Abstract
A phosphorus/nitrogen-rich oligomer with numerous reactive groups (PEI-P) was synthesized and used as highly efficient durable flame retardant for cotton fabric. The O=P–ONH4 and O=P–OH groups in PEI-P reacted with O–H group in cellulose during finishing process. PEI-P triggered the decomposition of cotton fabric in advance, while markedly increased the char yield at high temperature. Treated fabrics showed superior flame resistance and durability. With the add-on of 19.3%, treated fabric achieved an LOI value of 38.7%. It self-extinguished even after 50 laundering cycles during vertical burning test. The PHRR and THR decreased by 86.10% and 65.11% in contrast to control fabric, respectively. PEI-P exerted gaseous and condensed flame-retardant effects by restraining the release of flammable volatiles, producing nonflammable gases and catalyzing the formation of stable phosphorus/nitrogen-rich char layers. Compared to control fabric, treated fabrics obtained well-maintained crystal structure and physical properties.
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References
Abou-Okeil A, El-Sawy SM, Abdel-Mohdy FA (2013) Flame retardant cotton fabrics treated with organophosphorus polymer. Carbohydr Polym 92:2293–2298. https://doi.org/10.1016/j.carbpol.2012.12.008
Alongi J, Ciobanu M, Malucelli G (2012a) Sol–gel treatments on cotton fabrics for improving thermal and flame stability: Effect of the structure of the alkoxysilane precursor. Carbohydr Polym 87:627–635. https://doi.org/10.1016/j.carbpol.2011.08.036
Alongi J, Colleoni C, Malucelli G, Rosace G (2012b) Hybrid phosphorus-doped silica architectures derived from a multistep sol–gel process for improving thermal stability and flame retardancy of cotton fabrics. Polym Degrad Stabil 97:1334–1344. https://doi.org/10.1016/j.polymdegradstab.2012.05.030
Alongi J, Carletto RA, Di Blasio A, Carosio F, Bosco F, Malucelli G (2013) DNA: a novel, green, natural flame retardant and suppressant for cotton. J Mater Chem A 1:4779–4785. https://doi.org/10.1039/C3TA00107E
Carosio F, Fontaine G, Alongi J, Bourbigot S (2015) Starch-based layer by layer assembly: efficient and sustainable approach to cotton fire protection. ACS Appl Mater Inter 7:12158–12167. https://doi.org/10.1021/acsami.5b02507
Chang S, Condon B, Graves E, Uchimiya M, Fortier C, Easson M, Wakelyn P (2011) Flame retardant properties of triazine phosphonates derivative with cotton fabric. Fiber Polym 12:334–339. https://doi.org/10.1007/s12221-011-0334-7
Dong CH et al (2016) Flammability and thermal properties of cotton fabrics modified with a novel flame retardant containing triazine and phosphorus components. Text Res J 87:1367–1376. https://doi.org/10.1177/0040517516652349
French AD (2014) Idealized powder diffraction patterns for cellulose polymorphs. Cellulose 21:885–896. https://doi.org/10.1007/s10570-013-0030-4
Harifi T, Montazer M (2012) Past, present and future prospects of cotton cross-linking: New insight into nano particles. Carbohydr Polym 88:1125–1140. https://doi.org/10.1016/j.carbpol.2012.02.017
Jia Yl, Lu Y, Zhang GX, Liang YJ, Zhang FX (2017) Facile synthesis of an eco-friendly nitrogen-phosphorus ammonium salt to enhance the durability and flame retardancy of cotton. J Mater Chem A 5:9970–9981. https://doi.org/10.1039/C7TA01106G
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
Li P et al (2020b) 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 YC, Mannen S, Morgan AB, Chang S, Yang YH, Condon B, Grunlan JC (2011) Intumescent all-polymer multilayer nanocoating capable of extinguishing flame on fabric. Adv Mater 23:3926–3931. https://doi.org/10.1002/adma.201101871
Li XH, Chen HY, Wang WT, Liu YQ, Zhao PH (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
