CN114773956B - Organic/inorganic hybrid modified graphene waterborne epoxy cloud iron intermediate paint and preparation method and application thereof - Google Patents
Organic/inorganic hybrid modified graphene waterborne epoxy cloud iron intermediate paint and preparation method 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
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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
- C09D7/45—Anti-settling agents
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- 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
- C08K2003/2265—Oxides; Hydroxides of metals of iron
- C08K2003/2272—Ferric oxide (Fe2O3)
Abstract
An organic/inorganic hybridization modified graphene waterborne epoxy cloud iron intermediate paint and a preparation method and application thereof belong to the technical field of steel structure corrosion prevention. The graphene water-based epoxy cloud iron intermediate paint comprises a component A and a component B; the component A comprises the following components: 60-80% of aqueous epoxy emulsion, 4% of ethylene glycol monobutyl ether and the balance of organic/inorganic hybrid graphene silica sol; the component B comprises: epoxy curing agent, antirust pigment and filler, gray mica ferric oxide, dispersing agent, defoamer, anti-settling agent, thickener, leveling agent, ethylene glycol butyl ether acetate, ethylene glycol monobutyl ether and the balance deionized water. According to the invention, the organic/inorganic hybrid graphene silica sol is applied to the modification of the epoxy resin-based coating, so that the anti-sedimentation performance of the water-based coating is improved; the graphene silica sol has good dispersibility in the water-washing paint, the uniformity of film formation is improved, and the adhesion and corrosion resistance of the epoxy cloud iron intermediate paint are greatly improved due to the large lamellar structure of the graphene.
Description
Technical Field
The invention belongs to the technical field of steel structure corrosion prevention, and particularly relates to an organic/inorganic hybridization modified graphene water-based epoxy cloud iron intermediate paint, and a preparation method and application thereof.
Background
The solvent-type double-component epoxy coating has good corrosion resistance, however, the traditional epoxy resin coating mainly contains solvent, and the addition amount of the organic solvent is more and even reaches 80 percent (volume fraction). Volatile Organic Solvents (VOCs) do not participate in film formation, and can escape from a paint film after the coating is dried, so that the volatile organic solvents not only pollute the atmosphere, but also seriously damage human bodies. As environmental requirements become more stringent, aqueous epoxy coatings have been a necessary trend in development to replace solvent-based epoxy coatings. Because of the difference of film forming mechanisms, compared with solvent type paint, the water-based anticorrosive paint is difficult to form a high-quality coating with uniform composition and high integrity of structure, and has poor film forming property and abrasion resistance; residual water-based groups in the water-based anticorrosive paint have poor shielding capability on corrosive media such as water, oxygen and the like; because of the large surface tension of water, the water-based coating is difficult to achieve high infiltration and dispersion of pigment and filler, so that the improvement of the corrosion resistance of the water-based coating has become an important point in the development of environment-friendly coatings.
The current water paint system mainly comprises a primer, a middle paint and a top coat. The primer mainly plays a role in electrochemical protection, and when the coating is damaged, the primer contacts with electrolyte to form a primary cell, so that the rapid corrosion of the damaged part can be effectively prevented from causing the failure of the coating. The main function of the intermediate paint is a barrier function, and the main function of the finish paint is to increase the weather resistance of the coating. The intermediate paint is typically an epoxy cloud iron intermediate paint. The mica iron oxide is a two-dimensional lamellar structure, and can effectively increase the penetration distance of water vapor and oxygen ions in the coating. Therefore, the thicker the intermediate paint is, the better the anti-corrosion performance is, but the thicker the film thickness is, the cost is increased and the resource is wasted, so that the barrier permeability of the intermediate paint is required to be improved, and the consumption of the intermediate paint is reduced.
