A method and equipment for synthesizing structural disperse dyes

Abstract

The invention discloses a method for synthesizing a structural disperse dye and a synthesis device thereof, and relates to the technical field of disperse dyes. Raw material C: N-ethyl-N-hydroxyethyl (R1 / R2 substituent) aniline is selected and put into a synthesis device, and an acid binding agent is added to the raw material C, and then the temperature is raised to 70-100°C, and then benzoyl chloride is added dropwise, and after the reaction is completed, the coupling component to be obtained is obtained by stratification, and an acid medium is added to the synthesis device, so that the coupling component obtained in step one is dissolved in 3-50% acid medium, and an ice-water mixture is added to reduce the temperature in the synthesis device to -5-5°C and continuously stirred, and then the diazo liquid worth in step two is added dropwise for coupling. The purpose of the present invention is to overcome some of the shortcomings of some disperse dye structures, improve the sensitivity of dyes to alkali, expand the applicable range of dye pH, and enhance the covering power of dyes to color files. At the same time, the performance of the dye is also excellent, and a new dye structure is added.

Description

Technical Field

[0001] The invention relates to the technical field of disperse dyes, in particular to a synthesis method and synthesis equipment of a structured disperse dye. Background Art

[0002] Some disperse dyes with azo structures are very sensitive to alkali and are not resistant to reduction. Most disperse dyes with ester, cyano or amide groups will be hydrolyzed by alkali, affecting the normal color. Some varieties will not change color even when dyed at high temperature under neutral or weak alkaline conditions.

[0003] The covering power of disperse dyes on color scales is determined by the dye structure itself. Most dyes with high initial dyeing rate, slow diffusion and poor migration have poor covering power on color scales. Summary of the invention

[0004] In view of the deficiencies of the prior art, the present invention provides a method for synthesizing a structured disperse dye and a synthesis device thereof, which solve the problems raised in the above background technology.

[0005] To achieve the above objectives, the present invention is implemented by the following technical scheme: a method for synthesizing a structured disperse dye and a synthesis device thereof, including the structural general formula of the structured disperse dye:

[0006]

[0007] wherein the diazo component A is selected from any one of ① 3-amino-5-nitro-2,1-benzoisothiazole, ② 3-amino-6-nitro-benzothiazole, ③ 2-cyano-4-nitroaniline and ④ nitroaniline;

[0008] R 1 -Cl, -Br, -I, -NHCOCH 3 , and -H, -CH 3 Any of;

[0009] R 2 -H or -OCH 3 ;

[0010] The synthesis method comprises the following steps:

[0011] Step 1: Select raw material C: N-ethyl-N-hydroxyethyl (R1 / R2 substituent) aniline and put it into the synthesis equipment, add acid binding agent to raw material C, then heat to 70-100°C, then drop benzoyl chloride, after the reaction is completed, separate the layers to obtain the coupling component to be obtained, the structure of the coupling component is as follows:

[0012]

[0013] Step 2: When the diazo component is ①3-amino-5-nitro-2,1-benzoisothiazole, ②3-amino-6-nitro-benzothiazole, and ③2-cyano-4-nitroaniline, firstly dissolve nitrosyl sulfuric acid in sulfuric acid, mix and beat, then dropwise add the diazo component at 10-50°C, and react at 5-15°C for 3-5 hours to obtain a diazo liquid;

[0014] Step 3: Add an acidic medium to the synthesis equipment, dissolve the coupling component obtained in step 1 in 3-50% acidic medium, add an ice-water mixture to reduce the temperature in the synthesis equipment to -5-5°C and continue stirring, then drop the diazo solution obtained in step 2 to carry out coupling;

[0015] Step 4: The coupling reaction liquid end point is analyzed by a diazo component or coupling component to determine whether the reaction is complete. After the end point is reached, the temperature is raised to 50-80°C, filtered and washed until neutral to obtain a disperse dye filter cake.

