Abstract
A reactive flame retardant, diethylenetriamine phosphoramidite ammonium phosphoric acid (DETA-PAP), was synthesized for cotton fabrics. Phosphorus atoms were introduced into the flame retardant molecule through P(=O)–N covalent bonds. The P(=O)–N covalent bonds were stable yet not easily hydrolyzed due to p–π conjugation in the P(=O)–N group, and the polarization of N–P(=O)–O–C covalent bonds was relatively low, resulting in P(=O)–O–C covalent bond being stable as well. The Limiting oxygen index (LOI) values of cotton fabrics processed with 24 wt.% and 36 wt.% DETA-PAP after 50 cycles were 41.3% and 45.3%, respectively, according to the AATCC 61-2013 3A standard (strenuous washes). This shows that the cotton processed with DETA-PAP was both flame retardant and highly durable. The vertical flammability test, thermogravimetry, and cone calorimetry indicated that DETA-PAP-treated cotton displayed exceptional flame retardancy and that DETA-PAP underwent a condensed-phase flame-retardant mechanism. The EDS results revealed that DETA-PAP-treated cotton fabrics combined with fewer metal ions after washing than former flame retardants, confirming the high durability of DETA-PAP-treated cotton fabrics. DETA-PAP-cotton fabrics retained their whiteness, softness, and mechanical capabilities. All of the studies found that introducing P(=O)–N groups increased the durability of flame-retardant cotton fabrics significantly.
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References
Agarwal UP, Ralph SA, Baez C, Reiner RS (2021) Detection and quantitation of cellulose II by Raman spectroscopy. Cellulose 28:9069–9079. https://doi.org/10.1007/s10570-021-04124-x
Chen Y, Wan C, Liu S et al (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 X, Shi L, Fan Z, et al (2022) Bio-based coating of phytic acid, chitosan, and biochar for flame-retardant cotton fabrics. Polym Degrad Stab 199:109898. https://doi.org/10.1016/j.polymdegradstab.2022.109898
Dalal A, Bagotia N, Sharma KK et al (2021) One pot facile synthesis of self-extinguishable metal based flame retardant for cotton fabric. J Nat Fibers 00:1–15. https://doi.org/10.1080/15440478.2021.1994090
Devaraju S, Krishnadevi K, Naveena E, Alagar M (2021) Eco-friendly fully bio-based polybenzoxazine-silica hybrid materials by sol–gel approach. Polym Bull 78:4251–4260. https://doi.org/10.1007/s00289-020-03309-x
Ding D, Liu Y, Lu Y, et al (2022) Highly effective and durable P-N synergistic flame retardant containing ammonium phosphate and phosphonate for cotton fabrics. Polym Degrad Stab 200:109964. https://doi.org/10.1016/j.polymdegradstab.2022.109964
Fu C, Xu X, Yin GZ, et al (2022) Surface engineering for cellulose as a boosted Layer-by-Layer assembly: excellent flame retardancy and improved durability with introduction of bio-based “molecular glue.” Appl Surf Sci. https://doi.org/10.1016/j.apsusc.2022.152550
Huang T, Xu F, Zhao P et al (2021) A novel flame retardant for cotton containing ammonium phosphonic acid and phosphonate prepared from urea a novel flame retardant for cotton containing ammonium phosphonic acid and phosphonate prepared from urea. J Nat Fibers 00:1–14. https://doi.org/10.1080/15440478.2021.2002779
Huong NT, Khanh VTH, Linh NPD (2021) Optimizing content of Pyrovatex CP New and Knittex FFRC in flame retardant treatment for cotton fabric. Ind Textila 72:315–323. https://doi.org/10.35530/IT.072.03.1648
Kaurin T, Pušić T, Dekanić T, Flinčec Grgac S (2022) Impact of washing parameters on thermal characteristics and appearance of proban®&mdash Flame Retardant Material. Mater. 15
Lazar ST, Kolibaba TJ, Grunlan JC (2020) Flame-retardant surface treatments. Nat Rev Mater 5:259–275. https://doi.org/10.1038/s41578-019-0164-6
Lee D, Jang J (2020) Synergistic flame-retardant finishing of cotton using dichlorotriazinyl phosphonate and triethanolamine. Fibers Polym 21:343–349. https://doi.org/10.1007/s12221-020-9442-6
