CN111087833A - Industrial synthesis method of vat blue 6 - Google Patents
Industrial synthesis method of vat blue 6 Download PDFInfo
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- CN111087833A CN111087833A CN201911365680.6A CN201911365680A CN111087833A CN 111087833 A CN111087833 A CN 111087833A CN 201911365680 A CN201911365680 A CN 201911365680A CN 111087833 A CN111087833 A CN 111087833A
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- vat blue
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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
- C09B5/00—Dyes with an anthracene nucleus condensed with one or more heterocyclic rings with or without carbocyclic rings
- C09B5/24—Dyes with an anthracene nucleus condensed with one or more heterocyclic rings with or without carbocyclic rings the heterocyclic rings being only condensed with an anthraquinone nucleus in 1-2 or 2-3 position
- C09B5/44—Azines of the anthracene series
- C09B5/46—Para-diazines
- C09B5/48—Bis-anthraquinonediazines (indanthrone)
- C09B5/56—Preparation from starting materials already containing the indanthrene nucleus
- C09B5/58—Preparation from starting materials already containing the indanthrene nucleus by halogenation
-
- 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
- C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
- C09B67/0071—Process features in the making of dyestuff preparations; Dehydrating agents; Dispersing agents; Dustfree compositions
- C09B67/0077—Preparations with possibly reduced vat, sulfur or indigo dyes
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to the technical field of dyes, in particular to an industrial synthesis method of vat blue 6, which comprises the following steps: adding the solid of the vat blue 4 into an aromatic inert solvent to obtain a vat blue 4 solution or suspension; adding sulfonyl chloride into the reduction blue 4 solution or suspension, and controlling the temperature of the solution to be 20-40 ℃ in the adding process; after the addition is finished, heating for reaction; after the reaction is finished, adding water into the reaction liquid to dilute the material, and adding alkali to adjust the pH of the reaction liquid to 7-10; and after the pH of the reaction liquid is adjusted, heating and distilling the reaction liquid, transferring the materials to a filter press for filter pressing after the solvent is distilled, and then purging with hot water until the pH value is 5-8, and discharging to obtain a vat blue 6 finished product. The solvent used in the industrial synthesis method of vat blue 6 provided by the invention has good thermal stability and is easy to regenerate, the material quality can be further ensured, and meanwhile, the solvent can be recycled by water vapor distillation in a physical method, so that the resource is better utilized, and the discharge of waste acid and waste salt is reduced.
Description
Technical Field
The invention relates to the technical field of dyes, in particular to an industrial synthesis method of vat blue 6.
Background
The vat dyes are of various varieties, have excellent fastness, and are particularly outstanding in light fastness and washing fastness, so the vat dyes are all important dyes for cotton cloth dyes and printing. However, the problem of great environmental pollution is always accompanied in the production and use processes for a long time, the green technology in the dye production process is researched and developed, novel production equipment is designed, manufactured and applied, industrial production and application are carried out, raw material and energy consumption are reduced, the discharge amount of three wastes and treatment difficulty are reduced, clean process production is realized, the purposes of energy conservation and emission reduction are achieved, and the method has important economic and social significance and is very urgent work.
The vat blue 6 dye is anthraquinone vat dye, belongs to blue anthrone vat dye pigment, has the same structure with the pigment blue 64, gives green blue tone, has excellent application fastness and heat-resisting stability, has the light fastness of 7 grade, and resists chlorine bleaching. The dye is mainly used for dyeing cotton fibers, and has the advantages of good affinity, quick coloring, and moderate level-dyeing property. Less used for printing and more used for color matching. The dye can be used for dyeing silk, viscose fiber, viscose cotton and vinylon, and also can be used for the one-bath hot melting dyeing of polyester-cotton blended fabric and disperse dye.
The structural formula of vat blue 6 is as follows:
chemical name: vat blue 6
English name: vat Blue 6
CAS No.：130-20-1
The molecular formula is as follows: c28H12Cl2N2O4
Molecular weight: 511.31g/mol
The method for producing the vat blue 6 reported before comprises the steps of introducing chlorine into the vat blue 4 by using sulfuric acid as a solvent and adding manganese dioxide as a catalyst, chlorinating until the end point, filtering, washing by using 75% sulfuric acid, pulping the obtained material by adding fuming sulfuric acid, reducing the material in sodium sulfite solution, filtering and washing by water to obtain the vat blue 6. The process has high raw material consumption, difficult recovery and high production cost, and causes a large amount of waste acid to be discharged and serious environmental pollution.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: provides an industrial synthesis method of vat blue 6 with high raw material recycling rate, easily controlled process and low cost.
