Journal of Textile Research ›› 2026, Vol. 47 ›› Issue (04): 171-179.doi: 10.13475/j.fzxb.20251005001

• Dyeing and Finishing Engineering • Previous Articles     Next Articles

Supercritical CO2 water-free flame-retardant treatment of polyester fabrics

LIU Yanyan1, WANG Xiaoyan1, DU Jinmei1, ZHENG Zhenrong2, HAN Zhenbang2, XU Changhai1()   

  1. 1 College of Textiles & Clothing, Qingdao University, Qingdao, Shandong 266071, China
    2 School of Textile Science and Engineering, Tiangong University, Tianjin 300387, China
  • Received:2025-10-21 Revised:2026-01-21 Online:2026-04-15 Published:2026-04-15
  • Contact: XU Changhai E-mail:changhai_xu@qdu.edu.cn

RichHTML

5

PDF (PC)

15

Abstract:

Objective Polyester fabrics are flammable with molten dripping during combustion, limiting its application in various fields. Therefore, it is of great significance to impart flame retardancy to polyester fabrics. However, conventional flame-retardant modification of such fabrics leads to water pollution. Supercritical CO2 finishing technology avoids the use of organic solvents and water, as well as achieves zero waste in the finishing process, and it has attracted considerable attention as an eco-friendly flame-retardant method that can replace the existing water-based processes. This work aims to develop environmentally friendly, water-free flame retardant finishing technique using supercritical CO2.

Method The flame-retardant performance of several phosphorus/nitrogen-based flame retardants was investigated in supercritical CO2 fluid. Given the environmental advantages of this technology, the toxicity of eight structurally diverse flame retardants was predicted using the Toxicity Estimation Software Tool (T.E.S.T.). Particle size analysis confirmed that all flame retardants were in the nanometer range, suitable for supercritical CO2 processing. Scanning Electron Microscopy (SEM) was employed to examine the morphology of treated fibers and the deposition characteristics of flame retardants on the fabric surface. Flame retardancy was evaluated via Limiting Oxygen Index (LOI) and vertical burning tests, with particular attention to char length and melt-drip behavior. Correlation analysis was performed to identify key parameters influencing performance.

Results All the flame retardants with the particle sizes less than 1 μm were found suitable for supercritical CO2 flame retardant finishing. The results demonstrated that stronger binding energy between the flame retardant and the polyester fabric led to greater weight gain rate of the flame retardant on the fabric. The comprehensive evaluation of flame retardant performance revealed significant differences among the different flame retardants. 2-Carboxyethyl(phenyl) phosphinic acid(CEPPA), triphenyl phosphate and 9,10-Dihydro-9-oxa-10-phosphaphenanthrene-10-oxide(DOPO)exhibited high binding energy and significant weight gain rate and demonstrated the most outstanding overall performance, achieving a high LOI (>26%) compared to approximately 21% for untreated polyester fabrics and the elimination of melt-dripping. In addition, CEPPA possessed good durability of flame retardancy on polyester fabrics due to the high binding affinity. Sodium phytate also exhibited good flame retardancy, with LOI values all exceeding 26%, significantly enhancing the fire safety of polyester fabrics. However, the flame retardant durability of the polyester fabric treated with sodium phytate was poor because of its low binding affinity. In contrast, flame retardants such as melamine showed poor performance, with a damaged length even greater than that of untreated polyester fabric. The investigation into mechanical properties revealed that different flame retardants had varying impacts on the strength of fabric. Notably, tyrosine and DOPO can not only impart flame retardant properties to polyester fabrics, but also enhance the breaking strength of the fabrics to a certain extent.

Conclusion In supercritical CO2 flame-retardant finishing of polyester, binding energy between the flame retardant and the fabric, fabric weight gain, and wash resistance show a positive correlation. The type of flame retardant significantly influences the flame-retardant effect in the supercritical CO2 system. Among eight flame retardants, CEPPA, triphenyl phosphate, and DOPO had excellent flame-retardant efficacy. This study preliminarily confirms the feasibility of applying supercritical CO2 fluid technology to the flame-retardant finishing of polyester fabrics, providing a theoretical basis and practical reference for further research into water-free functional finishing technologies.

