纺织学报 ›› 2025, Vol. 46 ›› Issue (12): 142-151.doi: 10.13475/j.fzxb.20250304301

• 染整工程 • 上一篇    下一篇

含生物基组分的酸性染料的合成及其染色性能

陈铭1, 张豪1, 张子缘1, 杨清标1, 高吉1, 范存伟1, 孙戒2()   

  1. 1.南京工业大学 生物与制药工程学院, 江苏 南京 211816
    2.南京工业大学 食品与轻工学院, 江苏 南京 211816
  • 收稿日期:2025-03-21 修回日期:2025-09-21 出版日期:2025-12-15 发布日期:2026-02-06
  • 通讯作者: 孙戒(1980—),男,教授,博士。主要研究方向为染料、生物基材料表面活性剂等。E-mail: sunjie5516@126.cm。
  • 作者简介:陈铭(1999—),男,硕士生。主要研究方向为酸性染料。

Synthesis and dyeing properties of acid dyes containing bio-based moieties

CHEN Ming1, ZHANG Hao1, ZHANG Ziyuan1, YANG Qingbiao1, GAO Ji1, FAN Cunwei1, SUN Jie2()   

  1. 1. College of Biotechnology and Pharmaceutical Engineering, Nanjing Tech University, Nanjing, Jiangsu 211816, China
    2. College of Food Science and Light Industry, Nanjing Tech University, Nanjing, Jiangsu 211816, China
  • Received:2025-03-21 Revised:2025-09-21 Published:2025-12-15 Online:2026-02-06

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摘要： 针对当前染料生产中普遍依赖石化基化学品导致碳排放高,且部分工艺涉及有毒芳香胺的问题,以L-赖氨酸、1,5-戊二胺和2-呋喃甲胺为原料,合成了3种含生物基组分的新型蒽醌酸性染料(D1~D3),通过核磁共振氢谱、核磁共振碳谱、红外光谱技术确认了染料的化学结构;进一步研究了3种染料对羊毛织物的染色性能,并与商用酸性染料(酸性蓝25)进行了对比。结果表明:在染液pH值为6且未添加硫酸钠的条件下,染料D1、D2、D3的上染率分别达到96.5%、83.3%和97.5%,而酸性蓝25的上染率为97.1%;D1、D2、D3的半染时间分别为9.5、18、8.5 min,均短于酸性蓝25的25.6 min,体现出更快的染色速率优势,且均表现出良好的匀染性、提升性与直接性;染色热力学研究显示,D1~D3在羊毛织物上的吸附行为符合Langmuir吸附等温线,证实吸附过程为单分子层吸附;动力学分析则表明,羊毛对3种染料的吸附遵循伪二级动力学模型;色牢度测试结果显示,染料D1~D3的耐水洗色牢度和耐摩擦色牢度均达到3级以上,耐光色牢度在6级以上,具备较好的使用稳定性。

关键词: 染色, 染色动力学, 酸性染料, 吸附等温线, 羊毛织物

Abstract:

Objective Dyes are indispensable in the textile industry, and a large amount of dyes are consumed every year. In view of the problem that acid dyes synthesized with aromatic amines are banned due to carcinogenicity, it is of great importance to study for more eco-friendly and safer synthetic dyes. Novel anthraquinone acid dyes were prepared in this research by using bio-based amines and bromamine acid as raw materials, and their performance in wool dyeing was tested, aiming to obtain a dye containing a bio-based moieties.

Method Bio-based amines like L-lysine, 1,5-diaminopentane (decarboxylated from L-lysine), and 2-furanmethylamine were used to synthesize three acid dyes with bromamine acid by the Ullmann reaction. Their structural characterizations were carried out using 1H NMR spectra, 13C NMR spectra and FT-IR spectra. The dyeing properties of these dyes on wool fabrics were investigated using a UV-vis spectrophotometer and a color measurement instrument. Their dyeing performance was compared with Acid Blue 25, a dye that is commercially available. Dyeing kinetics and adsorption isotherms models of these novel dyes were also examined.

