Abstract
A novel effective halogen-free flame retardant (FR) rich in phosphorus (P) and nitrogen (N) was synthesized via Mannich and esterification reaction of ethanolamine, glyoxal, phosphoric acid and urea, and used for the preparation of durable flame retardant lyocell fabric (FR-lyocell). Its chemical structure was characterized by Fourier transform infrared spectra, 1H and 31P nuclear magnetic resonance spectra. Inductively coupled plasma emission spectrometry and elemental analysis were conducted to test the phosphorous, carbon and nitrogen contents. The results confirmed that the FR was successfully synthesized and grafted on the lyocell fabric via firm P–O–C covalent bonds. The limiting oxygen index of the FR-lyocell treated with 30 wt% flame retardant finishing solution is 44.6%, demonstrating high efficiency flame retardancy. The thermo-gravimetric analysis indicated that FR-lyocell degraded preferentially than that of the control sample and the char residue was 38.8 wt% at 800 °C in N2 atmosphere. In addition, the cone calorimeter test revealed that FR-lyocell could not be ignited and the peak of heat release rate was much lower than that of original specimen. Furthermore, the char residue of FR-lyocell is compact and the ID/IG value is 0.771, exhibiting a super degree of carbonization. Moreover, TG-IR result revealed that FR played dual flame-retardant effect in the gaseous and condensed phases. The flame retardant finishing has a negligible impact on the mechanical properties of the fibers. In summary, FR-lyocell exhibits excellent flame retardancy and superior char forming capability, which is suitable for the preparation of flame retardant lyocell fibers.
Graphic abstract
Similar content being viewed by others
References
Alongi J, Ciobanu M, Malucelli G (2011a) Novel flame retardant finishing systems for cotton fabrics based on phosphorus-containing compounds and silica derived from sol–gel processes. Carbohyd Polym 85:599–608. https://doi.org/10.1016/j.carbpol.2011.03.024
Alongi J, Tata J, Frache A (2011b) Hydrotalcite and nanometric silica as finishing additives to enhance the thermal stability and flame retardancy of cotton. Cellulose 18:179–190. https://doi.org/10.1007/s10570-010-9473-z
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(15):36–40. https://doi.org/10.1039/c3ta00107e
Bai BC, Kim EA, Jeon YP, Lee CW, In SJ, Lee YS, Im JS (2014) Improved flame retardant properties of lyocell fiber achieved by phosphorus compound. Mater Lett 135:226–228. https://doi.org/10.1016/j.matlet.2014.07.131
Chen L, Wang YZ (2009) A review on flame retardant technology in China. Part I: development of flame retardants. Polym Adv Technol 21:1–26. https://doi.org/10.1002/pat.1550
Chen XL, Huo LL, Jiao CM, Li SX (2013) TG-FTIR characterization of volatile compounds from flame retardant polyurethane foams materials. J Anal Appl Pyrol 100:186–191. https://doi.org/10.1016/j.jaap.2012.12.017
Cheng YY, He G, Barras A, Coffinier Y, Lu SX, Xu WG, Szunerits S, Boukherroub R (2017) One-step immersion for fabrication of superhydrophobic/superoleophilic carbon felts with fire resistance: fast separation and removal of oil from water. Chem Eng J 331:372–382. https://doi.org/10.1016/j.cej.2017.08.088
Ding HY, Huang K, Li SH, Xu LN, Xia JL, Li M (2017) Synthesis of a novel phosphorus and nitrogen-containing bio-based polyol and its application in flame retardant polyurethane foam. J Anal Appl Pyrol 128:102–113. https://doi.org/10.1016/j.jaap.2017.10.020
Dong CH, He PS, Lu Z, Wang SG, Sui SY, Liu J, Zhang L, Zhu P (2017) Preparation and properties of cotton fabrics treated with a novel antimicrobial and flame retardant containing triazine and phosphorus components. J Therm Anal Calorim 87(11):1–9. https://doi.org/10.1007/s10973-017-6604-x
Duan LJ, Yang HY, Song L, Hou YB, Wang W, Gui Z, Hu Y (2016) Hyperbranched phosphorus/nitrogen-containing polymer in combination with ammonium polyphosphate as a novel flame retardant system for polypropylene. Polym Degrad Stab 134:179–185. https://doi.org/10.1016/j.polymdegradstab.2016.10.004
