A method for preparing a tri-reactive orange dye

Abstract

This invention provides a method for preparing a tri-reactive orange dye, comprising: a primary condensation of cyanuric chloride with 2,4-diaminobenzenesulfonic acid, followed by hydrolysis and diazotization, a primary coupling with 3,5-diaminobenzoic acid, a secondary coupling with p-(β-hydroxyethyl sulfone sulfate)aniline diazonium salt, and a secondary condensation with p-(β-hydroxyethyl sulfone sulfate)aniline to obtain a dye paste. The dye structure is the dye prepared by this invention, which has good solubility, bright color, and can be used as a single-color dye or for blending with black dyes. It has high blackness, good compatibility, and maintains good fixation rate and color fastness while having low raw material cost, good economic efficiency, and high cost performance.

Description

Technical Field

[0001] This invention belongs to the field of reactive dye synthesis, and specifically relates to a method for preparing a dye with three reactive groups. Background Technology

[0002] Orange reactive dyes prepared using 3,5-diaminobenzoic acid as the core material exhibit good compatibility with most KN-type and some M-type and KM-type reactive dyes after the introduction of sulfuric acid-containing chain aliphatic reactive groups. They also show good absorption in the 400-500 nm wavelength range, making them commonly used in the blending and color matching of black dyes. For example, invention patent CN101117449A discloses a high-concentration composite reactive dye, which involves the preparation technology of an orange dye synthesized from 3,5-diaminobenzoic acid. The synthesized orange dye is mainly used as a filler color, maintaining good blackness when blended with the prepared black (navy blue, dark blue) dye, while solving the problem of low fixation rate and poor fastness of black dyes. The orange dye provided in this patent accounts for a small proportion in composite black dyes, generally not exceeding 30%, playing the role of filler and complementary color in black dye blending. It mainly solves the problem of insufficient blackness in market black dyes through compatibility and complementarity. However, as an orange dye, its color is not vibrant enough, limiting its use in single-color applications.

[0003] Invention patent CN 108102419A discloses an orange reactive dye suitable for digital inkjet printing. The orange dye synthesized in the patent using 3,5-diaminobenzoic acid as a raw material is used as a single-color dye. It has bright and beautiful colors and excellent wet fastness, but its solubility is average. The solubility at 90°C is only 100g / L, which barely meets the needs of single-color printing. When used for multi-color compounding, there is little room for choice. If it is used forcibly, a large amount of auxiliaries need to be added, resulting in high usage costs.

[0004] Invention patent CN 117777754A provides a high-fastness orange reactive dye and its preparation method, which improves the problems of poor color fixation effect and dyeing performance of reactive dyes. The color fixation rate can reach 86% and the fastness is excellent. However, the dye has a complex structure, large molecular weight, and difficult-to-control synthesis process. Some raw materials are expensive, and the amount of materials required for the same strength is large, resulting in high production costs and high prices. From a market perspective, the cost-effectiveness is low and the target audience is small.

[0005] In recent years, people's pursuit of quality of life has changed, and the downgrading of consumption by some residents has led to a shift in consumption habits from demanding high quality to demanding high cost-effectiveness. As part of home life, people tend to make balanced choices regarding the color saturation, functionality, comfort, and corresponding price of various fabrics during textile consumption. Dyeing and printing are essential processes in fabric processing and production, and their costs indirectly determine the price of the final home textiles. Therefore, the development of cost-effective dyes is indispensable. Summary of the Invention

[0006] The purpose of this invention is to provide a method for preparing dyes with three reactive groups. The raw materials are readily available and low in cost, the process is simple, and the resulting product has high purity, bright color, good solubility, excellent fixation rate and fastness. It can be used for both single color and compound dyes, has high cost performance and good reproducibility.