Graphene is used as a two-dimensional nano material, has extremely large specific surface area, conductivity and the like, and the lamellar structure of the graphene is overlapped layer by layer and staggered up and down, so that a compact physical barrier layer of tens to hundreds of layers can be formed in the coating, and the permeation resistance of the coating is greatly improved. Meanwhile, the electrostatic adsorption effect of the graphene can be firmly adsorbed with pigment and filler ions to improve the anti-sedimentation performance of the water-based paint, so that a new improvement way is brought for improving the compactness, barrier property, mechanical property and corrosion resistance of the water-based paint.
Although some patents and documents in recent years disclose graphene modified waterborne epoxy resins and preparation processes thereof, the current preparation processes are complex and a large amount of acid, alkali or toxic reagents are adopted in order to improve the dispersibility of graphene. The current common method is to prepare the water-based anti-corrosion coating by adding graphene dispersion liquid, but graphene is easy to agglomerate and is difficult to uniformly disperse in the water-based coating.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to design and provide an organic/inorganic hybridization modified graphene waterborne epoxy cloud iron intermediate paint, and a preparation method and application thereof. According to the preparation method, graphene and silica sol are combined to prepare graphene silica sol, and the graphene silica sol and the aqueous epoxy resin are uniformly mixed, so that the problem that graphene is difficult to disperse in the aqueous epoxy resin is solved. According to the organic/inorganic hybrid modified graphene waterborne epoxy cloud iron intermediate paint disclosed by the invention, the organic/inorganic hybrid graphene silica sol is applied to the modification of the epoxy resin-based paint, and the electrostatic adsorption effect of graphene can be firmly adsorbed with pigment and filler ions to improve the anti-sedimentation performance of the waterborne paint; on the other hand, the graphene silica sol has good dispersibility in the water-based paint, improves the uniformity of film formation, greatly improves the adhesive force and corrosion resistance of the epoxy cloud iron intermediate paint due to the large lamellar structure of graphene, and has good application prospect.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
the organic/inorganic hybridization modified graphene waterborne epoxy cloud iron intermediate paint is characterized by comprising a component A and a component B;
the component A comprises the following raw materials in percentage by mass: 60-80% of aqueous epoxy emulsion, 4% of ethylene glycol monobutyl ether and the balance of organic/inorganic hybrid graphene silica sol;
the component B comprises the following raw materials in percentage by mass: 25-27% of epoxy curing agent, 30-32% of antirust pigment and filler, 15-20% of gray mica ferric oxide, 1-2% of dispersing agent, 0.5-1.0% of defoaming agent, 0.8-1.2% of anti-settling agent, 3-3.5% of thickening agent, 0.4% of flatting agent, 2% of ethylene glycol butyl ether acetate, 2% of ethylene glycol monobutyl ether and the balance of deionized water.
The organic/inorganic hybrid modified graphene water-based epoxy iron cloud intermediate paint is characterized in that the mass ratio of the component A to the component B is 1:0.4-0.5, and the water-based epoxy emulsion comprises Beckopoox EP 384w/53WAMP.
The organic/inorganic hybrid modified graphene waterborne epoxy iron cloud intermediate paint is characterized in that the organic/inorganic hybrid graphene silica sol comprises an X component and a Y component;
the X component comprises: isopropyl alcohol, ethyl orthosilicate, a silane coupling agent, graphene oxide, the isopropyl alcohol: tetraethoxysilane TEOS: silane coupling agent: the adding proportion of the graphene oxide is 2-10 mL:2-20 mL:3-30 mL:0.1-1 mg, and the preferable adding proportion is 8mL:10 mL:0.5mg;
the Y component comprises: deionized water and isopropanol, wherein the volume ratio of the deionized water to the isopropanol is 1:7.
The organic/inorganic hybrid modified graphene water-based epoxy cloud iron intermediate paint is characterized in that the epoxy curing agent comprises Beckopoox EH 616w/67WA;
the antirust pigment and filler comprises one or a mixture of more of titanium dioxide, talcum powder and precipitated barium sulfate;
the mesh number of the gray mica iron oxide is 300-500 meshes;
the dispersant comprises Zetasperse 3800;
the defoamer comprises one or more of Tego aierx901w and Tego foam 845;
the anti-settling agent comprises one or a mixture of a plurality of fumed silica and organic bentonite;
the thickener is mixed liquid with the volume ratio of 3060 to water of 1:1;
the leveling agent comprises a mixture of one or more of AF3251 and AF 3588.
