阅读说明：本技术 一种低污染二芳胺基蒽醌型溶剂蓝78染料的制备方法 (Preparation method of low-pollution diarylamine anthraquinone solvent blue 78 dye ) 是由 周利霞 刘镛 李成 何磊 吴翔 陈子晖 王杰 徐勇 于 2020-12-22 设计创作，主要内容包括：本发明提供了一种低污染二芳胺基蒽醌型溶剂蓝78染料的制备方法。包括以下步骤向甲醇中依次加入N-甲基咪唑、4-溴丁酸,在40℃-60℃搅拌下缓慢滴加入50％氢氧化钠溶液,调节至pH>9,再加入氟硼酸,搅拌4小时-6小时,减压除去甲醇,得到第一混合物；将第一混合物升温至40℃-60℃,加入1,4-二羟基蒽醌、1,4-二羟基蒽醌隐色体、一甲胺,继续升温至50℃-65℃反应至终点,降温至30℃-45℃抽滤得滤饼和滤液；热水洗泡滤饼,收集洗泡液和滤液,进行蒸馏回收,热水洗涤滤饼至中性,干燥,得到溶剂蓝78染料。通过本发明的制备方法得到的溶剂蓝78染料△C为偏艳2.0,压力值<0.3,产品品质能够满足高端客户的应用需求。(The invention provides a preparation method of a low-pollution diarylamine anthraquinone solvent blue 78 dye. Sequentially adding N-methylimidazole and 4-bromobutyric acid into methanol, slowly dropwise adding a 50% sodium hydroxide solution at the temperature of 40-60 ℃ while stirring, adjusting the pH to be more than 9, adding fluoboric acid, stirring for 4-6 hours, and removing the methanol under reduced pressure to obtain a first mixture; heating the first mixture to 40-60 ℃, adding 1, 4-dihydroxyanthraquinone, 1, 4-dihydroxyanthraquinone leuco body and monomethylamine, continuously heating to 50-65 ℃, reacting to the end point, cooling to 30-45 ℃, and performing suction filtration to obtain a filter cake and a filtrate; washing the soaked filter cake with hot water, collecting the soaking liquid and the filtrate, distilling and recovering, washing the filter cake with hot water to be neutral, and drying to obtain the solvent blue 78 dye. The delta C of the solvent blue 78 dye obtained by the preparation method is slightly brilliant 2.0, the pressure value is less than 0.3, and the product quality can meet the application requirements of high-end customers.)

1. A preparation method of low-pollution diarylamine anthraquinone solvent blue 78 dye comprises the following steps:

sequentially adding N-methylimidazole and 4-bromobutyric acid into methanol, slowly dropwise adding a 50% sodium hydroxide solution under stirring at 40-60 ℃, adjusting the pH to be more than 9, adding fluoboric acid, stirring for 4-6 hours, and removing the methanol under reduced pressure to obtain a first mixture;

heating the first mixture to 40-60 ℃, adding 1, 4-dihydroxyanthraquinone, 1, 4-dihydroxyanthraquinone leuco body and monomethylamine, continuously heating to 50-65 ℃, reacting to the end point, cooling to 30-45 ℃, and performing suction filtration to obtain a filter cake and a filtrate;

washing and soaking the filter cake with hot water, collecting soaking liquid and filtrate, distilling and recovering, washing the filter cake with hot water to be neutral, and drying to obtain the solvent blue 78 dye.

2. The production method according to claim 1, wherein the weight ratio of the N-methylimidazole to the 4-bromobutyric acid is 0.6-0.7: 1.

3. The production method according to claim 1, wherein the weight ratio of methanol to N-methylimidazole is 1.0 to 1.2: 1.

4. The production method according to claim 1, wherein the weight ratio of the fluoroboric acid to 2-bromoethanol is from 0.5 to 1.5: 20-25.

5. The production method according to claim 1, wherein the weight ratio of monomethylamine to 1, 4-dihydroxyanthraquinone is 0.4 to 0.6: 1.

6. The method of preparing solvent blue 78 dye according to claim 1, wherein the weight ratio of the first mixture and the 1, 4-dihydroxyanthraquinone is 1.5-2: 1.

7. the preparation method according to claim 1, wherein the mass ratio of the 1, 4-dihydroxyanthraquinone leuco body to the first mixture is 0.08-0.2: 1.

8. the production method according to claim 1, wherein the temperature of the hot water is 80 to 100 ℃.

9. The production method according to claim 1, wherein the recovered solvent is distilled for production of the next batch.

10. The production method according to claim 9, wherein, when the solvent recovered by distillation is used for the production of the next batch, it is first heated to 100 ℃ to 110 ℃ to dehydrate it, and then 1, 4-dihydroxyanthraquinone and other raw materials are added to react.

