CN110499039B - Synthetic method of solvent blue 122 - Google Patents
Synthetic method of solvent blue 122 Download PDFInfo
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- CN110499039B CN110499039B CN201910782073.3A CN201910782073A CN110499039B CN 110499039 B CN110499039 B CN 110499039B CN 201910782073 A CN201910782073 A CN 201910782073A CN 110499039 B CN110499039 B CN 110499039B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/44—Palladium
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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
- C09B1/00—Dyes with anthracene nucleus not condensed with any other ring
- C09B1/50—Amino-hydroxy-anthraquinones; Ethers and esters thereof
- C09B1/51—N-substituted amino-hydroxy anthraquinone
- C09B1/514—N-aryl derivatives
- C09B1/5145—N-aryl derivatives only amino and hydroxy groups
Abstract
The invention relates to a synthesis method of solvent blue 122, which comprises the following steps: a, adding water, hydrochloric acid and p-aminoacetanilide into a reaction vessel, and uniformly stirring to obtain a first mixed solution; b, adding 1, 4-dihydroxy anthraquinone, 1, 4-dihydroxy anthraquinone leuco body, water and a catalyst CJ into another reaction container to obtain a second mixed solution, wherein the catalyst CJ is a catalyst taking one or more of alumina as a carrier and palladium as an active ingredient; and c, slowly and dropwise adding the first mixed solution into the second mixed solution for condensation reaction to obtain solvent blue 122. The invention prepares a balanced and stable solution by using hydrochloric acid and p-aminoacetanilide, and adds the solution dropwise into the materials, so that the reaction rate and the dissolving effect can be better controlled; water is used as a solvent, so that the operation environment is improved, the reaction period is simplified, the productivity is improved, and the cost is saved; the novel catalyst CJ greatly reduces the pollution of sewage to water, improves the conversion rate of products, and reduces the temperature and pressure of reaction.
Description
Technical Field
The invention relates to a synthesis method of a dye, and particularly relates to a synthesis method of solvent blue 122.
Background
The solvent blue 122 is an important solvent dye, also called transparent blue R and transparent blue 2RA, and its chemical name is N- [4- [ (4-hydroxyanthraquinone-1-yl) amino]Phenyl radical]Acetamide, named Solvent Blue 122 in English, with molecular formula C22H16N2O4Molecular weight is 372.37, CAS number is 67905-17-3. The product is purple black powder, is insoluble in water, is soluble in organic solvent such as benzene, chlorobenzene, xylene, DMF, etc., is dark green in concentrated sulfuric acid, and generates olive to red light blue precipitate after dilution. The solvent blue 122 can be used for coloring various resin plastics, such as polyacrylic resin, ABS resin, polystyrene, organic glass, polyester resin, polycarbonate and the like, so as to obtain red light blue; has excellent heat resistance, sun resistance and migration resistance, good tinting strength, high transparency and wide application range.
The existing process for chemically synthesizing solvent blue 122 is to condense 1, 4-dihydroxyanthraquinone, 1, 4-dihydroxyanthraquinone leuco body and p-aminoacetanilide in butanol by using boric acid as a catalyst to prepare the solvent blue 122. The process has the characteristics of easily obtained raw materials, but has the main defects of heavier smell and severe field environment because the butanol is used as a solvent. Meanwhile, the conversion rate of the reaction of the p-aminoacetanilide is low, the reaction maintenance time is long, the production efficiency is low, and the cost is invisibly increased.
In Chinese patent publication No. CN104341790A, 1, 4-dihydroxyanthraquinone leuco body and p-aminoacetanilide are reacted in water in the presence of one or more anionic surfactants at 120 deg.C for 22 hours in a special pressure kettle. After discharging, refining with DMF water solution to obtain crude product with yield of 91.65% and total yield of 81.74%. In the reaction process, because the water solubility of the raw materials is poor, the raw materials are easy to agglomerate, and the reaction is influenced. The reaction time is long, special devices are needed, the reaction requirement is high, and the industrial production operation is not easy to realize.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a method for synthesizing environment-friendly solvent blue 122.
