CN116496636A - A kind of synthetic technology of acid yellow - Google Patents

Abstract

The invention discloses a synthesis process of acid yellow, which comprises the following steps: s1: diazo reaction: dissolving 2.5-dichloroaniline in hydrochloric acid at a certain ratio, adding emulsifier, adding sodium nitrite solution, and detecting potassium iodide (oxidizing I ₂ ) When congo red is blue, sodium nitrite is eliminated by sulfamic acid to obtain diazonium solution; s2: the coupling component is dissolved: mixing 2-dibutylamino-4- (4' -sulfonic acid) phenethylamino-6-methylpyrimidine, an organic solvent and water, regulating pH to 10-11.5 with liquid alkali, stirring until the mixture is fully dissolved, and adding sodium carbonate and ice for later use; s3: adding diazonium solution into the solution for coupling reaction, adjusting pH to 6-6.5 with hydrochloric acid after the reaction is completed, heating up to evaporate butanone, adding salt, stirring at high temperature for 20-40 min, and suction filtering to obtain acid yellow. The invention aims to improve dyeing performance of the dye, improve dyeing fastness, ensure more complete raw material reaction, realize high yield and reduce raw material consumption.

Description

A kind of synthetic technology of acid yellow

technical field

The invention belongs to the field of manufacturing chemical dyes, and in particular relates to a synthesis process of acid yellow.

technical background

Acid yellow is a dye widely used in the printing and dyeing industry and in the field of pigment coloring. It is a new type of heterocyclic azo disperse dye, which can be dissolved in methanol, dichloromethane, etc., and dibutylamine group is introduced into the coupling component to make it have bright color, large absorption coefficient, high temperature dispersion stability and resistance Good alkalinity, superior fastness and strength properties, etc. Mainly used for dyeing and printing of polyester and its blended fabrics.

At present, there are the following methods for preparing Acid Yellow, the patent application number is 202010993593.1, which discloses a C.I. Acid Yellow 23 dye and its clean production process, using 2-acetyl-succinic acid dimethyl ester and p- The diazonium salt of aminobenzenesulfonic acid is coupled, the ring is closed, and then coupled with the diazonium salt of p-aminobenzenesulfonic acid, hydrolyzed, salted out with a mixed salt, and the mixed salt is separated and recovered to obtain C.I. Acid Yellow 23 dye. The patent application number is 201610210566.6. The benzidine compound and the acidic reagent are passed into the reactor, stirred and mixed; the nitrite is added to the reactor and stirred to react to obtain the diazonium salt; the base containing 5-pyrazolone is prepared and add it into the reactor to react with the diazonium salt to obtain the azo intermediate Ⅰ; prepare an alkaline solution of the same concentration of 5-pyrazolone and add it to the reactor to react with the azo intermediate Ⅰ to obtain the azo intermediate Body II; acid yellow N-R powder was obtained after salting out, filtering and drying.

As the application of acid yellow products is continuously developed and excavated, it has a good development prospect. Therefore, it is urgent to develop a clean production process with low energy consumption, simple operation, safety and environmental protection.

Contents of the invention

Aiming at the deficiencies of the prior art, the purpose of the present invention is to improve the dyeing performance, improve the color fastness, and the prepared product can meet the application requirements without purification, greatly reduce the production cost, and is suitable for the needs of large-scale clean production .

Technical scheme of the present invention is summarized as follows:

A preparation method of acid yellow, comprising the following steps:

S1: Diazo reaction: Dissolve 2,5-dichloroaniline in hydrochloric acid, keep warm at 40-70°C for 1.5-4.5 hours, add emulsifier to cool down to 25-30°C, add ice to cool down within 8-12 minutes After about 0-5°C, add sodium nitrite and 2-3 drops of potassium iodide and Congo red solution, after slowly heating up, use ice to control the temperature at 15-20°C for 40-80 minutes, when potassium iodide and Congo red both appear blue When the color changes, the diazonium salt is obtained, continue to add 1 to 2 mol of ice, and then use sulfamic acid to eliminate the remaining sodium nitrite to obtain the diazonium solution;

