Synergistic Effect of Phytic Acid Metal Salts and Intumescent Flame Retardants on the Flame Retardancy of Polyoxymethylene

HUANG Da; LU Shi-ke; ZHANG Ming-ying; ZHANG Deng-hui; LI Jian-tong; XU Yuan-qing; FANG Xiao-min

doi:10.14028/j.cnki.1003-3726.2026.26.067

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Synergistic Effect of Phytic Acid Metal Salts and Intumescent Flame Retardants on the Flame Retardancy of Polyoxymethylene

更新时间：2026-07-06

- Synergistic Effect of Phytic Acid Metal Salts and Intumescent Flame Retardants on the Flame Retardancy of Polyoxymethylene
- Polymer Bulletin Vol. 39, Issue 7, Pages: 1228-1238(2026)
- 作者机构：
  
  河南大学化学与分子科学学院　开封 475004
  河南省功能材料与催化反应工程研究中心　开封 475004
- 作者简介：
- 基金信息：
- DOI：10.14028/j.cnki.1003-3726.2026.26.067
  CLC：
- Received：23 March 2026，
  
  Accepted：14 April 2026，
  
  Online First：04 June 2026，
  
  Published：20 July 2026
- 稿件说明：
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黄达, 鲁世科, 张明瑛, 张登辉, 李建通, 徐元清, 房晓敏. 植酸金属盐与膨胀型阻燃剂对聚甲醛阻燃性能的协同效应. 高分子通报, 2026, 39(7), 1228–1238.

Huang, D.; Lu, S. K.; Zhang, M. Y.; Zhang, D. H.; Li, J. T.; Xu, Y. Q.; Fang, X. M. Synergistic effect of phytic acid metal salts and intumescent flame retardants on the flame retardancy of polyoxymethylene. Polym. Bull. (in Chinese), 2026, 39(7), 1228–1238.
黄达, 鲁世科, 张明瑛, 张登辉, 李建通, 徐元清, 房晓敏. 植酸金属盐与膨胀型阻燃剂对聚甲醛阻燃性能的协同效应. 高分子通报, 2026, 39(7), 1228–1238. DOI： 10.14028/j.cnki.1003-3726.2026.26.067.

Huang, D.; Lu, S. K.; Zhang, M. Y.; Zhang, D. H.; Li, J. T.; Xu, Y. Q.; Fang, X. M. Synergistic effect of phytic acid metal salts and intumescent flame retardants on the flame retardancy of polyoxymethylene. Polym. Bull. (in Chinese), 2026, 39(7), 1228–1238. DOI： 10.14028/j.cnki.1003-3726.2026.26.067.

摘要

采用聚磷酸铵(APP)基膨胀型阻燃剂(IFR)为主阻燃剂、植酸金属盐(PAMs)为协效剂阻燃改性聚甲醛(POM)，评估阻燃POM复合材料的阻燃性能与力学性能，并综合运用热重分析、锥形量热及拉曼光谱等，系统探究其阻燃作用机制。结果表明，PAMs/IFR协效改性聚甲醛表现出优异的阻燃性能，其中植酸镁(PAMg)和植酸锰(PAMn)的效果较好，当其添加1 wt%时，阻燃POM复合材料阻燃等级达到V-1级，LOI提高至52.0%。进一步分析发现，PAMs和IFR的复配比例对复合材料的阻燃性能具有显著影响，当添加5 wt% PAMn与25 wt% IFR时，阻燃等级达到V-0级，同时LOI达到最高值61.3%，而总热释放量(THR)比纯POM下降64.5%，比不含协效剂的POM/IFR体系下降47.2%。PAMs/IFR协效阻燃聚甲醛呈现出以凝聚相阻燃为主，兼有气相协同的阻燃机制，同时PAMs与IFR合适的复配使阻燃POM复合材料维持较高的力学性能。

Abstract

Polyoxymethylene (POM) was modified with ammonium polyphosphate (APP)-based intumescent flame retardant (IFR) as the main flame retardant and metal phosphate salts (PAMs) as the synergist. The flame retardancy and mechanical properties of the fabricated POM composites were evaluated

and the underlying flame-retardant mechanism was systematically elucidated using thermogravimetric analysis (TGA)

cone calorimetry

and Raman spectroscopy. The results showed that PAM/IFR co-modified POM exhibited excellent flame retardancy

with magnesium phosphate (PAMg) and manganese phosphate (PAMn) exhibiting optimal synergistic performance. At a loading of only 1 wt%

PAMg/PAMn endowed the POM composite with a V-1 flame retardant rating and a limiting oxygen index (LOI) of 52.0%. Further investigation revealed that the PAMs/IFR mass ratio significantly affected the flame retardancy of the composites. The optimal formulation (5 wt% PAMn + 25 wt% IFR) enabled the composite to achieve a V-0 flame retardant rating and a maximum LOI of 61.3%

along with a 64.5% reduction in total heat release (THR) relative to neat POM and a 47.2% reduction compared to the POM/IFR binary system. The flame-retardant mechanism of the PAMs/IFR system in POM was dominated by condensed-phase action

accompanied by a synergistic gas-phase effect. Moreover

the rational matching of PAMs and IFR allowed the flame-retardant POM composites to maintain favorable mechanical properties.

