fire safety of poly(lactic acid). ACS Sustain. Chem. Eng. 2024 , 12 , 6748−6761..

Wang, Y.; Zhang, Y.; Ma, L.; Gao, J.; Ge, H.; Zhu, Z. Layered charring agent with super strong carbonization for IFR system: achieving highly efficient flame retardancy of PLA by ultra-low addition IFR. Sustain. Mater.Technol. 2024 , 40 , e00924..

Jiang, P.; Zhang, S.; Bourbigot, S.; Chen, Z.; Duquesne, S.; Casetta, M. Surface grafting of sepiolite with a phosphaphenanthrene derivative and its flame-retardant mechanism on PLA nanocomposites. Polym. Degrad. Stabil. 2019 , 165 , 68−79..

Jia, Y.-W.; Zhao, X.; Fu, T.; Li, D.-F.; Guo, Y.; Wang, X.-L.; Wang, Y.-Z. Synergy effect between quaternary phosphonium ionic liquid and ammonium polyphosphate toward flame retardant PLA with improved toughness. Compos. Part B Eng. 2020 , 197 , 108192..

Xu, H.; Song, X.; Chen, D.; Chen, J.; Wang, Y.; Shi, J.; Yang, J.; Liu, L. Green vanillin coupled with P/N/Si flame retardant for poly (L-lactic acid). Mater. Today Commun. 2024 , 39 , 108553..

Zhan, W.; Li, L.; Chen, L.; Kong, Q.; Chen, M.; Chen, C.; Zhang, Q.;Jiang, J. Biomaterials in intumescent fire-retardant coatings: a review. Prog. Org. Coat. 2024 , 192 , 108483..

Liu, L.; Xu, Y.; Di, Y.; Xu, M.; Pan, Y.; Li, B. Simultaneously enhancing the fire retardancy and crystallization rate of biodegradable polylactic acid with piperazine-1,4-diylbis(diphenylphosphine oxide). Compos. Part B Eng. 2020 , 202 , 108407..

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