CN112226098A - Direct dye and preparation method thereof - Google Patents
Direct dye and preparation method thereof Download PDFInfo
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- CN112226098A CN112226098A CN201910633336.4A CN201910633336A CN112226098A CN 112226098 A CN112226098 A CN 112226098A CN 201910633336 A CN201910633336 A CN 201910633336A CN 112226098 A CN112226098 A CN 112226098A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B43/00—Preparation of azo dyes from other azo compounds
- C09B43/40—Preparation of azo dyes from other azo compounds by substituting hetero atoms by radicals containing other hetero atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
- C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
- C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
- C07D251/26—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
- C07D251/40—Nitrogen atoms
- C07D251/54—Three nitrogen atoms
- C07D251/70—Other substituted melamines
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Abstract
The invention discloses a direct dye and a preparation method thereof. 1) Mixing J acid and cyanuric chloride for reaction at 0-10 deg.c and pH 2.5-3.5 for 1-2 hr; 2) mixing the cyanuric chloride monochloride substitution product with 4-amino azobenzene-4' -sulfonic acid diazonium salt to perform coupling reaction at the temperature of 10-25 ℃ and the pH value of 7-8 for 2-3 hours; 3) mixing the coupling reaction product with ethanolamine to perform dichloro substitution reaction at 60-80 deg.c and pH 5-6 for 2-3 hr; 4) and mixing the dichloro substitution product of the coupling product with ethanolamine for reaction at 95-100 deg.c and pH 6.5-7.5 for 2-3 hr. In the industrial production, the invention saves the management of materials, improves the production efficiency and reduces the risk of wrong use of the materials.
Description
Technical Field
The invention relates to a direct dye and a preparation method thereof, belonging to the technical field of dyes.
Background
Direct red 253(C.I 284243) is a peach-red dye, has good water solubility, and particularly has more remarkable performance of dissolving in cold water. Meanwhile, the dye also has good direct dyeing property on paper dyeing and good stability in a wide pH range. It has a hue similar to that of direct red 254 on the market, but shows more excellent performances in terms of both the dye uptake and the light fastness.
The synthesis process of the comparative conventional direct red 253 is described in the dye handbook: 4-aminoazobenzene
Diazotization of-4' -sulfonic acid, coupling with J acid, condensation with cyanuric chloride, condensation of the product with ethanolamine (2 mol). The product obtained by diazotizing 4-amino azobenzene-4' -sulfonic acid and coupling with J acid is also a direct dye, named as direct red 254 in the dye handbook, the route is that the direct red 254 is synthesized firstly, the direct red 254 is condensed with cyanuric chloride, and the product is condensed with ethanolamine (2 mol). The process of the route is relatively simple, but the condensate of the direct red 254 and the cyanuric chloride in the first step route I-1 has a structure similar to that of the raw material direct red 254, only one more cyanuric chloride ring is added, so that the condensate cannot be distinguished by common analytical means such as TLC, ultraviolet-visible spectrum and HPLC liquid phase, and the conversion degree of the raw material in the reaction process is difficult to detect in real time. In addition, the three reaction processes of the routes I-1, I-2 and I-3 are red, so that the difficulty degree of monitoring the reaction processes is further increased. Meanwhile, the first step of reaction is carried out by reacting 254 with cyanuric chloride, 254 molecules are large, steric hindrance is increased, and reaction time is relatively prolonged.
Patent US4083840 discloses a compound structure which discloses the structure dye direct red 253 three synthetic processes are described in the patent claims and examples to obtain this structure: process (a), process (b), process (c). Wherein process (b) does not involve a chlorocyanoring structure, and is not relevant to this patent. The process (c) is characterized in that a direct red 254 structure is obtained firstly, and then the direct red 254 structure reacts with cyanuric chloride and ethanolamine, and the reaction sequence can be adjusted according to requirements. In summary, process (c) includes scheme I described in the dye handbook mentioned above and scheme II below.
Disclosure of Invention
In view of the above, the invention provides a direct dye and a preparation method thereof, which save material management, improve production efficiency and reduce the risk of material use errors in industrial production.
