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Facile two-step phosphazine-based network coating for flame retardant cotton

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Abstract

There is a need for durable flame retardant treatments for cotton fabric in order to reduce the risk associated with fires. Many current industrial treatments make use of toxic halogenated organic flame retardants or utilize formaldehyde-evolving chemistry. A facile two-step process is described to coat cotton fabric based on a spontaneous crosslinking reaction between branched polyethyleneimine (PEI) and hexachlorocyclotriphosphazene (HCCP). A coating produced from solutions of 10 wt% PEI and 5 wt% HCCP endows the cotton fabric with a high limiting oxygen index (33.8%), self-extinguishing behavior in open flame testing, and an 85% reduction in peak heat release rate. This treated fabric also maintains self-extinguishing behavior after a simulated washing test. This unique combination of properties is the result of a strongly networked coating that intumesces during burning. The simplicity of this treatment and its formaldehyde-free chemistry make it a good option for replacing organo-halogen and formaldehyde-evolving treatments.

Graphic abstract

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Abbreviations

PEI:

Branched polyethyleneimine

HCCP:

Hexachlorocyclotriphosphazene

Poly(PEI-co-HCCP):

Crosslinked polymers produced by reaction between PEI and HCCP

LOI:

Limiting oxygen index

MCC:

Microscale combustion calorimeter

TGA:

Thermogravimetric analysis

SEM:

Scanning electron microscopy

TG–FTIR:

Thermogravimetry–Fourier transform infrared spectroscopy

HRR:

Heat release rate

Tp :

Temperature at peak HRR

THR:

Total heat release

References

  1. Alongi J, Malucelli G (2015) Cotton flame retardancy: state of the art and future perspectives. RSC Adv 5:24239–24263. https://doi.org/10.1039/C5RA01176K

  2. Brancatelli G, Colleoni C, Massafra MR, Rosace G (2011) Effect of hybrid phosphorus-doped silica thin films produced by sol–gel method on the thermal behavior of cotton fabrics. Polym Degrad Stabil 96:483–490. https://doi.org/10.1016/j.polymdegradstab.2011.01.013

  3. Castellano A, Colleoni C, Iacono G, Mezzi A, Plutino MR, Malucelli G, Rosace G (2019) Synthesis and characterization of a phosphorous/nitrogen based sol-gel coating as a novel halogen- and formaldehyde-free flame retardant finishing for cotton fabric. Polym Degrad Stabil 162:148–159. https://doi.org/10.1016/j.polymdegradstab.2019.02.006

  4. Chan SY, Si L, Lee KI, Ng PF, Chen L, Yu B, Hu Y, Yuen RKK, Xin JH, Fei B (2018) A novel boron–nitrogen intumescent flame retardant coating on cotton with improved washing durability. Cellulose 25:843–857. https://doi.org/10.1007/s10570-017-1577-2

  5. Chen S, Li X, Li Y, Sun J (2015) Intumescent flame-retardant and self-healing superhydrophobic coatings on cotton Fabric. ACS Nano 9:4070–4076. https://doi.org/10.1021/acsnano.5b00121

  6. Dutkiewicz M, Przybylak M, Januszewski R, Maciejewski H (2018) Synthesis and flame retardant efficacy of hexakis (3-(triethoxysilyl) propyloxy) cyclotriphosphazene/silica coatings for cotton fabrics. Polym Degrad Stabil 148:10–18. https://doi.org/10.1016/j.polymdegradstab.2017.11.018

  7. Edwards B, Hauser P, El-Shafei A (2015) Nonflammable cellulosic substrates by application of novel radiation-curable flame retardant monomers derived from cyclotriphosphazene. Cellulose 22:275–287. https://doi.org/10.1007/s10570-014-0497-7

  8. Fontenot KR, Nguyen MM, Al-Abdul-Wahid MS, Easson MW, Chang S, Lorigan GA, Condon BD (2015) The thermal degradation pathway studies of a phosphazene derivative on cotton fabric. Polym Degrad Stabil 120:32–41. https://doi.org/10.1016/j.polymdegradstab.2015.04.032

  9. Gordon S (2006) Cotton fibre quality. In: Gordon S, Hsieh Y-L (eds) Cotton: science and technology. Woodhead Publishing, Cambridge, pp 68–95