[0007] A method for preparing a tri-reactive orange dye includes the following steps:

[0008] 1) Add ice and water to cyanuric chloride, add dispersant MF and inorganic salt, stir and slurry to obtain slurry;

[0009] 2) Add baking soda to ice water, then add 2,4-diaminobenzenesulfonic acid, stir until dissolved, and obtain 2,4-diaminobenzenesulfonic acid solution;

[0010] 3) The 2,4-diaminobenzenesulfonic acid solution obtained in step 2) is added dropwise to the pulp obtained in step 1) to carry out a condensation reaction. The pH value is adjusted to 1.0 to 1.5, the reaction temperature is -3 to 0℃, and a condensed solution is obtained after the reaction is complete.

[0011] 4) Add sodium carbonate solution dropwise to the first condensate, adjust the pH value to 8.0-9.0, and keep the reaction temperature at 0-5℃ to obtain a condensate hydrolysate from the hydrolysis reaction;

[0012] 5) Add a phosphorus-free defoamer and hydrochloric acid to a hydrolysate in sequence, and then add sodium nitrite solution dropwise. The reaction temperature is 0-5℃. The diazotization reaction yields a diazotized solution.

[0013] 6) Add baking soda and dispersant MF to the bottom water, then add 3,5-diaminobenzoic acid, stir until dissolved, and then add to a diazo solution. After the addition is complete, continue to use baking soda to maintain the pH value at 6.0-7.0. The reaction temperature is 5-12℃. The coupling reaction yields a primary coupling solution.

[0014] 7) Add ice and water to p-(β-hydroxyethyl sulfone sulfate) aniline, stir and slurry, add hydrochloric acid after slurrying, add sodium nitrite solution dropwise, and diazotize to obtain p-(β-hydroxyethyl sulfone sulfate) aniline diazo solution;

[0015] 8) Add p-(β-hydroxyethyl sulfone sulfate) aniline diazo solution to the primary coupling solution, then adjust the pH value to 4.5-5.0 with sodium bicarbonate, and the reaction temperature is 5-12℃ to obtain the secondary coupling solution.

[0016] 9) Add p-(β-hydroxyethyl sulfone sulfate) aniline dry powder to the secondary coupling solution again, slowly raise the temperature and keep it at 30-35°C, use baking soda to maintain the pH value at 4.5-5.5 for the reaction, then continue to raise the temperature and keep it at 40-45°C, use soda ash solution to maintain the pH value at 5.5-6.5 for the reaction for 2 hours to obtain the dye slurry.

[0017] The orange dye structure provided by this invention is as follows:

[0018]

[0019] The dye provided by this invention has three active groups, which ensures that the dyed fabric has good fastness. One of the groups is a triazine group, which can effectively inhibit the hydrolysis of the dye during high-temperature dyeing and solve the problem of reduced color fixation rate of some fabrics after dyeing. Furthermore, since the other two groups are divinyl sulfone sulfate type, they have good compatibility with black dyes such as CI Reactive Black 5 and have high coloring efficiency. They can also fix the color simultaneously when alkali is added after dyeing, resulting in good dyeing stability and high color fixation rate.

[0020] In step 1), a pulping process is added. The fineness of cyanuric chloride is improved by the friction and collision between the crushed ice and the material. The purpose of adding inorganic salts is to ensure that the material has sufficient fluidity below 0°C, making the reaction easier to proceed.

[0021] Preferably, in step 1), the mass ratio of cyanuric chloride, ice, and water is 1:5 to 10:3 to 8, and the dispersion and pulping treatment time is 1 to 3 hours.

[0022] Further preferably, in step 1), the amount of dispersant MF added is 0.5-2.0% of the mass of cyanuric chloride, and the inorganic salt is high-quality sodium chloride with a content of not less than 99.5% and an amount added is 10-40% of the mass of cyanuric chloride.

[0023] In step 2) of this invention, 2,4-diaminobenzenesulfonic acid has a double amino group and is highly reactive. It readily undergoes a multi-step ammonolysis reaction with cyanuric chloride to generate byproducts, which affects the conversion effect of the main reaction and reduces the purity of the condensate. Therefore, the condensation requires an extremely low temperature and controlled dropping rate.

