CN-121801345-B - Anti-ultraviolet dye with tannic acid as coupling component, and preparation method and application thereof

CN121801345BCN 121801345 BCN121801345 BCN 121801345BCN-121801345-B

Abstract

The invention belongs to the technical field of organic dyes, and particularly relates to an anti-ultraviolet dye with tannic acid as a coupling component, and a preparation method and application thereof. Adding diazonium salt solution of aromatic amine derivative into the mixed solution to react under stirring, continuing stirring to react after the addition is finished to obtain reaction solution, regulating pH of the reaction solution, evaporating, filtering and drying to obtain the anti-ultraviolet dye with tannic acid as coupling component. The anti-ultraviolet dye with tannic acid as the coupling component can simultaneously endow the color and the anti-ultraviolet function to the real silk during dyeing, has simple dyeing process, short time, small damage to the real silk, simple composition of dye liquor, easy treatment of subsequent wastewater, and low carbon and environmental protection in the whole dyeing process.

Inventors

LI FUQIANG
CHANG YUCHEN
HUANG HAOFEI
JIANG ZHAOHUI
CAI HONGZHEN
ZHANG CAIYUN
LI CHUNHONG
HAN XIAO

Assignees

山东理工大学

Dates

Publication Date: 20260512
Application Date: 20260305

Claims (10)