The technical scheme for solving the technical problems is as follows:
an industrial synthesis method of vat blue 6 comprises the following steps:
(1) adding the solid of the vat blue 4 into an aromatic inert solvent to obtain a vat blue 4 solution or suspension;
(2) adding sulfonyl chloride into the reduction blue 4 solution or suspension, and controlling the temperature of the solution to be 20-40 ℃ in the adding process; after the addition is finished, heating for reaction;
(3) after the reaction is finished, adding water into the reaction liquid to dilute the material, and adding alkali to adjust the pH of the reaction liquid to 7-10;
(4) after the pH of the reaction liquid is adjusted, heating and distilling the reaction liquid, condensing and collecting the evaporated vapor phase to a separator through a condenser, transferring the lower-layer solvent to a recovered solvent transfer tank for use in the next batch of reaction, and collecting the upper-layer water to a recovered water tank for use in the dilution of the next batch of materials; and after the solvent is distilled, transferring the material to a filter press for filter pressing, and then purging with hot water until the pH value is 5-8, and discharging to obtain a vat blue 6 finished product.
Preferably, the aromatic inert solvent in step (1) is selected from chlorobenzene, o-dichlorobenzene and nitrobenzene.
Preferably, the mass ratio of the aromatic inert solvent to the vat blue 4 material in the step (1) is 2-10: 1; further, in the step (1), the mass ratio of the aromatic inert solvent to the vat blue 4 material is 2-4: 1.
preferably, the mole ratio of the vat blue 4 to the sulfonyl chloride in the step (2) is 1: 1.5-8; further, the mole ratio of the vat blue 4 to the sulfonyl chloride in the step (2) is 1: 2.5 to 5.
Preferably, the heating reaction temperature in the step (2) is 70-90 ℃.
Preferably, the mass of the water added for diluting the materials in the step (3) is 1-10 times of that of the solid of the vat blue 4; further, the mass of water added for diluting the materials in the step (3) is 2-5 times that of the solid of the vat blue 4; the water may be replaced by the supernatant water recovered in step (4).
Preferably, the alkali added in the step (3) is selected from sodium hydroxide or sodium carbonate; further, the alkali to be added is selected from an aqueous solution of sodium hydroxide or sodium carbonate powder.
Preferably, the temperature of the hot water in the step (4) is 70-90 ℃.
Preferably, the method for synthesizing vat blue 6 further comprises the following steps: adding the solid of the vat blue 4 into an inert solvent for dissolving, heating to the temperature near the boiling point of the solvent, and dehydrating; specifically, the water in the vat blue 4 is removed by using a solvent which can be azeotroped with water, so that the water in the vat blue 4 is prevented from reacting with sulfonyl chloride to bring about byproducts in the step (2); and after the dehydration is finished, cooling to 20-40 ℃. The inventors found that if the moisture content in the dried product of the raw material vat blue 4 is 1% or more, it is necessary to perform a water removal step; the moisture content in the solid of the raw material vat blue 4 is not more than 5 percent, and the anhydrous vat blue 4 can be obtained by adopting the water removing scheme.
The Chinese naming of the compounds of the present invention conflicts with the structural formula, whichever is more.
The solvent used in the industrial synthesis method of vat blue 6 provided by the invention has good thermal stability and is easy to regenerate, the loss amount carried under steam pressure is smaller, the discharge of a large amount of waste acid caused by chlorination by the existing sulfuric acid method is reduced, the material quality can be further ensured, the solvent can be recycled by physical water vapor distillation, the resource can be better utilized, the discharge of waste acid and waste salt is reduced, and the method is an economic, green and environment-friendly production process route.
Detailed Description
The invention is illustrated but not limited by the following examples. The technical solutions protected by the present invention are all the simple replacements or modifications made by the skilled person in the art.
