阅读说明：本技术 一种分散蓝2bln的二硝化方法 (Dinitration method of disperse blue 2BLN ) 是由 林凤章 王永康 薛文龙 王守满 李青蛟 李丽颖 于明 于 2018-08-15 设计创作，主要内容包括：本发明属于化工技术领域,具体地说,涉及一种分散蓝2BLN的二硝化方法。所述的二硝化反应方法为：向反应釜中加入硫酸；然后加入硝酸；加完硝酸后再加入苯氧基物；加完苯氧基物后经反应、后处理得到二硝化产物。本发明采用先加入硝酸再加入苯氧基物的方法,这样硝酸溶解热与硝化反应热不同时释放,使得反应更易控制；而且先加入硝酸再加入苯氧基物可以使反应过程中硝酸始终处于过量状态,反应物一步达到反应终产物,避免了中间产物长时间存在,提高反应收率。(The invention belongs to the technical field of chemical industry, and particularly relates to a dinitration method of disperse blue 2 BLN. The dinitration reaction method comprises the following steps: adding sulfuric acid into the reaction kettle; then adding nitric acid; adding phenoxy material after adding nitric acid; after the phenoxy group substance is added, carrying out reaction and post-treatment to obtain a dinitrated product. According to the invention, the method of adding nitric acid and then adding phenoxy material is adopted, so that the dissolution heat of nitric acid and the nitration reaction heat are not released simultaneously, and the reaction is easier to control; and the nitric acid is added firstly and then the phenoxy substance is added, so that the nitric acid is always in an excessive state in the reaction process, the reactants reach a reaction final product in one step, the intermediate product is prevented from existing for a long time, and the reaction yield is improved.)

1. A dinitration method of disperse blue 2BLN is characterized in that the dinitration reaction method comprises the following steps: adding sulfuric acid into the reaction kettle; then adding nitric acid; adding phenoxy material after adding nitric acid; after the phenoxy group substance is added, carrying out reaction and post-treatment to obtain a dinitrated product.

2. The dinitration method according to claim 1, wherein after the addition of the nitric acid, the temperature of the reaction vessel is lowered to 5 to 10 ℃, and then the phenoxy compound is added to the reaction vessel, and the temperature in the reaction vessel is controlled to 8 to 15 ℃.

3. The dinitration process according to claim 2, wherein the phenoxy material is added in portions.

4. The dinitration method according to claim 3, wherein the phenoxy material is added at a rate of 3 to 10g/5 min.

5. A dinitration process according to any one of claims 1 to 4, wherein after the addition of phenoxy material, the reaction is carried out at 35 to 55 ℃ for 6 to 12 hours.

6. A dinitration process according to any one of claims 1 to 5, wherein the temperature in the reaction vessel is controlled to 15 to 25 ℃ during the addition of the nitric acid.

7. A dinitration process according to any one of claims 1 to 6, wherein the molar ratio of sulphuric acid to nitric acid and phenoxy groups is from 25 to 35: 6-9: 1.

8. the dinitration process according to any one of claims 1-7, wherein the nitric acid is added dropwise.

9. The dinitration method according to claim 8, wherein the nitric acid is added dropwise at a rate of 0.5-5 ml/min.

10. The dinitration method according to any one of claims 1 to 9, wherein the post-treatment is to slowly add the reactants into cold water at 0-20 ℃ to precipitate the material and obtain the dinitrated product.

Technical Field

The invention belongs to the technical field of chemical industry, and particularly relates to a dinitration method of disperse blue 2 BLN.

Background

Disperse blue 2BLN (C.I. disperse blue 56) is an important variety in disperse dyes, has bright color and excellent light fastness, can be used for color matching and can also be used in a single color, and is an indispensable color spectrum in old three samples. Although the sublimation resistance is inferior to that of the disperse blue BGL, the demand for producing the variety is still urgent.

Disperse blue 2BLN belongs to a low-temperature anthraquinone structure disperse dye, and has bright color light, good level-dyeing property, low dyeing temperature and stable product quality. However, some of its properties are not sufficient during use: the dyeing fastness is not ideal, the acid and alkali resistance is poor, the lifting power is not high, and the application range is influenced to a certain extent.

