A method for preparing CI reactive blue 49 color base by electrolysis

Abstract

A method for electrolytically preparing a CI Reactive Blue 49 chromophore belongs to the fields of fine chemicals and dye preparation. This method uses electrochemical in-situ chlorination to prepare 1-amino-4-chloroanthraquinone-2-sulfonic acid, which is then condensed with 1,3,5-trimethyl-2,4-diaminobenzenesulfonic acid in an autoclave to obtain a blue base. This method avoids the use of stannous chloride or chemical reducing agents, significantly reducing environmental pollution. There are no hydrolysis or debromination byproducts, the reaction raw materials are completely converted, and the amount of wash water used is reduced. The blue base yield exceeds 90%.

Description

Technical Field

[0001] The present invention relates to the field of fine chemicals, and in particular to a method for preparing a CI Reactive Blue 49 chromophore by electrolysis. Background Art

[0002] Reactive dyes produced based on the CI Reactive Blue 49 color base have the advantages of bright color, good wet fastness, good light fastness and strong applicability. They are widely used in dyeing and printing of cotton, linen, wool and other fibers and their blended fabrics.

[0003] The reaction is an Ullmann condensation reaction of 1-amino-4-bromoanthraquinone-2-sulfonic acid (bromoanic acid) and 1,3,5-trimethyl-2,4-diaminobenzenesulfonic acid (M acid) under the catalysis of copper salt. The process is as follows:

[0004]

[0005] Research has shown that monovalent copper is the catalyst for this reaction. Industry often uses stannous chloride to reduce divalent copper to monovalent copper to catalyze the reaction. Because monovalent copper is unstable in water and disproportionates to divalent copper and zero-valent copper, losing its catalytic activity, intermittent additions of stannous chloride and copper sulfate are necessary to maintain the monovalent copper concentration in the reaction system for the reaction to proceed smoothly. However, stannous chloride is toxic and poses a significant environmental risk. Furthermore, catalyst deactivation can lead to bromoamic acid side reactions, increasing the number of bromoamic acid hydrolysis and debromination byproducts:

[0006]

[0007] The presence of these byproducts affects the color of the finished dye, requiring large amounts of water to wash away, resulting in significant waste of water resources and further increasing the environmental burden. Patent CN116574036A uses organic ligands to stabilize monovalent copper for the preparation of the CI Reactive Blue 49 chromophore, but still requires the addition of a reducing agent such as ascorbic acid to enable the reaction to proceed. Therefore, research and development of a green and efficient method for preparing the CI Reactive Blue 49 chromophore is highly desirable. Summary of the Invention

[0008] The purpose of the present invention is to solve the above-mentioned problems of stannous chloride polluting the environment, debromination and hydrolysis of bromoamic acid, and the like, and to provide a method for preparing CI Reactive Blue 49 chromophore by electrolysis, thereby avoiding the use of stannous chloride and greatly reducing the byproducts of bromoamic acid hydrolysis and debromination, thereby solving the problem of severe environmental pollution in the reaction.

[0009] To achieve the above object, the technical solution of the present invention is as follows: A method for preparing CI Reactive Blue 49 chromophore by electrolysis, the reaction is as follows:

[0010]

[0011] The method includes the following two steps: (1) (2):

[0012] (1) 1-aminoanthraquinone-2-sulfonic acid is dissolved in hydrochloric acid as the electrolyte in the anode chamber, and hydrochloric acid of the same concentration is used as the electrolyte in the cathode chamber. Constant current electrolysis is performed to obtain 1-amino-4-chloroanthraquinone-2-sulfonic acid by in-situ chlorination in the anode chamber;

[0013] (2) The 1-amino-4-chloroanthraquinone-2-sulfonic acid obtained in step (1) is condensed with M acid in a pressure autoclave using water as solvent, sodium bicarbonate as base, and copper sulfate as catalyst to obtain CI Reactive Blue 49 color base.

[0014] in:

[0015] The mass percentage of the 1-aminoanthraquinone-2-sulfonic acid in hydrochloric acid is 1% to 15%, preferably 3% to 10%; the concentration of hydrochloric acid is 10% to 30%, preferably 15% to 25%;

[0016] The electrolysis conditions are:

[0017] The anode is a platinum electrode of different sizes or shapes; the cathode is a graphite electrode of different sizes or shapes; the power supply type is direct current, and the current density is 50~500 mA cm -2 , preferably 100~300 mA cm -2 The electrolytic cell type is an H-shaped electrolytic cell of various sizes or capacities, and the anode and cathode chambers are separated by a DuPont proton exchange membrane; the electrolysis temperature is 0~30℃, preferably 10~25℃; the electrolysis time is 3~12 h.

[0018] The molar ratio of 1-amino-4-chloroanthraquinone-2-sulfonic acid to M acid is 1:1.5-1:2.5, the molar ratio of 1-amino-4-chloroanthraquinone-2-sulfonic acid to sodium bicarbonate is 1:3-1:6, the molar ratio of 1-amino-4-chloroanthraquinone-2-sulfonic acid to copper sulfate is 1:005-1:0.2, and the concentration of 1-amino-4-chloroanthraquinone-2-sulfonic acid in the reaction system is 10%-15%.

[0019] The autoclave is a stainless steel reactor with a gas charging and discharging port that meets national standards. Before the reaction, nitrogen is used to replace the air in the autoclave three times;

[0020] The reaction time is 1-4 h, and the reaction temperature is 90-180° C., preferably 100-140° C.

[0021] Compared with the prior art, the present invention achieves the following technical effects:

[0022] The industrial production of the CI Reactive Blue 49 chromophore requires large amounts of stannous chloride or organic reducing agents to maintain the copper concentration of the catalyst. However, heavy metals and high COD levels in wastewater can cause significant environmental damage, and the formation of bromoamic acid byproducts cannot be fundamentally avoided, leading to high water consumption. The present invention utilizes electrochemical in-situ chlorination to prepare 1-amino-4-chloroanthraquinone-2-sulfonic acid, which is then condensed with M acid in an autoclave without the addition of a reducing agent to prepare the CI Reactive Blue 49 chromophore. This avoids the introduction of stannous chloride and organic reducing agents, significantly reducing environmental pollution, fundamentally eliminating bromoamic acid hydrolysis and debromination byproducts, and reducing water consumption. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] Figure 1 This is the mass spectrum of 1-aminoanthraquinone-2-sulfonic acid.

[0024] Figure 2 This is the mass spectrum of 1-amino-4-chloroanthraquinone-2-sulfonic acid.

[0025] Figure 3 This is a liquid chromatogram of the electrochemical in situ chlorination of 1-aminoanthraquinone-2-sulfonic acid to obtain 1-amino-4-chloroanthraquinone-2-sulfonic acid.

[0026] Figure 4 This is the mass spectrum of CI Reactive Blue 49 chromophore. DETAILED DESCRIPTION

[0027] Example 1

[0028] Take 2.3 g of 1-aminoanthraquinone-2-sulfonic acid, add deionized water and hydrochloric acid to prepare 50 mL of 15% hydrochloric acid solution as the electrolyte in the anode chamber, and the electrolyte in the cathode chamber is the same volume and concentration of hydrochloric acid solution. The anode and cathode chambers are separated by DuPont Nafion117 proton exchange membrane. 2 Platinum mesh electrodes cut into 2 × 2 cm 2 The graphite felt was ultrasonically cleaned with acetone and ultrapure water, and then assembled into a complete electrolysis device with the electrolytic cell. A magnet was added to the anode chamber, stirring was started, and the flow rate was 150 mAcm -2 The current density was 1000 nm and the electrolysis was carried out at 30°C for 7 h. Samples were taken for liquid chromatography analysis. The power was turned off and the electrolyte in the anode chamber was centrifuged to obtain a solid. After drying, it was 1-amino-4-chloroanthraquinone-2-sulfonic acid. The mass spectrum is shown in FIG. Figure 2 As shown, molecular weight 337, m / z 336 [MH] - , 673[2M-H] - .