Example 1:
(1) through detection, the water content of the raw material vat blue 4 dry powder material is 2%; adding 2000L chlorobenzene from a metering tank, starting stirring, putting 500Kg of a reduced blue 4 dry powder material into a 3000L condensation kettle once under the stirring condition, heating by steam to 110-112 ℃, dehydrating for 1 hour, and cooling;
(2) cooling to 30-35 ℃, dropwise adding 400Kg of sulfonyl chloride from the metering tank, heating the material to 80-85 ℃ after adding, carrying out heat preservation reaction for 5 hours, and sampling to measure the chlorine content of the material; stopping heating after the chlorine content is qualified;
(3) adding 500L of water into a reaction kettle to dilute the material, and then adding sodium hydroxide until the pH of the material is neutralized to 8-10 (the alkali dosage is based on the actual pH);
(4) the material is heated and distilled by the straight-through steam, the evaporated vapor phase is condensed and collected to a separator by a condenser, the solvent at the lower layer is transferred to a recovered solvent transfer tank and used for the next batch of reaction, and the water at the upper layer is collected to a recovered water tank and used for diluting the next batch of material; and after the solvent is distilled, transferring the material to a filter press for filter pressing, then purging with hot water at the temperature of 80-85 ℃ until the pH value is 5-8, discharging and packaging.
The reduced blue 6 obtained by this reaction was high-grade product with an intensity of 260, DC-0.03 and DH 0.11 by mass, yield: 99.6 percent.
Example 2:
(1) through detection, the water content in the raw material vat blue 4 dry powder material is 0.5%; adding the o-dichlorobenzene in an amount of 1500L from a metering tank, starting stirring, putting 500Kg of the reduced blue 4 dry powder material into a 3000L condensation kettle once under the stirring condition, heating to 100-110 ℃, uniformly stirring, and cooling;
(2) cooling to 30-35 ℃, dropwise adding 750Kg of sulfonyl chloride from the metering tank, heating the materials to 85-90 ℃ after adding, carrying out heat preservation reaction for 5 hours, and sampling to measure the chlorine content of the materials; stopping heating after the chlorine content is qualified;
(3) adding 1000L of the upper-layer water recovered in the step (4) into the reaction kettle to dilute the material, and then adding sodium carbonate until the pH of the material is neutralized to 7-9 (the alkali dosage is based on the actual pH);
(4) the material is heated and distilled by the straight-through steam, the evaporated vapor phase is condensed and collected to a separator by a condenser, the solvent at the lower layer is transferred to a recovered solvent transfer tank and used for the next batch of reaction, and the water at the upper layer is collected to a recovered water tank and used for diluting the next batch of material; and after the solvent is distilled, transferring the material to a filter press for filter pressing, then purging with hot water at the temperature of 80-85 ℃ until the pH value is 5-8, discharging and packaging.
The reduced blue 6 obtained by this reaction was high-grade product with an intensity of 260, DC-0.03 and DH 0.11 by mass, yield: 99.4 percent.
Example 3:
(1) through detection, the water content in the raw material vat blue 4 dry powder material is 1.0 percent; adding 1200L chlorobenzene from a metering tank, starting stirring, putting 500Kg of a reduced blue 4 dry powder material into a 2000L condensation pot once under the stirring condition, heating the steam to 110-112 ℃, dehydrating for 1 hour, and cooling;
(2) cooling to 30-35 ℃, dropwise adding 450Kg of sulfonyl chloride from the metering tank, heating the materials to 75-85 ℃ after adding, carrying out heat preservation reaction for 5 hours, and sampling to measure the chlorine content of the materials; stopping heating after the chlorine content is qualified;
(3) adding 750L of water into a reaction kettle to dilute the material, and then adding sodium hydroxide until the pH of the material is neutralized to 8-10 (the alkali dosage is based on the actual pH);
(4) the material is heated and distilled by the straight-through steam, the evaporated vapor phase is condensed and collected to a separator by a condenser, the solvent at the lower layer is transferred to a recovered solvent transfer tank and used for the next batch of reaction, and the water at the upper layer is collected to a recovered water tank and used for diluting the next batch of material; and after the solvent is distilled, transferring the material to a filter press for filter pressing, then purging with hot water at the temperature of 80-85 ℃ until the pH value is 5-8, discharging and packaging.
The reduced blue 6 obtained by this reaction was high-grade product with an intensity of 260, DC-0.03 and DH 0.11 by mass, yield: 99.8 percent.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various changes and modifications can be made without departing from the inventive concept of the present invention, and these changes and modifications are all within the scope of the present invention.