Echeverria CA, Handoko W, Pahlevani F, Sahajwalla V (2019) Cascading use of textile waste for the advancement of fibre reinforced composites for building applications. J Clean Prod 208:1524–1536. https://doi.org/10.1016/j.jclepro.2018.10.227
Feng YJ, Zhou Y, Li DK, He SA, Zhang FX, Zhang GX (2017) A plant-based reactive ammonium phytate for use as a flame retardant for cotton fabric. Carbohydr Polym 175:636–644. https://doi.org/10.1016/j.carbpol.2017.06.129
French AD (2014) Idealized powder diffraction patterns for cellulose polymorphs. Cellulose 21:885–896. https://doi.org/10.1007/s10570-013-0030-4
Gaan S, Sun G (2007) Effect of phosphorus and nitrogen on flame retardant cellulose: a study of phosphorus compounds. J Anal Appl Pyrolysis 78:371–377. https://doi.org/10.1016/j.jaap.2006.09.010
Gao WW, Zhang GX, Zhang FX (2015) Enhancement of flame retardancy of cotton fabrics by grafting a novel organic phosphorous-based flame retardant. Cellulose 22:2787–2796. https://doi.org/10.1007/s10570-015-0641-z
Grancaric AM, Botteri L, Alongi J, Malucelli G (2015) Synergistic effects occurring between water glasses and urea/ammonium dihydrogen phosphate pair for enhancing the flame retardancy of cotton. Cellulose 22:2825–2835. https://doi.org/10.1007/s10570-015-0671-6
He PS, Chen XY, Zhu P, Liu J, Fan GD, Sui SY, Lu Z, Dong CH (2018) Preparation and flame retardancy of reactive flame retardant for cotton fabric. J Therm Anal Calorim 132:1771–1781. https://doi.org/10.1007/s10973-018-7057-6
Ji YM, Chen GQ, Xing TL (2018) Rational design and preparation of flame retardant silk fabrics coated with reduced graphene oxide. Appl Surf Sci 474:203–210. https://doi.org/10.1016/j.apsusc.2018.03.120
Jia YL, Lu Y, Zhang GX, Liang YJ, Zhang FX (2017) Facile synthesis of an eco-friendly nitrogen-phosphorus ammonium salt to enhance durability and flame retardancy of cotton. J Mater Chem A 5:9970–9981. https://doi.org/10.1039/C7TA01106G
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
Joshi HD, Joshi DH, Patel MG (2010) Dyeing and finishing of lyocell union fabrics: an industrial study. Color Technol 126:194–200. https://doi.org/10.1111/j.1478-4408.2010.00248.x
Kazantsev OA, Arifullin IR, Savinova MV, Sivokhin AP, Bol’shakova YA, Shchegravina ES (2020) Two-stage one-pot synthesis of N-(dibutylaminomethyl)-methacrylamide by Mannich reaction in mild conditions with high yield. React Chem Eng 5(9):1791–1797. https://doi.org/10.1039/x0xx00000x
Li YC, Schulz J, Mannen S, Delhom C, Condon B, Chang S, Zammarano M, Grunlan JC (2010) Flame retardant behavior of polyelectrolyte-clay thin film assemblies on cotton fabric. ACS Nano 4:3325–3337. https://doi.org/10.1021/nn100467e
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 Stab 181:109302. https://doi.org/10.1016/j.polymdegradstab.2020.109302
Li P, Wang B, Liu YY, Xu YJ, Jiang ZM, Dong CH, Zhang L, Liu Y, Zhu P (2020b) Fully bio-based coating from chitosan and phytate for fire-safety and antibacterial cotton fabrics. Carbohyd Polym 237:116173. https://doi.org/10.1016/j.carbpol.2020.116173
Liang TY, Jiang ZL, Wang CS, Liu JL (2017) A facile one-step synthesis of flame retardant coatings on cotton fabric via ultrasound irradiation. J Appl Polym Sci 134(30):45114–45120. https://doi.org/10.1002/app.45114
Liu XH, Zhang QY, Cheng BW, Ren YL, Zhang YG, Ding C (2017a) 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 ZY, Xu MJ, Wang Q, Li B (2017b) A novel durable flame retardant cotton fabric produced by surface chemical grafting of phosphorus- and nitrogen-containing compounds. Cellulose 24:4069–4081. https://doi.org/10.1007/s10570-017-1391-x
Liu XH, Zhang YG, Cheng BW, Ren YL, Zhang QY, Ding C, Peng B (2018a) Preparation of durable and flame retardant lyocell fibers by a one-pot chemical treatment. Cellulose 25:6745–6758. https://doi.org/10.1007/s10570-018-2005-y