Key words: polyester, supercritical CO2, flame-retardant process, water-free finishing, nitrogen-based flame retardant, phosphorus-based flame retardant, flame retardant durability

CLC Number: 

  • TS195.5

Tab.1

Basic physicochemical properties of flame retardants"

阻燃剂 相对分子量 密度/(g·cm-3) 水溶性
三聚氰胺 126.12 1.70 微溶
植酸钠 923.81 1.20 易溶
酪氨酸 181.19 1.43 微溶
色氨酸 204.23 1.34 微溶
磷酸三苯酯 326.28 1.26 不溶
CEPPA 214.16 1.30 微溶
DOPO 216.00 1.33 不溶
二苯基磷酸 218.19 1.25 微溶

Fig.1

Diagram of supercritical CO2 flame-retardant treatment of polyester fabric"

Fig.2

Toxicity prediction of flame retardants. (a) LC50 (fathead minnow); (b) Developmental toxicity; (c) LD50 (rat oral)"

Fig.3

Particle size distribution of flame retardants. (a) Melamine; (b) Sodium phytate; (c) Tyrosine; (d) Tryptophan; (e) Triphenyl phosphate; (f) CEPPA; (g) DOPO; (h) Diphenyl phosphate"

Fig.4

Binding energy between flame retardants and polyester fabrics (a) and weight gain rate (b)"

Fig.5

SEM images of original polyester fabric and flame-retardant polyester fabrics. (a) Original polyester fabric; (b) Melamine treated polyester fabric; (c) Sodium phytate treated polyester fabric; (d) Tyrosine treated polyester fabric; (e) Tryptophan treated polyester fabric; (f) Triphenyl phosphate treated polyester fabric; (g) CEPPA treated polyester fabric; (h) DOPO treated polyester fabric; (i) Diphenyl phosphate treated polyester fabric"

Fig.6

Vertical combustion diagram of original polyester fabric and flame-retardant polyester fabrics. (a) Original polyester fabric; (b) Melamine treated polyester fabric; (c) Sodium phytate treated polyester fabric; (d) Tyrosine treated polyester fabric; (e) Tryptophan treated polyester fabric; (f) Triphenyl phosphate treated polyester fabric; (g) CEPPA treated polyester fabric; (h) DOPO treated polyester fabric; (i) Diphenyl phosphate treated polyester fabric"

Fig.7

Damage length of original polyester fabric and flame-retardant polyester fabrics"

Fig.8

LOI value of original polyester and flame- retardant polyester fabrics"

Tab.2

Flame retardant polyester fabric wash durability"

洗涤
次数		 植酸钠 DOPO CEPPA 磷酸三苯酯
LOI值 下降
率/%		 LOI值 下降
率/%		 LOI值 下降
率/%		 LOI值 下降
率/%
0 26.2 — 26.3 — 28.2 — 27.5 —
5 23.3 11.1 24.2 8.0 26.5 6.0 26.0 5.5
10 21.6 17.6 23.9 9.1 25.6 9.2 25.1 8.7

Fig.9

Strength loss of flame-retardant polyester fabrics"

