CN112210229A - Preparation method of cationic liquid dye - Google Patents
Preparation method of cationic liquid dye Download PDFInfo
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- CN112210229A CN112210229A CN201910627570.6A CN201910627570A CN112210229A CN 112210229 A CN112210229 A CN 112210229A CN 201910627570 A CN201910627570 A CN 201910627570A CN 112210229 A CN112210229 A CN 112210229A
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- water
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- cationic liquid
- target dye
- dye molecule
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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
- C09B43/11—Preparation of azo dyes from other azo compounds by introducing hydrocarbon radicals or substituted hydrocarbon radicals on primary or secondary amino groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D285/00—Heterocyclic compounds containing rings having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by groups C07D275/00 - C07D283/00
- C07D285/01—Five-membered rings
- C07D285/02—Thiadiazoles; Hydrogenated thiadiazoles
- C07D285/04—Thiadiazoles; Hydrogenated thiadiazoles not condensed with other rings
- C07D285/12—1,3,4-Thiadiazoles; Hydrogenated 1,3,4-thiadiazoles
- C07D285/125—1,3,4-Thiadiazoles; Hydrogenated 1,3,4-thiadiazoles with oxygen, sulfur or nitrogen atoms, directly attached to ring carbon atoms, the nitrogen atoms not forming part of a nitro radical
- C07D285/135—Nitrogen atoms
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Abstract
The invention discloses a preparation method of a cationic liquid dye. Taking a target dye molecule matrix as an initial raw material, dimethyl sulfate as a methylation reagent, and a weakly alkaline inorganic oxide as an acid-binding agent, carrying out methylation reaction in a weakly acidic system, methylating the target dye molecule matrix into target dye molecules, adding water and an organic solvent immiscible with water into the system, heating and dissolving, extracting inorganic salt ions into a water phase, cooling to room temperature, standing for phase separation, separating out the water phase, concentrating the organic phase, recovering the organic solvent, and preparing a cationic liquid dye from the rest organic matters. The method is simple and convenient to operate, can be well applied to industrial production, is low in cost, is green and environment-friendly in the whole process, improves the application performance of the existing product, and enlarges the application range of the existing product.
Description
Technical Field
The invention relates to a preparation method of a cationic liquid dye, belonging to the technical field of dyes.
Background
Currently, the existing preparation method of cationic liquid dyes (blue-159, red-46 and blue-41) is to take a target dye molecule parent as a starting material and dimethyl sulfate as a methylating agent to perform methylation reaction under a weak acid system to methylate the target dye molecule parent into a target dye molecule, and then perform standardized preparation to prepare a standardized commodity liquid dye.
The existing synthesis preparation process is applied to a weak alkaline inorganic oxide (magnesium oxide) serving as an acid-binding agent, the existence of the acid-binding agent can ensure that methylation reaction can be smoothly and completely carried out, the obtained liquid dye can be applied to dyeing of general paper, acrylic fibers, terylene and other general materials, but the acetone insoluble index is too high for dyeing of special materials (such as wigs), so that the dyeing performance is greatly reduced, and the application of products is further limited.
Disclosure of Invention
In view of the above, the invention provides a preparation method of a cationic liquid dye, which is simple and convenient to operate, can be better applied to industrial production, is low in cost, is green and environment-friendly in the whole process, improves the application performance of the existing product, and expands the application range of the existing product.
The invention solves the technical problems by the following technical means:
the invention relates to a method for preparing cationic liquid dye, which takes target dye molecule parent as initial raw material, and the structural formula is as follows:
dimethyl sulfate is a methylating agent, weakly alkaline inorganic oxide is an acid-binding agent, methylation reaction is carried out in a weakly acidic system, a target dye molecule matrix is methylated into a target dye molecule, then water and an organic solvent immiscible with water are added into the system, extraction is carried out after heating and dissolving, inorganic salt ions are extracted into a water phase, then the temperature is reduced to room temperature, standing and phase splitting are carried out, the water phase is separated out, the organic phase is concentrated and recovered, and the residual organic matter is used for preparing the cationic liquid dye.
The weakly alkaline inorganic oxide is magnesium oxide.
The weak acid system is acetic acid.
The organic solvent immiscible with water is at least one of dichloroethane, dichloromethane, chloroform, toluene and chlorobenzene.
The methylation reaction process is as follows: mixing a target dye molecule matrix, an acid binding agent, acetic acid and water according to a certain proportion, wherein the dosage of the acid binding agent is 0.5-1.05 times of the molar weight of the target dye molecule matrix, the mass ratio of the acetic acid to the water is 2:1, and the total mass of the acetic acid and the water is 4.0-5.0 times of that of a reaction substrate, putting the two into a reaction container together, dropwise adding a methylation reagent dimethyl sulfate at room temperature, wherein the dosage of the dimethyl sulfate is 2.0-3.0 times of the molar weight of the reaction substrate, and after dropwise adding, carrying out heat preservation reaction at room temperature until the substrate is completely converted.
The extraction process comprises the steps of uniformly mixing the materials with an extraction solvent, stirring for dissolving, standing, enabling target dye molecules to enter an organic phase, enabling inorganic impurity ions and other impurities with high solubility in water to enter a water phase, and then separating the organic phase from the water phase by phase separation.
The invention solves the problem of overhigh content of the acetone insoluble substance in the product through a specific technical scheme, ensures that the content of the acetone insoluble substance in the product is lower than 50ppm, recovers the excellent dyeing property characteristic of the product and enlarges the application range of the product.
The technological scheme of the present invention is that the original synthesis process is improved, and the target dye molecule precursor is first prepared into the methylation reaction in weak acid system, and the methylation reaction is then heated to dissolve and extract with certain amount of water and water immiscible organic solvent, such as dichloroethane, dichloromethane, chloroform, toluene, chlorobenzene, etc. the inorganic salt ion affecting the acetone insoluble matter content is extracted into water phase, the water phase is separated out, the organic phase is concentrated to recover the organic solvent, and the liquid dye is finally standardized to prepare the standard liquid dye in special specification.
(1) Compared with the original process, the method increases the steps of dissolving, extracting, phase splitting and solvent recovery, and is characterized by the steps of dissolving and extracting and the selection of the types and the dosage of the dissolving and extracting solvents; (2) the content of acetone insoluble substances in the product with the new specification is lower than 50ppm, the product performance of the product with the older specification is improved, the application range is increased, and the key point is that the content of the acetone insoluble substances is extremely low (less than 50 ppm); (3) the whole process has no three wastes, is a green and environment-friendly process technology, and is mainly developed and applied.
The invention has the beneficial effects that: (1) the method is simple and convenient to operate, and can be better applied to industrial production only by adding the steps of dissolving, extracting, phase splitting and solvent concentration and recovery on the basis of the original process; (2) the cost is increased less, only one raw material of the solvent for dissolving and extracting is added in the whole process, and the solvent can be recycled and reused, so that the process cost is increased less; (3) the whole process is relatively green and environment-friendly, and three wastes are not generated in the whole process, so that the process is a relatively green and environment-friendly technical process; (4) improves the application performance of the existing product and enlarges the application range of the existing product.
Detailed Description
The present invention will be described in detail with reference to the following specific examples, in which the method of the present invention for preparing a cationic liquid dye uses a target dye molecule precursor as a starting material, and the structural formula of the method is as follows:
dimethyl sulfate is a methylating agent, weakly alkaline inorganic oxide is an acid-binding agent, methylation reaction is carried out in a weakly acidic system, a target dye molecule matrix is methylated into a target dye molecule, then water and an organic solvent immiscible with water are added into the system, extraction is carried out after heating and dissolving, inorganic salt ions are extracted into a water phase, then the temperature is reduced to room temperature, standing and phase splitting are carried out, the water phase is separated out, the organic phase is concentrated and recovered, and the residual organic matter is used for preparing the cationic liquid dye.
The weakly alkaline inorganic oxide is magnesium oxide.
The weak acid system is acetic acid.
The organic solvent immiscible with water is at least one of dichloroethane, dichloromethane, chloroform, toluene and chlorobenzene.
The methylation reaction process is as follows: mixing a target dye molecule matrix, an acid binding agent, acetic acid and water according to a certain proportion, wherein the dosage of the acid binding agent is 0.5-1.05 times of the molar weight of the target dye molecule matrix, the mass ratio of the acetic acid to the water is 2:1, and the total mass of the acetic acid and the water is 4.0-5.0 times of that of a reaction substrate, putting the two into a reaction container together, dropwise adding a methylation reagent dimethyl sulfate at room temperature, wherein the dosage of the dimethyl sulfate is 2.0-3.0 times of the molar weight of the reaction substrate, and after dropwise adding, carrying out heat preservation reaction at room temperature until the substrate is completely converted.
