Inorganic Thermoplastic Flame Retardant as a Basic Component of Low-combustible Polymer Blends

Viktor A. Novikov; Elena V. Stegno; Andrey V. Grachev; Ali D. Aliev; Victor Yu. Bychkov; Irina O. Plyusnina; Uliana V. Nikulova; Aleksey V. Shapagin; Alexander Yu. Shaulov; Alexander A. Berlin

doi:10.1007/s10118-025-3528-y

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Inorganic Thermoplastic Flame Retardant as a Basic Component of Low-combustible Polymer Blends

RESEARCH ARTICLE | Updated：2026-02-13

- Inorganic Thermoplastic Flame Retardant as a Basic Component of Low-combustible Polymer Blends
- Inorganic Thermoplastic Flame Retardant as a Basic Component of Low-combustible Polymer Blends
- Chinese Journal of Polymer Science 2026年44卷第3期页码：894-904
- Affiliations：
  
  a.Semenov Federal Research Center for Chemical Physics Russian Academy of Sciences, Moscow 119991, Russia
  b.Frumkin Institute of Physical Chemistry and Electrochemistry Russian Academy of Sciences, Moscow 119071, Russia
- Author bio：
  
  shaulov@polymer.chph.ras.ru
- Funds：
  
  This work was financially supported by Ministry of Science and Higher Education of the Russian Federation. The authors would like to thank the Centre for Collective Use of Scientific Equipment of Frumkin Institute of Physical chemistry and Electrochemistry Russian academy of sciences (IPCE RAS, Russia) for some measurements taken using the centre’s equipment.
- DOI：10.1007/s10118-025-3528-y
  中图分类号：
- 收稿：2025-10-09，
  
  录用：2025-12-08，
  
  网络首发：2026-02-06，
  
  纸质出版：2026-03-15
- Accepted：
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Novikov, V. A.; Stegno, E. V.; Grachev, A. V.; Aliev, A. D.; Bychkov, V. Y.; Plyusnina, I. O.; Nikulova, U. V.; Shapagin, A. V.; Shaulov, A. Y.; Berlin, A. A. Inorganic thermoplastic flame retardant as a basic component of low-combustible polymer blends. Chinese J. Polym. Sci. 2026, 44, 894–904

Viktor A. Novikov, Elena V. Stegno, Andrey V. Grachev, et al. Inorganic Thermoplastic Flame Retardant as a Basic Component of Low-combustible Polymer Blends[J]. Chinese Journal of Polymer Science, 2026, 44(3): 894-904.
Novikov, V. A.; Stegno, E. V.; Grachev, A. V.; Aliev, A. D.; Bychkov, V. Y.; Plyusnina, I. O.; Nikulova, U. V.; Shapagin, A. V.; Shaulov, A. Y.; Berlin, A. A. Inorganic thermoplastic flame retardant as a basic component of low-combustible polymer blends. Chinese J. Polym. Sci. 2026, 44, 894–904 DOI： 10.1007/s10118-025-3528-y.

Viktor A. Novikov, Elena V. Stegno, Andrey V. Grachev, et al. Inorganic Thermoplastic Flame Retardant as a Basic Component of Low-combustible Polymer Blends[J]. Chinese Journal of Polymer Science, 2026, 44(3): 894-904. DOI： 10.1007/s10118-025-3528-y.

摘要

Hybrid blends of inorganic and organic polymers are obtained by the extrusion mixing method. When the melt cools

phase decay occurs. The oxygen index of the flexible hybrid is 55.

Abstract

A new principle for producing fire-resistant polymer materials with increased deformation properties using a flame retardant not as a heterogeneous additive

but as a thermoplastic flame retardant in a hybrid polymer mixture with a polyhydrocarbon is considered. Hybrid polymer blends of low-molecular ammonium polyphosphate (APP) with an ethylene-vinyl acetate copolymer (EVA) with an APP content of 80 wt% with enhanced deformation properties were obtained by extrusion mixing at various temperatures in the range from 200 °C to 250 °C. A chemical scheme for the transformations of the components during the formation of the composite is proposed. X-ray diffraction analysis showed the formation of new crystalline structures of APP. The phase structure of the systems corresponding to the model of a dispersed-filled composite in which EVA plays the role of a matrix

determining the deformation of the mixture

and the filler is ammonium polyphosphate

was studied by scanning electron microscopy (SEM). The method of FTIR microscopy showed chemical interactions between EVA and APP with the formation of amide groups. The conditions for obtaining compositions characterized by heat resistance of 210 °C

oxygen index of 55 and ultimate elongation at drawing of 213% were established.