Liu Y, Wang QQ, Jiang ZM, Zhang CJ, Li ZF, Chen HQ, 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 Pyrolysis 135:289–298. https://doi.org/10.1016/j.jaap.2018.08.024
Liu MS, Huang S, Zhang GX, Zhang FX (2019) An efficient anti-flaming phosphorus-containing guanazole derivative for cotton fabric. Cellulose 26(4):2791–2804. https://doi.org/10.1007/s10570-019-02275-6
Liu XH, Ding C, Peng B, Ren YL, Cheng BW, Lin SG, He J, Su XW (2020) Synthesis and application of a new, facile, and efficient sorbitol-based finishing agent for durable and flame retardant lyocell fibers. Cellulose 27(6):3427–3442. https://doi.org/10.1007/s10570-019-02894-z
Lu Y, Jia YL, Zhang GX, Zhang FX (2018a) 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
Lu Y, Jia YL, Zhou Y, Zou J, Zhang GX, Zhang FX (2018b) Straightforward one-step solvent-free synthesis of the flame retardant for cotton with excellent efficiency and durability. Carbohydr Polym 201:438–455. https://doi.org/10.1016/j.carbpol.2018.08.078
Mengal N, Syed U, Malik SA, Sahito IA, Jeong SH (2016) Citric acid based durable and sustainable flame retardant treatment for lyocell fabric. Carbohydr Polym 153:78–88. https://doi.org/10.1016/j.carbpol.2016.07.074
Naik AD, Fontaine G, Bellayer S, Bourbigot S (2015) Salen based Schiff bases to flame retard thermoplastic polyurethane mimicking operational strategies of thermosetting resin. RSC Adv 5:48224–48235. https://doi.org/10.1039/c5ra06242j
Parsa MR, Chaffee AL (2018) The effect of densification with NaOH on brown coal thermal oxidation behaviour and structure. Fuel 216:548–558. https://doi.org/10.1016/j.fuel.2017.11.135
Peng HY, Wang D, Li M, Zhang LP, Liu MM, Fu SH (2019) Ultra-small SiO2 nanospheres selt-pollinated on flowerlike MoS2 for simultaneously reinforcing mechanical, thermal and flame retardant properties of polyacrylonitrile fiber. Compos Part B-Eng 174:107037. https://doi.org/10.1016/j.compositesb.2019.107037
Peng Y, Niu M, Qin RH, Xue BX, Shao MQ (2020) Study on flame retardancy and smoke suppression of PET by the synergy between Fe2O3 and new phosphorus-containing silicone flame retardant. High Perform Polym 32(8):871–882. https://doi.org/10.1177/0954008320914365
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, Liu XH (2018) Preparation of flame retardant polyacrylonitrile fabric based on sol–gel and layer-by-layer assembly. Materials 11:483. https://doi.org/10.3390/ma11040483
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(11):6677–6689. https://doi.org/10.1007/s10570-020-03218-2
Sahito IA, Sun KC, Arbab AA, Qadir MB, Jeong SH (2015) Integrating high electrical conductivity and photocatalytic activity in cotton fabric by cationizing for enriched coating of negatively charged graphene oxide. Carbohydr Polym 130:299–306. https://doi.org/10.1016/j.carbpol.2015.05.010
Seddon H, Hall M, Horrocks AR (1996) The flame retardancy of lyocell fibres. Polym Degrad Stab 54:401–402. https://doi.org/10.1016/s0141-3910(96)00070-5
Shibata M, Oyamada S, Kobayashi S, Yaginuma D (2004) Mechanical properties and biodegradability of green composites based on biodegradable polyesters and lyocell fabric. J Appl Polym Sci 92:3857–3863. https://doi.org/10.1002/app.20405
Tian PX, Liu MS, Wan CY, Zhang GX, Zhang FX (2019) Synthesis of a formaldehyde-free flame retardant for cotton fabric. Cellulose 26(18):9889–9899. https://doi.org/10.1007/s10570-019-02751-z
Wan CY, Liu MS, Tian PX, Zhang GX, Zhang FX (2019a) Renewable vitamin B5 reactive N–P flame retardant endows cotton with excellent fire resistance and durability. Cellulose 27(3):1745–1761. https://doi.org/10.1007/s10570-019-02886-z
Wan CY, Tian PX, Liu MS, Zhang GX, Zhang FX (2019b) Synthesis of a phosphorus–nitrogen flame retardant endowing cotton with high whiteness and washability. Ind Crops Prod 141:111738. https://doi.org/10.1016/j.indcrop.2019.111738
