纺织学报 ›› 2025, Vol. 46 ›› Issue (04): 138-145.doi: 10.13475/j.fzxb.20231100201

• 染整工程 • 上一篇    下一篇

钼氧簇复合物整理剂制备及其整理棉织物的防紫外线性能

黄春月1, 黄鑫1(), 杜海娟1, 徐文杰2, 杨雪梅3, 万科研1, 李旭1, 高杰1   

  1. 1.中原工学院 智能纺织与织物电子学院, 河南 郑州 450007
    2.中纺标(福建)检测有限公司,福建 晋江 362200
    3.平顶山高新区电气装备产业园区 创新创业部, 河南 平顶山 467000
  • 收稿日期:2023-11-01 修回日期:2025-01-06 出版日期:2025-04-15 发布日期:2025-06-11
  • 通讯作者: 黄鑫(1984—),男,副教授,博士。主要研究方向为功能纺织助剂与染料的设计与研发。E-mail:xinhuang@zut.edu.cn。
  • 作者简介:黄春月(1998—),女,硕士生。主要研究方向为功能纺织助剂的研发。
  • 基金资助:
    河南省自然科学基金面上项目(242300421360);河南省高等学校青年骨干教师培养计划项目(2021GGJS107);中原工学院优势学科实力提升计划资助项目(GG202214);中原工学院自然科学基金青年基金项目(K2023QN005)

Preparation of octamolybdates complex finishing agents and their ultraviolet protection property for finishing cotton fabrics

HUANG Chunyue1, HUANG Xin1(), DU Haijuan1, XU Wenjie2, YANG Xuemei3, WAN Keyan1, LI Xu1, GAO Jie1   

  1. 1. College of Intelligent Textile and Fabric Electronics, Zhongyuan University of Technology, Zhengzhou, Henan 450007, China
    2. China Textile Standard (Fujian) Testing Services Co., Ltd., Jinjiang, Fujian 362200, China
    3. Department of Innovation and Entrepreneurship, Pingdingshan High-Tech Zone Electrical Equipment Industrial Park, Pingdingshan, Henan 467000, China
  • Received:2023-11-01 Revised:2025-01-06 Published:2025-04-15 Online:2025-06-11

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摘要： 为丰富防紫外线整理剂的品类,提升棉织物的防紫外线性能,采用有机阳离子化合物作为模板剂与钼氧簇复合,诱导产生2种不同端基结构的钼氧簇复合物作为整理剂,通过水热法将2种钼氧簇复合物原位生长到棉织物上,对棉织物进行防紫外线整理。借助X射线单晶衍射仪、扫描电镜、热重分析仪、紫外-可见分光光度计、傅里叶红外光谱仪对已获得的整理剂及其整理棉织物的结构进行表征,并对整理后织物的防紫外线性能进行测试。结果表明:2种整理剂整理棉织物的紫外线防护系数(UPF)分别可达到75.46和61.98;甲基端基钼氧簇盐整理剂1整理织物皂洗10次后UPF值为24.72,达到了AS/NZS 4399—2017《日光防护服评定和分级标准》中的最低防晒衣防护标准;羟基端基钼氧簇盐整理剂2整理织物皂洗10次后UPF值为44.99,达到了GB/T 18830—2009《纺织品防紫外线性能的评定》中规定的防紫外线产品的要求。

关键词: 钼氧簇, 功能整理剂, 单晶, 棉织物, 防紫外线, 功能纺织品

Abstract:

Objective Octamolybdates (Mo8) exhibit remarkable versatility in terms of size, shape, and other properties, making them widely applicable in various fields such as catalysis, medicine, photochromism, and beyond. Mo8-based composites possess plenty of advantages including structural stability, ease of preparation, excellent abrasion resistance, low cost, and efficient utilization of direct sunlight. These characteristics render them highly promising for applications in photoelectric conversion, photocatalytic oxidation of pollutants, UV protection, and antimicrobial activities. In this study, two types of Mo8-based complexes were constructed and utilized as anti-ultraviolet finishing agents to enhance the UV-resistant performance of cotton fabrics.

Method Two organic cationic compounds were synthesized through the reaction of 1,3-bis(bromomethyl) benzene with electron-donating group (—R). Crystal engineering and self-assembly technology were used to assemble two organic cationic compounds with molybdate under hydrothermal conditions. The constructed molybdenum oxide cluster complexes were processed onto cotton fabrics as anti-ultraviolet finishing agents. According to their structural characteristics and spectral analysis, the cotton fabric was treated by the in-situ synthetic hydrothermal method, and the dosage of the finishing agent was designed to explore the effect of the concentration of the finishing agent on the anti-ultraviolet effect of the cotton fabric. The structure, morphology, thermal stability and ultraviolet protection factor (UPF) of these two kinds of finishing agents were characterized and tested by X-single crystal diffractometer, Fourier transform infrared(IR) spectrometer, scanning electron microscope (SEM), thermogravimetric(TG) analyzer, and ultraviolet protection performance tester.