The organic/inorganic hybrid modified graphene water-based epoxy cloud iron intermediate paint is characterized in that the film forming thickness of the graphene water-based epoxy cloud iron intermediate paint is 100-160 mu m.
The preparation method of the organic/inorganic hybrid modified graphene water-based epoxy cloud iron intermediate paint is characterized by comprising the following steps of: preparing a component A and a component B, and uniformly mixing the component A and the component B according to the mass ratio of 1:0.4-0.5 to obtain the organic/inorganic hybrid modified graphene waterborne epoxy cloud iron intermediate paint;
the component A contains organic/inorganic hybrid graphene silica sol.
The preparation method of the organic/inorganic hybrid modified graphene water-based epoxy iron cloud intermediate paint is characterized by comprising the following steps of:
(1) Weighing the aqueous epoxy emulsion, stirring at the rotating speed of 400-600 rpm, adding ethylene glycol monobutyl ether, and continuously stirring for 15-25 min;
(1) Adding organic/inorganic hybrid graphene silica sol, stirring for 15-25 min at the rotation speed of 400-600 rpm, and filtering to obtain a component A;
the component A comprises the following raw materials in percentage by mass: 60-80% of aqueous epoxy emulsion, 4% of ethylene glycol monobutyl ether and the balance of organic/inorganic hybrid graphene silica sol.
The preparation method of the organic/inorganic hybrid modified graphene water-based epoxy cloud iron intermediate paint is characterized by comprising the following steps of:
(a) Weighing graphene oxide, adding the graphene oxide into a silane coupling agent, performing ultrasonic treatment, and dispersing at a rotating speed of 5000-10000 rpm for 20-120 minutes to obtain silane modified graphene oxide dispersion liquid;
the specific surface area of the graphene oxide is 100-200 m 2 Per gram, the proportion of-OH is less than 5%, and the grain diameter is 0.5-5 mu m;
(b) Weighing isopropyl alcohol and Tetraethoxysilane (TEOS), adding the isopropyl alcohol and the Tetraethoxysilane (TEOS) into the silane modified graphene oxide dispersion liquid obtained in the step (a), stirring for 3-5 min, uniformly mixing, and regulating the pH to 9-10 to obtain an X component;
(c) Weighing deionized water and isopropanol, uniformly mixing to obtain a Y component, and adding the Y component into the X component at a dropping rate of 0.3-0.7 mL/h to obtain a mixed solution;
(d) And (c) placing the mixed solution obtained in the step (c) in a constant-temperature water bath kettle with magnetic stirring at a temperature of 25-35 ℃ for low-speed stirring for 2 hours to fully hydrolyze, heating to 65-75 ℃ and then carrying out polycondensation reaction on Tetraethoxysilane (TEOS) and silane modified graphene dispersion liquid for 5-7 hours to generate the organic/inorganic hybrid graphene silica sol.
The preparation method of the organic/inorganic hybrid modified graphene water-based epoxy cloud iron intermediate paint is characterized by comprising the following steps of:
weighing an epoxy curing agent, sequentially adding deionized water, antirust pigment and filler, mica iron oxide, a thickening agent, a defoaming agent, a leveling agent and an anti-settling agent at a rotating speed of 400-600 rpm, and continuously stirring for 15-25 min;
(ii) adding ethylene glycol monobutyl ether and ethylene glycol butyl ether acetate, stirring uniformly at a rotation speed of 400-600 rpm, and filtering to obtain a component B.
Any one of the organic/inorganic hybrid modified graphene water-based epoxy cloud iron intermediate paint is matched with a primer and a top coat, and is applied to environment-friendly paint.
