CN109504238B - Single-component self-curing chromium-free zinc-aluminum anticorrosive paint and preparation and application thereof - Google Patents
Single-component self-curing chromium-free zinc-aluminum anticorrosive paint and preparation and application thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- 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
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- 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
- 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
- C09D5/10—Anti-corrosive paints containing metal dust
- C09D5/103—Anti-corrosive paints containing metal dust containing Al
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- C—CHEMISTRY; METALLURGY
- 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
- 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
- C09D5/10—Anti-corrosive paints containing metal dust
- C09D5/106—Anti-corrosive paints containing metal dust containing Zn
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- C—CHEMISTRY; METALLURGY
- 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
- C08K2003/0812—Aluminium
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
- C08K2003/0893—Zinc
Abstract
The invention belongs to the technical field of metal surface anticorrosion treatment, and discloses a single-component self-curing chromium-free zinc-aluminum anticorrosive paint, and preparation and application thereof. Diluting epoxy resin with a solvent, adding an aminosilane coupling agent, stirring at 60-90 ℃ for reaction, cooling, adding a silica sol and ammonium molybdate, and stirring and mixing at 45-70 ℃ to obtain a modified epoxy resin complex liquid; and uniformly dispersing zinc powder and aluminum powder in a metal powder wetting agent and a diluent, then adding the modified epoxy resin composite liquid, and uniformly stirring and mixing to obtain the single-component self-curing chromium-free zinc-aluminum anticorrosive paint. And coating the obtained anticorrosive paint on a metal substrate, and curing to obtain the chromium-free zinc-aluminum anticorrosive paint. The invention has the advantages of simple raw materials, easy operation of preparation process, no need of adding an epoxy resin curing agent, self-curing of the coating, convenient use, excellent mechanical property of the cured coating, inorganic corrosion resistance and organic corrosion resistance, and excellent corrosion resistance.
Description
Technical Field
The invention belongs to the technical field of metal surface anticorrosion treatment, and particularly relates to a single-component self-curing chromium-free zinc-aluminum anticorrosive paint, and preparation and application thereof.
Background
The dacromet technology is characterized in that flaky zinc powder, aluminum powder, chromic anhydride, a solvent and other additives are mixed and then uniformly coated on the surface of a workpiece, and then the mixture is cured at 300 ℃ to obtain a coating with anti-corrosion capability, and the coating is widely applied to the fields of automobiles, electric power, oil refining, machinery and the like. Compared with the traditional zinc electroplating layer by using an anticorrosion technology, the zinc electroplating layer overcomes the problems of no need of acid and alkali (plating solution), no hydrogen embrittlement, excellent heat resistance, better recoating capability and secondary and tertiary coating. More importantly, the corrosion resistance is greatly improved, the salt spray test time of the salt spray is greatly increased and is 7-10 times of that of the electrogalvanizing, and the price of the salt spray is equivalent to that of the electrogalvanizing. However, Cr6+Are highly toxic and carcinogenic, and their use is increasingly under strict control. At present, most of zinc-aluminum anticorrosive paint products are two-component, so that certain inconvenience is caused to construction. Therefore, the development of the single-component self-curing chromium-free zinc-aluminum anticorrosive paint and the coating has important significance.
Disclosure of Invention
In order to overcome the defects and shortcomings in the prior art, the invention aims to provide a preparation method of a single-component self-curing chromium-free zinc-aluminum anticorrosive paint.
The invention also aims to provide the one-component self-curing chromium-free zinc-aluminum anticorrosive paint prepared by the method.
The invention also aims to provide the application of the single-component self-curing chromium-free zinc-aluminum anticorrosive paint in metal substrate corrosion prevention.