Results X-ray single crystal diffraction analysis showed that finishing agent 1 belonged to the triclinic crystal system, and finishing agent 2 was of the monoclinic crystal system. The smallest asymmetrical unit of both finishing agents consisted of two cations and a classical [β-Mo8O26]4- cluster unit. Finishing agent 1 was with [C20H22N2]2+ cation, and finishing agent 2 with [C18H18N2O2]2+ cation. IR and SEM were used to characterize the chemical structure, morphology and state of the two finishing agents on the fabric. In the solid UV spectrum, both finishing agents exhibited strong absorption peaks and absorption bands in the 200-380 nm ultraviolet range, indicating their potential application in anti-ultraviolet finishing. The TG profiles revealed that both finishing agents demonstrated excellent thermal stability. SEM images of the fabrics treated with the finishing agents showed that finishing agent 1 was successfully deposited onto the fabric but with a relatively low attachment amount, while finishing agent 2 was not only successfully deposited but also evenly distributed on the fabric. Finishing agent 1 achieved a maximum UPF of 75.46 at a dosage of 10% (o.w.f.), whereas finishing agent 2 reached a UPF of 61.98 at the same dosage. After ten times of soap wash, the UPF value of the fabric treated with finishing agent 1 decreased from 75.46 to 24.72, and the UPF value of the fabric finished with finishing agent 2 declined from 61.98 to 44.99.

Conclusion Both finishing agents were successfully prepared, featuring a planar bulk structure, strong absorption in the ultraviolet region, and outstanding thermal stability up to approximately 300 ℃. The two types of Mo8-based finishing agents were used to treat cotton fabrics under the conditions of 10% (o.w.f) and hydrothermal in-situ growth at 130 ℃ for 10 h. The UPF values of finished cotton fabrics could reach 75.46 and 61.98, for agents 1 and 2, respectively. After 10 times soap wash, the UPF value of finishing agent 1 was reduced to 24.72, which still meets the minimum protective standard for sunscreen clothing according to AS/NZS 4399—2017 "Sun protective dothing-evaluation and classification" standard, while the UPF value of finishing agent 2 was dropped to 44.99, satisfying the requirements for anti-ultraviolet products according to GB/T 18830—2009 standard. Conclusively, molybdenum oxide cluster group composites demonstrate significant potential for application in anti-ultraviolet treatments.

Key words: octamolybdates, functional finishing agent, single crystal, cotton fabric, UV protection, functional textile

中图分类号: 

  • TS195.5

图1

制备有机阳离子化合物的反应式 注:R为—CH3或—OH。"

图2

整理剂的单元结构图与平面堆积图 注:以上结构图中省略了所有H原子。"

图3

整理剂的固体紫外-可见吸收光谱图"

图4

整理剂的红外光谱"

图5

整理剂的扫描电镜照片"

图6

整理剂的热重曲线"

图7

整理后棉织物的红外光谱图"

图8

整理后织物的扫描电镜照片"

表1

不同整理剂及用量整理棉织物的防紫外线性能"

试样 整理剂用量/
%(o.w.f)		 UV透射比平均值/% UPF值
T(UVA)AV T(UVB)AV
原样 无处理 19.95 13.98 6.52
0 28.13 11.41 7.18
整理剂1
整理织物		 2 6.07 3.15 39.10
4 4.79 1.66 48.43
6 5.73 1.10 59.63
8 3.74 1.09 70.68
10 3.12 1.07 75.46
整理剂2
整理织物		 2 7.27 2.06 34.89
4 4.19 1.74 45.89
6 4.58 1.49 50.44
8 3.32 1.48 56.21
10 3.27 1.29 61.98

表2

不同整理剂不同皂洗次数后棉织物的防紫外线性能"

试样 皂洗次数 UV透射比平均值/% UPF值
T(UVA)AV T(UVB)AV
原样 0 28.13 11.41 7.18
1 26.40 10.31 7.89
3 26.33 9.93 8.14
整理剂
1整理
织物		 0 3.12 1.07 75.46
1 3.31 1.42 56.82
3 6.65 1.41 47.51
5 8.80 1.79 36.08
10 9.25 2.98 24.72
整理剂
2整理
织物		 0 3.27 1.29 61.98
1 5.50 1.08 60.32
3 5.73 1.10 59.63
5 5.82 1.48 53.20
10 5.97 1.56 44.99
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