Compared with the prior art, the invention has the following beneficial effects:
1. the invention innovatively prepares the graphene into the graphene silica sol, realizes good dispersibility of the graphene in the epoxy resin, greatly improves the shielding performance of the coating, realizes the long-acting corrosion resistance of the coating, has the adhesive force of more than or equal to 5MPa, has the neutral salt fog resistance of more than 1000 hours and is 5%H-resistant 2 SO 4 The solution was soaked for 168 hours. The electrostatic adsorption effect of the graphene can be firmly adsorbed with pigment and filler ions, so that the anti-sedimentation performance of the water-based paint is improved.
2. According to the invention, after the graphene is subjected to silane modification, the graphene is polymerized with TEOS to prepare graphene silica sol, and the polymer chain of the graphene silica sol has rich anchoring groups, so that the graphene silica sol can be firmly adsorbed by electrostatic action with pigment and filler such as mica iron oxide, titanium dioxide and the like, and the anti-sedimentation performance of the water-based paint is improved.
Drawings
FIG. 1 is a flow chart of the process of the present invention.
Detailed Description
The invention will be further described with reference to examples and figures.
Example 1: preparation of organic-inorganic hybrid modified graphene waterborne epoxy cloud iron intermediate paint
The first step: preparation of organic-inorganic hybrid graphene silica sol
The X component comprises: isopropyl alcohol (8 mL) +tetraethylorthosilicate TEOS (10 mL) +silane coupling agent KH-560 (10 mL) +graphene oxide (0.5 mg);
the Y component comprises: deionized water (1 mL) +isopropyl alcohol (7 mL).
(1) The specific surface area is 100-200 m 2 Adding 0.5mg of graphene oxide with the particle size of 0.5-5 mu m into 10ml of silane coupling agent KH560, and circularly performing ultrasonic dispersion for 30 minutes to prepare silane modified graphene dispersion;
(2) Adding 8mL of isopropanol and 10mL of LTEOS into the silane modified graphene dispersion liquid, stirring for 3-5 min at room temperature, uniformly mixing, and adding NaOH to adjust the pH value of the solution to 9-10 to obtain an X component;
(3) Evenly mixing 1mL of deionized water with 7mL of isopropanol to prepare a Y component; subsequently adding the Y component into the X component at a dropping rate of 0.5 mL/h;
(4) Placing the mixed solution in a water bath kettle with magnetic stirring, and stirring at low speed for 2h, wherein the water bath temperature is 30 ℃, so that TEOS and KH-560 are fully hydrolyzed; and then heating the solution to 70 ℃ for heating reaction for 6 hours, and carrying out polycondensation reaction on TEOS and the silane modified graphene dispersion liquid during heating to generate the organic-inorganic hybrid graphene silica sol.
And a second step of: preparation of A-component
The following raw materials are prepared according to parts by weight: 80% of water-based epoxy resin, 4% of ethylene glycol monobutyl ether and 16% of organic-inorganic hybrid graphene silica sol, and adding the prepared raw materials into a reaction kettle to prepare the epoxy resin composite material according to the following steps:
(1) Adding water-based epoxy resin;
(2) Sequentially adding the organic-inorganic hybrid graphene silica sol and ethylene glycol monobutyl ether in a stirring state of 400 revolutions per minute, and continuously stirring for 15 minutes;
(3) And (5) filtering.
