阅读说明：本技术 一种低毒低害环保型溶剂绿3的合成方法 (Synthetic method of low-toxicity low-harm environment-friendly solvent green 3 ) 是由 周利霞 陈�胜 杨庆水 刘镛 于 2019-09-24 设计创作，主要内容包括：本发明涉及一种低毒低害环保型溶剂绿3的合成方法,包括如下步骤：(a)向反应容器中加入N-丁基咪唑、丙酮,缓慢滴加溴乙烷进行反应,再加入四氟硼酸钠进行阴离子交换,继续搅拌得到离子液体；(b)再向离子液体中加入1,4-二羟基蒽醌、1,4-二羟基蒽醌隐色体、对甲基苯胺,进行缩合反应得到第一混合溶液；(c)将第一混合溶液降温进行抽滤得滤饼和滤液,将滤饼进行洗涤后处理,得到溶剂绿3。本发明将合成得到的离子液体作为溶剂,并通过离子液体中有机阳离子及阴离子的选型,使缩合反应为双缩合,产物纯度明显提高至98％以上,收率达到95％以上,此外离子液体能够循环使用,成本大幅度下降,污染物排放量减少；获得的溶剂绿3染料△E<0.5,△C为偏艳,压力值<0.2。(The invention relates to a synthesis method of low-toxicity low-harm environment-friendly solvent green 3, which comprises the following steps: (a) adding N-butylimidazole and acetone into a reaction container, slowly dropwise adding ethyl bromide for reaction, adding sodium tetrafluoroborate for anion exchange, and continuously stirring to obtain an ionic liquid; (b) adding 1, 4-dihydroxy anthraquinone, 1, 4-dihydroxy anthraquinone leuco body and p-methylaniline into the ionic liquid, and carrying out condensation reaction to obtain a first mixed solution; (c) and cooling the first mixed solution, carrying out suction filtration to obtain a filter cake and filtrate, and washing the filter cake and carrying out aftertreatment to obtain a solvent green 3. The invention takes the synthesized ionic liquid as a solvent, and makes the condensation reaction be double condensation by selecting the types of organic cations and anions in the ionic liquid, the purity of the product is obviously improved to more than 98 percent, the yield reaches more than 95 percent, in addition, the ionic liquid can be recycled, the cost is greatly reduced, and the pollutant discharge amount is reduced; the obtained solvent green 3 dye has delta E less than 0.5, delta C of brilliant color and pressure value less than 0.2.)

1. A synthetic method of low-toxicity low-harm environment-friendly solvent green 3 is characterized by comprising the following steps:

(a) adding N-butylimidazole and acetone into a reaction container, slowly dropwise adding bromoethane under stirring for reaction, reacting for 2-4h, then adding sodium tetrafluoroborate for anion exchange, removing excessive bromoethane and acetone under reduced pressure, and continuously stirring to obtain an ionic liquid;

(b) heating the ionic liquid to 80-90 ℃, adding 1, 4-dihydroxyanthraquinone, 1, 4-dihydroxyanthraquinone leuco body and p-methylaniline into the ionic liquid, stirring, heating to 120-;

(c) cooling the first mixed solution to 40-50 ℃, carrying out suction filtration to obtain a filter cake and filtrate, washing the filter cake with hot water to obtain a bubble washing solution, combining the bubble washing solution and the filtrate, and distilling to obtain a second mixed solution; and carrying out post-treatment on the filter cake obtained by washing to obtain the solvent green 3.

2. The synthesis method of the low-toxicity low-harm environment-friendly solvent green 3 according to claim 1, characterized in that: in the step (a), the feeding mass ratio of the N-butylimidazole, the bromoethane and the sodium tetrafluoroborate is 1-1.1: 1: 1.

3. The synthesis method of the low-toxicity low-harm environment-friendly solvent green 3 according to claim 1, characterized in that: in the step (a), the feeding mass ratio of the acetone to the N-butylimidazole is 1.2-1.5: 1.

4. The synthesis method of the low-toxicity low-harm environment-friendly solvent green 3 according to claim 1, characterized in that: in the step (b), the ratio of the feeding mass of the p-methylaniline to the total feeding mass of the 1, 4-dihydroxyanthraquinone and the 1, 4-dihydroxyanthraquinone leuco body is 1-1.5: 1.

5. The synthesis method of the low-toxicity low-harm environment-friendly solvent green 3 according to claim 1, characterized in that: the feeding mass of the N-butylimidazole and the total feeding mass of the 1, 4-dihydroxyanthraquinone and the 1, 4-dihydroxyanthraquinone leuco body are in a ratio of 0.2-0.4: 1.

