CN102516186A - Preparation method for electroplating additive 5-chloro-benzotriazole - Google Patents

Abstract

The invention discloses a preparation method for an electroplating additive 5-chloro-benzotriazole, comprising the following preparation steps of: reducing 4-chloro-2-nitroaniline by the iron powder activated by hydrochloric acid to obtain a 4-chloro-1,2-phenylenediamine crude product; and directly performing diazotization and cyclization on the 4-chloro-1,2-phenylenediamine crude product to obtain the 5-chloro-benzotriazole. The preparation method for an electroplating additive 5-chloro-benzotriazole provided by the invention is simple in synthesis process, low in demands on equipment and suitable for large-scale production.

Description

The preparation method of electroplating additive 5-chlorobenzotriazole

Technical field

The invention belongs to the organic synthesis field, be specifically related to a kind of preparation method of electroplating additive 5-chlorobenzotriazole.

Background technology

Electroplating industry often need use electroplating additive to strengthen the resistance to corrosion of coating.The 5-chlorobenzotriazole is a kind of novel electroplating additive, and it can form dative bond with copper atom, alternately forms the chain title complex each other, and the surface composition multilayer proofing film at copper makes the copper surface no longer redox reaction take place and play effect against corrosion.Therefore, the 5-chlorobenzotriazole is widely used as the electroplating additive of copper and the brightening agent in the electropolishing solution, and copper coatings smooth finish is increased, and is not easy to change.In addition, it also has certain corrosion mitigating effect to non-ferrous metals such as silver.The 5-chlorobenzotriazole also is widely used as the additive of various materials such as brake solution, refrigerator oil, recirculated cooling water, hydraulicefficiency oil, para tape, antiseptic paper.

Along with the continuous expansion of 5-chlorobenzotriazole Application Areas, the research of its compound method also causes people's attention.The main synthetic route of external report has following three kinds:

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In three kinds of synthetic routes, back two kinds of route raw materials are difficult for obtaining, and article one route raw material is domestic to have producer to give birth to, and synthesis technique is had relatively high expectations to equipment, and it is low to have improved productive rate, can't accomplish scale production.

Summary of the invention

Technical problem to be solved by this invention is to provide a kind of synthesis technique simple, low for equipment requirements, is fit to the preparation method of the electroplating additive 5-chlorobenzotriazole of large-scale production.

For solving the problems of the technologies described above, the technical scheme that the present invention adopted is: the preparation method of electroplating additive 5-chlorobenzotriazole, and synthetic route is:

Synthesis step:

1) iron powder, water and concentrated hydrochloric acid are added in the reactor drum, volume of water is 20 ~ 25 times of hydrochloric acid volume, stirs, and heat temperature raising to 70 ~ 85 ℃ are behind reaction 30 ~ 45min; Cool to 60 ~ 65 ℃, stir down, slowly add 4-chloro-2-N-methyl-p-nitroaniline, after adding finishes; The ethanol that adds 1/15 ~ 1/20 98Wt.% of total reaction raw material volume again, reflux 5 ~ 6h, sampling PLC detects, and raw material 4-chloro-2-N-methyl-p-nitroaniline disappears; Stop heating, stir down, naturally cool to room temperature, regulate pH=7 ~ 8 with saturated sodium bicarbonate aqueous solution; With benzene extractive reaction liquid, steam benzene after, 4-chloro-1,2-phenylenediamine bullion;

Iron powder and concentrated hydrochloric acid and 4-chloro-2-N-methyl-p-nitroaniline mol ratio are: 6 ~ 8:1 ~ 1.5:1 ~ 2;

2) with step 1) gained 4-chloro-1,2-phenylenediamine bullion adds in the reactor drum, adds Glacial acetic acid min. 99.5 and water stirring and dissolving, and the volume of water is identical with the Glacial acetic acid min. 99.5 volume, reenters the vitriol oil; Cool to-5 ~ 5 ℃, and keep-5 ~ 5 ℃ to drip sodium nitrite in aqueous solution, dropwise, be warmed up to 75 ~ 85 ℃; Keep 75 ~ 85 ℃ of reaction 1.5 ~ 2h, add activated carbon then, be heated to boiling 20 ~ 30min, filtered while hot; The mother liquor cooling, drying gets product 5-chlorobenzotriazole;

4-chloro-1,2-phenylenediamine and Glacial acetic acid min. 99.5, the vitriol oil, the mol ratio of Sodium Nitrite is 1:6.5 ~ 8:0.25 ~ 0.4:18 ~ 25;

Said sodium nitrite in aqueous solution mass concentration is 80 ~ 90%.