Results The structure of the three novel anthraquinone acid dyes (D1-D3) containing bio-based components was confirmed by 1H NMR,13C NMR spectra and FT-IR spectra. The maximum absorption wavelengths (λmax) of the three dyes were 584, 594, and 540 nm, separately. When the wool fabric was dyed at pH 6 and 98 ℃ without any leveling agent, the dye-uptake was high, with 96.5% for D1, 83.3% for D2, 97.5% for D3, and 97.1% for Acid Blue 25, and the dye-uptake of D1 and D3 were close to that of Acid Blue 25. The half-dyeing time (t1/2) was 9.5 min for D1, 18 min for D2, and 8.5 min for D3, which was shorter than that of the Acid Blue 25 (25.6 min), indicating that the three bio-based acid dyes had faster dyeing rates. The standard deviation and substantivity values of D3 were 0.37 and 1 922.2, which were the best among the synthesized acid dyes and significantly better than those of Acid Blue 25, suggesting D3 had good leveling properties and substantivity. D1 and D2 exhibited σ and K values similar to Acid Blue 25, implying analogous leveling properties and substantivity. The K/S value increased from 4.2 to 25.2 for D1 dyed wool fabrics, from 7.8 to 36 for D2 dyed fabrics, and from 3.6 to 24.6 for D3 dyed fabrics, when the dye concentration increased from 0.5%(o.w.f) to 4%(o.w.f), and this signified D1-D3 had great build-up properties. The results of adsorption isotherms showed that the adsorption of D1-D3 on wool fabrics conformed to the monolayer adsorption characteristics and the Langmuir adsorption isotherm. The adsorption processes of the three dyes were consistent with the pseudo-second-order kinetic model, with determination coefficients (R2) all above 0.997. In terms of color fastness, washing fastness and rubbing fastness were above grade 3, and light fastness was above grade 6.

Conclusion In summary, three novel anthraquinone acid dyes were synthesized and characterized. The dyeing rate of these synthetic acid dyes was high and had a high exhaustion rate. The dyes containing bio-based components had good build-up properties, leveling properties, substantivity. The dyeing properties of D1-D3 were not weaker than the commercial Acid Blue 25 dye. The adsorption of dyes on wool conforms to the Langmuir adsorption isotherm. The pseudo-second-order kinetic model was favorable to describe the wool dyeing of the three dyes compared to the pseudo-first-order kinetic model. In terms of color fastness, the color fastness to washing and rubbing of dye D1-D3 were above grade 3, and the color fastness to light was above grade 6.

Key words: dyeing, dyeing kinetics, acid dye, adsorption isotherm, wool fabric

中图分类号: 

  • TQ615.1

图1

溴氨酸衍生酸性染料的合成路线"

图2

3种染料分子的化学结构"

图3

染色工艺"

表1

D1~D3的核磁共振氢谱和核磁共振碳谱"

染料
编号		 化学位移
核磁共振氢谱
(400 MHz,重水)		 核磁共振碳谱
(101 MHz,重水)
D1 8.28 ~ 8.19 (m, 2H), 7.87 (s, 1H), 7.84 ~ 7.77 (m, 2H), 7.63 (d, 1H), 6.43 (dd, 1H), 6.37 (d, 1H), 4.67 (s, 2H) 177.66, 146.95, 143.80, 142.13, 138.94, 136.05, 135.92, 131.31, 126.97, 116.84, 113.73, 113.05, 110.76, 107.61, 39.52
D2 8.25 (tt, 4H), 7.83~ 7.78 (m, 4H), 7.76 (s, 2H), 2.69 ~ 2.65 (m, 4H), 1.73~ 1.66 (m, 4H), 1.09~ 1.02 (m, 2H) 185.85, 174.74, 141.66, 138.41, 134.21, 133.52, 131.98, 126.75, 117.14, 114.15, 113.76, 70.36, 50.15, 31.18, 30.35, 19.47
D3 8.28 ~ 8.21 (m, 4H), 7.83 ~ 7.77 (m, 4H), 7.74 (s, 2H), 4.38 (t, 1H), 3.27~ 3.21 (m, 2H), 2.33 (q, 2H), 2.05 ~ 1.95 (m, 2H), 1.47 ~ 1.39 (m, 2H) 186.75, 143.11, 139.02, 134.01, 133.55, 132.28, 125.96, 116.74, 114.77, 114.03, 49.92, 32.53, 23.44

