Abstract
The development of multifunctional fabrics remains a necessity of high priority to meet the growing requirements in practical applications. However, developing flame retardant fabrics with antibacterial property and hydrophobicity still faces many challenges. In this study, novel multifunctional cotton fabrics with flame retardancy, antibacterial property, and hydrophobicity were successfully prepared by layer-by-layer (LBL) self-assembly. A novel flame retardant and antibacterial linear polymer P(AA-ADMH) containing a nitrogen flame-retardant and an antibacterial based on N-halamine was synthesized. To obtain versatile functionalities, P(AA-ADMH), phytic acid (PA), and γ-aminopropyl triethoxysilane (APS) were introduced to cotton fabrics by LBL self-assembly. The limiting oxygen index (LOI) of the modified cotton fabrics increased to 27.3%, and the peak of heat release rate (PHRR) decreased by 29.3%. Due to the presence of N-halamine structure, the modified cotton fabrics exhibited significant antibacterial efficacy within 30 min. In addition, the contact angle of the modified cotton fabrics was around 110° which could reduce the adhesion of bacteria on the modified fabrics. This study provides a novel method to potentially develop multifunctional cellulose textiles for the fields of fire safety and other protection.
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References
Arioli M, Manfredi A, Alongi J, Ferruti P, Ranucci E (2020) Highlight on the mechanism of linear polyamidoamine degradation in water. Polymers (Basel). https://doi.org/10.3390/polym12061376
Bentis A, Boukhriss A, Grancaric AM, El Bouchti M, El Achaby M, Gmouh S (2019) Flammability and combustion behavior of cotton fabrics treated by the sol gel method using ionic liquids combined with different anions. Cellulose 26(3):2139–2153. https://doi.org/10.1007/s10570-018-2206-4
Cao Y, Zhou M, Wang SF, Fu HQ (2022) Superhydrophobic and flame retardant polydimethylsiloxane coatings with layered double hydroxide and ammonium polyphosphate. Prog Org Coat. https://doi.org/10.1016/j.porgcoat.2022.107117
Chen T, Hong J, Peng CH, Chen GR, Yuan CH, Xu YT, Zeng BR, Dai LZ (2019) Superhydrophobic and flame retardant cotton modified with DOPO and fluorine-silicon-containing crosslinked polymer. Carbohydr Polym 208:14–21. https://doi.org/10.1016/j.carbpol.2018.12.023
Cheng XL, Li R, Du JM, Sheng JF, Ma KK, Ren XH, Huang TS (2015) Antimicrobial activity of hydrophobic cotton coated with N-halamine. Polym Adv Technol 26(1):99–103. https://doi.org/10.1002/pat.3426
de Oliveira CRS, Batistella MA, Lourenço LA, de Souza SMAGU, de Souza AAU (2021) Cotton fabric finishing based on phosphate/clay mineral by direct-coating technique and its influence on the thermal stability of the fibers. Prog Org Coat. https://doi.org/10.1016/j.porgcoat.2020.105949
de Oliveira CRS, Batistella MA, Ulson SMAG, de Souza AAU (2021) Functionalization of cellulosic fibers with a kaolinite-TiO2 nano-hybrid composite via a solvothermal process for flame retardant applications. Carbohydr Polym. https://doi.org/10.1016/j.carbpol.2021.118108
French AD (2014) Idealized powder diffraction patterns for cellulose polymorphs. Cellulose 21(2):885–896. https://doi.org/10.1007/s10570-013-0030-4
Gao D, Li YJ, Lyu B, Lyu LH, Chen SW, Ma JZ (2019) Construction of durable antibacterial and anti-mildew cotton fabric based on P(DMDAAC-AGE)/Ag/ZnO composites. Carbohydr Polym 204:161–169. https://doi.org/10.1016/j.carbpol.2018.09.087
Jiang ZM, Liu Y, Li R, Ren XH, Huang TS (2016) Preparation of antibacterial cellulose with a monochloro-s-triazine-based N-halamine biocide. Polym Adv Technol 27(4):460–465. https://doi.org/10.1002/pat.3691