[0029] Take 1.5 g of 1-amino-4-chloroanthraquinone-2-sulfonic acid, 1.65 g of M acid, 1.7 g of sodium bicarbonate, 0.11 g of copper sulfate pentahydrate, and then measure 11 mL of water and add it to a stainless steel autoclave. After nitrogen replacement 3 times, heat it to 100 ° C and start magnetic stirring. Keep warm for 3 hours, stop stirring and heating, cool to room temperature, dilute the material with water 2 times, heat it to 90 ° C, add 2% of the dilution volume of calcium carbonate and 1% of activated carbon, and filter to remove impurities. Adjust the pH to 2.5-3.0 with hydrochloric acid, stir for 2 hours, precipitate excess M acid, filter, rinse with water at 40 ° C, and detect by high performance liquid chromatography. It does not contain hydrolysis and dechlorination by-products. The product is CI Reactive Blue 49 dye color base with a yield of 89%. The liquid phase diagram is as follows Figure 3 As shown in the figure, the chromatographic peak at RT = 10.3 min is the target peak.

[0030] Mass spectra such as Figure 4 As shown, molecular weight 531, m / z 530 [MH] - .

[0031] Example 2

[0032] Take 5.5 g of 1-aminoanthraquinone-2-sulfonic acid, add deionized water and hydrochloric acid to prepare 100 mL of 20% hydrochloric acid solution as the electrolyte in the anode chamber, and the electrolyte in the cathode chamber is the same volume and concentration of hydrochloric acid solution. The anode and cathode chambers are separated by DuPont Nafion 117 proton exchange membrane. 2 The platinum electrode and the 0.8 mm diameter graphite rod were ultrasonically cleaned with acetone and ultrapure water in sequence, and then assembled into a complete electrolysis device with the electrolytic cell. A magnet was added to the anode chamber, stirring was started, and the electrolysis was carried out at 200 mA cm -2 The electrolysis was carried out at 25 °C for 6 h, and samples were taken for liquid chromatography analysis. The power was turned off, and the electrolyte in the anode chamber was centrifuged to separate the solid, which was 1-amino-4-chloroanthraquinone-2-sulfonic acid after drying.

[0033] 3 g of 1-amino-4-chloroanthraquinone-2-sulfonic acid, 3.6 g of M-acid, 3.3 g of sodium bicarbonate, and 0.2 g of copper sulfate pentahydrate were added to a stainless steel autoclave along with 21 mL of water. After nitrogen purge three times, the mixture was heated to 110°C with magnetic stirring. The mixture was kept warm for 3 hours, then stirring and heating were stopped. After cooling to room temperature, the mixture was diluted two-fold with water, heated to 90°C, and 2% of the dilution volume of calcium carbonate and 1% activated carbon were added. Impurities were removed by filtration. The pH was adjusted to 2.5-3.0 with hydrochloric acid. The mixture was stirred for 2 hours to precipitate excess M-acid, which was filtered and rinsed with water at 40°C. High-performance liquid chromatography (HPLC) confirmed the absence of hydrolysis and dechlorination byproducts. The product was the CI Reactive Blue 49 dye chromophore in a 91% yield.

[0034] Example 3

[0035] Take 3.2 g of 1-aminoanthraquinone-2-sulfonic acid, add deionized water and hydrochloric acid to prepare 50 mL of 18% hydrochloric acid solution as the electrolyte in the anode chamber, and the electrolyte in the cathode chamber is the same volume and concentration of hydrochloric acid solution. The anode and cathode chambers are separated by DuPont Nafion117 proton exchange membrane. 2 The platinum mesh electrode and the 0.8 mm diameter graphite rod were ultrasonically cleaned with acetone and ultrapure water in sequence, and then assembled into a complete electrolysis device with the electrolytic cell. A magnet was added to the anode chamber, stirring was started, and the electrolysis was carried out at 250 mA cm -2 The electrolysis was carried out at 30℃ for 7 h, and samples were taken for liquid chromatography analysis. The power was turned off, and the electrolyte in the anode chamber was centrifuged to separate the solid, which was 1-amino-4-chloroanthraquinone-2-sulfonic acid after drying.

[0036] 2.1 g of 1-amino-4-chloroanthraquinone-2-sulfonic acid, 3.2 g of M-acid, 2.3 g of sodium bicarbonate, and 0.15 g of copper sulfate pentahydrate were added to a stainless steel autoclave along with 15 mL of water. After nitrogen displacement three times, the mixture was heated to 180°C with magnetic stirring. The mixture was held at this temperature for 1 hour, then stirring and heating were stopped. After cooling to room temperature, the mixture was diluted two-fold with water, heated to 90°C, and 2% by volume of calcium carbonate and 1% activated carbon were added. Impurities were removed by filtration. The pH was adjusted to 2.5-3.0 with hydrochloric acid. The mixture was stirred for 2 hours to precipitate excess M-acid, filtered, and rinsed with water at 40°C. High-performance liquid chromatography (HPLC) confirmed the absence of hydrolysis and dechlorination byproducts. The product was the CI Reactive Blue 49 dye chromophore in 82% yield.

[0037] Example 4

[0038] Take 7.4 g of 1-aminoanthraquinone-2-sulfonic acid, add deionized water and hydrochloric acid to prepare 100 mL of 20% hydrochloric acid solution as the electrolyte in the anode chamber, and the electrolyte in the cathode chamber is the same volume and concentration of hydrochloric acid solution. The anode and cathode chambers are separated by DuPont Nafion 117 proton exchange membrane. 2 Platinum electrode cut into 2 × 2 cm 2 The graphite felt was ultrasonically cleaned with acetone and ultrapure water, and then assembled into a complete electrolysis device with the electrolytic cell. A magnet was added to the anode chamber, stirring was started, and the electrolysis device was operated at 150 mA cm -2 The electrolysis was carried out at a current density of 100 nm at 25°C for 8 h, samples were taken for liquid chromatography analysis, the power was turned off, and the electrolyte in the anode chamber was centrifuged to obtain a solid, which was dried to obtain 1-amino-4-chloroanthraquinone-2-sulfonic acid.

[0039] 3.4 g of 1-amino-4-chloroanthraquinone-2-sulfonic acid, 3.7 g of M-acid, 3.8 g of sodium bicarbonate, and 0.24 g of copper sulfate pentahydrate were added to a stainless steel autoclave along with 24 mL of water. After nitrogen displacement three times, the mixture was heated to 150°C with magnetic stirring. The mixture was held at this temperature for 2 h. Stirring and heating were stopped, and after cooling to room temperature, the mixture was diluted two-fold with water. The temperature was then raised to 90°C, and 2% of the dilution volume of calcium carbonate and 1% activated carbon were added. The mixture was then filtered to remove impurities. The pH was adjusted to 2.5-3.0 with hydrochloric acid, and the mixture was stirred for 2 h to precipitate excess M-acid. The mixture was filtered and rinsed with water at 40°C. High-performance liquid chromatography (HPLC) confirmed the absence of hydrolysis and dechlorination byproducts, and the product was the CI Reactive Blue 49 dye chromophore in 85% yield.