The invention solves the technical problems by the following technical means:
the invention relates to a direct dye and a preparation method thereof, which comprises the following four steps:
1) mixing J acid and cyanuric chloride to perform monochloro substitution reaction, wherein the reaction temperature is 0-10 ℃, the pH is 2.5-3.5, the reaction time is 1-2 hours, and the reaction equation is as follows:
2) the cyanuric chloride monochloride substitution product is mixed with 4-amino azobenzene-4' -sulfonic acid diazonium salt to carry out coupling reaction, the reaction temperature is 10-25 ℃, the pH value is 7-8, the reaction time is 2-3 hours, and the reaction equation is as follows:
3) mixing the coupling reaction product with ethanolamine to perform dichloro substitution reaction at 60-80 deg.c and pH 5-6 for 2-3 hr, and the reaction equation is as follows:
4) mixing the dichloro substitution product of the coupling product with ethanolamine to carry out trichloro substitution reaction, wherein the reaction temperature is 95-100 ℃, the pH value is 6.5-7.5, the reaction time is 2-3 hours, and the reaction equation is as follows:
judging the reaction end point of the step (1) by a dianisidine diazonium salt or aniline diazonium salt ring-infiltration method, and when the ring-infiltration shows that the J acid reactant completely reacts as the end point; or the reaction of the J acid substance is identified to be complete as the end point by liquid phase HPLC.
The reaction end point of the step (2) is judged by an H acid ring cementation method, and when the ring cementation shows that 4-amino-azo-benzene-4-sulfonic acid diazonium salt reactant completely reacts, the end point is obtained.
The reaction end point of the step (3) is the end point of no change of pH; or the end point is determined by liquid phase HPLC to determine the completion of the coupling product reaction.
The reaction end point of the step (4) is the end point of no change of pH; or the liquid phase HPLC is used for identifying that the reaction of the raw material dichloro substituent is completely the end point.
The acid-binding agent used for adjusting the pH value in the reaction process is at least one of sodium bicarbonate, triethylamine, ethanolamine or triethanolamine.
The biggest difference between the reaction route of the patent and the process (a) in the patent US4083840 is that after the J acid (2-amino-5-hydroxynaphthalene-7-sulfonic acid) reacts with cyanuric chloride in the first step, the dichloro substitution reaction with ethanolamine is not carried out immediately, but the coupling reaction with 4-aminoazobenzene-4' -sulfonic acid diazonium salt is carried out. After the coupling reaction is finished, the coupling product is subjected to dichloro substitution and trichloro substitution with 2 mol of ethanolamine.
The invention has the beneficial effects that: the process route of the direct red 253 has the greatest advantage that after monochloro reaction of J acid and cyanuric chloride, a product is firstly reacted with 4-amino-azobenzene-4' -sulfonic acid, and then dichloro substitution and trichloro substitution reaction of cyanuric chloride ring are carried out.
The monochloro substitution product of the J acid and the cyanuric chloride immediately carries out dichloro substitution with ethanolamine, and the third chlorine of the cyanuric chloride ring simultaneously carries out side reaction hydrolysis reaction. This may be related to the strong electron-withdrawing groups such as nitro and sulfonic acid groups in the structure.
After the monochloro substitution product of J acid and cyanuric chloride preferentially takes diazo coupling reaction with 4-amino-azobenzene-4' -sulfonic acid, the hydrolysis reaction of the third chlorine of the cyanuric chloride ring is greatly inhibited because the strong electron withdrawing effect of nitro and sulfonic group in the naphthalene ring and the steric hindrance effect of the group are weakened. Therefore, the subsequent dichloro substitution and trichloro substitution reaction on the cyanuric chloride ring can be smoothly carried out, and the purity and the yield of the product are improved.
The patent route provides an effective method for monitoring the reaction process and judging the end point. The method can be implemented in the amplification production, can effectively monitor the reaction process and judge the reaction end point in time, avoids the waste of invalid reaction time, improves the production efficiency and reduces the implementation difficulty.