In order to achieve the purpose, the invention adopts the technical scheme that: a method for synthesizing solvent blue 122, which comprises the following steps:
(a) adding water, hydrochloric acid and p-aminoacetanilide into a reaction container, and uniformly stirring at 40-50 ℃ to obtain a first mixed solution, wherein the feeding molar ratio of the p-aminoacetanilide to the hydrochloric acid is 1.05-1.25: 1;
(b) adding 1, 4-dihydroxy anthraquinone, 1, 4-dihydroxy anthraquinone leuco body, water and a catalyst CJ into another reaction container to obtain a second mixed solution, wherein the catalyst CJ is a catalyst taking one or more of alumina as a carrier and palladium as an active ingredient;
(c) slowly and dropwise adding the first mixed solution into the second mixed solution at 85-90 ℃ for condensation reaction, reacting for 10-14 hours at normal pressure after dropwise adding, and performing post-treatment to obtain the solvent blue 122.
The catalyst CJ is a high-efficiency catalyst, the conversion rate of the reaction can be improved, the reaction can be completed at 85-90 ℃ under normal pressure, hydrochloric acid generated by the condensation reaction in the step (c) can also help catalysis, boric acid is replaced, and pollution to a water body is greatly reduced.
Specifically, in the step (a), the molar ratio of the total feeding moles of the p-aminoacetanilide to the feeding moles of the hydrochloric acid is 1.05-1.25: 1.
Specifically, in the step (b), the ratio of the total mass of the 1, 4-dihydroxyanthraquinone and the 1, 4-dihydroxyanthraquinone leuco body to the mass of the catalyst CJ is 100: 2-6.
Specifically, the post-treatment in the step (c) is filtering while hot, washing the solid obtained by filtering with hot water to be neutral, and drying the obtained solid.
Specifically, in the step (c), the slow dripping time is 3-5 h.
Specifically, in the step (b), the catalyst CJ is prepared by adding 1 part of alumina into 5 parts of 2% boric acid solution by mass for acidification to form slurry, dropping the slurry into a ball for molding, drying, calcining at 350 ℃ to form a carrier, immersing in 100 parts of prepared 0.1% palladium-containing impregnation solution, drying, and calcining and activating at 500 ℃ to obtain the finished catalyst CJ.
The reaction equation of the present invention is as follows:
due to the application of the technical scheme, compared with the prior art, the invention has the following advantages: according to the synthesis method of the solvent blue 122, the hydrochloric acid and the p-aminoacetanilide are prepared into a balanced and stable solution, and the solution is dripped into the material, so that the reaction rate and the dissolution effect performance are better controlled, and the problems that the yield is influenced because the feeding is too fast, the material is agglomerated, even floats and the like, or the feeding is too slow, and the material is oxidized in the reaction process are solved; water is used as a solvent, so that the operation environment is greatly improved, a series of problems of later-stage solvent recovery, reuse and the like are solved, the reaction period is greatly simplified, the productivity is improved, and the cost is also saved; the novel catalyst CJ is used for replacing the prior boric acid and other catalysts, so that the pollution of boron in the sewage to a water body is greatly reduced, the conversion rate of a product is improved, and the temperature and the pressure of the reaction are reduced; compared with the conventional method, the yield of the solvent blue 122 synthesized by the synthesis method can be improved by about 8 percent, and better economic benefit and environmental benefit are obtained.
Drawings
FIG. 1 is a schematic flow chart of the present invention.
Detailed Description
The synthesis method of the solvent blue 122 comprises the following steps:
(a) adding water, hydrochloric acid and p-aminoacetanilide into a reaction container, uniformly stirring at 40-50 ℃ for 25-35 min to obtain a first mixed solution, wherein the feeding molar ratio of the p-aminoacetanilide to the hydrochloric acid is 1.05-1.25: 1;
(b) adding 1, 4-dihydroxy anthraquinone, 1, 4-dihydroxy anthraquinone leuco body, water and a catalyst CJ into another reaction container to obtain a second mixed solution, wherein the catalyst CJ is a catalyst taking one or more of alumina as a carrier and palladium as an active ingredient; the ratio of the total feeding mol of the 1, 4-dihydroxy anthraquinone and 1, 4-dihydroxy anthraquinone leuco bodies to the feeding mol of the hydrochloric acid is 1.05-1.25: 1, and the ratio of the total mass of the 1, 4-dihydroxy anthraquinone leuco bodies to the mass of the catalyst CJ is 100: 2-6;
(c) slowly and dropwise adding the first mixed solution into the second mixed solution at 85-90 ℃ for condensation reaction, completing dropwise adding for 3-5 hours, reacting at normal pressure for 10-14 hours, filtering while hot, washing the filtered solid with hot water to be neutral, and drying the obtained solid to obtain solvent blue 122.
