纺织学报 ›› 2024, Vol. 45 ›› Issue (07): 112-120.doi: 10.13475/j.fzxb.20230905701

• 染整工程 • 上一篇    下一篇

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

徐豫松1,2, 周杰1, 甘佳怡1,2, 张涛2,3(), 张先明1,2   

  1. 1.浙江理工大学 材料科学与工程学院, 浙江 杭州 310018
    2.浙江省现代纺织技术创新中心, 浙江 绍兴 312030
    3.浙江理工大学 艺术与设计学院, 浙江 杭州 310018
  • 收稿日期:2023-09-28 修回日期:2024-04-11 出版日期:2024-07-15 发布日期:2024-07-15
  • 通讯作者: 张涛(1981—),男,副教授,博士。主要研究方向为阻燃材料。E-mail:taoyuan0510@126.com。
  • 作者简介:徐豫松(1999—),男,硕士生。主要研究方向为水性聚氨酯阻燃涂料。
  • 基金资助:
    浙江省“尖兵”“领雁”研发攻关计划资助项目(2023C01095)

Preparation of phosphorus and nitrogen containing waterborne polyurethane and its application in polyester fabrics for flame retardant finishing

XU Yusong1,2, ZHOU Jie1, GAN Jiayi1,2, ZHANG Tao2,3(), ZHANG Xianming1,2   

  1. 1. School of Materials Science & Engineering, Zhejiang Sci-Tech University, Hangzhou, Zhejiang 310018, China
    2. Zhejiang Provincial Innovation Center of Advanced Textile Technology, Shaoxing, Zhejiang 312030, China
    3. School of Art & Design, Zhejiang Sci-Tech University, Hangzhou, Zhejiang 310018, China
  • Received:2023-09-28 Revised:2024-04-11 Published:2024-07-15 Online:2024-07-15

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摘要：

为提高水性聚氨酯(WPU)整理涤纶织物的阻燃效果,以含磷、氮希夫碱衍生物阻燃剂(DOPO-HAMB)为扩链剂合成本质阻燃WPU(FRWPU),通过浸渍法将FRWPU涂敷到涤纶织物表面,研究DOPO-HAMB在FRWPU中的质量百分比对热分解性能、阻燃性能、力学性能和耐水洗性能的影响。结果表明:与原涤纶织物相比,整理后涤纶织物最大热失重速率降低,降低幅度随DOPO-HAMB质量百分比的增加而增加;极限氧指数(LOI)提高至24.5%,比原涤纶织物提高了7.4%;垂直燃烧测试中的黑色烟雾减少,且损毁长度降低至9.7 cm;经向和纬向断裂强力、纬向断裂伸长率与原涤纶织物相比有所提升,而经向断裂伸长率有所降低;50次水洗后的LOI值为21.2%,仍然明显高于原涤纶织物。

关键词: 功能纺织品, 涤纶织物, 水性聚氨酯, 阻燃整理, 阻燃性能, 力学性能, 耐水洗性能

Abstract:

Objective Polyester fabric has many advantages, including good thermal stability, chemical resistance and excellent mechanical properties, which make it widely used in clothing, furnishings and packaging. However, polyester fabric has a low limiting oxygen index and is flammable. When it burns, the polyester fabric produces a large amount of molten droplets which could quickly spread the flames to other combustible materials, and releases a significant volume of toxic smoke. Statistics show that most casualties in fires are caused by smoke inhalation, with more than one-third of total fire casualties directly attributable to smoke poisoning. Therefore, it is crucial to modify polyester fabric to control the release of smoke as well as the formation of molten droplets during combustion.

Method The Schiff base derivative 4-(((4-hydroxyphenyl)imino)methyl)benzene-1,3-diol (HIMB) was prepared and reacted with 9,10-dihydro-9-oxo-10-phosphophenanthrene-10 oxide (DOPO) to obtain a phosphorus- and nitrogen-containing Schiff base derivative flame retardant 4-DOPO-(((4-hydroxyphenyl)amino)methyl) benzene 1,3-diol (DOPO-HAMB). DOPO-HAMB was used as a chain extender to introduce into the molecular main chain of waterborne polyurethane (WPU) to prepare inherently flame-retardant waterborne poly-urethane (FRWPU). FRWPU was then applied to the surface of polyester fabrics through an impregnation method, providing the polyester fabrics with flame retardant properties while ensuring mechanical performance.

