CN112210227B - Cationic golden dye and preparation method thereof - Google Patents
Cationic golden dye and preparation method thereof Download PDFInfo
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- CN112210227B CN112210227B CN201910618195.9A CN201910618195A CN112210227B CN 112210227 B CN112210227 B CN 112210227B CN 201910618195 A CN201910618195 A CN 201910618195A CN 112210227 B CN112210227 B CN 112210227B
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- golden yellow
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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
- C09B26/00—Hydrazone dyes; Triazene dyes
- C09B26/02—Hydrazone dyes
- C09B26/04—Hydrazone dyes cationic
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Abstract
The invention discloses a cationic golden dye and a preparation method thereof. Putting the dried golden yellow matrix and the acid-binding agent hydroxyl golden yellow raw powder into a reaction bottle, continuously adding dimethyl sulfate, quickly heating to 75-90 ℃, carrying out heat preservation reaction for 8-60 min, carrying out reduced pressure distillation after the reaction is finished, recovering excessive dimethyl sulfate for application, adding water into the residual materials, stirring at 60-65 ℃ for 30min, cooling to below 20 ℃, filtering, and drying to obtain golden yellow-28 raw powder of methyl sulfate, wherein the filtrate can be used for the post-treatment operation of the next batch. The invention cancels the use of production solvent, and reduces the production cost of the product; the production amount of process wastewater is reduced, and the production cost of products is further reduced; the excessive methylating agent can be recycled; the water for post-treatment can also be recycled and reused, thereby reducing the cost of three wastes treatment.
Description
Technical Field
The invention relates to a cationic golden dye and a preparation method thereof, belonging to the technical field of dyes.
Background
The existing golden yellow-28 synthesis process is carried out by taking a golden yellow-28 matrix as a starting material, dimethyl sulfate as a methylation reagent, dichloroethane as a solvent and magnesium oxide or sodium carbonate as an acid-binding agent at a reflux temperature (70-75 ℃), wherein the obtained product is cationic golden yellow-28 dye raw powder of monomethyl sulfate.
The defects of the prior art are as follows: (1) the golden yellow parent material is moist and has high water content (about 40 percent), so that the methylating agent dimethyl sulfate needs to be greatly excessive (excessive 120 percent), the production cost is increased, and the COD of the process wastewater is increased to further increase the wastewater treatment cost; (2) the acid-binding agent magnesium oxide used in the prior art is slightly soluble in water and insoluble in organic solvents, has poor acid-binding effect and can increase the post-treatment cost. The acid-binding agent sodium carbonate has a good acid-binding effect, but the salt content of the process wastewater can be increased, and the wastewater treatment cost can also be increased.
Aiming at the defects of the prior art, the method mainly reduces the dosage of a methylating agent dimethyl sulfate so as to reduce the production cost, and selects an acid-binding agent with excellent effect so as to reduce the production amount of process wastewater and the treatment cost thereof.
Disclosure of Invention
In view of the above, the invention provides a cationic golden dye and a preparation method thereof, which cancels the use of a production solvent and reduces the production cost of the product; the production amount of process wastewater is reduced, and the production cost of products is further reduced; the excessive methylating agent can be recycled; the water used for post-treatment can also be recycled and reused, thereby reducing the cost of three-waste treatment.
The invention solves the technical problems through the following technical means:
the invention relates to a cationic golden yellow dye and a preparation method thereof, wherein a golden yellow matrix dry product and an acid-binding agent hydroxyl golden yellow raw powder are put into a reaction bottle, dimethyl sulfate is continuously put into the reaction bottle, then the temperature is rapidly raised to 75-90 ℃, the reaction is carried out for 8-60 min under a heat preservation condition, after the reaction is finished, the excessive dimethyl sulfate is recovered by reduced pressure distillation for reuse, water is added into the residual materials, the mixture is stirred for 30min at the temperature of 60-65 ℃, then the temperature is reduced to below 20 ℃, the filtration and the drying are carried out, so that golden yellow-28 raw powder of methyl sulfate is obtained, and the filtrate can be used for the post-treatment operation of the next batch.
The molar ratio of the dry golden yellow parent product to the acid-binding agent hydroxyl radical golden yellow raw powder is 1: 0.2-0.8.
The mole number of the dimethyl sulfate is 4-8 times of that of the golden yellow matrix.
The added water is 4 times of the mass of the golden yellow parent dry product.
The water content of the golden yellow parent dry product is less than 5 percent.
And (3) distilling the filtrate under reduced pressure to recover dimethyl sulfate, adding water into the residual materials obtained after recovering dimethyl sulfate, heating to 60-65 ℃, stirring for 30min, cooling to below 20 ℃, filtering, taking the obtained filtrate as water required by the next batch of post-treatment, and supplementing the shortage with fresh water.