[0024] Preferably, in step 2), the amount of baking soda used is 0.8 to 1.2 times the mass of 2,4-diaminobenzenesulfonic acid.

[0025] Preferably, the condensation in step 3) is performed at a low temperature.

[0026] Further optimization involves controlling the reaction temperature to be between -3°C and 0°C.

[0027] Preferably, in step 3), the 2,4-diaminobenzenesulfonic acid solution is added over a period of 1.0 to 1.5 hours. The addition process is fast at first and then slow. Two-thirds of the 2,4-diaminobenzenesulfonic acid solution is added in the first half of the time, and the remaining part is added slowly in the second half of the time. The reaction continues for 1 to 2 hours.

[0028] Preferably, in step 3), cyanuric chloride is used in slight excess to reduce the probability of bicondensation reaction of 2,4-diaminobenzenesulfonic acid and reduce the residue of 2,4-diaminobenzenesulfonic acid.

[0029] After the first condensation, excess cyanuric chloride participates in subsequent unit reactions, forming various byproducts that affect the color and purity of the original pulp. Therefore, step 4) of this invention adds a hydrolysis process to solve the problem of slight excess cyanuric chloride. The endpoint of the hydrolysis reaction is detected by HPLC, requiring the purity of the main peak of the first condensate to be ≥96.5%, the residue of 2,4-diaminobenzenesulfonic acid ≤0.1%, and the residue of cyanuric chloride ≤0.05%.

[0030] In step 5) of this invention, the material is initially alkaline, requiring the addition of excess inorganic acid to provide a diazo reaction environment, while also solving the problem of excessive foaming during the acidification process.

[0031] Preferably, a phosphorus-free defoamer is added in advance in step 5). More preferably, a polyether-modified silicone defoamer is used, at a dosage of 0.001 to 0.01% of the volume of the hydrolysate.

[0032] Preferably, in step 5), the molar ratio of hydrochloric acid, sodium nitrite, and 2,4-diaminobenzenesulfonic acid is (2.5–3.5):(0.95–1.05):1; and the diazotization reaction in step 5) lasts for 2–4 hours.

[0033] Preferably, in step 6), the amount of dispersant MF added is 0.5 to 2.0% of the mass of 3,5-diaminobenzoic acid, the amount of sodium bicarbonate is 1.0 to 1.5 times the mass of 3,5-diaminobenzoic acid, and the reaction time is 3 to 5 hours.

[0034] Preferably, in step 7), the molar ratio of hydrochloric acid, sodium nitrite, and p-(β-hydroxyethyl sulfone sulfate) aniline is (1.0-1.1):(1.0-1.05):1, and the reaction time is 2-4 hours.

[0035] Preferably, the reaction time in step 8) is 4 to 6 hours.

[0036] Preferably, the molar ratio of cyanuric chloride in step 1), 2,4-diaminobenzenesulfonic acid in step 2), 3,5-diaminobenzoic acid in step 6), p-(β-hydroxyethyl sulfone sulfate) aniline in step 7) to p-(β-hydroxyethyl sulfone sulfate) aniline in step 9) is 1:(0.97~0.99):(0.94~0.98):(0.94~0.98):(0.93~0.97).

[0037] Compared with similar products, the beneficial effects of this invention are as follows:

[0038] (1) The synthesis process is simple, easy to control, has high production stability, and few quality accidents;

[0039] (2) The condensation conversion effect is good, the by-products are few, the raw materials can be fully utilized, and the dyes produced have the advantages of high yield and high purity.

[0040] (3) The dye has excellent solubility. The solubility at 50℃ can reach more than 200g / L. The printing and dyeing requirements are low, the salt dosage is small, the color is bright and the reproducibility is good.

[0041] (4) The product can also be used for black dye compounding, and has high compatibility. After dyeing, it is not easy to have color difference or color defects, the rework rate is low, and the fabric has good blackness.

