阅读说明：本技术 环保型2，6-二氯-4-硝基苯胺的制备方法 (Preparation method of environment-friendly 2, 6-dichloro-4-nitroaniline ) 是由 李百春 陈望全 钱军良 贺建斌 于 2020-06-02 设计创作，主要内容包括：本发明公开了环保型2,6-二氯-4-硝基苯胺的制备方法,属于环保领域,环保型2,6-二氯-4-硝基苯胺的制备方法,包括以下步骤：第一步,将邻二氯苯,即如式(I)所示的组分加入到硝酸和硫酸溶液中反应,得到间硝基-1,2-二氯苯,即如式(II)所示的组分；第二步,将第一步中得到的间硝基-1,2-二氯苯加入到氨水溶液内反应,得到2-氯-4-硝基苯胺,即如式(III)所示的组分；第三步,向第二步得到的2-氯-4-硝基苯胺中滴加盐酸和过氧化氢溶液,用新的制备方法,有效降低2,6-二氯-4-硝基苯胺制备过程中多氯酚的产生,更加环保符合OECO-Textile 100的要求,最终其制备方法在投入实际生产后的染料直接符合OECO-Textile 100的要求。(The invention discloses a preparation method of environment-friendly 2, 6-dichloro-4-nitroaniline, belonging to the field of environmental protection, and the preparation method of the environment-friendly 2, 6-dichloro-4-nitroaniline comprises the following steps: firstly, adding o-dichlorobenzene, namely a component shown as a formula (I), into a nitric acid and sulfuric acid solution for reaction to obtain m-nitro-1, 2-dichlorobenzene, namely a component shown as a formula (II); secondly, adding the m-nitro-1, 2-dichlorobenzene obtained in the first step into an ammonia solution for reaction to obtain 2-chloro-4-nitroaniline, namely the component shown in the formula (III); and thirdly, dripping hydrochloric acid and hydrogen peroxide solution into the 2-chloro-4-nitroaniline obtained in the second step, and effectively reducing the generation of polychlorinated phenol in the preparation process of the 2, 6-dichloro-4-nitroaniline by using a novel preparation method, so that the preparation method is more environment-friendly and meets the requirement of OECO-Textille 100, and finally the dye of the preparation method after being put into practical production directly meets the requirement of OECO-Textille 100.)

1. The preparation method of the environment-friendly 2, 6-dichloro-4-nitroaniline is characterized by comprising the following steps:

firstly, adding o-dichlorobenzene, namely a component shown as a formula (I), into a nitric acid and sulfuric acid solution for reaction to obtain m-nitro-1, 2-dichlorobenzene, namely a component shown as a formula (II);

secondly, adding the m-nitro-1, 2-dichlorobenzene obtained in the first step into an ammonia water solution for reaction to obtain 2-chloro-4-nitroaniline, namely the component shown in the formula (III), wherein the ammonia water solution is excessive so that the obtained 2-chloro-4-nitroaniline solution is alkaline;

thirdly, dripping hydrochloric acid and hydrogen peroxide solution into the 2-chloro-4-nitroaniline obtained in the second step, and obtaining the 2, 6-dichloro-4-nitroaniline as the formula (IV) after the reaction is completed and post-treatment;

2. the method for preparing environment-friendly 2, 6-dichloro-4-nitroaniline according to claim 1, characterized in that the reaction in the first step is specifically to add the component shown in formula (I) in a sulfuric acid environment, and then to drop nitric acid for nitration reaction.

3. The method for preparing environment-friendly 2, 6-dichloro-4-nitroaniline according to claim 1, wherein in the first step, the temperature of the o-dichlorobenzene reaction is 0-5 ℃ and the time is 3-5 hours, the molar ratio of the o-dichlorobenzene to the nitric acid to the sulfuric acid is 1: 1.1-1.5: 3-6.

