Journal of Textile Research ›› 2025, Vol. 46 ›› Issue (02): 161-169.doi: 10.13475/j.fzxb.20240905201

• Dyeing and Finishing Engineering • Previous Articles     Next Articles

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

GUO Qing1,2,3, MAO Yangshun1, REN Yajie1,2,3, LIU Jimin1,2,3, WANG Huaifang1,2,3(), ZHU Ping1,2,3   

  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. State Key Laboratory of Bio-Fibers and Eco-Textiles, Qingdao University, Qingdao, Shandong 266071, China
  • Received:2024-09-25 Revised:2024-10-30 Online:2025-02-15 Published:2025-03-04
  • Contact: WANG Huaifang E-mail:hfwang1980@163.com

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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

CLC Number: 

  • TS195.5

Fig.1

Preparation process of GA-DOPO treated wool fabric"

Fig.2

Ultraviolet-visible absorption spectra of reaction solution with time and photos of reaction solution with corresponding time"

Fig.3

K/S value of wool fabric treated with different substrates. (a) K/S curve of wool fabric; (b) K/S value of wool fabric at 360 nm"

Fig.4

LOI value of wool fabric treated with different substrates"

Fig.5

Vertical combustion of wool samples in air. (a)Untreated wool; (b) GA-treated wool; (c) DOPO-treated wool; (d) GA/DOP-treated wool"

Tab.1

Continued burning, negative burning time and length of damage of wool fabrics burned in air"

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

Fig.6

SEM images of wool fabric before and after treatment.(a)Untreated wool fabric; (b)Dyed flame retardant wool fabric"

Fig.7

EDS map element distribution of wool fabric before and after treatment. (a)Untreated wool fabric; (b)Dyed flame retardant wool fabric"

Tab.2

Surface element content of wool fabric before and after treatment"

样品 元素含量/%
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

Fig.8

ATR-FTIR spectra of wool fabric and dyed flame retardant wool fabric before and after washing"

Fig.9

TG (a) and DTG (b) curves of wool fabric before and after treatment"

Fig.10

Influence of cycle washing times on K/S value, limiting oxygen index(a)and vertical combustion performance(b)of dyed flame retardant wool fabric"

Fig.11

Tensile stress-strain curve of wool fabric before and after treatment"

Tab.3

Physical properties of wool fabric before and after treatment"

样品 断裂强力/N 手感
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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