Results Photos and scanning electron microscopy images of the actual polyester fabrics before and after the treatment showed that the treated polyester fabric had a slight yellowing compared to the original polyester fabric, with no significant change in transparency. Scanning electron microscopy images showed that the surface of the treated polyester fabric was coated and the gaps between fibers were almost filled. Thermogravimetric experiments demonstrated that the temperature at 5% thermal decomposition, the temperature at the maximum rate of decomposition, and the char yield at 650 ℃ of the treated polyester fabric were all lower than that of the raw polyester fabric. The results of the limiting oxygen index (LOI) and vertical burning tests indicated that the raw polyester fabric had an LOI value of only 17.1%, the WPU treated fabric's LOI was 19.2%, and when DOPO-HAMB was introduced into the WPU molecular main chain, the LOI value of the FRWPU12 (the mass percentage of DOPO-HAMB in WPU is 12%) treated fabric increased to 24.5%, which was 7.4% higher than that of the raw polyester fabric. The raw polyester fabric continued to burn for 18 s after ignition, with a damage length reaching 30 cm, producing dripping that ignites the cotton beneath. However, the FRWPU12 treated fabric did not continue burning and was self-extinguished immediately after removing from the flame, with a damage length of only 9.7 cm and no dripping during combustion. Scanning electron microscopy images and energy dispersive X-ray spectroscopy spectra of the char residue showed that the surface of the char from the raw polyester fabric was fragmented and contained only C and O elements, while the char from the FRWPU3 (the mass percentage of DOPO-HAMB in WPU is 3%) and FRWPU12 treated polyester fabrics was smooth and dense, containing P in addition to C and O, indicating the principal role of P from DOPO-HAMB in the WPU molecular main chain was in the condensed phase. Tensile test of the polyester fabric before and after treatment revealed that the warp and weft breaking strength of the raw polyester fabric were 508 N and 253 N, and the warp and weft elongations at break were 34.0% and 16.9%, respectively. After treatment, the maximum warp breaking strength of the polyester fabric increased to 521 N, and the maximum weft breaking strength to 567 N, with the highest weft breaking at break up to 23.8%. The increase in warp and weft breaking strengths are attributable to the WPU and FRWPU between adjacent fibers, which increased the tightness of the yarns and the connection strength between the yarns. In the water-fastness test, the FRWPU12 treated fabric showed a significantly higher LOI value than the raw polyester fabric even after 50 washing cyeles with water, indicating good water washability of FRWPU12 on the polyester fabric surface.

Conclusion A phosphorus-and nitrogen-containing Schiff base derivative flame retardant, DOPO-HAMB, was synthesized and introduced into the main molecular chain of WPU as a chain extender to obtain FRWPU. The WPU and FRWPU were then applied to the surface of the polyester fabric by an impregnation method. When the mass percentage of DOPO-HAMB in WPU is 12%, the LOI value of the treated fabric reaches 24.5%, the length of damage in the vertical burning test is significantly decreases, and no dripping occurs during combustion. Compared with the raw polyester fabric, the warp and weft tensile breaking strength of the treated polyester fabric are improved to a certain extent. Moreover, the LOI value of the treated polyester fabric after 50 washing cycles remains significantly higher than that of the raw polyester fabric, demonstrating good water washability.

Key words: functional textile, polyester fabric, waterborne polyurethane, flame-retardant finishing, flame retardant property, mechanical property, washablility

中图分类号: 

  • TS195.59

图1

涤纶织物整理工艺示意图"

图2

整理前后涤纶织物的实物照片和FE-SEM照片"

图3

原涤纶织物及FRWPU12整理织物的红外吸收光谱"

图4

整理前后涤纶织物热分解曲线图"

表1

整理前后涤纶织物氮气气氛下的热分解性能"

样品 T5%/℃ Tmax/℃ Rmax/
(%·min-1)		 650 ℃时
残炭量/%
原涤纶织物 351.1 443.3 34.3 15.9
WPU整理织物 295.2 432.3 21.2 10.9
FRWPU3整理织物 299.8 432.9 19.1 11.9
FRWPU12整理织物 296.7 412.3 18.7 12.7

表2

整理前后涤纶织物的垂直燃烧性能和LOI值"

样品 垂直燃烧性能 LOI值/
%
续燃
时间/s		 阴燃
时间/s		 损毁
长度/cm		 是否
熔滴
原涤纶织物 18 0 30.0 是 17.1
WPU整理织物 19 0 30.0 是 19.2
FRWPU3整理织物 0 0 17.1 是 21.5
FRWPU12整理织物 0 0 9.7 否 24.5

图5

整理前后涤纶织物垂直燃烧测试照片"

图6

整理前后涤纶织物燃烧后残炭表面FE-SEM照片和EDS谱图"

表3

FRWPU12整理织物水洗后的LOI值"

水洗次数 LOI值/%
0 24.5
5 23.7
10 22.9
25 21.8
50 21.2

图7

整理前后涤纶织物拉伸测试后断裂处照片"

表4

整理前后涤纶织物的断裂强力和断裂伸长率"

样品 断裂强力/N 断裂伸长率/%
经向 纬向 经向 纬向
原涤纶织物 508±14 253±14 34.0 16.9
WPU整理织物 516±15 491±14 29.4 23.4
FRWPU3整理织物 513±17 567±15 31.3 25.2
FRWPU12整理织物 521±14 497±13 31.8 23.8
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