Jiang ZM, Li H, He YW, Liu Y, Dong CH, Zhu P (2019) Flame retardancy and thermal behavior of cotton fabrics based on a novel phosphorus-containing siloxane. Appl Surf Sci 479:765–775. https://doi.org/10.1016/j.apsusc.2019.02.159
Jin X, Li WN, Wang SH, Li YY, Yang CH, Lu Z, Dong CH (2023) Developing flame-retardant, antibacterial cotton fabric by incorporating a linear polysiloxane-based coating. Ind Crop Prod. https://doi.org/10.1016/j.indcrop.2022.115934
Kang ZZ, Zhang B, Jiao YC, YiH Xu, He QZ, Liang J (2013) High-efficacy antimicrobial cellulose grafted by a novel quaternarized N-halamine. Cellulose 20(2):885–893
Kong Q, Li ZG, Ding F, Ren XH (2021) Hydrophobic N-halamine based POSS block copolymer porous films with antibacterial and resistance of bacterial adsorption performances. Chem Eng J 410:128407
Li P, Wang B, Xu YJ, Jiang ZM, Dong CH, Liu Y, Zhu P (2019a) Ecofriendly flame-retardant cotton fabrics: preparation, flame retardancy, thermal degradation properties, and mechanism. ACS Sustain Chem Eng 7(23):19246–19256. https://doi.org/10.1021/acssuschemeng.9b05523
Li SS, Lin XH, Liu Y, Li R, Ren XH, Huang TS (2019b) Phosphorus-nitrogen-silicon-based assembly multilayer coating for the preparation of flame retardant and antimicrobial cotton fabric. Cellulose 26(6):4213–4223. https://doi.org/10.1007/s10570-019-02373-5
Li P, Wang B, Liu YY, Xu YJ, Jiang ZM, Dong CH, Zhang L, Liu Y, Zhu P (2020) Fully bio-based coating from chitosan and phytate for fire-safety and antibacterial cotton fabrics. Carbohydr Polym 237:116173. https://doi.org/10.1016/j.carbpol.2020.116173
Li N, Kang GW, Liu H, Qiu WW, Wang Q, Liu L, Wang XL, Yu JY, Li FX, Wu DQ (2022) Fabrication of eco-friendly and efficient flame retardant modified cellulose with antibacterial property. J Colloid Interface Sci 618:462–474. https://doi.org/10.1016/j.jcis.2022.03.078
Lin DM, Zeng XR, Li HQ, Lai XJ, Wu TY (2019) One-pot fabrication of superhydrophobic and flame-retardant coatings on cotton fabrics via sol-gel reaction. J Colloid Interface Sci 533:198–206. https://doi.org/10.1016/j.jcis.2018.08.060
Ma W, Li L, Ren X, Huang TS (2019) Rational design of cotton substrates with enhanced UV–blocking, high antibacterial efficiency and prominent hydrophobicity. Cellulose 26(9):5757–5768
Maia MT, Noronha VT, Oliveira NC, Alves AC, Faria AF, Martinez DTS, Ferreira OP, Paula AJ (2022) Silica nanoparticles and surface silanization for the fabrication of water-repellent cotton fibers. ACS Appl Nano Mater. https://doi.org/10.1021/acsanm.1c03346
Makhlouf G, Abdelkhalik A, Ameen H (2021) Synthesis of a novel highly efficient flame-retardant coating for cotton fabrics with low combustion toxicity and antibacterial properties. Cellulose 28(13):8785–8806. https://doi.org/10.1007/s10570-021-04076-2
Manfredi A , Carosio F , Ferruti P , Ranucci E , Alongi J (2018) Linear polyamidoamines as novel biocompatible phosphorus-free surface-confined intumescent flame retardants for cotton fabrics. Polym Degrad Stabil 151:52–64. https://doi.org/10.1016/j.polymdegradstab.2018.02.020
Mostofi Sarkari N, Doğan Ö, Bat E, Mohseni M, Ebrahimi M (2019) Assessing effects of (3-aminopropyl)trimethoxysilane self-assembled layers on surface characteristics of organosilane-grafted moisture-crosslinked polyethylene substrate: a comparative study between chemical vapor deposition and plasma-facilitated in situ grafting methods. Appl Surf Sci. https://doi.org/10.1016/j.apsusc.2019.143751
Mu T, Pan NY, Wang YF, Ren XH, Huang TS (2018) Antibacterial coating of cellulose by Iso-bifunctional reactive N-halamine with the dyeing process of reactive dye. Fiber Polym 19(11):2284–2289