Li G, You F, Zhou S et al (2022a) Preparations, characterizations, thermal and flame retardant properties of cotton fabrics finished by boron-silica sol-gel coatings. Polym Degrad Stab 202:110011. https://doi.org/10.1016/j.polymdegradstab.2022.110011
Li N, Chen P, Liu D et al (2022b) Novel P/Si based nanoparticles for durable flame retardant application on cotton. Cellulose 29:2063–2076. https://doi.org/10.1007/s10570-021-04309-4
Li XL, Shi XH, Chen MJ et al (2022c) Biomass-based coating from chitosan for cotton fabric with excellent flame retardancy and improved durability. Cellulose 29:5289–5303. https://doi.org/10.1007/s10570-022-04566-x
Liao Y, Chen Y, Wan C et al (2021) International journal of biological macromolecules 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
Ma Y, Luo X, Liu L et al (2021) Eco-friendly, efficient and durable fireproof cotton fabric prepared by a feasible phytic acid grafting route. Cellulose 28:3887–3899. https://doi.org/10.1007/s10570-021-03767-0
Magovac E, Vončina B, Budimir A et al (2021) Environmentally benign phytic acid-based nanocoating for multifunctional flame-retardant/antibacterial cotton. Fibers. https://doi.org/10.3390/fib9110069
Makhlouf G, Abdelkhalik A, Ameen H (2022) Preparation of highly efficient chitosan-based flame retardant coatings with good antibacterial properties for cotton fabrics. Prog Org Coatings 163:106627. https://doi.org/10.1016/j.porgcoat.2021.106627
Ortelli S, Malucelli G, Blosi M et al (2019) NanoTiO 2 @DNA complex: a novel eco, durable, fire retardant design strategy for cotton textiles. J Colloid Interface Sci 546:174–183. https://doi.org/10.1016/j.jcis.2019.03.055
Qi L, Qiu S, Xi J et al (2022) Construction of super-hydrophobic, highly effective flame retardant coating for cotton fabric with superior washability and abrasion resistance. J Colloid Interface Sci 607:2019–2028. https://doi.org/10.1016/j.jcis.2021.10.021
Rao W, Shi J, Yu C et al (2021) Highly efficient, transparent, and environment-friendly flame-retardant coating for cotton fabric. Chem Eng J 424:130556. https://doi.org/10.1016/j.cej.2021.130556
Salmeia KA, Gaan S, Malucelli G (2016) Recent advances for flame retardancy of textiles based on phosphorus chemistry
Shao ZB, Deng C, Tan Y et al (2014) Ammonium polyphosphate chemically-modified with ethanolamine as an efficient intumescent flame retardant for polypropylene. J Mater Chem A 2:13955–13965. https://doi.org/10.1039/c4ta02778g
Shariatinia Z, Javeri N, Shekarriz S (2015) Flame retardant cotton fibers produced using novel synthesized halogen-free phosphoramide nanoparticles. Carbohydr Polym 118:183–198. https://doi.org/10.1016/j.carbpol.2014.11.039
Shi XH, Liu QY, Li XL et al (2022) Construction phosphorus/nitrogen-containing flame-retardant and hydrophobic coating toward cotton fabric via layer-by-layer assembly. Polym Degrad Stab. https://doi.org/10.1016/j.polymdegradstab.2022.109839
Sun C, Guo Z, Zhou M et al (2021a) Heteroatoms-doped porous carbon electrodes with three-dimensional self-supporting structure derived from cotton fabric for high-performance wearable supercapacitors. J Power Sources 482:228934. https://doi.org/10.1016/j.jpowsour.2020.228934
Sun L, Xie Y, Wu J et al (2021b) A novel P/N-based flame retardant synthesized by one-step method toward cotton materials and its flame-retardant mechanism. Cellulose 28:3249–3264. https://doi.org/10.1007/s10570-021-03728-7
Sun L, Wang S, Zhang J, et al (2020) Triazine groups and its application on. 7386–7394. https://doi.org/10.1039/c9nj06268h
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
Ur Rehman Z, Kaseem M, Churchill DG et al (2022) Macro and micro thermal investigation of nanoarchitectonics-based coatings on cotton fabric using new quaternized starch. RSC Adv 12:2888–2900. https://doi.org/10.1039/d1ra09197b