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references

Liu, Y. ; Wang, Z. Y. ; Wang, Q. Effects of magnesium hydroxide and its synergistic systems on the flame retardance of polyformaldehyde . J. Appl. Polym. Sci. , 2012 , 125 ( 2 ), 968 – 974 .

Wong, J. F. ; Chan, J. X. ; Hassan, A. ; Mohamad, Z. ; Hashim, S. ; Abd Razak, J. ; Ching, Y. C. ; Yunos, Z. ; Yahaya, R. Use of synthetic wollastonite nanofibers in enhancing mechanical, thermal, and flammability properties of polyoxymethylene nanocomposites . Polym. Compos. , 2022 , 43 ( 11 ), 7845 – 7858 .

Kang, X. L. ; Liu, Y. ; Chen, N. X. ; Feng, W. L. ; Liu, B. Y. ; Xu, Y. Q. ; Li, J. T. ; Ding, T. ; Fang, X. M. Influence of modified ammonium polyphosphate on the fire behavior and mechanical properties of polyformaldehyde . J. Appl. Polym. Sci. , 2021 , 138 ( 14 ), 50156 .

Sun, A. J. ; Luo, F. L. ; Chen, R. ; Shih, T. M. ; Guo, S. Y. Toward supertough and heat-resistant binary blend: polyoxymethylene/elastomer via in-situ graft copolymer formation during one-pot reactive melt blending . J. Polym. Res. , 2023 , 30 ( 3 ), 101 .

Yang, Z. ; Chen, X. T. ; Lu, S. K. ; Wang, Z. H. ; Li, J. T. ; Liu, B. Y. ; Fang, X. M. ; Ding, T. ; Xu, Y. Q. Synergistic flame retardant properties of polyoxymethylene with surface modified intumescent flame retardant and calcium carbonate . Polymers , 2023 , 15 ( 3 ), 537 .

Sun, S. Y. ; He, Y. D. ; Wang, X. D. ; Wu, D. Z. Flammability characteristics and performance of halogen-free flame-retarded polyoxymethylene based on phosphorus-nitrogen synergistic effects . J. Appl. Polym. Sci. , 2010 , 118 ( 1 ), 611 – 622 .

Wang, Z. Y. ; Liu, Y. ; Wang, Q. Flame retardant polyoxymethylene with aluminium hydroxide/melamine/novolac resin synergistic system . Polym. Degrad. Stab. , 2010 , 95 ( 6 ), 945 – 954 .

Zhang, Q. ; Chen, Y. H. Synergistic effects of ammonium polyphosphate/melamine intumescent system with macromolecular char former in flame-retarding polyoxymethylene . J. Polym. Res. , 2011 , 18 ( 2 ), 293 – 303 .

张镔 , 张新悦 , 程瑞良 , 李建通 , 刘保英 , 房晓敏 , 丁涛 , 薛冬峰 . 离子液体阻燃剂研究进展 . 化学研究 , 2024 , 35 ( 3 ), 198 – 206 .

鲁世科 , 杨正 , 王振华 , 房晓敏 , 刘保英 , 李建通 . 磷钼酸铵金属盐协同膨胀型阻燃剂阻燃聚甲醛 . 高分子材料科学与工程 , 2022 , 38 ( 12 ), 47 – 55 .

Liu, B. W. ; Zhao, H. B. ; Wang, Y. Z. Advanced flame-retardant methods for polymeric materials . Adv. Mater. , 2022 , 34 ( 46 ), 2107905 .

Wang, J. ; Guo, Y. ; Zhao, S. P. ; Huang, R. Y. ; Kong, X. J. A novel intumescent flame retardant imparts high flame retardancy to epoxy resin . Polym. Adv. Technol. , 2020 , 31 ( 5 ), 932 – 940 .

Hu, X. M. ; Wang, D. M. Enhanced fire behavior of rigid polyurethane foam by intumescent flame retardants . J. Appl. Polym. Sci. , 2013 , 129 ( 1 ), 238 – 246 .

Gu, L. M. ; Shi, Y. N. ; Zhang, L. Y. Study on surface modification and properties of bio-based intumescent flame retardant . J. Therm. Anal. Calorim. , 2023 , 148 ( 18 ), 9519 – 9535 .

Jiang, L. C. ; Gao, M. ; Xiao, L. Q. ; Wang, X. L. ; Zhou, W. L. Improving the flame retardancy efficiency and mechanical properties of the intumescent flame retarded low-density polyethylene by the dual actions of polyurea microencapsulation and aluminum hypophosphite . J. Appl. Polym. Sci. , 2023 , 140 ( 10 ), e53589 .

