CN110003784B - Anti-corrosion coating of aluminum alloy material, preparation method and anti-corrosion method thereof - Google Patents
Anti-corrosion coating of aluminum alloy material, preparation method and anti-corrosion method thereof Download PDFInfo
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
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- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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- C09D7/61—Additives non-macromolecular inorganic
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/65—Additives macromolecular
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
Abstract
The invention discloses an anticorrosive coating of an aluminum alloy material, and a preparation method and an anticorrosive method thereof, wherein the anticorrosive coating comprises a silane coupling agent, sodium carboxymethyl cellulose, nano silicon dioxide, water-soluble polyurethane, polyacrylamide, water and a sulfydryl-containing ionic liquid. The anti-corrosion coating for the aluminum alloy material provided by the invention has the advantages of good stability, strong anti-corrosion capability, strong adhesive force with the surface of the aluminum alloy and the like, and is a water-based coating, green and environment-friendly, and does not pollute the environment.
Description
The application is a divisional application of an invention patent application (the invention name is an aluminum alloy material anticorrosive coating, a preparation method and an anticorrosive method thereof, the application number is 201710367136X, and the application date is 2017.5.23) of the applicant's royal benefit.
Technical Field
The invention relates to a metal anti-corrosion coating and an anti-corrosion method, in particular to an anti-corrosion coating of an aluminum alloy material, a preparation method thereof and an anti-corrosion method of the aluminum alloy material.
Background
Aluminum alloys have the advantages of low density, high strength, easy formability, etc., and thus are widely used. According to statistics, in recent years, the annual growth rate of the aluminum alloy consumption in the global range is up to more than 20%, and the trend of continuous growth is in progress. However, the aluminum alloy is corroded in different degrees when used in various environments, and particularly in humid environments, seawater, acid environments or alkali environments, on one hand, the performance of the aluminum alloy is affected, so that potential safety hazards are caused, and on the other hand, a large amount of waste is caused. Therefore, after the aluminum alloy product is manufactured, the surface of the aluminum alloy product is coated with paint to realize corrosion prevention. Researchers in this field have also conducted extensive research into anticorrosion coatings for aluminum alloy protection.
However, the existing anticorrosive coatings for aluminum alloy materials have a few problems, and firstly, the anticorrosive coatings and the aluminum alloy materials have low bonding force and are easy to fall off, so that the anticorrosive effect is lost; secondly, the existing anticorrosive paint has low anticorrosive performance and poor stability, and cannot be stored for a long time; thirdly, the existing coating uses a large amount of organic solvent, so that the cost is high, the environmental and human health are harmed, and a large amount of three wastes are generated in the preparation process and the use process.
Disclosure of Invention
The present invention has been made in view of the above problems of the conventional anticorrosive coatings, and provides an anticorrosive coating for an aluminum alloy material, a method for producing the same, and a method for preventing corrosion of an aluminum alloy material.
In order to achieve the object of the present invention, in a first aspect, the present invention provides an anticorrosive coating for an aluminum alloy material, wherein the anticorrosive coating comprises a silane coupling agent, sodium carboxymethyl cellulose, nano-silica, water-soluble polyurethane, polyacrylamide, water, and a mercapto group-containing ionic liquid.
In the present invention, preferably, the silane coupling agent is used in an amount of 0.3 to 0.8 part by weight, the sodium carboxymethyl cellulose is used in an amount of 0.5 to 1 part by weight, the nano-silica is used in an amount of 0.5 to 1 part by weight, the water-soluble polyurethane is used in an amount of 2 to 5 parts by weight, the polyacrylamide is used in an amount of 1 to 2 parts by weight, and the water is used in an amount of 20 to 50 parts by weight, based on 1 part by weight of the thiol-containing ionic liquid.