  10. Haile M, Fincher C, Fomete S, Grunlan JC (2015) Water-soluble polyelectrolyte complexes that extinguish fire on cotton fabric when deposited as pH-cured nanocoating. Polym Degrad Stabil 114:60–64. https://doi.org/10.1016/j.polymdegradstab.2015.01.022

  11. Horrocks A (1986) Flame-retardant finishing of textiles. Rev Prog Color Relat Top 16:62–101. https://doi.org/10.1111/j.1478-4408.1986.tb03745.x

  12. Jiang Z, Xu D, Ma X, Liu J, Zhu P (2019) Facile synthesis of novel reactive phosphoramidate siloxane and application to flame retardant cellulose fabrics. Cellulose 26:5783–5796. https://doi.org/10.1007/s10570-019-02465-2

  13. Kasprzak A, Popławska M, Bystrzejewski M, Łabędź O, Grudziński IP (2015) Conjugation of polyethylenimine and its derivatives to carbon-encapsulated iron nanoparticles. RSC Adv 5:85556–85567. https://doi.org/10.1039/C5RA17912B

  14. Köhler J, Kühl S, Keul H, Möller M, Pich A (2014) Synthesis and characterization of polyamine-based cyclophosphazene hybrid microspheres. J Polym Sci Part A Polym Chem 52:527–536. https://doi.org/10.1002/pola.27028

  15. Laufer G, Kirkland C, Morgan AB, Grunlan JC (2012) Intumescent multilayer nanocoating, made with renewable polyelectrolytes, for flame-retardant cotton. Biomacromol 13:2843–2848. https://doi.org/10.1021/bm300873b

  16. Li X, Chen H, Wang W, Liu Y, Zhao P (2015) Synthesis of a formaldehyde-free phosphorus–nitrogen flame retardant with multiple reactive groups and its application in cotton fabrics. Polym Degrad Stabil 120:193–202. https://doi.org/10.1016/j.polymdegradstab.2015.07.003

  17. Li S, Lin X, Liu Y, Li R, Ren X, Huang TS (2019) Phosphorus–nitrogen–silicon-based assembly multilayer coating for the preparation of flame retardant and antimicrobial cotton fabric. Cellulose 26:4213–4223. https://doi.org/10.1007/s10570-019-02373-5

  18. Liu W, Chen L, Wang Y-Z (2012) A novel phosphorus-containing flame retardant for the formaldehyde-free treatment of cotton fabrics. Polym Degrad Stabil 97:2487–2491. https://doi.org/10.1016/j.polymdegradstab.2012.07.016

  19. Liu L, Huang Z, Pan Y, Wang X, Song L, Hu Y (2018a) Finishing of cotton fabrics by multi-layered coatings to improve their flame retardancy and water repellency. Cellulose 25:4791–4803. https://doi.org/10.1007/s10570-018-1866-4

  20. Liu Y, Wang Q-Q, Jiang Z-M, Zhang C-J, Li Z-F, Chen H-Q, Zhu P (2018b) Effect of chitosan on the fire retardancy and thermal degradation properties of coated cotton fabrics with sodium phytate and APTES by LBL assembly. J Anal Appl Pyrol 135:289–298. https://doi.org/10.1016/j.jaap.2018.08.024

  21. Lyon RE, Walters R (2002) A microscale combustion calorimeter. Federal Aviation Administration, Washington, DC

  22. Mayer-Gall T, Knittel D, Gutmann JS, Opwis K (2015) Permanent flame retardant finishing of textiles by allyl-functionalized polyphosphazenes. ACS Appl Mater Interfaces 7:9349–9363. https://doi.org/10.1021/acsami.5b02141

  23. Morgan AB (2019) The future of flame retardant polymers-unmet needs and likely new approaches. Polym Rev 59:25–54. https://doi.org/10.1080/15583724.2018.1454948

  24. Nguyen T-M, Chang S, Condon B, Slopek R, Graves E, Yoshioka-Tarver M (2013) Structural effect of phosphoramidate derivatives on the thermal and flame retardant behaviors of treated cotton cellulose. Ind Eng Chem Res 52:4715–4724. https://doi.org/10.1021/ie400180f

  25. Nie S, Jin D, Yang J-N, Dai G, Luo Y (2019) Fabrication of environmentally-benign flame retardant cotton fabrics with hydrophobicity by a facile chemical modification. Cellulose 26:5147–5158. https://doi.org/10.1007/s10570-019-02431-y