6. The synthesis method of the low-toxicity low-harm environment-friendly solvent green 3 according to claim 1, characterized in that: in the step (c), the temperature of the second mixed solution is raised to 100-110 ℃ for dehydration, so as to obtain a first recovery solution which is used as the ionic liquid in the step (a) for reuse, and then the steps (b) and (c) are carried out, so as to obtain the solvent green 3.

7. The synthesis method of the low-toxicity low-harm environment-friendly solvent green 3 according to claim 1, characterized in that: in the step (c), the temperature of the hot water is 80-90 ℃, and the post-treatment is to wash the filter cake to be neutral by using the hot water of 80-100 ℃ and then dry the filter cake.

Technical Field

The invention relates to a synthesis method of a dye, in particular to a synthesis method of low-toxicity low-harm environment-friendly solvent green 3.

Background

Solvent Green 3 is also called oil soluble Green 5B and transparent Green 5B, its chemical name is 1, 4-di (p-methylanilino) -anthraquinone, English name is Solvent Green 3, molecular formula is C₂₈H₂₂N₂O₂Molecular weight 418.49, CAS number 128-80-3. The product is blue black powder, is insoluble in water, is soluble in organic solvent such as chloroform, benzene, chlorobenzene, xylene, DMF, etc., is blue in concentrated sulfuric acid, and is diluted with water to generate blue green precipitate. Melting point 213 ℃. The light fastness in PS can reach 7-8 grades, and the heat resistance in PS can reach 300 ℃. The solvent green 3 is mainly used for coloring various resins, and is also used for coloring virgin stock of polyester fibers and coloring petroleum products, coatings and the like; it can also be used for manufacturing color master batch for terylene, and is applied to coloring daily plastics, organic glass, PVC packaging materials, industrial grease, printing ink and the like.

At present, the general process for producing the solvent green 3 comprises the steps of adding ethanol into a condensation kettle through a metering tank, starting stirring, adding p-toluidine, boric acid, 1, 4-dihydroxy anthraquinone and 1, 4-dihydroxy anthraquinone leuco bodies, sealing a cover after adding, opening a condenser to feed in and discharge water, heating steam in a jacket, heating to 80-110 ℃ about 1 hour, keeping the temperature for 15 hours under a reflux state, continuously cooling to 40-50 ℃, starting a kettle bottom valve to discharge the materials, feeding the materials into a filtration tank, vacuumizing to dry mother liquor, and washing a filter cake 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 green 3. The solvent green 3 product produced by the process has poor quality and poor color light reproducibility, the hue delta E is more than 0.5 and accounts for about 50 percent of the total yield, and part of single-batch products can reach qualified quality only by solvent refining, thereby causing resource waste; excessive toxic solvent p-toluidine needs to be recovered, the recovery process has poor operation site environment, poisoning events of operators often occur in industry, and meanwhile, the environment is also polluted; the reaction yield is low, about 86%, and the competitive double condensation and hydrolysis side reactions generated in the reaction process are not easy to control, so that the reaction selectivity is influenced, and further the product yield is influenced.

Disclosure of Invention

The invention aims to overcome the defects of the prior art and provide a method for synthesizing solvent green 3 with high conversion rate.

In order to achieve the purpose, the invention adopts the technical scheme that: a synthetic method of low-toxicity low-harm environment-friendly solvent green 3 comprises the following steps:

(a) adding N-butylimidazole and acetone into a reaction container, slowly dropwise adding ethyl bromide under stirring for reaction, reacting for 2-4h, then adding sodium tetrafluoroborate for anion exchange, and continuously stirring to obtain an ionic liquid;

(b) heating the ionic liquid to 80-90 ℃, adding 1, 4-dihydroxyanthraquinone, 1, 4-dihydroxyanthraquinone leuco body and p-methylaniline into the ionic liquid, stirring, heating to 120-;

(c) cooling the first mixed solution to 40-50 ℃, carrying out suction filtration to obtain a filter cake and filtrate, washing the filter cake with hot water to obtain a bubble washing solution, combining the bubble washing solution and the filtrate, and distilling to obtain a second mixed solution; and carrying out post-treatment on the filter cake obtained by washing to obtain the solvent green 3.

Specifically, in the step (a), the feeding mass ratio of the N-butylimidazole, the bromoethane and the sodium tetrafluoroborate is 1-1.1: 1: 1.

Specifically, in the step (a), the feeding mass ratio of the acetone to the N-butylimidazole is 1.2-1.5: 1.

Preferably, in the step (a), the feeding mass ratio of the acetone to the N-butylimidazole is 1.2-1.25: 1.

Specifically, in the step (b), the ratio of the feeding mass of the p-methylaniline to the total feeding mass of the 1, 4-dihydroxyanthraquinone and the 1, 4-dihydroxyanthraquinone leuco body is 1-1.5: 1.

Preferably, in the step (b), the ratio of the feeding mass of the p-methylaniline to the total feeding mass of the 1, 4-dihydroxyanthraquinone and the 1, 4-dihydroxyanthraquinone leuco body is 1.3-1.5: 1.