The extraction process comprises the steps of uniformly mixing the materials with an extraction solvent, stirring for dissolving, standing, enabling target dye molecules to enter an organic phase, enabling inorganic impurity ions and other impurities with high solubility in water to enter a water phase, and then separating the organic phase from the water phase by phase separation.
The target dye molecule parent is obtained by taking a dye intermediate molecule as a raw material and carrying out methylation reaction on the dye intermediate molecule, wherein the specific molecular structure of the target dye molecule is as follows:
the methylation reaction conditions are as follows: the method comprises the steps of putting a reaction substrate (a target dye molecule matrix), an acid-binding agent, acetic acid and water into a reaction container according to a certain proportion (the dosage of the acid-binding agent is 0.5-1.05 times of the molar quantity of the reaction substrate and is preferably 0.6 times of the molar quantity, the dosage ratio of the acetic acid to the water is 2:1, and the total mass of the acetic acid and the water is 4.0-5.0 times of the reaction substrate), dropwise adding a methylation reagent dimethyl sulfate (the dosage is 2.0-3.0 times of the molar quantity of the reaction substrate and is preferably 2.8 times of the molar quantity) at room temperature, and keeping the temperature at room temperature after dropwise adding until the substrate is completely converted.
The specific embodiment is as follows:
33g of blue-159 precursor dry product and 2.3g of magnesium oxide are added into a 500ml four-mouth reaction bottle, and then 50g of water and 100g of acetic acid are added and stirred uniformly. Slowly dripping 33.0g of dimethyl sulfate at room temperature (20-25 ℃), and controlling the temperature in the pot to be 20-25 ℃ (finishing dripping about 1 hour). Controlling the temperature of the material at 20-25 ℃, preserving heat and stirring for 3 hours; sampling was performed for methylation endpoint (TLC: n-butanol: water: 4: 1: 5 or toluene: ethanol: 4:1, end of reaction as soon as the parent plaque disappeared)
Extraction is a process in which a solute is extracted from a solution of the solute in a solvent other than the one in which the solute is soluble, by utilizing the difference in solubility of the solute in the solvents.
The extraction process utilizes the difference of the solubility of target dye molecules in a material system and unnecessary inorganic ions and other impurities in a product in an aqueous phase and an organic phase, the material and an extraction solvent are uniformly mixed and stirred for dissolution and standing, so that the target dye molecules enter the organic phase, the inorganic impurity ions and the impurities with higher solubility in water enter the aqueous phase, and then the organic phase and the aqueous phase are separated by phase separation, thereby achieving the effect of removing the inorganic ions and the other impurities.
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 method for preparing cationic liquid dye is characterized in that target dye molecule parent is used as starting material, and the structural formula is as follows:
dimethyl sulfate is a methylating agent, weakly alkaline inorganic oxide is an acid-binding agent, methylation reaction is carried out in a weakly acidic system, a target dye molecule matrix is methylated into a target dye molecule, then water and an organic solvent immiscible with water are added into the system, extraction is carried out after heating and dissolving, inorganic salt ions are extracted into a water phase, then the temperature is reduced to room temperature, standing and phase splitting are carried out, the water phase is separated out, the organic phase is concentrated and recovered, and the residual organic matter is used for preparing the cationic liquid dye.
2. A method of dyeing a cationic liquid according to claim 1, characterized in that: the weakly alkaline inorganic oxide is magnesium oxide.
3. A method of dyeing a cationic liquid according to claim 1, characterized in that: the weak acid of the weak acid system is acetic acid.
4. A method of dyeing a cationic liquid according to claim 1, characterized in that: the organic solvent immiscible with water is at least one of dichloroethane, dichloromethane, chloroform, toluene and chlorobenzene.