In the patent route, other steps can be sequentially and continuously carried out except that 4-amino azo-benzene-4' -sulfonic acid diazonium salt needs to be filtered out. Therefore, as long as the 4-amino azo-benzene-4' -sulfonic acid diazonium salt is prepared in advance, the process can be simplified, the continuous operation can be realized, and a good foundation is laid for industrial continuous and even automatic operation. The fluoacid agent used in the method acts as a reactant and an acid-binding agent, and the reaction is promoted to be carried out to the right by neutralization of hydrochloric acid. Therefore, in industrial production, the management of materials is saved, the production efficiency is improved, and the risk of material use errors is reduced.
Detailed Description
The synthesis process of the comparative conventional direct red 253 is described in the dye handbook: diazotization of 4-aminoazobenzene-4' -sulfonic acid, coupling with J acid, condensation with cyanuric chloride, condensation of the product with ethanolamine (2 mol). The product obtained by diazotizing 4-amino azobenzene-4' -sulfonic acid and coupling with J acid is also a direct dye, named as direct red 254 in the dye handbook, the route is that the direct red 254 is synthesized firstly, the direct red 254 is condensed with cyanuric chloride, and the product is condensed with ethanolamine (2 mol). This patent is named route I.
The process of the route is relatively simple, but the condensate of the direct red 254 and the cyanuric chloride in the first step route I-1 has a structure similar to that of the raw material direct red 254, only one more cyanuric chloride ring is added, so that the common analytical means such as TLC, ultraviolet-visible spectrum and HPLC liquid phase can not be used for distinguishing, and the conversion degree of the raw material in the reaction process is difficult to detect in real time. In addition, the three reaction processes of the routes I-1, I-2 and I-3 are red, so that the difficulty degree of monitoring the reaction processes is further increased. Meanwhile, the first step of reaction is carried out by reacting 254 with cyanuric chloride, 254 molecules are large, steric hindrance is increased, and reaction time is relatively prolonged.
Patent US4083840 discloses a compound structure, the structural formula of which is shown below:
wherein D is the following structure:
r is hydrogen or the following structure:
when X is-SO3M, R is cyanuric chloride ring and R8＝H，R5＝CH2CH2OH，Y＝NHCH2CH2OH, the structure disclosed is dye direct red 253 three synthetic processes to obtain this structure are described in the patent specification and examples: process (a), process (b), process (c). Wherein process (b) does not involve chlorineA cyanoring structure, independent of the patent. The process (c) is characterized in that a direct red 254 structure is obtained firstly, and then the direct red 254 structure reacts with cyanuric chloride and ethanolamine, and the reaction sequence can be adjusted according to requirements. In summary, process (c) includes scheme I and scheme II below as described in my aforementioned dye handbook.
In route II, II-1 and II-2 react easily, namely, primary chlorine substitution and secondary chlorine substitution of cyanuric chloride, and after 2 moles of ethanolamine are grafted, the condensate (product after substitution) needs to be filtered out and then reacts with 254. Therefore, the reaction process is complex, the raw materials and the products are not colored in the reaction of cyanuric chloride and ethanolamine, the reaction process cannot be monitored by a coloring method such as a ring penetration method, and the reaction process is difficult to control. Process (a) is described in US patent US4083840 as: after diazotization of an aromatic amine of the structure,
and the following structure:
coupling at the position indicated by the arrow gives the product. When the substituent is a suitable group (R ═ cyanuric chloride ring), the direct red 253 structure is obtained. The reaction scheme is shown in scheme III:
the first step of the reaction in the route is easier, and the J acid can be detected by a dianisidine diazonium salt or aniline diazonium salt ring penetration method. And 4-amino-azo-benzene-4' -sulfonic acid can be prepared in advance in the whole process and then can be continuously reacted. But the biggest defect is that the inventor has proved that the product with higher purity can not be obtained through experiments, and the purity is about 30 percent through liquid phase HPLC detection. The reason is that in route III-2, the secondary substitution of cyanuric chloride is carried out, with hydrolysis of the cyanuric chloride ring by another chlorine. This results in a low purity of the final product and a large difference in hue compared to the standard.