1. An anti-ultraviolet dye using tannic acid as a coupling component is characterized by having the following structural formula: , Wherein, the structural formulas of R 1 、R 2 、R 3 、R 4 and R 5 are as follows: , Wherein, the structural formulas of R 6 、R 7 and R 8 are-H, Or (b) Wherein R 9 and R 10 are independently selected from one of-H, -COONa, -SO 3 Na、-NO 2 、-COOH、-SO 3 H, -OH, -SH or-CN, R 11 、R 12 and R 13 are independently selected from one of-H, -COONa, -SO 3 Na、-OH、-SO 3 H or-COOH, and R 11 、R 12 and R 13 cannot be-H at the same time; when R 1 、R 2 、R 3 、R 4 is the same as R 5 , R 6 、R 7 and R 8 cannot be both-H.
2. A process for producing an ultraviolet-resistant dye comprising tannic acid as a coupling component as claimed in claim 1, characterized by comprising the steps of: (1) Adding diazonium salt solution of aromatic amine derivative into the mixed solution for reaction under stirring, and continuing stirring for reaction after the addition is finished to obtain reaction solution; (2) The pH of the reaction solution is regulated, evaporated, filtered and dried to obtain the anti-ultraviolet dye with tannic acid as a coupling component; The preparation method of the mixed solution in the step (1) is that under the anaerobic condition, tannic acid and water are evenly mixed and then alkali liquor is added to obtain the mixed solution.
3. The process for producing an anti-ultraviolet dye comprising tannic acid as a coupling component according to claim 2, wherein the process for producing a diazonium salt solution of an aromatic amine derivative in step (1) is one or two of the following processes: Sequentially adding an aromatic amine derivative and an acid solution into water for reaction to obtain an aromatic amine derivative acidic salt solution, cooling the aromatic amine derivative acidic salt solution, adding a sodium nitrite aqueous solution, and stirring for reaction to obtain a diazonium salt solution of the aromatic amine derivative; sequentially adding an aromatic amine derivative and an alkali solution into water for reaction to obtain an aromatic amine derivative alkaline salt solution, adding sodium nitrite into the aromatic amine derivative alkaline salt solution to obtain a mixed solution, adding the mixed solution into an acid solution for reaction under stirring, and continuing stirring for reaction after the addition is finished to obtain a diazonium salt solution of the aromatic amine derivative.
4. The process for preparing an anti-ultraviolet dye comprising tannic acid as a coupling component according to claim 3, wherein in the first process, the aromatic amine derivative comprises one of aniline, paranitroaniline, metanitroaniline, 2, 4-dinitroaniline, para-aminophenol, metaaminophenol, 2-amino-1, 4-dihydroxybenzene, 2-amino-1, 3-benzenediol, 4-aminophenylthiophenol, 3-aminophenylthiophenol, paracyanoaniline, metacyanoaniline, 1-amino-2-naphthol or 8-amino-2-naphthol, the ratio of water to the aromatic amine derivative is 2-100:1, wherein the aromatic amine derivative is in mmol, the reaction is carried out at room temperature until the aromatic amine derivative is completely dissolved, the temperature is reduced to 0-10 ℃, the concentration of the aqueous sodium nitrite solution is 10-50wt.%, the molar ratio of the aromatic amine derivative to the aqueous sodium nitrite solution is 1:1.1, the time of the stirring is 0.5-5h, the temperature of the stirring is 0-10 ℃, the molar ratio of the aqueous hydrogen sulfate solution is 0:1.20 mol/mol of the aromatic amine derivative to the aqueous hydrogen sulfate solution, the reaction is carried out at a temperature of 0-10 ℃.
5. The method for preparing an anti-ultraviolet dye comprising tannic acid as a coupling component according to claim 3, wherein the aromatic amine derivative in method II comprises one of p-aminobenzoic acid, m-aminobenzoic acid, 4-aminophthalic acid, p-aminobenzenesulfonic acid, m-aminobenzenesulfonic acid, 2, 4-disulfonic aniline, 4-amino-1-naphthalenesulfonic acid, 5-amino-1-naphthalenesulfonic acid, 8-amino-2-naphthalenesulfonic acid, 2-amino-5, 7-naphthalenedisulfonic acid, 1-amino-2-naphthol-4-sulfonic acid, 1-amino-8-naphthol-3, 6-disulfonic acid, 2-amino-5-naphthol-7-sulfonic acid, or 2-amino-8-naphthol-6-sulfonic acid.
6. The process for preparing an anti-ultraviolet dye using tannic acid as a coupling component according to claim 3, wherein the ratio of water to an aromatic amine derivative in the second process is 2-100:1, wherein the aromatic amine derivative is calculated in terms of mmol in terms of mL, the reaction is carried out at room temperature until the aromatic amine derivative is completely dissolved, the pH of an alkaline salt solution of the aromatic amine derivative is 7-8, the molar ratio of the aromatic amine derivative to sodium nitrite is 1:1-1.1, the reaction temperature of the mixed solution added into an acid solution is 0-10 ℃, the stirring reaction time is 0.5-5h, the stirring reaction temperature is 0-10 ℃, the concentration of an alkali solution is one or more of sodium bicarbonate aqueous solution, sodium carbonate aqueous solution or sodium hydroxide aqueous solution, the concentration of the alkali solution is 1-40wt.%, the acid solution is hydrochloric acid solution or sulfuric acid solution, the molar ratio of the aromatic amine derivative to hydrogen ions in the acid solution is 1:2-10, and the concentration of hydrogen ions in the acid solution is 0.2-20mol/L.
7. The process for preparing an anti-ultraviolet dye comprising tannic acid as a coupling component according to claim 2, wherein the reaction temperature is controlled to be 0-10 ℃ and the pH is adjusted to be 6-9 by adding an alkali solution in the step (1), wherein the alkali solution is one of sodium carbonate aqueous solution, sodium bicarbonate aqueous solution or sodium hydroxide aqueous solution, the alkali solution concentration is 1-40wt.%, the temperature of the stirring reaction is 0-10 ℃, and the stirring reaction time is 0.5-2 hours.
8. The process for producing an ultraviolet-resistant dye comprising tannic acid as a coupling component according to claim 2, wherein the ratio of tannic acid to water in the step (1) is 1 to 40:1, wherein tannic acid is calculated as mmol and water is calculated as L, the molar ratio of tannic acid to diazonium salt of aromatic amine derivative in diazonium salt solution of aromatic amine derivative is 1:1 to 10, the pH of the mixed solution is 6 to 9, and the alkali solution is one or more of sodium bicarbonate aqueous solution, sodium carbonate aqueous solution or sodium hydroxide aqueous solution, and the concentration of alkali solution is 1 to 40wt.%.
9. The method for preparing an anti-ultraviolet dye using tannic acid as a coupling component according to claim 2, wherein in the step (2), the pH is adjusted to 2-6 by adding an acid solution, the acid solution is a hydrochloric acid solution or a sulfuric acid solution, the concentration of hydrogen ions in the acid solution is 0.2-20mol/L, the evaporation is reduced pressure distillation or rotary evaporation, the evaporation temperature is 50-80 ℃, the drying is vacuum drying or inert gas-protected anaerobic drying, and the drying temperature is 50-80 ℃.
10. Use of a uv-resistant dye according to claim 1, with tannic acid as coupling component, for dyeing real silk textiles.