Beneficial effect of the present invention: the preparation method of electroplating additive 5-chlorobenzotriazole provided by the present invention, synthesis technique is simple, and is low for equipment requirements, is fit to the preparation method of the electroplating additive 5-chlorobenzotriazole of large-scale production.

Embodiment

1) 120g iron powder, 480mL water and 24mL concentrated hydrochloric acid are added in the reactor drum, stir, heat temperature raising to 70 ~ 85 ℃ are behind the reaction 45min; Cool to 60 ~ 65 ℃, stir down, slowly add 85g4-chloro-2-N-methyl-p-nitroaniline, after adding finishes; The ethanol that adds the 98Wt.% of 32mL again, reflux 5.5h, sampling PLC detects, and raw material 4-chloro-2-N-methyl-p-nitroaniline disappears; Stop heating, stir down, naturally cool to room temperature, regulate pH=7 ~ 8 with saturated sodium bicarbonate aqueous solution; With benzene extractive reaction liquid, steam benzene after, 4-chloro-1,2-phenylenediamine bullion;

2) with step 1) gained 4-chloro-1,2-phenylenediamine bullion adds in the reactor drum, adds 210mL Glacial acetic acid min. 99.5 and 210mL water stirring and dissolving, reenters the 10mL vitriol oil; Cool to-5 ~ 5 ℃, and keep-5 ~ 5 ℃ to drip the 685g Sodium Nitrite 120mL aqueous solution, dropwise, be warmed up to 75 ~ 85 ℃; Keep 75 ~ 85 ℃ of reaction 2h, add activated carbon then, be heated to boiling 30min, filtered while hot; The mother liquor cooling, drying gets product 5-chlorobenzotriazole 108g; Productive rate 82%, m.p.159 ~ 162 ℃, 157 ~ 159 ℃ of literature values.

Claims (1)

1. the preparation method of electroplating additive 5-chlorobenzotriazole, its preparation process is:

1) iron powder, water and concentrated hydrochloric acid are added in the reactor drum, volume of water is 20～25 times of hydrochloric acid volume, stirs, and heat temperature raising to 70～85 ℃ are behind reaction 30～45min; Cool to 60～65 ℃, stir down, slowly add 4-chloro-2-N-methyl-p-nitroaniline, after adding finishes; The ethanol that adds 1/15～1/20 98Wt.% of total reaction raw material volume again, reflux 5～6h, sampling PLC detects, and raw material 4-chloro-2-N-methyl-p-nitroaniline disappears; Stop heating, stir down, naturally cool to room temperature, regulate pH=7～8 with saturated sodium bicarbonate aqueous solution; With benzene extractive reaction liquid, steam benzene after, 4-chloro-1,2-phenylenediamine bullion;

Said iron powder and concentrated hydrochloric acid and 4-chloro-2-N-methyl-p-nitroaniline mol ratio are 6～8: 1～1.5: 1～2;

2) with step 1) gained 4-chloro-1,2-phenylenediamine bullion adds in the reactor drum, adds Glacial acetic acid min. 99.5 and water stirring and dissolving, and the volume of water is identical with the Glacial acetic acid min. 99.5 volume, reenters the vitriol oil; Cool to-5～5 ℃, and keep-5～5 ℃ to drip sodium nitrite in aqueous solution, dropwise, be warmed up to 75～85 ℃; Keep 75～85 ℃ of reaction 1.5～2h, add activated carbon then, be heated to boiling 20～30min, filtered while hot; The mother liquor cooling, drying gets product 5-chlorobenzotriazole;

Said 4-chloro-1,2-phenylenediamine and Glacial acetic acid min. 99.5, the vitriol oil, the mol ratio of Sodium Nitrite is 1: 6.5～8: 0.25～0.4: 18～25;

Said sodium nitrite in aqueous solution mass concentration is 80～90%.