S2: Coupling component dissolution: mix 2-dibutylamino-4-(4'-sulfonic acid) phenethylamino-6-methylpyrimidine, organic solvent and water, and adjust pH=10～11.5 with liquid caustic Finally, stir until it is completely dissolved, then add soda ash and ice for later use;

S3: Coupling reaction: add diazonium solution to the solution obtained in S2 for coupling reaction, add 2 to 3 drops of resorcinol dropwise and stir for 20 to 55 minutes. When it drops to 8.5-9, stop adding ice and stir for 5 minutes, then continue to adjust the pH to 10-10.5 with liquid caustic soda, and continue the coupling, in which the temperature is kept at 3-10°C for 1-3 hours, and then the temperature is raised to 15-45°C to continue Keep warm for 0.5-1.5 hours until the coupling is completed; after reaching the end point, use hydrochloric acid to slowly adjust the pH to 6-6.5, after adjustment, heat up to 95-100°C to steam butanone, after steaming, cool down slightly to 90-95°C, add salt and stir at high temperature for 20 After ~40 minutes, a granular product was obtained, and acid yellow was obtained after suction filtration after cooling down.

Preferably, the amount ratio of 2,5-dichloroaniline, hydrochloric acid, sodium nitrite, sulfamic acid and emulsifier in the step S1 is (0.04-0.06) mol:(0.1-0.2) mol:(0.05- 0.07) mol: (0.002-0.005) mol: (1-3) g.

Preferably, the ratio of 2,5-dichloroaniline to hydrochloric acid in the step S1 is 1:3.3.

Preferably, the emulsifier is T-80 or fatty acid methyl ester ethoxylate.

Preferably, the amount ratio of 2-dibutylamino-4-(4'-sulfonic acid) phenethylamino-6-methylpyrimidine, butanone, liquid caustic soda and soda ash in the step S2 is (0.04 -0.06) mol: (1.5-2.5 mol): (0.01-0.03) mol: (3-5) g.

Preferably, the organic solvent in the step S2 is butanone or acetone.

Preferably, the amount of organic solvent used in the step S2 is 0.5-1.5 mol.

Preferably, the salt in step S3 includes one or more of sodium chloride, potassium chloride, and sodium sulfate.

Preferably, the salt is used in an amount of 6-12% by volume.

Preferably, the temperature of the cooling suction filtration in the step S3 is 25-30°C.

Preferably, the end point of the reaction in step S3 is reached when the junction of resorcinol and the wet circle of the material does not show yellow.

Beneficial effects of the present invention:

In the present invention, use 2.5-dichloroaniline to carry out diazo reaction to prepare diazonium salt, and carry out coupling reaction with 2-dibutylamino-4-(4'-sulfonic acid) phenethylamino-6-methylpyrimidine. Advantages The acid yellow dye produced is resistant to sunlight, sublimation and friction, and has good covering properties; the reaction of raw materials is more complete, the yield is high, the consumption of raw materials is reduced, the production cost is saved, and the conventional coupling yield is not high, resulting in low purity. The problem is that the product can meet the application requirements without purification, which greatly reduces the production cost, and provides a new preparation method for the synthesis of the azo dye.

Description of drawings

Fig. 1 is the preparation method flowchart of acid yellow of the present invention;

Detailed ways

The present invention will be further described in detail below in conjunction with the embodiments, so that those skilled in the art can implement it with reference to the description.

The preparation method of the acid yellow of this embodiment may further comprise the steps:

S1: Diazo reaction: Dissolve 2,5-dichloroaniline in hydrochloric acid, keep warm at 40-70°C for 1.5-4.5 hours, add emulsifier to cool down to 25-30°C, add ice to cool down within 8-12 minutes After about 0-5°C, add sodium nitrite and 2-3 drops of potassium iodide and Congo red solution, after slowly heating up, use ice to control the temperature at 15-20°C for 60 minutes, when potassium iodide and Congo red are both blue , to obtain diazonium salt, continue to add 1 to 2 mol of ice, and then use sulfamic acid to eliminate the remaining sodium nitrite to obtain diazonium solution. The consumption ratio of described 2,5-dichloroaniline, hydrochloric acid, sodium nitrite, sulfamic acid, emulsifier is (0.04-0.06) mol: (0.1-0.2) mol: (0.05-0.07) mol: (0.002- 0.005) mol: (1-3) g.

