CN113480919A - Low-VOC high-corrosion-resistance environment-friendly epoxy coating and preparation method thereof - Google Patents

Low-VOC high-corrosion-resistance environment-friendly epoxy coating and preparation method thereof Download PDF

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CN113480919A
CN113480919A CN202110743723.0A CN202110743723A CN113480919A CN 113480919 A CN113480919 A CN 113480919A CN 202110743723 A CN202110743723 A CN 202110743723A CN 113480919 A CN113480919 A CN 113480919A
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stirring
zif
corrosion
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罗义云
张建军
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Suzhou Carraway New Materials Co ltd
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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
    • 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
    • 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
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    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
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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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    • 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
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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
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2237—Oxides; Hydroxides of metals of titanium
    • C08K2003/2241—Titanium dioxide

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Abstract

The invention discloses a low-VOC high-corrosion-resistance environment-friendly epoxy coating which comprises the following components in percentage by mass: 20-25% of epoxy resin, 1.5-2% of petroleum resin, 5-8% of methyl isobutyl ketone, 1-2% of polyamide wax, 0.5-0.8% of wetting dispersant, 0.2-0.4% of acrylate defoamer, 4-6% of titanium dioxide, 0.2-0.4% of iron oxide yellow, 0.3-0.5% of carbon black, 25-35% of alumina, 25-35% of feldspar powder, 2-3% of n-butyl alcohol, 0.3-0.6% of methyl silane and 3-5% of reinforcing filler; the reinforcing filler is TiO modified by polymer2A/ZIF-8 composite material. The invention also disclosesA preparation method of the epoxy coating. The epoxy coating prepared by the invention has the advantages of low VOC content, good stability, good corrosion resistance and excellent mechanical property.

Description

Low-VOC high-corrosion-resistance environment-friendly epoxy coating and preparation method thereof
The technical field is as follows:
the invention relates to the field of high polymer materials, in particular to a low-VOC high-corrosion-resistance environment-friendly epoxy coating and a preparation method thereof.
Background art:
the phenomenon of damage to metallic materials by chemical or electrochemical action in the surrounding medium is known as corrosion. The corrosive behavior of metals is spontaneous in chemical thermodynamics and metals corrode to varying degrees in different environments. At present, metals and metal alloys are widely applied and occupy an important position in national economic development, but when the alloy is used, the corrosion of the metal surface can not only cause property loss, but also cause major accidents.
With the development of science and technology, the anti-corrosion treatment on the metal surface effectively reduces the loss caused by metal corrosion and also improves the use safety of the metal. The main technologies currently used for metal corrosion prevention are corrosion medium treatment, electrochemical protection, coating protection, etc., wherein the method for inhibiting metal surface corrosion by adopting an anticorrosive coating has low cost and convenient operation, and is gradually widely applied. The anticorrosive coating is mainly formed by coating anticorrosive paint on the surface of metal. The anticorrosive paint mainly comprises components such as a film forming substance, a pigment, a filler, a solvent, an auxiliary agent and the like, wherein the water-based epoxy resin paint is simple to prepare, and has excellent adhesive force and low shrinkage; has better corrosion resistance and permeability resistance to water, medium acid, alkali, salt and solvent, and is widely applied.
The patent (application number: CN201911084959.7) provides a water-based epoxy resin anticorrosive paint and a preparation method thereof, the method firstly prepares a bismuth vanadate and graphene oxide heterojunction composite material through high-pressure hydrothermal reaction, then compounds the bismuth vanadate and graphene oxide heterojunction composite material with water-based epoxy resin to prepare the water-based epoxy resin anticorrosive paint, the water-based epoxy resin anticorrosive paint is coated on the surface of metal, electrons generated by the bismuth vanadate and graphene oxide heterojunction composite material in the coating are transferred to the surface of the metal and enriched when meeting light, the self-corrosion potential of the metal is reduced, and the light-induced cathode protection effect is achieved. Meanwhile, the graphene oxide nanosheet layer has a reinforcing and toughening effect on a coating formed by compounding the aqueous epoxy resin, and the graphene oxide nanosheet layer and the formed compact coating have a physical barrier effect on various corrosion effects. But there is little research on how to improve the bonding force between the coating and the metal to further improve the durability of the corrosion resistance of the coating.