  26. Pan H, Song L, Ma L, Pan Y, Liew KM, Hu Y (2014) Layer-by-layer assembled thin films based on fully biobased polysaccharides: chitosan and phosphorylated cellulose for flame-retardant cotton fabric. Cellulose 21:2995–3006. https://doi.org/10.1007/s10570-014-0276-5

  27. Qiu S, Xin W, Yu B, Feng X, Mu X, Yuen RKK, Yuan H (2017) Flame-retardant-wrapped polyphosphazene nanotubes: a novel strategy for enhancing the flame retardancy and smoke toxicity suppression of epoxy resins. J Hazard Mater 325:327–339. https://doi.org/10.1016/j.jhazmat.2016.11.057

  28. Shafizadeh F, Bradbury AG, DeGroot WF, Aanerud TW (1982) Role of inorganic additives in the smoldering combustion of cotton cellulose. Ind Eng Chem Prod Res Dev 21:97–101. https://doi.org/10.1021/i300005a021

  29. Tawiah B, Yu B, Yang W, Yuen RKK, Fei B (2019) Facile flame retardant finishing of cotton fabric with hydrated sodium metaborate. Cellulose 26:4629–4640. https://doi.org/10.1007/s10570-019-02371-7

  30. Wang S, Sui X, Li Y, Li J, Xu H, Zhong Y, Zhang L, Mao Z (2016) Durable flame retardant finishing of cotton fabrics with organosilicon functionalized cyclotriphosphazene. Polym Degrad Stabil 128:22–28. https://doi.org/10.1016/j.polymdegradstab.2016.02.009

  31. Wang D, Zhong L, Zhang C, Zhang F, Zhang G (2018) A novel reactive phosphorous flame retardant for cotton fabrics with durable flame retardancy and high whiteness due to self-buffering. Cellulose 25:5479–5497. https://doi.org/10.1007/s10570-018-1964-3

  32. Weil ED, Levchik SV (2008) Flame retardants in commercial use or development for textiles. J Fire Sci 26:243–281. https://doi.org/10.1177/0734904108089485

  33. Wen P, Tai Q, Hu Y, Yuen RKK (2016) Novel cyclotriphosphazene-based intumescent flame retardant (IFR) against the combustible polypropylene. Ind Eng Chem Res 55:298018–298024. https://doi.org/10.1021/acs.iecr.6b01527

  34. Xu F, Zhong L, Xu Y, Zhang C, Zhang F, Zhang G (2019) Highly efficient flame-retardant and soft cotton fabric prepared by a novel reactive flame retardant. Cellulose 26:4225–4240. https://doi.org/10.1007/s10570-019-02374-4

  35. Yang G, Wu W-H, Wang Y-H, Jiao Y-H, Lu L-Y, Qu H-Q, Qin X-Y (2018) Synthesis of a novel phosphazene-based flame retardant with active amine groups and its application in reducing the fire hazard of epoxy resin. J Hazard Mater 366:78–87. https://doi.org/10.1016/j.jhazmat.2018.11.093

  36. Zhao B, Liu Y-T, Zhang C-Y, Liu D-Y, Li F, Liu Y-Q (2017) A novel phosphoramidate and its application on cotton fabrics: synthesis, flammability and thermal degradation. J Anal Appl Pyrol 125:109–116. https://doi.org/10.1016/j.jaap.2017.04.011

  37. Zope IS, Foo S, Seah DGJ, Akunuri AT, Dasari A (2017) Development and evaluation of a water-based flame retardant spray coating for cotton fabrics. ACS Appl Mater Interfaces 9:40782–40791. https://doi.org/10.1021/acsami.7b09863

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Acknowledgments

The authors want to acknowledge the National Natural Science Foundation of China (Grant 21975226) and China Scholarship Council (CSC: 201808140038). The authors wish to express thanks to Miss Kai-Li Song for her assistance with limiting oxygen index (LOI) tests.

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Correspondence to Bin Zhao or Jaime C. Grunlan.

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Zhao, B., Kolibaba, T.J., Lazar, S. et al. Facile two-step phosphazine-based network coating for flame retardant cotton. Cellulose (2020). https://doi.org/10.1007/s10570-020-03047-3

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Keywords

  • Flame retardant
  • Cotton
  • Hexachlorocyclotriphosphazene
  • Branched polyethyleneimine