阅读说明：本技术 一种铝镜缓蚀剂 (Aluminum mirror corrosion inhibitor ) 是由 龚新明 于 2020-11-10 设计创作，主要内容包括：本发明公开了一种铝镜缓蚀剂,原料包括：10～20份植酸和槲皮素复合物,2～5份表面活性剂,80～100份溶剂。植酸和槲皮素复合物的制备方法为：将槲皮素加入丙酮中溶解,再加入γ-氯丙基三甲氧基硅烷,反应得到硅烷改性槲皮素；将硅烷改性槲皮素加入无水乙醇中,搅拌溶解得到硅烷改性槲皮素乙醇溶液；将硅烷改性槲皮素乙醇溶液逐滴加入植酸水溶液中,反应得到所述植酸和槲皮素复合物。本发明在缓蚀剂中加入植酸和槲皮素复合物,可以与铝作用在镀铝层表面形成一层三维网络结构保护膜,形成的保护膜可以提高铝镜保护漆层与镀铝层的结合力,并且可以在保护漆层损坏时对镀铝层进行保护,防止腐蚀的扩展。(The invention discloses an aluminum mirror corrosion inhibitor which comprises the following raw materials: 10-20 parts of phytic acid and quercetin compound, 2-5 parts of surfactant and 80-100 parts of solvent. The preparation method of the phytic acid and quercetin compound comprises the following steps: dissolving quercetin in acetone, adding gamma-chloropropyltrimethoxysilane, and reacting to obtain silane modified quercetin; adding the silane modified quercetin into absolute ethyl alcohol, and stirring and dissolving to obtain a silane modified quercetin ethanol solution; and (3) dropwise adding the silane modified quercetin ethanol solution into the phytic acid aqueous solution, and reacting to obtain the phytic acid and quercetin compound. The phytic acid and the quercetin compound are added into the corrosion inhibitor, so that a three-dimensional network structure protective film can be formed on the surface of the aluminum plating layer under the action of aluminum, the formed protective film can improve the binding force between the aluminum mirror protective paint layer and the aluminum plating layer, and the aluminum plating layer can be protected when the protective paint layer is damaged, so that the corrosion expansion is prevented.)

1. An aluminum mirror corrosion inhibitor is characterized in that the corrosion inhibitor comprises the following raw materials in parts by weight,

10-20 parts of phytic acid and quercetin compound

2-5 parts of surfactant

80-100 parts of a solvent.

2. The aluminum mirror corrosion inhibitor as claimed in claim 1, wherein the preparation method of the phytic acid and quercetin compound comprises the following steps:

(1) adding quercetin into acetone, stirring for dissolving, adding gamma-chloropropyltrimethoxysilane, stirring for reacting at 70-90 ℃ for 12-24 h, evaporating to remove the solvent, and drying to obtain silane modified quercetin;

(2) adding the silane modified quercetin into absolute ethyl alcohol, and stirring and dissolving to obtain a silane modified quercetin ethanol solution;

(3) and (3) dropwise adding the silane modified quercetin ethanol solution into the phytic acid aqueous solution, stirring and reacting for 2-4 h at 70-80 ℃, and drying to obtain the phytic acid and quercetin compound.

3. The aluminum mirror corrosion inhibitor according to claim 2, wherein the mass-to-volume ratio of quercetin to acetone in step (1) is 1 g: (10-15 mL), wherein the mass ratio of the quercetin to the gamma-chloropropyltrimethoxysilane is 1: (2-3).

4. The corrosion inhibitor for aluminum mirrors as claimed in claim 2, wherein the mass fraction of the silane-modified quercetin in the silane-modified quercetin ethanol solution in step (2) is 1-5%.

5. The aluminum mirror corrosion inhibitor according to claim 2, wherein the weight percentage of the phytic acid aqueous solution in the step (3) is 5-10%, and the volume ratio of the phytic acid aqueous solution to the quercetin ethanol solution is (3-5): 1.

6. the aluminum mirror corrosion inhibitor according to claim 1 or 2, wherein the raw material further comprises 1-3 parts of potassium chlorate.