The process conditions during reduced pressure distillation are as follows: the pressure is-0.1 MPa, and the temperature is 125-130 DEG C
The method changes the raw material golden yellow mother body tide product into a golden yellow mother body dry product (the moisture content is less than 5 percent); (2) removing dichloroethane as a special solvent, taking dimethyl sulfate as a methylation reagent and a solvent at the same time, and recovering and reusing excessive dimethyl sulfate after the reaction is finished; (3) the acid-binding agent is changed into a dried gold yellow raw powder (organic alkali) of hydroxide radical, and the dried gold yellow raw powder is finally converted into a methyl sulfate radical product in an excessive dimethyl sulfate system, so that no waste is generated, and the wastewater amount generated in the whole process is greatly reduced; (4) the reaction temperature is mild (75-90 ℃), the reaction time is short (8-10 min), the reaction speed is high, and the method is suitable for a pipeline reaction production mode.
The filtrate can be used as the water obtained by the next batch of post-treatment for recycling, thereby reducing the generation of process wastewater. The specific operation method comprises the following steps: adding water into the residual materials obtained after the last batch is subjected to reduced pressure distillation to recover dimethyl sulfate, heating to 60-65 ℃, stirring for 30min, cooling to below 20 ℃, filtering, and taking the obtained filtrate as water (the shortage is supplemented by fresh water) required by the next batch of post-treatment to reduce the generation of waste water and further reduce the process cost of the product. Vacuum distillation, also known as vacuum distillation, is an important method for separating and purifying compounds, and is particularly suitable for separating and purifying high-boiling substances and compounds which are thermally decomposed, oxidized or polymerized before the boiling point in atmospheric distillation.
The boiling point of the compound always changes with the difference of the external pressure, and when some compounds with higher boiling point (especially more than 200 ℃) are distilled under normal pressure, the phenomena of decomposition, oxidation or polymerization and the like are generated when the boiling point is not reached due to the rising of the temperature. In this case, atmospheric distillation cannot be used, and reduced pressure distillation should be used. These phenomena are avoided by lowering the boiling point of the liquid by reducing the pressure in the system.
The boiling point of dimethyl sulfate used in the invention is 188 ℃ under normal pressure, and the compound is easy to decompose at the boiling point temperature, but the excessive dimethyl sulfate in the invention can only be effectively separated from the product at a lower temperature by using a reduced pressure distillation method to achieve the purpose of recycling and reducing the process cost. The process conditions during the reduced pressure distillation are as follows: -0.1MPa, 125-130 ℃.
The invention has the beneficial effects that: (1) the use of a solvent is cancelled, and the excessive dimethyl sulfate is used as a reactant and a solvent and can be recycled; (2) the acid-binding agent is selected to be replaced by different anions (hydroxide ions) of the product, so that no waste is generated; (3) the reaction time is short, the reaction speed is high, and the method is suitable for being applied to a pipeline production mode; (4) greatly reduces the production of three wastes and reduces the production cost of products.
Detailed Description
The invention will be described in detail with reference to specific embodiments, in the cationic golden yellow dye and the preparation method thereof, dry golden yellow matrix and acid-binding agent hydroxyl golden yellow raw powder are put into a reaction bottle, dimethyl sulfate is continuously put into the reaction bottle, then the temperature is rapidly raised to 75-90 ℃, the temperature is kept for reaction for 8-60 min, after the reaction is finished, the excessive dimethyl sulfate is recovered by reduced pressure distillation for application, the residual materials are stirred for 30min at 60-65 ℃, then the temperature is reduced to below 20 ℃ for filtration and drying, and golden yellow-28 raw powder of methyl sulfate is obtained, and the filtrate can be used for the post-treatment operation of the next batch.
The molar ratio of the dry golden yellow parent product to the acid-binding agent hydroxyl radical golden yellow raw powder is 1: 0.2-0.8.
The mole number of the dimethyl sulfate is 4-8 times of that of the golden yellow matrix.
The added water is 4 times of the mass of the golden yellow parent dry product.
The water content of the golden yellow parent dry product is less than 5 percent.
And (3) distilling the filtrate under reduced pressure to recover dimethyl sulfate, adding water into the residual materials obtained after recovering dimethyl sulfate, heating to 60-65 ℃, stirring for 30min, cooling to below 20 ℃, filtering, taking the obtained filtrate as water required by the next batch of post-treatment, and supplementing the shortage with fresh water.
The process conditions during reduced pressure distillation are as follows: the pressure is-0.1 MPa, and the temperature is 125-130 ℃.
Example 1
A cationic golden yellow dye and its preparation method, put golden yellow matrix dry product, acid-binding agent hydroxyl golden yellow raw powder into reaction flask, continue throwing dimethyl sulfate, then heat up to 86 degrees C fast, keep warm and react for 30min, after finishing the reaction, decompress and distill and reclaim excessive dimethyl sulfate and apply mechanically, the surplus supplies are stirred under 63 degrees C for 30min, cool to under 20 degrees C after cooling to get golden yellow-28 raw powder of methyl sulfate, the filtrate can be used for the post-treatment operation of the next batch.
The molar ratio of the dry golden yellow parent product to the acid-binding agent is 1: 0.6.
The mole number of the dimethyl sulfate is 7 times of that of the golden yellow parent body.
The added water is 4 times of the mass of the golden yellow parent dry product.