[1] CHEN F, QI P, LIU J, et al. Fully bio-based flame retardant and antibacterial coating for polyethylene terephthalate fabric[J]. Progress in Organic Coatings, 2023, 182: 107637.
doi: 10.1016/j.porgcoat.2023.107637
[2] 徐豫松, 周杰, 甘佳怡, 等. 含磷氮水性聚氨酯的制备及其在涤纶织物阻燃整理中应用[J]. 纺织学报, 2024, 45(7): 112-120.
XU Yusong, ZHOU Jie, GAN Jiayi, et al. Preparation of phosphorus and nitrogen containing waterborne polyurethane and its application in polyester fabrics for flame retardant finishing[J]. Journal of Textile Research, 2024, 45(7): 112-120.
doi: 10.1177/004051757504500205
[3] 王以红, 潘虹, 沈勇, 等. DOPO-APTES的制备及其对涤纶织物阻燃抗熔滴性能的研究[J]. 功能材料, 2024, 55(2): 2201-2206, 2223.
doi: 10.3969/j.issn.1001-9731.2024.02.025
WANG Yihong, PAN Hong, SHEN Yong, et al. Preparation of DOPO-APTES and its study on flame retardant and anti-melt-drop properties of polyester fabrics[J]. Journal of Functional Materials, 2024, 55(2): 2201-2206, 2223.
doi: 10.3969/j.issn.1001-9731.2024.02.025
[4] LAZAR S T, KOLIBABA T J, GRUNLAN J C. Flame-retardant surface treatments[J]. Nature Reviews Materials, 2020, 5(4): 259-275.
doi: 10.1038/s41578-019-0164-6
[5] 周曼, 蔡再生. 常规阻燃纺织纤维与高性能阻燃纤维的分类及发展趋势[J]. 国际纺织导报, 2019, 47(10): 6-10.
ZHOU Man, CAI Zaisheng. Classification and future development of conventional flame-retardant textile fibers and high-performance flame-retardant fibers[J]. Melliand China, 2019, 47(10): 6-10.
[6] 赵萌, 姜秋实, 刘姝, 等. 涤纶织物的阻燃研究及发展[J]. 化学与粘合, 2013, 35(3): 62-66.
ZHAO Meng, JIANG Qiushi, LIU Shu, et al. Research and development of flame retardant of polyester fabric[J]. Chemistry and Adhesion, 2013, 35(3): 62-66.
[7] 肖云超, 杨雅茹, 郭健鑫, 等. 高温自交联抗熔滴阻燃涤纶织物的制备及其性能[J]. 纺织学报, 2023, 44(11): 151-159.
doi: 10.13475/j.fzxb.20220906301
XIAO Yunchao, YANG Yaru, GUO Jianxin, et al. Preparation and properties of high temperature self-crosslinked anti-dripping and flame-retardant polyester fabric[J]. Journal of Textile Research, 2023, 44(11): 151-159.
doi: 10.13475/j.fzxb.20220906301
[8] 李好帅, 郑兆临, 刘雁雁, 等. 涤纶织物全生物基阻燃抗熔滴涂层的构建[J]. 毛纺科技, 2024, 52(4): 31-37.
LI Haoshuai, ZHENG Zhaolin, LIU Yanyan, et al. Construction of fully bio-based flame-retardant anti-dripping coatings on polyester fabric[J]. Wool Textile Journal, 2024, 52(4): 31-37.
[9] 张小芳, 吴亚容, 邢志奇, 等. 涤纶织物的硅溶胶-凝胶阻燃抗熔滴整理[J]. 印染, 2018, 44(6): 1-6.
ZHANG Xiaofang, WU Yarong, XING Zhiqi, et al. Flame retardant and anti-dripping finishing of PET fabric with sol-gel process[J]. China Dyeing & Finishing, 2018, 44(6): 1-6.
[10] WU W, FAN B, ZHOU Q Q, et al. Distribution of disperse dyes between supercritical CO2 and polyester fibers: a combined molecular dynamics simulation and experimental study[J]. Journal of Cleaner Production, 2024, 481: 144162.
doi: 10.1016/j.jclepro.2024.144162
[11] WU W, GE H F, ZHOU Q Q, et al. A method to improve dye-uptakes of less soluble disperse dyes for polyester fibers in supercritical CO2 fluid: a theoretical and experimental study[J]. The Journal of Supercritical Fluids, 2024, 205: 106152.
doi: 10.1016/j.supflu.2023.106152
[12] 宋洁, 蔡涛, 郑福尔, 等. 涤纶针织鞋材超临界CO2无水染色性能[J]. 纺织学报, 2023, 44(5): 46-53.