[0016] Furthermore, in the step 1, the molar ratio of raw material C, acid binding agent and benzoyl chloride is 1:(0.5-0.7):(1.00-1.1), and the acid binding agent is any one of sodium carbonate, sodium bicarbonate and magnesium oxide.

[0017] Furthermore, in step 2, the concentration of nitrosyl sulfuric acid is 28%-48%, and the concentration of sulfuric acid is 70%-95%.

[0018] Furthermore, the acidic medium in step three is any one of sulfuric acid, hydrochloric acid and acetic acid.

[0019] Further, the synthesis equipment for producing a structural disperse dye comprises: a reactor body 1, bases 2 are installed on both sides of the bottom of the reactor body 1, and a reactor cover 3 is installed above the reactor body 1, a motor 4 is installed above the reactor cover 3, and a first feed port 5 is installed on one side of the reactor body 1, and a second feed port 6 is installed on the other side of the reactor body 1, a first rotary valve 7 is installed inside the reactor body 1, and the output end of the motor 4 is rotatably connected to the first rotary valve 7, one side of the first rotary valve 7 is connected to a filling pipe 8, and one end of the filling pipe 8 extends to the outside of the reactor body 1. Side kettle body, a stirring shaft 9 is installed below the first rotary valve 7, and second rotary valves 10 are installed on both sides of the stirring shaft 9, a stirring rod 11 is installed on the side of the second rotary valve 10 away from the stirring shaft 9, and a spray hole is provided on the surface of the stirring rod 11, and the interiors of the stirring shaft 9 and the stirring rod 11 are both hollow structures, the stirring shaft 9 is connected with the stirring rod 11 through the second rotary valve 10, a mixing hopper 12 is installed at the end of the stirring shaft 9 away from the first rotary valve 7, a discharge valve 13 is installed at the bottom of the reactor body 1, and a dripping pipe 14 is installed on one side of the reactor body 1, and a dripping valve 15 is installed above the dripping pipe 14.

[0020] The present invention provides a method for synthesizing a structural disperse dye and a synthesis device thereof, which has the following

[0021] Beneficial effects:

[0022] The purpose of the present invention is to overcome some of the shortcomings of some dispersed dye structures, improve the sensitivity of dyes to alkali, expand the pH application range of dyes, and enhance the coverage of dyes to color files. At the same time, the performance of the dyes is also excellent, and a new dye structure is added;

[0023] Different diazo components can be coupled with different coupling components containing benzoyl groups prepared by the present invention to obtain disperse dyes with different color lights. The coupling components prepared at the same time can also react to generate a variety of different coupling components for the different substituents R1 and R2 groups, and can generate a single coupling component or a mixed coupling component. After reacting with the diazo component at the same time, disperse dyes with a single structure can also be generated. Disperse dyes with mixed structures can be obtained, and commercial products can be obtained through commercialization treatment to obtain monochrome products or compound products. BRIEF DESCRIPTION OF THE DRAWINGS

[0024] Figure 1 The present invention is a schematic diagram of the structure of a synthetic device for structural disperse dyes.

[0025] In the figure: 1. Reactor body; 2. Base; 3. Reactor cover; 4. Motor; 5. First feed inlet; 6. Second feed inlet; 7. First rotary valve; 8. Filling pipe; 9. Stirring shaft; 10. Second rotary valve; 11. Stirring rod; 12. Mixing hopper; 13. Discharge valve; 14. Drip pipe; 15. Drip valve. DETAILED DESCRIPTION

[0026] The following embodiments of the present invention are described in further detail in conjunction with the accompanying drawings and examples. The following examples are used to illustrate the present invention, but are not intended to limit the scope of the present invention.