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references

[Rychlý, J.; Veselý, K.; Gál, E.; Kummer, M.; Jančář, J.; Rychlá, L. Use of thermal methods in the characterization of the high-temperature decomposition and ignition of polyolefins and EVA copolymers filled with Mg(OH) 2 , Al(OH) 3 and CaCO 3. Polym. Degrad. Stabil . 1990 , 30 , 57−72..

[Wang, N. N.; Xiang, D. H.; Mo, P. S.; Lu, Y. Flame-retardant low-density polyethylene with aluminium hydroxide/commercial fire retardants FR01 synergistic system. Adv. Mat. Res . 2013 , 652−654 , 485−489..

Xu, Zhi-sheng; Yan, L.; Chen, L. Synergistic flame retardant effects between aluminum hydroxide and halogen-free flame retardants in high density polyethylene composi tes. Procedia Eng. 2016 , 135 , 631−636..

Pasini, S. M.; Batistella, M. A.; Ulson de Souza, S. M. A. G.; Wang, J.; Hotza, D.; Ulson de Souza, A. A. Thermal degradation and flammability of TiO 2 –polyetherimide nanocomposite fibers. Polym. Bull. 2019 , 77 , 4937−4958..

Arzhakova, O. V.; Kopnov, A. Yu.; Chaplygin, D. K.; Yarysheva, A. Yu.; Dolgova, A. A. Flame-retardant nanocomposite polymeric materials based on high-density polyethylene and aluminum hydroxide nanoparticles. Russ. J. Gen. Chem. 2022 , 92 , 1963−1971..

Li, J.; Zhao, H.; Liu, H.; Sun, J.; Wu, J.; Liu, Q.; Zheng, Y.; Zheng, P. Recent advances in metal-family flame retardants: a review. RSC Adv. 2023 , 13 , 22639−22662..

Hasnat, M. R.; Hassan, M. K.; Saha, S. Flame retardant polymer composite and recent inclusion of magnesium hydroxide filler material: a bibliometric analysis towards further study scope. Fire. 2023 , 6 , 180..

Li, X.-M.; Yang, R.-J. Study on blooming of tetrabromobisphenol a bis(2,3-dibromopropyl ether ) in blends with polypropylene. J. Appl. Polym. Sci. 2006 , 101 , 20−24..

Chen, X.-S.; Yu, Z.-Z.; Liu, W.; Zhang, S. Synergistic effect of decabromodiphenyl ethane and montmorillonite on flame retardancy of polypropylene. Polym. Degrad. Stabil. 2009 , 94 , 1520−1525..

DiGangi, J.; Blum, A.; Bergman, Å.; de Wit, C. A.; Lucas, D.; Mortimer, D.; Schecter, A.; Scheringer, M.; Shaw, S. D.; Webster, T. F. San antonio statement on brominated and chlorinated flame retardants. Environ. Health Perspect. 2010 , 118 , A516−A518..

Kumar, M.; Barbhai, M. D. Sustainable fire safety solutions: bioactive natural polysaccharides and secondary metabolites as innovative fire retardants for textiles. Emerg. Manag. Sci. Tech. 2023 , 3 , 1−13..

Wang, J.; Li, L.; Yu, K.; Jia, Y.; Zhang, J.; Wang, Z.; Kwok Kit Richard, Y.; Lu, Y. Functionalized MXenes nanosheets inspired flame retardant epoxy composites: Mechanisms investigation and safety evaluation. Constr. Build. Mater. 2025 , 464 , 140124..

Li, Y.; Qi , L.; Liu, Y.; Qiao, J.; Wang, M.; Liu, X.; Li, S. Recent advances in halogen-free flame retardants for polyolefin cable sheath materials. Polymers. 2022 , 14 , 2876..

Shen, J.; Liang, J.; Lin, X.; Lin, H.; Yu, J.; Wang, S. The flame-retardant mechanisms and preparation of polymer composites and their potential application in construction engineering. Polymers. 2022 , 14 , 82..

Chulieva, O. Effect of flame retardant fillers on the fire resistance and physicalmechanical properties of polymeric compositions. Eastern-European J. Enterp. Technol. 2017 , 5 , 65−70..

Troitzsch, J. H. Fire performance durability of flame retardants in polymers and coatings. Adv. Ind. Eng. Polym. Res. 2024 , 7 , 263−272..

[Golynko-Vol’fson, S. L.; Sychev, M. M.; Sudakas, L. G.; Skoblo, L. I., in C hemical Foundations of the Technology and Application of Phosphate Binders and Coatings (in Russia), Khimiya, Leningrad, 1970 , p. 5.

[Sudakas, L.G., in Phosphate Binding Systems (in Russia), Quintet, St. Peterburg, 2008 , p. 100..

