Preparation of a halogen-free P/N/Si flame retardant monomer with reactive siloxy groups and its application in cotton fabrics

doi:10.1016/j.cjche.2016.09.015

Abstract

Abstract: A novel halogen-free phosphorus-nitrogen-silicon flame retardant monomer with reactive siloxy groups, N-(diphenylphosphino)-1,1-diphenyl-N-(3-(triethoxysilyl)propyl) phosphinamine (DPTA) has been synthesized and was applied to the fire-resistant finishing of cotton fabrics. The molecular structure of DPTA has been well characterized by elemental analysis, FTIR, ¹H NMR, and ³¹P NMR spectroscopies. The chemically-grafted cotton fabrics, which were treated with 25 wt% DPTA, were obtained and confirmed by attenuated total reflectance Fourier infrared spectroscopy (ATR-FTIR). The flame retardancy and thermal property of the treated samples were investigated by limited oxygen index (LOI), vertical flammability test (VFT), thermogravimetric analysis (TGA) and microscale combustion calorimeter (MCC). It is noted that in vertical flammability test, the treated samples extinguished immediately upon removing the ignition source, whereas the untreated one was completely burned out. Furthermore, TGA and MCC tests revealed that the treated samples produced a high char formation and a low heated release during combustion. The surface morphology of the untreated and treated samples and the char residues after LOI tests were observed by scanning electron microscopy (SEM). Therefore, all the results showed that the treated cotton fabrics with 25 wt% DPTA apparently improved the fireresistant and thermal performances.

Key words: P/N/Si flame retardant, Synthesis, Cotton fabrics, Flame retardancy

摘要： A novel halogen-free phosphorus-nitrogen-silicon flame retardant monomer with reactive siloxy groups, N-(diphenylphosphino)-1,1-diphenyl-N-(3-(triethoxysilyl)propyl) phosphinamine (DPTA) has been synthesized and was applied to the fire-resistant finishing of cotton fabrics. The molecular structure of DPTA has been well characterized by elemental analysis, FTIR, ¹H NMR, and ³¹P NMR spectroscopies. The chemically-grafted cotton fabrics, which were treated with 25 wt% DPTA, were obtained and confirmed by attenuated total reflectance Fourier infrared spectroscopy (ATR-FTIR). The flame retardancy and thermal property of the treated samples were investigated by limited oxygen index (LOI), vertical flammability test (VFT), thermogravimetric analysis (TGA) and microscale combustion calorimeter (MCC). It is noted that in vertical flammability test, the treated samples extinguished immediately upon removing the ignition source, whereas the untreated one was completely burned out. Furthermore, TGA and MCC tests revealed that the treated samples produced a high char formation and a low heated release during combustion. The surface morphology of the untreated and treated samples and the char residues after LOI tests were observed by scanning electron microscopy (SEM). Therefore, all the results showed that the treated cotton fabrics with 25 wt% DPTA apparently improved the fireresistant and thermal performances.

关键词: P/N/Si flame retardant, Synthesis, Cotton fabrics, Flame retardancy

Peihua Zhao, Kuankuan Xiong, Wentao Wang, Yaqing Liu. Preparation of a halogen-free P/N/Si flame retardant monomer with reactive siloxy groups and its application in cotton fabrics[J]. , 2017, 25(9): 1322-1328.