And a third step of: preparation of B-component
The following raw materials are prepared according to parts by weight: 26% of epoxy curing agent, 30% of antirust pigment and filler, 17.5% of gray mica iron oxide, 2% of dispersing agent, 1.0% of defoaming agent, 1.2% of anti-settling agent, 3% of thickening agent, 0.4% of leveling agent, 2% of ethylene glycol butyl ether acetate, 2% of ethylene glycol monobutyl ether and 14.9% of deionized water. The prepared raw materials are added into a reaction kettle for preparation according to the following steps:
(1) Adding a water-based epoxy curing agent;
(2) Deionized water, a dispersing agent, a defoaming agent, an anti-settling agent, a thickening agent and a leveling agent are sequentially added in a stirring state of 400 revolutions per minute, the rotating speed is increased to 1500 revolutions per minute after uniform stirring, and the dispersing is carried out for 20 minutes;
(3) Reducing the rotating speed to 300 rpm, adding antirust pigment filler and 325-mesh gray mica iron oxide, and increasing the rotating speed to 1000 rpm for 20 minutes;
(4) Reducing the rotating speed to 500 r/min, adding ethylene glycol butyl ether acetate and ethylene glycol monobutyl ether, and stirring for 10 min;
(5) And (5) filtering.
Fourth step: mixing and spraying
Mixing the component A and the component B according to the mass ratio of 1:0.46, stirring for 15 minutes, and spraying according to a conventional method. The preparation flow chart of the method is shown in figure 1.
Example 2: preparation of organic-inorganic hybrid modified graphene waterborne epoxy cloud iron intermediate paint
The first step: preparation of organic-inorganic hybrid graphene silica sol
The X component comprises: isopropyl alcohol (8 mL) +tetraethylorthosilicate TEOS (10 mL) +silane coupling agent KH-560 (10 mL) +graphene oxide (0.5 mg);
the Y component comprises: deionized water (1 mL) +isopropyl alcohol (7 mL)
(1) The specific surface area is 100-200 m 2 Adding 0.5mg of graphene oxide with the particle size of 0.5-5 mu m into 10ml of silane coupling agent KH560, and circularly performing ultrasonic dispersion for 30 minutes to prepare silane modified graphene dispersion;
(2) Adding 8mL of isopropanol and 10mL of TEOS into the silane modified graphene dispersion liquid, stirring for 3-5 min at room temperature, uniformly mixing, and adding NaOH to adjust the pH value of the solution to 9-10 to obtain an X component;
(3) Evenly mixing 1mL of deionized water with 7mL of isopropanol to prepare a Y component; subsequently adding the Y component into the X component at a dropping rate of 0.5 mL/h;
(4) Placing the mixed solution in a water bath kettle with magnetic stirring, and stirring at low speed for 2h, wherein the water bath temperature is 30 ℃, so that TEOS and KH-560 are fully hydrolyzed;
and then heating the solution to 70 ℃ for heating reaction for 6 hours, and carrying out polycondensation reaction on TEOS and the silane modified graphene dispersion liquid during heating to generate the organic-inorganic hybrid graphene silica sol.
And a second step of: preparation of A-component
The following raw materials are prepared according to parts by weight: 60% of water-based epoxy resin, 4% of ethylene glycol monobutyl ether and 36% of organic-inorganic hybrid graphene silica sol, and adding the prepared raw materials into a reaction kettle to prepare the epoxy resin composite material according to the following steps:
(1) Adding water-based epoxy resin;
(2) Sequentially adding the organic-inorganic hybrid graphene silica sol and ethylene glycol monobutyl ether in a stirring state of 400 revolutions per minute, and continuously stirring for 15 minutes;
(3) And (5) filtering.
And a third step of: preparation of B-component
The following raw materials are prepared according to parts by weight: 26% of epoxy curing agent, 30% of antirust pigment and filler, 17.5% of gray mica iron oxide, 2% of dispersing agent, 1.0% of defoaming agent, 1.2% of anti-settling agent, 3% of thickening agent, 0.4% of leveling agent, 2% of ethylene glycol butyl ether acetate, 2% of ethylene glycol monobutyl ether and 14.9% of deionized water. The prepared raw materials are added into a reaction kettle for preparation according to the following steps:
(1) Adding a water-based epoxy curing agent;
(2) Deionized water, a dispersing agent, a defoaming agent, an anti-settling agent, a thickening agent and a leveling agent are sequentially added in a stirring state of 400 revolutions per minute, the rotating speed is increased to 1500 revolutions per minute after uniform stirring, and the dispersing is carried out for 20 minutes;
(3) Reducing the rotating speed to 300 rpm, adding antirust pigment filler and 325-mesh gray mica iron oxide, and increasing the rotating speed to 1000 rpm for 20 minutes;
(4) Reducing the rotating speed to 500 r/min, adding ethylene glycol butyl ether acetate and ethylene glycol monobutyl ether, and stirring for 10 min;
(5) And (5) filtering.