Claims (10)
1. An industrial synthesis method of vat blue 6 is characterized by comprising the following steps:
(1) adding the solid of the vat blue 4 into an aromatic inert solvent to obtain a vat blue 4 solution or suspension;
(2) adding sulfonyl chloride into the reduction blue 4 solution or suspension, and controlling the temperature of the solution to be 20-40 ℃ in the adding process; after the addition is finished, heating for reaction;
(3) after the reaction is finished, adding water into the reaction liquid to dilute the material, and adding alkali to adjust the pH of the reaction liquid to 7-10;
(4) after the pH of the reaction liquid is adjusted, heating and distilling the reaction liquid, condensing and collecting the evaporated vapor phase to a separator through a condenser, transferring the lower-layer solvent to a recovered solvent transfer tank for use in the next batch of reaction, and collecting the upper-layer water to a recovered water tank for use in the dilution of the next batch of materials; after the solvent is distilled, transferring the material to a filter press for filter pressing, and then, purging with hot water until the pH value is 5-8, and discharging to obtain a vat blue 6 finished product;
2. the industrial synthesis method of vat blue 6, according to claim 1, wherein in step (1), the aromatic inert solvent is selected from chlorobenzene, o-dichlorobenzene and nitrobenzene.
3. The industrial synthesis method of vat blue 6 as claimed in claim 1, wherein the mass ratio of the aromatic inert solvent to the vat blue 4 in step (1) is 2-10: 1.
4. the industrial synthesis method of vat blue 6 as claimed in claim 3, wherein the mass ratio of the aromatic inert solvent to the vat blue 4 material in step (1) is 2-4: 1.
5. the industrial synthesis method of vat blue 6 according to claim 1, wherein the mole ratio of vat blue 4 to sulfonyl chloride in step (2) is 1: 1.5 to 8.
6. The industrial synthesis method of vat blue 6 according to claim 1, wherein the temperature of the heating reaction in step (2) is 70-90 ℃.
7. The industrial synthesis method of vat blue 6 as claimed in claim 1, wherein the mass of water added for diluting the material in step (3) is 1-10 times of that of vat blue 4 solid; the water can be replaced with the supernatant water recovered in step (4).
8. The industrial synthesis method of vat blue 6, according to claim 1, wherein the base added in step (3) is selected from sodium hydroxide or sodium carbonate.
9. The industrial synthesis method of vat blue 6 according to claim 1, wherein the temperature of hot water in step (4) is 70-90 ℃.
10. The industrial synthesis method of vat blue 6 according to any of claims 1 to 9, wherein said method for synthesizing vat blue 6 further comprises the following steps: adding the solid of the vat blue 4 into an inert solvent for dissolving, heating to the temperature near the boiling point of the solvent, and dehydrating; and after the dehydration is finished, cooling to 20-40 ℃.
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| CN201911365680.6A CN111087833A (en) | 2019-12-26 | 2019-12-26 | Industrial synthesis method of vat blue 6 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112778789A (en) * | 2021-01-06 | 2021-05-11 | 贺潇寒 | Method for chlorinating blue anthrone, violanthrone or isoviolanthrone |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112778789A (en) * | 2021-01-06 | 2021-05-11 | 贺潇寒 | Method for chlorinating blue anthrone, violanthrone or isoviolanthrone |
| CN112778789B (en) * | 2021-01-06 | 2021-11-12 | 贺潇寒 | Method for chlorinating blue anthrone, violanthrone or isoviolanthrone |
| WO2022147994A1 (en) * | 2021-01-06 | 2022-07-14 | 贺潇寒 | Method for chlorinating indanthrone blue, violanthrone or isoviolanthrone |
| EP4053220A4 (en) * | 2021-01-06 | 2022-12-14 | He, Xiaohan | Method for chlorinating indanthrone blue, violanthrone or isoviolanthrone |
| US20230159761A1 (en) * | 2021-01-06 | 2023-05-25 | Xiaohan HE | Method for chlorinating blue anthrone, violanthrone or isoviolantrone |
| US11939475B2 (en) | 2021-01-06 | 2024-03-26 | Xiaohan HE | Method for chlorinating blue anthrone, violanthrone or isoviolantrone |
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