阅读说明：本技术 一种质子化亚胺分子及其金属铜缓蚀剂的合成方法 (Protonated imine molecule and synthesis method of metal copper corrosion inhibitor thereof ) 是由 廖芳芳 马艺文 张琳 谢换鑫 王震强 高放 张胜涛 于 2018-12-21 设计创作，主要内容包括：本发明提供一种质子化亚胺分子及其金属铜缓蚀剂的合成方法。本发明的质子化亚胺缓蚀剂分子在浓度为0.5M的硫酸溶液中对金属铜有缓蚀作用；由于增加了分子中的杂原子数以及碳碳双键数和碳氮双键数,有助于提高缓蚀剂分子的缓蚀效应；且合成方法简单,原料低毒环保。(The invention provides a method for synthesizing a protonated imine molecule and a metal copper corrosion inhibitor thereof. The protonized imine corrosion inhibitor molecule has a corrosion inhibition effect on metal copper in a sulfuric acid solution with the concentration of 0.5M; because the number of the hetero atoms, the number of carbon-carbon double bonds and the number of carbon-nitrogen double bonds in the molecules are increased, the corrosion inhibition effect of the corrosion inhibitor molecules is improved; and the synthesis method is simple, and the raw materials are low in toxicity and environment-friendly.)

1. A protonated imine molecule having the formula:

。

2. the use of the compounds of claim 1 as corrosion inhibitors for copper metal, characterized in that: the compound is:

(N1E, N2E) -N1, N2-bis- ((E) -3- (2-methoxyphenyl) -allylidene) -1, 2-diethylamine,

(N1Z) -N1, N4-bis- ((E) -3- (2-methoxyphenyl) -allylidene) -1, 4-butanediamine,

(N1E, N6Z) -N1, N6-bis- ((E) -3- (2-methoxyphenyl) -allylidene) -1, 6-hexanediamine,

(N1E, N8Z) -N1, N8-bis- ((E) -3- (2-methoxyphenyl) -allylidene) -1, 8-octanediamine,

(N1E, N6Z) -N1, N6-bis- ((E) -3- (2-methoxyphenyl) -allylidene) -1, 6-hexanediamine.

3. A synthetic method of a metal copper corrosion inhibitor is characterized by comprising the following steps:

reaction of o-methoxycinnamaldehyde with H₂N-(CH₂)_n-H₂Adding N into a 100mL three-neck ground flask, and adding absolute ethyl alcohol as a solvent;

in this step, o-methoxycinnamaldehyde and H₂N-(CH₂)_n-H₂The mass ratio of N is: 2: 1-1.2, n is a natural number;

heating for full reaction under the protection of inert gas;

after the reaction is finished, removing the ethanol solution by spinning

Adding solvent into the reactor, crystallizing, filtering to obtain solid

Washing the solid, and recrystallizing to obtain a target compound intermediate product:

and 6, adding the intermediate product into a 1M sulfuric acid solution, stirring under heating, fully reacting, and spin-drying to obtain the metal copper corrosion inhibitor product.

In the step, the mass ratio of the intermediate product to the sulfuric acid is as follows: 1: 2-2.5.

4. The method for synthesizing the metal copper corrosion inhibitor according to claim 3, wherein the method comprises the following steps: in step 1), H₂N-(CH₂)_n-H₂N is a saturated carbon chain in the middle and amino groups at two endsA compound (I) is provided.

5. The method for synthesizing the metal copper corrosion inhibitor according to claim 3, wherein the method comprises the following steps: in step 1), H₂N-(CH₂)_n-H₂N is ethylenediamine, butanediamine, hexanediamine or octanediamine.

6. The method for synthesizing the metallic copper corrosion inhibitor according to claim 3 or 5, wherein the method comprises the following steps: in step 2 ], the sufficient reaction time is 24 hours.

7. The method for synthesizing the metallic copper corrosion inhibitor according to claim 3 or 6, wherein the method comprises the following steps: in the step 4), the solvent used for crystallization is a mixture of methanol and n-hexane.

8. The method for synthesizing the metal copper corrosion inhibitor according to claim 3, wherein the method comprises the following steps: in step 5), the solvent used for recrystallization is a mixture of methanol and dichloromethane.

9. The method for synthesizing the metal copper corrosion inhibitor according to claim 3, wherein the method comprises the following steps: in the step 5, the time of the reaction is 1 hour.

10. The use of the metallic copper corrosion inhibitor product obtained by the method of claims 3 to 9, wherein: and adding the metal copper corrosion inhibitor product into the acidic liquid when the metal copper to be protected is in an environment of being soaked in the acidic liquid.

Technical Field

The invention relates to a corrosion inhibition technology of copper.

Background

The existing copper corrosion inhibitor has a certain corrosion inhibition effect on metal copper in a sulfuric acid solution with the concentration of 0.5M, but the corrosion inhibition efficiency is not high, and a compound of the copper corrosion inhibitor generally has toxicity and certain pollution to the environment.