More preferably, the amount of the silane coupling agent is 0.3 to 0.5 part by weight, the amount of the sodium carboxymethyl cellulose is 0.5 to 0.8 part by weight, the amount of the nano silicon dioxide is 0.5 to 1 part by weight, the amount of the water-soluble polyurethane is 3 to 5 parts by weight, the amount of the polyacrylamide is 1 to 1.5 parts by weight, and the amount of the water is 25 to 50 parts by weight, based on 1 part by weight of the thiol-containing ionic liquid;
more preferably, the silane coupling agent is used in an amount of 0.4 parts by weight, the sodium carboxymethylcellulose is used in an amount of 0.8 parts by weight, the nano-silica is used in an amount of 1 part by weight, the water-soluble polyurethane is used in an amount of 4 parts by weight, the polyacrylamide is used in an amount of 1.2 parts by weight, and the water is used in an amount of 45 parts by weight, relative to 1 part by weight of the thiol-containing ionic liquid.
In the invention, the inventor finds that the ionic liquid with the sulfhydryl group can strengthen the bonding of the coating to the aluminum alloy material and can play a role in homogenizing the coating so as to enable the coating to be uniform and fine, and preferably, the ionic liquid with the sulfhydryl group is 1-methyl-3- (mercaptoethyl) imidazole tetrafluoroborate or 1-methyl-3- (mercaptopropyl) imidazole tetrafluoroborate.
In the present invention, the silane coupling agent is also preferably a silane coupling agent having a mercapto group, for example, γ -mercaptopropyltriethoxysilane or γ -mercaptopropyltrimethoxysilane.
The invention also provides a method for preparing the anticorrosive coating of the aluminum alloy material, wherein the method comprises the step of uniformly mixing the silane coupling agent, the sodium carboxymethyl cellulose, the nano silicon dioxide, the water-soluble polyurethane, the polyacrylamide and the mercapto ionic liquid to obtain the anticorrosive coating of the aluminum alloy material. In the invention, the mixing mode can adopt a method conventionally used in the field, such as mechanical stirring, and the stirring speed can be 500-1000 r/min.
The invention also provides an anti-corrosion method for the aluminum alloy material, which comprises the steps of coating the anti-corrosion coating or the anti-corrosion coating prepared by the method on the surface of the aluminum alloy material, and then drying at high temperature.
In a preferred aspect of the present invention, the high temperature drying conditions include: the temperature is 90-110 ℃, and the drying time is 6-8 hours; the thickness of the coating formed on the surface of the aluminum alloy material after the anticorrosive coating is dried at high temperature is 0.1-1 micron.
In the present invention, the starting materials of the present invention can be prepared by the prior art or commercially available. For example, the water-soluble polyurethane can be obtained by polymerizing conventional polyisocyanate monomers and polyhydric alcohols, and the commercially available products include PU-100, PU-200, PU-300, PU-400 and PU-500 type aqueous polyurethane resin dispersions (solid content is 30-40%) of Xingtai refining plant of Tianchang.
The anti-corrosion coating of the aluminum alloy material provided by the invention has the following advantages:
1) the anticorrosive coating has strong adhesive force with the surface of the aluminum alloy, can be more tightly attached to the surface of the aluminum alloy, cannot fall off, and has better anticorrosive performance.
2) The anticorrosive coating has good stability and still has good performance after being stored for more than 6 months.
3) The anticorrosive coating is green and environment-friendly and does not pollute the environment.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. However, these examples are only illustrative and are not intended to limit the scope of the present invention.
Preparation example 1
Under the protection of nitrogen, adding 41g N-methylimidazole and 100ml of acetonitrile into a dry three-neck flask, heating to 60 ℃, dropwise adding 84g of 2-bromoethanethiol, keeping the temperature, stirring and reacting for 14 hours, monitoring the reaction completion, carrying out reduced pressure concentration to obtain a light yellow viscous liquid, then washing with acetone for three times, carrying out reduced pressure concentration and drying to obtain brominated 1-methyl-3- (mercaptoethyl) imidazole; adding brominated 1- (mercaptoethyl) -3-methylimidazole, 60g of sodium fluoborate and 50ml of acetone into another three-neck flask, heating to 50 ℃, keeping the temperature, stirring for reaction for 12 hours, carrying out suction filtration, carrying out reduced pressure concentration on filtrate to obtain a crude product of 1-methyl-3- (mercaptoethyl) imidazole tetrafluoroborate, dissolving the crude product in dichloromethane, filtering, and carrying out reduced pressure concentration on the filtrate to obtain 96.8g of light yellow liquid 1-methyl-3- (mercaptoethyl) imidazole tetrafluoroborate, wherein the yield is 84.2%.1HNMR(400MHz,D2O, DSS external standard), 8.72(s, 1H); 7.45(s, 1H); 7.37(s, 1H); 4.25-4.31 (t, 2H); 3.82(s, 3H); 2.88 to 2.92(t, 2H).