The purpose of the invention is realized by the following technical scheme:
a preparation method of a single-component self-curing chromium-free zinc-aluminum anticorrosive paint comprises the following preparation steps:
(1) diluting 30-40 parts by mass of epoxy resin with 5-10 parts by mass of solvent, adding 0.5-1 part by mass of aminosilane coupling agent, stirring and reacting for 2-5 h at 60-90 ℃, cooling, adding 0.5-2 parts by mass of silica sol and 0.5-3 parts by mass of ammonium molybdate, stirring and mixing for 2-6 h at 45-70 ℃, and naturally cooling to obtain modified epoxy resin complex liquid;
(2) uniformly dispersing 20-35 parts by mass of zinc powder and 1-12 parts by mass of aluminum powder in 10-30 parts by mass of metal powder wetting agent and 1-10 parts by mass of diluent, adding 25-40 parts by mass of modified epoxy resin composite liquid, and uniformly stirring and mixing to obtain the single-component self-curing chromium-free zinc-aluminum anticorrosive coating.
Preferably, the epoxy resin in the step (1) refers to epoxy resin E-44 (with an epoxy value of 0.44); the solvent is n-butanol; the amino silane coupling agent is 3-aminopropyl triethoxysilane.
Preferably, the silica sol in step (1) is prepared by the following steps: adding tetraethoxysilane into absolute ethyl alcohol, then adding a mixed solution prepared from the absolute ethyl alcohol, deionized water and concentrated acid, uniformly stirring, and aging for 2 hours to 4 days to obtain the silicon dioxide sol. Further, the volume ratio of the ethyl orthosilicate to the absolute ethyl alcohol is (5-20) to (10-70); the volume ratio of the absolute ethyl alcohol to the deionized water to the concentrated acid in the mixed solution is (5-40): 1-15): 0.1-3; the concentrated acid is at least one of concentrated hydrochloric acid with the mass fraction of 35%, concentrated sulfuric acid with the mass fraction of 98% and concentrated nitric acid with the mass fraction of 65%.
Preferably, the zinc powder in the step (2) is flaky zinc powder with a flake diameter of 10-15 microns and a thickness of 0.1-0.2 microns.
Preferably, the aluminum powder in the step (2) is scaly aluminum powder with a flake diameter of 10-12 microns and a thickness of 0.1-0.2 microns.
Preferably, the metal powder wetting agent in the step (2) is at least one of ethyl acetate, butyl methacrylate and dioctyl phthalate.
Preferably, the diluent in the step (2) is at least one of 1, 2-propylene glycol methyl ether, isooctanol and n-butanol.
A single-component self-curing chromium-free zinc-aluminum anticorrosive paint is prepared by the method.
The single-component self-curing chromium-free zinc-aluminum anticorrosive paint is applied to corrosion prevention of metal substrates.
Preferably, the application process is as follows: coating the single-component self-curing chromium-free zinc-aluminum anticorrosive coating on a metal substrate, and baking at 180-250 ℃ for 30-60 min for curing to obtain the chromium-free zinc-aluminum anticorrosive coating.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) the invention has simple raw materials, selects single organic resin, has easy operation of preparation process, can stably store the single-component coating liquid, does not need to add an epoxy resin curing agent, can self-cure the coating at high temperature and has convenient use.
(2) Compared with the traditional Dacromet coating and some water-based chromium-free Dacromet coatings, the coating curing temperature is low, and the energy consumption is saved.
(3) According to the invention, the silica sol and the aminosilane modified epoxy resin are selected, so that the epoxy resin is toughened and enhanced, the coating adhesion is provided, and the cured coating has excellent mechanical properties.
(4) The modified epoxy resin prepared by the invention forms an organic-inorganic composite network after being cured, and the coating has the characteristics of inorganic corrosion resistance and organic corrosion resistance and excellent corrosion resistance.
Detailed Description
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto.
