CN111925665B - Preparation method of active violet 5 - Google Patents
Preparation method of active violet 5 Download PDFInfo
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- CN111925665B CN111925665B CN202010842042.5A CN202010842042A CN111925665B CN 111925665 B CN111925665 B CN 111925665B CN 202010842042 A CN202010842042 A CN 202010842042A CN 111925665 B CN111925665 B CN 111925665B
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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
- C09B62/00—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves
- C09B62/44—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group not directly attached to a heterocyclic ring
- C09B62/503—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group not directly attached to a heterocyclic ring the reactive group being an esterified or non-esterified hydroxyalkyl sulfonyl or mercaptoalkyl sulfonyl group, a quaternised or non-quaternised aminoalkyl sulfonyl group, a heterylmercapto alkyl sulfonyl group, a vinyl sulfonyl or a substituted vinyl sulfonyl group, or a thiophene-dioxide group
- C09B62/507—Azo dyes
- C09B62/515—Metal complex azo dyes
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Abstract
The invention discloses a preparation method of active violet 5, and belongs to the field of dyes. A preparation method of active violet 5 comprises the following steps: s1: performing acylation reaction on H acid and acetic anhydride in a container, heating, adding sodium carbonate to adjust the pH value, and hydrolyzing to the end point to obtain H acid acylation liquid; s2: step S1, after the reaction is finished, adding para-ester diazonium salt, adding soda water to adjust the pH value, and coupling to obtain a coupling solution; s3: adding copper sulfate into the obtained coupling liquid, then mixing one or more than two of persulfate and percarbonate to prepare an oxidant, adding the oxidant into the coupling liquid to obtain an oxidation complex reactant; s4: and S3, after the oxidation and complexation are finished, adding alkali to adjust the pH value, filtering to remove insoluble substances, and spray-drying to obtain the active violet 5 dye product, wherein in the production process of the active violet 5, one or more than two of persulfate and percarbonate are mixed without adopting the traditional hydrogen peroxide to participate in the copper oxide complex reaction, so that the reaction is mild, the side effect is less, and the yield is improved.
Description
Technical Field
The invention relates to the field of dyes, in particular to a preparation method of active violet 5.
Background
The active violet 5 is a chemical substance, has a molecular formula of C20H16N3Na3O15S4, and is named as active violet 5 in Chinese; 5- (acetylamino) -4-hydroxy-3- [ [ 2-hydroxy-4- [ [2- (sulfooxy) ethyl ] sulfonyl ] phenyl ] azo ] -2-naphthalenesulfonic acid trisodium salt, molecular weight 735.5814.
The structural formula is as follows:
the current process of active violet 5 is that H acid and acetic anhydride are firstly acylated, then coupled with para-ester diazonium salt, hydrogen peroxide and copper sulfate are added for complexation, and finally potassium chloride is added for salting out and filtering to obtain the active violet 5.
However, in the existing process for producing the active violet 5, due to the fact that hydrogen peroxide has more oxidation side reactions and low yield, a large amount of waste water is easily generated, the environment is polluted, and the national environmental protection concept is not facilitated.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a preparation method of active violet 5.
In order to solve the above problems, the present invention adopts the following technical solutions.
A preparation method of active violet 5 comprises the following steps:
s1: acylation reaction
Performing acylation reaction on H acid and acetic anhydride in a container, heating, adding sodium carbonate to adjust the pH value, and hydrolyzing to the end point to obtain H acid acylation liquid;
s2: coupling reaction
Step S1, after the reaction is finished, adding para-ester diazonium salt, adding soda water to adjust the pH value, and coupling to obtain a coupling solution;
s3: copper oxide complex
Adding copper sulfate into the obtained coupling liquid, then mixing one or more than two of persulfate and percarbonate to prepare an oxidant, adding the oxidant into the coupling liquid to obtain an oxidation complex reactant;
s4: finished product
And step S3, adding alkali to adjust the pH value after the oxidation and complexation are finished, filtering to remove insoluble substances, and spray drying to obtain the active violet 5 dye product.
Further, the persulfate is any one or a mixture of two or more of sodium persulfate, potassium persulfate and ammonium persulfate, and the percarbonate is any one or a mixture of two or more of sodium percarbonate, potassium percarbonate and ammonium bicarbonate.