The preparation process of the catalyst CJ comprises the following steps: adding 1 part of alumina into 5 parts of boric acid solution with the mass part of 2% for acidification to form slurry, then dropping balls for molding, drying, calcining at 350 ℃ to form a carrier, then soaking in 100 parts of prepared 0.1% palladium-containing impregnation solution, drying, calcining at 500 ℃ and activating to obtain a finished product of the catalyst CJ.
Preparation of a 0.1% palladium-containing dip: the precursor of palladium can be selected from palladium-containing metal compounds such as palladium tetraammine dichloride, palladium chloride and the like, and the palladium chloride is selected in the application. The solvent used for dissolving the palladium precursor is deionized water, hydrochloric acid solution and alcohol (methanol or ethanol).
The invention will be further described with reference to specific examples, but the scope of protection of the invention is not limited thereto:
example 1
This example provides a method for synthesizing solvent blue 122, which comprises the following steps:
(a) sequentially adding 30ml of hot water, 20g of 30% hydrochloric acid and 30g of p-aminoacetanilide into a four-neck flask, heating and stirring, and maintaining the temperature at 40-50 ℃ for 30min to fully dissolve the p-aminoacetanilide to obtain a first mixed solution;
(b) in another four-neck flask, 80ml of water, 28g of 1, 4-dihydroxy anthraquinone, 8g of 1, 4-dihydroxy anthraquinone leuco body and 0.8g of catalyst CJ are added to obtain a second mixed solution;
(c) heating the second mixed solution, stirring to 85-90 ℃, dropwise adding the first mixed solution into the second mixed solution for 3-4 hours, maintaining for 12 hours, cooling, and detecting a reaction end point by HPLC; and after the end point is reached, filtering while hot, washing the solid obtained by filtering with hot water to be neutral, and drying the obtained solid to obtain 53.6g of navy blue 122 powder with the content of 94.64 percent and the yield of 96.0 percent.
Example 2
This example provides a synthesis of solvent blue 122, which is substantially the same as that in example 1, except that 25.92g of p-aminoacetanilide is added in step (b), and finally 53.1g of solvent blue 122 powder with 93.45% content and 95.16% yield is obtained by filtering, washing with hot water to neutrality and drying the filter cake.
Example 3
This example provides a synthesis of solvent blue 122, which is substantially the same as that in example 1, except that 30.86g of p-aminoacetanilide is added in step (b), and finally 54.2g of solvent blue 122 powder with 92.15% content and 97.13% yield is obtained after filtration, hot water washing to neutrality and drying of the filter cake.
Example 4
This example provides a synthesis of solvent blue 122, which is substantially the same as that in example 1, except that in step (b), catalyst CJ 2g is added, and finally, the mixture is filtered, washed with hot water to neutrality, and the filter cake is dried to obtain solvent blue 122 powder 53.2g, with a content of 93.22% and a yield of 95.3%.
Example 5
This example provides a synthesis of solvent blue 122, which is substantially the same as that in example 1, except that in step (b), 2.16g of catalyst CJ is added, and finally, the mixture is filtered, washed with hot water to be neutral, and the filter cake is dried to obtain 53.4g of solvent blue 122 powder with 93.46% content and 95.7% yield.
Example 6
This example provides a synthesis of solvent blue 122, which is substantially the same as that in example 1, except that in step (b), 0.72g of catalyst CJ is added, and finally, the mixture is filtered, washed with hot water to neutrality, and the filter cake is dried to obtain 51.9g of solvent blue 122 powder, the content of which is 92.34%, and the yield of which is 92.91%.
Comparative example 1
The comparative example provides a synthesis method of solvent blue 122, which adopts a general process, and specifically comprises the following steps: adding 120ml of butanol, 30ml of water, 30g of 1, 4-dihydroxyanthraquinone, 6g of 1, 4-dihydroxyanthraquinone leuco body, 6g of boric acid and 30g of p-aminoacetanilide into a four-neck flask in sequence, erecting a water separator, heating for dehydration, refluxing at 98 ℃, slowly separating water to 105 ℃, maintaining for 24 hours, separating water for about 12 hours, detecting the reaction end point by HPLC (high performance liquid chromatography), adding water to evaporate the butanol after the end point is reached, carrying out hot filtration, washing with hot water to be neutral, draining, putting a filter cake into the four-neck flask, adding 120ml of 80% DMF (dimethyl formamide) aqueous solution, pulping at 80 ℃, carrying out normal-temperature filtration, drying the filter cake to obtain 48.2g of a finished product with the content of 89.82% and the yield of 86.38%.
