Abstract
A novel DOPO derived multi-claw reactive flame retardant (DMCFR) was designed to improve the flame retardancy of lyocell fabric. The chemical structure of DMCFR was identified by proton nuclear magnetic resonance (1H-NMR) and Fourier transform infrared spectroscopy (FT-IR). The chemical structure and elemental composition of the modified lyocell fabric were investigated by FT-IR and X-ray photoelectron spectroscopy. The vertical burning test, limiting oxygen index (LOI) and cone calorimetry were applied to evaluate the flame retardancy of the original and treated samples. The results showed that the peak heat release rate and total heat release of the flame retardant lyocell (FR-lyocell) were significantly reduced by 90.6% and 65.5% compared to control sample. In addition, the LOI value of FR-lyocell fabric was up to 33% and remained 26% even after 20 laundering cycles (LCs). The thermal stability and char-forming capacity of the samples were measured by thermogravimetric analysis, and the residual char of the treated sample was as high as 9.15% and 42.5% under air and nitrogen atmosphere respectively, which were much higher than that of the original sample. Furthermore, the flame retardant mechanism was evidenced via scanning electron microscopy (SEM), Raman spectroscopy, thermogravimetric combined with Fourier transform infrared spectroscopy (TG-IR) and pyrolysis–gas chromatography-mass spectrometry (PyGC-MS), which supported the condensed and gas phase flame retardant mechanism.
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References
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
Bai ZM, Jiang SD, Tang G, Hu Y, Song L, Yuen RKK (2014) Enhanced thermal properties and flame retardancy of unsaturated polyester-based hybrid materials containing phosphorus and silicon. Polym Adv Technol 25:223–232. https://doi.org/10.1002/pat.3227
Bentis A, Boukhriss A, Gmouh S (2020) Flame-retardant and water-repellent coating on cotton fabric by titania-boron sol-gel method. Sol-Gel Sci Technol 94:719–730. https://doi.org/10.1007/s10971-020-05224-z
Cai HH, Liu ZL, Xu MT, Chen L, Chen X, Cheng L, Li Z, Dai FY (2021) High performance flexible silk fabric electrodes with antibacterial, flame retardant and UV resistance for supercapacitors and sensors. Electrochim Acta 390:138895. https://doi.org/10.1016/j.electacta.2021.138895
Carrillo F, Colom X, Canavate X (2010) Properties of regenerated cellulose lyocell fiber-reinforced composites. J Reinf Plast Compos 29:359–371. https://doi.org/10.1177/0731684408097777
Chantarasiri N, Damrongkosit T, Jangwong W, Sridaeng D, Suebphan S (2004) Synthesis, characterization and thermal properties of metal-containing polyurethane-ureas from hexadentate Schiff base metal complexes. Eur Polym J 40:1867–1874. https://doi.org/10.1016/j.eurpolymj.2004.04.009
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
Chen Y, Wan CY, Liu SD, Wang P, Zhang GX (2021) A novel flame retardant based on polyhydric alcohols and P-N synergy for treatment of cotton fabrics. Cellulose 28:1781–1793. https://doi.org/10.1007/s10570-020-03615-7
Cheng XW, Wu YX, Hu BQ, Guan JP (2020) Facile preparation of an effective intumescent flame-retardant coating for cotton fabric. Surf Innov 8:315–322. https://doi.org/10.1680/jsuin.20.00021