Fourth step: mixing and spraying
Mixing the component A and the component B according to the mass ratio of 1:0.4, stirring for 15 minutes, and spraying according to a conventional method.
Example 3: preparation of organic-inorganic hybrid modified graphene waterborne epoxy cloud iron intermediate paint
The first step: preparation of organic-inorganic hybrid graphene silica sol
The X component comprises: isopropyl alcohol (8 mL) +tetraethylorthosilicate TEOS (10 mL) +silane coupling agent KH-560 (10 mL) +graphene oxide (0.5 mg);
the Y component comprises: deionized water (1 mL) +isopropyl alcohol (7 mL)
(1) The specific surface area is 100-200 m 2 Adding 0.5mg of graphene oxide with the particle size of 0.5-5 mu m into 10ml of silane coupling agent KH560, and circularly performing ultrasonic dispersion for 30 minutes to prepare silane modified graphene dispersion;
(2) Adding 8mL of isopropanol and 10mL of LTEOS into the silane modified graphene dispersion liquid, stirring for 3-5 min at room temperature, uniformly mixing, and adding NaOH to adjust the pH value of the solution to 9-10 to obtain an X component;
(3) Evenly mixing 1mL of deionized water with 7mL of isopropanol to prepare a Y component; subsequently adding the Y component into the X component at a dropping rate of 0.5 mL/h;
(4) Placing the mixed solution in a water bath kettle with magnetic stirring, and stirring at low speed for 2h, wherein the water bath temperature is 30 ℃, so that TEOS and KH-560 are fully hydrolyzed;
and then heating the solution to 70 ℃ for heating reaction for 6 hours, and carrying out polycondensation reaction on TEOS and the silane modified graphene dispersion liquid during heating to generate the organic-inorganic hybrid graphene silica sol.
And a second step of: preparation of A-component
The following raw materials are prepared according to parts by weight: 80% of water-based epoxy resin, 4% of ethylene glycol monobutyl ether and 16% of organic-inorganic hybrid graphene silica sol, and adding the prepared raw materials into a reaction kettle to prepare the epoxy resin composite material according to the following steps:
(1) Adding water-based epoxy resin;
(2) Sequentially adding the organic-inorganic hybrid graphene silica sol and ethylene glycol monobutyl ether in a stirring state of 400 revolutions per minute, and continuously stirring for 15 minutes;
(3) And (5) filtering.
And a third step of: preparation of B-component
The following raw materials are prepared according to parts by weight: 26% of epoxy curing agent, 30% of antirust pigment and filler, 17.5% of gray mica iron oxide, 2% of dispersing agent, 1.0% of defoaming agent, 1.2% of anti-settling agent, 3% of thickening agent, 0.4% of leveling agent, 2% of ethylene glycol butyl ether acetate, 2% of ethylene glycol monobutyl ether and 14.9% of deionized water. The prepared raw materials are added into a reaction kettle for preparation according to the following steps:
(1) Adding a water-based epoxy curing agent;
(2) Deionized water, a dispersing agent, a defoaming agent, an anti-settling agent, a thickening agent and a leveling agent are sequentially added in a stirring state of 400 revolutions per minute, the rotating speed is increased to 1500 revolutions per minute after uniform stirring, and the dispersing is carried out for 20 minutes;
(3) Reducing the rotating speed to 300 rpm, adding antirust pigment filler and 325-mesh gray mica iron oxide, and increasing the rotating speed to 1000 rpm for 20 minutes;
(4) Reducing the rotating speed to 500 r/min, adding ethylene glycol butyl ether acetate and ethylene glycol monobutyl ether, and stirring for 10 min;
(5) And (5) filtering.