Vishwakarma A, Reddy VJ, Kandola BK et al (2021) Egg white protein-hypophosphorous acid-based fire retardant single bilayer coating assembly for cotton fabrics. Cellulose 28:10689–10705. https://doi.org/10.1007/s10570-021-04208-8
Wan C, Liu M, Liu S et al (2021) An efficient and durable DOPO/H3PO4-based flame retardant for cotton fabric. Cellulose 28:7421–7434. https://doi.org/10.1007/s10570-021-03981-w
Xu L, Wang W, Yu D (2017a) 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 L, Wang W, Yu D (2017b) 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 F, Zhang G, Wang P, Dai F (2022) Durable and high-efficiency casein-derived phosphorus-nitrogen-rich flame retardants for cotton fabrics. Cellulose 29:2681–2697. https://doi.org/10.1007/s10570-022-04430-y
Yu S, Xia Z, Kiratitanavit W et al (2021a) Facile microwave assisted flame retardant treatment for cotton fabric using a biobased industrial byproduct: phytic acid. Cellulose 28:10655–10674. https://doi.org/10.1007/s10570-021-04191-0
Yu Z, Liu J, He H et al (2021b) Flame-retardant PNIPAAm/sodium alginate/polyvinyl alcohol hydrogels used for fire-fighting application: Preparation and characteristic evaluations. Carbohydr Polym 255:117485. https://doi.org/10.1016/j.carbpol.2020.117485
Zeng F, Qin Z, Li T et al (2020) Boosting phosphorus–nitrogen–silicon synergism through introducing graphene nanobrick wall structure for fabricating multifunctional cotton fabric by spray assisted layer-by-layer assembly. Cellulose 27:6691–6705. https://doi.org/10.1007/s10570-020-03235-1
Zhang F, Liao Y, Chen Y et al (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
Zhao P, Xu F, Chen Y et al (2022) A novel durable flame retardant for cotton fabrics based on diethylenetriamine. Polym Degrad Stab 195:109796. https://doi.org/10.1016/j.polymdegradstab.2021.109796
Zheng D, Zhou J, Wang Y et al (2018) A reactive flame retardant ammonium salt of diethylenetriaminepenta ( methylene-phosphonic acid ) for enhancing flame retardancy of cotton fabrics. Cellulose 25:787–797. https://doi.org/10.1007/s10570-017-1543-z
Zheng XT, Dong YQ, Liu XD, et al (2022) Fully bio-based flame-retardant cotton fabrics via layer-by-layer self assembly of laccase and phytic acid. J Clean Prod 350:131525. https://doi.org/10.1016/j.jclepro.2022.131525
Zouari R, Gargoubi S, Visileanu E (2021) Effect of plasma grafting with Hexamethyldisiloxane on comfort and flame resistance of cotton fabric. Ind Textila 72:225–230. https://doi.org/10.35530/IT.072.02.1842
Zouari R, Gargoubi S (2021) Enhancing flame resistance of cellulosic fibers using an ecofriendly coating. Coatings 11:1–11. https://doi.org/10.3390/coatings11020179
Acknowledgments
The Petroleum and Chemical Industry Engineering Laboratory of Non-halogen Flame Retardants for Polymers, Beijing Technology and Business University, China, provided funding for this work through its Open Project Program (BTBUFR21-2).
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The Petroleum and Chemical Industry Engineering Laboratory of Non-halogen Flame Retardants for Polymers, Beijing Technology and Business University, China, provided funding for this work through its Open Project Program (BTBUFR21-2).
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YY: Formal analysis, Investigation, Data Curation, Writing-Original Draft. QT: Software, Investigation. SD: Investigation, Resources. YC: Research grant, Software. YL: Software, Formal analysis. YL: Methodology, Validation. GZ: Resources, Writing-Review & Editing.
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Yang, Y., Tang, Q., Diao, S. et al. Formaldehyde-free, high-durability flame retardant with phosphoramidite and reactive ammonium phosphoric acid for cotton fabrics. Cellulose 30, 10487–10501 (2023). https://doi.org/10.1007/s10570-023-05512-1
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DOI: https://doi.org/10.1007/s10570-023-05512-1