Example 1
The single-component self-curing chromium-free zinc-aluminum anticorrosive paint and the coating are prepared by the following method:
(1) adding 10 unit volume of ethyl orthosilicate into 40 unit volume of absolute ethyl alcohol, slowly adding a mixed solution prepared from 20 unit volume of absolute ethyl alcohol, 2 unit volume of deionized water and 0.8 unit volume of concentrated nitric acid (65% mass fraction), uniformly stirring, and aging for 2 hours to prepare silicon dioxide sol;
(2) adding 7 parts by mass of n-butyl alcohol into 30 parts by mass of epoxy resin E-44 (the epoxy value is 0.44) for dilution, adding 0.6 part by mass of 3-aminopropyltriethoxysilane, stirring and reacting for 2 hours at 80 ℃, cooling for standby application, then adding 1 part by mass of silica sol and 2 parts by mass of ammonium molybdate into the amino modified epoxy resin, stirring and mixing for 2 hours at 55 ℃, and naturally cooling to obtain a modified epoxy resin complex liquid;
(3) dispersing 33 parts by mass of flaky zinc powder (with the sheet diameter of 10-15 micrometers and the thickness of 0.1-0.2 micrometer) and 7 parts by mass of flaky aluminum powder (with the sheet diameter of 10-12 micrometers and the thickness of 0.1-0.2 micrometer) in 20 parts by mass of ethyl acetate and 7 parts by mass of 1, 2-propylene glycol methyl ether, uniformly stirring, adding 33 parts by mass of prepared modified epoxy resin composite liquid into the metal powder dispersion liquid, and uniformly mixing the modified epoxy resin composite liquid and the metal powder dispersion liquid by stirring to obtain the single-component self-curing chromium-free zinc-aluminum anticorrosive paint containing the modified epoxy resin;
(4) the prepared single-component self-curing chromium-free zinc-aluminum anticorrosive coating is coated on a tinplate (12cm multiplied by 5cm multiplied by 0.28cm), and is baked at 200 ℃ for 40min for curing to obtain the chromium-free zinc-aluminum anticorrosive coating. The tinplate is polished by 500# abrasive paper, washed clean by clear water and dried to remove surface grease.
In order to determine the hardness of the prepared chromium-free zinc-aluminum anticorrosive coating, the method of ASTM D3363-05 is adopted for determination. The procedure for the determination was as follows: the tinplate coated with the coating to be tested is placed horizontally, the wooden pencil is polished smoothly, and from the hardest pencil, the pencil is fixed by using a coating pencil hardness tester, so that the pencil and the test coating form a 45-degree angle and point to the direction opposite to that of an experimenter. The tester is pushed away from the experimenter by fingertips on the side surface of the tester. The test hardness was gradually decreased until a pencil lead was found that neither pierced nor scratched the coating surface within a distance of 3 mm.
In order to determine the adhesion of the prepared chromium-free zinc-aluminum anticorrosive coating, the adhesion is determined by using the method of ASTM D3359-08 (ISO 2409-2007). The test procedure was as follows: and cutting 11 mutually parallel cutting marks with the interval of 1mm on the coating by using a paint film scriber, and then vertically cutting the cutting marks with the same number and the same interval as the cutting marks on the coating to form the grids. After cutting, the chips are lightly brushed away along the directions of the two diagonal lines of the square by using a soft brush. A3M scotch tape was glued to the grid parallel to the score line, rubbed flat with the finger abdomen, and allowed to vent air bubbles. Grasping one end of the adhesive tape, tearing within 0.5-1.0s at an angle close to 60 degrees, and detecting the state of the cutting part.
In order to evaluate the corrosion resistance of the prepared chromium-free zinc-aluminum anticorrosive coating, rapid test of ammonium nitrate resistance is selected. The test procedure was as follows: heating 20% ammonium nitrate solution by mass fraction to 70 +/-5 ℃ in water bath. The tinplate pieces coated with the test coatings were immersed in the ammonium nitrate solution and suspended for fixation. The operation avoids the contact between the sample and between the sample and the wall of the beaker. During the test, the temperature of the ammonium nitrate solution was controlled to 70 + -1 deg.C.
In order to determine the salt spray time of the prepared chromium-free zinc-aluminum anticorrosive coating, GB6458-86 metal covering layer-neutral salt spray test (NSS test) is adopted for determination. The test procedure was as follows: the sample plates are exposed in a salt spray test box with the temperature of 35 +/-2 ℃, the surface to be tested faces upwards, the exposure angle of each sample plate in the box and the vertical included angle form 20 +/-5 degrees (the sample plates are not contacted with each other and are not contacted with the box body), atomized sodium chloride solution is sprayed in during the experiment, the sample plates are inspected for 1 time within 48 hours, the sample plates are inspected for 1 time within 2 times within 72 hours until the sample plates have corrosion traces, and the time is recorded.
