基于漆酶一步催化法的羊毛织物原位染色及阻燃功能化

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基于漆酶一步催化法的羊毛织物原位染色及阻燃功能化

Simultaneous in-situ dyeing and flame retardant functionalization of wool fabrics based on laccase catalysis

基于漆酶一步催化法的羊毛织物原位染色及阻燃功能化

Simultaneous in-situ dyeing and flame retardant functionalization of wool fabrics based on laccase catalysis

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doi:10.13475/j.fzxb.20240905201

纺织学报 ›› 2025, Vol. 46 ›› Issue (02): 161-169.doi: 10.13475/j.fzxb.20240905201

郭庆¹^,²^,³, 毛阳顺¹, 任亚杰¹^,²^,³, 刘济民¹^,²^,³, 王怀芳¹^,²^,³(), 朱平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:2024-09-25 修回日期:2024-10-30 出版日期:2025-02-15 发布日期:2025-03-04
通讯作者: 王怀芳(1980—),女,副教授,博士。主要研究方向为功能纤维及功能纺织品。E-mail: hfwang1980@163.com。
作者简介:郭庆(1999—),男,硕士生。主要研究方向为功能纤维及功能纺织品。
第一联系人：
说明:本文入选中国纺织工程学会第25届陈维稷论文卓越行动计划
基金资助:
国家自然科学基金重大项目(51991354)

GUO Qing¹^,²^,³, MAO Yangshun¹, REN Yajie¹^,²^,³, LIU Jimin¹^,²^,³, WANG Huaifang¹^,²^,³(), ZHU Ping¹^,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:2024-09-25 Revised:2024-10-30 Published:2025-02-15 Online:2025-03-04

摘要：

针对羊毛织物的传统染色及阻燃整理工艺流程复杂、条件苛刻、损伤织物并可能污染环境等问题,采用生物酶法,以没食子酸(GA)和9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物(DOPO)为底物,通过漆酶催化作用,在温和条件下采用一步法在羊毛织物上同步实现染色和阻燃功能化。借助紫外-可见光谱仪、测色仪、氧指数仪、扫描电子显微镜、能量色散谱仪及红外光谱仪等对GA、DOPO、GA/DOPO混合物反应液及其处理后织物的形貌和化学组成进行测试与表征,对GA与DOPO及羊毛的反应机制进行分析,并对处理后织物的染色性能、阻燃性能、热稳定性、强力及手感性能等进行测试。结果表明:GA与DOPO之间能够发生共聚反应,并与羊毛通过接枝交联附着在羊毛织物表面,赋予其一定牢度的颜色与阻燃性能;经GA和DOPO共同处理后羊毛织物呈褐色,K/S值达到4.98,极限氧指数达到27.5%,织物强力较未处理羊毛提升46%左右,且处理得到的织物样品仍保持羊毛优良的手感。

关键词: 漆酶, 没食子酸, 9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物, 羊毛织物, 染色, 阻燃, 功能纺织品

Abstract:

Objective Wool fabrics is widely used in apparel, upholstery and industrial applications due to properties such as comfort, biocompatibility, breathability, and hygroscopicity. Conventional dyeing methods for wool products require boiling at high temperatures, consuming large amounts of energy and chemicals, and exerting a detrimental effect on the fabric's inherent properties. In addition, durable flame retardancy for wool fabrics are generally produced by baking phosphorus-containing compounds, usually in the presence of cross-linking agents, at high temperature, or by treating wool fabrics with metal complexes, such as potassium hexafluorotitanic, which lead to yellowing of the fabrics, damage to strength, and heavy metal problems. Consequently, the development of facile and eco-friendly dyeing and flame retardant methods for wool fabrics is essential.

Method A laccase-catalyzed one-step process using gallic acid (GA) and 9,10-dihydro-9-oxa-10-phosphaphenanthrene 10-oxide (DOPO)as substrates was used to achieve simultaneous dyeing and flame retardant functionalization of wool fabrics. The reaction mechanism of GA and DOPO was analyzed with help of UV-visible spectrometer. The morphology, chemical composition, color and the flame retardancy of the treated fabrics were tested and characterized by means of scanning electron microscope, EDS, infrared spectrometer, colorimeter and oxygen index meter.

