Preparation method of three-active-group orange dye

Abstract

The invention provides a preparation method of a three-active-group orange dye, which comprises the following steps: carrying out primary condensation on cyanuric chloride and 2, 4-diaminobenzene sulfonic acid, hydrolyzing, diazotizing, carrying out primary coupling with 3, 5-diaminobenzoic acid, carrying out secondary coupling with p-(beta-hydroxyethyl sulfone sulfate) aniline diazonium salt, carrying out secondary condensation with p-(beta-hydroxyethyl sulfone sulfate) aniline, and carrying out secondary coupling with 3, 5-diaminobenzoic acid to obtain the three-active-group orange dye. The dye prepared in the invention has the advantages of good solubility, bright color, high blackness, good compatibility, low raw material cost, good economical efficiency and high cost performance, can be used as a single-color dye, can also be used for black dye compounding, and has the advantages of good fixation rate and color fastness.

Description

Technical Field

[0001] The invention belongs to the field of reactive dye synthesis, and in particular relates to a method for preparing a dye with three reactive groups. Background Art

[0002] The orange reactive dye prepared with 3,5-diaminobenzoic acid as the parent core raw material has good compatibility with most KN type and some M type and KM type reactive dyes after introducing the chain fatty reactive group containing sulfuric acid. At the same time, it has good absorption effect in the wavelength range of 400-500nm, so it is often used in the compounding and toning of black dyes. For example, the invention patent CN101117449A discloses a high-concentration composite reactive dye, which involves the preparation technology of orange dye synthesized with 3,5-diaminobenzoic acid as raw material. The synthesized orange dye is mainly used as a filling color. After compounding with the prepared black (navy blue, dark blue) dye, it can maintain good blackness, and solves the problem of low fixation rate and poor fastness of black dye. The orange dye provided in the patent does not account for a high proportion in the composite black dye, generally not exceeding 30%, and plays the role of filling and complementary color of black dye compounding. It mainly solves the problem of insufficient blackness of black dyes in the market through compatibility and complementarity, but as an orange dye, the color is not bright enough, and there are certain restrictions on the use of single color.

[0003] Invention patent CN 108102419A discloses an orange reactive dye suitable for digital inkjet printing. The orange dye synthesized with 3,5-diaminobenzoic acid as raw material in the patent is used as a monochrome dye with 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 monochrome printing. There is little choice when used for multi-color compounding. Forced use requires the addition of a large amount of additives, and the cost of use is relatively high.

[0004] Invention patent CN 117777754A provides a high-fastness orange reactive dye and a preparation method thereof, which improves the problem of poor fixation effect and dyeing performance of reactive dyes. The fixation rate can reach 86% and the fastness is excellent. However, the dye has a complex structure, a large molecular weight, and a difficult synthesis process. The price of some raw materials is high, and the required amount of feed is large under the same strength. The production cost is high, resulting in a high price. From a market perspective, the cost performance is low and the audience is small.

[0005] In recent years, people's pursuit of quality of life has also changed. The consumption downgrade of some residents has also changed their consumption habits from high-quality demand to high cost-effectiveness. As part of home life, people tend to make a balanced choice between the color saturation, functionality, comfort and corresponding price of various fabrics in the process of textile consumption. Dyeing and printing are necessary components of fabric processing and production, and their cost indirectly determines the price of terminal home textiles. Therefore, the development of cost-effective dyes is essential. Summary of the invention

[0006] The object of the present invention is to provide a method for preparing a dye with three active groups, the raw materials are easily available and the cost is low, the process is simple, the prepared product has high purity, bright color, good solubility, excellent color fixation rate and fastness, can be used for both single color and compound, has high cost performance and good reproducibility.

[0007] A method for preparing a three-active-group orange dye comprises the following steps:

[0008] 1) adding ice and water to cyanuric chloride, adding dispersant MF and inorganic salt, stirring and beating to obtain a beating material;

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

[0010] 3) adding the 2,4-diaminobenzenesulfonic acid solution obtained in step 2) dropwise to the pulp obtained in step 1) to carry out a condensation reaction, adjusting the pH value to 1.0 to 1.5 and the reaction temperature to -3 to 0°C, and obtaining a condensate after the reaction is complete;

[0011] 4) adding pure alkali solution to the first shrinkage solution, adjusting the pH value to 8.0-9.0, the reaction temperature to 0-5°C, and performing a hydrolysis reaction to obtain a shrinkage solution;

[0012] 5) Add a phosphorus-free defoamer and hydrochloric acid to the hydrolyzed solution in sequence, and then dropwise add a sodium nitrite solution, the reaction temperature is 0-5°C, and a diazotization reaction is performed to obtain a diazo solution;