Wang LH, Ren YL, Wang XL, Zhao JY, Zhang Y, Zeng Q, Gu YT (2016) Fire retardant viscose fiber fabric produced by graft polymerization of phosphorus and nitrogen-containing monomer. Cellulose 23:2689–2700. https://doi.org/10.1007/s10570-016-0970-6
Wang DF, Zhong L, Zhang C, Li SN, Tian PX, Zhang FX, Zhang GX (2018a) Ecofriendly synthesis of a highly efficient phosphorus flame retardant based on xylitol and application on cotton fabric. Cellulose 26:2123–2138. https://doi.org/10.1007/s10570-018-2193-5
Wang Z, Shu X, Zhu H, Xie L, Cheng S, Zhang Y (2018b) Characteristics of biochars prepared by co-pyrolysis of sewage sludge and cotton stalk intended for use as soil amendments. Environ Technol 41(11):1347–1357. https://doi.org/10.1080/09593330.2018.1534891
Wang B, Xu YJ, Li P, Zhang FQ, Liu Y, Li P (2020) Flame-retardant polyester/cotton blend with phosphorus/nitrogen/silicon-containing nano-coating by layer-by-layer assembly. Appl Surf Sci 509:145323. https://doi.org/10.1016/j.apsusc.2020.145323
Wei DD, Dong CH, Chen ZH, Liu J, Li Q, Lu Z (2018) A novel cyclic copolymer containing Si/P/N used as flame retardant and water repellent agent on cotton fabrics. J Appl Polym Sci. https://doi.org/10.1002/app.47280
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
Xu L, Jiang Y, Qiu R (2017) Parametric study and global sensitivity analysis for co-pyrolysis of rape straw and waste tire via variance-based decomposition. Bioresour Technol 247:545–552. https://doi.org/10.1016/j.biortech.2017.09.141
Xu F, Zhong L, Xu Y, Feng SY, Zhang C, Zhang FX, Zhang GX (2018) Highly efficient flame retardant kraft paper. Polymers 54:1884–1897. https://doi.org/10.1007/s10853-018-2911-2
Yang TT, Guan JP, Tang RC, Chen GQ (2018) Condensed tannin from Dioscorea cirrhosa tuber as an eco-friendly and durable flame retardant for silk textile. Ind Crops Prod 115:16–25. https://doi.org/10.1016/j.indcrop.2018.02.018
Zhang XS, Shi MW (2019) Flame retardant vinylon/poly(m-phenylene isophthalamide) blended fibers with synergistic flame retardancy for advanced fireproof textiles. J Hazard Mater 365:9–15. https://doi.org/10.1016/j.jhazmat.2018.10.091
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(14):8369–8383. https://doi.org/10.1007/s10570-020-03333-0
Zhu SW, Shi WF (2003) Thermal degradation of a new flame retardant phosphate methacrylate polymer. Polym Degrad Stab 80:217–222. https://doi.org/10.1016/S0141-3910(02)00401-9
Acknowledgments
The authors are very grateful to the financial supports of the National Natural Science Foundation of China (No. 51573134) and the National Key Research and Development Program of China (2017YFB0309000).
Author information
Authors and Affiliations
Contributions
YBG and MYX contributed equally to this work. YBG conceived the idea and designed the experiments. MYX contributed to the material fabrication. YBG conducted the thermal properties measurement and analyzed the corresponding results. MYX was responsible for the SEM images, the combustion testing, FT-IR measurements. YBG and MYX contributed to the cone calorimeter test and the corresponding analysis. YLR and XHL co-wrote and revised the manuscript. All authors commented on the final manuscript.
Corresponding authors
Ethics declarations
Conflict of interest
The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper. All the authors listed have approved the manuscript enclosed.
Ethical statement
All authors state that they adhere to the Ethical Responsibilities of Authors. In addition, the work is compliance with ethical standards.
Additional information
Publisher's Note
Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
Rights and permissions
About this article
Cite this article
Guo, Y., Xiao, M., Ren, Y. et al. Synthesis of an effective halogen-free flame retardant rich in phosphorus and nitrogen for lyocell fabric. Cellulose 28, 7355–7372 (2021). https://doi.org/10.1007/s10570-021-03975-8
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s10570-021-03975-8