Compared with the process (a) in the patent US4083840, the process route of the direct red 253 has the greatest advantage that after monochloro reaction of J acid and cyanuric chloride, the product is firstly reacted with 4-amino-azobenzene-4' -sulfonic acid, and then dichloro substitution and trichloro substitution reaction of cyanuric chloride ring are carried out.
As mentioned above, the monochloro-substituted products of the J-acid and cyanuric chloride immediately undergo a dichloro-substitution with ethanolamine, the third chlorine of the cyanuric chloride ring being simultaneously hydrolyzed by a side reaction. This may be related to the strong electron-withdrawing groups such as nitro and sulfonic acid groups in the structure.
After the monochloro substitution product of J acid and cyanuric chloride preferentially takes diazo coupling reaction with 4-amino-azobenzene-4' -sulfonic acid, the hydrolysis reaction of the third chlorine of the cyanuric chloride ring is greatly inhibited because the strong electron withdrawing effect of nitro and sulfonic group in the naphthalene ring and the steric hindrance effect of the group are weakened. Therefore, the subsequent dichloro substitution and trichloro substitution reaction on the cyanuric chloride ring can be smoothly carried out, and the purity and the yield of the product are improved.
Secondly, compared to route i, this patent route provides an efficient method to perform monitoring of the reaction process and end point determination. The method can be implemented in the amplification production, can effectively monitor the reaction process and judge the reaction end point in time, avoids the waste of invalid reaction time, improves the production efficiency and reduces the implementation difficulty.
Third, in contrast to scheme II, the steps of this patent scheme can be performed sequentially and continuously, except that the 4-aminoazo-benzene-4' -sulfonic acid diazonium salt needs to be filtered off. Therefore, as long as the 4-amino azo-benzene-4' -sulfonic acid diazonium salt is prepared in advance, the process can be simplified, the continuous operation can be realized, and a good foundation is laid for industrial continuous and even automatic operation.
Fourth, the fluoroacid used in the route of this patent acts both as a reactant and as an acid-binding agent, and neutralization with hydrochloric acid promotes the reaction to the right. Therefore, in industrial production, the management of materials is saved, the production efficiency is improved, and the risk of material use errors is reduced.
The present invention will be described in detail with reference to the following specific examples, which are a direct dye and a preparation method thereof, and the specific examples are as follows:
comparative example (route iii):
1. route III-1:
10.76g of cyanuric chloride are added to 100g of water and stirred to form a fine, homogeneous suspension. Cooling to 0-5 deg.C, slowly adding prepared J-acid solution (14.33g J acid, 100g water, controlling temperature at 25 deg.C, adding ethanolamine to dissolve completely), maintaining the temperature at 25 deg.C, adding J-acid solution into the reaction bottle, maintaining the temperature at 0-5 deg.C for about one hour. After the dropwise addition, 10g of water was added to rinse the beaker. Testing pH value, detecting pH change, determining end point with dianisidine diazonium salt dripping ring, maintaining pH value at 2.5-3.0(pH value lower than 2.5 dripping)Ethanolamine). When the pH value is constant or the J acid reaction is judged to be complete by a ring penetration method, the cyanuric chloride monochloride waiting substance is obtained.
2. Route III-2 and route III-3:
after the first-order chlorine substitution reaction is finished, the temperature is immediately raised to 63-68 ℃ to test the pH value. In the process of temperature rise, 12.5g of ethanolamine solution (prepared into 50% aqueous solution) is added to adjust the pH value, and the pH value is controlled to be 5.0-5.5. Sampling every other hour for liquid phase HPLC, and controlling the reaction time to be 2-3 hours.
When the pH value is kept constant, then the temperature is raised to 80 ℃, and 50% ethanolamine solution is added in the temperature raising process to maintain the system pH value to be 5.5-6.0; when the pH value is kept stable, the reaction is stopped, the reaction time is controlled to be 2 hours, and the temperature is naturally reduced to 15-20 ℃ to prepare the coupling reaction.
3. Route III-4
100g of water was added to the flask, stirring was turned on and 14.8g of SAAB was added. Then, the temperature was increased to 90 ℃ and the mixture was stirred for 15 minutes. At the same time, a sodium sulfite solution was prepared (3.7 g of sodium sulfite and 7.4g of water) for use.