[0013] 6) Add baking soda and dispersant MF to the bottom water, then add 3,5-diaminobenzoic acid, stir to dissolve and add to the diazo solution, continue to use baking soda to maintain the pH value at 6.0-7.0, the reaction temperature is 5-12°C, and the coupling reaction is carried out to obtain a coupling solution;

[0014] 7) adding ice and water to p-(β-hydroxyethyl sulfone sulfate)aniline, stirring and beating, adding hydrochloric acid after beating, adding sodium nitrite solution dropwise, and performing diazotization reaction to obtain p-(β-hydroxyethyl sulfone sulfate)aniline diazo liquid;

[0015] 8) adding p-(β-hydroxyethyl sulfone sulfate) aniline diazo solution to the primary coupling solution, and then adjusting the pH value to 4.5-5.0 with baking soda, the reaction temperature to 5-12° C., and performing coupling reaction to obtain a secondary coupling solution;

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

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

[0018]

[0019] The dye provided by the present invention has three active groups, which ensure that the printed and dyed fabric has good fastness, and one of the groups is an s-triazine group, which can effectively inhibit the hydrolysis of the dye in the high-temperature dyeing process, and solve the problem of decreased color fixation rate of some fabrics after dyeing. In addition, because the other two groups are of the bisvinyl sulfone sulfate type, it has good adaptability with black dyes such as CI Reactive Black 5, and has high coloring efficiency. When alkali is added after the dye is colored, the color can be fixed synchronously, so that the dyeing stability is good and the color fixation rate is high.

[0020] In step 1), a beating process is added to improve the fineness of cyanuric chloride through the friction and collision between the crushed ice and the material, and 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 1:5-10:3-8, and the dispersion and pulping treatment time is 1-3 hours.

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

[0023] In step 2) of the present invention, 2,4-diaminobenzenesulfonic acid has a diamino group and is highly active. It is easy to undergo a multi-step aminolysis reaction with cyanuric chloride to generate by-products, which affects the conversion effect of the main reaction and reduces the purity of the condensed product. Therefore, a very low temperature is required for the primary condensation and the dripping speed is controlled.

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

[0025] Preferably, the primary condensation in step 3) is carried out at low temperature.

[0026] More preferably, the reaction temperature is controlled at -3 to 0°C.

[0027] Preferably, in step 3), the dripping time of the 2,4-diaminobenzenesulfonic acid solution is controlled to be 1.0 to 1.5 hours, and the dripping process is fast at first and then slow, with 2 / 3 of the 2,4-diaminobenzenesulfonic acid solution dripped in the first half of the time and the remaining part slowly dripped in the second half of the time, and then the reaction is continued for 1 to 2 hours.

[0028] Preferably, in step 3), cyanuric chloride is slightly excessive to reduce the probability of the 2,4-diaminobenzenesulfonic acid shrinkage reaction and reduce the residual 2,4-diaminobenzenesulfonic acid.

[0029] After the first condensation is completed, the excess cyanuric chloride will participate in the subsequent unit reaction to form various by-products, affecting the color and purity of the original pulp. Therefore, the hydrolysis process is added in step 4) of the present invention to solve the problem of slight excess of cyanuric chloride. The end point of the hydrolysis reaction is detected by HPLC, requiring the main peak purity of the first condensation product to be ≥96.5%, the residual 2,4-diaminobenzenesulfonic acid to be ≤0.1%, and the residual cyanuric chloride to be ≤0.05%.

[0030] In step 5) of the present invention, the material is initially alkaline, and an excess of inorganic acid needs to be added to provide a diazo reaction environment and solve the problem of heavy foam 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 in an amount of 0.001 to 0.01% of the volume of the hydrolyzed solution.

[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) is performed for 2-4 hours.

[0033] Preferably, in step 6), the dosage of dispersant MF is 0.5-2.0% of the mass of 3,5-diaminobenzoic acid, the dosage of baking soda is 1.0-1.5 times of the mass of 3,5-diaminobenzoic acid, and the reaction time is 3-5 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) and 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 invention has the following beneficial effects:

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

[0039] (2) The condensation conversion effect is good, the by-product is small, 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, with a solubility of more than 200 g / L at 50°C. It has low requirements for printing and dyeing, requires less salt, and has bright colors and good reproducibility after coloring.

[0041] (4) The product can also be used for compounding black dyes with 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 of low cost. The application performance meets the requirements of the mid-end and some high-end markets, and the cost performance is high. DETAILED DESCRIPTION

[0043] Embodiment 1:

[0044] Add 800 kg of bottom water and 1200 kg of crushed ice into a 15-cubic-meter reaction pot, 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 a beating liquid.

[0045] Add 1000 kg of ice water to the 5-cubic-meter dissolving pot①, put in 250 kg of baking soda, and then add 270 kg of 2,4-diaminobenzenesulfonic acid and stir to dissolve, to obtain 2,4-diaminobenzenesulfonic acid solution for use.