Further, the oxidizing agent in the step S3 is a mixture of sodium persulfate, potassium persulfate, and sodium percarbonate.
Further, the ratio of the H acid, the acetic anhydride, the para-ester diazonium salt, the oxidant, the copper sulfate and the potassium chloride is in a range of 1: 1.5-2.0:1.0-1.05:1.01-1.45: 1.0-1.1.
Further, the acylation reaction in the step S1 is carried out at the temperature of 15-40 ℃ for 2-3 hours, then the temperature is raised to 85-90 ℃, sodium carbonate is added to adjust the pH value to 8-8.2, and the hydrolysis is carried out to the end point; the hydrolysis end point is that the purity of the acetyl H acid is more than 97 percent by HPLC detection, and the temperature is reduced to 3-18 ℃ after the hydrolysis is finished.
Further, the temperature of the coupling reaction in the step S2 is 5-10 ℃, the time is 1-2 hours, and the pH is adjusted to 6.5-6.8.
Further, the temperature of the complexation reaction in the step S3 is 5-40 ℃, the pH is controlled to be 2-5, and the time is 5-6 hours.
Further, in the step S4, when no red color appears on the paper color layer in the paper color layer analysis method, the oxidation is complexed to the end point.
Further, the pH is adjusted to 6.0 to 6.5 in step S4.
Further, salting out is carried out on the filtrate in the step S4, and the active violet 5 dye product can be obtained.
Compared with the prior art, the invention has the advantages that:
in the production process of the active violet 5, the traditional hydrogen peroxide is not adopted, one or more than two of persulfate and percarbonate are adopted to be mixed to participate in the copper oxide complex reaction, the reaction is mild, the side effect is less, the yield is improved, in addition, a direct spray drying mode is adopted, when no salting-out process exists, no waste water is generated basically, and the concept of national environmental protection is facilitated.
Detailed Description
The technical scheme in the embodiment of the invention is clearly and completely described below; obviously; the described embodiments are only some of the embodiments of the invention; but not all embodiments, are based on the embodiments of the invention; all other embodiments obtained by a person skilled in the art without making any inventive step; all fall within the scope of protection of the present invention.
Example 1:
1. acylation reaction
Adding 440kg of H acid and 221kg of acetic anhydride into a 5t reaction kettle, reacting for 2 hours at the temperature of 20-30 ℃, then heating to 85-90 ℃, adding soda ash to adjust the pH value of 8-8.2, hydrolyzing to the end point (the HPLC detection content is more than 97%) to obtain an H acid acylation liquid, cooling to about 5 ℃, and then transferring to a 15t reaction kettle.
2. Coupling reaction
3300KG diazonium salt is quickly added to the H acid acylation liquid at 5-10 deg.C, coupled for 2 hours, and then 20% soda water is added to adjust pH to 6.5-6.8.
3. Copper oxide complexing:
adding 326KG copper sulfate into 1200KG ice water, stirring until the copper sulfate is completely dissolved to obtain a copper sulfate solution, quickly adding the copper sulfate solution into the coupling solution, wherein the pH value is 4.8-5.0 generally, stirring for 30 minutes, controlling the temperature within 10-15 ℃, then slowly adding 310KG sodium persulfate, monitoring the temperature in real time, adding a proper amount of crushed ice for cooling when the temperature exceeds 15 ℃, controlling the pH value to be 2-5, and stirring for 5-6 hours again, wherein the end point is that no red dye exists on a paper color layer.
4. Drying
And (3) slowly adding baking soda into the dye mother liquor oxidized to the end point to adjust the pH value to be 6.0-6.2, filtering after the pH value is stabilized, and collecting the filtrate for spraying.
5. Spray drying the virgin pulp to obtain the active violet 5 dye with the yield of 93 percent.
Example 2:
1. acylation reaction
Adding 440kg of H acid and 240kg of acetic anhydride into a 5t reaction pot at the temperature of 20-25 ℃, reacting for 2.5 hours, then heating to 85-90 ℃, adding soda ash to adjust the pH value of 8-8.2, hydrolyzing to the end point (the purity of acetyl H acid is more than 97% by HPLC) to obtain an H acid acylation liquid, cooling to 12 ℃, and transferring to a 15t reaction pot.