Ding HL, Qiu SL, Wang X, Song L, Hu Y (2021) Highly flame retardant, low thermally conducting, and hydrophobic phytic acid-guanazole-cellulose nanofiber composite foams. Cellulose 28:9769–9783. https://doi.org/10.1007/s10570-021-04159-0
D’Silva K, Fernandes A, Rose M (2004) Brominated organic micropollutants–Igniting the flame retardant issue. Crit Rev Environ Sci Technol 34:141–207. https://doi.org/10.1080/10643380490430672
Fink HP, Weigel P, Purz HJ, Ganster J (2001) Structure formation of regenerated cellulose materials from NMMO-solutions. Prog Polym Sci 26:1473–1524. https://doi.org/10.1016/S0079-6700(01)00025-9
Gaan S, Mauclaire L, Rupper P, Salimova V, Tran TT, Heuberger M (2011) Thermal degradation of cellulose acetate in presence of bis-phosphoramidates. J Anal Appl Pyrolysis 90:33–41. https://doi.org/10.1016/j.jaap.2010.10.005
Gou TT, Wu X, Zhao QY, Chang S, Wang P (2021) Novel phosphorus/nitrogen-rich oligomer with numerous reactive groups for durable flame-retardant cotton fabric. Cellulose 28:7405–7419. https://doi.org/10.1007/s10570-021-03980-x
Gu JJ, Yan XF, Li JW, Qian YW, Zhu CK, Qi DM (2021) Durable flame-retardant behavior of cotton textile with a water-based ammonium vinyl phosphonate. Polym Degrad Stabil 191:109658. https://doi.org/10.1016/j.polymdegradstab.2021.109658
Guo YB, Xiao MY, Ren YL, Liu YS, Wang Y, Guo X, Liu XH (2021) Synthesis of an effective halogen-free flame retardant rich in phosphorus and nitrogen for lyocell fabric. Cellulose 28:7355–7372. https://doi.org/10.1007/s10570-021-03975-8
Han X, Zhang XH, Guo Y, Liu XY, Zhao XJ, Zhou H, Zhang SL, Zhao T (2021) Synergistic effects of ladder and cage structured phosphorus-containing POSS with tetrabutyl titanate on flame retardancy of vinyl epoxy resins. Polymers 13:1363. https://doi.org/10.3390/polym13091363
He FM, Liu BW, Chen L, Guo DM, Ding XM, Xiao YF, Zhao HB, Li WD, Wang YZ (2021) Novel polyamide 6 composites based on Schiff-base containing phosphonate oligomer: high flame retardancy, great processability and mechanical property. Compos Pt A-Appl Sci Manuf 146:106423. https://doi.org/10.1016/j.compositesa.2021.106423
Hou YB, Liu LX, Qiu SL, Zhou X, Gui Z, Hu Y (2018) DOPO-modified two-dimensional co-based metal-organic framework: preparation and application for enhancing fire safety of poly(lactic acid). ACS ACS Appl Mater Interfaces 10:8274–8286. https://doi.org/10.1021/acsami.7b19395
Huang S, Feng YJ, Li SN, Zhou Y, Zhang FX, Zhang GX (2019) A novel high whiteness flame retardant for cotton. Polym Degrad Stabil 164:157–166. https://doi.org/10.1016/j.polymdegradstab.2019.03.014
Huo SQ, Wang J, Yang S, Li C, Wang XL, Cai HP (2019) Synthesis of a DOPO-containing imidazole curing agent and its application in reactive flame retarded epoxy resin. Polym Degrad Stabil 159:79–89. https://doi.org/10.1016/j.polymdegradstab.2018.11.021
Huo SQ, Song PA, Yu B, Ran SY, Chevali VS, Liu L, Fang ZP, Wang H (2021) Phosphorus-containing flame retardant epoxy thermosets: recent advances and future perspectives. Prog Polym Sci 114:101366. https://doi.org/10.1016/j.progpolymsci.2021.101366
Jeong SH, Heo JH, Lee JW, Kim MJ, Park CH, Lee JH (2021) Bioinspired adenosine triphosphate as an “All-In-One” green flame retardant via extremely intumescent char formation. ACS Appl Mater Interfaces 13:22935–22945. https://doi.org/10.1021/acsami.1c02021