[0042] (5) The raw materials are widely available and low in cost. The application performance meets the requirements of the mid-range and some high-end markets, and the cost performance is high. Detailed Implementation

[0043] Example 1:

[0044] Add 800 kg of bottom water and 1200 kg of crushed ice to a 15 cubic meter reaction vessel, then add 200 kg of cyanuric chloride, 2 kg of dispersant MF, and 50 kg of high-quality sodium chloride. Stir and beat for 2 hours to obtain the pulp.

[0045] Add 1000 kg of ice water to a 5 cubic meter dissolving pot ①, add 250 kg of baking soda, and then add 270 kg of 2,4-diaminobenzenesulfonic acid. Stir and dissolve to obtain 2,4-diaminobenzenesulfonic acid solution for later use.

[0046] Add the 2,4-diaminobenzenesulfonic acid solution from the 5 cubic meter dissolving pot ① dropwise into the slurry in the 15 cubic meter reaction pot to begin the first condensation reaction. Add about 2 / 3 of the volume in about 30-40 minutes, and add the remaining 1 / 3 in another 30-40 minutes. During the addition process, monitor the reaction pH and temperature to ensure that the pH value is between 1.0 and 1.5 and the temperature is controlled between -3 and 0℃. After the addition is complete, use baking soda to maintain the pH value at 1.0-1.5 and continue the reaction for 1.5 hours until the endpoint.

[0047] Add the prepared 20% soda ash solution dropwise to the condensate in the 15 cubic meter reaction vessel, adjust the pH value to 8.0-9.0, keep the reaction temperature for 30 minutes, and then take a sample for HPLC detection. The main peak purity is ≥96.5%, the residue of 2,4-diaminobenzenesulfonic acid is ≤0.1%, the residue of cyanuric chloride is ≤0.05%, and the hydrolysis reaches the reaction endpoint.

[0048] After the hydrolysis endpoint is reached, 100 ml of polyether-modified silicone defoamer is added to the 15 cubic meter reaction vessel, followed by 400 kg of 30% hydrochloric acid. Then, sodium nitrite solution (prepared from 72.5 kg of sodium nitrite and 170 kg of water) is added dropwise, and the temperature is controlled at 0-5℃. After the addition is complete, the reaction is carried out for 3 hours.

[0049] Add 600 kg of water to a 5-cubic-meter dissolving pot ②, then add 170 kg of baking soda and 2 kg of dispersant MF. Next, add 160 kg of 3,5-diaminobenzoic acid and stir to dissolve. After dissolving, quickly add the solution to a diazo solution. After adding the solution, maintain the pH value at 6.0-7.0 with a small amount of baking soda and control the temperature at 5-12℃. The coupling reaction is carried out for 4 hours to obtain a first coupling solution.

[0050] Add 600 kg of water and 1000 kg of ice to a 5 cubic meter diazo reactor. Then add 300 kg of dry powder of p-(β-hydroxyethyl sulfone sulfate)aniline ①, stir and slurry. Add 130 kg of 30% hydrochloric acid, stir for 5 minutes, and then add sodium nitrite solution (prepared from 70 kg of sodium nitrite and 160 kg of water) dropwise. Control the temperature at 0-5℃ and react for 3 hours after the addition is complete. After the reaction time is up, quickly add the diazo solution of p-(β-hydroxyethyl sulfone sulfate)aniline ① to the primary coupling solution, and then slowly adjust the pH with sodium bicarbonate to maintain the pH value at 4.5-5.0. Control the temperature at 5-12℃, and continue the reaction for 5 hours after the pH stabilizes.

[0051] When the reaction time is up, add 295 kg of dry powder of p-(β-hydroxyethyl sulfone sulfate) aniline ②, turn on the steam and slowly raise the temperature, keep it at 30-35℃, use baking soda to maintain the pH value at 4.5-5.5, and after reacting for 3 hours, continue to raise the temperature and keep it at 40-45℃, use 20% soda ash solution to maintain the pH value at 5.5-6.5, and continue to react for 2 hours to obtain the dye slurry.

[0052] Example 2:

[0053] The difference from Example 1 is that 2.5 kg of dispersant MF and 52 kg of high-quality sodium chloride were added before the first condensation and pulping.