2. Coupling reaction
3330KG diazonium salt is quickly added into an H acid acylation liquid at 5-10 ℃, coupled for 2 hours, and then added with 20 percent of soda water to adjust the pH value to 6.5-6.8.
3. Copper oxide complexing:
1200KG of ice water is added with 326KG copper sulfate and stirred until the copper sulfate solution is completely dissolved to obtain a copper sulfate solution, the copper sulfate solution is quickly added into the coupling solution, the pH value is 4.8-5.0 generally, the stirring action is carried out for 30 minutes, the temperature is controlled within 15-20 ℃, then 212KG sodium percarbonate is slowly added, the temperature is monitored in real time, when the temperature exceeds 10 ℃, a proper amount of crushed ice is added for cooling, the pH value is controlled to be 2-5, the stirring is carried out for 5-6 hours, and the end point is that no red dye exists on a paper color layer.
4. Drying
And (3) slowly adding baking soda into the dye mother liquor oxidized to the end point to adjust the pH value to be 6.0-6.2, filtering after stabilization, and collecting the filtrate for spraying.
5. Spray drying the primary pulp to obtain the active violet 5 dye with the yield of 94%.
Example 3:
1. acylation reaction
Adding 440kg of H acid and 280kg of acetic anhydride into a 5t reaction pot at the temperature of 20-25 ℃, reacting for 2.5 hours, then heating to 85-90 ℃, adding soda ash to adjust the pH value of 8-8.2, hydrolyzing to the end point (the purity of acetyl H acid is more than 97% by HPLC) to obtain an H acid acylation liquid, cooling to 5 ℃, and transferring to a 15t reaction pot.
2. Coupling reaction
3350KG diazonium salt is quickly added into an H acid acylation liquid at 5-10 ℃, coupled for 2 hours, and then added with 20 percent of soda water to adjust the pH value to 6.5-6.8.
3. Copper oxide complexing:
adding 400KG of copper sulfate into 1200KG of ice water, stirring until the copper sulfate is completely dissolved to obtain a copper sulfate solution, quickly adding the copper sulfate solution into the coupling solution, wherein the pH value is 4.8-5.0 generally, stirring for 30 minutes, controlling the temperature within 10-15 ℃, then slowly adding 212KG of sodium persulfate and 100KG of potassium percarbonate, monitoring the temperature in real time, adding a proper amount of crushed ice for cooling when the temperature exceeds 10 ℃, controlling the pH value to be 2-5, and stirring for 5-6 hours again, wherein the end point is that no red dye exists on a paper color layer.
4. Drying
And (3) slowly adding baking soda into the dye mother liquor oxidized to the end point to adjust the pH value to be 6.0-6.2, filtering after stabilization, and collecting the filtrate for spraying.
5. Spray drying the primary pulp to obtain the active violet 5 dye with the yield of 95%.
Example 4:
1. acylation reaction
Adding 440kg of H acid and 240kg of acetic anhydride into a 5t reaction pot at the temperature of 20-25 ℃, reacting for 2.5 hours, then heating to 85-90 ℃, adding soda ash to adjust the pH value of 8-8.2, hydrolyzing to the end point (the purity of acetyl H acid is more than 97% by HPLC) to obtain an H acid acylation liquid, cooling to 6 ℃, and transferring to a 15t reaction pot.
2. Coupling reaction
3300KG diazonium salt is quickly added to the H acid acylation liquid at 5-10 deg.C, coupled for 2 hours, and then 20% soda water is added to adjust pH to 6.5-6.8.
3. Copper oxide complexing:
adding 340KG copper sulfate into 1200KG ice water, stirring until the copper sulfate solution is completely dissolved to obtain a copper sulfate solution, quickly adding the copper sulfate solution into the coupling solution, wherein the pH value is 4.8-5.0 generally, stirring for 30 minutes, controlling the temperature within 5-10 ℃, then slowly adding 212KG sodium persulfate and 100KG sodium percarbonate, monitoring the temperature in real time, adding a proper amount of crushed ice for cooling when the temperature exceeds 10 ℃, controlling the pH value to be 2-5, and stirring for 5-6 hours again, wherein the end point is that no red dye exists on a paper color layer.