Specifically, the ratio of the feeding mass of the N-butylimidazole to the total feeding mass of the 1, 4-dihydroxyanthraquinone and the 1, 4-dihydroxyanthraquinone leuco body is 0.2-0.4: 1.

Specifically, in the step (c), the temperature of the second mixed solution is raised to 100-110 ℃ for dehydration, so as to obtain a first recovery solution which is used as the ionic liquid in the step (a) for reuse, and then the steps (b) and (c) are carried out, so as to obtain the solvent green 3.

Specifically, in the step (c), the temperature of the hot water is 80-90 ℃, and the post-treatment is to wash the filter cake to be neutral by using the hot water at 80-100 ℃ and then dry the filter cake.

Preferably, in the step (c), the post-treatment is to wash the filter cake to be neutral by using hot water with the temperature of 90-100 ℃.

In the invention, as the Ionic Liquids (ILs for short) have non-volatility, VOC emission caused by volatilization in the processes of material pumping, filtering and distillation of the traditional organic solvent and solvent loss caused by volatilization can be avoided in the industrial production process; the ionic liquid has good 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 many times after being heated to 110 ℃ for dehydration, the loss is extremely low, 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.

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: the invention relates to a synthesis method of low-toxicity low-harm environment-friendly solvent green 3, which is characterized in that the synthesized ionic liquid is used as a solvent, and the type selection of organic cations and anions in the ionic liquid is adopted, so that the condensation reaction is a double condensation reaction, the high selectivity is realized, impurities generated by low selectivity caused by competitive single condensation and hydrolysis side reactions in the prior art are avoided, the product purity is obviously improved to more than 98%, the yield is more than 95%, in addition, the synthesized ionic liquid can be recycled, the production cost is greatly reduced, the economic benefit is obvious, and the pollutant discharge amount is reduced; the obtained solvent green 3 dye has delta E less than 0.5, delta C of more gorgeous color and pressure value less than 0.2, and the product quality can meet the application requirements of high-end customers.

Drawings

FIG. 1 is a schematic process flow diagram of the present invention.

Detailed Description

The synthesis method of the low-toxicity low-harm environment-friendly solvent green 3 comprises the following steps:

(a) adding N-butylimidazole and acetone into a reaction container, slowly dropwise adding ethyl bromide under stirring to react, adding sodium tetrafluoroborate to perform anion exchange after reacting for 2-4h, continuously stirring for 4-6h, and removing acetone through reduced pressure distillation to obtain ionic liquid; the mass ratio of the N-butylimidazole to the bromoethane to the sodium tetrafluoroborate is 1-1.1: 1:1, and the mass ratio of the acetone to the N-butylimidazole is 1.2-1.5: 1.

(b) Heating the ionic liquid to 80-90 ℃, adding 1, 4-dihydroxyanthraquinone, 1, 4-dihydroxyanthraquinone leuco body and p-methylaniline into the ionic liquid, stirring and heating to 120-130 ℃ for condensation reaction, and determining a reaction end point by using HPLC (high performance liquid chromatography) detection to obtain a first mixed solution; the feeding mass of the p-methylaniline and the total feeding mass of the 1, 4-dihydroxy anthraquinone and 1, 4-dihydroxy anthraquinone leuco bodies are in a ratio of 1-1.5: 1; the ratio of the feeding mass of the N-butylimidazole to the total feeding mass of the 1, 4-dihydroxyanthraquinone and 1, 4-dihydroxyanthraquinone leuco bodies is 0.2-0.4: 1;

(c) cooling the first mixed solution to 40-50 ℃, carrying out suction filtration to obtain a filter cake and filtrate, washing the filter cake with hot water at 80-90 ℃ to obtain a bubble washing solution, combining the bubble washing solution and the filtrate, and distilling to obtain a second mixed solution; and carrying out post-treatment on the washed filter cake, washing the filter cake to be neutral by using hot water at the temperature of 80-100 ℃, and drying to obtain a solvent green 3. And (3) heating the second mixed solution to 100-110 ℃ for dehydration to obtain a first recovery solution which is used as the ionic liquid in the step (a) for repeated use, and then performing the steps (b) and (c) to obtain the solvent green 3.

Preferably, in the step (a), the feeding mass ratio of the acetone to the N-butylimidazole is 1.2-1.25: 1; in the step (b), the ratio of the feeding mass of the p-methylaniline to the total feeding mass of the 1, 4-dihydroxy anthraquinone and 1, 4-dihydroxy anthraquinone leuco bodies is 1.3-1.5: 1; in the step (c), the post-treatment is to wash the filter cake to be neutral by using hot water at 90-100 ℃.

The invention will be further described with reference to specific examples, but the scope of protection of the invention is not limited thereto: