Journal of Textile Research ›› 2025, Vol. 46 ›› Issue (04): 138-145.doi: 10.13475/j.fzxb.20231100201

• Dyeing and Finishing Engineering • Previous Articles     Next Articles

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 Online:2025-04-15 Published:2025-06-11
  • Contact: HUANG Xin E-mail:xinhuang@zut.edu.cn

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

CLC Number: 

  • TS195.5

Fig.1

Reaction formula for preparation of organic cationic compounds"

Fig.2

Unit structure diagram and flat stacking drawings of two finishing agents. (a) Unit structure diagram of finishing agent 1;(b) Unit structure diagram of finishing agent 2;(c)Flat stacking drawings of finishing agent 1;(d) Flat stacking drawings of finishing agent 2"

Fig.3

Solid UV-Vis absorption spectra of finishing agents"

Fig.4

Infrared spectra of finishing agents"

Fig.5

SEM images of finishing agents. (a) Finishing agent 1;(b) Finishing agent 2"

Fig.6

TG plots of finishing agents"

Fig.7

Infrared spectra of cotton fabric after finishing"

Fig.8

SEM image of finished fabric with finishing agent 1(a) and finishing agent 2(b)"

Tab.1

Ultraviolet protection property of cotton fabrics after finishing with different finishing agents and dosages"

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

Tab.2

Ultraviolet protection property of cotton fabrics with different finishing agents and different soaping times"