4. Drying
Adding sodium bicarbonate slowly into the dye mother liquor until the oxidation is finished to adjust the pH value to 6.0-6.2. And filtering after stabilization, and collecting filtrate for spraying.
5. Spray drying the primary pulp to obtain the active violet 5 dye with the yield of 94%.
Example 5:
1. acylation reaction
Adding 440kg of H acid and 240kg of acetic anhydride into a 5t reaction pot at the temperature of 20-25 ℃, reacting for 2.5 hours, then heating to 85-90 ℃, adding soda ash to adjust the pH value of 8-8.2, hydrolyzing to the end point (the purity of acetyl H acid is more than 97% by HPLC) to obtain an H acid acylation liquid, cooling to 12 ℃, and transferring to a 15t reaction pot.
2. Coupling reaction
The diazo salt is added into the H acid acylation liquid at 13-18 ℃ quickly, the coupling is carried out for 2 hours, and 20 percent of soda water is added to adjust the pH value to 6.5-6.8.
3. Copper oxide complexing:
1200KG of ice water is added with 330KG copper sulfate and stirred until a copper sulfate solution is obtained completely, the copper sulfate solution is quickly added into the coupling solution, the pH value is 4.8-5.0 generally, the stirring action is carried out for 30 minutes, the temperature is controlled within 10-15 ℃, then 212KG sodium percarbonate and 100KG potassium percarbonate are slowly added, the temperature is monitored in real time, when the temperature exceeds 15 ℃, a proper amount of crushed ice is added for cooling, the pH is controlled to be 2-5, the stirring is carried out for 5-6 hours, and the end point is that no red dye exists on a paper color layer.
4. Drying
And (3) slowly adding baking soda into the dye mother liquor oxidized to the end point to adjust the pH value to be 6.0-6.2, filtering after stabilization, and collecting the filtrate for spraying.
5. Spray drying the primary pulp to obtain the active violet 5 dye with the yield of 94%.
Comparative example 6:
1. acylation reaction
Adding 440kg of H acid and 221kg of acetic anhydride into a 5t reaction pot, reacting at 20-30 ℃ for 2.5 hours, heating to 85-90 ℃, adding soda ash to adjust the pH value to 8-8.2, hydrolyzing to the end point (the purity of acetyl H acid is more than 97% by HPLC) to obtain an H acid acylation liquid, cooling to 15 ℃, and transferring to a 15t reaction pot.
2. Coupling reaction
The diazo salt is quickly added into H acid acylation liquid at 15-20 ℃, coupled for 2 hours, and added with 20% soda water to adjust the pH value to 6.5-6.8.
3. Copper oxide complexing:
adding 1000KG of water into a 5t reaction kettle, adding 326KG copper sulfate, heating to 60 ℃, stirring until the mixture is completely dissolved to obtain a copper sulfate solution, quickly adding the copper sulfate solution into the coupling solution, wherein the pH value is 4.8-5.0 generally, stirring for 30 minutes, controlling the temperature within 23 ℃, injecting hydrogen peroxide by using a 3-hour trickle, naturally raising the temperature to 25-30 ℃, controlling the temperature not to exceed 30 ℃, cooling by adding a proper amount of crushed ice, after the addition is finished, stirring for 3 hours, oxidizing to the end point, wherein the end point is that no red dye exists on a paper color layer. Volume 11000-12000L.
4. Salting out and drying
Measuring the volume of the dye mother liquor oxidized to the end point, slowly adding 25% potassium chloride according to the volume, preserving the heat at 20-23 ℃, stirring and salting out, stirring for 5 hours, separating out a large amount of materials, stopping stirring for 2 hours, performing spot clear filter pressing, drying, finally performing 11.5T/1.3KMol volume, collecting filter cakes, adding 6000L of bottom water, pulping, and slowly adding sodium bicarbonate to adjust the pH value to 6.0-6.2; after stabilization, the stirring is stopped for spraying.
5. And (3) spray-drying the primary pulp to obtain the active violet 5 dye with the yield of 75%.
The above; but are merely preferred embodiments of the invention; the scope of the invention is not limited thereto; any person skilled in the art is within the technical scope of the present disclosure; the technical scheme and the improved concept of the invention are equally replaced or changed; are intended to be covered by the scope of the present invention.
