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Flame retardant polyvinyl alcohol composite with excellent comprehensive properties prepared using Cu2O/chitosan and phosphorus-based flame retardants

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Abstract

Polyvinyl alcohol (PVA) has good film-forming and barrier properties and can be used as packaging and biomedical materials, etc. However, PVA burns easily and is prone to melt dropping, limiting its wider application. In this study, Cu2O/Cs was prepared by coating chitosan (Cs) on the surface of cuprous oxide (Cu2O), and mixed with ammonium polyphosphate (APP) and phytic acid (PA) to prepare PVA composites. The results showed that the limiting oxygen index (LOI) value of the PVA composite with 8% (by weight) APP and 2% (by weight) Cu2O/Cs as flame retardants was 30.6%, which was 50.7% higher than that of pure PVA. Compared with pure PVA, its composite peak heat release rate (pHRR) was significantly reduced by 81.1%, and its total heat release rate (THR) was also markedly reduced by 67.7%, while its time to ignition (TTI) was increased by 41 s. The main reasons were that the gas generated by APP decomposition during heating reduced the concentration of combustible gas, the generated phosphorus-containing substances promoted the dehydration and carbonization of PVA, and Cu2O and chitosan (Cs) improved the compactness of the carbon layer. In particular, the incorporation of Cu2O/Cs improved the mechanical properties of our PVA composites compared with those containing only APP and PA. In short, the combination of Cu2O/Cs and phosphorus-based flame retardants improved the flame retardant performance of PVA at low additions while taking into account the mechanical properties. This is expected to expand the range of applications of PVA.

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Data availability

The data that support the findings of this study are available from the corresponding author upon reasonable request.

References

  1. Chen J, Zheng M, Tan KB, Lin J, Chen M, Zhu Y (2022) Polyvinyl alcohol/xanthan gum composite film with excellent food packaging, storage and biodegradation capability as potential environmentally-friendly alternative to commercial plastic bag. Int J Biol Macromol 212:402411

    Article  Google Scholar 

  2. Qiang Y, Jing G, Sen Z, Fucheng G, Yue Y, Qiang Y, Xin Z, Yi X (2023) PVA/PEO/PVA-g-APEG nanofiber membranes with cytocompatibility and anti-cell adhesion for biomedical applications. Colloid Surface A 657:130638

    Article  Google Scholar 

  3. Yang J, Chan KY, Venkatesan H, Kim E, Adegun MH, Lee JH, Shen X, Kim JK (2022) Superinsulating BNNS/PVA composite aerogels with high solar reflectance for energy-efficient buildings. Nano-Micro Lett 14:54

    Article  CAS  Google Scholar 

  4. Shu-juan Y, Shi-yan L, Deng-feng T, Yong-fei Z (2021) Nitrogen and phosphorus co-doped carbon dots for developing highly flame retardant poly (vinyl alcohol) composite films. Eur Polym J 164:110970

    Google Scholar 

  5. Shui Y, Chao C, Keji L, Junling W, Zhirong W, Haobo Z, Wei W, Yan Z, Yan Q (2023) Fire-safe epoxy composite realized by MXenes based nanostructure with vertically arrayed MOFs derived from interfacial assembly strategy. Chem Eng J 465:143039

    Article  Google Scholar 

  6. Qinghong K, Haojie Z, Shuai H, Ting W, Fang Z, Yunlong Z, Yuan W, Junhao Z (2022) Influence of multiply modified FeCu-montmorillonite on fire safety and mechanical performances of epoxy resin nanocomposites. Thermochim Acta 707:179112

    Article  Google Scholar 

  7. Jia P, Zhu Y, Lu J, Wang B, Song L, Wang B, Hu Y (2022) Multifunctional fireproof electromagnetic shielding polyurethane films with thermal management performance. Chem Eng J 439:135673

    Article  CAS  Google Scholar 

  8. Sun FC, Fu JH, Peng YX, Jiao XM, Liu H, Du FP, Zhang YF (2021) Dual-functional intumescent fire-retardant/self-healing water-based plywood coatings. Prog Org Coat 154:106187

    Article  CAS  Google Scholar 

  9. Luo L, Liu W, Zhai L, Xie W, Gan L, Wang H, Huang J, Liu C (2020) Synergistic flame retardancy of aqueous hybridization between iron phosphonate and ammonium polyphosphate towards polyethyleneimine-based foam. Iran Polym J 29:265–274