[0046] Add the 2,4-diaminobenzenesulfonic acid solution in the 5-cubic-meter dissolving pot① to the pulping liquid in the 15-cubic-meter reaction pot to start a condensation reaction. It takes about 30 to 40 minutes to drip 2 / 3 of the volume, and another 30 to 40 minutes to drip the remaining 1 / 3. Pay attention to the reaction pH and reaction temperature during the dripping process to ensure that the pH value is between 1.0 and 1.5, and control the temperature at -3 to 0℃. After dripping, use baking soda to maintain the pH value at 1.0 to 1.5, and continue the reaction for 1.5 hours to the end point.

[0047] Add the prepared 20% pure alkali solution to the 15-cubic-meter reaction pot, adjust the pH value to 8.0-9.0, keep warm for 30 minutes, and then take samples for HPLC detection. The main peak purity is ≥96.5%, the residual 2,4-diaminobenzenesulfonic acid is ≤0.1%, the residual cyanuric chloride is ≤0.05%, and the hydrolysis reaches the reaction end point.

[0048] After the hydrolysis end point is reached, first add 100 ml of polyether modified silicone defoamer to the 15-cubic-meter reaction pot, then slowly add 400 kg of 30% hydrochloric acid, and then drop sodium nitrite solution (prepared with 72.5 kg of sodium nitrite and 170 kg of water), control the temperature at 0-5°C, and react for 3 hours after the addition is completed.

[0049] Add 600 kg of bottom water to the 5-cubic-meter dissolving pot ②, add 170 kg of baking soda and 2 kg of dispersant MF, then add 160 kg of 3,5-diaminobenzoic acid and stir to dissolve. After dissolution, quickly add it to the diazo solution. After adding, use a small amount of baking soda to maintain the pH value at 6.0-7.0. Control the temperature at 5-12°C and carry out coupling reaction for 4 hours to obtain a primary coupling liquid.

[0050] Add 600kg of bottom water and 1000kg of ice to a 5-cubic-meter diazo reactor, add 300kg of p-(β-hydroxyethyl sulfone sulfate) aniline① dry powder, stir and slurry, add 130kg of 30% hydrochloric acid, stir for 5 minutes, then drop sodium nitrite solution (prepared from 70kg of sodium nitrite and 160kg of water), control the temperature at 0-5℃, and react for 3h. After the reaction time is up, quickly add p-(β-hydroxyethyl sulfone sulfate) aniline① diazo solution to the primary coupling solution, then slowly adjust the pH with baking soda to maintain the pH value at 4.5-5.0, control the temperature at 5-12℃, and continue the reaction for 5h after the pH stabilizes.

[0051] When the reaction time is up, add 295 kg of p-(β-hydroxyethyl sulfone sulfate) aniline② dry powder, turn on the steam and slowly raise the temperature, keep it at 30-35°C, use baking soda to maintain the pH value at 4.5-5.5, react for 3 hours and continue to raise the temperature, keep it at 40-45°C, use 20% pure alkali solution to maintain the pH value at 5.5-6.5, and continue the reaction for 2 hours to obtain the dye stock.

[0052] Embodiment 2:

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

[0054] Embodiment 3:

[0055] Different from Example 1, p-(β-hydroxyethyl sulfone sulfate) aniline ① consumption is 305kg, p-(β-hydroxyethyl sulfone sulfate) aniline ② consumption is 300kg.

[0056] Comparative Example 1:

[0057] The difference from Example 1 is that no high-quality sodium chloride is added before the primary condensation pulping, the primary condensation temperature is 0-5°C, and the 2,4-diaminobenzenesulfonic acid solution is evenly added dropwise to the pulping liquid for 1.5 hours.

[0058] Comparative Example 2:

[0059] The sample was synthesized according to Example 24 of the specific implementation method in the Chinese patent specification of application No. 2007100127464.

[0060] Comparative Example 3:

[0061] The sample was synthesized according to Example 1 of the specific implementation method in the Chinese patent specification of application number 2017113757954.

[0062] The dye products prepared in Examples 1-3 were compared with the samples in Comparative Examples 1 to 3. Table 1 shows the solubility, fixation rate, purity and some colorimetric data of the dyes, wherein the colorimetric data are obtained by testing other samples at the same concentration using Example 1 as the standard sample; Table 2 shows the rubbing fastness, washing fastness, compatibility with CI Reactive Black 5, and the test results of the dyeing blackness after compounding with CI Reactive Black 5 and CI Reactive Red 111 at the optimal ratio of the examples and comparative examples, wherein the compatibility is determined by measuring the SERF difference of the dye and combining it with the infiltration ring method for comprehensive evaluation, and is classified into good (<15%), general (15% to 30%), and poor (>30%).

