磷/氮阻燃剂原位沉积对棉织物的耐久阻燃改性

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磷/氮阻燃剂原位沉积对棉织物的耐久阻燃改性

Modification of cotton fabric by in-situ deposition of phosphorus/nitrogen flame retardants for durable flame retardancy

磷/氮阻燃剂原位沉积对棉织物的耐久阻燃改性

Modification of cotton fabric by in-situ deposition of phosphorus/nitrogen flame retardants for durable flame retardancy

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doi:10.13475/j.fzxb.20240902401

纺织学报 ›› 2025, Vol. 46 ›› Issue (02): 180-187.doi: 10.13475/j.fzxb.20240902401

张洁¹^,², 郭鑫源¹^,², 关晋平¹^,²(), 程献伟¹^,², 陈国强¹^,²

1.苏州大学纺织与服装工程学院, 江苏苏州 215021
2.苏州大学纺织行业纺织材料阻燃整理重点实验室, 江苏苏州 215021

收稿日期:2024-09-29 修回日期:2024-10-31 出版日期:2025-02-15 发布日期:2025-03-04
通讯作者: 关晋平(1976—),女,教授,博士。主要研究方向为纺织品阻燃科学研究、纺织品可持续染整技术。E-mail:guanjinping@suda.edu.cn。
作者简介:张洁(2000—),女,硕士生。主要研究方向为涤纶/棉混纺织物的耐久阻燃改性。
第一联系人：
说明:本文入围中国纺织工程学会第25届陈维稷论文卓越行动计划
基金资助:
苏州市产业前瞻与关键核心技术项目(SYC2022017);国家自然科学基金项目(22408247)

ZHANG Jie¹^,², GUO Xinyuan¹^,², GUAN Jinping¹^,²(), CHENG Xianwei¹^,², CHEN Guoqiang¹^,²

1. College of Textile and Clothing Engineering, Soochow University, Suzhou, Jiangsu 215021, China
2. Key Laboratory of Flame Retardancy Finishing of Textile Materials (CNTAC), Soochow University, Suzhou, Jiangsu 215021, China

Received:2024-09-29 Revised:2024-10-31 Published:2025-02-15 Online:2025-03-04

摘要：

针对棉织物极易燃烧,引燃后火焰迅速蔓延的问题,采用四羟甲基硫酸磷、双氰胺和环状磷酸酯阻燃剂FRC-1进行缩聚反应,通过原位沉积的方法对棉织物进行改性以提高其阻燃性能。对改性棉织物的结构特征、燃烧行为、阻燃性能、耐水洗性能和阻燃机制等进行研究。结果表明:改性棉织物具有优异的阻燃性能和耐水洗性能,其损毁长度降至7.5 cm,极限氧指数升高至29.7%,经50次洗涤后改性棉织物仍能自熄,损毁长度为11.0 cm,极限氧指数为26.4%;改性棉织物的热释放速率峰值仅为41.6 kW/m²,下降了86.9%;在燃烧过程中,缩聚产物中的含磷阻燃基团早期裂解促进了棉织物的脱水和炭化,并形成了石墨化程度很高的炭层,有效地隔绝了氧气和热量;同时磷基自由基的猝灭效应也有利于阻燃性能的提高,因此阻燃剂在固相和气相均起到阻燃功能;此外,原位沉积改性对棉织物的强力性能影响较小。

关键词: 棉织物, 阻燃性能, 耐久性, 磷/氮阻燃剂, 阻燃织物, 功能纺织品

Abstract:

Objective Cotton fabrics are known for their softness, wearing comfort, moisture absorption and breathability, and are widely used in clothing, decoration, construction and other fields. However, cotton fabrics would burn rapidly and the burning is accompanied by obvious phenomena of secondary ignition and shadow ignition, which needs improving for the fire safety of cotton fabrics. Proban technology is known to offer flame retardant durability, low cost and minimal impact on mechanical properties to cotton fabrics, but it is limited by the complex ammonia fumigation process, which largely restricts its application.