[0027] Embodiment 1:

[0028] like Figure 1 As shown, the present invention provides a technical solution: first, 50 grams of one of the raw materials C (N-ethyl-N-hydroxyethyl-m-toluidine) is added to the interior of the reactor body 1 of the synthesis equipment through the first feed port 5, and then the temperature is raised to 70°C by using an external heating device, and then the motor 4 is started to drive the stirring rod 11 to rotate through the stirring shaft 9, and 6 grams of the acid binding agent magnesium oxide is added through the second feed port 6 under stirring conditions, and then the temperature is raised to 80-90°C, and then the dripping valve 15 is opened to start dripping 41 grams of benzoyl chloride into the interior of the reactor body 1 through the dripping pipe, and after the dripping is completed, the temperature is kept for 3 hours until it is qualified, and after it is qualified, the temperature is lowered to 60-70°C, 50 grams of water is added, and the mixture is allowed to stand for stratification. After stratification, 77 grams of D coupling component are obtained, with a yield of more than 99%, and a liquid phase detection HPLC of 98%;

[0029] Then select 24 grams of A (3-amino-5-nitrobenzisothiazole) in the general formula of the diazo component and add it to 85-95% sulfuric acid, keep it warm at 45-60℃ for 1.0-1.5 hours to completely dissolve the diazo component. Then cool it to 0-20℃, open the dripping valve 15, and start dripping 40 grams of nitrosyl sulfuric acid into the interior of the reactor body 1 through the dripping pipe. After the dripping is completed, keep it warm for 3-5 hours, and finally end the insulation to detect the end point, and use it after it passes the test.

[0030] Before waiting for the diazo reaction to be completed, add 250 grams of water to the beaker, add 10 grams of sulfuric acid and 50 grams of acetic acid under stirring and mix evenly, then add 0.5 grams of emulsifier and 0.3 grams of urea, add a small amount of ice and 35 grams of coupling components under stirring, add ice and cool to 0-5℃ after they are completely dissolved, and then start to drop the diazo liquid that has reacted. The dropping time is controlled within 1-2 hours. After the diazo liquid is added, keep warm for 2-3 hours until the diazo liquid disappears, then add 400 ml of water, raise the temperature to 60-70℃ and keep warm for 1-2 hours, filter and wash until the filter cake is neutral, and after drying, obtain 53.5 grams of filter cake, the filter cake yield is 90.6%, HPLC 92.5%, and the following disperse blue dye structure is obtained:

[0031]

[0032] Embodiment 2:

[0033] like Figure 1 As shown, the present invention provides a technical solution: firstly, the coupling component D in Example 1 is selected and remains unchanged.

[0034] Select 20 grams of the diazo component of general formula A (2-cyano-4-nitroaniline), add it to 40 grams of 75-95% sulfuric acid under stirring, control the temperature at 10-20°C, stir for 2-3 hours after adding the diazo component, cool to 5-15°C and start to drop 36 grams of nitrosyl sulfuric acid, the dropping time is controlled to about 1 hour, keep warm for 2-3 hours after the dropping, and set aside after testing to be qualified;

[0035] Before waiting for the diazo reaction to be completed, add 200 grams of water to the beaker, add 10 grams of sulfuric acid and 50 grams of acetic acid under stirring and mix evenly, then add 0.5 grams of emulsifier and 0.3 grams of urea, add a small amount of ice and 35 grams of coupling components under stirring, add ice and cool to 0-5℃ after dissolving completely, and start dripping the diazo liquid that has reacted. The dripping time is controlled within 1-2 hours. After dripping the diazo liquid, keep warm for 1.5-2 hours until the diazo liquid disappears, then add 350ml of water, heat to 60-70℃, keep warm for 1-2 hours, filter and wash until the filter cake is neutral. After drying, 53.2 grams of filter cake are obtained, the filter cake yield is 95%, and HPLC is 94.3%. The following dispersed purple structure is obtained:

[0036]

[0037] Embodiment 3:

[0038] The present invention provides a technical solution: first, 50 grams of a raw material C (N-ethyl-N-hydroxyethylaniline) is added into the interior of the reactor body 1 of the synthesis equipment through the first feed port 5, and the temperature is raised to 70°C, 6.5 grams of magnesium oxide, an acid binding agent, is added under stirring, the temperature is raised to 80-90°C, 44.5 grams of benzoyl chloride is added dropwise, and the temperature is kept for 3 hours after the addition is completed until the temperature is qualified, and then the temperature is lowered to 60-70°C, 55 grams of water is added, and the mixture is allowed to stand for stratification. After stratification, 80.5 grams of E coupling component is obtained, the yield is 99%, and the liquid phase detection HPLC is 98%.