Fourth step: mixing and spraying
Mixing the component A and the component B according to the mass ratio of 1:0.5, stirring for 15 minutes, and spraying according to a conventional method.
Comparative example 1:
unlike example 1, purified water was used instead of the inorganic hybrid graphene silica sol.
Comparative example 2:
unlike example 1, the inorganic hybrid graphene silica sol was replaced with purified water, and the a component and the B component were mixed in a mass ratio of 1:1, stirred for 15 minutes, and sprayed according to a conventional method.
The manufacturer and technical parameters of the main raw materials in the examples of the present invention are shown in Table 1.
TABLE 1 Main raw Material factories and technical parameters in the examples of the invention
And (3) performance detection:
the primers prepared in examples 1-3 and comparative examples 1-2 were sprayed on white iron plates at a thickness of 75 to 100. Mu.m, dried and left for 14 days, and then subjected to coating adhesion and 5%H resistance 2 SO 4 Solution soaking and neutral salt spray resistance detection, wherein the test conditions of the neutral salt spray performance are as follows:
concentration of the settled salt solution: (50+ -10) g/LNaCl
Test chamber temperature: (35+2) DEG C
Salt spray lifting rate: (1.0-2.0) ml/(80 cm) 2 h)
Sedimentation salt solution pH (25 ℃): 6.5 to 7.2
The performance test results are shown in table 2 below:
TABLE 2 Performance test results
Claims (9)
1. The organic/inorganic hybridization modified graphene waterborne epoxy cloud iron intermediate paint is characterized by comprising a component A and a component B;
the component A comprises the following raw materials in percentage by mass: 60-80% of aqueous epoxy emulsion, 4% of ethylene glycol monobutyl ether and the balance of organic/inorganic hybrid graphene silica sol;
the component B comprises the following raw materials in percentage by mass: 25-27% of epoxy curing agent, 30-32% of rust-proof pigment and filler, 15-20% of gray mica ferric oxide, 1-2% of dispersing agent, 0.5-1.0% of defoaming agent, 0.8-1.2% of anti-settling agent, 3-3.5% of thickening agent, 0.4% of flatting agent, 2% of ethylene glycol butyl ether acetate, 2% of ethylene glycol monobutyl ether and the balance of deionized water;
the organic/inorganic hybrid graphene silica sol comprises an X component and a Y component;
the X component comprises: isopropyl alcohol, ethyl orthosilicate, a silane coupling agent, graphene oxide, the isopropyl alcohol: ethyl orthosilicate: silane coupling agent: the adding proportion of the graphene oxide is 2-10 mL, 2-20 mL, 3-30 mL and 0.1-1 mg;
the Y component comprises: deionized water and isopropanol, wherein the volume ratio of the deionized water to the isopropanol is 1-1.5:7;
the preparation method of the organic/inorganic hybrid graphene silica sol comprises the following steps:
(a) Weighing graphene oxide, adding the graphene oxide into a silane coupling agent, performing ultrasonic treatment, and dispersing at a rotating speed of 5000-10000 rpm for 20-120 minutes to obtain silane modified graphene oxide dispersion liquid;
the specific surface area of the graphene oxide is 100-200 m 2 Per gram, the proportion of-OH is less than 5%, and the grain diameter is 0.5-5 mu m;
(b) Weighing isopropanol and ethyl orthosilicate, adding the isopropanol and the ethyl orthosilicate into the silane modified graphene oxide dispersion liquid obtained in the step (a), stirring for 3-5 min, uniformly mixing, and regulating the pH to 9-10 to obtain an X component;
(c) Weighing deionized water and isopropanol, uniformly mixing to obtain a Y component, and adding the Y component into the X component at a dropping rate of 0.3-0.7 mL/h to obtain a mixed solution;
(d) And (c) placing the mixed solution obtained in the step (c) in a constant-temperature water bath kettle with magnetic stirring at a temperature of 25-35 ℃ for low-speed stirring for 2 hours to fully hydrolyze, heating to 65-75 ℃ and then carrying out polycondensation reaction for 5-7 hours to generate the organic/inorganic hybrid graphene silica sol.