4. The method for preparing environment-friendly 2, 6-dichloro-4-nitroaniline according to claim 1, wherein in the second step, the mass percentage of the ammonia water in the reaction is 20-25%, and the molar ratio of m-nitro-1, 2-dichlorobenzene to ammonia is 1: 5 to 10.

5. The method for preparing environment-friendly 2, 6-dichloro-4-nitroaniline according to claim 1, wherein in the third step, the mass percent of the hydrochloric acid solution is 25-35%, the mass percent of the hydrogen peroxide solution is 25-35%, and the molar ratio of the 2-chloro-4-nitroaniline, the hydrochloric acid solution and the hydrogen peroxide solution is 1: 1.2-1.5: 2-10.

6. The process for preparing environmentally friendly 2, 6-dichloro-4-nitroaniline according to claim 1, wherein the post-treatment in the third step comprises neutralization, temperature-raising crystal-transformation and filtration washing.

7. A method for preparing a dye having a structure shown in formula (V) from the environmentally-friendly 2, 6-dichloro-4-nitroaniline of claims 1-6, characterized in that the dye preparation further comprises a fourth step of adding the prepared 2, 6-dichloro-4-nitroaniline into a nitrosyl sulfuric acid and sulfuric acid solution to obtain a component shown in formula (V-1), and then adding the component into an ice water solution of a coupling component for reaction to obtain the dye having a structure shown in formula (V):

8. the method for preparing the structural dye as shown in the formula (V) by using the environment-friendly 2, 6-dichloro-4-nitroaniline according to claim 7, wherein the mass percent of the nitrosyl sulfuric acid solution is 40-45%, the mass percent of the sulfuric acid solution is 96-98%, and the molar ratio of the 2, 6-dichloro-4-nitroaniline, the nitrosyl sulfuric acid and the sulfuric acid is 1: 1.05-1: 2 to 5.

9. Use of azo dyes prepared from the environmentally friendly 2, 6-dichloro-4-nitroaniline of claims 1-6 in dyeing.

Technical Field

The invention relates to the field of environmental protection, in particular to a preparation method of environment-friendly 2, 6-dichloro-4-nitroaniline.

Background

2, 6-dichloro-4-nitroaniline is a very important intermediate of a benzene series azo disperse dye, and is a diazo component of disperse orange S-4RL, disperse orange C-2R, disperse orange 5 and the like, but most of the traditional preparation methods adopt a direct chlorination method for synthesis:

the reaction process generates a large amount of polychlorobenzene, while the production of a large amount of polychlorophenol and polychlorobenzene during the dye synthesis process do not meet the requirements of OECO-Textile 100.

Disclosure of Invention

1. Technical problem to be solved

Aiming at the problems in the prior art, the first purpose of the invention is to provide a preparation method of environment-friendly 2, 6-dichloro-4-nitroaniline, which can reduce the generation of polychlorinated phenol and polychlorinated benzene in the preparation process of the 2, 6-dichloro-4-nitroaniline, and finally the dye of the preparation method directly meets the requirements of OECO-Textile 100 after being put into practical production;

the second invention aims to provide a method for preparing the dye with the structure shown in the formula (V) by using environment-friendly 2, 6-dichloro-4-nitrobenzene, namely a novel preparation process of environment-friendly 2, 6-dichloro-4-nitroaniline which is further specifically applied to the preparation of the environment-friendly dye;

the third invention aims to provide the application of azo dye prepared from environment-friendly 2, 6-dichloro-4-nitroaniline in dyeing.

2. Technical scheme

In order to solve the above problems, the present invention adopts the following technical solutions.