SONG Jie, CAI Tao, ZHENG Fuer, et al. Research on supercritical CO2 waterless dyeing property of polyester knitted shoe materials[J]. Journal of Textile Research, 2023, 44(5): 46-53.
[13] 陆同庆, 龙家杰, 张培群, 等. 涤纶织物超临界二氧化碳染色研究[J]. 染料与染色, 2004, 41(6): 346-347.
LU Tongqing, LONG Jiajie, ZHANG Peiqun, et al. A study on dyeing polyester fabrics in supercritical carbon dioxide[J]. Dyestuffs and Coloration, 2004, 41(6): 346-347.
[14] LONG J J, XU H M, CUI C L, et al. A novel plant for fabric rope dyeing in supercritical carbon dioxide and its cleaner production[J]. Journal of Cleaner Production, 2014, 65: 574-582.
doi: 10.1016/j.jclepro.2013.08.008
[15] 龙家杰, 陈锋, 魏晓晨, 等. 纺织品超临界CO2无水染色的产业化进程[J]. 染整技术, 2015, 37(8): 1-6.
LONG Jiajie, CHEN Feng, WEI Xiaochen, et al. Industrialization process of textile supercritical CO2 anhydrous dyeing[J]. Textile Dyeing and Finishing Journal, 2015, 37(8): 1-6.
[16] 郑环达, 郑来久. 超临界流体染整技术研究进展[J]. 纺织学报, 2015, 36(9): 141-148.
ZHENG Huanda, ZHENG Laijiu. Research development of supercritical fluid dyeing and finishing technology[J]. Journal of Textile Research, 2015, 36(9): 141-148.
[17] 董君婕, 郑振荣, 周洁, 等. 天冬氨酸/赖氨酸基于超临界CO2流体的涤纶阻燃整理及工艺条件探索[J]. 消防科学与技术, 2025, 44(7): 962-969.
DONG Junjie, ZHENG Zhenrong, ZHOU Jie, et al. Supercritical CO2 fluid flame-retardant processing of polyethylene terephthalate(PET)fabric treated with aspartic acid/lysine and exploration of process conditions[J]. Fire Science and Technology, 2025, 44(7): 962-969.
[18] ZHONG W P, YU Z, ZHANG Z X. Development of polyamide12 composite foam by supercritical CO2: the effect of flame retardants on foaming behavior and properties[J]. European Polymer Journal, 2022, 179: 111562.
doi: 10.1016/j.eurpolymj.2022.111562
[19] KE H Z, FANG Q, HAN Y T, et al. Facile flame-retardant finishing for cotton in supercritical CO2[J]. Textile Research Journal, 2022, 92(13/14): 2306-2316.
doi: 10.1177/00405175221074068
[20] ZHENG Z R, DONG J J, WANG J, et al. Amino acid flame-retardant finishing of poly-(ethylene terephthalate) (PET) fabrics based on supercritical CO2[J]. Journal of CO2 Utilization, 2024, 86: 102918.
[21] KRESSE G, FURTHMÜLLER J. Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set[J]. Physical Review B, Condensed Matter, 1996, 54(16): 11169-11186.
doi: 10.1103/PhysRevB.54.11169
[22] 乔国岳, 刘居陶, 孙剑飞, 等. 超临界CO2脱附作用调控负载纳米颗粒结晶动力学研究[J]. 化工学报, 2021, 72(11): 5849-5857.
doi: 10.11949/0438-1157.20210763
QIAO Guoyue, LIU Jutao, SUN Jianfei, et al. Study on crystallization kinetics of supported nanoparticles controlled by desorption of supercritical carbon dioxide[J]. CIESC Journal, 2021, 72(11): 5849-5857.
[23] 程万里. 染料化学[M]. 北京: 中国纺织出版社, 2010: 251.
CHENG Wanli. Dye chemistry[M]. Beijing: China Textile & Apparel Press, 2010: 251.
[1] AO Limin, XU Haowen. Principle of compact covering technology and its control effect on hairiness of staple yarn [J]. Journal of Textile Research, 2026, 47(04): 113-119.
[2] SHI Meiwu. Review of new antimicrobial technologies for textiles [J]. Journal of Textile Research, 2026, 47(03): 201-207.
[3] REN Yi, FENG Qingguo, CHEN Yuheng, WANG Yanyan. Impact of combing processing on comfort properties of polyester/cotton blended fabrics [J]. Journal of Textile Research, 2026, 47(02): 103-110.