Technical Field

The invention relates to a preparation method of a dye, in particular to a preparation method of a low-pollution diarylamine anthraquinone solvent blue 78 dye, belonging to the technical field of dye preparation.

Background

Solvent Blue 78, also known as transparent Blue GP or disperse Blue 14, is known by the chemical name 1, 4-bis (methylamino) anthraquinone, is known by the name Solvent Blue 78, and has the molecular formula C₁₆H₁₄N₂O₂Molecular weight is 266.29, CAS number is 2475-44-7. The appearance is blue black powder, is insoluble in water, and is soluble in methanol, ethanol, glacial acetic acid, nitrobenzene, pyridine and toluene. In concentrated sulfuric acid, it is red brown. The solvent blue 78 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; it can also be used for making fireworks, and has the advantages of good heat resistance, sun-proof property and migration resistance, good tinting strength, high transparency and wide application range.

At present, the general process for producing solvent blue 78 is as follows: adding water into a 10000L condensation kettle through a flowmeter, starting stirring, adding sodium hydroxide, adding 1, 4-dihydroxy anthraquinone which is packaged and measured, covering a kettle cover, adding 40% monomethylamine through a metering tank, then opening a jacket steam inlet valve, starting airtight heating, heating to 70-75 ℃, keeping the temperature, reacting for 10 hours, sampling and measuring the condensation end point. After the reaction end point is reached, the jacket is filled with water and cooled to 40-45 ℃, a kettle bottom valve is opened to discharge the material, the material enters a filter press, mother liquor is pumped out, and filter cakes are washed to be neutral by hot water at 80-90 ℃; and drying the filter cake in an oven, crushing, mixing and packaging to obtain a finished product of the solvent blue 78. The solvent blue 78 product produced by the process has poor quality and poor color-light consistency, the saturation Delta C usually accounts for about 60 percent of the total yield with the gray shade of 3-4, and part of single-batch products can reach qualified quality only by solvent refining, thereby causing resource waste and pollution to the environment; the reaction yield is low, about 87%, the side reactions of single condensation and hydrolysis generated in the reaction process are not easy to control, and the reaction selectivity is influenced, so that the product yield is influenced.

Disclosure of Invention

The invention aims to overcome the defects of the prior art and provides a preparation method of solvent blue 78 dye, which has the advantages of low pollution, high product yield and good hue.

In order to solve the technical problems, the invention provides a preparation method of a low-pollution diarylamine anthraquinone solvent blue 78 dye, which comprises the following steps:

sequentially adding N-methylimidazole and 4-bromobutyric acid into methanol, slowly dropwise adding a 50% sodium hydroxide solution under stirring at 40-60 ℃, adjusting the pH to be more than 9, adding fluoboric acid, stirring for 4-6 hours, and removing the methanol under reduced pressure to obtain a first mixture;

heating the first mixture to 40-60 ℃, adding 1, 4-dihydroxyanthraquinone, 1, 4-dihydroxyanthraquinone leuco body and monomethylamine, continuously heating to 50-65 ℃, reacting to the end point, cooling to 30-45 ℃, and performing suction filtration to obtain a filter cake and a filtrate;

washing the soaked filter cake with hot water, collecting the soaking liquid and the filtrate, distilling and recovering, washing the filter cake with hot water to be neutral, and drying to obtain the solvent blue 78 dye.

In one embodiment of the invention, the weight ratio of N-methylimidazole to 4-bromobutyric acid is from 0.6 to 0.7: 1; the weight ratio of the methanol to the N-methylimidazole is 1.0-1.2: 1; the weight ratio of the fluoboric acid to the 2-bromoethanol is 0.5-1.5: 20-25.

In one embodiment of the invention, the weight ratio of monomethylamine to 1, 4-dihydroxyanthraquinone is from 0.4 to 0.6:1 (preferably from 0.5 to 0.6: 1). The weight ratio of the first mixture to the 1, 4-dihydroxyanthraquinone is 1.5-2: 1 (preferably 1.8-2: 1). The mass ratio of the 1, 4-dihydroxy anthraquinone leuco body to the first mixture is 0.08-0.2: 1 (preferably 0.08-0.1: 1).

In one embodiment of the invention, the hot water has a temperature of 80-100 ℃.

In one embodiment of the invention, the recovered solvent is distilled for the next batch of preparation. When the solvent recovered by distillation is used for the preparation of the next batch, the solvent is heated to 100-110 ℃ for dehydration, and then 1, 4-dihydroxy anthraquinone and other raw materials are added for reaction.