Dong, L. P. ; Deng, C. ; Li, R. M. ; Cao, Z. J. ; Lin, L. ; Chen, L. ; Wang, Y. Z. Poly(piperazinyl phosphamide): a novel highly-efficient charring agent for an EVA/APP intumescent flame retardant system . RSC Adv. , 2016 , 6 ( 36 ), 30436 – 30444 .

Yang, Z. ; Kang, X. L. ; Lu, S. K. ; Wang, Z. H. ; Fang, X. M. ; Li, J. T. ; Liu, B. Y. ; Ding, T. ; Xu, Y. Q. Synergistic effects of molybdenum disulfide on a novel intumescent flame retardant polyformaldehyde system . J. Appl. Polym. Sci. , 2023 , 140 ( 4 ), e53385 .

Patra, A. ; Kjellin, S. ; Larsson, A. C. Phytic acid-based flame retardants for cotton . Green Mater. , 2020 , 8 ( 3 ), 123 – 130 .

Mokhena, T. C. ; Sadiku, E. R. ; Ray, S. S. ; Mochane, M. J. ; Matabola, K. P. ; Motloung, M. Flame retardancy efficacy of phytic acid: an overview . J. Appl. Polym. Sci. , 2022 , 139 ( 27 ), e52495 .

Hou, Y. B. ; Xu, Z. M. ; Chu, F. K. ; Gui, Z. ; Song, L. ; Hu, Y. ; Hu, W. Z. A review on metal-organic hybrids as flame retardants for enhancing fire safety of polymer composites . Compos. Part B Eng. , 2021 , 221 , 109014 .

Wang, L. Y. ; Wei, Y. ; Deng, H. B. ; Lyu, R. Q. ; Zhu, J. J. ; Yang, Y. B. Synergistic flame retardant effect of barium phytate and intumescent flame retardant for epoxy resin . Polymers , 2021 , 13 ( 17 ), 2900 .

Cheng, L. Y. ; Wu, W. H. ; Meng, W. H. ; Xu, S. ; Han, H. D. ; Yu, Y. F. ; Qu, H. Q. ; Xu, J. Z. Application of metallic phytates to poly(vinyl chloride) as efficient biobased phosphorous flame retardants . J. Appl. Polym. Sci. , 2018 , 135 ( 33 ), 46601 .

Song, W. M. ; Zhang, L. Y. ; Li, P. ; Ni, Y. P. ; Liu, Y. The fabrication of flame-retardant viscose fabrics with phytic acid-based flame retardants: balancing efficient flame retardancy and tensile strength . Int. J. Biol. Macromol. , 2024 , 260 , 129596 .

He, S. ; Gao, Y. Y. ; Zhao, Z. Y. ; Huang, S. C. ; Chen, Z. X. ; Deng, C. ; Wang, Y. Z. Fully bio-based phytic acid–basic amino acid salt for flame-retardant polypropylene . ACS Appl. Polym. Mater. , 2021 , 3 ( 3 ), 1488 – 1498 .

Liu, W. ; Shi, R. ; Zhang, Z. J. ; Yan, M. Q. ; Chen, X. S. ; Chen, Y. Y. Coordination driven layer-by-layer deposition technology used for fabrication of flame retardant polyamide 66 fabric . Polym. Adv. Technol. , 2021 , 32 ( 8 ), 3232 – 3241 .

Lu, Z. H. ; Feng, W. L. ; Kang, X. L. ; Wang, J. L. ; Xu, H. ; Wang, Y. P. ; Liu, B. Y. ; Fang, X. M. ; Ding, T. Synthesis of siloxane-containing benzoxazine and its synergistic effect on flame retardancy of polyoxymethylene . Polym. Adv. Technol. , 2019 , 30 ( 11 ), 2686 – 2694 .

El Gazi, M. ; Sonnier, R. ; Giraud, S. ; Batistella, M. ; Basak, S. ; Dumazert, L. ; Hajj, R. ; El Hage, R. Fire behavior of thermally thin materials in cone calorimeter . Polymers , 2021 , 13 ( 8 ), 1297 .

张冰 . 典型植酸基阻燃剂改性硬质聚氨酯泡沫复合材料的制备及性能研究 . 安徽工业大学硕士学位论文 , 2020 .

Yang, S. ; Hu, Y. F. ; Zhang, Q. X. Synthesis of a phosphorus—nitrogen-containing flame retardant and its application in epoxy resin . High Perform. Polym. , 2019 , 31 ( 2 ), 186 – 196 .

Schartel, B. Phosphorus-based flame retardancy mechanisms: old hat or a starting point for future development . Materials , 2010 , 3 ( 10 ), 4710 – 4745 .

Hu, F. Z. ; He, X. ; Lv, W. Z. ; Fang, Y. ; Jiang, G. D. ; Shen, Y. C. Synergistic effects of manganese phytate decorated kaolinite in PE/PAPP composites with superior fire safety properties . J. Appl. Polym. Sci. , 2025 , 142 ( 34 ), e57363 .

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