The invention content is as follows:
the invention aims to solve the technical problem that aiming at the defects of the prior art, the invention provides the low-VOC high-corrosion-resistance environment-friendly epoxy coating and the preparation method thereof, the invention prepares the TiO2/ZIF-8 composite material with the micro-nano structure, and then coats polyacrylate on the surface of the composite material, so that the prepared reinforcing filler has good compatibility with a coating matrix, and when the prepared coating is used for the anti-corrosion treatment of a metal matrix, the effect is good, and the binding force with the matrix is strong.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
the low-VOC high-corrosion-resistance environment-friendly epoxy coating comprises the following components in percentage by mass:
20-25% of epoxy resin, 1.5-2% of petroleum resin, 5-8% of methyl isobutyl ketone, 1-2% of polyamide wax, 0.5-0.8% of wetting dispersant, 0.2-0.4% of acrylate defoamer, 4-6% of titanium dioxide, 0.2-0.4% of iron oxide yellow, 0.3-0.5% of carbon black, 25-35% of alumina, 25-35% of feldspar powder, 2-3% of n-butyl alcohol, 0.3-0.6% of methyl silane and 3-5% of reinforcing filler; the reinforcing filler is a TiO2/ZIF-8 composite material modified by polymer.
Preferably, the epoxy resin is bisphenol A type liquid epoxy resin, and the solid content is 100%; the petroleum resin is C9 aromatic base liquid hydrocarbon resin or C10 aromatic base liquid hydrocarbon resin; the wetting dispersant is a high molecular weight alkyl ammonium salt copolymer; the defoaming agent is an acrylate defoaming agent; the methylsilane is 3- (2, 3-glycidoxy) propyl trimethoxy silane.
In order to better solve the technical problems, the technical scheme adopted by the invention is as follows:
a preparation method of a low-VOC high-corrosion-resistance environment-friendly epoxy coating comprises the following steps:
(1) respectively preparing a methanol solution of zinc nitrate hexahydrate and a methanol solution of 2-methylimidazole, mixing the methanol solutions of zinc nitrate hexahydrate and 2-methylimidazole, stirring at room temperature, then carrying out centrifugal separation, washing the obtained precipitate with methanol, and finally drying to obtain ZIF-8 particles;
(2) dispersing ZIF-8 particles in absolute ethyl alcohol, adding hexadecyl trimethyl ammonium bromide, stirring and dispersing, then dropwise adding ammonia water to adjust the pH value of the solution to 11, slowly dropwise adding tetrabutyl titanate, violently stirring for 24 hours, then centrifuging, washing obtained precipitates by using ethanol and deionized water in sequence, and then drying to obtain a TiO2/ZIF-8 composite material;
(3) mixing and uniformly stirring a TiO2/ZIF-8 composite material, sodium dodecyl sulfate and deionized water, then adding methyl methacrylate, ethyl acrylate and acrylic acid, stirring and dispersing, heating to 70-80 ℃, adding potassium persulfate, stirring and reacting for 1-3h, cooling to room temperature after the reaction is finished, filtering reaction liquid, and drying the obtained solid to obtain a polymer modified TiO2/ZIF-8 composite material;
(4) adding epoxy resin into a stirrer, adding petroleum resin, methyl isobutyl ketone, polyamide wax and an acrylate defoaming agent while stirring, stirring for the first time, heating and adjusting the stirring speed for the first time, adding titanium dioxide, iron oxide yellow, carbon black, aluminum oxide, feldspar powder and a polymer modified TiO2/ZIF-8 composite material, stirring for the second time, heating and adjusting the stirring speed for the second time, adding n-butyl alcohol and methyl silane, stirring for the third time, and stirring for 5-10 minutes to obtain the coating.
Preferably, in the step (1), the concentrations of the methanol solution of zinc nitrate hexahydrate and the methanol solution of 2-methylimidazole are 0.12 to 0.14mol/L and 0.45 to 0.55mol/L, respectively, and the volume ratio of the two is 1: 1.