After stirring, adding liquid alkali to adjust the pH value of the solution to be about 9-10 (about 7g is added, and the solution is brown clear liquid after dissolution); when the pH value reaches 6.5, the solution is slowly dripped to prevent the pH value from being higher. After the pH was adjusted, stirring was continued for 10 minutes. After the pH is constant, a prepared sodium sulfite solution is added, and the temperature is kept at 90 ℃ for 15 minutes.
A flask (mechanical stirrer, thermometer) was prepared, 18.25g of hydrochloric acid and 30g of water were added, and the temperature was lowered to 10 ℃ or lower. Starting stirring, adding the prepared SAAB solution (the temperature is controlled to be 80-90 ℃, 20g of water is used for cleaning the beaker), and controlling the temperature to be 30-40 ℃ in the process. The feeding time is controlled to be about 30 minutes.
Stirring for 10 minutes, sampling and detecting by using test paper, wherein congo red and potassium iodide test paper are required to show blue. And (5) detecting to be qualified, and keeping the temperature for 40 minutes at the temperature of 40-45 ℃. The process continues with test paper requiring that both congo red and potassium iodide test paper appear blue.
And (4) after heat preservation, adding ice blocks to cool the material to 3-7 ℃, and slowly adjusting the pH value to 2.8-3.0 by using 15% liquid alkali (without adding the liquid alkali, and recording the amount of the liquid alkali). And after the pH value is qualified, stirring for 30 minutes, and continuously measuring the pH value again to be 2.8-3.0.
Clear with a small amount of ice water for later use.
And immediately adding the diazonium salt slurry into the coupling solution obtained by the reaction, controlling the temperature to be 15-20 ℃, continuously detecting the pH value, adjusting and controlling the pH value to be 8.0-8.2 by triethylamine, finishing the addition of the diazonium salt, and detecting the coupling end point when stirring for 5 minutes to require that the diazonium salt is completely reacted. If an excess of diazonium salt is detected, the coupling component is added until the diazonium salt disappears. The product is obtained as direct red 253.
The liquid phase HPLC monitoring results are shown in the following table: the flask was washed to prevent loss of diazonium salt and was ready for filter pressing. Preparing ice water with the temperature of 0-5 ℃, adding 100g of ice water into a Buchner funnel once, carrying out suction filtration and pressure drying for multiple times, and washing until the pH value is more than 5.5 and the color of the filtrate is clear. (the process is as fast as possible to prevent decomposition of the diazonium salt).
Adding the filter-pressed diazonium salt damp into the same amount of deionized water (the damp: water is 1:1) at 0 ℃, and uniformly stirring
Patent route example 1:
1 patent line-1
9.8g of cyanuric chloride are added to 100g of water and stirred to form a fine, homogeneous suspension. Cooling to 0-5 deg.C, slowly adding prepared J-acid solution (13.0g J acid, 100g water, controlled temperature 25 deg.C, adding ethanolamine to dissolve completely), adding J-acid solution into the reaction flask via constant pressure funnel, and controlling temperature at 5-10 deg.C for about one hour. After the dropwise addition, 10g of water was added to rinse the beaker. Testing pH, detecting pH change, and maintaining pH at 3.0-3.5(pH lower than 2.5Ethanol Amines as pesticides). When the pH is constant (end of 3 hours), cyanuric chloride monochloride is obtained. Sampling and measuring the liquid phase.
2. Line of the patent-2
100g of water was added to the flask, stirring was turned on and 14.8g of SAAB was added. Then, the temperature was increased to 90 ℃ and the mixture was stirred for 15 minutes. Meanwhile, preparing a sodium sulfite solution for later use.
And after stirring, adding 30% liquid alkali to adjust the pH value of the solution to about 9-10. The solution is brown clear liquid after dissolution); when the pH value reaches 6.5, the solution is slowly dripped to prevent the pH value from being higher. After the pH was adjusted, stirring was continued for 10 minutes. After the pH is constant, a prepared sodium sulfite solution is added, and the temperature is kept at 90 ℃ for 15 minutes.