Jiang W, Jin FL, Park SJ (2015) Synthesis of a novel phosphorus-nitrogen-containing intumescent flame retardant and its application to fabrics. J Ind Eng Chem 27:40–43. https://doi.org/10.1016/j.jiec.2015.01.010
Kundu CK, Wang X, Hou YB, Hu Y (2018) Construction of flame retardant coating on polyamide 6.6 via UV grafting of phosphorylated chitosan and sol-gel process of organo-silane. Carbohydr Polym 181:833–840. https://doi.org/10.1016/j.carbpol.2017.11.069
Kundu CK, Wang X, Rahman MZ, Song L, Hu Y (2020) Application of Chitosan and DOPO derivatives in fire protection of polyamide 66 textiles: towards a combined gas phase and condensed phase activity. Polym Degrad Stabil 176:109158. https://doi.org/10.1016/j.polymdegradstab.2020.109158
Lessan F, Montazer M, Moghadam MB (2011) A novel durable flame-retardant cotton fabric using sodium hypophosphite, nano TiO2 and maleic acid. Thermochim Acta 520:48–54. https://doi.org/10.1016/j.tca.2011.03.012
Levchik SV, Weil ED (2006) A review of recent progress in phosphorus-based flame retardants. J Fire Sci 24:345–364. https://doi.org/10.1177/0734904106068426
Li N, Ming J, Yuan RC, Fan S, Liu L, Li FX, Wang XL, Yu JY, Wu DQ (2019) Novel eco-friendly flame retardants based on nitrogen-silicone schiff base and application in cellulose. ACS Sustain Chem Eng 8:290–301. https://doi.org/10.1021/acssuschemeng.9b05338
Li SS, Liu Y, Liu YS, Wang Q (2021a) Synergistic effect of piperazine pyrophosphate and epoxy-octavinyl silsesquioxane on flame retardancy and mechanical properties of epoxy resin. Compos Pt B-Eng 223:109115. https://doi.org/10.1016/j.compositesb.2021.109115
Li XL, Zhang J, Zhang L, Ruiz de Luzuriaga AR, Rekondo A, Wang DY (2021b) Recyclable flame-retardant epoxy composites based on disulfide bonds: flammability and recyclability. Compos Commun 25:100754. https://doi.org/10.1016/j.coco.2021.100754
Liao Y, Chen Y, Wan CY, Zhang GX, Zhang FX (2021) An eco-friendly N-P flame retardant for durable flame-retardant treatment of cotton fabric. Int J Biol Macromol 187:251–261. https://doi.org/10.1016/j.ijbiomac.2021.07.130
Ling C, Guo LM (2019) A novel, eco-friendly and durable flame-retardant cotton-based hyperbranched polyester derivative. Cellulose 27:2357–2368. https://doi.org/10.1007/s10570-019-02923-x
Liodakis S, Fetsis IK, Agiovlasitis IP (2009) The fire-retarding effect of inorganic phosphorus compounds on the combustion of cellulosic materials. J Therm Anal Calorim 98:285–291. https://doi.org/10.1007/s10973-009-0307-x
Liu YL, Wei WL, Chen WY (2003) Reversibility of hydration and dehydration reactions of a phosphaphenanthrene oxide (DOPO) pendent group on polyamide. Polym Int 52:1275–1279. https://doi.org/10.1002/pi.1214
Liu H, Xu K, Cai HL, Su JX, Liu X, Fu ZE, Chen MC (2012) Thermal properties and flame retardancy of novel epoxy based on phosphorus-modified Schiff-base. Polym Adv Technol 23:114–121. https://doi.org/10.1002/pat.1832
Liu XH, Zhang QY, Cheng BW, Ren YL, Zhang YG, Ding C (2017) Durable flame retardant cellulosic fibers modified with novel, facile and efficient phytic acid-based finishing agent. Cellulose 25:799–811. https://doi.org/10.1007/s10570-017-1550-0
Liu J, Dong CH, Zhang Z, Kong DZ, Sun H, Lu Z (2020a) Multifunctional flame-retarded and hydrophobic cotton fabrics modified with a cyphosphorus/polysiloxane copolymer. Cellulose 27:3531–3549. https://doi.org/10.1007/s10570-020-03016-w