Preferably, in the step (1), the time of the room-temperature stirring treatment is 20-25h, and the stirring speed is 1000-2000 rpm.
Preferably, in the step (2), the ratio of the amount of the ZIF-8 particles to the amount of the cetyltrimethylammonium bromide to the amount of the tetrabutyl titanate is 0.15g to 0.17 g: 0.1-0.3 g: 0.15 ml.
Preferably, in the step (3), the amounts of the components are 5-7 parts by weight of the TiO2/ZIF-8 composite material, 1 part by weight of sodium dodecyl sulfate, 200 parts by weight of deionized water, 50-80 parts by weight of methyl methacrylate, 10-20 parts by weight of ethyl acrylate, 10-20 parts by weight of acrylic acid and 2-3 parts by weight of potassium persulfate.
Preferably, the rotation speeds of the first stirring, the second stirring and the third stirring are respectively 800-1000 rpm, 1000-1200 rpm and 600-800 rpm.
Preferably, when the first temperature rise and the stirring speed are adjusted, the temperature rises to 45 ℃, and the stirring speed is adjusted to 200-300 r/min.
Preferably, when the temperature is raised for the second time and the stirring speed is adjusted, the temperature is raised to 60-70 ℃, the stirring speed is adjusted to 200-300 r/min, and then the heat preservation stirring is continued for 10-15 min.
Due to the adoption of the technical scheme, the invention has the following beneficial effects:
the water-based epoxy resin coating provided by the invention comprises epoxy resin, petroleum resin, methyl isobutyl ketone, polyamide wax, wetting dispersant, acrylate defoaming agent, titanium dioxide, iron oxide yellow, carbon black, alumina, feldspar powder, n-butyl alcohol, methyl silane and reinforcing filler; the reinforcing filler is a polymer modified TiO2/ZIF-8 composite material, the epoxy resin adopted by the invention is bisphenol A type liquid epoxy resin, the solid content is 100%, the high solid content and the low viscosity are achieved, the mechanical property and the heat resistance are excellent, the petroleum resin is C9 aromatic base liquid hydrocarbon resin or C10 aromatic base liquid hydrocarbon resin, the volatile matter content is low, and the viscosity of the epoxy coating can be obviously reduced; the methyl isobutyl ketone is used as a diluent of the epoxy coating to replace the traditional dimethylbenzene, so that the environment is protected and the toxicity is low; the polyamide wax has excellent thixotropy, can provide the best anti-settling and anti-sagging effects, and does not agglomerate and return coarse particles; the wetting dispersant is a high molecular weight alkyl ammonium salt copolymer, the content of active ingredients is more than 96%, organic and inorganic pigments can be effectively stabilized, and particularly, the dispersibility of the wetting dispersant to carbon black is better; the defoaming agent is an acrylate defoaming agent, and can quickly break bubbles generated in the production process of the coating; the titanium dioxide is rutile titanium dioxide, has good dispersibility and excellent weather resistance, is not easy to pulverize and the like; the iron oxide yellow is mainly used for adjusting the color of the coating and has the characteristics of weather resistance, water resistance and the like; the main component of the aluminum oxide is aluminum oxide, and the aluminum oxide mainly has the effects of increasing the sedimentation resistance and the sagging resistance of the coating, helping the leveling of a wet film and improving the corrosion resistance of the coating; the feldspar powder mainly comprises SiO2, K2O, Na2O and the like, so that the wear resistance, impact resistance and other properties of the coating can be improved, the solid content of the coating is improved, and the cost of the coating is reduced; the n-butyl alcohol can effectively dissolve trace urea formaldehyde resin and melamine formaldehyde resin in the epoxy coating to keep the stability of the epoxy coating and increase the conductivity of the epoxy coating; the methylsilane is 3- (2, 3-epoxypropoxy) propyl trimethoxy silane, can obviously improve the adhesive force of the coating, a base material and finish paint, and improves the anti-corrosion performance of the coating. The reinforcing filler has good dispersibility in the matrix, and can effectively improve the hydrophobic property and the corrosion resistance of the coating.