Claims (10)
1. A preparation method of active violet 5 is characterized by comprising the following steps: the method comprises the following steps:
s1: acylation reaction
Performing acylation reaction on H acid and acetic anhydride in a container, heating, adding sodium carbonate to adjust the pH value, and hydrolyzing to the end point to obtain H acid acylation liquid;
s2: coupling reaction
Step S1, after the reaction is finished, adding para-ester diazonium salt, adding soda water to adjust the pH value, and coupling to obtain a coupling solution;
s3: copper oxide complex
Adding copper sulfate into the obtained coupling liquid, then mixing one or more than two of persulfate and percarbonate to prepare an oxidant, adding the oxidant into the coupling liquid, and controlling the pH value to obtain an oxidation complex reactant;
s4: finished product
And step S3, adding alkali to adjust the pH value after the oxidation and complexation are finished, filtering to remove insoluble substances, and spray drying to obtain the active violet 5 dye product.
2. The method of claim 1, wherein the method further comprises: the persulfate is any one or a mixture of more than two of sodium persulfate, potassium persulfate and ammonium persulfate, and the percarbonate is any one or a mixture of more than two of sodium percarbonate, potassium percarbonate and ammonium bicarbonate.
3. The method of claim 2, wherein the method comprises: the oxidant in the step S3 is a mixture of sodium persulfate, potassium persulfate and sodium percarbonate.
4. The method of claim 1, wherein the method further comprises: the ratio of the H acid, the acetic anhydride, the para-ester diazonium salt, the oxidant and the copper sulfate is 1: 1.5-2.0:1.0-1.05:1.01-1.45: 1.0-1.1.
5. The method of claim 1, wherein the method further comprises: and S1, the acylation reaction is carried out at 15-40 ℃ for 2-3 hours, the temperature is raised to 85-90 ℃, sodium carbonate is added to adjust the pH value to 8-8.2, and the hydrolysis end point is that the purity of the acetyl H acid detected by HPLC is more than 97%.
6. The method of claim 1, wherein the method further comprises: the temperature of the coupling reaction in the step S2 is 5-10 ℃, the time is 1-2 hours, and the pH is adjusted to 6.5-6.8.
7. The method of claim 1, wherein the method further comprises: and S3, the temperature of the complexation reaction is 5-40 ℃, the pH is controlled to be 2-5, and the time is 5-6 hours.
8. The method of claim 1, wherein the method further comprises: in the step S4, when no red color appears on the paper color layer in the paper color layer analysis method, the oxidation is complexed to the end point.
9. The method of claim 1, wherein the method further comprises: the pH is adjusted to 6.0-6.5 in step S4.
10. The method of claim 1, wherein the method further comprises: and S4, filtering to remove insoluble substances, and salting out the filtrate to obtain the active violet 5 dye product.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| PL168108B1 (en) * | 1992-08-21 | 1996-01-31 | Zaklady Przemyslu Barwnikow Bo | Method of obtaining metal complex reactive violet dye constituting a derivative of s-azine |
| CN102329523A (en) * | 2010-07-13 | 2012-01-25 | 明德国际仓储贸易(上海)有限公司 | Reactive printing dye and application of liquid composition thereof |
| CN106459607A (en) * | 2014-04-22 | 2017-02-22 | 美利肯公司 | Organic Colorant Complexes From Reactive Dyes And Articles Containing The Same |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI425055B (en) * | 2009-08-21 | 2014-02-01 | Everlight Chem Ind Corp | Reactive printing dye and its aqueoues composition application |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| PL168108B1 (en) * | 1992-08-21 | 1996-01-31 | Zaklady Przemyslu Barwnikow Bo | Method of obtaining metal complex reactive violet dye constituting a derivative of s-azine |
| CN102329523A (en) * | 2010-07-13 | 2012-01-25 | 明德国际仓储贸易(上海)有限公司 | Reactive printing dye and application of liquid composition thereof |
| CN106459607A (en) * | 2014-04-22 | 2017-02-22 | 美利肯公司 | Organic Colorant Complexes From Reactive Dyes And Articles Containing The Same |
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