[0054] Example 3:

[0055] The difference from Example 1 is that the amount of p-(β-hydroxyethyl sulfone sulfate) aniline ① is 305 kg and the amount of p-(β-hydroxyethyl sulfone sulfate) aniline ② is 300 kg.

[0056] Comparative Example 1:

[0057] The difference from Example 1 is that no high-quality sodium chloride was added before the first condensation and pulping, the first condensation temperature was 0-5°C, and 2,4-diaminobenzenesulfonic acid solution was uniformly added dropwise to the pulping solution over a period of 1.5 hours.

[0058] Comparative Example 2:

[0059] The sample was synthesized according to Example 24 of the specific embodiments described in the Chinese Patent Specification No. 2007100127464.

[0060] Comparative Example 3:

[0061] The sample was synthesized according to Example 1 of the specific embodiments described in the Chinese Patent Specification No. 2017113757954.

[0062] The dye products prepared in Examples 1-3 were compared with the samples of Comparative Examples 1-3. Table 1 shows the solubility, fixation rate, purity, and some colorimetric data of the dyes. The colorimetric data were obtained by testing other samples at the same concentration with Example 1 as the standard sample. Table 2 shows the rubbing fastness, washing fastness, compatibility with CI Reactive Black 5, and the dyeing blackness test results after compounding with CI Reactive Black 5 and CI Reactive Red 111 in the optimal ratio for the examples and comparative examples. The compatibility was comprehensively evaluated by measuring the difference in SERF values ​​of the dyes and combining it with the percolation method, and graded as good (<15%), average (15%-30%), and poor (>30%).

[0063] Table 1. Performance tests of some dye products prepared in Examples 1-3 and samples from Comparative Examples 1-3.

[0064]

[0065] Table 2. Performance tests of the dye products prepared in Examples 1-3 and samples from Comparative Examples 1-3.

[0066]

[0067] As shown in Table 1, the orange dye obtained by this invention exhibits excellent solubility, high purity, good fixation rate, and vibrant color. Comparative Example 1, produced using a relatively traditional condensation reaction method, resulted in dyes with lower purity and a negative impact on color. While Comparative Example 2 showed relatively high solubility, it still lagged behind the product of this invention, exhibiting lower purity and less vibrant color. Comparative Example 3, although vibrant in color, had only moderate solubility, limiting its application. As shown in Table 2, the orange dye obtained by this invention possesses good fastness and stable quality. It exhibits good compatibility and high blackness when used in black dye blends. Although Comparative Example 3 showed excellent fastness, its structure is that of a single triazine reactive dye, which differs significantly from vinyl sulfone sulfate-type black dyes, resulting in poor compatibility and moderate blackness.

Claims

1. A method for preparing a tri-reactive orange dye, characterized in that, Includes the following steps: 1) Add ice and water to cyanuric chloride, add dispersant MF and inorganic salt, stir and slurry to obtain slurry; 2) Add baking soda to ice water, then add 2,4-diaminobenzenesulfonic acid, stir until dissolved, and obtain 2,4-diaminobenzenesulfonic acid solution; 3) The 2,4-diaminobenzenesulfonic acid solution obtained in step 2) is added dropwise to the pulp obtained in step 1) to carry out a condensation reaction. The pH value is adjusted to 1.0 to 1.5, the reaction temperature is -3 to 0℃, and a condensed solution is obtained after the reaction is complete. 4) Add sodium carbonate solution dropwise to the first condensate, adjust the pH value to 8.0-9.0, and keep the reaction temperature at 0-5℃ to obtain a condensate hydrolysate from the hydrolysis reaction; 5) Add a phosphorus-free defoamer and hydrochloric acid to a hydrolysate in sequence, and then add sodium nitrite solution dropwise. The reaction temperature is 0-5℃. The diazotization reaction yields a diazotized solution. 6) Add baking soda and dispersant MF to the bottom water, then add 3,5-diaminobenzoic acid, stir until dissolved, and then add to a diazo solution. After the addition is complete, continue to use baking soda to maintain the pH value at 6.0-7.