The water content of the golden yellow parent dry product is less than 5 percent.
Distilling the filtrate under reduced pressure to recover dimethyl sulfate, adding water into the residual materials, heating to 63 deg.C, stirring for 30min, cooling to below 20 deg.C, filtering, and collecting filtrate as water for post-treatment of next batch.
The process conditions during reduced pressure distillation are as follows: the pressure is-0.1 MPa and the temperature is 128 ℃.
Example 2
A cationic golden yellow dye and its preparation method, put golden yellow matrix dry product, acid-binding agent hydroxyl golden yellow raw powder into reaction flask, continue throwing dimethyl sulfate, then heat up to 80 ℃ rapidly, keep warm and react for 50min, after finishing the reaction, decompress and distill and reclaim excessive dimethyl sulfate and apply mechanically, after adding water to the residual material, stir at 65 ℃ for 30min, cool to below 20 ℃, filter, dry and get golden yellow-28 raw powder of methyl sulfate, the filtrate can be used for the post-treatment operation of the next batch.
The molar ratio of the dry golden yellow parent product to the acid-binding agent is 1: 0.5.
The mole number of the dimethyl sulfate is 7 times of that of the golden yellow parent body.
The added water is 4 times of the mass of the golden yellow parent dry product.
The water content of the golden yellow parent dry product is less than 5 percent.
Distilling the filtrate under reduced pressure to recover dimethyl sulfate, adding water into the residual materials, heating to 65 deg.C, stirring for 30min, cooling to below 20 deg.C, filtering, and collecting filtrate as water for post-treatment of next batch.
The process conditions during reduced pressure distillation are as follows: the pressure is-0.1 MPa and the temperature is 125 ℃.
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 (1)
1. A preparation method of a cationic golden yellow dye is characterized by comprising the steps of putting a golden yellow matrix dry product and an acid-binding agent hydroxyl golden yellow raw powder into a reaction bottle, continuously putting dimethyl sulfate, quickly heating to 75-90 ℃, carrying out heat preservation reaction for 8-60 min, carrying out reduced pressure distillation after the reaction is finished, recovering excessive dimethyl sulfate for application, adding water into the rest materials, stirring at 60-65 ℃ for 30min, cooling to below 20 ℃, filtering, drying to obtain golden yellow-28 raw powder of methyl sulfate, and sleeving the filtrate for the post-treatment operation of the next batch; the molar ratio of the dried golden yellow matrix to the acid-binding agent hydroxyl golden yellow raw powder is 1: 0.2-0.8; the mole number of the dimethyl sulfate is 4-8 times of that of the golden yellow matrix; the added water is 4 times of the mass of the dried golden precursor; the moisture content of the golden yellow parent dry product is less than 5 percent; adding water into the residual materials obtained after recovering dimethyl sulfate by vacuum distillation of the filtrate, heating to 60-65 ℃, stirring for 30min, cooling to below 20 ℃, filtering, taking the obtained filtrate as water required by the next batch of post-treatment, and supplementing the shortage with fresh water; the process conditions during reduced pressure distillation are as follows: the pressure is-0.1 MPa, and the temperature is 125-130 ℃.
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| CN112210227B true CN112210227B (en) | 2022-06-10 |
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0229980A2 (en) * | 1985-12-21 | 1987-07-29 | Bayer Ag | Process for the manufacture of cationic hydrazone dyes |
| JP2001019866A (en) * | 1999-07-08 | 2001-01-23 | Orient Chem Ind Ltd | Preparation of azamethine salt-forming substance dye, and oil-soluble dye ink |
| 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 |
| CN101245195A (en) * | 2008-03-14 | 2008-08-20 | 上海富圆染化有限公司 | Novel heterocycle azo cationic dye and manufacture method thereof |
| CN101724290A (en) * | 2009-12-10 | 2010-06-09 | 杭州璟江瑞华科技有限公司 | Preparation method of environment-friendly zinc-free cationic dye |
| CN105417815A (en) * | 2015-11-06 | 2016-03-23 | 南京师范大学 | Method for treating salt-containing organic wastewater during production of cationic golden yellow dye X-GL |
-
2019
- 2019-07-10 CN CN201910618195.9A patent/CN112210227B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0229980A2 (en) * | 1985-12-21 | 1987-07-29 | Bayer Ag | Process for the manufacture of cationic hydrazone dyes |
| JP2001019866A (en) * | 1999-07-08 | 2001-01-23 | Orient Chem Ind Ltd | Preparation of azamethine salt-forming substance dye, and oil-soluble dye ink |
| 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 |
| CN101245195A (en) * | 2008-03-14 | 2008-08-20 | 上海富圆染化有限公司 | Novel heterocycle azo cationic dye and manufacture method thereof |
| CN101724290A (en) * | 2009-12-10 | 2010-06-09 | 杭州璟江瑞华科技有限公司 | Preparation method of environment-friendly zinc-free cationic dye |
| CN105417815A (en) * | 2015-11-06 | 2016-03-23 | 南京师范大学 | Method for treating salt-containing organic wastewater during production of cationic golden yellow dye X-GL |
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