The process route of disperse blue 2BLN (c.i. disperse blue 56) includes mercury process and non-mercury process, wherein the mercury process includes sulfonation, and the sulfonation must introduce sulfonic acid group on anthraquinone benzene ring by using mercury as catalyst, thereby causing mercury hazard. On average, ten kilograms of metallic mercury are consumed per ton of anthraquinone fed. Furthermore, 2, 4-dinitrophenol is removed from the 1,5- [2, 4-dinitrophenoxy ] -4, 8-dinitroanthraquinone hydrolyzate, which is said to be carcinogenic, again resulting in phenolic contamination. Therefore, the mercury process is gradually abandoned, and most manufacturers at home and abroad produce the mercury-free mercury.

The non-mercury method comprises the following steps: firstly, anthraquinone and mixed acid are subjected to primary nitration reaction to obtain 1, 5-dinitroanthraquinone, then the 1, 5-dinitroanthraquinone is subjected to phenoxy reaction to obtain 1, 5-diphenoxy anthraquinone, and then the obtained 1, 5-diphenoxy anthraquinone is subjected to secondary nitration, hydrolysis, reduction and bromination to obtain disperse blue 2 BLN. Compared with the mercury method, the method reduces the working procedures and avoids the mercury damage.

In the non-mercury process, the dinitration process is basically the same in the current domestic various factory processes, namely, phenoxy material is dissolved in sulfuric acid at the temperature of 5-10 ℃, the molecular ratio of the sulfuric acid to the phenoxy material is 30:1, then nitric acid is dripped into the mixture at the temperature of 10-20 ℃, the molecular ratio is 7.5-8.5, the mixture is heated to 40 ℃ after the nitric acid is added for 2 hours, the mixture is kept warm for about 8 hours, the mixture is cooled to 10 ℃, and nitrate is dripped into the mixture at the temperature of 0-5 ℃ while the dilution water is kept. The dinitration process is found to have the following problems in actual production: 1) in the process of dropping nitric acid into the slurry for reaction, the concentration of reactants is greater than that of nitric acid, so that various intermediate products such as primary substitution, secondary substitution and the like are generated, the stability of the intermediate products is poor, and other impurities are easily generated; 2) the nitration reaction is a strong exothermic reaction, the mixing of nitric acid and sulfuric acid can release a lot of heat, and the reaction heat and the dissolution heat are released simultaneously, which is unfavorable for the reaction process.

The present invention has been made in view of this situation.

Disclosure of Invention

The invention aims to overcome the defects of the prior art and provide a dinitration method for disperse blue 2 BLN.

In order to solve the technical problems, the invention adopts the following technical scheme:

a dinitration method of disperse blue 2BLN, wherein said dinitration method is: adding sulfuric acid into the reaction kettle; then adding nitric acid; adding phenoxy material after adding nitric acid; after the phenoxy group substance is added, carrying out reaction and post-treatment to obtain a dinitrated product.

The dinitration method in the disperse blue 2BLN non-mercury process is basically the same in the prior domestic various factory processes, for example, phenoxy material is dissolved in sulfuric acid at the temperature of 5-10 ℃, the molecular ratio of the sulfuric acid to the phenoxy material is 30:1, then nitric acid is dripped into the mixture at the temperature of 10-20 ℃, the molecular ratio is 7.5-8.5, the mixture is heated to 40 ℃ after the nitric acid is added for 2 hours, the mixture is kept at the temperature for about 8 hours, the mixture is cooled to 10 ℃, and the nitrated substance is dripped into the mixture at the temperature of 0-5 ℃ while the dilution water temperature is maintained. The reaction formula is as follows:

the phenoxy radical is a mixture of 1, 5-diphenoxy anthraquinone and 1, 8-diphenoxy anthraquinone. The dinitrated product obtained after dinitration is therefore also a mixture. The dinitration method is found to have the following problems in actual production: 1) in the process of dropping nitric acid into the slurry for reaction, if the concentration of reactants is greater than that of nitric acid, phenoxy substances are excessive, 1 nitro group, 2 nitro groups, 3 nitro groups, 4 nitro groups and 5 nitro group substituted intermediate products can be generated, the stability of the intermediate products is poor, other impurities are easily generated, and the dinitrated product has low purity and low yield; and if the final nitric acid is not sufficient, these intermediate products cannot be converted into the final product; 2) the nitration reaction is a strong exothermic reaction, the mixing of nitric acid and sulfuric acid can release a lot of heat, and the reaction heat and the dissolution heat are released simultaneously, which is unfavorable for the reaction process.