Liu QY, Wang DH, Li ZK, Li ZF, Peng XL, Liu CB, Zhang Y, Zheng PL (2020b) Recent developments in the flame-retardant system of epoxy resin. Materials 13:2145. https://doi.org/10.3390/ma13092145
Liu YS, Guo YB, Ren YL, Wang Y, Guo X, Liu XH (2020c) Phosphorylation of sodium copper chlorophyll enables color-fasten and durable flame retardant wool fibers. Polym Degrad Stabil 179:109286. https://doi.org/10.1016/j.polymdegradstab.2020.109286
Liu J, Kong DZ, Dong CH, Zhang Z, Wang S, Sun H, Lu Z (2021a) Preparation of a novel P/Si polymer and its synergistic flame retardant application on cotton fabric. Cellulose 28:8735–8749. https://doi.org/10.1007/s10570-021-04054-8
Liu LB, Xu Y, Pan Y, Xu MJ, Di YF, Li B (2021b) Facile synthesis of an efficient phosphonamide flame retardant for simultaneous enhancement of fire safety and crystallization rate of poly (lactic acid). Chem Eng J 421:127761. https://doi.org/10.1016/j.cej.2020.127761
Lu Y, Jia YL, Zhang GX, Zhang FX (2018) An eco-friendly intumescent flame retardant with high efficiency and durability for cotton fabric. Cellulose 25:5389–5404. https://doi.org/10.1007/s10570-018-1930-0
Luo YF, Wang HL, Wang H, Jin LZ, Du ZL, Wang HB, Cheng X (2021) Preparation and performance of waterborne polyurethane coatings based on the synergistic flame retardant of ferrocene, phosphorus and nitrogen. J Appl Polym Sci 138:e51331. https://doi.org/10.1002/app.51331
Pan Y, Zhao HT (2018) A novel blowing agent polyelectrolyte for fabricating intumescent multilayer coating that retards fire on cotton fabric. J Appl Polym Sci 135:46583. https://doi.org/10.1002/app.46583
Paosawatyanyong B, Jermsutjarit P, Bhanthumnavin W (2012) Surface nanomodification of cotton fiber for flame retardant application. J Nanosci Nanotechnol 12:748–753. https://doi.org/10.1166/jnn.2012.5367
Perret B, Schartel B, Stoss K, Ciesielski M, Diederichs J, Doring M, Kramer J, Altstadt V (2011) Novel DOPO-based flame retardants in high-performance carbon fibre epoxy composites for aviation. Eur Polym J 47:1081–1089. https://doi.org/10.1016/j.eurpolymj.2011.02.008
Pethsangave DA, Khose RV, Wadekar PH, Some S (2019) Novel approach toward the synthesis of a phosphorus-functionalized polymer-based graphene composite as an efficient flame retardant. ACS Sustain Chem Eng 7:11745–11753. https://doi.org/10.1021/acssuschemeng.9b01975
Qian LJ, Qiu Y, Liu J, Xin F, Chen YJ (2014) The flame retardant group-synergistic-effect of a phosphaphenanthrene and triazine double-group compound in epoxy resin. J Appl Polym Sci 131:39709. https://doi.org/10.1002/app.39709
Rahman F, Langford KH, Scrimshaw MD, Lester JN (2001) Polybrominated diphenyl ether (PBDE) flame retardants. Sci Total Environ 275:1–17. https://doi.org/10.1016/S0048-9697(01)00852-X
Ren YL, Zhang Y, Zhao JY, Wang XL, Zeng Q, Gu YT (2016) Phosphorus-doped organic-inorganic hybrid silicon coating for improving fire retardancy of polyacrylonitrile fabric. J Sol-Gel Sci Technol 82:280–288. https://doi.org/10.1007/s10971-016-4273-z
Ren YL, Huo TG, Qin YW (2018) Preparation of phosphorus-containing and nitrogen-containing durable flame retardant polyacrylonitrile fabric via surface chemical modification. Fire Mater 42:925–932. https://doi.org/10.1002/fam.2647