According to the invention, zinc salt and 2-methylimidazole are used as raw materials to prepare ZIF-8 particles, the ZIF-8 particles have good chemical stability, then a nano titanium dioxide layer is deposited on the surface of the ZIF-8 particles in situ, and finally a polyacrylate layer is coated on the surface of the ZIF-8 particles. The paint prepared by the invention has low VOC content, does not contain benzene rings, is environment-friendly and nontoxic, and the like.
The specific implementation mode is as follows:
in order to better understand the present invention, the following examples further illustrate the invention, the examples are only used for explaining the invention, not to constitute any limitation of the invention.
Example 1
(1) Respectively preparing a 0.12mol/L zinc nitrate hexahydrate methanol solution and a 0.45 mol/L2-methylimidazole methanol solution, mixing the zinc nitrate hexahydrate methanol solution and the 2-methylimidazole methanol solution in a volume ratio of 1:1, stirring at room temperature under the condition of 1000 revolutions per minute for 20 hours, then carrying out centrifugal separation, washing the obtained precipitate with methanol, and finally drying to obtain ZIF-8 particles;
(2) dispersing 0.15gg ZIF-8 particles in 50ml of absolute ethyl alcohol, adding 0.1g of hexadecyl trimethyl ammonium bromide, stirring and dispersing, then dropwise adding 25 wt% ammonia water to adjust the pH value of the solution to 11, slowly dropwise adding 0.15ml of tetrabutyl titanate, violently stirring for 24 hours, then centrifuging, washing the obtained precipitate with ethanol and deionized water in sequence, and then drying to obtain a TiO2/ZIF-8 composite material;
(3) mixing and uniformly stirring 5 parts by weight of TiO2/ZIF-8 composite material, 1 part by weight of sodium dodecyl sulfate and 100 parts by weight of deionized water, then adding 50 parts by weight of methyl methacrylate, 10 parts by weight of ethyl acrylate and 10 parts by weight of acrylic acid, stirring and dispersing, heating to 70 ℃, adding 2 parts by weight of potassium persulfate, stirring and reacting for 1 hour, cooling to room temperature after the reaction is finished, filtering the reaction liquid, and drying the obtained solid to obtain the polymer modified TiO2/ZIF-8 composite material;
(4) adding 24 parts by weight of bisphenol A liquid epoxy resin into a stirrer, adding 1.5 parts by weight of C9 aromatic base liquid hydrocarbon resin, 7 parts by weight of methyl isobutyl ketone, 2 parts by weight of polyamide wax, 0.4 part by weight of acrylate defoaming agent, 0.8 part by weight of high molecular weight alkyl ammonium salt copolymer while stirring, stirring for the first time at 800 revolutions per minute, then heating to 45 ℃ and adjusting the stirring speed to 200 revolutions per minute, adding 5 parts by weight of titanium dioxide, 0.4 part by weight of iron oxide yellow, 0.5 part by weight of carbon black, 25 parts by weight of aluminum oxide, 25 parts by weight of feldspar powder, 5 parts by weight of polymer modified TiO2/ZIF-8 composite material, stirring for the second time at 1000 revolutions per minute, then heating to 60 ℃ and adjusting the stirring speed to 300 revolutions per minute, stirring for 10 minutes while keeping warm, adding 3 parts by weight of n-butyl alcohol, 0.4 part by weight of 3- (2,3 glycidoxy) propyl trimethoxy silane, the mixture was stirred at 600 rpm for 10 minutes to obtain a coating.
