纺织学报 ›› 2024, Vol. 45 ›› Issue (08): 205-214.doi: 10.13475/j.fzxb.20231001001

• 染整工程 • 上一篇    下一篇

γ-脲基丙基三乙氧基硅烷/苯基膦酸阻燃抗菌棉织物的制备及其性能

刘慧1,2,3,4, 李平1,2,3,4, 朱平1,2,3,4, 刘云1,2,3,4()   

  1. 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 新型防火阻燃材料开发与应用国家地方联合工程研究中心, 山东 青岛 266071
    4.青岛大学 青岛市阻燃纺织材料重点实验室, 山东 青岛 266071
  • 收稿日期:2023-10-07 修回日期:2024-04-29 出版日期:2024-08-15 发布日期:2024-08-21
  • 通讯作者: 刘云(1982—),女,教授,博士。主要研究方向为功能纤维及纺织品。E-mail:liuyun0215@126.com。
  • 作者简介:刘慧(1991—),女,博士生。主要研究方向为阻燃纤维及纺织品。
  • 基金资助:
    国家自然科学基金重大项目(51991354)

Preparation and properties of flame retardant and antibacterial cotton fabrics treated by γ-urea-propyltriethoxysilane/phenylphosphonic acid

LIU Hui1,2,3,4, LI Ping1,2,3,4, ZHU Ping1,2,3,4, LIU Yun1,2,3,4()   

  1. 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. National Engineering Research Center for Advanced Fire-Safety Materials D & A (Shandong), Qingdao, Shandong 266071, China
    4. Qingdao Key Laboratory of Flame-Retardant Textile Materials, Qingdao, Shandong 266071, China
  • Received:2023-10-07 Revised:2024-04-29 Published:2024-08-15 Online:2024-08-21

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摘要：

针对棉织物易燃烧、易为有害细菌的滋生提供适宜生长环境,给人们正常生活带来重大安全隐患和健康危害等问题,采用 γ-脲基丙基三乙氧基硅烷(TESPR)和苯基膦酸(PPOA),通过溶胶-凝胶法制备了阻燃抗菌棉织物。借助扫描电子显微镜、热重分析仪、锥型量热测试仪、万能材料试验机、织物透气仪等对制得的阻燃棉织物进行表征,研究了其阻燃性能、热稳定性能、力学性能、抗菌性能以及透气性能等。结果表明:TESPR/PPOA成功附着于棉织物表面,极限氧指数达到27.2%;TESPR/PPOA涂层阻燃整理棉织物初始热降解温度低于未处理棉织物,但高温区的残炭量增加,表明在低温区生成的残炭能够作为隔热屏障保护内部棉织物;此外,TESPR/PPOA在棉织物表面的沉积,在大幅度提升抗菌性能的同时,保留了较好的透气性。

关键词: 阻燃性能, 抗菌性能, 棉织物, γ-脲基丙基三乙氧基硅烷, 苯基膦酸, 功能性纺织品

Abstract:

Objective Cotton fabrics are extensively utilized for their softness and wearing comfort, but the flammability is a significant drawback. Reports indicate that the human casualties and financial losses caused by fires related to cotton fabrics are unimaginably high every year. Therefore, it is crucial to improve the flame-retardancy of cotton fabrics. Unfortunately, the most widely used halogen-containing flame retardants face restrictions due to the production of halogenated hydrocarbons when burned. In addition, cotton fabrics with a single flame-retardant function are no longer sufficient to meet normal application needs, and customers demand that flame-retardant cotton fabrics would also possess functions such as waterproofing, antibacterial properties, and UV resistance. Consequently, the development of additives to enhance the flame retardancy and antibacterial functions for cotton fabrics is essential.

Method γ-urea-propyltriethoxysilane (TESPR) and phenylphosphonic acid (PPOA) were utilized in the preparation of flame-retardant cotton fabrics using the sol-gel technique. The flame-retardant cotton fabrics were subsequently analyzed using various techniques, including scanning electron microscopy, thermogravimetric analysis, vertical flame test, cone calorimetry test, antibacterial activities, universal material testing machine, and fabric air permeability testing.

Results The results indicated that the TESPR-PPOA coating was successfully deposited on the surface of cotton fabrics. The thermogravimetric analysis revealed that although the initial thermal degradation temperature of TESPR/PPOA flame retardant cotton fabrics was lower compared with that of cotton fabrics, the char residues in the high-temperature zone were increased. Moreover, TESPR/PPOA flame retardant cotton fabrics was able to succeed a rapid self-extinguishment after the igniter was removed, with the afterflame time and the afterglow time being reduced to 0 s. Meanwhile, the damaged length of TESPR/PPOA flame retardant cotton fabrics obtained from vertical flame test was 8.1 cm, and the limiting oxygen index reached 27.2%. Compared with that of cotton fabrics, the peak heat release rate value of TESPR/PPOA flame retardant cotton fabrics decreased from 124 kW/m2 to 94 kW/m2, and the total heat release value decreased from 4.1 MJ/m2 to 3.6 MJ/m2. After the flame retardant treatment, smoke release was effectively mitigated. The total smoke production value of flame retardant fabrics was smaller than that of cotton fabrics. In addition, the antibacterial properties of TESPR/PPOA flame retardant cotton fabrics against E. coli and S. aureus were 99.83% and 99.28%. However, the mechanical properties of the flame retardant cotton fabrics were deteriorated severely due to the acidity of PPOA. The warp breaking force decreased from about 308 N to 242 N in the warp directions, and the weft breaking force decreased from about 329 N to 272 N in the weft directions. Therefore, the breaking force of TESPR/PPOA flame retardant cotton fabrics in the warp and weft directions was reduced by approximately 21.43% and 17.3% respectively compared with that of cotton fabrics. Fortunately, compared with that of cotton fabrics, the air permeability of TESPR/PPOA flame retardant cotton fabrics decreased from about 708.8 mm/s to 583.8 mm/s, reduced by only about 17.7%. Therefore, TESPR/PPOA flame retardant cotton fabrics retained better air permeability compared with that of cotton fabrics.