Nabipour H, Wang X, Rahman MZ, Song L, Hu Y (2020) An environmentally friendly approach to fabricating flame retardant, antibacterial and antifungal cotton fabrics via self-assembly of guanazole-metal complex. J Clean Prod. https://doi.org/10.1016/j.jclepro.2020.122832
Pan NY, Liu Y, Fan XY, Jiang ZM, Ren XH, Liang J (2016) Preparation and characterization of antibacterial graphene oxide functionalized with polymeric N-halamine. J Mater Sci 52(4):1996–2006. https://doi.org/10.1007/s10853-016-0488-1
Pan Y, Liu LX, Wang X, Song L, Hu Y (2018) Hypophosphorous acid cross-linked layer-by-layer assembly of green polyelectrolytes on polyester-cotton blend fabrics for durable flame-retardant treatment. Carbohydr Polym 201:1–8. https://doi.org/10.1016/j.carbpol.2018.08.044
Rao WH, Shi JJ, Yu CB, Zhao HB, Wang YZ (2021) Highly efficient, transparent, and environment-friendly flame-retardant coating for cotton fabric. Chem Eng J. https://doi.org/10.1016/j.cej.2021.130556
Rosace G, Colleoni C, Trovato V, Iacono G, Malucelli G (2017) Vinylphosphonic acid/methacrylamide system as a durable intumescent flame retardant for cotton fabric. Cellulose 24(7):3095–3108
Tian CC, Wu F, Jiao WL, Liu XY, Yin X, Si Y, Yu JY, Ding B (2021) Antibacterial and antiviral N-halamine nanofibrous membranes with nanonet structure for bioprotective applications. Compos Commun. https://doi.org/10.1016/j.coco.2021.100668
Wang DF, Zhong L, Zhang C, Li SN, Tian PX, Zhang FX, Zhang GX (2018a) Eco-friendly synthesis of a highly efficient phosphorus flame retardant based on xylitol and application on cotton fabric. Cellulose 26(3):2123–2138. https://doi.org/10.1007/s10570-018-2193-5
Wang DF, Zhong L, Zhang C, Zhang FX, Zhang GX (2018b) A novel reactive phosphorous flame retardant for cotton fabrics with durable flame retardancy and high whiteness due to self-buffering. Cellulose 25(10):5479–5497
Wang B, Li P, Xu YJ, Jiang ZM, Dong CH, Liu Y, Zhu P (2020) Bio-based, nontoxic and flame-retardant cotton/alginate blended fibres as filling materials: Thermal degradation properties, flammability and flame-retardant mechanism. Compos Part B Eng. https://doi.org/10.1016/j.compositesb.2020.108038
Wang SH, Sun L, Li YY, Wang HX, Liu J, Zhu P, Dong CH (2021) Properties of flame-retardant cotton fabrics: Combustion behavior, thermal stability and mechanism of Si/P/N synergistic effect. Ind Crop Prod. https://doi.org/10.1016/j.indcrop.2021.114157
Wang SH, Sun L, Li YY, Wang HX, Ji L, Zhu P, Dong CH (2021b) Properties of flame-retardant cotton fabrics: Combustion behavior, thermal stability and mechanism of Si/P/N synergistic effect. Ind Crop Prod 173:114157
Wang LJL, Xu YJ, Liu Y, Zhu P (2022a) Flame retardation of polyester/cotton blended fabrics via intumescent sol-gel coatings. Polym Degrad Stabil 204:110115
Wang CB, Wu J, Miao ZW, Zhang XF, Yan DP, Liu WW, Wu DZ, Wu ZP (2022) Permanent P/N-rich polymeric coating capable of extinguishing flame on cotton fabrics. Prog Org Coat. https://doi.org/10.1016/j.porgcoat.2022.107004
Xia L, Dai J, Wang XH, Xue MJ, Xu YT, Yuan CH, Dai LZ (2022) Facile fabrication of multifunctional cotton fabric by AgNC@boronate polymer/crosslinked chitosan. Carbohydr Polym. https://doi.org/10.1016/j.carbpol.2022.119384
Xu F, Zhong L, Xu Y, Zhang C, Wang P, Zhang FX, Zhang GX (2019) Synthesis of three novel amino acids-based flame retardants with multiple reactive groups for cotton fabrics. Cellulose 26(12):7537–7552
Xu DH, Wang SJ, Hu JW, Liu Y, Jiang ZM, Zhu P (2021) Enhancing antibacterial and flame-retardant performance of cotton fabric with an iminodiacetic acid-containing N-halamine. Cellulose 28(5):3265–3277. https://doi.org/10.1007/s10570-021-03716-x