[0039] Select 24 grams of A (3-amino-5-nitrobenzisothiazole) in the general formula of the diazo component and add it to 85-95% sulfuric acid, keep it warm at 45-60℃ for 1.0-1.5 hours to completely dissolve the diazo component. Then cool it to 0-20℃, start adding 40 grams of nitrosyl sulfuric acid, keep it warm for 3-5 hours after the addition is complete, and finally stop keeping warm and detect the end point. If it is qualified, it will be ready for use.

[0040] Before waiting for the diazo reaction to be completed, add 250 grams of water to the beaker, add 10 grams of sulfuric acid and 50 grams of acetic acid under stirring and mix evenly, then add 0.5 grams of emulsifier and 0.3 grams of urea, add a small amount of ice and 34 grams of coupling components under stirring, add ice and cool to 0-5℃ after dissolving completely, and start dripping the diazo liquid that has reacted. The dripping time is controlled within 1-2 hours. After dripping the diazo liquid, keep warm for 2-3 hours until the diazo liquid disappears, then add 400ml of water, heat to 60-75℃ and keep warm for 1-2 hours, filter and wash until the filter cake is neutral. After drying, 52.6 grams of filter cake are obtained, the filter cake yield is 90.1%, HPLC 92.5%, and the following disperse blue dye structure is obtained:

[0041]

[0042] Embodiment 4:

[0043] First, the coupling component E in Example 3 is taken unchanged.

[0044] Select 20 grams of the diazo component of general formula A (2-cyano-4-nitroaniline), add it to 40 grams of 75-95% sulfuric acid under stirring, and control the temperature at 10-20°C. After adding the diazo component, stir for 2-3 hours, cool to 5-15°C and start adding 36 grams of nitrosyl sulfuric acid dropwise, the adding time is controlled to about 1 hour, keep warm for 2-3 hours after the addition, and set aside after testing.

[0045] Before waiting for the diazo reaction to be completed, add 250 grams of water to the beaker, add 10 grams of sulfuric acid and 50 grams of acetic acid under stirring and mix evenly, then add 0.5 grams of emulsifier and 0.3 grams of urea, add a small amount of ice and 34 grams of coupling components under stirring, add ice and cool to 0-5℃ after dissolving completely, and then start to drop the diazo liquid that has reacted. The dropping time is controlled within 1-2 hours. After the diazo liquid is added, keep warm for 2-3 hours until the diazo liquid disappears, then add 400ml of water and heat to 60-75℃ and keep warm for 1-2 hours, filter and wash until the filter cake is neutral. After drying, 55.9 grams of filter cake are obtained, the filter cake yield is 96%, and HPLC is 93.1%. The following dispersed purple structure is obtained:

[0046]

[0047] According to the embodiments, different diazo components can be coupled with different coupling components containing benzoyl groups prepared by the present invention to obtain disperse dyes of different colors. The coupling components prepared at the same time can also react to generate a variety of different coupling components for the difference of substituent R1 and R2 groups, and can generate a single coupling component or a mixed coupling component. At the same time, disperse dyes of a single structure can be generated after reacting with the diazo component, and disperse dyes of mixed structures can be generated, and monochromatic products or compound products can be obtained after commercialization.

[0048] According to the present invention, the disperse dyes obtained in the examples are processed for commercial use, and the examples are as follows:

[0049] The performance parameters of the disperse dyes of the present invention are as follows:

[0050]

[0051] The embodiments of the present invention are given for the purpose of illustration and description, and are not intended to be exhaustive or to limit the invention to the disclosed forms. Many modifications and variations will be apparent to those of ordinary skill in the art. The embodiments are selected and described in order to better illustrate the principles and practical applications of the present invention and to enable those of ordinary skill in the art to understand the present invention and thereby design various embodiments with various modifications suitable for specific uses.