Example 2
(1) Respectively preparing a 0.14mol/L zinc nitrate hexahydrate methanol solution and a 0.55 mol/L2-methylimidazole methanol solution, mixing the zinc nitrate hexahydrate methanol solution and the 2-methylimidazole methanol solution in a volume ratio of 1:1, stirring at room temperature under 2000 revolutions per minute for 25 hours, then carrying out centrifugal separation, washing the obtained precipitate with methanol, and finally drying to obtain ZIF-8 particles;
(2) dispersing 0.17g of ZIF-8 particles in 50ml of absolute ethanol, adding 0.3g of hexadecyl trimethyl ammonium bromide, stirring and dispersing, then dropwise adding 25 wt% ammonia water to adjust the pH value of the solution to 11, slowly dropwise adding 0.15ml of tetrabutyl titanate, violently stirring for 24 hours, then centrifuging, washing the obtained precipitate with ethanol and deionized water in sequence, and then drying to obtain a TiO2/ZIF-8 composite material;
(3) mixing and uniformly stirring 7 parts by weight of TiO2/ZIF-8 composite material, 1 part by weight of sodium dodecyl sulfate and 100 parts by weight of deionized water, then adding 80 parts by weight of methyl methacrylate, 20 parts by weight of ethyl acrylate and 20 parts by weight of acrylic acid, stirring and dispersing, heating to 80 ℃, adding 3 parts by weight of potassium persulfate, stirring and reacting for 3 hours, cooling to room temperature after the reaction is finished, filtering the reaction liquid, and drying the obtained solid to obtain the polymer modified TiO2/ZIF-8 composite material;
(4) adding 24 parts by weight of bisphenol A liquid epoxy resin into a stirrer, adding 1.5 parts by weight of C9 aromatic base liquid hydrocarbon resin, 7 parts by weight of methyl isobutyl ketone, 2 parts by weight of polyamide wax, 0.4 part by weight of acrylate defoaming agent, 0.8 part by weight of high molecular weight alkyl ammonium salt copolymer while stirring, stirring for the first time at 1000 revolutions per minute, then heating to 45 ℃ and adjusting the stirring speed to 300 revolutions per minute, adding 5 parts by weight of titanium dioxide, 0.4 part by weight of iron oxide yellow, 0.5 part by weight of carbon black, 25 parts by weight of aluminum oxide, 25 parts by weight of feldspar powder, 5 parts by weight of polymer modified TiO2/ZIF-8 composite material, stirring for the second time at 1200 revolutions per minute, then heating to 70 ℃ and adjusting the stirring speed to 200 revolutions per minute, stirring for 15 minutes while keeping the temperature, adding 3 parts by weight of n-butyl alcohol, 0.4 part by weight of 3- (2,3 glycidoxy) propyl trimethoxy silane, the mixture was stirred at 800 rpm for 5 minutes to obtain a coating.
Example 3
(1) Respectively preparing a 0.13mol/L zinc nitrate hexahydrate methanol solution and a 0.55 mol/L2-methylimidazole methanol solution, mixing the zinc nitrate hexahydrate methanol solution and the 2-methylimidazole methanol solution in a volume ratio of 1:1, stirring at room temperature under 1500 rpm for 20 hours, then carrying out centrifugal separation, washing the obtained precipitate with methanol, and finally drying to obtain ZIF-8 particles;
(2) dispersing 0.16g of ZIF-8 particles in 50ml of absolute ethyl alcohol, adding 0.2g of hexadecyl trimethyl ammonium bromide, stirring and dispersing, then dropwise adding 25 wt% ammonia water to adjust the pH value of the solution to 11, slowly dropwise adding 0.15ml of tetrabutyl titanate, violently stirring for 24 hours, then centrifuging, washing the obtained precipitate with ethanol and deionized water in sequence, and then drying to obtain a TiO2/ZIF-8 composite material;
(3) mixing and uniformly stirring 5 parts by weight of TiO2/ZIF-8 composite material, 1 part by weight of sodium dodecyl sulfate and 100 parts by weight of deionized water, then adding 75 parts by weight of methyl methacrylate, 13 parts by weight of ethyl acrylate and 15 parts by weight of acrylic acid, stirring and dispersing, heating to 80 ℃, adding 2 parts by weight of potassium persulfate, stirring and reacting for 2 hours, cooling to room temperature after the reaction is finished, filtering the reaction liquid, and drying the obtained solid to obtain the polymer modified TiO2/ZIF-8 composite material;
(4) adding 24 parts by weight of bisphenol A liquid epoxy resin into a stirrer, stirring while adding 1.5 parts by weight of C10 aromatic base liquid hydrocarbon resin, 7 parts by weight of methyl isobutyl ketone, 2 parts by weight of polyamide wax, 0.4 part by weight of acrylate defoaming agent, 0.8 part by weight of high molecular weight alkyl ammonium salt copolymer, stirring for the first time at 1000 revolutions per minute, then heating to 45 ℃ and adjusting the stirring speed to 300 revolutions per minute, adding 5 parts by weight of titanium dioxide, 0.4 part by weight of iron oxide yellow, 0.5 part by weight of carbon black, 25 parts by weight of aluminum oxide, 25 parts by weight of feldspar powder, 5 parts by weight of polymer modified TiO2/ZIF-8 composite material, stirring for the second time at 1100 revolutions per minute, then heating to 70 ℃ and adjusting the stirring speed to 200 revolutions per minute, stirring for 15 minutes while keeping the temperature, adding 3 parts by weight of n-butyl alcohol, 0.4 part by weight of 3- (2,3 glycidoxy) propyl trimethoxy silane, stirring at 800 rpm for 10 minutes to obtain the coating.