Example 2
The single-component self-curing chromium-free zinc-aluminum anticorrosive paint and the coating are prepared by the following method:
(1) adding 10 unit volume of ethyl orthosilicate into 40 unit volume of absolute ethyl alcohol, slowly adding a mixed solution prepared from 20 unit volume of absolute ethyl alcohol, 2 unit volume of deionized water and 0.8 unit volume of concentrated nitric acid (65% mass fraction), uniformly stirring, and aging for 2 hours to prepare silicon dioxide sol;
(2) adding 7 parts by mass of n-butyl alcohol into 30 parts by mass of epoxy resin E-44 (the epoxy value is 0.44) for dilution, adding 0.6 part by mass of 3-aminopropyltriethoxysilane, stirring and reacting for 2 hours at 80 ℃, cooling for standby application, then adding 1 part by mass of silica sol and 2 parts by mass of ammonium molybdate into the amino modified epoxy resin, stirring and mixing for 2 hours at 55 ℃, and naturally cooling to obtain a modified epoxy resin complex liquid;
(3) dispersing 30 parts by mass of flaky zinc powder (with the sheet diameter of 10-15 micrometers and the thickness of 0.1-0.2 micrometer) and 10 parts by mass of flaky aluminum powder (with the sheet diameter of 10-12 micrometers and the thickness of 0.1-0.2 micrometer) in 15 parts by mass of ethyl acetate, 5 parts by mass of butyl methacrylate and 10 parts by mass of 1, 2-propylene glycol methyl ether, uniformly stirring, adding 30 parts by mass of prepared modified epoxy resin composite liquid into the metal powder dispersion liquid, and uniformly stirring to mix the two to obtain the single-component self-curing chromium-free zinc-aluminum anticorrosive paint containing the modified epoxy resin;
(4) the preparation method and test method of the anticorrosive coating of this example were the same as those of example 1.
Example 3
The single-component self-curing chromium-free zinc-aluminum anticorrosive paint and the coating are prepared by the following method:
(1) adding 10 unit volume of ethyl orthosilicate into 40 unit volume of absolute ethyl alcohol, slowly adding a mixed solution prepared from 20 unit volume of absolute ethyl alcohol, 2 unit volume of deionized water and 0.8 unit volume of concentrated nitric acid (65% mass fraction), uniformly stirring, and aging for 2 hours to prepare silicon dioxide sol;
(2) adding 7 parts by mass of n-butyl alcohol into 30 parts by mass of epoxy resin E-44 (the epoxy value is 0.44) for dilution, adding 0.6 part by mass of 3-aminopropyltriethoxysilane, stirring and reacting for 2 hours at 80 ℃, cooling for standby application, then adding 1 part by mass of silica sol and 2 parts by mass of ammonium molybdate into the amino modified epoxy resin, stirring and mixing for 2 hours at 55 ℃, and naturally cooling to obtain a modified epoxy resin complex liquid;
(3) dispersing 30 parts by mass of flaky zinc powder (with the sheet diameter of 10-15 micrometers and the thickness of 0.1-0.2 micrometer) and 10 parts by mass of flaky aluminum powder (with the sheet diameter of 10-12 micrometers and the thickness of 0.1-0.2 micrometer) in 15 parts by mass of ethyl acetate, 5 parts by mass of dioctyl phthalate, 5 parts by mass of 1, 2-propylene glycol methyl ether and 5 parts by mass of n-butyl alcohol, uniformly stirring, adding 30 parts by mass of prepared modified epoxy resin composite liquid into the metal powder dispersion liquid, and uniformly stirring to mix the two to obtain the single-component self-curing chromium-free zinc-aluminum anticorrosive paint containing the modified epoxy resin;
(4) the preparation method and test method of the anticorrosive coating of this example were the same as those of example 1.