Shaulov, A. Yu.; Vladimirov, L. V.; Grachev, A. V.; Lalayan, V. M.; Nechvolodova, E. M.; Sakovich, R. A.; Skachkova, V. K.; Stegno, E. V.; Tkachenko, L. A.; Patlazhan, S. A.; Berlin, A. A. Inorganic and hybrid polymers and composites. Russ. J. Phys. Chem. B. 2020 , 14 , 183−189..

Tick, P. A. Water durable glasses with ultra low melting temperature. Phys. Chem. Glas. 1984 , 25 , 149−154..

Xu, X. J.; Day, D. E. Properties and structure of Sn-P-O-F glasses. Phys. Chem. Glas. 1990 , 31 , 183−188..

Ding, J. Y.; Shin, P. Y.; Yung, S. W.; Hsu, K. L.; Chin, T.-S. The properties and structure of Sn-Ca-P-O-F glasses. Mater. Chem. Phys. 2003 , 82 , 61−67..

Polishchuk, S. A.; Ignat’eva, L. N.; Marchenko, Yu. V.; Bouznik, V. M. Oxyfluoride glasses (a review). Glass Phys. Chem. 2011 , 37 , 1−20..

Brekhovskikh, M. N.; Dmitruk, L. N.; Moiseeva, L. V.; Fedorov, V. A. Glasses based on fluorides of metals of the I–IV groups: synthesis, properties, and application. Inorg. Mater. 2009 , 45 , 1477−1493..

Nenakhov, S. A.; Pimenova, V. P. Physico-chemical foaming fire-retardant coatings based on ammonium polyphosphate (review of the literature). Fire Explos. Saf. 2010 , 19 , 11−58..

Strauss, U. P.; Treitler, T. L. Degradation of Polyphosphates in Solution. I. Kinetics and mechanism of the hydrolysis at branching points in polyphosphate chains. J. Am. Chem. Soc. 1956 , 16 , 2161−2169..

de Jager, H.-J.; Heyns, A. M. Kinetics of acid-catalyzed hydrolysis of a polyphosphate in water. J. Phys. Chem. 1998 , 102 , 2838−2841..

Torres-Dorante, L. O.; Claassen, N.; Steingrobe, B.; Olfs, H. W. Hydrolysis rates of inorganic polyphosphates in aqueous solution as well as in soils and effects on P availability. J. Plant Nutr. Soil Sci. 2005 , 168 , 352−358..

Siat, С.; Le Bras, M.; Bourbigot, S. Combustion behaviour of ethylene vinyl acetate copolymer-based intumescent formulations using oxygen consumption calorimetry. Fire Mater. 1998 , 22 , 119−128..

Mosnácek, J.; Basfar, A. A.; Shukri, T. M.; Bahattab, M. A. Poly(ethylene vinyl acetate) (EVA)/low density polyethylene (LDPE)/ammonium polyphosphate (APP) composites cross-linked by dicumyl peroxide for wire and cable applications. Polym. J. 2008 , 40 , 460−464..

Vahabi, H.; Gholami, F.; Karaseva, V.; Laoutid, F.; Mangin, R.; Sonnier, R.; Saeb, M. R. Novel nanocomposites based on poly(ethylene-co-vinyl acetate) for coating applications: the complementary actions of hydroxyapatite, MWCNTs and ammonium polyphosphate on flame retardancy. Prog. Org. Coat. 2017 , 117 , 207−217..

Galiguzov, A. A.; Yashin, N. V.; Avdeev, V. V. Thermal properties of materials based on ethylene vinyl acetate and various flame retardants during thermal oxidative degradation. Plastičeskie massy. 2024 , 5 , 3−10..

Cai, X. X.; Wang, D. Y.; Peng, H. Q. Flame-retardant mechanism of EVA modified with expandable graphite and ammonium polyphosphate. Polym. Mater. Sci. Eng. 2008 , 24 , 109−112..

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 , 30436−30444..

Presti, С.; Ferry, L.; Alauzin, J. G. Functionalized nanodiamond as potential synergist in flame-retardant ethylene vinyl acetate. Diamond Relat. Mater. 2017 , 76 , 141−149..

Lou, F.; Wu, K.; Wang, Q.; Qian, Z.; Li, S.; Guo, W. Improved flame-retardant and ceramifiable properties of eva composites by combination of ammonium polyphosphate and aluminum hydroxide. Polymers 2019 , 11 , 125..

Xu, J.; Ou, H.; Shan, X.; Liu, B.; Jiang, J.; Xu, G. Investigation of novel intumescent flame-retardant low-density polyethylene based on SiO2@MAPP and double pentaerythritol. J. Appl. Polym. Sci. 2020 , 137 , 49242..

Batting, A.; Sanchez-Olivares, G.; Rockel, D.; Maldonado-Santoyo, M.; Schartel, B. Waste not, want not: the use of le ather waste in flame retarded EVA. Mater. Design. 2021 , 210 , 110100..