Method Different concentrations of tetrakis(hydroxymethyl)phosphonium sulfate (THPS), dicyandiamide (DCD), and cyclic phosphate ester flame-retardant FRC-1 were used to prepare the solution at 80 ℃ oscillation for 10 min. The cotton fabrics were immersed in the solution for impregnation for 10 min, followed by two further immersion and two rolling processes. The rolling rate was 100%, and the fabric was then dried at 80 ℃ for 3 min, then baked at 150 ℃ for 3 min. THPS was used to form amine macromolecules with anionic FRC-1 electrostatic interaction, aiming to form more complex condensation products within the fibers. The complex condensation products were formed within the fiber to enable the cotton fabrics with efficient and durable flame-retardant properties.

Results Experiment showed that the cotton fabric burned fiercely with obvious continuation of combustion and the phenomenon of negative combustion. The length of damage was 30 cm, and the LOI value was only 18.6%. After the flame-retardant finishing, the flame retardancy of the modified cotton fabric was improved, and the flame was self-extinguished within 6 s, and the length of damage was reduced to 7.5 cm, and the LOI reached 29.7%, when the concentration of FRC-1 was 80 g/L and the concentration of THPS was 100 g/L. The modified cotton fabric exhibited good self-extinguishing performance after 50 times of home washing, when the destruction length was 11.0 cm, and the LOI was 26.4%. These still satisfy the performance requirements for grade B1 according to GB/T 17591—2006 Flame-retardant Fabrics. The heat release rate and total heat release of the modified cotton fabrics were greatly reduced, indicating that the flame-retardant coating obviously inhibited the heat release performance of cotton fabrics, and the fire hazard of modified cotton fabrics was reduced. The early decomposition of phosphorus-containing compound in the heating process promoted dehydration and charring of cotton fabrics. The modified fabrics showed high thermal stability with the formation of more residual carbon under high-temperature conditions, leaving a char layer with high degree of graphitization, effectively isolating oxygen and heat. In the combustion process, a large number of non-combustible volatile substances were produced, diluting the concentration of flammable gases, and the quenching effect of the phosphorus radical was also beneficial for improving flame retardancy. It is evident that the phosphorus-containing flame-retardant groups in the polycondensation products played a flame-retardant role in the solid phase and gas phase. The physical properties of the modified cotton fabrics did not change significantly and did not affect their subsequent use.

Conclusion The condensation product of tetrakis(hydroxymethyl)phosphine sulphate, dicyandiamide and the cyclic phosphate ester FRC-1 shows a high level of flame retardancy on cotton fabrics. Even after 50 home washing cycles, the modified cotton fabrics were able to pass the vertical flame test and meet the requirements of Class B1. Thermal analysis, thermogravimetric infrared analysis, cone calorimetry, carbon residue analysis and physical property analysis showed that the phosphorus-containing polycondensates effectively improved the flame retardancy of the modified cotton fabrics through the mechanism of solid-phase and gas-phase flame retardancy. In conclusion, phosphorus-containing polycondensates have a great potential to be used as a sustainable and effective flame-retardant method for modified cotton fabrics.

Key words: cotton fabric, flame retardancy, washing durability, nitrogen/phosphorus flame retardant, flame reardamts fabric, functional textile

中图分类号:

TS156

张洁, 郭鑫源, 关晋平, 程献伟, 陈国强. 磷/氮阻燃剂原位沉积对棉织物的耐久阻燃改性[J]. 纺织学报, 2025, 46(02): 180-187.

ZHANG Jie, GUO Xinyuan, GUAN Jinping, CHENG Xianwei, CHEN Guoqiang. Modification of cotton fabric by in-situ deposition of phosphorus/nitrogen flame retardants for durable flame retardancy[J]. Journal of Textile Research, 2025, 46(02): 180-187.

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链接本文: http://www.fzxb.org.cn/CN/10.13475/j.fzxb.20240902401

http://www.fzxb.org.cn/CN/Y2025/V46/I02/180

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气体氛围	织物	T_5% / ℃	T_max1/ ℃	T_max2/ ℃	700 ℃时的残炭量/%
氮气	棉织物	234	360	—	7.80
	改性棉织物	223	305	—	39.00
空气	棉织物	229	350	451	0.15
	改性棉织物	222	299	500	15.80

织物	断裂强力/N	断裂伸长率/%	白度/%
原棉织物	256.9±6.6	4.60±0.17	88.8±0.3
改性棉织物	254.7±9.6	4.46±0.20	88.4±1.5

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