[0040] Example 5

[0041] Take 10 g of 1-aminoanthraquinone-2-sulfonic acid, add deionized water and hydrochloric acid to prepare 150 mL of 15% hydrochloric acid solution as the electrolyte in the anode chamber, and the electrolyte in the cathode chamber is the same volume and concentration of hydrochloric acid solution. The anode and cathode chambers are separated by DuPont Nafion117 proton exchange membrane. 2 The platinum electrode and the 0.8 mm diameter graphite rod were ultrasonically cleaned with acetone and ultrapure water in sequence, and then assembled into a complete electrolysis device with the electrolytic cell. A magnet was added to the anode chamber, stirring was started, and the electrolysis was carried out at 100 mA cm -2 The electrolysis was carried out at 30 °C for 10 h, and samples were taken for liquid chromatography analysis. The power was turned off, and the electrolyte in the anode chamber was centrifuged to obtain a solid, which was dried to obtain 1-amino-4-chloroanthraquinone-2-sulfonic acid.

[0042] 5.7 g of 1-amino-4-chloroanthraquinone-2-sulfonic acid, 8.6 g of M-acid, 6.3 g of sodium bicarbonate, and 0.4 g of copper sulfate pentahydrate were added to a stainless steel autoclave along with 40 mL of water. After nitrogen displacement three times, the mixture was heated to 110°C with magnetic stirring. The mixture was held at this temperature for 2 hours, then stirring and heating were stopped. After cooling to room temperature, the mixture was diluted two-fold with water, heated to 90°C, and 2% of the dilution volume of calcium carbonate and 1% activated carbon were added. Impurities were removed by filtration. The pH was adjusted to 2.5-3.0 with hydrochloric acid. The mixture was stirred for 2 hours to precipitate excess M-acid, filtered, and rinsed with water at 40°C. High-performance liquid chromatography (HPLC) confirmed the absence of hydrolysis and dechlorination byproducts. The product was the CI Reactive Blue 49 dye chromophore in 90% yield.

[0043] Example 6

[0044] Take 12.5 g of 1-aminoanthraquinone-2-sulfonic acid, add deionized water and hydrochloric acid to prepare 150 mL of 20% hydrochloric acid solution as the electrolyte in the anode chamber, and the electrolyte in the cathode chamber is the same volume and concentration of hydrochloric acid solution. The anode and cathode chambers are separated by DuPont Nafion 117 proton exchange membrane. 2 The platinum mesh electrode and the 0.8 mm diameter graphite rod were ultrasonically cleaned with acetone and ultrapure water in sequence, and then assembled into a complete electrolysis device with the electrolytic cell. A magnet was added to the anode chamber, stirring was started, and the electrolysis was carried out at 250 mA cm -2 The electrolysis was carried out at 25 °C for 10 h, and samples were taken for liquid chromatography analysis. The power was turned off, and the electrolyte in the anode chamber was centrifuged to separate the solid, which was 1-amino-4-chloroanthraquinone-2-sulfonic acid after drying.

[0045] 6.5 g of 1-amino-4-chloroanthraquinone-2-sulfonic acid, 8.5 g of M-acid, 7.2 g of sodium bicarbonate, and 0.46 g of copper sulfate pentahydrate were added to a stainless steel autoclave along with 46 mL of water. After nitrogen purge three times, the mixture was heated to 100°C and magnetic stirring was initiated. The mixture was kept warm for 3 hours, then stirring and heating were stopped. After cooling to room temperature, the mixture was diluted 200% with water, heated to 90°C, and 2% calcium carbonate and 1% activated carbon (the dilution volume) were added. Impurities were removed by filtration. The pH was adjusted to 2.5-3.0 with hydrochloric acid. The mixture was stirred for 2 hours to precipitate excess M-acid, filtered, and rinsed with water at 40°C. High-performance liquid chromatography (HPLC) confirmed the absence of hydrolysis and dechlorination byproducts. The product was the CI Reactive Blue 49 dye chromophore in 89% yield.

[0046] Example 7

[0047] Take 8.9 g of 1-aminoanthraquinone-2-sulfonic acid, add deionized water and hydrochloric acid to prepare 100 mL of 18% hydrochloric acid solution as the electrolyte in the anode chamber, and the electrolyte in the cathode chamber is the same volume and concentration of hydrochloric acid solution. The anode and cathode chambers are separated by DuPont Nafion 117 proton exchange membrane. 2 Platinum electrode cut into 2 × 2 cm 2 The graphite felt was ultrasonically cleaned with acetone and ultrapure water, and then assembled into a complete electrolysis device with the electrolytic cell. A magnet was added to the anode chamber, stirring was started, and the electrolysis was carried out at 220 mA cm -2 The electrolysis was carried out at 30 °C for 9 h with a current density of 1.5 wt %. Samples were taken for liquid chromatography analysis. The power was turned off and the electrolyte in the anode chamber was centrifuged to obtain a solid which was dried to obtain 1-amino-4-chloroanthraquinone-2-sulfonic acid.

[0048] 4.2 g of 1-amino-4-chloroanthraquinone-2-sulfonic acid, 5.9 g of M-acid, 4.7 g of sodium bicarbonate, and 0.3 g of copper sulfate pentahydrate were added to a stainless steel autoclave along with 30 mL of water. After nitrogen displacement three times, the mixture was heated to 130°C with magnetic stirring. The mixture was held at this temperature for 3 hours, then stirring and heating were stopped. After cooling to room temperature, the mixture was diluted two-fold with water, heated to 90°C, and 2% of the dilution volume of calcium carbonate and 1% activated carbon were added. Impurities were removed by filtration. The pH was adjusted to 2.5-3.0 with hydrochloric acid. The mixture was stirred for 2 hours to precipitate excess M-acid, filtered, and rinsed with water at 40°C. High-performance liquid chromatography (HPLC) confirmed the absence of hydrolysis and dechlorination byproducts. The product was the CI Reactive Blue 49 dye chromophore in 83% yield.

[0049] Example 8

[0050] Take 5.4 g of 1-aminoanthraquinone-2-sulfonic acid, add deionized water and hydrochloric acid to prepare 100 mL of 20% hydrochloric acid solution as the electrolyte in the anode chamber, and the electrolyte in the cathode chamber is the same volume and concentration of hydrochloric acid solution. The anode and cathode chambers are separated by DuPont Nafion 117 proton exchange membrane. 2 The platinum electrode and the 0.8 mm diameter graphite rod were ultrasonically cleaned with acetone and ultrapure water in sequence, and then assembled into a complete electrolysis device with the electrolytic cell. A magnet was added to the anode chamber, stirring was started, and the flow rate was 190 mA cm -2 The electrolysis was carried out at a current density of 100 nm at 25°C for 8 h, samples were taken for liquid chromatography analysis, the power was turned off, and the electrolyte in the anode chamber was centrifuged to obtain a solid, which was dried to obtain 1-amino-4-chloroanthraquinone-2-sulfonic acid.