7. The aluminum mirror corrosion inhibitor as claimed in claim 1, wherein the surfactant comprises (1-2) by mass: 1 polyethylene glycol octyl phenyl ether and octadecylamine.

8. The aluminum mirror corrosion inhibitor according to claim 1, wherein the solvent comprises the following components in a mass ratio of (3-5): 1 water and ethylene glycol.

Technical Field

The invention relates to the technical field of metal corrosion inhibitors, in particular to an aluminum mirror corrosion inhibitor.

Background

The prior common glass mirror comprises a silver mirror and an aluminum mirror, and although the silver mirror has high reflectivity and long service life, the price is higher; the aluminum mirror has low cost and simple production process, so the aluminum mirror has high market share. Because aluminum is easily oxidized in air, the conventional method for producing glass aluminum mirrors generally comprises sputtering a layer of metallic aluminum as a reflective layer on the surface of glass by vacuum coating, and then coating a protective paint on the reflective layer to prevent the aluminum layer from chemical corrosion and physical damage.

For example, in the Chinese patent document, "a high reflective aluminum mirror and its manufacturing method", its publication No. CN104714264A, the mirror coating of the mirror coating is composed of a reflection-enhancing composite layer, an aluminum layer, a protective layer, and a primer in order from the glass substrate to the outsideLayer, finish paint layer. Before a functional layer-an aluminum layer reflecting layer of the high-reflection aluminum mirror is plated, a reflection-improving composite layer is plated, so that the reflection rate of the high-reflection aluminum mirror is improved, and the binding force between an aluminum layer and a glass substrate is enhanced; simultaneously adding a layer of Si behind the aluminum layer₃N₄The aluminum layer is protected from being damaged by oxidation and painting, and the reflectivity of the aluminum mirror is increased.

However, in the prior art, the bonding force between the protective paint on the surface of the aluminum mirror and the aluminum layer is poor, and the protective paint near the cutting part is easy to fall off and not easy to repair when the aluminum mirror is cut, so that the aluminum layer around the cut aluminum mirror is exposed, easy to oxidize and discolor by air, and the service life of the aluminum mirror is influenced.

Disclosure of Invention

The invention provides an aluminum mirror corrosion inhibitor, aiming at overcoming the problems that the bonding force between a protective paint on the surface of an aluminum mirror and an aluminum layer is poor, the protective paint near a cutting part is easy to fall off and repair when the aluminum mirror is cut, the aluminum layer around the cut aluminum mirror is exposed and easy to oxidize and discolor by air, and the service life of the aluminum mirror is influenced.

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

an aluminum mirror corrosion inhibitor comprises the following raw materials in parts by weight,

10-20 parts of phytic acid and quercetin compound

2-5 parts of surfactant

80-100 parts of a solvent.

The phytic acid and the quercetin compound are added into the corrosion inhibitor, the phytic acid is a natural substance extracted from the action of grains, the molecules of the phytic acid have 24 oxygen atoms, 12 hydroxyl groups and 6 phosphate groups which can be matched with metal, and the phytic acid is an rare metal polydentate chelating agent, and the phytic acid has strong chelating capacity on the metal, so the phytic acid can effectively form a layer of monomolecular protective film on the surface of the metal through the chelating action to avoid the corrosion of the metal, and the phytic acid is an environment-friendly metal surface corrosion inhibitor component. However, the phytic acid has insufficient corrosion inhibition effect on the aluminum surface under an acidic condition, so in the prior art, the phytic acid and other corrosion inhibitors are generally compounded for use to improve the corrosion inhibition effect. The invention selects the quercetin and the phytic acid for compounding, the quercetin can form coordinate bonds with aluminum, so that molecules are adsorbed on the surface of the aluminum plating layer to form a chemical conversion film, and the chemical conversion film formed by the synergistic action of the quercetin and the phytic acid can improve the corrosion inhibition effect of the aluminum plating layer in the aluminum mirror.