Ren YL, Liu YS, Wang Y, Guo X, Liu XH (2020) Preparation of durable and flame retardant lyocell fabrics by using a biomass-based modifier derived from vitamin C. Cellulose 27:6677–6689. https://doi.org/10.1007/s10570-020-03218-2
Shi YQ, Fu T, Xu YJ, Li DF, Wang XL, Wang YZ (2018) Novel phosphorus-containing halogen-free ionic liquid toward fire safety epoxy resin with well-balanced comprehensive performance. Chem Eng J 354:208–219. https://doi.org/10.1016/j.cej.2018.08.023
Sun YF, Liu CY, Hong Y, Liu RP, Zhou XD (2019) Synthesis and application of self-crosslinking and flame retardant waterborne polyurethane as fabric coating agent. Prog Org Coat 137:105323. https://doi.org/10.1016/j.porgcoat.2019.105323
Sun L, Wang HX, Li WN, Zhang JJ, Zhang Z, Lu Z, Zhu P, Dong CH (2021) Preparation, characterization and testing of flame retardant cotton cellulose material: flame retardancy, thermal stability and flame-retardant mechanism. Cellulose 28:3789–3805. https://doi.org/10.1007/s10570-020-03632-6
Tao Y, Liu C, Li P, Wang B, Xu YJ, Jiang ZM, Liu Y, Zhu P (2021) A flame-retardant PET fabric coating: flammability, anti-dripping properties, and flame-retardant mechanism. Prog Org Coat 150:105971. https://doi.org/10.1016/j.porgcoat.2020.105971
Tian PX, Lu Y, Wang DF, Zhang GX, Zhang FX (2019) Synthesis of a new N-P durable flame retardant for cotton fabrics. Polym Degrad Stabil 165:220–228. https://doi.org/10.1016/j.polymdegradstab.2019.04.024
Vasiljevic J, Jerman I, Jaksa G, Alongi J, Malucelli G, Zorko M, Tomsic B, Simoncic B (2015) Functionalization of cellulose fibres with DOPO-polysilsesquioxane flame retardant nanocoating. Cellulose 22:1893–1910. https://doi.org/10.1007/s10570-015-0599-x
Velencoso MM, Battig A, Markwart JC, Schartel B, Wurm FR (2018) Molecular firefighting-How modern phosphorus chemistry can help solve the challenge of flame retardancy. Angew Chem-Int Edit 57:10450–10467. https://doi.org/10.1002/anie.201711735
Wang X, Kalali EN, Wang DY (2015) Renewable cardanol-based surfactant modified layered double hydroxide as a flame retardant for epoxy resin. ACS Sustain Chem Eng 3:3281–3290. https://doi.org/10.1021/acssuschemeng.5b00871
Wang S, Kong DZ, Chen HF, Wang Z, Lu Z (2022) Construction of a novel B/N/Si synergistic flame retardant system and its application on cotton fabric. Ind Crops Prod 178:114574. https://doi.org/10.1016/j.indcrop.2022.114574
Wei G, Shuo C (2021) Durable flame retardant hybrid sol-gel coating on poly(ethylene terephthalate) fabric and its flame retardant mechanism. Text Res J. https://doi.org/10.1177/00405175211040874
Xiao MY, Guo YB, Zhang JY, Liu YS, Ren YL, Liu XH (2021) Diethylene triamine penta methylene phosphonic acid encountered silver ions: a convenient method for preparation of flame retardant and antibacterial lyocell fabric. Cellulose 28:7465–7481. https://doi.org/10.1007/s10570-021-04000-8
Xie KL, Gao AQ, Zhang YS (2013) Flame retardant finishing of cotton fabric based on synergistic compounds containing boron and nitrogen. Carbohydr Polym 98:706–710. https://doi.org/10.1016/j.carbpol.2013.06.014
Xie WQ, Huang SW, Tang DL, Liu SM, Zhao JQ (2020) Biomass-derived Schiff base compound enabled fire-safe epoxy thermoset with excellent mechanical properties and high glass transition temperature. Chem Eng J 394:123667. https://doi.org/10.1016/j.cej.2019.123667