S2: Coupling component dissolution: mix 2-dibutylamino-4-(4'-sulfonic acid) phenethylamino-6-methylpyrimidine, organic solvent and water, and adjust pH=10～11.5 with liquid caustic Afterwards, stir until completely dissolved, then add soda ash and ice for later use; The dosage ratio is (0.04-0.06) mol:(1.5-2.5 mol):(0.01-0.03) mol:(3-5) g; the organic solvent is 0.5-1.5 mol of butanone or acetone.

S3: Coupling reaction: Add diazonium solution to the solution obtained in S2 for coupling reaction, add 2 to 3 drops of resorcinol dropwise and stir for 20 to 55 minutes. When it drops to 8.5-9, stop adding ice and stir for 5 minutes, then continue to adjust the pH to 10-10.5 with liquid caustic soda, and continue the coupling, in which the temperature is kept at 3-10°C for 1-3 hours, and then the temperature is raised to 15-45°C to continue Keep warm for 0.5-1.5 hours until the coupling is completed; after reaching the end point, use hydrochloric acid to slowly adjust the pH to 6-6.5, after adjustment, heat up to 95-100°C to steam methyl ethyl ketone, cool down to 90-95°C after steaming, add 6-12% The volume of salt was stirred at high temperature for 20 to 40 minutes to obtain a granular product, which was cooled and filtered to obtain acid yellow. The salt includes one or more of sodium chloride, potassium chloride, and sodium sulfate.

Example 1

The preparation method of the acid yellow of a kind of embodiment, comprises the following steps:

S1: Diazo reaction: mix 20g of hydrochloric acid, 8.1g of 2.5-dichloroaniline, and 50g of water, heat it up to 50°C and keep it warm for 2 hours until there is no flaky raw material, then add 2g of T-80 and drop it to 25~ 30°C, add 30g of ice within 8-12 minutes to cool down to about 0-5°C, add 3.7g of sodium nitrite, 10g of water and 2-3 drops of potassium iodide and Congo red solution, after slowly heating up, use ice to control the temperature at Incubate at 15-20°C for 60 minutes. When both potassium iodide and Congo red appear blue, a diazonium salt is obtained. After adding 20 g of ice, use 0.4 g of sulfamic acid to eliminate the remaining sodium nitrite to obtain a diazonium solution;

S2: Coupling component dissolution: mix 21g of 2-dibutylamino-4-(4'-sulfonic acid)phenethylamino-6-methylpyrimidine, 70g of methyl ethyl ketone and 30g of water, and mix with 9g of liquid caustic soda Adjust the pH to 10-11.5 and stir until completely dissolved, then add 4g of soda ash and 90g of ice for later use;

S3: Coupling reaction: add the diazo solution obtained in S1 to the solution obtained in S2 for coupling reaction, add 2 to 3 drops of resorcinol dropwise and stir for 40 minutes, use ice to control the temperature at 5 to 8°C in the middle and later stages, when the pH value When the temperature drops to 8.5-9, stop adding ice and stir for 5 minutes, continue to adjust the pH to 10-10.5 with liquid caustic soda for coupling, and keep warm at 5-8°C for 2 hours, then raise the temperature to 25-30°C and continue to keep warm for 1 hour until Coupling is completed; when the junction of resorcinol and the wet circle of the material does not show yellow, reach the end of the reaction, slowly adjust the pH to 6-6.5 with hydrochloric acid, after adjustment, heat up to 95-100°C to steam methyl ethyl ketone, and cool down slightly after steaming To 90-95°C, add 35g of sodium chloride and stir at high temperature for 30 minutes, if there is a crystal form, cool down to 25-30°C, if there is no crystal form, continue to add 8g of sodium chloride to obtain a granular product, cool down to 25-30°C and pump After filtration, 30.02 g of yellow crystals were obtained, with a yield of 98.1%, and a liquid chromatography content of 98.31%, which met the application requirements without purification.