Yang YY, Guo ZP, Huang W, Zhang SY, Huang JJ, Yang HJ, Zhou YS, Xu WL, Gu SJ (2020) Fabrication of multifunctional textiles with durable antibacterial property and efficient oil-water separation via in situ growth of zeolitic imidazolate framework-8 (ZIF-8) on cotton fabric. Appl Surf Sci 503:144079
Yang ZM, Ren XH, Liu Y (2021) N-halamine modified ceria nanoparticles: Antibacterial response and accelerated wound healing application via a 3D printed scaffold. Compos Part B Eng. https://doi.org/10.1016/j.compositesb.2021.109390
Yin ML, Chen XL, Li R, Huang D, Fan XY, Ren XH, Huang TS (2016) Preparation and characterization of antimicrobial PVA hybrid films with N-halamine modified chitosan nanospheres. J Appl Polym Sci. https://doi.org/10.1002/app.44204
Zhang D, Williams BL, Shrestha SB, Nasir Z, Becher EM, Lofink BJ, Santos VH, Patel H, Peng X, Sun L (2017) Flame retardant and hydrophobic coatings on cotton fabrics via sol-gel and self-assembly techniques. J Colloid Interface Sci 505:892–899. https://doi.org/10.1016/j.jcis.2017.06.087
Zhang FX, Gao WW, Jia YL, Lu Y, Zhang GX (2018) A concise water-solvent synthesis of highly effective, durable, and eco-friendly flame-retardant coating on cotton fabrics. Carbohydr Polym 199:256–265. https://doi.org/10.1016/j.carbpol.2018.05.085
Zhang SM, Demir B, Ren XH, Worley SD, Broughton RM, Huang TS (2019) Synthesis of antibacterial N-halamine acryl acid copolymers and their application onto cotton. J Appl Polym Sci. https://doi.org/10.1002/app.47426
Zhang SM, Li L, Ren XH, Huang TS (2020) N-halamine modified multiporous bacterial cellulose with enhanced antibacterial and hemostatic properties. Int J Biol Macromol 161:1070–1078
Zhang AN, Liu BW, Zhao HB, Wang YZ (2022) Eco-friendly and durable flame-retardant coating for cotton fabrics based on dynamic coordination of Ca2+-tannin acid. Prog Org Coat. https://doi.org/10.1016/j.porgcoat.2022.106964
Zheng DD, Zhou JF, Zhong L, Zhang FX, Zhang GX (2016) A novel durable and high-phosphorous-containing flame retardant for cotton fabrics. Cellulose 23(3):2211–2220
Zheng YX, Pan NY, Liu Y, Ren XH (2021) Novel porous chitosan/N-halamine structure with efficient antibacterial and hemostatic properties. Carbohydr Polym 253:117205. https://doi.org/10.1016/j.carbpol.2020.117205
Zhou TC, Xu HD, Cai L, Wang JJ (2020) Construction of anti-flame network structures in cotton fabrics with pentaerythritol phosphate urea salt and nano SiO2. Appl Surf Sci 507:145175
Acknowledgments
The authors gratefully acknowledge the financial support from the Fundings.
Funding
This work is supported by Postgraduate Research & Practice Innovation Program of Jiangsu Province (KYCX22_2355), the Natural Science Foundation of Jiangsu Province (BK20190606), and China Postdoctoral Science Foundation (2020M681486).
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XC: Data curation, Conceptualization, Methodology, Investigation, Writing-original draft, Formal analysis, Validation. FD: Methodology, Software. SZ: Visualization, Formal analysis. YL: Conceptualization, Investigation, Funding acquisition. XH: Conceptualization, Resources, Writing-review & editing. XR: Conceptualization, Resources, Supervision, Writing-review & editing, Funding acquisition.
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Chen, X., Ding, F., Zhang, S. et al. Flame-retardant, antibacterial and hydrophobic multifunctional coatings on cotton fabrics via layer-by-layer self-assembly. Cellulose 30, 6679–6694 (2023). https://doi.org/10.1007/s10570-023-05287-5
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DOI: https://doi.org/10.1007/s10570-023-05287-5