5. A method of dyeing a cationic liquid according to claim 1, characterized in that: the methylation reaction process is as follows: mixing a target dye molecule matrix, an acid binding agent, acetic acid and water according to a certain proportion, wherein the dosage of the acid binding agent is 0.5-1.05 times of the molar weight of the target dye molecule matrix, the mass ratio of the acetic acid to the water is 2:1, and the total mass of the acetic acid and the water is 4.0-5.0 times of that of a reaction substrate, putting the two into a reaction container together, dropwise adding a methylation reagent dimethyl sulfate at room temperature, wherein the dosage of the dimethyl sulfate is 2.0-3.0 times of the molar weight of the reaction substrate, and after dropwise adding, carrying out heat preservation reaction at room temperature until the substrate is completely converted.
6. A method of dyeing a cationic liquid according to claim 1, characterized in that: the extraction process comprises the steps of uniformly mixing the materials with an extraction solvent, stirring for dissolving, standing, enabling target dye molecules to enter an organic phase, enabling inorganic impurity ions and other impurities with high solubility in water to enter a water phase, and then separating the organic phase from the water phase by phase separation.
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| CN201910627570.6A CN112210229A (en) | 2019-07-12 | 2019-07-12 | Preparation method of cationic liquid dye |
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Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4268438A (en) * | 1978-03-15 | 1981-05-19 | Bayer Aktiengesellschaft | Cationic 1,3,4-thiadiazole dyestuffs |
| DE3035056A1 (en) * | 1980-09-17 | 1982-04-01 | Bayer Ag, 5090 Leverkusen | Thiadiazole azo dyestuff prodn. by one stage reaction - from amino-thiadiazole, coupler, nitrite and proton donor, for dyeing polyester or polyamide |
| DE3028168A1 (en) * | 1980-07-25 | 1982-04-01 | Bayer Ag, 5090 Leverkusen | METHOD FOR QUATERNATING 1,3,4-THIADIAZOLE AZO DYES |
| US5869731A (en) * | 1995-07-03 | 1999-02-09 | Bayer Aktiengesellschaft | Method for reducing the toxicity of spent liquors and novel cationic dyes |
| CN1513172A (en) * | 2001-03-28 | 2004-07-14 | An optica data storage medium containing diaze hemicyanine dye as light-absorbing compound in infomration layer | |
| CN1556839A (en) * | 2001-09-24 | 2004-12-22 | 西巴特殊化学品控股有限公司 | Cationic reactive dyes |
| CN1667050A (en) * | 2004-03-10 | 2005-09-14 | 杭州近江化工染料有限公司 | Method for preparing high concentration liquid cationic dyes |
| CN1743383A (en) * | 2004-09-01 | 2006-03-08 | 上海汇友精密化学品有限公司 | New process for cation dye parent quaterisation |
| CN101466797A (en) * | 2006-06-13 | 2009-06-24 | 西巴控股公司 | Tricationic dyes |
-
2019
- 2019-07-12 CN CN201910627570.6A patent/CN112210229A/en active Pending
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4268438A (en) * | 1978-03-15 | 1981-05-19 | Bayer Aktiengesellschaft | Cationic 1,3,4-thiadiazole dyestuffs |
| DE3028168A1 (en) * | 1980-07-25 | 1982-04-01 | Bayer Ag, 5090 Leverkusen | METHOD FOR QUATERNATING 1,3,4-THIADIAZOLE AZO DYES |
| DE3035056A1 (en) * | 1980-09-17 | 1982-04-01 | Bayer Ag, 5090 Leverkusen | Thiadiazole azo dyestuff prodn. by one stage reaction - from amino-thiadiazole, coupler, nitrite and proton donor, for dyeing polyester or polyamide |
| US5869731A (en) * | 1995-07-03 | 1999-02-09 | Bayer Aktiengesellschaft | Method for reducing the toxicity of spent liquors and novel cationic dyes |
| CN1513172A (en) * | 2001-03-28 | 2004-07-14 | An optica data storage medium containing diaze hemicyanine dye as light-absorbing compound in infomration layer | |
| CN1556839A (en) * | 2001-09-24 | 2004-12-22 | 西巴特殊化学品控股有限公司 | Cationic reactive dyes |
| CN1667050A (en) * | 2004-03-10 | 2005-09-14 | 杭州近江化工染料有限公司 | Method for preparing high concentration liquid cationic dyes |
| CN1743383A (en) * | 2004-09-01 | 2006-03-08 | 上海汇友精密化学品有限公司 | New process for cation dye parent quaterisation |
| CN101466797A (en) * | 2006-06-13 | 2009-06-24 | 西巴控股公司 | Tricationic dyes |
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