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
Xu K, He YQ, Tian X, Wang BB, Cao Y, Wang B, Xia YZ, Quan FY (2021) Smoldering suppression and synergistic effect of alginate fiber-based composite paper by flame-retardant lyocell fiber. J Appl Polym Sci 139:e51580. https://doi.org/10.1002/app.51580
Yan J, Xu PF, Zhang PK, Fan HJ (2021) Surface-modified ammonium polyphosphate for flame-retardant and reinforced polyurethane composites. Colloid Surf A-Physicochem Eng Asp 626:127092. https://doi.org/10.1016/j.colsurfa.2021.127092
Yang CQ, He QL (2011) Applications of micro-scale combustion calorimetry to the studies of cotton and nylon fabrics treated with organophosphorus flame retardants. J Anal Appl Pyrolysis 91:125–133. https://doi.org/10.1016/j.jaap.2011.01.012
Yang J, Wen XD, Zhang XJ, Hu XY, Fan LN, Jia DX, Xu QB, Fu FY, Diao HY, Liu XD (2021) A lipid coating on cotton fibers with enhanced adsorption capability for fabric functionalization. Cellulose 28:5957–5971. https://doi.org/10.1007/s10570-021-03893-9
Zhang SK, Chen CX, Duan C, Hu HC, Li HL, Li JG, Liu YS, Ma XJ, Stavik J, Ni YH (2018) Regenerated Cellulose by the lyocell process, a brief review of the process and properties. BioResources 13:4577–4592. https://doi.org/10.15376/biores.13.2.Zhang
Zhang Z, Dong CH, Liu J, Kong DZ, Sun L, Lu Z (2019) 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
Zhang QY, Liu XH, Ren YL, Zhang YG, Cheng BW (2020) Fabrication of a high phosphorus-nitrogen content modifier with star structure for effectively enhancing flame retardancy of lyocell fibers. Cellulose 27:8369–8383. https://doi.org/10.1007/s10570-020-03333-0
Zhang FX, Liao Y, Chen Y, Lu Y, Wan CY, Zhang GX (2021) One-step green synthesis of eco-friendly novel N-P synergistic flame retardant for cotton fabric. Cellulose 28:8205–8219. https://doi.org/10.1007/s10570-021-04049-5
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
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This research was financially supported by the National Natural Science Foundation of China (No. 51573134), the National Key Research and Development Program of China (2017YFB0309000), and the Beijing Tianjin Hebei collaborative innovation community construction project (No. 20541401D).
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This research was financially supported by the National Natural Science Foundation of China (No. 51573134), the National Key Research and Development Program of China (2017YFB0309000), and the Beijing Tianjin Hebei collaborative innovation community construction project (No. 20541401D).
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WT: Investigation, Formal analysis, Visualization, Writing–original draft. YR: Formal analysis, Methodology, Validation, Supervision. YG: Methodology, Resources, Visualization. YL: Resources, Software. XL: Supervision, Conceptualization, Writing-Review & Editing. HQ: Supervision, Writing-Review & Editing.
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Tan, W., Ren, Y., Guo, Y. et al. A novel multi-claw reactive flame retardant derived from DOPO for endowing lyocell fabric with high effective flame retardancy. Cellulose 29, 6941–6962 (2022). https://doi.org/10.1007/s10570-022-04690-8
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DOI: https://doi.org/10.1007/s10570-022-04690-8