[Wang, Z. Z.; Zhang, B.; Jiang, P. K. Flammability and mechanical properties of eva composites containing ammonium polyphosphate microcapsules. Adv. Mat. Res . 2012 , 466−467 , 267−271..

Wang, B.; Qian, X.; Shi, Y.; Yu, B.; Hong, N.; Song, L.; Hu, Y. Cyclodextrin microencapsulated ammonium polyphosphate: preparation and its performance on the thermal, flame retardancy and mechanical properties of ethylene vinyl acetate copolymer. Compos. B: Eng. 2015 , 69 , 22−30..

Prut, E. V.; Zelenetskii, A. N. Chemical modification and blending of polymers in an extruder reactor. Russ. Chem. Rev. 2001 , 70 , 65−79..

Urman, K.; Otaigbe, J. U. New phosphate glass/polymer hybrids‒Current status and future prospects. Prog. Polym. Sci. 2007 , 32 , 1462−1498..

Shaulov, A. Yu.; Vladimirov, L. V.; Avramenko, N. V.; Grachev, A. V.; Parfenova, A. M. Low-temperature phosphate composition. Russ. Chem. Bull. 2022 , 71 , 2103−2107..

Stegno, E. V.; Bychkov, V. Yu.; Abramova, N. A.; Grachev, A. V.; Lalayan, V. M.; Shaulov, A. Yu.; Berlin, A. A. Low-melting hybrid thermoplastics of ammonium polyphosphate. Russ. J. Phys. Chem. B. 2024 , 18 , 740−744..

Shaulov, A. Yu.; Grachev, A. V.; Avramenko, N. V.; Bychkov, V. Yu.; Lyubimov, A. V.; Berlin, A. A. Ultralow melting ammonium polyphosphate compounds. Glass Phys. Chem. 2024 , 50 , 61−67..

Plyusnina, I. O.; Budylin, N. Yu.; Shapagin, A. V. Phase equilibria, diffusion and structure in the epoxypolycaprolactone system. Polymers 2023 , 15 , 117..

[Dechant, J. in Ultrarotspektroskopische Untersuchungen an Polymeren , Akademie-Verlag, Berlin, 1972 , p. 157.

[Kuptsov, A. Kh.; Zhizhin, G. N., in FT Raman and FTIR Spectra of Polymers (in Russia), Technosphera, Moscow, 2013 , p. 29.

Cheng, J.; Niu, S.; Ma, D.; Zhou, Y.; Zhang, F.; Qu, W.; Wang, D.; Li, S.; Zhang, X.; Chen, X. Effects of ammonium polyphosphate microencapsulated on flame retardant and mechanical properties of the rigid polyurethane foam. J. Appl. Polym. Sci. 2020 , 137 , 49591..

Yang, Y.; Dai, Z.; Liu, M.; Jiang, H.; Fan, C.; Wang, B.; Tang, G.; Wang, H. Flame retardant rigid polyurethane foam composites based on microencapsulated ammonium polyphosphate and microencapsulated expanded graphite. J. Macromol. Sci. 2021 , 58 , 659−668..

Wang, W.; McMurray, J. S. A selective method for the preparation of primary amides: synthesis of Fmoc-l-4-carboxamidophenylalanine and other compounds. Tetrahedron Lett. 1999 , 40 , 2501−2504..

Li, X.-Y.; Kang, J.-X.; Ma, Y.-N.; Chen, X. Synthesis of primary amides by a one-pot reaction of ammonia gas with esters or tertiary amides. Cell Rep. Phys. Sci. 2024 , 5 , 102337..

Nakamura, T.; Takayanagi, H.; Nakahata, M.; Okubayashi, T.; Baba, H.; Ishii, Y.; Watanabe, G.; Tanabe, D.; Nabeshima, T. Amide cyclodextrin that recognises monophosphate anions in har mony with water molecules. Chem. Sci. 2025 , 16 , 171−181..

[Nielsen, L. E.; Landel, R. F., in Mechanical Properties of Polymers and Composites , 2nd ed, Marcel Dekker, New York, 1994 , p. 124.

Bazhenov, S. L. The effect of particles on failure modes of filled polymers. Polym. Eng. Sci. 1995 , 35 , 813−822..

Ponomareva, N. R.; Goncharuk, G. P.; Grigor'ev, Yu. A.; Obolonkova, E. S.; Serenko, O. A. Deformation behavior of composites based on low-density polyethylene and hollow glass spheres. Russ. J. Appl. Chem. 2009 , 82 , 1472−1478..

[Miyamoto, K.; Huang, X.; Hashimoto, N.; Fujita, O.; Fernandez-Pello, C. Limiting oxygen concentration (LOC) of burning polyethylene insulated wires under external radiation. Fire Saf. J. 2016 , 86 , 32−40..

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