However, the phytic acid and the quercetin are directly mixed and compounded, and the phytic acid molecules and the quercetin molecules have competitive adsorption on the surface of the aluminum plating layer, so that the uniformity of a formed chemical conversion film layer is influenced, and the corrosion inhibition effect is improved to a limited extent; and the monomolecular protective film layer formed by the phytic acid and the quercetin is very thin, is easy to damage under external force and is not beneficial to long-term use of the aluminum mirror. The phytic acid and the quercetin compound can form a uniform protective film with a three-dimensional network structure on the surface of an aluminum plating layer, so that the thickness of the protective film is effectively increased, the long-acting corrosion inhibition effect on the aluminum plating layer of the aluminum mirror can be realized, and the aluminum mirror is prevented from discoloring.

The phytic acid, the quercetin compound and the surfactant are added into the solvent to form a water-based corrosion inhibitor, when the corrosion inhibitor is used, the aluminum mirror is immersed into the corrosion inhibitor for reaction for a period of time, and after being taken out and dried, the chemical conversion protective film with a three-dimensional structure can be formed, so that the use is convenient; after the aluminum coating layer is loaded with the protective film layer, a protective paint layer can be continuously coated on the protective film layer, because the organic protective film layer formed on the surface of the aluminum coating layer by the phytic acid and quercetin compound has similar chemical properties with organic paint, and active groups such as hydroxyl, phosphate and the like contained in the protective film layer can also have chemical action with the organic coating layer, the aluminum coating layer treated by the corrosion inhibitor can have stronger binding force with the protective paint layer, the damage of the aluminum mirror protective paint layer during cutting and edging is reduced, and the aluminum coating layer can be protected when the protective paint layer is damaged, so that the corrosion is prevented from expanding.

Preferably, the preparation method of the phytic acid and quercetin compound comprises the following steps:

(1) adding quercetin into acetone, stirring for dissolving, adding gamma-chloropropyltrimethoxysilane, stirring for reacting at 70-90 ℃ for 12-24 h, evaporating to remove the solvent, and drying to obtain silane modified quercetin;

(2) adding the silane modified quercetin into absolute ethyl alcohol, and stirring and dissolving to obtain a silane modified quercetin ethanol solution;

(3) and (3) dropwise adding the silane modified quercetin ethanol solution into the phytic acid aqueous solution, stirring and reacting for 2-4 h at 70-80 ℃, and drying to obtain the phytic acid and quercetin compound.

When the phytic acid and quercetin compound is prepared, firstly, through the step (1), adding quercetin into acetone by using gamma-chloropropyltrimethoxysilane (1), stirring and dissolving, then adding the gamma-chloropropyltrimethoxysilane, stirring and reacting at 70-90 ℃ for 12-24 h, evaporating to remove a solvent, and drying to obtain silane modified quercetin;

(2) adding the silane modified quercetin into absolute ethyl alcohol, and stirring and dissolving to obtain a silane modified quercetin ethanol solution;

(3) and (3) dropwise adding the silane modified quercetin ethanol solution into the phytic acid aqueous solution, stirring and reacting for 2-4 h at 70-80 ℃, and drying to obtain the phytic acid and quercetin compound. Carrying out condensation reaction with quercetin to obtain silane modified quercetin; and (3) performing dehydration condensation reaction between silicon hydroxyl generated by hydrolysis of silane in the silane-modified quercetin and phosphorus hydroxyl in phytic acid molecules, so that the phytic acid and the quercetin are connected by using the silane, and obtaining the phytic acid and quercetin compound.

The silane molecules in the silane modified quercetin can be hydrolyzed to generate three silicon hydroxyl groups, so that the three phytic acid molecules can be gathered together, and a protective film with a three-dimensional network structure is formed on the surface of the aluminum-plated layer through the chemical action between the quercetin at two ends and the phytic acid molecules and the aluminum-plated layer and the intersection and interpenetration of the middle silane chain segments, so that the thickness of the protective film is effectively increased, and the protective film is prevented from being damaged under external force. And the protective film with the three-dimensional network structure increases the roughness and the specific surface area of the protective film, thereby improving the adhesive force of the protective film on the surface of the aluminized layer and improving the corrosion inhibition performance of the aluminum mirror.

Preferably, the mass-to-volume ratio of quercetin to acetone in step (1) is 1 g: (10-15 mL), wherein the mass ratio of the quercetin to the gamma-chloropropyltrimethoxysilane is 1: (2-3).

Preferably, the mass fraction of the silane-modified quercetin in the silane-modified quercetin ethanol solution in the step (2) is 1-5%.

Preferably, the mass fraction of the phytic acid aqueous solution in the step (3) is 5-10%, and the volume ratio of the phytic acid aqueous solution to the quercetin ethanol solution is (3-5): 1.

preferably, the raw material also comprises 1-3 parts of potassium chlorate. When the phytic acid and the quercetin compound directly form a protective film on the surface of the aluminum plating layer, the film forming speed is slow, so that the protective film is easy to generate defects, and the corrosion inhibition effect is influenced. Therefore, the potassium chlorate is added into the corrosion inhibitor as an auxiliary film forming agent, and the potassium chlorate can effectively improve the film forming speed and the film forming compactness of the phytic acid and quercetin compound, so that the corrosion inhibition effect of the corrosion inhibitor on the aluminum mirror is further improved.

Preferably, the surfactant comprises the following components in a mass ratio of (1-2): 1 polyethylene glycol octyl phenyl ether and octadecylamine.

Preferably, the solvent comprises the following components in a mass ratio of (3-5): 1 water and ethylene glycol.

Therefore, the invention has the following beneficial effects:

(1) the phytic acid and the quercetin are connected through silane to form a phytic acid and quercetin compound, the phytic acid and the quercetin compound can act with aluminum after the phytic acid and the quercetin compound are added into a corrosion inhibitor, a three-dimensional network structure protective film is formed on the surface of an aluminum coating of the aluminum mirror, the formed protective film can improve the bonding force between a protective paint layer of the aluminum mirror and the aluminum coating, and the aluminum coating can be protected when the protective paint layer is damaged to prevent the corrosion from expanding;

(2) the potassium chlorate is added into the corrosion inhibitor as an auxiliary film forming agent, and the potassium chlorate can effectively improve the film forming speed and the film forming compactness of the phytic acid and quercetin compound, so that the corrosion inhibition effect of the corrosion inhibitor on the aluminum mirror is further improved.

Detailed Description

The invention is further described with reference to specific embodiments.

In the present invention, all raw materials are commercially available or commonly used in the industry, if not specified.

Example 1:

an aluminum mirror corrosion inhibitor comprises the following raw materials in parts by weight:

the preparation method of the phytic acid and quercetin compound comprises the following steps:

(1) adding quercetin into acetone for dissolving, wherein the mass-volume ratio of the quercetin to the acetone is 1 g: 12mL, adding gamma-chloropropyltrimethoxysilane with the mass ratio of 2.5:1 to the quercetin, stirring and reacting for 18h at 80 ℃, evaporating to remove the solvent and drying to obtain silane modified quercetin;

(2) adding the silane modified quercetin into absolute ethyl alcohol, stirring and dissolving to obtain a silane modified quercetin ethanol solution with the mass concentration of 3%;

(3) dropwise adding the silane modified quercetin ethanol solution into a phytic acid aqueous solution with the mass concentration of 8%, wherein the volume ratio of the phytic acid aqueous solution to the quercetin ethanol solution is 4: stirring and reacting for 3h at the temperature of 1 and 75 ℃, and drying to obtain the phytic acid and quercetin compound.

Example 2:

an aluminum mirror corrosion inhibitor comprises the following raw materials in parts by weight:

the preparation method of the phytic acid and quercetin compound comprises the following steps:

(1) adding quercetin into acetone for dissolving, wherein the mass-volume ratio of the quercetin to the acetone is 1 g: 10mL, adding gamma-chloropropyltrimethoxysilane with the mass ratio of 2:1 to the quercetin, stirring and reacting for 24 hours at 70 ℃, evaporating to remove the solvent and drying to obtain silane modified quercetin;

(2) adding the silane modified quercetin into absolute ethyl alcohol, stirring and dissolving to obtain a silane modified quercetin ethanol solution with the mass concentration of 1%;

(3) dropwise adding the silane modified quercetin ethanol solution into a phytic acid aqueous solution with the mass concentration of 5%, wherein the volume ratio of the phytic acid aqueous solution to the quercetin ethanol solution is 3: stirring and reacting for 4h at the temperature of 1 and 70 ℃, and drying to obtain the phytic acid and quercetin compound.