Claims

1. A method for synthesizing a structured disperse dye, characterized in that: The general structural formula of the structural disperse dye is: wherein the diazo component A is selected from ① 3-amino-5-nitro-2,1-benzisothiazole, ② 3-amino-6-nitro-benzothiazole, ③ 2-cyano-4-nitroaniline; R1 is -Cl, -Br, -I, -NHCOCH 3， and any one of -H, -CH3; R2 is -H or -OCH3; The synthesis method comprises the following steps: Step 1: Select raw material C: N-ethyl-N-hydroxyethylaniline containing R1 and R2 substituents is placed in the synthesis equipment, and an acid binding agent is added to the raw material C, and then the temperature is raised to 70-100°C, and then benzoyl chloride is added dropwise. After the reaction is completed, the coupling component to be prepared is obtained by layering. The structure of the coupling component is as follows: Step 2: When the diazo component is any one of ①3-amino-5-nitro-2,1-benzisothiazole, ②3-amino-6-nitro-benzothiazole, and ③2-cyano-4-nitroaniline, firstly dissolve nitrosyl sulfuric acid in sulfuric acid, mix and beat, then dropwise add the diazo component at 10-50° C., react at 5-15° C. for 3-5 hours to obtain a diazo liquid; Step 3: Add an acidic medium to the synthesis equipment, dissolve the coupling component obtained in step 1 in 3-50% acidic medium, add an ice-water mixture to reduce the temperature in the synthesis equipment to -5-5°C and continue stirring, then drop the diazo solution obtained in step 2 to carry out coupling; Step 4: The coupling reaction liquid end point is analyzed by a permeation circle to determine whether the diazo component or the coupling component has reacted completely. After the detection end point is reached, the temperature is raised to 50-80°C, filtered and washed until neutral to obtain a disperse dye filter cake; In the step 1, the molar ratio of raw material C, acid binding agent and benzoyl chloride is 1:(0.5-0.7):(1.00-1.1), and the acid binding agent is any one of sodium carbonate, sodium bicarbonate and magnesium oxide; In the step 2, the concentration of nitrosyl sulfuric acid is 28%-48%, and the concentration of sulfuric acid is 70%-95%; The acidic medium in step 3 is any one of sulfuric acid, hydrochloric acid and acetic acid.

2. A synthetic device for structural disperse dyes, used in the synthetic method for structural disperse dyes according to claim 1, characterized in that: The synthesis equipment comprises: a reactor body (1), bases (2) are installed on both sides of the bottom of the reactor body (1), a reactor cover (3) is installed above the reactor body (1), a motor (4) is installed above the reactor cover (3), a first feed inlet (5) is installed on one side of the reactor body (1), and a second feed inlet (6) is installed on the other side of the reactor body (1), a first rotary valve (7) is installed inside the reactor body (1), and the output end of the motor (4) is rotatably connected to the first rotary valve (7), one side of the first rotary valve (7) is connected to a filling pipe (8), and one end of the filling pipe (8) extends to the outer reactor body of the reactor body (1), and the lower end of the first rotary valve (7) is connected to the outer reactor body of the reactor body (1). A stirring shaft (9) is installed on the side of the reactor body (1), and second rotary valves (10) are installed on both sides of the stirring shaft (9); a stirring rod (11) is installed on the side of the second rotary valve (10) away from the stirring shaft (9), and a spray hole is arranged on the surface of the stirring rod (11); the interiors of the stirring shaft (9) and the stirring rod (11) are both hollow structures; the stirring shaft (9) is connected to the stirring rod (11) through the second rotary valve (10); a mixing hopper (12) is installed on the end of the stirring shaft (9) away from the first rotary valve (7); a discharge valve (13) is installed at the bottom of the reactor body (1); a dripping pipe (14) is installed on one side of the reactor body (1), and a dripping valve (15) is installed above the dripping pipe (14).

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