Conclusion The results presented above demonstrate that the deposition of TESPR/PPOA can endow better flame retardant effect and better antibacterial properties to cotton fabrics, while TESPR/PPOA flame retardant cotton fabrics maintain better air permeability compared with that of untreated cotton fabrics. Additionally, the TESPR/PPOA coating has a certain inhibitory effect on the peak heat release rate. However, it is worth noting that the mechanical properties of these flame retardant cotton fabrics experience a certain degree of reduction in tensile strength and the study did not investigate their wash durability. In future research, further optimization of the fabrication process is necessary to minimize the impact on the mechanical properties of the cotton fabrics, and it is also important to comprehensively explore the fabric characteristics such as water wash resistance to improve efficiency and broaden its potential applications in areas such as clothing, home furnishings, and decoration.

Key words: flame retardancy, antibacterial property, cotton fabric, γ-urea-propyltriethoxysilane, phenyl-phosphonic acid, functional fabric

中图分类号: 

  • TS195.2

图1

棉织物的SEM照片及表面元素分布图"

表1

阻燃整理前后棉织物在氮气氛围下的TG和DTG数据"

样品 T5%/
℃		 Tmax/
℃		 Rmax/
(%·min-1)		 700 ℃时的
残炭量/%
原棉织物 318 355 25.2 8.8
TESPR阻燃整理棉织物 315 361 20.4 17.9
TESPR/PPOA阻燃
整理棉织物		 223 288 11.8 31.6

图2

阻燃整理前后棉织物在氮气氛围下的TG和DTG曲线"

表2

阻燃整理前后棉织物在空气氛围下的TG和DTG数据"

样品 T5%/
℃		 第1阶段 第2阶段 700 ℃
时的残
炭量/
%
Tmax/
℃		 Rmax/
(%·
min-1)		 Tmax/
℃		 Rmax/
(%·
min-1)
原棉织物 307 339 38.1 468 2.5 1.4
TESPR阻燃整
理棉织物		 299 340 31.8 488 2.2 4.1
TESPR/PPOA阻
燃整理棉织物		 234 283 7.7 496 2.0 4.7

图3

阻燃整理前后棉织物在空气氛围下的TG和DTG曲线"

图4

棉织物垂直燃烧后的数码与SEM照片及阻燃整理棉织物残炭的表面元素分布图"

表3

阻燃整理前后棉织物的垂直燃烧和极限氧指数测试结果"

样品 质量增加
率/%		 续燃时
间/s		 阴燃时
间/s		 损毁长
度/cm		 LOI值/
%
原棉织物 0.0 8±2 9±3 30±0 17.8
TESPR阻燃整
理棉织物		 17.4±0.5 3±2 3±4 30±0 19.4
TESPR/PPOA
阻燃整理棉织物		 17.8±0.6 0 0 8.1±1.2 27.2

图5

阻燃整理前后棉织物的热释放速率曲线"

表4

阻燃整理前后棉织物的微型量热测试结果"

样品 最大热释
放速率/
(W·g-1)		 到达最大
热释放速
率温度/℃		 总热释放/
(kJ·g-1)		 热释放
能力/
(J·(g·
K)-1)
原棉织物 263±4 375 11.1±0.3 248±16
TESPR阻燃整
理棉织物		 277±2 374 10.3±0.5 252±18
TESPR/PPOA
阻燃整理棉织物		 106±4 280 5.0±0.2 95±13

图6

阻燃整理前后棉织物的HRR、THR曲线"

表5

阻燃整理前后棉织物CCT测试结果"

样品 点燃
时间/
s		 最大热
释放
速率/
(kW·
m-2)		 到达最
大热释
放速率
时间/s		 总热
释放/
(MJ·
m-2)		 总烟产
生量/
m2		 平均热
释放速
率/
(kW·
m-2)
原棉织物 19 124 45 4.1 6.3 14.5
TESPR阻燃整
理棉织物		 22 99 45 4.5 0.6 16.2
TESPR/PPOA
阻燃整理棉织物		 16 94 35 3.6 0.1 13.0

图7

阻燃整理前后棉织物的COP和CO2P曲线"

图8

阻燃整理前后棉织物热降解过程中挥发产物的三维红外光谱图"

图9

阻燃整理前后棉织物在Tmax时的红外光谱图"

图10

阻燃整理前后棉织物对金黄色葡萄球菌和大肠杆菌的抗菌性能"

表6

阻燃整理前后棉织物经纬向的断裂强力、透气性和手感"

样品 断裂强力/N 透气率/
(mm·s-1)		 悬垂性/
%		 折皱回
复率/%		 相对手
感值/%		 挠度/
%		 软度/
%		 平滑度/
%
经向 纬向
原棉织物 308.0±19.0 329.0±21.0 708.8±11.1 15.8 75.0 0.0 32.6 62.8 49.5
TESPR阻燃整理棉织物 287.0±21.0 296.0±19.0 695.3±10.6 16.2 68.2 2.2 32.8 60.3 46.2
TESPR/PPOA阻燃整理棉织物 242.0±24.0 272.0±22.0 583.8±12.3 16.7 67.6 2.4 33.6 61.7 48.8
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