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
[1] 肖顶. 防紫外纤维及织物研究进展[J]. 山东化工, 2021, 50(10): 75-76.
XIAO Ding. Progress of research on UV-protective fibres and fabrics[J]. Shandong Chemical Industry, 2021, 50(10): 75-76.
[2] 杨洋, 习智华, 李文燕, 等. 棉织物抗紫外整理工艺及测试标准的研究[J]. 纺织科学与工程学报, 2016, 33(4): 33-36.
YANG Yang, XI Zhihua, LI Wenyan, et al. Research on anti-ultraviolet finishing process and test standard of cotton fabric[J]. Journal of Textile Science and Engineering, 2016, 33(4): 33-36.
[3] 朱平. 功能纤维及功能纺织品[M]. 北京: 中国纺织出版社,2006: 125.
ZHU Ping. Functional fibers and functional textiles[M]. Beijing: China Textile & Apparel Press, 2006: 125.
[4] 帅旗, 孙硕, 成世杰, 等. 氮硼掺杂碳量子点/异氰酸酯型微胶囊复合整理棉织物及其防紫外线性能[J]. 纺织学报, 2023, 44(8): 126-132.
SHUAI Qi, SUN Shuo, CHENG Shijie, et al. Nitrogen-boron doped carbon quantum dots/isocyanate-based microcapsule composite finishing of cotton fabrics and their UV protection properties[J]. Journal of Textile Research, 2023, 44(8): 126-132.
[5] 刘小东, 高世会. 纯棉织物防紫外功能整理研究进展[J]. 纺织导报, 2021 (12): 49-50.
LIU Xiaodong, GAO Shihui. Research progress of UV protection function finishing of cotton fabric[J]. China Textile Leader, 2021 (12): 49-50.
[6] 钱如山, 朱传龙, 顾娇, 等. 纺织品抗紫外线整理剂的发展现状[J]. 上海工程技术大学学报, 2013, 27(3): 261-265.
QIAN Rushan, ZHU Chuanlong, GU Jiao, et al. Development status of anti-ultraviolet finishing agents for textiles[J]. Journal of Shanghai University of Engineering Science, 2013, 27(3): 261-265.
[7] 何为纺织品的抗紫外线整理,常见的紫外吸收剂有哪些?[J]. 网印工业, 2019 (10): 45-48.
What is UV-resistant finishing of textiles and what are the common UV absorbers?[J]. Screen Printing Industry, 2019 (10): 45-48.
[8] 李朝辉, 胡志波, 李艳霞. 苯并三唑类紫外吸收剂及其检测方法研究进展[J]. 中国纤检, 2021 (2): 70-73.
LI Chaohui, HU Zhibo, LI Yanxia. Progress in the study of benzotriazoles as ultraviolet absorbers and their detection methods[J]. China Fiber Inspection, 2021(2): 70-73.
[9] 李丽丽, 袁亮, 唐雨霞, 等. 聚多巴胺/壳聚糖改性棉织物的茶色素染色及其抗菌和防紫外线性能[J]. 纺织学报, 2024, 45(3): 106-113.
LI Lili, YUAN Liang, TANG Yuxia, et al. Tea pigment dyeing and antibacterial and anti-ultraviolet properties of polydopamine/chitosan modified cotton fabrics[J]. Journal of Textile Research, 2024, 45(3): 106-113.
[10] 盛宇, 徐丽慧, 孟云, 等. 用SiO2/TiO2复合气凝胶制备超疏水光催化防紫外线织物[J]. 纺织学报, 2019, 40(7): 90-96.
SHENG Yu, XU Lihui, MENG Yun, et al. Preparation of superhydrophobic photocatalytic anti-ultraviolet fabrics with SiO2/TiO2 composite aerogels[J]. Journal of Textile Research, 2019, 40(7): 90-96.
[11] 赵雪, 张安歌, 田洪瑞, 等. 基于Keggin型杂多酸的无机-有机杂化物的合成和光催化活性[J]. 高等学校化学学报, 2021, 42(6): 1723-1729.
doi: 10.7503/cjcu20200845
ZHAO Xue, ZHANG Ange, TIAN Hongrui, et al. Synthesis and photocatalytic activity of inorganic-organic hybrids based on Keggin-type heteropolyacids[J]. Chemical Research in Chinese Universities, 2021, 42(6): 1723-1729.
[12] 郁佳, 郑琳娟, 张莉, 等. 缺位型多钼酸盐改性棉织物的制备及抗紫外性能[J]. 印染助剂, 2020, 37(11): 25-28.
YU Jia, ZHENG Linjuan, ZHANG Li, et al. Preparation and UV resistance of absent polymolybdate modified cotton fabrics[J]. Textile Auxiliaries, 2020, 37(11): 25-28.
[13] HEBEISH A, SHARAF S, FAROUK A. Utilization of chitosan nanoparticles as a green finish in multifunctionalization of cotton textile[J]. International Journal of Biological Macromolecules, 2013, 60(3): 10-17.
[14] 梁志结, 程海兵, 刘慧, 等. 多钼氧酸盐光致变色的研究进展[J]. 南通大学学报(自然科学版), 2023, 22(1): 16-25.
LIANG Zhijie, CHENG Haibing, LIU Hui, et al. Progress of photochromism of polymolybdate[J]. Journal of Nantong University (Natural Science Edition), 2023, 22(1): 16-25.
[15] VASILOPOULOU M, DOUVAS A M, PALILIS L C, et al. Old metal oxide clusters in new applications: spontaneous reduction of Keggin and Dawson polyoxometalate layers by a metallic electrode for improving efficiency in organic optoelectronics[J]. Journal of the American Chemical Society, 2015, 137(21): 6844-6856.
doi: 10.1021/jacs.5b01889 pmid: 25951374
[16] 韩正波, 安海艳, 王力, 等. 有机-无机杂化料{[Na2(H2O)4]2[γ-Mo8O26·(Gly-Gly)2]}·4H2O的合成及晶体结构[J]. 高等学校化学学报, 2003, 24(9): 1558-1560.
HAN Zhengbo, AN Haiyan, WANG Li, et al. Synthesis and crystal structure of organic-inorganic hybrid material {[Na2(H2O)4]2[γ-Mo8O26·(Gly-Gly)2]}·4H2O[J]. Chemical Research in Chinese Universities, 2003, 24(9): 1558-1560.
[17] 肖刚. 季铵型阳离子活性染料[J]. 染料与染色, 2005, 42(1): 10-14.
XIAO Gang. Quaternary ammonium cationic reactive dyes[J]. Dyestuffs and Dyeing, 2005, 42(1): 10-14.
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