Preparation example 2
Under the protection of nitrogen, adding 41g N-methylimidazole and 100ml of acetonitrile into a dry three-neck flask, heating to 60 ℃, dropwise adding 85g of 3-bromopropanethiol, keeping the temperature, stirring and reacting for 18 hours, monitoring the reaction completion, carrying out reduced pressure concentration to obtain a light yellow viscous liquid, then washing with acetone for three times, and carrying out reduced pressure concentration to obtain brominated 1-methyl-3- (mercaptoethyl) imidazole; adding brominated 1- (mercaptoethyl) -3-methylimidazole, 60g of sodium fluoroborate and 50ml of acetone into another three-neck flask, heating to 50 ℃, keeping the temperature, stirring for reaction for 12 hours, performing suction filtration, performing reduced pressure concentration on filtrate to obtain a crude product of 1-methyl-3- (mercaptoethyl) imidazole tetrafluoroborate, and dissolving the crude product into the solutionAfter the reaction mixture was filtered through methylene chloride, the filtrate was concentrated under reduced pressure to obtain 99.7g of 1-methyl-3- (mercaptopropyl) imidazole tetrafluoroborate as a pale yellow liquid with a yield of 81.7%.1HNMR(400MHz,D2O, DSS external standard), 8.74(s, 1H); 7.45(s, 1H); 7.35(s, 1H); 4.21-4.28 (t, 2H); 3.80(s, 3H); 2.67-2.73 (t, 2H); 2.38 to 2.44(m, 2H).
Example 1
Adding 0.4Kg of silane coupling agent, 0.8Kg of sodium carboxymethylcellulose, 1Kg of nano-silica, 4Kg of water-soluble polyurethane, 1.2Kg of polyacrylamide and 1Kg of mercapto group-containing ionic liquid (1-methyl-3- (mercaptoethyl) imidazole tetrafluoroborate) into 45Kg of water, and mechanically stirring and mixing uniformly at 1000 revolutions per minute to obtain the anticorrosive coating A1 of the aluminum alloy material.
Example 2
Adding 0.3Kg of silane coupling agent, 0.6Kg of sodium carboxymethylcellulose, 1Kg of nano-silica, 3Kg of water-soluble polyurethane, 1Kg of polyacrylamide and 1Kg of mercapto group-containing ionic liquid (1-methyl-3- (mercaptoethyl) imidazole tetrafluoroborate) into 50Kg of water, and mechanically stirring and mixing uniformly at 1000 revolutions per minute to obtain the anticorrosive coating A2 of the aluminum alloy material.
Example 3
Adding 0.5Kg of silane coupling agent, 0.5Kg of sodium carboxymethylcellulose, 0.5Kg of nano-silicon dioxide, 5Kg of water-soluble polyurethane, 1.5Kg of polyacrylamide and 1Kg of mercapto group-containing ionic liquid (1-methyl-3- (mercaptopropyl) imidazole tetrafluoroborate) into 25Kg of water, and mechanically stirring and mixing uniformly at 1000 r/min to obtain the anticorrosive coating A3 of the aluminum alloy material.
Example 4
Adding 0.6Kg of silane coupling agent, 0.5Kg of sodium carboxymethylcellulose, 0.5Kg of nano-silicon dioxide, 2Kg of water-soluble polyurethane, 1Kg of polyacrylamide and 0.5Kg of sulfydryl-containing ionic liquid (1-methyl-3- (mercaptoethyl) imidazole tetrafluoroborate) into 45Kg of water, and mechanically stirring and mixing uniformly at 1000 r/min to obtain the anticorrosive coating A4 of the aluminum alloy material.