[0051] 2.8 g of 1-amino-4-chloroanthraquinone-2-sulfonic acid, 3.1 g of M-acid, 3.1 g of sodium bicarbonate, and 0.2 g of copper sulfate pentahydrate were added to a stainless steel autoclave along with 20 mL of water. After nitrogen purge three times, the mixture was heated to 110°C with magnetic stirring. The mixture was incubated for 1 hour, then stirring and heating were stopped. After cooling to room temperature, the mixture was diluted two-fold with water, heated to 90°C, and 2% of the dilution volume of calcium carbonate and 1% activated carbon were added. The mixture was filtered to remove impurities. The pH was adjusted to 2.5-3.0 with hydrochloric acid. The mixture was stirred for 2 hours to precipitate excess M-acid, filtered, and rinsed with water at 40°C. High-performance liquid chromatography (HPLC) confirmed the absence of hydrolysis and dechlorination byproducts. The product was the CI Reactive Blue 49 dye chromophore in 88% yield.

[0052] Example 9

[0053] Take 7.6 g of 1-aminoanthraquinone-2-sulfonic acid, add deionized water and hydrochloric acid to prepare 100 mL of 15% hydrochloric acid solution as the electrolyte in the anode chamber, and the electrolyte in the cathode chamber is the same volume and concentration of hydrochloric acid solution. The anode and cathode chambers are separated by DuPont Nafion 117 proton exchange membrane. 2 The platinum mesh electrode and the 0.8 mm diameter graphite rod were ultrasonically cleaned with acetone and ultrapure water in sequence, and then assembled into a complete electrolysis device with the electrolytic cell. A magnet was added to the anode chamber, stirring was started, and the current was 200 mA cm -2 The electrolysis was carried out at 30℃ for 7 h, and samples were taken for liquid chromatography analysis. The power was turned off, and the electrolyte in the anode chamber was centrifuged to separate the solid, which was 1-amino-4-chloroanthraquinone-2-sulfonic acid after drying.

[0054] 2.7 g of 1-amino-4-chloroanthraquinone-2-sulfonic acid, 3.2 g of M-acid, 3 g of sodium bicarbonate, and 0.19 g of copper sulfate pentahydrate were added to a stainless steel autoclave along with 11 mL of water. After nitrogen displacement three times, the mixture was heated to 100°C and magnetic stirring was initiated. The mixture was kept warm for 5 hours, then stirring and heating were stopped. After cooling to room temperature, the mixture was diluted two-fold with water, heated to 90°C, and 2% of the dilution volume of calcium carbonate and 1% activated carbon were added. Impurities were removed by filtration. The pH was adjusted to 2.5-3.0 with hydrochloric acid. The mixture was stirred for 2 hours to precipitate excess M-acid, filtered, and rinsed with water at 40°C. High-performance liquid chromatography (HPLC) confirmed the absence of hydrolysis and dechlorination byproducts. The product was the CI Reactive Blue 49 dye chromophore in 87% yield.

[0055] Example 10

[0056] Take 2.3 g of 1-aminoanthraquinone-2-sulfonic acid, add deionized water and hydrochloric acid to prepare 50 mL of 18% hydrochloric acid solution as the electrolyte in the anode chamber, and the electrolyte in the cathode chamber is the same volume and concentration of hydrochloric acid solution. The anode and cathode chambers are separated by DuPont Nafion117 proton exchange membrane. 2 Platinum electrode cut into 2 × 2 cm 2 The graphite felt was ultrasonically cleaned with acetone and ultrapure water, and then assembled into a complete electrolysis device with the electrolytic cell. A magnet was added to the anode chamber, stirring was started, and the flow rate was 300 mAcm -2 The electrolysis was carried out at a current density of 100 nm at 25°C for 8 h, samples were taken for liquid chromatography analysis, the power was turned off, and the electrolyte in the anode chamber was centrifuged to obtain a solid, which was dried to obtain 1-amino-4-chloroanthraquinone-2-sulfonic acid.

[0057] 1.3 g of 1-amino-4-chloroanthraquinone-2-sulfonic acid, 2 g of M-acid, 1.5 g of sodium bicarbonate, and 0.09 g of copper sulfate pentahydrate were added to a stainless steel autoclave along with 9 mL of water. After nitrogen displacement three times, the mixture was heated to 130°C with magnetic stirring. The mixture was held at this temperature for 2 h. Stirring and heating were stopped, and after cooling to room temperature, the mixture was diluted two-fold with water. The temperature was then raised to 90°C, and 2% of the dilution volume of calcium carbonate and 1% of activated carbon were added. The mixture was then filtered to remove impurities. The pH was adjusted to 2.5-3.0 with hydrochloric acid, and the mixture was stirred for 2 h to precipitate excess M-acid. The mixture was filtered and rinsed with water at 40°C. High-performance liquid chromatography (HPLC) confirmed the absence of hydrolysis and dechlorination byproducts, and the product was the CI Reactive Blue 49 dye chromophore in 87% yield.

[0058] Example 11

[0059] Take 4.7 g of 1-aminoanthraquinone-2-sulfonic acid, add deionized water and hydrochloric acid to prepare 50 mL of 15% hydrochloric acid solution as the electrolyte in the anode chamber, and the electrolyte in the cathode chamber is the same volume and concentration of hydrochloric acid solution. The anode and cathode chambers are separated by DuPont Nafion117 proton exchange membrane. 2 The platinum electrode and the 0.8 mm diameter graphite rod were ultrasonically cleaned with acetone and ultrapure water in sequence, and then assembled into a complete electrolysis device with the electrolytic cell. A magnet was added to the anode chamber, stirring was started, and the flow rate was 300 mAcm -2 The electrolysis was carried out at 30 °C for 10 h, and samples were taken for liquid chromatography analysis. The power was turned off, and the electrolyte in the anode chamber was centrifuged to obtain a solid, which was dried to obtain 1-amino-4-chloroanthraquinone-2-sulfonic acid.

[0060] 3 g of 1-amino-4-chloroanthraquinone-2-sulfonic acid, 3.3 g of M-acid, 3.3 g of sodium bicarbonate, and 0.2 g of copper sulfate pentahydrate were added to a stainless steel autoclave along with 20 mL of water. After nitrogen displacement three times, the mixture was heated to 120°C with magnetic stirring. The mixture was held at this temperature for 2 h. Stirring and heating were stopped, and after cooling to room temperature, the mixture was diluted two-fold with water. The temperature was then raised to 90°C, and 2% of the dilution volume of calcium carbonate and 1% of activated carbon were added. The mixture was then filtered to remove impurities. The pH was adjusted to 2.5-3.0 with hydrochloric acid, and the mixture was stirred for 2 h to precipitate excess M-acid. The mixture was filtered and rinsed with water at 40°C. High-performance liquid chromatography (HPLC) confirmed the absence of hydrolysis and dechlorination byproducts, and the product was the CI Reactive Blue 49 dye chromophore in 90% yield.

[0061] Example 12

[0062] Take 6.6 g of 1-aminoanthraquinone-2-sulfonic acid, add deionized water and hydrochloric acid to prepare 100 mL of 20% hydrochloric acid solution as the electrolyte in the anode chamber, and the electrolyte in the cathode chamber is the same volume and concentration of hydrochloric acid solution. The anode and cathode chambers are separated by DuPont Nafion 117 proton exchange membrane. 2 The platinum mesh electrode and the 0.8 mm diameter graphite rod were ultrasonically cleaned with acetone and ultrapure water in sequence, and then assembled into a complete electrolysis device with the electrolytic cell. A magnet was added to the anode chamber, stirring was started, and the current was 300 mA cm -2 The electrolysis was carried out at 25 °C for 10 h, and samples were taken for liquid chromatography analysis. The power was turned off, and the electrolyte in the anode chamber was centrifuged to separate the solid, which was 1-amino-4-chloroanthraquinone-2-sulfonic acid after drying.

