耐久高效磷/氮协同阻燃剂的制备及其在棉织物上的应用

doi:10.13475/j.fzxb.20230705201

纺织学报 ›› 2024, Vol. 45 ›› Issue (07): 121-129.doi: 10.13475/j.fzxb.20230705201

耐久高效磷/氮协同阻燃剂的制备及其在棉织物上的应用

李旭¹^,²^,³, 刘祥吉¹^,²^,³, 靳鑫¹^,²^,³, 杨承昊¹^,²^,³, 董朝红¹^,²^,³()

1.青岛大学纺织服装学院, 山东青岛 266071
2.青岛大学功能纺织品与先进材料研究院, 山东青岛 266071
3.青岛大学生物多糖纤维成形与生态纺织国家重点实验室, 山东青岛 266071

收稿日期:2023-07-25 修回日期:2024-04-10 出版日期:2024-07-15 发布日期:2024-07-15
通讯作者: 董朝红(1968—),女,教授,博士。主要研究方向为功能助剂及功能纺织品。E-mail: dongzhh11@163.com。
作者简介:李旭(1999—),男,硕士生。主要研究方向为功能性纤维及功能性纺织品。
基金资助:
国家自然科学基金重大项目(51991354);山东省自然科学基金面上项目(ZR2023ME190);省部共建生物多糖纤维成形与生态纺织国家重点实验室自主课题-重点项目(ZDKT202110)

Preparation of durable and efficient P/N synergical flame retardant and its application on cotton fabrics

LI Xu¹^,²^,³, LIU Xiangji¹^,²^,³, JIN Xin¹^,²^,³, YANG Chenghao¹^,²^,³, DONG Chaohong¹^,²^,³()

1. College of Textiles & Clothing, Qingdao University, Qingdao, Shandong 266071, China
2. Institute of Functional Textiles and Advanced Materials, Qingdao University, Qingdao, Shandong 266071, China
3. State Key Laboratory of Bio-Fibers and Eco-Textiles, Qingdao University, Qingdao, Shandong 266071, China

Received:2023-07-25 Revised:2024-04-10 Published:2024-07-15 Online:2024-07-15

摘要/Abstract

摘要：

为解决棉纺织品易燃易引发火灾及阻燃处理棉织物耐久性等问题,以五氧化二磷和乙醇胺为原料制备了一种膨胀型磷/氮协效阻燃剂(2-羟乙基)磷酰胺铵盐(AHPA),并通过轧—烘—焙工艺将其整理于棉织物上。采用傅里叶变换红外光谱和核磁共振光谱表征了AHPA的化学结构;对阻燃处理后的棉织物进行垂直燃烧和极限氧指数测试,通过热重和锥形量热测试评估了其热稳定性,并分析了其阻燃耐久性能。结果表明:阻燃剂AHPA被成功合成,其与棉织物之间形成了稳定的共价键;阻燃处理后棉织物的极限氧指数(LOI)显著提高,且损毁长度大幅降低;在阻燃剂AHPA质量浓度为300 g/L时,LOI值由18 %增加到52.9 %,损毁长度由300 mm减小至45 mm;阻燃处理后棉织物的热降解过程和燃烧途径均发生了显著变化,热稳定性得到显著提高;在50次循环水洗后,LOI值仍能保持在31.6 %左右,具有良好的阻燃耐久性能。

关键词: 棉织物, 阻燃剂, 阻燃织物, 功能性纺织品, 磷/氮协效, 阻燃性能

Abstract:

Objective Cotton fabric is one of the most common natural fabrics, and has excellent moisture absorption, breathability, thermal insulation and softness, which are widely used in clothing, household tems, military and other fields. Unfortunately, the limiting oxygen index of cotton fabric is only 18 %, and it is easily ignited in the air, causing fire accidents. In addition, the flame retardant durability of flame-retardant cotton fabrics is also very important. Hence, it is necessary to prepare efficient and durable flame-retardant cotton fabrics.

Method The ammonium phosphate (AHPA) flame retardant was prepared from phosphorus pentoxide and ethanolamine. The P/N-type flame retardant AHPA was heated to produce acidic substances such as polyphosphoric acid, which promoted the dehydration of the fabrics and formed a dense carbon layer. During this process, P/N-type flame retardant AHPA generated non-flammable gases, which isolated heat and oxygen, diluted combustible gases, and hindered flame spread. Flame retardant cotton fabrics were prepared by common rolling-baking-baking finishing process. The thermal stability and mechanical properties of flame retardant cotton fabrics were analyzed by vertical flammability test, limiting oxygen index test, thermogravimetric test, cone calorimetry test and universal material test.