Comparative example 2
This comparative example provides a synthesis of solvent blue 122 which is essentially the same as that of example 1 except that 24.6g of p-aminoacetanilide are added in step (b), and finally filtered, washed with hot water to neutrality and the filter cake dried to give solvent blue 122 powder 48.9g, 83.25% content and 87.54% yield.
Comparative example 3
This comparative example provides a synthesis of solvent blue 122, which is substantially the same as that of example 1, except that in step (b), catalyst CJ is not added, catalyst boric acid is replaced, and finally, the solution is filtered, washed with hot water to neutrality, and the filter cake is dried to obtain solvent blue 122 powder 47.2g, with a content of 80.45% and a yield of 84.49%.
The solvent blue 122 material synthesized by the synthesis method has obvious crystal form and uniform particle size distribution, so that the good washing water permeability is ensured, about 8 tons of water is saved for each ton of product, and the drying speed of the material is ensured.
The above embodiments are merely illustrative of the technical ideas and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and not to limit the protection scope of the present invention. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.
Claims (3)
1. A method for synthesizing solvent blue 122 is characterized by comprising the following steps:
(a) adding water, hydrochloric acid and p-aminoacetanilide into a reaction container, and uniformly stirring at 40-50 ℃ to obtain a first mixed solution, wherein the feeding molar ratio of the p-aminoacetanilide to the hydrochloric acid is 1.05-1.25: 1;
(b) adding 1, 4-dihydroxy anthraquinone, 1, 4-dihydroxy anthraquinone leuco body, water and a catalyst CJ into another reaction container to obtain a second mixed solution; the preparation process of the catalyst CJ is as follows: adding 1 part of alumina into 5 parts of boric acid solution with the mass part of 2% for acidification to form slurry, then dropping balls for forming and drying, calcining at 350 ℃ to form a carrier, then soaking in 100 parts of prepared 0.1% palladium-containing impregnation liquid, drying, calcining at 500 ℃ and activating to obtain a finished product of the catalyst CJ;
(c) slowly dripping the first mixed solution into the second mixed solution at 85-90 ℃ for condensation reaction, reacting for 10-14 hours at normal pressure after dripping, and performing post-treatment to obtain the solvent blue 122; the total feeding mol ratio of the 1, 4-dihydroxy anthraquinone, the 1, 4-dihydroxy anthraquinone leuco body and the hydrochloric acid is 1.05-1.25: 1; the ratio of the total mass of the 1, 4-dihydroxyanthraquinone and the 1, 4-dihydroxyanthraquinone leuco body to the mass of the catalyst CJ is 100: 2-6.
2. The method for synthesizing solvent blue 122 according to claim 1, wherein: and (d) filtering while the solution is hot, washing the solid obtained by filtering with hot water to be neutral, and drying the obtained solid.
3. The method for synthesizing solvent blue 122 according to claim 1, wherein: and (d), slowly dripping for 3-5 h.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US1931264A (en) * | 1931-01-12 | 1933-10-17 | Du Pont | Process for the manufacture of quinizarine green and related products |
| GB2013701A (en) * | 1978-02-03 | 1979-08-15 | Ici Ltd | An Improved Process for the Preparation of Arylamino Derivatives of Anthraquinone |
| CN101406837A (en) * | 2008-10-24 | 2009-04-15 | 傅骐 | Method for preparing palladium catalyst with alkali resistance for production of hydrogen peroxide and product |
| CN104341790B (en) * | 2014-09-25 | 2017-03-29 | 宁波龙欣精细化工有限公司 | 1 hydroxyl, 4 aryl amine anthraquinone product of purification and preparation method thereof |
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Denomination of invention: A synthetic method of solvent blue 122 Effective date of registration: 20220215 Granted publication date: 20210212 Pledgee: Hefei Science and Technology Rural Commercial Bank Co.,Ltd. Tongling sub branch Pledgor: ANHUI QINGKE RUIJIE NEW MATERIAL CO.,LTD. Registration number: Y2022980001535 |
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Date of cancellation: 20230116 Granted publication date: 20210212 Pledgee: Hefei Science and Technology Rural Commercial Bank Co.,Ltd. Tongling sub branch Pledgor: ANHUI QINGKE RUIJIE NEW MATERIAL CO.,LTD. Registration number: Y2022980001535 |