Li P, Wang B, Xu YJ, Jiang ZM, Dong CH, Liu Y, Zhu P (2019) Ecofriendly flame-retardant cotton fabrics: Preparation, flame retardancy, thermal degradation properties, and mechanism. ACS Sustain Chem Eng 7:19246–19256. https://doi.org/10.1021/acssuschemeng.9b05523
Li P, Liu C, Xu YJ, Jiang ZM, Liu Y, Zhu P (2020a) Novel and eco-friendly flame-retardant cotton fabrics with lignosulfonate and chitosan through LbL: Flame retardancy, smoke suppression and flame-retardant mechanism. Polym Degrad Stabil 181:109302. https://doi.org/10.1016/j.polymdegradstab.2020.109302
Li SN, Huang S, Xu F, Zhao TF, Zhang FX, Zhang GX (2020c) Imparting superhydrophobicity and flame retardancy simultaneously on cotton fabrics. Cellulose 27:3989–4005. https://doi.org/10.1007/s10570-020-03041-9
Ling C, Guo LM (2020) Preparation of a flame-retardant coating based on solvent-free synthesis with high efficiency and durability on cotton fabric. Carbohydr Polym 230:115648. https://doi.org/10.1016/j.carbpol.2019.115648
Liu W, Chen L, Wang YZ (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
Liu SD, Wan CY, Chen Y, Chen R, Zhang FX, Zhang GX (2020) A novel high-molecular-weight flame retardant for cotton fabrics. Cellulose 27:3501–3515. https://doi.org/10.1007/s10570-020-03020-0
Lu Y, Jia YL, Zhou Y, Zou J, Zhang GX, Zhang FX (2018) Straightforward one-step solvent-free synthesis of the flame retardant for cotton with excellent efficiency and durability. Carbohydr Polym 201:438–445. https://doi.org/10.1016/j.carbpol.2018.08.078
Nguyen TM, Chang S, Condon B, Slopek R (2012) Synthesis of a novel flame retardant containing phosphorus-nitrogen and its comparison for cotton fabric. Fibers Polym 13:963–970. https://doi.org/10.1007/s12221-012-0963-5
Nguyen TM, Chang S, Condon B, Thomas TP, Azadi P (2014) Thermal decomposition reactions of cotton fabric treated with piperazine-phosphonates derivatives as a flame retardant. J Anal Appl Pyrol 110:122–129. https://doi.org/10.1016/j.jaap.2014.08.006
Qiu SL et al (2019) Air-stable polyphosphazene-functionalized few-layer black phosphorene for flame retardancy of epoxy resins. Small 15:1805175. https://doi.org/10.1002/smll.201805175
Qu ZC et al (2020) Surface functionalization of few-layer black phosphorene and its flame retardancy in epoxy resin. Chem Eng J 382:122991. https://doi.org/10.1016/j.cej.2019.122991
Rosace G, Castellano A, Trovato V, Iacono G, Malucelli G (2018) Thermal and flame retardant behaviour of cotton fabrics treated with a novel nitrogen-containing carboxyl-functionalized organophosphorus system. Carbohydr Polym 196:348–358. https://doi.org/10.1016/j.carbpol.2018.05.012
Schartel B et al (2016) Flame retardancy of polymers: The role of specific reactions in the condensed phase. Macromol Mater Eng 301:9–35. https://doi.org/10.1002/mame.201500250
Suryaprabha T, Sethuraman MG (2020) Fabrication of a superhydrophobic and flame-retardant cotton fabric using a DNA-based coating. J Mater Sci 55:11959–11969. https://doi.org/10.1007/s10853-020-04911-0
Wan CY, Tian PX, Liu MS, Zhang GX, Zhang FX (2019) Synthesis of a phosphorus-nitrogen flame retardant endowing cotton with high whiteness and washability. Ind Crop Prod 141:111738. https://doi.org/10.1016/j.indcrop.2019.111738
Wan CY, Liu MS, He PP, Zhang GX, Zhang FX (2020) A novel reactive flame retardant for cotton fabric based on a thiourea-phosphoric acid polymer. Ind Crop Prod 154:112625. https://doi.org/10.1016/j.indcrop.2020.112625
Wang S et al (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
Wang WJ et al (2020) Constructing eco-friendly flame retardant coating on cotton fabrics by layer-by-layer self-assembly. Cellulose 27:5377–5389. https://doi.org/10.1007/s10570-020-03140-7
Wang N, Liu YS, Xu CA, Liu Y, Wang Q (2017) Acid-base synergistic flame retardant wood pulp paper with high thermal stability. Carbohydr Polym 178:123–130. https://doi.org/10.1016/j.carbpol.2017.08.099