Results The test results showed that the flame retardant AHPA was successfully synthesized,and the fiber surface had been successfully covered by the flame retardant. When the concentration of flame retardant AHPA was set to 300 g/L, the LOI value of flame retardant cotton fabric had been increased to 52.9 % from 18 %, with only 45 mm damaged carbon length. The heat release rate and total heat release of the treated cotton fabrics were decreased by 86.1 % and 31.5 %, respectively. The flame spread rate (FIGRA) and mean effective heat combustion (Mean-EHC) were decreased from 6 kW/(m²·s) and 23.5 MJ/kg to 0.3 kW/(m²·s) and 15.3 MJ/kg, respectively, representing 95 % and 34.9 % reductions in each perspective. The AHPA flame retardant worked to reduce the heat release and the combustion efficiency with improved safety. In nitrogen and air atmosphere, the carbon residue of flame-retardant cotton fabrics had been greatly increased compared to the pristine cotton fabric, indicating that the thermal stability of the flame-retardant treated cotton fabrics had been greatly improved. The breaking force of the finished cotton fabrics was decreased in both warp and weft directions. After 50 washing cycles, the LOI value of the flame retardant cotton fabrics maintained at about 31.6 %.

Conclusion In summary, the flame retardant AHPA endows cotton fabrics with efficient and durable flame retardant properties, self-extinguishing of fire, discontinuous smoldering phenomenon, and excellent washing durability. The flame retardant AHPA can be applied to cotton fabrics used for bedding, carpets, curtains and so on. In following-up research work, the mechanical strength of the flame retardant cotton fabrics needs be optimized, and the total smoke release should be reduced.

Key words: cotton fabric, flame retardant, flame retardant fabric, functional textile, phosphorus and nitrogen synergy, flame retardant property

中图分类号:

TS195.5

李旭, 刘祥吉, 靳鑫, 杨承昊, 董朝红. 耐久高效磷/氮协同阻燃剂的制备及其在棉织物上的应用[J]. 纺织学报, 2024, 45(07): 121-129.

LI Xu, LIU Xiangji, JIN Xin, YANG Chenghao, DONG Chaohong. Preparation of durable and efficient P/N synergical flame retardant and its application on cotton fabrics[J]. Journal of Textile Research, 2024, 45(07): 121-129.

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链接本文: http://www.fzxb.org.cn/CN/10.13475/j.fzxb.20230705201

http://www.fzxb.org.cn/CN/Y2024/V45/I07/121

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阻燃剂质量浓度/ (g·L^-1)	质量增加率/ %	续燃时间/ s	阴燃时间/ s	损毁长度/ mm	LOI值/ %
0(未处理棉织物)	0	8	13	300	18.0±0.2
100	12.21	0	0	63	37.5±0.2
200	20.23	0	0	53	47.9±0.2
300	28.24	0	0	45	52.9±0.1
400	33.35	0	0	42	54.3±0.1

浸渍温度/℃	质量增加率/%	损毁长度/mm	LOI值/%
60	26.56	51	49.0±0.2
70	28.24	45	52.9±0.1
80	28.91	45	53.5±0.1
90	29.74	43	54.0±0.2

样品	TTI/ s	pk-HRR/ (kW·m^-2)	t_pk-HRR/ s	THR/ (MJ·m^-2)	TSP/ m²	残余质量分数/%	FIGRA/ (kW·m^-2·s^-1)	平均有效燃烧热/ (MJ·kg^-1)
未处理棉织物	20±1	228.0±0.5	38±1	9.84±0.01	0.102±0.001	3.2±0.2	6	23.5±0.9
阻燃处理棉织物	—	31.6±0.7	104±2	6.74±0.02	0.399±0.001	14.5±0.2	0.3	15.3±1.4

测试气氛	样品	T_onset/℃	T_max/℃	R_max/(%·℃^-1)	790 ℃时的残炭量/%
氮气	未处理棉织物	270	365	1.60	0.6
氮气	阻燃处理棉织物	214	259	0.55	37.1
空气	未处理棉织物	261	375	0.95	0
空气	阻燃处理棉织物	208	273	0.56	8.0

阻燃剂质量浓度/ (g·L^-1)	断裂强力/N
阻燃剂质量浓度/ (g·L^-1)	经向	纬向
(未处理棉织物)	442.65±5.51	420.78±5.29
100	414.74±1.74	333.92±6.87
200	395.46±2.00	260.34±7.02
300	404.23±4.45	261.97±9.63
400	404.67±4.03	269.28±8.05

耐久高效磷/氮协同阻燃剂的制备及其在棉织物上的应用

Preparation of durable and efficient P/N synergical flame retardant and its application on cotton fabrics

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