2. An organic/inorganic hybrid modified graphene aqueous epoxy cloud iron intermediate paint as claimed in claim 1, wherein said isopropyl alcohol: ethyl orthosilicate: silane coupling agent: the addition ratio of graphene oxide was 8mL:10 mL:0.5mg.
3. The organic/inorganic hybrid modified graphene aqueous epoxy cloud iron intermediate paint according to claim 1, wherein the mass ratio of the component A to the component B is 1:0.4-0.5, and the aqueous epoxy emulsion comprises Beckopoox EP 384w/53WAMP.
4. An organic/inorganic hybrid modified graphene aqueous epoxy cloud iron intermediate paint as claimed in claim 1, wherein said epoxy curing agent comprises beckoox EH 616w/67WA;
the antirust pigment and filler comprises one or a mixture of more of titanium dioxide, talcum powder and precipitated barium sulfate;
the mesh number of the gray mica iron oxide is 300-500 meshes;
the dispersant comprises Zetasperse 3800;
the defoamer comprises one or more of Tego aierx901w and Tego foam 845;
the anti-settling agent comprises one or a mixture of a plurality of fumed silica and organic bentonite;
the thickener is mixed liquid with the volume ratio of 3060 to water of 1:1;
the leveling agent comprises a mixture of one or more of AF3251 and AF 3588.
5. The organic/inorganic hybrid modified graphene aqueous epoxy cloud iron intermediate paint disclosed in claim 1 is characterized in that the film thickness of the graphene aqueous epoxy cloud iron intermediate paint is 100-160 μm.
6. The method for preparing the organic/inorganic hybrid modified graphene aqueous epoxy cloud iron intermediate paint according to any one of claims 1 to 5, which is characterized by comprising the following steps: preparing a component A and a component B, and uniformly mixing the component A and the component B according to the mass ratio of 1:0.4-0.5 to obtain the organic/inorganic hybrid modified graphene waterborne epoxy cloud iron intermediate paint;
the component A contains organic/inorganic hybrid graphene silica sol.
7. The preparation method of the organic/inorganic hybrid modified graphene water-based epoxy cloud iron intermediate paint as claimed in claim 6, wherein the preparation method of the A component comprises the following steps:
weighing the aqueous epoxy emulsion, stirring at a rotating speed of 400-600 rpm, adding ethylene glycol monobutyl ether, and continuously stirring for 15-25 min;
adding the organic/inorganic hybrid graphene silica sol, stirring for 15-25 min at the rotating speed of 400-600 r/min, and filtering to obtain a component A;
the component A comprises the following raw materials in percentage by mass: 60-80% of aqueous epoxy emulsion, 4% of ethylene glycol monobutyl ether and the balance of organic/inorganic hybrid graphene silica sol.
8. The preparation method of the organic/inorganic hybrid modified graphene aqueous epoxy cloud iron intermediate paint as claimed in claim 6, wherein the preparation method of the component B comprises the following steps:
weighing an epoxy curing agent, sequentially adding deionized water, antirust pigment and filler, mica iron oxide, a thickening agent, a defoaming agent, a leveling agent and an anti-settling agent at a rotating speed of 400-600 revolutions per minute, and continuously stirring for 15-25 minutes;
(ii) adding ethylene glycol monobutyl ether and ethylene glycol butyl ether acetate, stirring uniformly at a rotation speed of 400-600 rpm, and filtering to obtain a component B.
9. An organic/inorganic hybrid modified graphene waterborne epoxy cloud iron intermediate paint as claimed in any one of claims 1-5, matched with a primer and a top coat, for use as an environment-friendly coating.
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