Wang P, Xia L, Jian RK, Ai YF, Zheng XL, Chen GL, Wang JS (2018) Flame-retarding epoxy resin with an efficient P/N/S-containing flame retardant: Preparation, thermal stability, and flame retardance. Polym Degrad Stabil 149:69–77. https://doi.org/10.1016/j.polymdegradstab.2018.01.026
Xu LJ, Wang W, Yu D (2017a) Durable flame retardant finishing of cotton fabrics with halogen-free organophosphonate by UV photoinitiated thiol-ene click chemistry. Carbohydr Polym 172:275–283. https://doi.org/10.1016/j.carbpol.2017.05.054
Xu LJ, Wang W, Yu D (2017b) Preparation of a reactive flame retardant and its finishing on cotton fabrics based on click chemistry. RSC Adv 7:2044–2050. https://doi.org/10.1039/C6RA26075F
Xu F, Zhong L, Zhang C, Wang P, Zhang FX, Zhang GX (2019) Novel high-efficiency casein-based P–N-containing flame retardants with multiple reactive groups for cotton fabrics. ACS Sustain Chem Eng 7:13999–14008. https://doi.org/10.1021/acssuschemeng.9b02474
Yang JC, Liao W, Deng SB, Cao ZJ, Wang YZ (2016) Flame retardation of cellulose-rich fabrics via a simplified layer-by-layer assembly. Carbohydr Polym 151:434–440. https://doi.org/10.1016/j.carbpol.2016.05.087
Yang ZW, Zhang YY, Fu FY, Liu XD (2017) Single-faced flame resistance of cotton fabrics modified via mist copolymerization. RSC Adv 7:53871–53877. https://doi.org/10.1039/C7RA11461C
Yoshioka-Tarver M et al (2012) Enhanced flame retardant property of fiber reactive halogen-free organophosphonate. Ind Eng Chem Res 51:11031–11037. https://doi.org/10.1021/ie300964g
Zhang Y et al (2019) Eco-friendly flame retardant and electromagnetic interference shielding cotton fabrics with multi-layered coatings. Chem Eng J 372:1077–1090. https://doi.org/10.1016/j.cej.2019.05.012
Zhang FX, Lu Y, Wan CY, Tian PX, Liu MS, Zhang GX (2020a) A bio-resourced mannitol phospholipid ammonium reactive flame retardant for cotton with efficient antiflaming and durability. Cellulose 27:4803–4815. https://doi.org/10.1007/s10570-020-03064-2
Zhang Z, Dong CH, Liu J, Kong DZ, Sun L, Lu Z (2020b) Preparation of a synergistic reactive flame retardant based on silicon, phosphorus and nitrogen and its application to cotton fabrics. Cellulose 27:1799–1815. https://doi.org/10.1007/s10570-019-02900-4
Zhao XJ, Xiao HH, Wang QS, Ping P, Sun JH (2013) Study on spontaneous combustion risk of cotton using a micro-calorimeter technique. Ind Crop Prod 50:383–390. https://doi.org/10.1016/j.indcrop.2013.07.064
Zhao B, Liu YT, Zhang CY, Liu DY, Li F, Liu YQ (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
Zhao ZL, Jin Q, Zhang NE, Guo XR, Yan H (2018) Preparation of a novel polysiloxane and its synergistic effect with ammonium polyphosphate on the flame retardancy of polypropylene. Polym Degrad Stabil 150:73–85. https://doi.org/10.1016/j.polymdegradstab.2018.02.007
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. https://doi.org/10.1016/j.apsusc.2019.145175
Acknowledgments
This work was financially supported by the National Natural Science Foundation of China (Grant No. 21905233), the Fundamental Research Funds for the Central Universities (Grant No. XDJK2020C024), the Science and Technology Innovation Program of Chengdu-Chongqing Economic Circle Construction of Chongqing Education Commission of China (Grant No. KJCX2020008), the Jiaxing Project of Science and Technology (Grant No. 2020AD10019) and the Open Project Program of Key Laboratory of Yarn Materials Forming and Composite Processing Technology of Zhejiang Province (Grant No. MTC-2020-18).
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Gou, T., Wu, X., Zhao, Q. et al. Novel phosphorus/nitrogen-rich oligomer with numerous reactive groups for durable flame-retardant cotton fabric. Cellulose 28, 7405–7419 (2021). https://doi.org/10.1007/s10570-021-03980-x
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DOI: https://doi.org/10.1007/s10570-021-03980-x