[4] ZHANG Jichao, LIU Yuchen, ZHANG Hao, GENG Jiajun, CAI Shuo, YANG Rumeng, LIU Ying, WEI Peng. Regulating monomer composition for structure and properties of naphthyl liquid crystalline polyarylate fiber [J]. Journal of Textile Research, 2026, 47(02): 65-72.
[5] ZHOU Yu, WEI Bing, HAO Kuangrong, GAO Lei, WANG Huaping. Polyester fiber ultrastructure segmentation algorithm based on improved U-Mamba network [J]. Journal of Textile Research, 2026, 47(01): 72-79.
[6] SHI Binlin, DONG Zhijia, MA Pibo, CONG Honglian, WU Guangjun, LIU Bo. Structural design of robot neck joint covering using whole-garment knitting technology [J]. Journal of Textile Research, 2025, 46(12): 116-122.
[7] SHEN Xinyi, LI Jiawei, SHAO Yu, GUO Dingtao, HE Guiping, ZHAO Lei, QI Dongming, YOUSSEF Yehya Abel-Gawad, KAFAFY Hany Hassan Ahmed Mohamed. Preparation and printing properties of reactive polymer encapsulated carbon black direct printing ink with high color fastness [J]. Journal of Textile Research, 2025, 46(12): 152-162.
[8] YANG Yingxue, GAO Nianzhao, DENG Nianming, JIANG Jinghui, DONG Qingqi, LIU Xiangdong. Recent advances in recycling of polyethylene terephthalate textiles waste [J]. Journal of Textile Research, 2025, 46(12): 251-259.
[9] YAO Xiaojun, XU Enting, YANG Xueyuan, FANG Lei, BAO Wei, FANG Kuanjun. Regulation of polyvinylpyrrolidone on structure and properties of polyethylene terephthalate hollow fiber membranes [J]. Journal of Textile Research, 2025, 46(12): 66-73.
[10] YE Hui, CONG Honglian, HE Haijun. Preparation and properties of phase change hollow polyester fibers based on binary fatty acids [J]. Journal of Textile Research, 2025, 46(11): 188-195.
[11] CAI Liyun, OUYANG Chenghui, HUANG Zeyang, WANG Chengcheng, GUAN Yu, FU Shaohai, ZHANG Liping. Preparation of colored latex particles and their application in printing of polyester-cotton fabrics [J]. Journal of Textile Research, 2025, 46(10): 135-142.
[12] JIANG Tingguo, KUANG Jun, SI Hu, ZHANG Yumei, CHEN Ye, WANG Huaping. Study on crystallization kinetics of titanium polyester for industrial yarns [J]. Journal of Textile Research, 2025, 46(08): 53-61.
[13] XU Wenhao, CHEN Lin, XU Shimei, WANG Xiuli, WANG Yuzhong. Transformation rule of polyester glycolysis products in methanol transesterification [J]. Journal of Textile Research, 2025, 46(06): 1-7.
[14] SHI Sheng, WANG Yazhou, WANG Shuhua, PANG Mingke, LI Xin, ZHANG Meiling, GAO Chengyong. Preparation of fluorinated waterborne polyurethane from waste polyester fibers by alcoholysis [J]. Journal of Textile Research, 2025, 46(06): 8-16.
[15] ZHU Menghui, GE Meitong, DONG Zhijia, CONG Honglian, MA Pibo. Structure and heat-moisture properties evaluation of double-sided wool/polyester weft-knitted fabrics [J]. Journal of Textile Research, 2025, 46(05): 179-185.
Viewed
Full text


Abstract

Cited
  Shared   
  Discussed   
No Suggested Reading articles found!
京ICP备14006648号
Copyright 2021 © Editorial office of Journal of Textile Research
Supported by Beijing Magtech Co.Ltd