纺织学报 ›› 2026, Vol. 47 ›› Issue (04): 171-179.doi: 10.13475/j.fzxb.20251005001

• 染整工程 • 上一篇    下一篇

基于超临界CO2的涤纶织物无水阻燃整理

刘雁雁1, 王小艳1, 杜金梅1, 郑振荣2, 韩振邦2, 许长海1()   

  1. 1 青岛大学 纺织服装学院, 山东 青岛 266071
    2 天津工业大学 纺织科学与工程学院, 天津 300387
  • 收稿日期:2025-10-21 修回日期:2026-01-21 出版日期:2026-04-15 发布日期:2026-04-15
  • 通讯作者: 许长海(1975—),男,教授,博士。主要研究方向为多功能纤维与纺织品及颜色化学和科学。E-mail: changhai_xu@qdu.edu.cn。
  • 作者简介:刘雁雁(1982—),女,博士生。主要研究方向为纺织品染整及功能整理。
  • 基金资助:
    山东省重大科技创新项目(2023CXGC010610)

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 Published:2026-04-15 Online:2026-04-15

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摘要：

为开发绿色环保的涤纶织物无水阻燃整理工艺,选取3种氮系、5种磷系阻燃剂,通过超临界CO2整理技术分别将其负载于涤纶织物。对阻燃剂的毒性进行预测,测试分析其粒径分布,系统表征整理后涤纶织物的表面形貌,探究阻燃剂与涤纶织物的结合能与质量增加率的关系,同时系统评估了整理后涤纶织物的阻燃性能和耐洗性能。研究结果表明:8种阻燃剂均属于低毒性化合物,其粒径分布呈单峰对数正态分布,粒径均小于1 μm;8种阻燃剂均可有效负载于涤纶织物表面,证实超临界CO2技术适用于涤纶织物的阻燃整理;阻燃剂与涤纶的结合能与织物质量增加率、耐洗性均呈正相关,较高的结合能及较大的质量增加率均有助于提升涤纶织物阻燃性能;其中,经2-羧乙基苯基次膦酸、磷酸三苯酯和9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物整理后的涤纶织物,展现出较为优异的阻燃性能和耐久性能。

关键词: 涤纶, 超临界CO2, 阻燃整理, 无水整理, 氮系阻燃剂, 磷系阻燃剂, 阻燃耐久性

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

中图分类号: 

  • TS195.5

表1

阻燃剂的基本物化性质"

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

图1

超临界CO2涤纶织物阻燃整理示意图"

图2

阻燃剂的毒性预测"

图3

阻燃剂的粒径分布"

图4

阻燃剂与涤纶织物的结合能及涤纶织物的质量增加率"

图5

原涤纶织物及阻燃涤纶织物的SEM照片"

图6

原涤纶织物及阻燃涤纶织物的垂直燃烧图"

图7

原涤纶织物及阻燃涤纶织物的损毁长度"

图8

原涤纶织物及阻燃涤纶织物的LOI值"

表2

阻燃涤纶织物耐洗性"

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

图9

阻燃涤纶织物的强力损失率"

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