[0063] 3.1 g of 1-amino-4-chloroanthraquinone-2-sulfonic acid, 4 g of M-acid, 3.5 g of sodium bicarbonate, and 0.2 g of copper sulfate pentahydrate were added to a stainless steel autoclave along with 22 mL of water. After nitrogen purge three times, the mixture was heated to 150°C with magnetic stirring. The mixture was held at this temperature for 1 h, then stirring and heating were stopped. After cooling to room temperature, the mixture was diluted two-fold with water, heated to 90°C, and 2% of the dilution volume of calcium carbonate and 1% activated carbon were added. Impurities were removed by filtration. The pH was adjusted to 2.5-3.0 with hydrochloric acid. The mixture was stirred for 2 h to precipitate excess M-acid, which was filtered and rinsed with water at 40°C. High-performance liquid chromatography (HPLC) confirmed the absence of hydrolysis and dechlorination byproducts. The product was the CI Reactive Blue 49 dye chromophore in 83% yield.

[0064] Example 13

[0065] Take 8 g of 1-aminoanthraquinone-2-sulfonic acid, add deionized water and hydrochloric acid to prepare 150 mL of 15% hydrochloric acid solution as the electrolyte in the anode chamber, and the electrolyte in the cathode chamber is the same volume and concentration of hydrochloric acid solution. The anode and cathode chambers are separated by DuPont Nafion117 proton exchange membrane. 2 The platinum electrode and the 0.8 mm diameter graphite rod were ultrasonically cleaned with acetone and ultrapure water in sequence, and then assembled into a complete electrolysis device with the electrolytic cell. A magnet was added to the anode chamber, stirring was started, and the electrolysis was carried out at 290 mAcm -2 The electrolysis was carried out at 30 °C for 9 h with a current density of 1.5 wt %. Samples were taken for liquid chromatography analysis. The power was turned off and the electrolyte in the anode chamber was centrifuged to obtain a solid which was dried to obtain 1-amino-4-chloroanthraquinone-2-sulfonic acid.

[0066] 4.6 g of 1-amino-4-chloroanthraquinone-2-sulfonic acid, 6.9 g of M-acid, 5.1 g of sodium bicarbonate, and 0.33 g of copper sulfate pentahydrate were added to a stainless steel autoclave along with 33 mL of water. After nitrogen displacement three times, the mixture was heated to 140°C with magnetic stirring. The mixture was held at this temperature for 3 hours, then stirring and heating were stopped. After cooling to room temperature, the mixture was diluted two-fold with water, heated to 90°C, and 2% of the dilution volume of calcium carbonate and 1% activated carbon were added. Impurities were removed by filtration. The pH was adjusted to 2.5-3.0 with hydrochloric acid. The mixture was stirred for 2 hours to precipitate excess M-acid, filtered, and rinsed with water at 40°C. High-performance liquid chromatography (HPLC) confirmed the absence of hydrolysis and dechlorination byproducts. The product was the CI Reactive Blue 49 dye chromophore in 81% yield.

[0067] Example 14

[0068] Take 4.1 g of 1-aminoanthraquinone-2-sulfonic acid, add deionized water and hydrochloric acid to prepare 100 mL of 18% hydrochloric acid solution as the electrolyte in the anode chamber, and the electrolyte in the cathode chamber is the same volume and concentration of hydrochloric acid solution. The anode and cathode chambers are separated by DuPont Nafion 117 proton exchange membrane. 2 Platinum electrode cut into 2 × 2 cm 2 The graphite felt was ultrasonically cleaned with acetone and ultrapure water, and then assembled into a complete electrolysis device with the electrolytic cell. A magnet was added to the anode chamber, stirring was started, and the electrolysis device was operated at 150 mA cm -2 The electrolysis was carried out at 25 °C for 5 h, and samples were taken for liquid chromatography analysis. The power was turned off, and the electrolyte in the anode chamber was centrifuged to separate the solid, which was 1-amino-4-chloroanthraquinone-2-sulfonic acid after drying.

[0069] 1.5 g of 1-amino-4-chloroanthraquinone-2-sulfonic acid, 1.7 g of M-acid, 1.7 g of sodium bicarbonate, and 0.11 g of copper sulfate pentahydrate were added to a stainless steel autoclave along with 11 mL of water. After nitrogen purge three times, the mixture was heated to 110°C with magnetic stirring. The mixture was incubated for 4 hours, then stirring and heating were stopped. After cooling to room temperature, the mixture was diluted two-fold with water, heated to 90°C, and 2% of the dilution volume of calcium carbonate and 1% activated carbon were added. Impurities were removed by filtration. The pH was adjusted to 2.5-3.0 with hydrochloric acid. The mixture was stirred for 2 hours to precipitate excess M-acid, filtered, and rinsed with water at 40°C. High-performance liquid chromatography (HPLC) confirmed the absence of hydrolysis and dechlorination byproducts. The product was the CI Reactive Blue 49 dye chromophore in 82% yield.

[0070] Example 15

[0071] Take 7.2 g of 1-aminoanthraquinone-2-sulfonic acid, add deionized water and hydrochloric acid to prepare 150 mL of 15% hydrochloric acid solution as the electrolyte in the anode chamber, and the electrolyte in the cathode chamber is the same volume and concentration of hydrochloric acid solution. The anode and cathode chambers are separated by DuPont Nafion 117 proton exchange membrane. 2 The platinum mesh electrode and the 0.8 mm diameter graphite rod were ultrasonically cleaned with acetone and ultrapure water in sequence, and then assembled into a complete electrolysis device with the electrolytic cell. A magnet was added to the anode chamber, stirring was started, and the current was 200 mA cm -2 The electrolysis was carried out at 30 °C for 6 h with a current density of 1.5 wt %. Samples were taken for liquid chromatography analysis. The power was turned off and the electrolyte in the anode chamber was centrifuged to obtain a solid, which was dried to obtain 1-amino-4-chloroanthraquinone-2-sulfonic acid.

[0072] 3.9 g of 1-amino-4-chloroanthraquinone-2-sulfonic acid, 4.7 g of M-acid, 4.3 g of sodium bicarbonate, and 0.28 g of copper sulfate pentahydrate were added to a stainless steel autoclave along with 28 mL of water. After nitrogen purge three times, the mixture was heated to 120°C with magnetic stirring. The mixture was kept warm for 2 hours, then stirring and heating were stopped. After cooling to room temperature, the mixture was diluted two-fold with water, heated to 90°C, and 2% of the dilution volume of calcium carbonate and 1% activated carbon were added. The mixture was filtered to remove impurities. The pH was adjusted to 2.5-3.0 with hydrochloric acid. The mixture was stirred for 2 hours to precipitate excess M-acid, filtered, and rinsed with water at 40°C. High-performance liquid chromatography (HPLC) confirmed the absence of hydrolysis and dechlorination byproducts. The product was the CI Reactive Blue 49 dye chromophore in 87% yield.