Example 2

S1: Diazo reaction: Mix 21g of hydrochloric acid, 6.5g of 2.5-dichloroaniline, and 50g of water, heat up to 40°C and keep it warm for 1 hour until there are no flaky raw materials, then add 1.5g of T-80 and drop to 25 ~30°C, add 30g of ice within 8~12 minutes to cool down to about 0~5°C, add 2.9g of sodium nitrite, 10g of water and 2~3 drops of potassium iodide and Congo red solution, after slowly heating up, use ice to control the temperature Incubate at 15-20°C for 60 minutes. When both potassium iodide and Congo red are blue, the diazonium salt is obtained. After adding 20 g of ice, use 0.4 g of sulfamic acid to eliminate the remaining sodium nitrite to obtain the diazonium solution;

S2: Dissolution of coupling components: 17g of 2-dibutylamino-4-(4'-sulfonic acid)phenethylamino-6-methylpyrimidine, 65g of butanone and 30g of water were mixed, and mixed with 7.6g of liquid Adjust the pH to 10-11.5 with alkali and stir until completely dissolved, then add 4g of soda ash and 90g of ice for later use;

S3: Coupling reaction: add the diazonium solution obtained in S1 to the solution obtained in S2 for coupling reaction, add 2 to 3 drops of resorcinol dropwise and stir for 30 minutes, and use ice to control the temperature at 4 to 6°C in the middle and later stages, when the pH value When the temperature drops to 8.5-9, stop adding ice and stir for 5 minutes, continue to adjust the pH to 10-10.5 with liquid caustic soda for coupling, and keep warm at 4-6°C for 1 hour, then raise the temperature to 15-20°C and continue to keep warm for 1 hour until Coupling is completed; when the junction of resorcinol and material does not show yellow, the end point of the reaction is reached, and the pH is slowly adjusted to 6-6.5 with hydrochloric acid. After adjustment, the temperature is raised to 95-100°C to steam butanone, and the temperature is slightly lowered after steaming. To 90-95°C, add 35g of sodium chloride and stir at high temperature for 30 minutes, if there is a crystal form, cool down to 25-30°C, if there is no crystal form, continue to add 8g of sodium chloride to obtain a granular product, cool down to 25-30°C and pump After filtration, 24.98 g of yellow crystals were obtained, with a yield of 97.4%, and a liquid chromatography content of 99.24%, which met the application requirements without purification.

Example 3

S1: Diazo reaction: Mix 30g of hydrochloric acid, 9.7g of 2.5-dichloroaniline, and 50g of water, heat up to 60°C for 3 hours until there is no flaky raw material, then add 2.5g of T-80 and drop to 25 ~30°C, add 30g of ice within 8~12 minutes to cool down to about 0~5°C, add 4.2g of sodium nitrite, 10g of water and 2~3 drops of potassium iodide and Congo red solution, after slowly heating up, use ice to control the temperature Incubate at 15-20°C for 60 minutes. When both potassium iodide and Congo red are blue, the diazonium salt is obtained. After adding 20 g of ice, use 0.4 g of sulfamic acid to eliminate the remaining sodium nitrite to obtain the diazonium solution;

S2: Dissolution of coupling components: Mix 25g of 2-dibutylamino-4-(4'-sulfonic acid)phenethylamino-6-methylpyrimidine, 75g of methyl ethyl ketone and 30g of water, and mix with 12g of liquid caustic soda Adjust the pH to 10-11.5 and stir until completely dissolved, then add 4g of soda ash and 90g of ice for later use;

S3: Coupling reaction: Add the diazo solution obtained in S1 to the solution obtained in S2 for coupling reaction, add 2 to 3 drops of resorcinol dropwise and stir for 50 minutes, use ice to control the temperature at 8 to 10°C in the middle and later stages, when the pH value When the temperature drops to 8.5-9, stop adding ice and stir for 5 minutes, continue to adjust the pH to 10-10.5 with liquid caustic soda for coupling, and keep warm at 8-10°C for 1 hour, then raise the temperature to 40-45°C and continue to keep warm for 1 hour until Coupling is completed; when the junction of resorcinol and the wet circle of the material does not show yellow, reach the end of the reaction, slowly adjust the pH to 6-6.5 with hydrochloric acid, after adjustment, heat up to 95-100°C to steam methyl ethyl ketone, and cool down slightly after steaming To 90-95°C, add 35g of sodium chloride and stir at high temperature for 30 minutes, if there is a crystal form, cool down to 25-30°C, if there is no crystal form, continue to add 8g of sodium chloride to obtain a granular product, cool down to 25-30°C and pump After filtration, 35.38 g of yellow crystals were obtained, with a yield of 95.8%, and a liquid chromatography content of 97.32%, which met the application requirements without purification.