Example 4
The single-component self-curing chromium-free zinc-aluminum anticorrosive paint and the coating are prepared by the following method:
(1) adding 10 unit volume of ethyl orthosilicate into 40 unit volume of absolute ethyl alcohol, slowly adding a mixed solution prepared from 20 unit volume of absolute ethyl alcohol, 2 unit volume of deionized water and 0.8 unit volume of concentrated nitric acid (65% mass fraction), uniformly stirring, and aging for 2 hours to prepare silicon dioxide sol;
(2) adding 7 parts by mass of n-butyl alcohol into 30 parts by mass of epoxy resin E-44 (the epoxy value is 0.44) for dilution, adding 0.6 part by mass of 3-aminopropyltriethoxysilane, stirring and reacting for 2 hours at 80 ℃, cooling for standby application, then adding 1 part by mass of silica sol and 2 parts by mass of ammonium molybdate into the amino modified epoxy resin, stirring and mixing for 2 hours at 55 ℃, and naturally cooling to obtain a modified epoxy resin complex liquid;
(3) dispersing 28 parts by mass of flaky zinc powder (with the sheet diameter of 10-15 micrometers and the thickness of 0.1-0.2 micrometer) and 12 parts by mass of flaky aluminum powder (with the sheet diameter of 10-12 micrometers and the thickness of 0.1-0.2 micrometer) in 25 parts by mass of ethyl acetate and 10 parts by mass of 1, 2-propylene glycol methyl ether, uniformly stirring, adding the prepared 25 parts by mass of modified epoxy resin composite liquid into the metal powder dispersion liquid, and uniformly mixing the two through stirring to obtain the single-component self-curing chromium-free zinc-aluminum anticorrosive paint containing the modified epoxy resin;
(4) the preparation method and test method of the anticorrosive coating of this example were the same as those of example 1.
Example 5
The single-component self-curing chromium-free zinc-aluminum anticorrosive paint and the coating are prepared by the following method:
(1) adding 10 unit volume of ethyl orthosilicate into 40 unit volume of absolute ethyl alcohol, slowly adding a mixed solution prepared from 20 unit volume of absolute ethyl alcohol, 2 unit volume of deionized water and 0.8 unit volume of concentrated nitric acid (65% mass fraction), uniformly stirring, and aging for 2 hours to prepare silicon dioxide sol;
(2) adding 7 parts by mass of n-butyl alcohol into 30 parts by mass of epoxy resin E-44 (the epoxy value is 0.44) for dilution, adding 0.6 part by mass of 3-aminopropyltriethoxysilane, stirring and reacting for 2 hours at 80 ℃, cooling for standby application, then adding 2 parts by mass of silica sol and 2 parts by mass of ammonium molybdate into the amino modified epoxy resin, stirring and mixing for 4 hours at 65 ℃, and naturally cooling to obtain a modified epoxy resin complex liquid;
(3) dispersing 33 parts by mass of flaky zinc powder (with the sheet diameter of 10-15 micrometers and the thickness of 0.1-0.2 micrometer) and 7 parts by mass of flaky aluminum powder (with the sheet diameter of 10-12 micrometers and the thickness of 0.1-0.2 micrometer) in 20 parts by mass of ethyl acetate and 10 parts by mass of 1, 2-propylene glycol methyl ether, uniformly stirring, adding 30 parts by mass of prepared modified epoxy resin composite liquid into the metal powder dispersion liquid, and uniformly mixing the two through stirring to obtain the single-component self-curing chromium-free zinc-aluminum anticorrosive paint containing the modified epoxy resin;
(4) the preparation method and test method of the anticorrosive coating of this example were the same as those of example 1.
