阅读说明：本技术 一种1-氨基-4-萘磺酸钠的绿色制备方法 (Green preparation method of 1-amino-4-sodium naphthalenesulfonate ) 是由 刘万兴 刘秀峥 邓长镇 杜振 曹翠莲 于 2020-05-26 设计创作，主要内容包括：本发明公开了一种1-氨基-4-萘磺酸钠的绿色制备方法,涉及化工染料中间体技术领域,包括以下步骤：将1-萘胺、表面活性剂、有机溶剂添加到反应装置中,并进行升温搅拌,升温至50-70℃开始慢慢滴加硫酸生成硫酸铵盐,滴加温度低于85℃,10-20min滴加完毕,成盐时有白色固体颗粒析出；随后升温到175-190℃,转位进行磺化反应,持续回流反应4-8h；冷却至100-105℃,加水稀释的同时并加入碳酸钠调节溶液pH,搅拌并降温至70-80℃,保温静置分层,将上层水相冷却至15-21℃,经过结晶过滤后得到1-氨基-4-萘磺酸钠。本发明使用液相磺化法改进1,4酸钠的合成路线,降低了反应能垒,实现常压且低温条件下进行反应。(The invention discloses a green preparation method of 1-amino-4-sodium naphthalenesulfonate, relating to the technical field of chemical dye intermediates and comprising the following steps: adding 1-naphthylamine, a surfactant and an organic solvent into a reaction device, heating and stirring, slowly dripping sulfuric acid to generate ammonium sulfate salt when the temperature is raised to 50-70 ℃, wherein the dripping temperature is lower than 85 ℃, and white solid particles are separated out when the dripping is finished within 10-20min after salifying; then heating to 175-190 ℃, performing transposition sulfonation reaction, and continuously performing reflux reaction for 4-8 h; cooling to 100-105 ℃, adding water for dilution, adding sodium carbonate for regulating the pH value of the solution, stirring, cooling to 70-80 ℃, preserving heat, standing for layering, cooling the upper-layer water phase to 15-21 ℃, and crystallizing and filtering to obtain the sodium 1-amino-4-naphthalenesulfonate. The invention uses a liquid phase sulfonation method to improve the synthetic route of the sodium 1,4, reduces the reaction energy barrier and realizes the reaction under the conditions of normal pressure and low temperature.)

1. A green preparation method of 1-amino-4-sodium naphthalenesulfonate is characterized by comprising the following steps: the method comprises the following steps: adding 1-naphthylamine, a surfactant and an organic solvent into a reaction device, heating and stirring, slowly dripping sulfuric acid to generate ammonium sulfate salt when the temperature is raised to 50-70 ℃, wherein the dripping temperature is lower than 85 ℃, and white solid particles are separated out when the dripping is finished within 10-20min after salifying; then heating to 175-190 ℃, performing transposition sulfonation reaction, and continuously performing reflux reaction for 4-8 h; cooling to 100-105 ℃, adding water for dilution, adding sodium carbonate for regulating the pH value of the solution, stirring, cooling to 70-80 ℃, preserving heat, standing for layering, cooling the upper-layer water phase to 15-21 ℃, and crystallizing and filtering to obtain the sodium 1-amino-4-naphthalenesulfonate.

2. The green preparation method of sodium 1-amino-4-naphthalenesulfonate according to claim 1, characterized in that: the separated lower layer organic adjacent dichlorobenzene is used for sulfonation recycling.

3. The green preparation method of sodium 1-amino-4-naphthalenesulfonate according to claim 1, characterized in that: the surfactant is any one of tween 60, tween 80, span 60 and span 80.

4. The green preparation method of sodium 1-amino-4-naphthalenesulfonate according to claim 1, characterized in that: the organic solvent is any one of mesitylene, o-dichlorobenzene, ethylene glycol monobutyl ether, 3, 4-dichlorotoluene, nitrobenzene and tetrabromoethane.

5. The green preparation method of sodium 1-amino-4-naphthalenesulfonate according to claim 1, characterized in that: and the reaction device is provided with a reflux dehydration device.

Technical Field

The invention relates to the technical field of chemical dye intermediates, in particular to a green preparation method of 1-amino-4-sodium naphthalenesulfonate.

Background

Sodium 1-amino-4-naphthalenesulfonate (sodium 1,4 for short) is an important intermediate for synthesizing acidic (direct and active) dye, and can also be used as antidote for nitrite and iodine poisoning. The sodium 1,4 complex can be used for chemoreceptors and absorbers, clinical medical research, and also can be used in the fields of optical devices, thermal switches, optical switches, information storage element materials, DNA structure probes, DNA molecule optical switches, DNA footprint reagents, DNA fragmentation reagents and the like.

Sodium 1,4 (1-amino-4-naphthalene sulfonate) is an important intermediate for medicine, chemical engineering and dye, and its complex can be used in chemoreceptor and absorber and clinical medicine research. Due to the important application, the domestic and international market demand is large at present. However, the existing production process still adopts the traditional baking sulfonation method, and has poor working conditions, high energy consumption and low yield.

Disclosure of Invention

The invention aims to provide a green preparation method of 1-amino-4-sodium naphthalenesulfonate.

In order to achieve the purpose, the invention provides the following technical scheme:

a green preparation method of 1-amino-4-sodium naphthalene sulfonate comprises the following steps: adding 1-naphthylamine, a surfactant and an organic solvent into a reaction device, heating and stirring, slowly dripping sulfuric acid to generate ammonium sulfate salt when the temperature is raised to 50-70 ℃, wherein the dripping temperature is lower than 85 ℃, and white solid particles are separated out when the dripping is finished within 10-20min after salifying; then heating to 175-190 ℃, performing transposition sulfonation reaction, and continuously performing reflux reaction for 4-8 h; cooling to 100-105 ℃, adding water for dilution, adding sodium carbonate for regulating the pH value of the solution, stirring, cooling to 70-80 ℃, preserving heat, standing for layering, cooling the upper-layer water phase to 15-21 ℃, and crystallizing and filtering to obtain the sodium 1-amino-4-naphthalenesulfonate.

Further, the separated lower layer organic adjacent dichlorobenzene is used for sulfonation recycling.

Further, the surfactant is any one of tween 60, tween 80, span 60 and span 80.

Further, the organic solvent is any one of mesitylene, o-dichlorobenzene, ethylene glycol monobutyl ether, 3, 4-dichlorotoluene, nitrobenzene and tetrabromoethane.

Furthermore, a reflux dehydration device is arranged on the reaction device.

Compared with the prior art, the invention has the beneficial effects that: the invention uses a liquid phase sulfonation method to improve the synthetic route of the sodium 1,4, reduces the reaction energy barrier and realizes the reaction under the conditions of normal pressure and low temperature. The surfactant forms a protective layer between the generated product and the reaction device, so that wall built-up materials are reduced, and the generation amount of tar is reduced; on the other hand, the surfactant will enhance the mixing between the solvent and the sulfonic acid, improving the dispersing and suspending ability of the 1-amino-4-naphthalenesulfonic acid.

Detailed Description

The technical solutions in the embodiments of the present invention are clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.