Example 5
Adding 0.4Kg of silane coupling agent, 0.8Kg of sodium carboxymethylcellulose, 1Kg of nano-silica, 4Kg of water-soluble polyurethane, 1.2Kg of polyacrylamide and 0.2Kg of mercapto group-containing ionic liquid (1-methyl-3- (mercaptoethyl) imidazole tetrafluoroborate) into 45Kg of water, and mechanically stirring and mixing uniformly at 1000 r/min to obtain the anticorrosive coating A5 of the aluminum alloy material.
Example 6
Adding 0.4Kg of silane coupling agent, 0.2Kg of sodium carboxymethylcellulose, 1Kg of nano-silica, 4Kg of water-soluble polyurethane, 1.2Kg of polyacrylamide and 0.2Kg of mercapto group-containing ionic liquid (1-methyl-3- (mercaptoethyl) imidazole tetrafluoroborate) into 45Kg of water, and mechanically stirring and mixing uniformly at 1000 r/min to obtain the anticorrosive coating A6 of the aluminum alloy material.
Example 7
Adding 0.4Kg of silane coupling agent, 0.8Kg of sodium carboxymethylcellulose, 1Kg of nano-silica, 4Kg of water-soluble polyurethane, 1.2Kg of polyacrylamide and 1Kg of mercapto group-containing ionic liquid (brominated 1-methyl-3- (mercaptoethyl) imidazolium salt) into 45Kg of water, and mechanically stirring and mixing uniformly at 1000 revolutions per minute to obtain the anticorrosive coating A7 of the aluminum alloy material.
Comparative example 1
Adding 0.4Kg of silane coupling agent, 0.8Kg of sodium carboxymethylcellulose, 1Kg of nano-silica, 4Kg of water-soluble polyurethane and 1.2Kg of polyacrylamide into 45Kg of water, and mechanically stirring and mixing uniformly at 1000 r/min to obtain the anticorrosive coating D1 of the aluminum alloy material.
Comparative example 2
Adding 0.4Kg of silane coupling agent, 0.8Kg of sodium carboxymethylcellulose, 1Kg of nano-silica, 4Kg of water-soluble polyurethane, 1.2Kg of polyacrylamide and 1Kg of ionic liquid (1-methyl-3-ethylimidazole tetrafluoroborate) into 45Kg of water, and mechanically stirring and mixing uniformly at 1000 revolutions per minute to obtain the anticorrosive coating D2 of the aluminum alloy material.
Comparative example 3
0.4Kg of silane coupling agent, 1Kg of nano-silica, 4Kg of water-soluble polyurethane, 1.2Kg of polyacrylamide and 1Kg of mercapto group-containing ionic liquid (1-methyl-3- (mercaptoethyl) imidazole tetrafluoroborate) are added into 45Kg of water, mechanically stirred at 1000 r/min and uniformly mixed to obtain the anticorrosive coating D3 of the aluminum alloy material.
Test example 1
The coatings prepared by the methods of examples 1 to 7 and comparative examples 1 to 3 were respectively coated on aluminum alloy test blocks on the day (0 day) after preparation, on the day 60 days after preparation, on the day 120 days after preparation and on the day 180 days after preparation and storage, and dried and cured at 110 ℃ to obtain a coating with a thickness of 0.8 μm, and then rust area measurement was performed after 200h salt spray test. Specific results are shown in table 1. The test block was made of 6061 aluminum alloy (available from Jiangsu Yangdong aluminum Co., Ltd.) with a size of 200mm 30mm 3mm
TABLE 1
The salt spray test is carried out by referring to the method of GB/T1771-2007, and as can be seen from the table above, the anticorrosive coating provided by the invention has good stability, still has good performance after being stored for more than 6 months, and has good protection effect on aluminum alloy.