Example 6
The single-component self-curing chromium-free zinc-aluminum anticorrosive paint and the coating are prepared by the following method:
(1) adding 10 unit volume of ethyl orthosilicate into 40 unit volume of absolute ethyl alcohol, slowly adding a mixed solution prepared from 20 unit volume of absolute ethyl alcohol, 2 unit volume of deionized water and 0.8 unit volume of concentrated nitric acid (65% mass fraction), uniformly stirring, and aging for 2 hours to prepare silicon dioxide sol;
(2) adding 7 parts by mass of n-butyl alcohol into 30 parts by mass of epoxy resin E-44 (the epoxy value is 0.44) for dilution, adding 0.6 part by mass of 3-aminopropyltriethoxysilane, stirring and reacting for 2 hours at 80 ℃, cooling for standby application, then adding 2 parts by mass of silica sol and 1 part by mass of ammonium molybdate into the amino modified epoxy resin, stirring and mixing for 2 hours at 65 ℃, and naturally cooling to obtain a modified epoxy resin complex liquid;
(3) dispersing 30 parts by mass of flaky zinc powder (with the sheet diameter of 10-15 micrometers and the thickness of 0.1-0.2 micrometer) and 10 parts by mass of flaky aluminum powder (with the sheet diameter of 10-12 micrometers and the thickness of 0.1-0.2 micrometer) in 10 parts by mass of ethyl acetate, 10 parts by mass of butyl methacrylate and 10 parts by mass of 1, 2-propylene glycol methyl ether, uniformly stirring, adding 30 parts by mass of prepared modified epoxy resin composite liquid into the metal powder dispersion liquid, and uniformly stirring to mix the two to obtain the single-component self-curing chromium-free zinc-aluminum anticorrosive paint containing the modified epoxy resin;
(4) the preparation method and test method of the anticorrosive coating of this example were the same as those of example 1.
Example 7
The single-component self-curing chromium-free zinc-aluminum anticorrosive paint and the coating are prepared by the following method:
(1) adding 10 unit volume of ethyl orthosilicate into 40 unit volume of absolute ethyl alcohol, slowly adding a mixed solution prepared from 20 unit volume of absolute ethyl alcohol, 2 unit volume of deionized water and 0.8 unit volume of concentrated nitric acid (65% mass fraction), uniformly stirring, and aging for 2 hours to prepare silicon dioxide sol;
(2) adding 7 parts by mass of n-butyl alcohol into 30 parts by mass of epoxy resin E-44 (the epoxy value is 0.44) for dilution, adding 0.9 part by mass of 3-aminopropyltriethoxysilane, stirring and reacting for 3 hours at 80 ℃, cooling for standby application, then adding 2 parts by mass of silica sol and 2 parts by mass of ammonium molybdate into the amino modified epoxy resin, stirring and mixing for 4 hours at 65 ℃, and naturally cooling to obtain a modified epoxy resin complex liquid;
(3) dispersing 30 parts by mass of flaky zinc powder (with the sheet diameter of 10-15 micrometers and the thickness of 0.1-0.2 micrometer) and 10 parts by mass of flaky aluminum powder (with the sheet diameter of 10-12 micrometers and the thickness of 0.1-0.2 micrometer) in 10 parts by mass of ethyl acetate and 10 parts by mass of 1, 2-propylene glycol methyl ether, uniformly stirring, adding 40 parts by mass of prepared modified epoxy resin composite liquid into the metal powder dispersion liquid, and uniformly mixing the modified epoxy resin composite liquid and the metal powder dispersion liquid by stirring to obtain the single-component self-curing chromium-free zinc-aluminum anticorrosive paint containing the modified epoxy resin;
(4) the preparation method and test method of the anticorrosive coating of this example were the same as those of example 1.