图4

染料和溴氨酸的红外光谱"

表2

不同pH值下的上染率"

染料
编号		 上染率E/%
pH=3 pH=4 pH=6 pH=7
D1 96.2 95.5 96.5 48.2
D2 80.1 83.4 83.3 68.4
D3 97.3 97.3 97.5 90.0

图5

不同硫酸钠质量浓度下的上染率"

表3

硫酸钠质量浓度对匀染性的影响"

染料
编号		 不同硫酸钠质量浓度下的匀染性(σ值)
0 g/L 0.2 g/L 0.4 g/L 0.8 g/L 1.0 g/L
D1 0.98 0.91 0.86 0.77 0.72
D2 0.90 0.88 0.80 0.71 0.69
D3 0.37 0.37 0.33 0.26 0.22

表4

染料的颜色参数"

染料编号 K/S值 L*值 a*值 b*值 C*值 H*值
D1 16.1 27.23 7.31 -26.55 29.53 282.39
D2 20.8 27.61 7.30 -33.78 36.56 278.19
D3 13.2 39.09 10.06 -13.25 18.64 307.20

图6

染料用量对K/S值的影响"

图7

羊毛织物的上染速率曲线"

表5

染料的σ,t1/2和K值"

染料 σ t1/2/min K
D1 0.98 9.5 1 389.5
D2 0.90 18 244.4
D3 0.37 8.5 1 922.2
AB25 0.93 25.6 1 650.7

图8

染料D1~D3的吸附等温线"

图9

Freundlich 吸附等温线"

表6

不同吸附模型拟合的方程及参数"

染料
编号		 Freundlich吸附等温线 Langmuir吸附等温线
方程 KF m R2 方程 K1 Q0 RL R2
D1 lnqe=2.23+0.95lnCe 9.29 1.05 0.960 1 q e=0.025+0.13 1 C e 0.19 40 0.06~0.84 0.971
D2 lnqe=0.11+1.21lnCe 1.12 0.83 0.996 1 q e=0.012+1.02 1 C e 0.01 83.33 0.56~0.99 0.985
D3 lnqe=2.27+0.64lnCe 9.68 1.56 0.934 1 q e=0.022+0.060 1 C e 0.37 45.45 0.03~0.73 0.962

图10

Langmuir 吸附等温线"

图11

羊毛织物对染料D1~D3的吸附曲线"

图12

不同染料的伪一级动力学模型"

表7

不同染料的吸附动力学"

染料
编号		 qe/(mg·g-1) 伪一级动力学模型 伪二级动力学模型
k1 qe,cal/(mg·g-1) R2 k2 qe,cal/(mg·g-1) R2
D1 18.7 0.112 7.01 0.756 0.053 6 16.9 0.997
D2 17.8 0.108 5.47 0.846 0.071 5 17.6 0.999
D3 23.2 0.123 5.75 0.712 0.067 6 23.2 0.999

图13

不同染料的伪二级动力学模型"

表8

羊毛织物上 D1~D3 的色牢度"

染料
编号		 耐摩擦色牢度 耐皂洗色牢度 耐光色
牢度
干 湿 变色 沾色
棉 羊毛
D1 4 4 5 4~5 5 7~8
D2 5 4~5 4~5 4~5 4~5 7~8
D3 4~5 4 4 4 3 6~7
AB25 5 5 5 5 5 7~8
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