Results The results demonstrated that the use of laccase as a catalyst enabled the grafting, cross-linking and absorption of GA and DOPO with wool, facilitating the in-situ dyeing and fire retardant modification of wool. The ultraviolet spectroscopy analysis and the color of the samples indicated that the copolymerization of DOPO and GA hinders the polymerization of GA, resulting in a weakened copolymerization and a lower K/S value for GA-DOPO-Wool in comparison to GA-Wool. The limit oxygen index and vertical burning tests demonstrated the effective flame retardant properties of the GA-DOPO-Wool. This phenomenon may be attributed to the reaction between DOPO and GA or GA polymers, which acted as a bridge between the wool and DOPO, thereby increasing the amount of DOPO grafted and adsorbed onto the wool fibers. The results of the EDS and FT-IR tests provided further validation of the interfacial reaction between the substrate and the wool. The thermal gravimetric analysis demonstrated that GA treated wool has an enhanced heat stability, possibly due to the cross-linking reaction between GA and the side chains of the wool. Furthermore, the decomposition of DOPO produced phosphoric and phosphoric acids upon heating and facilitated the dehydration and combustion of wool, forming a barrier that delays the degradation of wool fibers. The color fastness and flame retardancy of GA-DOPO-Wool were found to be excellent, even after 30 times home laundering cycle. Furthermore, the intermolecular bonding between the substrate and the wool fibers resulted in an approximate 46% increase in tensile strength of the treated wool following coloration and chemical modification, accompanied by a slight increase in elongation. Additionally, the data on the tactile properties of the treated wool indicated that the wool retained its inherent excellent tactile quality despite a slight decrease in surface smoothness.

Conclusion The copolymerization of GA with DOPO is catalyzed by laccase and the resulted polymer is grafted and crosslinked to the wool. The yielded compound is shown to adhere to the surface of the wool, imparting a dark brown color and flame retardant properties to the wool. The K/S value of the treated wool is 4.98, and the ultimate oxygen index is 27.5%. Furthermore, the treated fabrics exhibits excellent water resistance. After the treatment, the mechanical properties of wool fabrics are enhanced possibly due to the cross-linking with the wool. It is worth noting that the process presented in this paper does not affect the fabric hand, which is a merit of the treated fabrics for applications in daily life and industry.

Key words: laccase, gallic acid, 9,10-dihydro-9-oxa-10-phosphaphenanthrene 10-oxide, wool fabric, dyeing, flame retardant, functional textile

中图分类号:

TS195.5

郭庆, 毛阳顺, 任亚杰, 刘济民, 王怀芳, 朱平. 基于漆酶一步催化法的羊毛织物原位染色及阻燃功能化[J]. 纺织学报, 2025, 46(02): 161-169.

GUO Qing, MAO Yangshun, REN Yajie, LIU Jimin, WANG Huaifang, ZHU Ping. Simultaneous in-situ dyeing and flame retardant functionalization of wool fabrics based on laccase catalysis[J]. Journal of Textile Research, 2025, 46(02): 161-169.

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链接本文: http://www.fzxb.org.cn/CN/10.13475/j.fzxb.20240905201

http://www.fzxb.org.cn/CN/Y2025/V46/I02/161

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样品	元素含量/%
样品	C	N	O	S	P
未处理羊毛	48.74	16.30	29.34	8.75	0.60
染色阻燃羊毛	52.97	10.46	23.05	5.62	4.77

样品	断裂强力/N		手感
样品	经向	纬向	硬挺度	柔软度	光滑度
未处理羊毛	280±8.2	240±6.3	48.2	80.7	89.5
染色阻燃羊毛	410±7.6	320±6.1	47.1	80.8	84.3

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样品处理	续燃时间/s	阴燃时间/s	损毁长度/mm
未处理	30	3	30
GA处理	34	5	30
DOPO处理	20	10	21
GA/DOPO处理	0	20	6

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