The invention relates to a preparation method of solvent 78 dye, belonging to a new green synthesis method of low-pollution diarylamine anthraquinone dye, which comprises the following steps:

(a) sequentially adding methanol, N-methylimidazole and 4-bromobutyric acid into a reaction container, slowly dropwise adding a 50% sodium hydroxide solution at 50 ℃ while stirring and cooling until the pH is greater than 9, then adding fluoboric acid, stirring for 5 hours to dissolve, and removing the methanol under reduced pressure to obtain a first mixture; the weight ratio of the N-methylimidazole to the 4-bromobutyric acid is 0.6-0.7: 1; the weight ratio of the methanol to the N-methylimidazole is 1.0-1.2: 1;

(b) heating the first mixture to 50 ℃, adding 1, 4-dihydroxyanthraquinone, 1, 4-dihydroxyanthraquinone leuco body and monomethylamine, uniformly stirring, and then continuously heating to 60 ℃ to react until the end point; determining the reaction end point by HPLC detection; then cooling to 30-40 ℃ and carrying out suction filtration to obtain a filter cake and filtrate; the weight ratio of monomethylamine to 1, 4-dihydroxy anthraquinone is 0.4-0.5: 1; the weight ratio of the first mixture to the 1, 4-dihydroxy anthraquinone is 1.5-2: the mass ratio of the 1, 1, 4-dihydroxy anthraquinone leuco body to the first mixture is 0.1-0.2: 1;

(c) washing and soaking the filter cake with a proper amount of hot water, collecting soaking liquid and filtrate, and distilling and recovering; washing the filter cake with hot water to neutrality, and drying.

The preparation method of the low-pollution diarylamine anthraquinone solvent blue 78 dye adopts the ionic liquid to replace the traditional low-carbon alcohol or organic amine as the reaction solvent:

firstly, because the ionic liquid has non-volatility, the decomposition temperature of the ionic liquid is as high as 420 ℃, and VOC emission and solvent loss caused by pyrolysis in the processes of material pumping, filtering and distillation of the traditional organic solvent can be avoided in the industrial production process;

secondly, because the ionic liquid has better high-temperature stability, the safety of the industrial production process is greatly improved, although the ionic liquid is 2-4 times more expensive than the traditional organic solvent at the present stage, the ionic liquid can be recycled for a plurality of times after being heated to 110 ℃ for dehydration, the loss is extremely small, and the overall cost is not obviously increased. The ionic liquid has the advantages of no odor, no pollution, no flammability, easy separation from products, easy recovery, repeated and repeated recycling, convenient use and the like, is an ideal substitute of the traditional volatile solvent, effectively avoids the problems of serious environment, health, safety, equipment corrosion and the like caused by the use of the traditional organic solvent, and is a genuine and environment-friendly green solvent. Is suitable for the cleaning technology advocated at present and the requirement of sustainable development, and has been widely accepted and accepted by people. It is believed that the process can achieve more remarkable economic and social benefits as the application of the ionic liquid is popularized.

And the excessive toxic solvent, namely monomethylamine, needs to be recycled and reused in the production process of the general process, so that the operation site environment of the recycling process is poor, and the environment is polluted. The ionic liquid is adopted as the reaction solvent, so that the environmental protection is realized, the reaction can be completely carried out only by slight excess of monomethylamine, the operation of recovering the toxic reagent monomethylamine is not needed in the reaction mother liquor, the safety of the production process is greatly improved, and the discharge amount of three wastes is obviously reduced.

Fourthly, the ionic liquid in the nucleophilic substitution reaction is not only used as a green solvent, but also through the selection of organic cations in the ionic liquid, five ionic liquid types of 1-hydroxyethyl-3-methylimidazole bromine salt, 1-butyl-3-methylimidazole tetrafluoroborate, 1-allyl-3-butylimidazole chloride salt, 1-ethylmethyl ether-3-methylimidazole bromine salt, N, N, N ', N' -tetramethyl hexanediamine chloroaluminate are screened, finally, the applicable ionic liquid is found, the reaction obtains surprisingly high selectivity, impurities generated by low selectivity due to competitive single condensation and hydrolysis side reactions in the prior art can be avoided, the purity of the product is obviously improved, the HPLC purity of the final product is improved from less than 90 percent to more than 95 percent, compared with the prior art, the yield can be improved by about 5-10 percent and can reach more than 95 percent, the production cost is greatly reduced, the economic benefit is obvious, and the pollutant discharge amount is reduced; more importantly, the obtained solvent blue 78 dye has delta E of less than 1.0, delta C of more than 2.0 and pressure value of less than 0.3, and the product quality can meet the application requirements of high-end customers.

Drawings

FIG. 1 shows the reaction equation of the low-contamination diarylamine anthraquinone type solvent blue 78 dye of the present invention.

FIG. 2 is a process flow diagram of the production method of the low-pollution diarylamine anthraquinone type solvent blue 78 dye of the present invention.