Firstly, adding o-dichlorobenzene, namely a component shown as a formula (I), into a nitric acid and sulfuric acid solution for reaction to obtain m-nitro-1, 2-dichlorobenzene, namely a component shown as a formula (II);

secondly, adding the m-nitro-1, 2-dichlorobenzene obtained in the first step into an ammonia water solution for reaction to obtain 2-chloro-4-nitroaniline, namely the component shown in the formula (III), wherein the ammonia water solution is excessive so that the obtained 2-chloro-4-nitroaniline solution is alkaline;

thirdly, dripping hydrochloric acid and hydrogen peroxide solution into the 2-chloro-4-nitroaniline obtained in the second step, and obtaining the 2, 6-dichloro-4-nitroaniline as the formula (IV) after the reaction is completed and post-treatment;

further, the reaction in the first step is specifically to add the components shown in the formula (I) in a sulfuric acid environment, and then dropwise add nitric acid to carry out nitration reaction.

Further, in the first step, the temperature of the o-dichlorobenzene reaction is 0-5 ℃, the time is 3-5 hours, and the molar ratio of the o-dichlorobenzene to the nitric acid to the sulfuric acid is 1: 1.1-1.5: 3-6.

Further, in the second step, the mass percentage of the ammonia water in the reaction is 20-25%, and the molar ratio of the m-nitro-1, 2-dichlorobenzene to the ammonia (NH3) is 1: 5 to 10.

Further, in the third step, the mass percent of the hydrochloric acid solution is 25-35%, the mass percent of the hydrogen peroxide solution is 25-35%, and the molar ratio of the 2-chloro-4-nitroaniline, the hydrochloric acid solution and the hydrogen peroxide solution is 1: 1.2-1.5: 2-10.

Further, the post-treatment in the third step comprises neutralization, temperature rise crystal transformation and filtration washing.

A method for preparing a dye having a structure shown in formula (V) by using the environmentally friendly 2, 6-dichloro-4-nitroaniline of claim 1, wherein the dye is prepared by the following steps:

firstly, adding o-dichlorobenzene, namely a component shown as a formula (I), into a nitric acid and sulfuric acid solution for reaction to obtain m-nitro-1, 2-dichlorobenzene, namely a component shown as a formula (II);

secondly, adding the m-nitro-1, 2-dichlorobenzene obtained in the first step into an ammonia solution for reaction to obtain 2-chloro-4-nitroaniline, namely the component shown in the formula (III);

thirdly, dripping hydrochloric acid and hydrogen peroxide solution into the 2-chloro-4-nitroaniline obtained in the second step, and obtaining the 2, 6-dichloro-4-nitroaniline after the reaction is completed and post-treatment;

fourthly, adding the prepared 2, 6-dichloro-4-nitroaniline into nitrosyl sulfuric acid and sulfuric acid solution to obtain a component shown as a formula (V-1), and then adding the component into ice water solution of a coupling component for reaction to obtain the dye with the structure shown as the formula (V).

Further, the mass percent of the nitrosyl sulfuric acid solution is 40-45%, the mass percent of the sulfuric acid solution is 96-98%, and the molar ratio of the 2, 6-dichloro-4-nitroaniline, the nitrosyl sulfuric acid and the sulfuric acid is 1: 1.05-1: 2 to 5.

An application of azo dye prepared from the environment-friendly 2, 6-dichloro-4-nitroaniline in dyeing.

3. Advantageous effects

Compared with the prior art, the invention has the advantages that:

compared with the existing method in life, the preparation method is more environment-friendly, the generation of polychlorinated phenol and polychlorinated benzene is greatly reduced in the preparation process, and finally the dye of the preparation method directly meets the requirements of OECO-Textille 100 after being put into actual production.

Secondly, preparing the dye with the structure shown in the formula (V) by using the 2, 6-dichloro-4-nitroaniline prepared by the method.

Thirdly, the environment-friendly 2, 6-dichloro-4-nitroaniline prepared by the method is prepared into azo dye to be applied to dyeing.

Detailed Description

The technical scheme in the embodiment of the invention is clearly and completely described below; obviously; the described embodiments are only some of the embodiments of the invention; but not all embodiments, are based on the embodiments of the invention; all other embodiments obtained by a person skilled in the art without making any inventive step; all fall within the scope of protection of the present invention.