Example 4
(1) Respectively preparing a 0.13mol/L zinc nitrate hexahydrate methanol solution and a 0.5 mol/L2-methylimidazole methanol solution, mixing the zinc nitrate hexahydrate methanol solution and the 2-methylimidazole methanol solution in a volume ratio of 1:1, stirring at room temperature under 1500 rpm for 24 hours, then carrying out centrifugal separation, washing the obtained precipitate with methanol, and finally drying to obtain ZIF-8 particles;
(2) dispersing 0.16g of ZIF-8 particles in 50ml of absolute ethanol, adding 0.15g of hexadecyl trimethyl ammonium bromide, stirring and dispersing, then dropwise adding 25 wt% ammonia water to adjust the pH value of the solution to 11, slowly dropwise adding 0.15ml of tetrabutyl titanate, violently stirring for 24 hours, then centrifuging, washing the obtained precipitate with ethanol and deionized water in sequence, and then drying to obtain a TiO2/ZIF-8 composite material;
(3) mixing and uniformly stirring 6 parts by weight of TiO2/ZIF-8 composite material, 1 part by weight of sodium dodecyl sulfate and 100 parts by weight of deionized water, then adding 60 parts by weight of methyl methacrylate, 15 parts by weight of ethyl acrylate and 15 parts by weight of acrylic acid, stirring and dispersing, heating to 80 ℃, adding 3 parts by weight of potassium persulfate, stirring and reacting for 2 hours, cooling to room temperature after the reaction is finished, filtering the reaction liquid, and drying the obtained solid to obtain the polymer modified TiO2/ZIF-8 composite material;
(4) adding 24 parts by weight of bisphenol A liquid epoxy resin into a stirrer, stirring while adding 1.5 parts by weight of C10 aromatic base liquid hydrocarbon resin, 7 parts by weight of methyl isobutyl ketone, 2 parts by weight of polyamide wax, 0.4 part by weight of acrylate defoaming agent, 0.8 part by weight of high molecular weight alkyl ammonium salt copolymer, stirring for the first time at 900 revolutions per minute, then heating to 45 ℃ and adjusting the stirring speed to 250 revolutions per minute, adding 5 parts by weight of titanium dioxide, 0.2-0.4 part by weight of iron oxide yellow, 0.5 part by weight of carbon black, 25 parts by weight of aluminum oxide, 25 parts by weight of feldspar powder, 5 parts by weight of polymer modified TiO2/ZIF-8 composite material, stirring for the second time at 1100 revolutions per minute, heating to 60 ℃ and adjusting the stirring speed to 250 revolutions per minute, stirring for 15 minutes under heat preservation, adding 3 parts by weight of n-butyl alcohol, 0.4 part by weight of 3- (2,3 glycidoxy) propyl trimethoxy silane, the mixture was stirred at 700 rpm for 5 minutes to obtain a coating.
Comparative example
The TiO2/ZIF-8 composite material modified by the polymer is not added into the coating, and other preparation processes are the same as those in the example 4.