[0073] Example 16

[0074] Take 6.1 g of 1-aminoanthraquinone-2-sulfonic acid, add deionized water and hydrochloric acid to prepare 100 mL of 20% hydrochloric acid solution as the electrolyte in the anode chamber, and the electrolyte in the cathode chamber is the same volume and concentration of hydrochloric acid solution. The anode and cathode chambers are separated by DuPont Nafion 117 proton exchange membrane. 2 The platinum mesh electrode and the 0.8 mm diameter graphite rod were ultrasonically cleaned with acetone and ultrapure water in sequence, and then assembled into a complete electrolysis device with the electrolytic cell. A magnet was added to the anode chamber, stirring was started, and the flow rate was 120 mA cm -2 The electrolysis was carried out at 25 °C for 7 h, and samples were taken for liquid chromatography analysis. The power was turned off, and the electrolyte in the anode chamber was centrifuged to separate the solid, which was 1-amino-4-chloroanthraquinone-2-sulfonic acid after drying.

[0075] 2.7 g of 1-amino-4-chloroanthraquinone-2-sulfonic acid, 3.5 g of M-acid, 3 g of sodium bicarbonate, and 0.19 g of copper sulfate pentahydrate were added to a stainless steel autoclave along with 19 mL of water. After nitrogen displacement three times, the mixture was heated to 130°C with magnetic stirring. The mixture was maintained at this temperature for 3 hours. Stirring and heating were stopped, and after cooling to room temperature, the mixture was diluted two-fold with water. The temperature was then raised to 90°C, and 2% of the dilution volume of calcium carbonate and 1% of activated carbon were added. Impurities were removed by filtration. The pH was adjusted to 2.5-3.0 with hydrochloric acid, and the mixture was stirred for 1 hour to precipitate excess M-acid. The mixture was filtered and rinsed with water at 40°C. High-performance liquid chromatography (HPLC) confirmed the absence of hydrolysis and dechlorination byproducts, and the product was the CI Reactive Blue 49 dye chromophore in a yield of 77%.

[0076] Example 17

[0077] Take 3.5 g of 1-aminoanthraquinone-2-sulfonic acid, add deionized water and hydrochloric acid to prepare 100 mL of 15% hydrochloric acid solution as the electrolyte in the anode chamber, and the electrolyte in the cathode chamber is the hydrochloric acid solution of the same volume and concentration. The anode and cathode chambers are separated by DuPont Nafion 117 proton exchange membrane. 2 The platinum electrode and the 0.8 mm diameter graphite rod were ultrasonically cleaned with acetone and ultrapure water in sequence, and then assembled into a complete electrolysis device with the electrolytic cell. A magnet was added to the anode chamber, stirring was started, and the flow rate was 280 mA cm -2 The electrolysis was carried out at 25 °C for 4 h, and samples were taken for liquid chromatography analysis. The power was turned off, and the electrolyte in the anode chamber was centrifuged to separate the solid, which was 1-amino-4-chloroanthraquinone-2-sulfonic acid after drying.

[0078] 1.9 g of 1-amino-4-chloroanthraquinone-2-sulfonic acid, 2.7 g of M-acid, 2.1 g of sodium bicarbonate, and 0.13 g of copper sulfate pentahydrate were added to a stainless steel autoclave along with 13 mL of water. After nitrogen displacement three times, the mixture was heated to 110°C with magnetic stirring. The mixture was maintained at this temperature for 4 hours. Stirring and heating were stopped, and after cooling to room temperature, the mixture was diluted two-fold with water. The temperature was then raised to 90°C, and 2% of the dilution volume of calcium carbonate and 1% activated carbon were added. Impurities were removed by filtration. The pH was adjusted to 2.5-3.0 with hydrochloric acid, and the mixture was stirred for 2 hours to precipitate excess M-acid. The mixture was filtered and rinsed with water at 40°C. High-performance liquid chromatography (HPLC) confirmed the absence of hydrolysis and dechlorination byproducts, and the product was the CI Reactive Blue 49 dye chromophore in a yield of 92%.

[0079] Example 18

[0080] Take 5.9 g of 1-aminoanthraquinone-2-sulfonic acid, add deionized water and hydrochloric acid to prepare 100 mL of 18% hydrochloric acid solution as the electrolyte in the anode chamber, and the electrolyte in the cathode chamber is the same volume and concentration of hydrochloric acid solution. The anode and cathode chambers are separated by DuPont Nafion 117 proton exchange membrane. 2 The platinum mesh electrode and the 0.8 mm diameter graphite rod were ultrasonically cleaned with acetone and ultrapure water in sequence, and then assembled into a complete electrolysis device with the electrolytic cell. A magnet was added to the anode chamber, stirring was started, and the flow rate was 280 mA cm -2 The electrolysis was carried out at 25 °C for 4 h, and samples were taken for liquid chromatography analysis. The power was turned off, and the electrolyte in the anode chamber was centrifuged to separate the solid, which was 1-amino-4-chloroanthraquinone-2-sulfonic acid after drying.

[0081] 2.4 g of 1-amino-4-chloroanthraquinone-2-sulfonic acid, 3.6 g of M-acid, 2.7 g of sodium bicarbonate, and 0.17 g of copper sulfate pentahydrate were added to a stainless steel autoclave along with 17 mL of water. After nitrogen displacement three times, the mixture was heated to 100°C and magnetic stirring was initiated. The mixture was maintained at this temperature for 3 hours. Stirring and heating were discontinued, and after cooling to room temperature, the mixture was diluted two-fold with water. The temperature was then raised to 90°C, and 2% of the dilution volume of calcium carbonate and 1% activated carbon were added. Impurities were removed by filtration. The pH was adjusted to 2.5-3.0 with hydrochloric acid, and the mixture was stirred for 2 hours to precipitate excess M-acid. The mixture was filtered and rinsed with water at 40°C. High-performance liquid chromatography (HPLC) confirmed the absence of hydrolysis and dechlorination byproducts, and the product was the CI Reactive Blue 49 dye chromophore in 82% yield.

[0082] Example 19

[0083] Take 8.8 g of 1-aminoanthraquinone-2-sulfonic acid, add deionized water and hydrochloric acid to prepare 150 mL of 15% hydrochloric acid solution as the electrolyte in the anode chamber, and the electrolyte in the cathode chamber is the same volume and concentration of hydrochloric acid solution. The anode and cathode chambers are separated by DuPont Nafion 117 proton exchange membrane. 2 The platinum electrode and the 0.8 mm diameter graphite rod were ultrasonically cleaned with acetone and ultrapure water in sequence, and then assembled into a complete electrolysis device with the electrolytic cell. A magnet was added to the anode chamber, stirring was started, and the flow rate was 120 mA cm -2 The electrolysis was carried out at 30 °C for 8 h with a current density of 1.5 wt %. Samples were taken for liquid chromatography analysis. The power was turned off and the electrolyte in the anode chamber was centrifuged to obtain a solid which was dried to obtain 1-amino-4-chloroanthraquinone-2-sulfonic acid.

[0084] 5 g of 1-amino-4-chloroanthraquinone-2-sulfonic acid, 5.5 g of M-acid, 5.6 g of sodium bicarbonate, and 0.36 g of copper sulfate pentahydrate were added to a stainless steel autoclave along with 35 mL of water. After nitrogen displacement three times, the mixture was heated to 150°C with magnetic stirring. The mixture was held at this temperature for 2 h. Stirring and heating were stopped, and after cooling to room temperature, the mixture was diluted two-fold with water. The temperature was then raised to 90°C, and 2% of the dilution volume of calcium carbonate and 1% activated carbon were added. The mixture was then filtered to remove impurities. The pH was adjusted to 2.5-3.0 with hydrochloric acid, and the mixture was stirred for 2 h to precipitate excess M-acid. The mixture was filtered and rinsed with water at 40°C. High-performance liquid chromatography (HPLC) confirmed the absence of hydrolysis and dechlorination byproducts, and the product was the CI Reactive Blue 49 dye chromophore in 84% yield.