    Article  CAS  Google Scholar 

  10. Ozlem Albayrak H, Mehmet Atilla T (2023) Synergistic effect of organically modified sepiolite clay in intumescent flame retardant polyolefin elastomer-based cable outer sheath compounds. Iran Polym J32:93–102

    Article  Google Scholar 

  11. Yide L, Jiuyong Y, Kai L, Xiankai L, Yanzhi X (2023) Enhanced flame retardant performance of poly(vinyl alcohol) composites based on phosphorus-metal ion synergistic effect. New J Chem 47:15942–15950

    Article  Google Scholar 

  12. Lin JS, Liu Y, Wang DY, Qin Q, Wang YZ (2011) Poly(vinyl alcohol)/ammonium polyphosphate systems improved simultaneously both fire retardancy and mechanical properties by montmorillonite. Ind Eng Chem Res 50:9998–10005

    Article  CAS  Google Scholar 

  13. Jiang M, Zhu Q, Song X, Gu Y, Zhang P, Li C, Cui J, Ma J, Tie Z, Jin Z (2022) Batch-scale synthesis of nanoparticle-agminated three-dimensional porous Cu@Cu2O microspheres for highly selective electrocatalysis of nitrate to ammonia. Environ Sci Technol 56:10299–10307

    Article  CAS  PubMed  Google Scholar 

  14. Chen MJ, Wang X, Li XL, Liu XY, Zhong L, Wang HZ, Liu ZG (2017) The synergistic effect of cuprous oxide on an intumescent flame-retardant epoxy resin system. RSC Adv 7:35619–35628

    Article  CAS  Google Scholar 

  15. Yang Z, Li H, Niu G, Wang J, Zhu D (2021) Poly(vinylalcohol)/chitosan-based high-strength, fire-retardant and smoke-suppressant composite aerogels incorporating aluminum species via freeze drying. Compos B Eng 219:108919

    Article  CAS  Google Scholar 

  16. Zhang Y, Jiang M, Zhang Y, Cao Q, Wang X, Han Y, Sun G, Li Y, Zhou J (2019) Novel lignin-chitosan-PVA composite hydrogel for wound dressing. Mater Sci Eng C 104:110002

    Article  CAS  Google Scholar 

  17. Mombini S, Mohammadnejad J, Bakhshandeh B, Narmani A, Nourmohammadi J, Vahdat S, Zirak S (2019) Chitosan-PVA-CNT nanofibers as electrically conductive scaffolds for cardiovascular tissue engineering. Int J Biol Macromol 140:278–287

    Article  CAS  PubMed  Google Scholar 

  18. Sivakami MS, Gomathi T, Venkatesan J, Jeong HS, Kim SK, Sudha PN (2013) Preparation and characterization of nano chitosan for treatment wastewaters. Int J Biol Macromol 57:204–212

    Article  CAS  PubMed  Google Scholar 

  19. Wan Ngah WS, Endud CS, Mayanar R (2002) Removal of copper(II) ions from aqueous solution onto chitosan and cross-linked chitosan beads. React Funct Polym 50:181–190

    Article  Google Scholar 

  20. Yan J, Li M, Wang H, Lian X, Fan Y, Xie Z, Niu B, Li W (2021) Preparation and property studies of chitosan-PVA biodegradable antibacterial multilayer films doped with Cu2O and nano-chitosan composites. Food Control 126:108049

    Article  CAS  Google Scholar 

  21. Zhang F, Li Y, GuYE WZ, Wang C (2011) One-pot solvothermal synthesis of a Cu2O/Graphene nanocomposite and its application in an electrochemical sensor for dopamine. Mikrochim Acta 173:103–109

    Article  CAS  Google Scholar 

  22. Liu S, Kang M, Yan F, Peng D, Yang Y, He L, Wang M, Fang S, Zhang Z (2015) Electrochemical DNA biosensor based on microspheres of cuprous oxide and nano-chitosan for Hg(II) detection. Electrochim Acta 160:64–73

    Article  CAS  Google Scholar 

  23. Sreedhar B, Aparna Y, Sairam M, Hebalkar N (2007) Preparation and characterization of HAP/carboxymethyl chitosan nanocomposites. J Appl Polym Sci 105:928–934

    Article  CAS  Google Scholar 

  24. Wu Y, Xu L, Jiang Y (2020) Preparation and thermal properties of modified Cu2O/polypropylene (PP) composite. Materials 13:309

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  25. Holland BJ, Hay JN (2001) The thermal degradation of poly(vinyl alcohol). Polymer 42:6775–6783