It was examined that the ZIF-8 particles prepared in the above examples had an average diameter of 0.7. + -. 0.05. mu.m, and TiO2 deposited on the surface of the ZIF-8 particles had an average particle size of 20. + -.2 nm.
The coatings prepared in the above examples and comparative examples were uniformly applied to the surface of an aluminum substrate using a tinplate of 50mm x 120mm x 0.5mm as a substrate, cured to give a 0.25mm coating, and the coating was subjected to a performance test. The test method and test results are as follows.
1. Impact strength of coating
After the coating is cured, the sample is placed on a concave hole of a pillow block of a film coating impactor, the film coating is upward, and the distance between the impacted point and the edge of the test piece is not less than 15 mm. The weight is fixed at a certain height of the sliding barrel by the control device, the control button is pressed, the weight falls on the punch freely, the weight is lifted, and the test plate is taken out. And observing with a 4-time magnifying glass to judge whether the coating has the phenomena of cracks, wrinkles, peeling and the like. And recording the height of the heavy hammer on the test plate, and carrying out three times of impact tests on the same test plate. The experiment was carried out under constant temperature conditions. The standard is GB/T1732.93.
2. Adhesion force
Reference is made to the national standard GB/T1720.79(89) paint film adhesion determination (circled method).
3. Hardness of coating
Measurement of pencil hardness the coating hardness was measured using a pencil of known hardness, and expressed as the pencil hardness at which the coating was not scratched, which was 13-grade in total from 6H to 6B, 6H being the hardest and 6B being the softest, according to the regulations of the national standard GB/T6739-2006.
4. Chemical resistance test
The ability of the coating to resist chemical agents was tested using a surface drop method according to national standard 17657-1999. 2-3 drops of hydrochloric acid (37%) and sodium hydroxide (10%) are respectively dropped on the horizontally placed coating, 24 hours later, the coating is washed by clean water to remove pollutants, and the coating is placed for 1 hour and then subjected to appearance inspection.
5. VOC content testing
The test was carried out according to the standard GB/T23985-2009.
The test results are shown in tables 1 and 2:
TABLE 1
Figure BDA0003143202960000101
TABLE 2
Figure BDA0003143202960000102
Figure BDA0003143202960000111
The test results show that the TiO2/ZIF-8 composite material modified by the polymer is added into the epoxy coating matrix, so that the corrosion resistance of the coating can be improved, the mechanical property of the coating is improved to a certain extent, and the binding force between the coating and the matrix is good.
Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.

Claims (10)

1. The low-VOC high-corrosion-resistance environment-friendly epoxy coating is characterized in that: the composite material comprises the following components in percentage by mass:
20-25% of epoxy resin, 1.5-2% of petroleum resin, 5-8% of methyl isobutyl ketone, 1-2% of polyamide wax, 0.5-0.8% of wetting dispersant, 0.2-0.4% of acrylate defoamer, 4-6% of titanium dioxide, 0.2-0.4% of iron oxide yellow, 0.3-0.5% of carbon black, 25-35% of alumina, 25-35% of feldspar powder, 2-3% of n-butyl alcohol, 0.3-0.6% of methyl silane and 3-5% of reinforcing filler; the reinforcing filler is TiO modified by polymer2A/ZIF-8 composite material.
2. The low-VOC high-corrosion-resistant environment-friendly epoxy coating according to claim 1, wherein: the epoxy resin is bisphenol A type liquid epoxy resin, and the solid content is 100 percent; the petroleum resin is C9 aromatic base liquid hydrocarbon resin or C10 aromatic base liquid hydrocarbon resin; the wetting dispersant is a high molecular weight alkyl ammonium salt copolymer; the defoaming agent is an acrylate defoaming agent; the methylsilane is 3- (2, 3-glycidoxy) propyl trimethoxy silane.