[0085] Example 20

[0086] Take 4.2 g of 1-aminoanthraquinone-2-sulfonic acid, add deionized water and hydrochloric acid to prepare 100 mL of 20% hydrochloric acid solution as the electrolyte in the anode chamber, and the electrolyte in the cathode chamber is the same volume and concentration of hydrochloric acid solution. The anode and cathode chambers are separated by DuPont Nafion 117 proton exchange membrane. 2 Platinum electrode cut into 2 × 2 cm 2 The graphite felt was ultrasonically cleaned with acetone and ultrapure water, and then assembled into a complete electrolysis device with the electrolytic cell. A magnet was added to the anode chamber, stirring was started, and the electrolysis device was operated at 150 mA cm -2 The electrolysis was carried out at 25 °C for 6 h, and samples were taken for liquid chromatography analysis. The power was turned off, and the electrolyte in the anode chamber was centrifuged to separate the solid, which was 1-amino-4-chloroanthraquinone-2-sulfonic acid after drying.

[0087] 2.4 g of 1-amino-4-chloroanthraquinone-2-sulfonic acid, 3.6 g of M-acid, 2.7 g of sodium bicarbonate, and 0.17 g of copper sulfate pentahydrate were added to a stainless steel autoclave along with 17 mL of water. After nitrogen displacement three times, the mixture was heated to 140°C with magnetic stirring. The mixture was held at this temperature for 2 h. Stirring and heating were stopped, and after cooling to room temperature, the mixture was diluted two-fold with water. The temperature was then raised to 90°C, and 2% of the dilution volume of calcium carbonate and 1% activated carbon were added. The mixture was then filtered to remove impurities. The pH was adjusted to 2.5-3.0 with hydrochloric acid, and the mixture was stirred for 2 h to precipitate excess M-acid. The mixture was filtered and rinsed with water at 40°C. High-performance liquid chromatography (HPLC) confirmed the absence of hydrolysis and dechlorination byproducts, and the product was the CI Reactive Blue 49 dye chromophore in 85% yield.

[0088] Example 21

[0089] Take 10.5 g of 1-aminoanthraquinone-2-sulfonic acid, add deionized water and hydrochloric acid to prepare 150 mL of 18% hydrochloric acid solution as the electrolyte in the anode chamber, and the electrolyte in the cathode chamber is the same volume and concentration of hydrochloric acid solution. The anode and cathode chambers are separated by DuPont Nafion 117 proton exchange membrane. 2 The platinum electrode and the 0.8 mm diameter graphite rod were ultrasonically cleaned with acetone and ultrapure water in sequence, and then assembled into a complete electrolysis device with the electrolytic cell. A magnet was added to the anode chamber, stirring was started, and the current was 200 mA cm -2 The electrolysis was carried out at 30 °C for 8 h with a current density of 1.5 wt %. Samples were taken for liquid chromatography analysis. The power was turned off and the electrolyte in the anode chamber was centrifuged to obtain a solid which was dried to obtain 1-amino-4-chloroanthraquinone-2-sulfonic acid.

[0090] 6 g of 1-amino-4-chloroanthraquinone-2-sulfonic acid, 7.2 g of M-acid, 6.7 g of sodium bicarbonate, and 0.43 g of copper sulfate pentahydrate were added to a stainless steel autoclave along with 43 mL of water. After nitrogen displacement three times, the mixture was heated to 100°C and magnetic stirring was initiated. The mixture was held at this temperature for 3 hours, then stirring and heating were stopped. After cooling to room temperature, the mixture was diluted two-fold with water, heated to 90°C, and 2% of the dilution volume of calcium carbonate and 1% activated carbon were added. Impurities were removed by filtration. The pH was adjusted to 2.5-3.0 with hydrochloric acid. The mixture was stirred for 2 hours to precipitate excess M-acid, filtered, and rinsed with water at 40°C. High-performance liquid chromatography (HPLC) confirmed the absence of hydrolysis and dechlorination byproducts. The product was the CI Reactive Blue 49 dye chromophore in 89% yield.

[0091] Example 22

[0092] Take 6.3 g of 1-aminoanthraquinone-2-sulfonic acid, add deionized water and hydrochloric acid to prepare 100 mL of 20% hydrochloric acid solution as the electrolyte in the anode chamber, and the electrolyte in the cathode chamber is the same volume and concentration of hydrochloric acid solution. The anode and cathode chambers are separated by DuPont Nafion 117 proton exchange membrane. 2 The platinum electrode and the 0.8 mm diameter graphite rod were ultrasonically cleaned with acetone and ultrapure water in sequence, and then assembled into a complete electrolysis device with the electrolytic cell. A magnet was added to the anode chamber, stirring was started, and the flow rate was 180 mA cm -2 The electrolysis was carried out at 25 °C for 7 h, and samples were taken for liquid chromatography analysis. The power was turned off, and the electrolyte in the anode chamber was centrifuged to separate the solid, which was 1-amino-4-chloroanthraquinone-2-sulfonic acid after drying.

[0093] 3.2 g of 1-amino-4-chloroanthraquinone-2-sulfonic acid, 3.5 g of M-acid, 3.6 g of sodium bicarbonate, and 0.23 g of copper sulfate pentahydrate were added to a stainless steel autoclave along with 23 mL of water. After nitrogen purge three times, the mixture was heated to 120°C with magnetic stirring. The mixture was kept warm for 2 hours, then stirring and heating were stopped. After cooling to room temperature, the mixture was diluted two-fold with water, heated to 90°C, and 2% of the dilution volume of calcium carbonate and 1% activated carbon were added. Impurities were removed by filtration. The pH was adjusted to 2.5-3.0 with hydrochloric acid. The mixture was stirred for 2 hours to precipitate excess M-acid, filtered, and rinsed with water at 40°C. High-performance liquid chromatography (HPLC) confirmed the absence of hydrolysis and dechlorination byproducts. The product was the CI Reactive Blue 49 dye chromophore in 90% yield.

[0094] Example 23

[0095] Take 8.7 g of 1-aminoanthraquinone-2-sulfonic acid, add deionized water and hydrochloric acid to prepare 150 mL of 15% hydrochloric acid solution as the electrolyte in the anode chamber, and the electrolyte in the cathode chamber is the same volume and concentration of hydrochloric acid solution. The anode and cathode chambers are separated by DuPont Nafion 117 proton exchange membrane. 2 Platinum electrode cut into 2 × 2 cm 2 The graphite felt was ultrasonically cleaned with acetone and ultrapure water in sequence, and then assembled into a complete electrolysis device with the electrolytic cell. A magnet was added to the anode chamber, stirring was started, and the electrolysis was carried out at 300 mA cm -2 The electrolysis was carried out at 30 °C for 9 h with a current density of 1.5 wt %. Samples were taken for liquid chromatography analysis. The power was turned off and the electrolyte in the anode chamber was centrifuged to obtain a solid which was dried to obtain 1-amino-4-chloroanthraquinone-2-sulfonic acid.