Disclosure of Invention

The invention aims to provide a protonated imine molecule, which is characterized by having the following structural formula:

the invention claims the application of the compound as a metal copper corrosion inhibitor.

The invention claims a synthetic method of a metal copper corrosion inhibitor, which is characterized by comprising the following steps:

reaction of o-methoxycinnamaldehyde with H₂N-(CH₂)_n-H₂Adding N into a 100mL three-neck ground flask, and adding absolute ethyl alcohol as a solvent;

in this step, o-methoxycinnamaldehyde and H₂N-(CH₂)_n-H₂The mass ratio of N is: 2: 1-1.2, n is a natural number;

fully reacting at 45 ℃ under the protection of inert gas;

after the reaction is finished, removing the ethanol solution by spinning

Adding solvent into the reactor, crystallizing, filtering to obtain solid

Washing the solid, and recrystallizing to obtain a target compound intermediate product:

and 6, adding the intermediate product into a 1M sulfuric acid solution, stirring at 50 ℃, fully reacting, and spin-drying to obtain the metal copper corrosion inhibitor product.

In the step, the mass ratio of the intermediate product to the sulfuric acid is as follows: 1: 2-2.5.

The synthetic route is as follows:

further, in step 1), H₂N-(CH₂)_n-H₂N is a compound with a saturated carbon chain in the middle and amino groups at two ends.

Further, in step 1), H₂N-(CH₂)_n-H₂N is ethylenediamine, butanediamine, hexanediamine or octanediamine.

Further, in step 2 ], the sufficient reaction time is 24 hours.

Further, in the step 4), the solvent used for crystallization is a mixture of methanol and n-hexane, and the volume ratio of the methanol to the n-hexane is 1: 2.

Further, in step 5), the solvent used for recrystallization is a mixture of methanol and dichloromethane, and the volume ratio of the methanol to the dichloromethane is 2: 1.

Further, in the step 5 ], the reaction time is 1 hour.

Further, the metal copper corrosion inhibitor product is added into the acidic liquid when the metal copper to be protected is in the environment of being soaked in the acidic liquid, and the concentration of the metal copper corrosion inhibitor product is 0.5 mol/L.

The corrosion inhibitor of the protonized imine has a corrosion inhibition effect on metal copper in a sulfuric acid solution with the concentration of 0.5M; the molecular structure increases the number of hetero atoms, carbon-carbon double bonds and carbon-nitrogen double bonds, which is beneficial to improving the corrosion inhibition effect of the corrosion inhibitor molecules; and the synthesis method is simple, and the raw materials are low in toxicity and environment-friendly.

Drawings

FIG. 1 preparation of (N1E, N2E) -N1, N2-bis- ((E) -3- (2-methoxyphenyl) -allylidene) -1, 2-diethylamine in the present example¹H nuclear magnetic resonance spectrogram.

FIG. 2 Tafel polarization curves from electrochemical tests using (N1E, N2E) -N1, N2-bis- ((E) -3- (2-methoxyphenyl) -allylidene) -1, 2-diethylamine.

FIG. 3 electrochemical impedance spectra from electrochemical testing with (N1E, N2E) -N1, N2-bis- ((E) -3- (2-methoxyphenyl) -allylidene) -1, 2-diethylamine.

FIG. 4 shows the spectrum obtained by IR spectroscopy using (N1E, N2E) -N1, N2-bis- ((E) -3- (2-methoxyphenyl) -allylidene) -1, 2-diethylamine.

FIG. 5 is a scanning electron micrograph of the polished smooth copper sheet surface.

FIG. 6 is a scanning electron micrograph of the copper surface after soaking a smooth copper sheet in a 0.5M sulfuric acid solution for 7 days.

FIG. 7 scanning electron micrograph of copper surface after soaking a smooth copper sheet in a sulfuric acid solution containing 0.1mM (N1E, N2E) -N1, N2-di- ((E) -3- (2-methoxyphenyl) -allylidene) -1, 2-diethylamine for 7 days.

TABLE 1 Tafel polarization analysis data from electrochemical testing with (N1E, N2E) -N1, N2-bis- ((E) -3- (2-methoxyphenyl) -allylidene) -1, 2-diethylamine.

TABLE 2 electrochemical impedance analysis data from electrochemical testing with (N1E, N2E) -N1, N2-bis- ((E) -3- (2-methoxyphenyl) -allylidene) -1, 2-diethylamine.

Detailed Description

The present invention is further illustrated by the following examples, but it should not be construed that the scope of the above-described subject matter is limited to the following examples. Various substitutions and alterations can be made without departing from the technical idea of the invention and the scope of the invention is covered by the present invention according to the common technical knowledge and the conventional means in the field.