The acid yellow prepared by the present invention has the advantages of high yield, high product purity, low reaction temperature and energy saving, and is especially suitable for industrial production

The above-mentioned embodiments are only to illustrate the technical concept and characteristics of the present invention, and the purpose is to enable those skilled in the art to understand the content of the present invention and implement it accordingly, and not to limit the protection scope of the present invention. All equivalent changes or modifications made according to the spirit of the present invention shall fall within the protection scope of the present invention.

Claims (9)

1. A method for preparing acid yellow, which is characterized by comprising the following steps:

s1: diazo reaction: dissolving 2, 5-dichloroaniline in hydrochloric acid, preserving heat for 1.5-4.5 hours at 40-70 ℃, adding an emulsifying agent, cooling to 25-30 ℃, adding ice for cooling to about 0-5 ℃ within 8-12 minutes, adding sodium nitrite and 2-3 drops of potassium iodide and Congo red solution, slowly heating, controlling the temperature at 15-20 ℃ by ice, preserving heat for 40-80 minutes to obtain diazonium salt, and removing residual sodium nitrite by sulfamic acid after adding ice to obtain diazonium solution;

s2: the coupling component is dissolved: mixing 2-dibutylamino-4- (4' -sulfonic acid) phenethylamino-6-methylpyrimidine, an organic solvent and water, regulating pH to 10-11.5 with liquid alkali, stirring until the mixture is fully dissolved, and adding sodium carbonate and ice for later use;

s3: coupling reaction: adding diazonium solution into the solution obtained by S2 for coupling reaction, dropwise adding 2-3 drops of resorcinol, stirring for 20-55 minutes, controlling the temperature at 3-10 ℃ by using ice in the middle and later stages, stopping adding ice when the pH value is reduced to 8.5-9, stirring for 5 minutes, continuously adjusting the pH value to be 10-10.5 by using liquid alkali, and continuously reacting, wherein the solution is kept at 3-10 ℃ for 1-3 hours, and then heated to 15-45 ℃ for continuously keeping the temperature for 0.5-1.5 hours until coupling is finished; and slowly adjusting the pH value to 6-6.5 by using hydrochloric acid after reaching the end point, heating to 95-100 ℃ after adjusting, steaming butanone, cooling to 90-95 ℃ after steaming, adding salt, stirring at high temperature for 20-40 minutes to obtain a granular product, and filtering after reducing to a certain temperature to obtain acid yellow.

2. The method for synthesizing acid yellow according to claim 1, wherein the amount ratio of 2, 5-dichloroaniline, hydrochloric acid, sodium nitrite, sulfamic acid and emulsifier in the step S1 is (0.04-0.06) mol, (0.1-0.2) mol, (0.05-0.07) mol, (0.002-0.005) mol, (1-3) g.

3. The method according to claim 1, wherein the emulsifier in the step S1 is T-80 or fatty acid methyl ester ethoxylate.

4. The method for synthesizing acid yellow according to claim 1, wherein the dosage ratio of 2-dibutyl amino-4- (4' -sulfonic acid) phenethyl amino-6-methyl pyrimidine, butanone, liquid caustic soda and sodium carbonate in the step S2 is (0.04-0.06) mol (0.01-0.03) mol (3-5) g.

5. The method for synthesizing acid yellow according to claim 1, wherein the organic solvent in the step S2 is butanone or acetone.

6. The method for synthesizing acid yellow according to claim 5, wherein the amount of the organic solvent is 0.5 to 1.5mol.

7. The method for synthesizing acid yellow according to claim 1, wherein the salt in the step S3 comprises one or more of sodium chloride, potassium chloride and sodium sulfate.

8. The method for synthesizing acid yellow according to claim 7, wherein the salt is used in an amount of 6 to 12% by volume.

9. The method for synthesizing acid yellow according to claim 1, wherein the temperature of the suction filtration after the step S3 is reduced to a certain temperature is 25-30 ℃.