[0096] 4.7 g of 1-amino-4-chloroanthraquinone-2-sulfonic acid, 6.6 g of M-acid, 5.2 g of sodium bicarbonate, and 0.33 g of copper sulfate pentahydrate were added to a stainless steel autoclave along with 33 mL of water. After nitrogen displacement three times, the mixture was heated to 100°C and magnetic stirring was initiated. The mixture was maintained at this temperature for 3 hours. Stirring and heating were discontinued, and after cooling to room temperature, the mixture was diluted two-fold with water. The temperature was then raised to 110°C, and 2% of the dilution volume of calcium carbonate and 1% activated carbon were added. The mixture was then filtered to remove impurities. The pH was adjusted to 2.5-3.0 with hydrochloric acid, and the mixture was stirred for 2 hours to precipitate excess M-acid. The mixture was filtered and rinsed with water at 40°C. High-performance liquid chromatography (HPLC) confirmed the absence of hydrolysis and dechlorination byproducts, and the product was the CI Reactive Blue 49 dye chromophore in a 91% yield.

[0097] Example 24

[0098] Take 3.4 g of 1-aminoanthraquinone-2-sulfonic acid, add deionized water and hydrochloric acid to prepare 50 mL of 18% hydrochloric acid solution as the electrolyte in the anode chamber, and the electrolyte in the cathode chamber is the same volume and concentration of hydrochloric acid solution. The anode and cathode chambers are separated by DuPont Nafion117 proton exchange membrane. 2 The platinum electrode and the 0.8 mm diameter graphite rod were ultrasonically cleaned with acetone and ultrapure water in sequence, and then assembled into a complete electrolysis device with the electrolytic cell. A magnet was added to the anode chamber, stirring was started, and the electrolysis was carried out at 150 mA cm -2 The electrolysis was carried out at 25 °C for 7 h, and samples were taken for liquid chromatography analysis. The power was turned off, and the electrolyte in the anode chamber was centrifuged to separate the solid, which was 1-amino-4-chloroanthraquinone-2-sulfonic acid after drying.

[0099] 1.6 g of 1-amino-4-chloroanthraquinone-2-sulfonic acid, 2.1 g of M-acid, 1.8 g of sodium bicarbonate, and 0.11 g of copper sulfate pentahydrate were added to a stainless steel autoclave along with 11 mL of water. After nitrogen displacement three times, the mixture was heated to 130°C with magnetic stirring. The mixture was held at this temperature for 2 h. Stirring and heating were stopped, and after cooling to room temperature, the mixture was diluted two-fold with water. The temperature was then raised to 90°C, and 2% of the dilution volume of calcium carbonate and 1% activated carbon were added. Impurities were removed by filtration. The pH was adjusted to 2.5-3.0 with hydrochloric acid, and the mixture was stirred for 2 h to precipitate excess M-acid. The mixture was filtered and rinsed with water at 40°C. High-performance liquid chromatography (HPLC) confirmed the absence of hydrolysis and dechlorination byproducts, and the product was the CI Reactive Blue 49 dye chromophore in 87% yield.

[0100] Example 25

[0101] Take 2 g of 1-aminoanthraquinone-2-sulfonic acid, add deionized water and hydrochloric acid to prepare 50 mL of 15% hydrochloric acid solution as the electrolyte in the anode chamber, and the electrolyte in the cathode chamber is the same volume and concentration of hydrochloric acid solution. The anode and cathode chambers are separated by DuPont Nafion117 proton exchange membrane. 2 The platinum mesh electrode and the 0.8 mm diameter graphite rod were ultrasonically cleaned with acetone and ultrapure water in sequence, and then assembled into a complete electrolysis device with the electrolytic cell. A magnet was added to the anode chamber, stirring was started, and the electrolysis was carried out at 250 mA cm -2 The electrolysis was carried out at 30 °C for 11 h with a current density of 1.5 wt %. Samples were taken for liquid chromatography analysis. The power was turned off and the electrolyte in the anode chamber was centrifuged to obtain a solid, which was dried to obtain 1-amino-4-chloroanthraquinone-2-sulfonic acid.

[0102] 1.2 g of 1-amino-4-chloroanthraquinone-2-sulfonic acid, 1.3 g of M-acid, 1.3 g of sodium bicarbonate, and 0.1 g of copper sulfate pentahydrate were added to a stainless steel autoclave along with 9 mL of water. After nitrogen displacement three times, the mixture was heated to 140°C with magnetic stirring. The mixture was held at this temperature for 1 hour, then stirring and heating were stopped. After cooling to room temperature, the mixture was diluted two-fold with water, heated to 90°C, and 2% of the dilution volume of calcium carbonate and 1% activated carbon were added. Impurities were removed by filtration. The pH was adjusted to 2.5-3.0 with hydrochloric acid. The mixture was stirred for 2 hours to precipitate excess M-acid, which was filtered and rinsed with water at 40°C. High-performance liquid chromatography (HPLC) confirmed the absence of hydrolysis and dechlorination byproducts. The product was the CI Reactive Blue 49 dye chromophore in 89% yield.

Claims

1. A method for preparing CI Reactive Blue 49 chromophore by electrolysis, characterized in that: The following steps are involved: ； (1) 1-aminoanthraquinone-2-sulfonic acid is dissolved in hydrochloric acid as the electrolyte in the anode chamber, and hydrochloric acid solution is used as the electrolyte in the cathode chamber. Constant current electrolysis is used to in-situ chlorinate in the anode chamber to obtain 1-amino-4-chloroanthraquinone-2-sulfonic acid; (2) The 1-amino-4-chloroanthraquinone-2-sulfonic acid obtained in step (1) is condensed with 1,3,5-trimethyl-2,4-diaminobenzenesulfonic acid in a pressure autoclave using water as solvent, sodium bicarbonate as base, and copper sulfate as catalyst to obtain the CI Reactive Blue 49 color base.

2. The method for preparing the CI Reactive Blue 49 chromophore by electrolysis according to claim 1, wherein: The mass percentage of the 1-aminoanthraquinone-2-sulfonic acid in the hydrochloric acid is 1% to 15%, and the concentration of the hydrochloric acid is 10% to 30%.

3. The method for preparing the CI Reactive Blue 49 chromophore by electrolysis according to claim 1, wherein: The anode of the electrolysis was a platinum electrode; the cathode was a graphite electrode; the power supply type was direct current, and the current density was 50~500 mA cm -2 The electrolytic cell type is an H-shaped electrolytic cell, and the anode and cathode chambers are separated by a proton exchange membrane; the electrolysis temperature is 0~30℃; and the electrolysis time is 3~12 h.

4. The method for preparing the CI Reactive Blue 49 chromophore by electrolysis according to claim 1, wherein: The molar ratio of 1-amino-4-chloroanthraquinone-2-sulfonic acid to 1,3,5-trimethyl-2,4-diaminobenzenesulfonic acid is 1:1.5-1:2.5, the molar ratio of 1-amino-4-chloroanthraquinone-2-sulfonic acid to sodium bicarbonate is 1:3-1:6, the molar ratio of 1-amino-4-chloroanthraquinone-2-sulfonic acid to copper sulfate is 1:0.05-1:0.2, and the mass percentage of 1-amino-4-chloroanthraquinone-2-sulfonic acid in the reaction system is 10%-20%.

5. The method for preparing the CI Reactive Blue 49 chromophore by electrolysis according to claim 1, wherein: The pressure autoclave is a stainless steel reactor with gas charging and discharging ports, and nitrogen is used to replace the air in the autoclave before the reaction.

6. The method for preparing the CI Reactive Blue 49 chromophore by electrolysis according to claim 1, wherein: The condensation time is 1-4 h, and the reaction temperature is 90-180°C.

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