    Article  CAS  Google Scholar 

  26. Wenzong X, Chengwen X, Julan L, Ding D, Yi Z, Yaocheng Z (2022) A guanidine phosphate-assisted boron nitride network enabled simultaneous improvements in flame resistance and thermal conductivity of polyvinyl alcohol (PVA). Polym Degrad Stab 206:110178

    Article  Google Scholar 

  27. Li J, Li Y, Song Y, Niu S, Li N (2017) Ultrasonic-assisted synthesis of polyvinyl alcohol/phytic acid polymer film and its thermal stability, mechanical properties and surface resistivity. UltrasonSonochem 39:853–862

    CAS  Google Scholar 

  28. Zhang Z, Li X, Ma Z, Ning H, Zhang D, Wang Y (2020) A facile and green strategy to simultaneously enhance the flame retardant and mechanical properties of poly(vinyl alcohol) by introduction of a bio-based polyelectrolyte complex formed by chitosan and phytic acid. Dalton Trans 49:11226–11237

    Article  CAS  PubMed  Google Scholar 

  29. Wang Z, Yan F, Pei H, Li J, Cui Z, He B (2018) Antibacterial and environmentally friendly chitosan/polyvinyl alcohol blend membranes for air filtration. Carbohydr Polym 198:241–248

    Article  CAS  PubMed  Google Scholar 

  30. Reguieg F, Ricci L, Bouyacoub N, Belbachir M, Bertoldo M (2019) Thermal characterization by DSC and TGA analyses of PVA hydrogels with organic and sodium MMT. Polym Bull 77:929–948

    Article  Google Scholar 

  31. Xiang A, Yin D, He Y, Li Y, Tian H (2020) Multifunctional nucleating agents with simultaneous plasticizing, solubilizing, nucleating and their effect on polyvinyl alcohol foams. J Supercrit Fluids 170:105156

    Article  Google Scholar 

  32. Zhirong X, Zihui X, Ran T, Liangchen M, Jing Z, Junfeng X, Tao Y (2022) Combustion and thermal properties of flame retardant polyurethane foam with ammonium polyphosphate synergized by phosphomolybdic acid. Front Mater 9:944368

    Article  Google Scholar 

  33. Xu W, Wang G, Xu J, Liu Y, Chen R, Yan H (2019) Modification of diatomite with melamine coated zeolitic imidazolate framework-8 as an effective flame retardant to enhance flame retardancy and smoke suppression of rigid polyurethane foam. J Hazard Mater 379:120819

    Article  CAS  PubMed  Google Scholar 

  34. Ghada M, Aksam A, Heba A (2021) Preparation of highly efficient chitosan-based flame retardant coatings with good antibacterial properties for cotton fabrics. Prog Org Coat 163:106627

    Google Scholar 

  35. Xu W, Liu L, Zhang B, Hu Y, Xu B (2016) Effect of molybdenum trioxide-loaded graphene and cuprous oxide-loaded graphene onflame retardancy and smoke suppression of polyurethane elastomer. Ind Eng Chem Res 55:4930–4941

    Article  CAS  Google Scholar 

  36. Tu H, Wang J (1996) An XPS investigation of thermal degradation and charring processes for PVC and PVC/Cu2O systems in the condensed phaseII. Polym Degrad Stab 54:195–203

    Article  CAS  Google Scholar 

  37. Zhou Y, Chu F, Qiu S, Guo W, Zhang S, Xu Z, Hu W, Hu Y (2020) 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 399:123015

    Article  CAS  PubMed  Google Scholar 

Download references

Acknowledgements

The authors express their gratitude to the Natural Science Foundation of Anhui Province (Joint Foundation) (2208085UM03) and Anhui Province Key Research and Development Program (202304a05020023) for their support.

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Authors and Affiliations

  1. Anhui Jianzhu University, 292 Ziyun Road, Hefei, 230601, Anhui, China

    Wenzong Xu, Yi Zhang, Ziyi Xuan & Maotong Zhao

  2. Anhui Wanwei Group Co., Ltd., 56 Chaowei Road, Chaohu, 238000, Anhui, China

    Julan Liu & Lulu Su

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  1. Wenzong Xu
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  2. Yi Zhang
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Correspondence to Wenzong Xu.

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Xu, W., Zhang, Y., Liu, J. et al. Flame retardant polyvinyl alcohol composite with excellent comprehensive properties prepared using Cu2O/chitosan and phosphorus-based flame retardants. Iran Polym J (2024). https://doi.org/10.1007/s13726-024-01327-4

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