3. The preparation method of the low-VOC high-corrosion-resistance environment-friendly epoxy coating according to claim 1 or 2, characterized by comprising the following steps:
(1) respectively preparing a methanol solution of zinc nitrate hexahydrate and a methanol solution of 2-methylimidazole, mixing the methanol solutions of zinc nitrate hexahydrate and 2-methylimidazole, stirring at room temperature, then carrying out centrifugal separation, washing the obtained precipitate with methanol, and finally drying to obtain ZIF-8 particles;
(2) dispersing ZIF-8 particles in absolute ethyl alcohol, adding hexadecyl trimethyl ammonium bromide, stirring and dispersing, then dropwise adding ammonia water to adjust the pH value of the solution to 11, slowly dropwise adding tetrabutyl titanate, violently stirring for 24 hours, then centrifuging, washing obtained precipitates by using ethanol and deionized water in sequence, and then drying to obtain TiO2a/ZIF-8 composite material;
(3) adding TiO into the mixture2Mixing and stirring uniformly a/ZIF-8 composite material, sodium dodecyl sulfate and deionized water, then adding methyl methacrylate, ethyl acrylate and acrylic acid, stirring and dispersing, heating to 70-80 ℃, adding potassium persulfate, stirring and reacting for 1-3h, cooling to room temperature after the reaction is finished, filtering the reaction solution, and drying the obtained solid to obtain polymer modified TiO2a/ZIF-8 composite material;
(4) adding epoxy resin into a stirrer, adding petroleum resin, methyl isobutyl ketone, polyamide wax and acrylate defoaming agent while stirring, stirring for the first time, heating for the first time, adjusting the stirring speed, adding titanium dioxide, iron oxide yellow, carbon black, aluminum oxide, feldspar powder and polymer modified TiO2And (3) stirring the/ZIF-8 composite material for the second time, then heating the mixture for the second time, adjusting the stirring speed, adding n-butyl alcohol and methyl silane, stirring the mixture for the third time, and stirring the mixture for 5 to 10 minutes to obtain the coating.
4. The preparation method of the low-VOC high-corrosion-resistance environment-friendly epoxy coating according to claim 3, characterized in that: in the step (1), the concentrations of the methanol solution of zinc nitrate hexahydrate and the methanol solution of 2-methylimidazole are 0.12-0.14mol/L and 0.45-0.55mol/L respectively, and the volume ratio of the two is 1: 1.
5. The preparation method of the low-VOC high-corrosion-resistance environment-friendly epoxy coating according to claim 3, characterized in that: in the step (1), the time of the room-temperature stirring treatment is 20-25h, and the stirring speed is 1000-.
6. The preparation method of the low-VOC high-corrosion-resistance environment-friendly epoxy coating according to claim 3, characterized in that: in the step (2), the dosage ratio of ZIF-8 particles, cetyl trimethyl ammonium bromide and tetrabutyl titanate is 0.15g-0.17 g: 0.1-0.3 g: 0.15 ml.
7. The preparation method of the low-VOC high-corrosion-resistance environment-friendly epoxy coating according to claim 3, characterized in that: in the step (3), the dosage of each component is TiO in parts by weight25-7 parts of/ZIF-8 composite material, 1 part of sodium dodecyl sulfate, 100 parts of deionized water, 50-80 parts of methyl methacrylate, 10-20 parts of ethyl acrylate, 10-20 parts of acrylic acid and 2-3 parts of potassium persulfate.
8. The preparation method of the low-VOC high-corrosion-resistance environment-friendly epoxy coating according to claim 3, characterized in that: the rotating speeds of the first stirring, the second stirring and the third stirring are respectively 800-1000 revolutions per minute, 1000-1200 revolutions per minute and 600-800 revolutions per minute.
9. The preparation method of the low-VOC high-corrosion-resistance environment-friendly epoxy coating according to claim 3, characterized in that: and when the temperature is increased for the first time and the stirring speed is adjusted, the temperature is increased to 45 ℃, and the stirring speed is adjusted to 200-300 revolutions per minute.
10. The preparation method of the low-VOC high-corrosion-resistance environment-friendly epoxy coating according to claim 3, characterized in that: and when the temperature is raised for the second time and the stirring speed is adjusted, raising the temperature to 60-70 ℃, adjusting the stirring speed to 200-300 r/min, and then continuing to stir for 10-15 min under heat preservation.
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