A flask (mechanical stirrer, thermometer) was prepared, 18.25g of hydrochloric acid and 30g of water were added, and the temperature was lowered to 10 ℃ or lower. Starting stirring, adding the prepared SAAB solution (the temperature is controlled to be 80-90 ℃, 20g of water is used for cleaning the beaker), and controlling the temperature to be 30-40 ℃ in the process. The feeding time is controlled to be about 30 minutes.
Stirring for 10 minutes, sampling and detecting by using test paper, wherein congo red and potassium iodide test paper are required to show blue. And (5) detecting to be qualified, and keeping the temperature for 40 minutes at the temperature of 40-45 ℃. The process continues with test paper requiring that both congo red and potassium iodide test paper appear blue.
And (4) after heat preservation, adding ice blocks to cool the material to 3-7 ℃, and slowly adjusting the pH value to 2.8-3.0 by using 15% liquid alkali (without adding the liquid alkali, and recording the amount of the liquid alkali). The flask was washed with a small amount of ice water to prevent loss of diazonium salt and prepared for pressure filtration. Preparing ice water with the temperature of 0-5 ℃, adding 100g of ice water into a Buchner funnel once, carrying out suction filtration and press drying for multiple times, and washing the filtrate until the color becomes clear.
Adding the diazo salt damp product subjected to pressure filtration into the same amount of deionized water (the damp product: water is 1:1) at 0 ℃, and uniformly stirring for later use.
Controlling the temperature to be 10-15 ℃, immediately adding the diazonium salt slurry into the cyanuric chloride monochloride substitution product obtained by the reaction, continuously detecting the pH value, adjusting and controlling the pH value to be 8 by using ethanolamine, completely adding the diazonium salt, uniformly stirring, sampling and detecting the liquid phase, and detecting the coupling end point by using an H acid ring penetration method. The J acid condensate was required to be in excess and the SAAB diazonium salt disappeared. The reaction time is 2-3 hours.
3. Patent line-3 and patent line-4
After the coupling is finished, the temperature is immediately raised to80℃Then, 7g of 50% ethanolamine solution was added to test the pH. And controlling the pH value to be 5 until the coupling monochloro reaction is finished, reacting for 2 hours, and sampling every other hour to perform liquid phase test.
Then the temperature is raised to 98 ℃, the pH value is tested, 10g of 50 percent ethanolamine solution is added to maintain the pH value of the system to be 7-7.5, the reaction is carried out for 2 hours, and samples are taken every 1 hour until the monochloride is completely reacted after the reactant-coupling. Naturally cooling to room temperature, filtering with filter paper, and collecting the lower layer filtrate to obtain direct red 253 liquid.
The liquid phase HPLC monitoring results are shown in the following table:
compared with the comparative example, the purity of the cyanuric chloride dichloro-substituted product HPLC obtained after the patent route-3 is obviously and greatly improved. This is because the coupling reaction is carried out first, and the hydrolysis reaction of the third chlorine at the time of substitution of dichloro as a side reaction is greatly suppressed. The HPLC purity of the final product is also greatly improved. The liquid phase results at the end of scheme-2 show that cyanuric chloride dichloride substitution products have also been generated, indicating that the scheme-3 step was carried out in advance at the stage of scheme-2.
Patent route example 2:
2.1 route to patent-1
9.8g of cyanuric chloride are added to 100g of water and stirred to form a fine, homogeneous suspension. Cooling to 0-5 deg.C, slowly adding prepared J-acid solution (13.0g J acid, 100g water, controlled temperature 25 deg.C, adding ethanolamine to dissolve completely), adding J-acid solution into the reaction flask via constant pressure dropping funnel, and controlling temperature to 0-5 deg.C for about one hour. After the dropwise addition, 10g of water was added to rinse the beaker. Testing pH value, detecting pH change, and maintaining pH value at 2.5-3.0(pH is lower than 2.5, and adding ethanolamine dropwise). When the pH is constant (end of 3 hours), cyanuric chloride monochloride is obtained. Sampling and measuring the liquid phase.