Description

Anti-ultraviolet dye with tannic acid as coupling component, and preparation method and application thereof Technical Field The invention belongs to the technical field of organic dyes, and particularly relates to an anti-ultraviolet dye with tannic acid as a coupling component, and a preparation method and application thereof. Background Silk has soft luster and good comfort, is known as 'fiber queen', and is a high-grade textile material. At present, chemical synthetic dyes, mainly acid dyes and reactive dyes are used for dyeing real silk, wherein the acid dyes are required to be carried out under acid conditions and higher dyeing temperature, so that the real silk is easy to generate grey injury to damage the luster of the real silk, the wet processing fastness of the dyeing is poor, and the reactive dyes solve the problem of poor wet fastness of real silk fabrics, but have a series of problems of dye hydrolysis, poor leveling property, difficult color changing, high salt content of waste water and the like. In addition, the dyeing of the chemical synthetic dye only endows the color of the silk, but cannot endow the silk with ultraviolet resistance and other functional effects. With the increasing attention of people on environmental and health problems, the environmental hidden trouble and raw material bottleneck problem of chemical synthetic dyes are gradually highlighted, so that the development of natural environment-friendly dyes has become a hotspot of industrial research, and vegetable dyes are of great concern. The plant dye can be used for dyeing real silk, and simultaneously can endow the real silk with certain antibacterial and ultraviolet-resistant functions, and the plant dye commonly used at present comprises sappan wood (Jiang Jian, zhang Hui, deng Yongqin, and the like), sappan wood pigment ultraviolet-resistant modification and functional dyeing of the silk fabric [ J ]. Silk, 2025,62 (11): 54-61.), tea polyphenol (Fang Jiaojiao, zhao Peihong, zhao Yitao, and the like), preparation of tea stem catechin and dyeing and functional modification of the silk fabric [ J ]. Modern textile technology, 2024,32 (06): 1-8), semen cassiae (Wang Tian), high-fastness dyeing of the silk fabric by semen cassiae extract, functional research [ J ]. Silk, 2020,57 (10): 6-11, and the like. However, vegetable dyes have the disadvantages of difficult mass production, poor color fastness, high cost, difficult repetition of dyeing and the like, so that the industrial application cannot be realized. Therefore, the advantages of the chemical synthetic dye and the plant dye are combined, and the development of a novel dye with dyeing and anti-ultraviolet functions is of great significance. Chinese patent CN102321383A discloses a preparation method of a vegetable tannin dye liquor and application thereof in silk fabric dyeing, which is prepared by taking larch bark, waxberry bark, black wattle bark, valonea or Chinese gall as raw materials and acetone or water as an extracting agent, or taking tannin extract products of larch, waxberry, black wattle, valonea and Chinese gall as raw materials and water as an extracting agent, wherein the vegetable tannin dye liquor prepared by the method or dye prepared by the dye liquor is applied to silk fabric dyeing, has remarkable dyeing effect, effectively solves the technical problem of low dyeing fastness of the vegetable dye liquor in the prior art, and can obtain more abundant dyeing effect by combining with mordant dyeing technology. However, the method for preparing the dye liquor is complex, high in energy consumption and high in cost, and the dyeing quality is unstable due to the influence of multiple factors such as raw material production places and maturity and is not suitable for industrialization. Disclosure of Invention The invention aims to provide an anti-ultraviolet dye taking tannic acid as a coupling component, which is prepared from tannic acid which can be derived from plants and can be biologically degraded through diazotization and coupling reaction, and the preparation method is simple and low in production cost. The structural formula of the anti-ultraviolet dye with tannic acid as a coupling component is as follows: , Wherein, the structural formulas of R 1、R2、R3、R4 and R 5 are as follows: , Wherein, the structural formulas of R 6、R7 and R 8 are-H, Or (b)One of the following; wherein R 9 and R 10 are independently selected from one of-H, -COONa (sodium carboxylate), SO 3 Na (sodium sulfonate), NO 2、-COOH、-SO3 H, -OH, -SH or-CN, R 11、R12 and R 13 are independently selected from one of-H, -COONa (sodium carboxylate), SO 3 Na (sodium sulfonate), OH, -SO 3 H or-COOH, and R 11、R12 and R 13 cannot be both-H; when R 1、R2、R3、R4 is the same as R 5, R 6、R7 and R 8 cannot be both-H. The preparation method of the uvioresistant dye with tannic acid as a coupling component comprises the following steps: (1) Adding diazonium salt solution of aromatic amine derivative