Test example 2
The coatings obtained in examples 1 to 7 and comparative examples 1 to 3 were respectively applied by brush coating to aluminum alloy test pieces M1 to M10, dried and cured at 110 ℃ to give coating thicknesses of 0.8 μ M, and the coated M1 to M10 aluminum alloy test pieces were tested using 6061 aluminum alloy (available from Jiangsu Yangdong aluminum Co., Ltd.) having a size of 200mm 30mm 3 mm. Specific test methods and results are shown in table 2:
TABLE 2
Wherein the adhesion is tested according to GB/T5210-2006; salt spray resistance was tested according to GB/T1771-2007; the acid resistance and the alkali resistance are tested according to GB/T9274-1988, and the acid resistance is 5% H2SO4At 25 ℃ in the presence ofOf (1); the alkali resistance is carried out under the conditions of 3 percent NaOH and 25 ℃; the salt water resistance is tested according to GB/T1763-1989.
In conclusion, the anti-corrosion coating for the aluminum alloy material, which is provided by the invention, has the advantages of good stability and strong anti-corrosion capability, has strong adhesive force with the surface of the aluminum alloy, can be more tightly attached to the surface of the aluminum alloy, is a water-based coating, is environment-friendly, and does not pollute the environment.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Claims (6)
1. The anticorrosive coating for the aluminum alloy material is characterized by comprising a silane coupling agent, sodium carboxymethyl cellulose, nano silicon dioxide, water-soluble polyurethane, polyacrylamide, water and sulfydryl-containing ionic liquid;
relative to 1 part by weight of the sulfydryl-containing ionic liquid, the using amount of the silane coupling agent is 0.3-0.5 part by weight, the using amount of the sodium carboxymethyl cellulose is 0.5-0.8 part by weight, the using amount of the nano silicon dioxide is 0.5-1 part by weight, the using amount of the water-soluble polyurethane is 3-5 parts by weight, the using amount of the polyacrylamide is 1-1.5 parts by weight, and the using amount of the water is 25-50 parts by weight;
the mercapto-containing ionic liquid can be 1-methyl-3- (mercaptoethyl) imidazole tetrafluoroborate or 1-methyl-3- (mercaptopropyl) imidazole tetrafluoroborate.
2. The anticorrosive coating according to claim 1, wherein the silane coupling agent is used in an amount of 0.4 part by weight, the sodium carboxymethylcellulose is used in an amount of 0.8 part by weight, the nano-silica is used in an amount of 1 part by weight, the water-soluble polyurethane is used in an amount of 4 parts by weight, the polyacrylamide is used in an amount of 1.2 parts by weight, and the water is used in an amount of 45 parts by weight, relative to 1 part by weight of the mercapto group-containing ionic liquid.
3. The anticorrosive coating according to claim 1 or 2, wherein the silane coupling agent is γ -mercaptopropyltriethoxysilane or γ -mercaptopropyltrimethoxysilane in the anticorrosive coating.
4. The method for preparing the anticorrosive coating according to claim 1, characterized by comprising adding a silane coupling agent, sodium carboxymethylcellulose, nano-silica, water-soluble polyurethane, polyacrylamide and a mercapto group-containing ionic liquid into water, and uniformly mixing to obtain the anticorrosive coating of the aluminum alloy material.
5. A method for preventing corrosion of an aluminum alloy material, which comprises applying the anticorrosive coating according to any one of claims 1 to 3 on the surface of the aluminum alloy material, and then drying at a high temperature, wherein the conditions of drying at a high temperature comprise: the temperature is 90-110 ℃, and the drying time is 6-8 hours.
6. The method of claim 5, wherein the thickness of the coating formed on the surface of the aluminum alloy material after the coating is dried at a high temperature is 0.1 to 1 μm.
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| CN108184693A (en) * | 2018-01-30 | 2018-06-22 | 东兰县广元养殖专业合作社 | A kind of etch-proof rabbit-hutch |
| CN109535970A (en) * | 2018-11-21 | 2019-03-29 | 天津市杰利凯科技有限公司 | A kind of metal surface anticorrosive passivator |
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| CN107057548B (en) | 2019-07-26 |
| CN110003784A (en) | 2019-07-12 |
| CN107057548A (en) | 2017-08-18 |
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