2. Line of the patent-2
100g of water was added to the flask, stirring was turned on and 14.8g of SAAB was added. Then, the temperature was increased to 90 ℃ and the mixture was stirred for 15 minutes. Meanwhile, preparing a sodium sulfite solution for later use.
And after stirring, adding 30% liquid alkali to adjust the pH value of the solution to about 9-10. The solution is brown clear liquid after dissolution); when the pH value reaches 6.5, the solution is slowly dripped to prevent the pH value from being higher. After the pH was adjusted, stirring was continued for 10 minutes. After the pH is constant, a prepared sodium sulfite solution is added, and the temperature is kept at 90 ℃ for 15 minutes.
A flask (mechanical stirrer, thermometer) was prepared, 18.25g of hydrochloric acid and 30g of water were added, and the temperature was lowered to 10 ℃ or lower. Starting stirring, adding the prepared SAAB solution (the temperature is controlled to be 80-90 ℃, 20g of water is used for cleaning the beaker), and controlling the temperature to be 30-40 ℃ in the process. The feeding time is controlled to be about 30 minutes.
Stirring for 10 minutes, sampling and detecting by using test paper, wherein congo red and potassium iodide test paper are required to show blue. And (5) detecting to be qualified, and keeping the temperature for 40 minutes at the temperature of 40-45 ℃. The process continues with test paper requiring that both congo red and potassium iodide test paper appear blue.
And (4) after heat preservation, adding ice blocks to cool the material to 3-7 ℃, and slowly adjusting the pH value to 2.8-3.0 by using 15% liquid alkali (without adding the liquid alkali, and recording the amount of the liquid alkali). The flask was washed with a small amount of ice water to prevent loss of diazonium salt and prepared for pressure filtration. Preparing ice water with the temperature of 0-5 ℃, adding 100g of ice water into a Buchner funnel once, carrying out suction filtration and press drying for multiple times, and washing the filtrate until the color becomes clear.
Adding the diazo salt damp product subjected to pressure filtration into the same amount of deionized water (the damp product: water is 1:1) at 0 ℃, and uniformly stirring for later use.
Controlling the temperature to be 15-20 ℃, immediately adding the diazonium salt slurry into the cyanuric chloride monochloride substitution product obtained by the reaction, continuously detecting the pH value, adjusting and controlling the pH value to be 7 by using ethanolamine, completely adding the diazonium salt, uniformly stirring, sampling and detecting the liquid phase, and detecting the coupling end point by using an H acid ring penetration method. The J acid condensate was required to be in excess and the SAAB diazonium salt disappeared. The reaction time is 2-3 hours.
3. Patent line-3 and patent line-4
After the coupling is complete, the temperature is immediately raised to 80 ℃ and 7g of a 50% ethanolamine solution are added and the pH is measured. And controlling the pH value to be 5 until the coupling monochloro reaction is finished, reacting for 2 hours, and sampling every other hour to perform liquid phase test.
Then the temperature is raised to 98 ℃, the pH value is tested, 15g of 50 percent ethanolamine solution is added to maintain the pH value of the system to be 6.5-7.0, the reaction is carried out for 3 hours, and samples are taken every 1 hour until the cyanuric chloride dichlorinated reactant is completely reacted. Naturally cooling to room temperature, filtering with filter paper, and collecting the lower layer filtrate to obtain direct red 253 liquid.
The liquid phase HPLC monitoring results are shown in the following table:
compared with the comparative example, the purity of the cyanuric chloride dichloro-substituted product HPLC obtained after the patent route-3 is obviously and greatly improved. This is because the coupling reaction is carried out first, and the hydrolysis reaction of the third chlorine at the time of substitution of dichloro as a side reaction is greatly suppressed. Furthermore, this time, due to the optimization of the coupling conditions, the reaction of scheme-3 was not carried out earlier at the end of scheme-2 than in scheme example 1. The HPLC purity of the final product is accordingly increased.
Finally, the above embodiments are only for illustrating the technical solutions of the present invention and not for limiting, although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions may be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, and all of them should be covered in the claims of the present invention.