According to the invention, the method of adding nitric acid and then adding phenoxy material is adopted, so that the dissolution heat of nitric acid and the nitration reaction heat are not released simultaneously, and the reaction is easier to control; and the nitric acid is added firstly, and then the phenoxy substance is added, so that the nitric acid is always in an excessive state in the reaction process, the reactant reaches a reaction final product in one step, the intermediate product is prevented from existing for a long time, and the yield and the purity of the dinitration reaction are improved.

Further, after the nitric acid is added, the temperature of the reaction kettle is reduced to 5-10 ℃, then the phenoxy material is added, and the temperature in the reaction kettle is controlled to be 8-15 ℃.

In the invention, when the phenoxy material is added, the temperature in the reaction kettle is strictly controlled, and meanwhile, the temperature in the reaction kettle in the whole process of adding the phenoxy material is strictly controlled, so that the generation of other impurities is avoided.

Furthermore, the phenoxy materials are added in a batch mode.

Further, the adding speed of the phenoxy material is 3-10 g/5 min.

According to the invention, the phenoxy group is added in a batch mode, and the adding speed is controlled to be 3-10 g/5min, so that the phenoxy group is ensured to fully react.

Further, after the phenoxy group substance is added, heating to 35-55 ℃, and reacting for 6-12 hours in a heat preservation manner.

Further, in the process of adding the nitric acid, controlling the temperature in the reaction kettle to be 15-25 ℃.

Further, the molar ratio of the sulfuric acid to the nitric acid to the phenoxy group is 25-35: 6-9: 1.

further, the nitric acid is added in a dropwise manner.

Further, the dropping speed of the nitric acid is 0.5-5 ml/min.

Further, the post-treatment comprises the step of slowly adding the reactant into cold water at the temperature of 0-20 ℃, and separating out the material to obtain a dinitrated product.

Disperse blue 2BLN belongs to a low-temperature anthraquinone structure disperse dye, and has bright color light, good level-dyeing property, low dyeing temperature and stable product quality. However, some of its properties are not sufficient during use: the dyeing fastness is not ideal, the acid and alkali resistance is poor, the lifting power is not high, and the application range is influenced to a certain extent.

The invention surprisingly finds that the soaping fastness and the sublimation fastness resistance of the disperse blue 2BLN prepared by combining the dinitration method with the traditional preparation process are obviously better than those of the disperse blue 2BLN prepared by combining the dinitration method with the traditional preparation process in the prior art. This may be due to the fact that some of the intermediates in the conventional process are not converted to the final product and are not easily removed, resulting in poor soaping fastness and sublimation fastness properties of the final product, which is dispersed in blue 2 BLN. The dinitration method adopts a mode of firstly adding sulfuric acid, then adding nitric acid and then adding a phenoxy substance, strictly controls the temperature before and during the addition of the phenoxy substance, adopts a mode of adding the phenoxy substance in batches and strictly controls the adding speed, and fully avoids the generation of intermediate products substituted by 1 nitro group, 2 nitro groups, 3 nitro groups, 4 nitro groups and 5 nitro groups in dinitration reaction by combining the traditional process, thereby improving the soaping fastness and the sublimation fastness resistance.

After adopting the technical scheme, compared with the prior art, the invention has the following beneficial effects:

according to the invention, the method of adding nitric acid and then adding phenoxy material is adopted, so that the dissolution heat of nitric acid and the nitration reaction heat are not released simultaneously, and the reaction is easier to control; and the nitric acid is added firstly and then the phenoxy substance is added, so that the nitric acid is always in an excessive state in the reaction process, the reactants reach a reaction final product in one step, the intermediate product is prevented from existing for a long time, and the reaction yield is improved.

Meanwhile, surprisingly, the soaping fastness and the sublimation fastness resistance of the disperse blue 2BLN prepared by combining the dinitration method with the traditional preparation process are obviously better than those of the disperse blue 2BLN prepared by combining the dinitration method with the traditional preparation process in the prior art.

Detailed Description

In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments will be clearly and completely described below with reference to the embodiments of the present invention, and the following embodiments are used for illustrating the present invention and are not intended to limit the scope of the present invention.