References

[1] A.R. Horrocks, Developments in flame retardants for heat and fire resistant textiles-The role of char formation and intumescence, Polym. Degrad. Stab. 54(1996) 143-154.
[2] J.V. Beninate, B.J. Trask, G.L. Drake, Durable flame-retardant treatments for blends of cotton, wool, and polyester, Text. Res. J. 51(1981) 217-224.
[3] A. Abou-Okeil, S.M. El-Sawy, F.A. Abdel-Mohdy, Flame retardant cotton fabrics treated with organophosphorus polymer, Carbohydr. Polym. 92(2013) 2293-2298.
[4] A.R. Horrocks, B.K. Kandola, P.J. Davies, S. Zhang, S.A. Padbury, Developments in flame retardant textiles-A review, Polym. Degrad. Stab. 88(2005) 3-12.
[5] T.M.D. Nguyen, S. Chang, B. Condon, M. Uchimiya, C. Fortier, Development of an environmentally friendly halogen-free phosphorus-nitrogen bond flame retardant for cotton fabrics, Polym. Adv. Technol. 23(2012) 1555-1563.
[6] H. Yuan, W. Xing, P. Zhang, L. Song, Y. Hu, Functionalization of cotton with UV-cured flame retardant coatings, Ind. Eng. Chem. Res. 51(2012) 5394-5401.
[7] B. Edwards, A. El-Shafei, P. Hauser, P. Malshe, Towards flame retardant cotton fabrics by atmospheric pressure plasma-induced graft polymerization:Synthesis and application of novel phosphoramidate monomers, Surf. Coat. Technol. 209(2012) 73-79.
[8] Z. Bai, X. Wang, G. Tang, L. Song, Y. Hu, R.K.K. Yuen, Structure-property relationships of synthetic organophosphorus flame retardant oligomers by thermal analysis, Thermochim. Acta 565(2013) 17-26.
[9] G.H. Hsiue, W.J. Wang, F.C. Chang, Synthesis, characterization, thermal and flameretardant properties of silicon-based epoxy resins, J. Appl. Polym. Sci. 73(1999) 1231-1238.
[10] J. Alongi, C. Colleoni, G. Rosace, G. Malucelli, Phosphorus-and nitrogen-doped silica coatings for enhancing the flame retardancy of cotton:Synergisms or additive effects, Polym. Degrad. Stab. 98(2013) 579-589.
[11] G. Laufer, C. Kirkland, A.B. Morgan, J.C. Grunlan, Intumescent multilayer nanocoating, made with renewable polyelectrolytes, for flame-retardant cotton, Biomacromolecules 13(2012) 2843-2848.
[12] J. Vasiljević, S. Hadžić, I. Jerman, L. Černe, B. Tomšič, J. Medved, M. Godec, B. Orel, B. Simončič, Study of flame-retardant finishing of cellulose fibres:Organic-inorganic hybrid versus conventional organophosphonate, Polym. Degrad. Stab. 98(2013) 2602-2608.
[13] X. Li, H. Chen, W. Wang, Y. Liu, P. Zhao, Synthesis of a formaldehyde-free phosphorus-nitrogen flame retardant with multiple reactive groups and its application in cotton fabrics, Polym. Degrad. Stab. 120(2015) 193-202.
[14] J. Alongi, C. Colleoni, G. Malucelli, G. Rosace, Hybrid phosphorus-doped silica architectures derived from a multistep sol-gel process for improving thermal stability and flame retardancy of cotton fabrics, Polym. Degrad. Stab. 97(2012) 1334-1344.
[15] G. Brancatelli, C. Colleoni, M.R. Massafra, G. Rosace, Effect of hybrid phosphorusdoped silica thin films produced by sol-gel method on the thermal behavior of cotton fabrics, Polym. Degrad. Stab. 96(2011) 483-490.
[16] S. Hu, Y. Hu, L. Song, The potential of functionalized organic-inorganic hybrid materials for influencing the thermal stability of cotton fabrics, Sci. Adv. Mater. 4(2012) 985-993.
[17] X. Mu, B. Yuan, W. Hu, S. Qiu, L. Song, Y. Hu, Flame retardant and antidripping properties of polylactic acid/poly(bis(phenoxy)phosphazene)/expandable graphite composite and its flame retardant mechanism, RSC Adv. 5(2015) 76068-76078.
[18] D. Wu, P. Zhao, Y. Liu, X. Liu, X. Wang, Halogen free flame retardant rigid polyurethane foam with a novel phosphorus-nitrogen intumescent flame retardant, J. Appl. Polym. Sci. 131(2014) 39581.
[19] F. Carosio, G. Laufer, J. Alongi, G. Camino, J.C. Grunlan, Layer-by-layer assembly of silica-based flame retardant thin film on PET fabric, Polym. Degrad. Stab. 96(2011) 745-750.
[20] P. Zhao, X. Li, M. Zhang, S. Liu, W. Liang, Y. Liu, Highly flame-retarding cotton fabrics with a novel phosphorus/nitrogen intumescent flame retardant, Korean J. Chem. Eng. 31(2014) 1592-1597.