Claims (6)
1. A direct dye and a preparation method thereof are characterized by comprising the following four steps:
1) mixing J acid and cyanuric chloride to perform monochloro substitution reaction, wherein the reaction temperature is 0-10 ℃, the pH is 2.5-3.5, the reaction time is 1-2 hours, and the reaction equation is as follows:
2) the cyanuric chloride monochloride substitution product is mixed with 4-amino azobenzene-4' -sulfonic acid diazonium salt to carry out coupling reaction, the reaction temperature is 10-25 ℃, the pH value is 7-8, the reaction time is 2-3 hours, and the reaction equation is as follows:
3) mixing the coupling reaction product with ethanolamine to perform dichloro substitution reaction at 60-80 deg.c and pH 5-6 for 2-3 hr, and the reaction equation is as follows:
4) mixing the dichloro substitution product of the coupling product with ethanolamine to carry out trichloro substitution reaction, wherein the reaction temperature is 95-100 ℃, the pH value is 6.5-7.5, the reaction time is 2-3 hours, and the reaction equation is as follows:
2. a direct dye and a process for preparing the same according to claim 1, wherein: judging the reaction end point of the step (1) by a dianisidine diazonium salt or aniline diazonium salt ring-infiltration method, and when the ring-infiltration shows that the J acid reactant completely reacts as the end point; or the reaction of the J acid substance is identified to be complete as the end point by liquid phase HPLC.
3. A direct dye and a process for preparing the same according to claim 1, wherein: the reaction end point of the step (2) is judged by an H acid ring cementation method, and when the ring cementation shows that 4-amino-azo-benzene-4-sulfonic acid diazonium salt reactant completely reacts, the end point is obtained.
4. A direct dye and a process for preparing the same according to claim 1, wherein: the reaction end point of the step (3) is the end point of no change of pH; or the end point is determined by liquid phase HPLC to determine the completion of the coupling product reaction.
5. A direct dye and a process for preparing the same according to claim 1, wherein: the reaction end point of the step (4) is the end point of no change of pH; or the liquid phase HPLC is used for identifying that the reaction of the raw material dichloro substituent is completely the end point.
6. A direct dye and a process for preparing the same according to claim 1, wherein: the acid-binding agent used for adjusting the pH value in the reaction process is at least one of sodium bicarbonate, triethylamine, ethanolamine or triethanolamine.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN117070077A (en) * | 2023-08-17 | 2023-11-17 | 浙江闰土染料有限公司 | Red direct dye and preparation method thereof |
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| US4083840A (en) * | 1975-04-24 | 1978-04-11 | Sandoz Ltd. | Disazo dyes having a 6-amino or substituted triazinylamino-1-hydroxynaphthalene-3-sulfonic acid coupling component radical |
| CN101899225A (en) * | 2010-07-17 | 2010-12-01 | 青岛大学 | X-type active light-resistant red azo dye and preparation method thereof |
| CN103305022A (en) * | 2012-03-16 | 2013-09-18 | 上海汇友精密化学品有限公司 | Azo type direct dye and preparation method thereof |
| CN103911018A (en) * | 2014-03-21 | 2014-07-09 | 沈阳化工大学 | Method for preparing direct red 253 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US4083840A (en) * | 1975-04-24 | 1978-04-11 | Sandoz Ltd. | Disazo dyes having a 6-amino or substituted triazinylamino-1-hydroxynaphthalene-3-sulfonic acid coupling component radical |
| GB1537767A (en) * | 1975-04-24 | 1979-01-04 | Sandoz Ltd | Water-soluble disazo dyestuffs |
| CN101899225A (en) * | 2010-07-17 | 2010-12-01 | 青岛大学 | X-type active light-resistant red azo dye and preparation method thereof |
| CN103305022A (en) * | 2012-03-16 | 2013-09-18 | 上海汇友精密化学品有限公司 | Azo type direct dye and preparation method thereof |
| CN103911018A (en) * | 2014-03-21 | 2014-07-09 | 沈阳化工大学 | Method for preparing direct red 253 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN117070077A (en) * | 2023-08-17 | 2023-11-17 | 浙江闰土染料有限公司 | Red direct dye and preparation method thereof |
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