Example 3:

an aluminum mirror corrosion inhibitor comprises the following raw materials in parts by weight:

the preparation method of the phytic acid and quercetin compound comprises the following steps:

(1) adding quercetin into acetone for dissolving, wherein the mass-volume ratio of the quercetin to the acetone is 1 g: 12mL, adding gamma-chloropropyltrimethoxysilane with the mass ratio of 2.5:1 to the quercetin, stirring and reacting for 18h at 80 ℃, evaporating to remove the solvent and drying to obtain silane modified quercetin;

(2) adding the silane modified quercetin into absolute ethyl alcohol, stirring and dissolving to obtain a silane modified quercetin ethanol solution with the mass concentration of 3%;

(3) dropwise adding the silane modified quercetin ethanol solution into a phytic acid aqueous solution with the mass concentration of 8%, wherein the volume ratio of the phytic acid aqueous solution to the quercetin ethanol solution is 4: stirring and reacting for 3h at the temperature of 1 and 75 ℃, and drying to obtain the phytic acid and quercetin compound.

Example 4:

an aluminum mirror corrosion inhibitor comprises the following raw materials in parts by weight:

the preparation method of the phytic acid and quercetin compound comprises the following steps:

(1) adding quercetin into acetone for dissolving, wherein the mass-volume ratio of the quercetin to the acetone is 1 g: 12mL, adding gamma-chloropropyltrimethoxysilane with the mass ratio of 2.5:1 to the quercetin, stirring and reacting for 18h at 80 ℃, evaporating to remove the solvent and drying to obtain silane modified quercetin;

(2) adding the silane modified quercetin into absolute ethyl alcohol, stirring and dissolving to obtain a silane modified quercetin ethanol solution with the mass concentration of 3%;

(3) dropwise adding the silane modified quercetin ethanol solution into a phytic acid aqueous solution with the mass concentration of 8%, wherein the volume ratio of the phytic acid aqueous solution to the quercetin ethanol solution is 4: stirring and reacting for 3h at the temperature of 1 and 75 ℃, and drying to obtain the phytic acid and quercetin compound.

Example 5:

an aluminum mirror corrosion inhibitor comprises the following raw materials in parts by weight:

the preparation method of the phytic acid and quercetin compound comprises the following steps:

(1) adding quercetin into acetone for dissolving, wherein the mass-volume ratio of the quercetin to the acetone is 1 g: 15mL, adding gamma-chloropropyltrimethoxysilane with the mass ratio of the gamma-chloropropyltrimethoxysilane to the quercetin of 3:1, stirring and reacting at 90 ℃ for 12 hours, evaporating to remove the solvent and drying to obtain silane modified quercetin;

(2) adding the silane modified quercetin into absolute ethyl alcohol, stirring and dissolving to obtain a silane modified quercetin ethanol solution with the mass concentration of 5%;

(3) dropwise adding the silane modified quercetin ethanol solution into a phytic acid aqueous solution with the mass concentration of 8%, wherein the volume ratio of the phytic acid aqueous solution to the quercetin ethanol solution is 5: stirring and reacting for 2h at the temperature of 1 and 80 ℃, and drying to obtain the phytic acid and quercetin compound.

Comparative example 1:

an aluminum mirror corrosion inhibitor comprises the following raw materials in parts by weight:

comparative example 2:

an aluminum mirror corrosion inhibitor comprises the following raw materials in parts by weight:

comparative example 3:

an aluminum mirror corrosion inhibitor comprises the following raw materials in parts by weight:

comparative example 4:

an aluminum mirror corrosion inhibitor comprises the following raw materials in parts by weight:

the preparation method of the silane modified quercetin comprises the following steps:

(1) adding quercetin into acetone for dissolving, wherein the mass-volume ratio of the quercetin to the acetone is 1 g: 12mL, adding gamma-chloropropyltrimethoxysilane with the mass ratio of 2.5:1 to the quercetin, stirring and reacting at 80 ℃ for 18h, evaporating to remove the solvent, and drying to obtain the silane modified quercetin.

Comparative example 5:

an aluminum mirror corrosion inhibitor comprises the following raw materials in parts by weight:

the preparation method of the silane modified phytic acid comprises the following steps:

(1) adding gamma-chloropropyltrimethoxysilane into absolute ethyl alcohol, and uniformly dispersing to obtain a silane solution with the mass concentration of 3%;

(2) dropwise adding a silane solution into a phytic acid aqueous solution with the mass concentration of 8%, wherein the volume ratio of the phytic acid aqueous solution to the silane solution is 4: stirring and reacting for 3h at the temperature of 1 and 75 ℃, and drying to obtain the silane modified phytic acid.

The corrosion inhibition performance of the corrosion inhibitor in the above examples and comparative examples on the aluminum mirror is tested, and the test method comprises the following steps: respectively placing the aluminized aluminum mirror in the corrosion inhibitors in the above examples and comparative examples, soaking for 30min, taking out, and drying at 60 ℃; then, a protective paint layer with the thickness of 40 mu m is sprayed and coated on the surface of the aluminum coating layer treated by the corrosion inhibitor (the protective paint adopts Duralux mirror back coating of Zhejiang Fengqi paint sealant Co., Ltd.); drying at 150 ℃ to obtain a finished product of the aluminum mirror; cutting the finished product aluminum mirror into 2cm by 2cm and edging to obtain an aluminum mirror sample; the aluminum mirror sample was placed in a 5% NaOH aqueous solution at 25 ℃ for 12 hours, and the color change of the aluminum plating layer was observed, with the results shown in Table 1.

Table 1: and (5) testing the corrosion inhibition performance of the aluminum mirror.

As can be seen from table 1, in examples 1 to 5, after the aluminum plating layer of the aluminum mirror is treated by using the corrosion inhibitor of the present invention, the cut aluminum mirror can maintain no discoloration for more than 10 hours in the NaOH aqueous solution, and the corrosion inhibitor with sodium chlorate added in examples 3 to 5 has better corrosion inhibition performance compared with the corrosion inhibitor without sodium chlorate added in examples 1 and 2, and does not discolor within 12 hours, which proves that the corrosion inhibitor with sodium chlorate added therein can effectively improve corrosion inhibition performance. The reason why the edge portion of the aluminum mirror in examples 1 and 2 was discolored may be due to damage of the protective paint layer upon cutting and edging.

Compared with the corrosion inhibitor in the embodiment 1, the corrosion inhibitor in the comparative examples 1 and 2 only contains phytic acid or quercetin, or the phytic acid and the quercetin in the comparative example 3 are compounded for use, so that the corrosion inhibition effect is obviously reduced, and the edge of the corrosion inhibitor is quickly discolored when the corrosion inhibitor is soaked in a sodium hydroxide aqueous solution. In comparative example 4 and comparative example 5, only silane is used to modify quercetin or phytic acid, the corrosion inhibition effect is obviously reduced compared with that in example 1, the slow release effect of the silane-modified phytic acid is better than that of the silane-modified quercetin, probably because in the silane-modified phytic acid, a plurality of phytic acids can be gathered and a three-dimensional structure can also be generated due to the effect of three silicon hydroxyl groups generated by the hydrolysis of silane, but because no quercetin exists at the end part, the structure of the quercetin-modified phytic acid is not as compact as the three-dimensional network structure formed by the phytic acid and the quercetin compound in the invention, so that the corrosion inhibition performance is reduced, and the three-dimensional network structure formed by the phytic acid and the quercetin compound in the invention is proved to be capable of effectively improving the corrosion inhibition performance of the corrosion.