Detailed Description

Example 1

This example provides a method for producing a low-pollution diarylamine anthraquinone type solvent blue 78 dye, the reaction mechanism of which is shown in fig. 1, the process flow of which is shown in fig. 2, and the method comprises the following steps:

(a) sequentially adding 800 kg of methanol and 800 kg of N-methylimidazole into a reaction vessel, then slowly dropwise adding 1200 kg of 4-bromobutyric acid while stirring and cooling, slowly dropwise adding 50% sodium hydroxide solution to a pH value of more than 9 while stirring and cooling at 50 ℃, then adding 50 kg of fluoboric acid, stirring for 5 hours to dissolve, and then removing the methanol under reduced pressure to obtain a first mixture;

(b) heating the first mixture to 50 ℃, adding 1200 kg of 1, 4-dihydroxy anthraquinone, 300 kg of 1, 4-dihydroxy anthraquinone leuco body and 580 kg of monomethylamine, uniformly stirring, and then continuously heating to 55 ℃ to react until the end point; determining the reaction end point by HPLC detection; cooling to 35 ℃, opening a bottom valve of the kettle, discharging the materials into a filter tank, and pumping the mother liquor to obtain a filter cake and filtrate;

(c) washing and soaking the filter cake with 500 kilograms of hot water, collecting washing and soaking liquid and filtrate, and distilling to recover the solvent; washing the filter cake to be neutral by using hot water at the temperature of 90-100 ℃, and drying, crushing and packaging to obtain 1582 kg of finished product solvent blue 78; the yield thereof was found to be 95.1%. Delta C2.714 is brilliant and the pressure value is 0.23.

Example 2

This example provides a process for the production of a low-contamination diarylamine anthraquinone solvent blue 78 dye, which is essentially the same as that of example 1, except that: the amount of the monomethylamine added in the step (b) is 600 kg; finally drying, crushing and packaging to obtain 1594 kg of finished product solvent blue 78; the yield thereof was found to be 95.8%. Delta C2.395 is slightly brilliant, and the pressure value is 0.19.

Example 3

This example provides a process for the production of a low-contamination diarylamine anthraquinone solvent blue 78 dye, which is essentially the same as that of example 1, except that: 270 kg of 1, 4-dihydroxy anthraquinone leuco body is added in the step (b); finally drying, crushing and packaging to obtain 1592 kg of finished product solvent blue 78; the yield thereof was found to be 95.7%. Δ C2.164 is brilliant and the pressure value is 0.26.

Example 4

This example provides a process for the production of a low-contamination diarylamine anthraquinone solvent blue 78 dye, which is essentially the same as that of example 1, except that: the adding amount of the N-methylimidazole in the step (a) is 670 kg; finally, 1580 kg of finished product solvent blue 78 is obtained after drying, crushing and packaging; the yield thereof was found to be 95%. Δ C2.117 is brilliant and the pressure value is 0.22.

Example 5

This example provides a process for the production of a low-contamination diarylamine anthraquinone solvent blue 78 dye, which is essentially the same as that of example 1, except that: stirring uniformly in the step (b), continuously heating to 100 ℃ for reaction, and finally drying, crushing and packaging to obtain 1589 kg of finished product solvent blue 78; the yield thereof was found to be 95.5%. Δ C2.207 is brilliant and the pressure value is 0.21.

Comparative example 1

The comparative example provides a comparative production method of solvent blue 78 dye, which is carried out by adopting a general process, and specifically comprises the following steps: 2200 kg of water is added into a condensation kettle through a metering tank, stirring is started, 450 kg of monomethylamine, 100 kg of boric acid, 800 kg of 1, 4-dihydroxy anthraquinone and 180 kg of 1, 4-dihydroxy anthraquinone leuco body are added, a cover is closed after the addition, a condenser is opened to feed and discharge water, jacket steam is fed to raise the temperature to 80-110 ℃ about 1 hour, the temperature is kept for 8 hours under a reflux state, the temperature is kept to be 40-50 ℃, a kettle bottom valve is started to discharge the material to enter a filtration tank, mother liquor is vacuumized and dried, and filter cakes are washed to be neutral by hot water at 80-90 ℃; the filter cake is dried in a drying oven, and 1431 kg of finished product of solvent blue 78 is obtained after crushing, mixing and packaging, and the yield is 86%. DeltaC-3.317 is ash-biased and the pressure value is 0.61.

Comparative example 2

This comparative example is the same as example 1 except that the mixture was stirred for 11 hours to dissolve and then methanol was removed under reduced pressure to obtain a first mixture; stirring evenly, then continuing to heat to 110 ℃ and reacting to the end point. 1437 kg of finished product solvent blue 78 is obtained, the yield is 86.4 percent, the Delta C-2.964 is slightly gray, and the pressure value is 0.36.

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.