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

[0064]

[0065] Table 2 Another part of the performance test of the dye products prepared in Examples 1-3 and the samples of Comparative Examples 1 to 3

[0066]

[0067] It can be seen from Table 1 that the orange dye obtained by the present invention has excellent solubility, high purity, good color fixation rate, and bright color. Comparative Example 1 adopts a more traditional condensation reaction, and the purity of the obtained dye is low, and it has a certain negative impact on the color. Although the sample of Comparative Example 2 has a relatively high solubility, it is still different from the product of the present invention, and the purity is not high compared with the product of the present invention, and the color is not bright enough. Although the sample of Comparative Example 3 has bright color, it has general solubility and has certain limitations in application. It can be seen from Table 2 that the orange dye obtained by the present invention has good fastness and stable quality. It has good compatibility and high blackness after being compounded with black dyes. Although the sample of Comparative Example 3 has excellent fastness, it is a single triazine reactive dye in structure, which is very different in compatibility with vinyl sulfone sulfate type black dyes, and thus has poor compatibility and general blackness.

Claims

1. A method for preparing a three-active group orange dye, characterized in that: The steps include: 1) adding ice and water to cyanuric chloride, adding dispersant MF and inorganic salt, stirring and beating to obtain a beating material; 2) Add baking soda to ice water, then add 2,4-diaminobenzenesulfonic acid, stir to dissolve, and obtain 2,4-diaminobenzenesulfonic acid solution; 3) adding the 2,4-diaminobenzenesulfonic acid solution obtained in step 2) dropwise to the pulp obtained in step 1) to carry out a condensation reaction, adjusting the pH value to 1.0 to 1.5 and the reaction temperature to -3 to 0°C, and obtaining a condensate after the reaction is complete; 4) adding pure alkali solution to the first shrinkage solution, adjusting the pH value to 8.0-9.0, the reaction temperature to 0-5°C, and performing a hydrolysis reaction to obtain a shrinkage solution; 5) Add a phosphorus-free defoamer and hydrochloric acid to the hydrolyzed solution in sequence, and then dropwise add a sodium nitrite solution, the reaction temperature is 0-5°C, and a diazotization reaction is performed to obtain a diazo solution; 6) Add baking soda and dispersant MF to the bottom water, then add 3,5-diaminobenzoic acid, stir to dissolve and add to the diazo solution, continue to use baking soda to maintain the pH value at 6.0-7.0, the reaction temperature is 5-12°C, and the coupling reaction is carried out to obtain a coupling solution; 7) adding ice and water to p-(β-hydroxyethyl sulfone sulfate)aniline, stirring and slurrying, adding hydrochloric acid after slurrying, adding sodium nitrite solution dropwise, the reaction temperature is 0-5°C, and diazotization reaction is performed to obtain p-(β-hydroxyethyl sulfone sulfate)aniline diazo liquid; 8) adding p-(β-hydroxyethyl sulfone sulfate) aniline diazo solution to the primary coupling solution, and then adjusting the pH value to 4.5-5.0 with baking soda, the reaction temperature to 5-12° C., and performing coupling reaction to obtain a secondary coupling solution; 9) Add p-(β-hydroxyethyl sulfone sulfate) aniline powder to the secondary coupling solution again, raise the temperature, keep it at 30-35°C, use baking soda to maintain the pH value at 4.5-5.5 for reaction, then continue to raise the temperature, keep it at 40-45°C, use pure alkali solution to maintain the pH value at 5.5-6.5 for reaction, and obtain the dye stock paste.

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

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

4. The preparation method of the three-reactive-group orange dye according to claim 1, characterized in that: In step 3), the dripping time of the 2,4-diaminobenzenesulfonic acid solution is controlled to be 1.0 to 1.5 hours, and the dripping process is fast at first and then slow: 2 / 3 of the 2,4-diaminobenzenesulfonic acid solution is dripped in the first half of the time, and the remaining part is dripped in the second half of the time; and then the reaction is continued for 1 to 2 hours.

5. The method for preparing a three-reactive-group orange dye according to claim 1, characterized in that: In the step 5), the phosphorus-free defoaming agent is a polyether-modified organic silicon defoaming agent, and the amount used is 0.001-0.01% of the volume of the hydrolyzed solution.

6. The method for preparing a three-reactive-group orange dye according to claim 1, characterized in that: In the 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 the step 5) takes 2-4 hours.

7. The method for preparing a three-reactive-group orange dye according to claim 1, characterized in that: In the step 6), the dosage of the dispersant MF is 0.5-2.0% of the mass of 3,5-diaminobenzoic acid, the dosage of baking soda is 1.0-1.5 times of the mass of 3,5-diaminobenzoic acid, and the reaction time is 3-5 hours.

8. The method for preparing a three-reactive-group orange dye according to claim 1, characterized in that: In the 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 a three-reactive-group 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 three-reactive-group orange dye according to any one of claims 1 to 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) and 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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