0. The reaction temperature is 5-12℃. The coupling reaction yields a primary coupling solution. 7) Add ice and water to p-(β-hydroxyethyl sulfone sulfate) aniline, stir and slurry, add hydrochloric acid after slurrying, add sodium nitrite solution dropwise, and diazotize at 0-5℃ to obtain p-(β-hydroxyethyl sulfone sulfate) aniline diazo solution. 8) Add p-(β-hydroxyethyl sulfone sulfate) aniline diazo solution to the primary coupling solution, then adjust the pH value to 4.5-5.0 with sodium bicarbonate, and the reaction temperature is 5-12℃ to obtain the secondary coupling solution. 9) Add p-(β-hydroxyethyl sulfone sulfate) aniline dry powder to the secondary coupling solution again, raise the temperature and keep it at 30-35℃, use sodium bicarbonate to maintain the pH value at 4.5-5.5 for the reaction, then continue to raise the temperature and keep it at 40-45℃, use soda ash solution to maintain the pH value at 5.5-6.5 for the reaction, and obtain the dye slurry.

2. The method for preparing the tri-reactive orange dye according to claim 1, characterized in that, In step 1), the amount of dispersant MF added is 0.5-2.0% of the mass of cyanuric chloride, and the amount of inorganic salt, sodium chloride, is 10-40% of the mass of cyanuric chloride.

3. The method for preparing the tri-reactive orange dye according to claim 1, characterized in that, In step 2), the amount of baking soda used is 0.8 to 1.2 times the mass of 2,4-diaminobenzenesulfonic acid.

4. The method for preparing the tri-reactive orange dye according to claim 1, characterized in that, In step 3), the 2,4-diaminobenzenesulfonic acid solution is added over a period of 1.0 to 1.5 hours. The addition process is fast at first and then slow: 2 / 3 of the 2,4-diaminobenzenesulfonic acid solution is added in the first half of the time, and the remaining part is added in the second half of the time; then the reaction continues for 1 to 2 hours.

5. The method for preparing the tri-reactive orange dye according to claim 1, characterized in that, In step 5), the phosphorus-free defoamer is a polyether-modified organosilicon defoamer, and the dosage is 0.001 to 0.01% of the volume of the hydrolysate.

6. The method for preparing the tri-reactive orange dye according to claim 1, characterized in that, In step 5), the molar ratio of hydrochloric acid, sodium nitrite, and 2,4-diaminobenzenesulfonic acid is (2.5–3.5):(0.95–1.05):1; the diazotization reaction in step 5) lasts for 2–4 hours.

7. The method for preparing the tri-reactive orange dye according to claim 1, characterized in that, In step 6), the amount of dispersant MF added is 0.5 to 2.0% of the mass of 3,5-diaminobenzoic acid, the amount of sodium bicarbonate is 1.0 to 1.5 times the mass of 3,5-diaminobenzoic acid, and the reaction time is 3 to 5 hours.

8. The method for preparing the tri-reactive orange dye according to claim 1, characterized in that, In step 7), the molar ratio of hydrochloric acid, sodium nitrite, and p-(β-hydroxyethyl sulfone sulfate) aniline is (1.0–1.1):(1.0–1.05):1, and the reaction time is 2–4 hours.

9. The method for preparing the tri-reactive orange dye according to claim 1, characterized in that, The reaction time in step 8) is 4 to 6 hours.

10. The method for preparing the tri-reactive orange dye according to any one of claims 1-9, characterized in that, The molar ratio of cyanuric chloride in step 1), 2,4-diaminobenzenesulfonic acid in step 2), 3,5-diaminobenzoic acid in step 6), p-(β-hydroxyethyl sulfone sulfate) aniline in step 7) to p-(β-hydroxyethyl sulfone sulfate) aniline in step 9) is 1:(0.97~0.99):(0.94~0.98):(0.94~0.98):(0.93~0.97).

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