The main performance indicators achievable with the coatings tested in the above examples are shown in table 1:
TABLE 1
| Examples | Hardness of | Adhesion force | Rapid test for ammonium nitrate resistance | Neutral salt spray test |
| 1 | 4H | ISO 1 | >3.5h | >1000h |
| 2 | 3H | ISO 1 | >3.5h | >1200h |
| 3 | 3H | ISO 1 | >3.5h | >1200h |
| 4 | 3H | ISO 1 | >3.5h | >1000h |
| 5 | 4H | ISO 1 | >3.5h | >1200h |
| 6 | 4H | ISO 1 | >3.5h | >1400h |
| 7 | 4H | ISO 1 | >3.5h | >1400h |
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. A preparation method of a single-component self-curing chromium-free zinc-aluminum anticorrosive paint is characterized by comprising the following preparation steps:
(1) diluting 30-40 parts by mass of epoxy resin with 5-10 parts by mass of solvent, adding 0.5-1 part by mass of aminosilane coupling agent, stirring and reacting for 2-5 h at 60-90 ℃, cooling, adding 0.5-2 parts by mass of silica sol and 0.5-3 parts by mass of ammonium molybdate, stirring and mixing for 2-6 h at 45-70 ℃, and naturally cooling to obtain modified epoxy resin complex liquid;
(2) uniformly dispersing 20-35 parts by mass of zinc powder and 1-12 parts by mass of aluminum powder in 10-30 parts by mass of metal powder wetting agent and 1-10 parts by mass of diluent, adding 25-40 parts by mass of modified epoxy resin composite liquid, and uniformly stirring and mixing to obtain the single-component self-curing chromium-free zinc-aluminum anticorrosive coating.
2. The preparation method of the one-component self-curing chromium-free zinc-aluminum anticorrosive paint according to claim 1, characterized in that: the epoxy resin in the step (1) is epoxy resin E-44; the solvent is n-butanol; the amino silane coupling agent is 3-aminopropyl triethoxysilane.
3. The preparation method of the one-component self-curing chromium-free zinc-aluminum anticorrosive paint according to claim 1, wherein the silica sol in the step (1) is prepared by the following steps: adding tetraethoxysilane into absolute ethyl alcohol, then adding a mixed solution prepared from the absolute ethyl alcohol, deionized water and concentrated acid, uniformly stirring, and aging for 2 hours to 4 days to obtain the silicon dioxide sol.
4. The preparation method of the one-component self-curing chromium-free zinc-aluminum anticorrosive paint according to claim 3, characterized in that: the volume ratio of the ethyl orthosilicate to the absolute ethyl alcohol is (5-20) to (10-70); the volume ratio of the absolute ethyl alcohol to the deionized water to the concentrated acid in the mixed solution is (5-40): 1-15): 0.1-3; the concentrated acid is at least one of concentrated hydrochloric acid with the mass fraction of 35%, concentrated sulfuric acid with the mass fraction of 98% and concentrated nitric acid with the mass fraction of 65%.
5. The preparation method of the one-component self-curing chromium-free zinc-aluminum anticorrosive paint according to claim 1, characterized in that: the zinc powder in the step (2) is flaky zinc powder with the flake diameter of 10-15 microns and the thickness of 0.1-0.2 microns.
6. The preparation method of the one-component self-curing chromium-free zinc-aluminum anticorrosive paint according to claim 1, characterized in that: the aluminum powder in the step (2) is scaly aluminum powder with the flake diameter of 10-12 microns and the thickness of 0.1-0.2 microns.
7. The preparation method of the one-component self-curing chromium-free zinc-aluminum anticorrosive paint according to claim 1, characterized in that: in the step (2), the metal powder wetting agent is at least one of ethyl acetate, butyl methacrylate and dioctyl phthalate; the diluent is at least one of 1, 2-propylene glycol methyl ether, isooctanol and n-butanol.
8. A single-component self-curing chromium-free zinc-aluminum anticorrosive paint is characterized in that: prepared by the method of any one of claims 1 to 7.
9. The use of the one-component self-curing chromium-free zinc-aluminum anticorrosive coating of claim 8 in the corrosion prevention of metal substrates.
10. The application of the one-component self-curing chromium-free zinc-aluminum anticorrosive coating in metal substrate corrosion prevention according to claim 9 is characterized in that the application process comprises the following steps: coating the single-component self-curing chromium-free zinc-aluminum anticorrosive coating on a metal substrate, and baking at 180-250 ℃ for 30-60 min for curing to obtain the chromium-free zinc-aluminum anticorrosive coating.
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