CN114773956A - A kind of organic/inorganic hybrid modified graphene water-based epoxy micaceous iron intermediate paint and preparation method and application thereof - Google Patents

Abstract

An organic/inorganic hybrid modified graphene water-based epoxy micaceous iron oxide intermediate paint and a preparation method and application thereof, belonging to the technical field of steel structure corrosion prevention. The graphene water-based epoxy micaceous iron oxide intermediate paint comprises a component A and a component B; the component A comprises: 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 filler, gray mica iron oxide, dispersant, defoaming agent, anti-settling agent, thickening agent, leveling agent, ethylene glycol butyl ether acetate, ethylene glycol monobutyl ether and the balance of deionized water. According to the invention, the organic/inorganic hybrid graphene silica sol is applied to the modification of the epoxy resin-based paint, so that the anti-settling property of the water-based paint is improved; the graphene silica sol has good dispersibility in the water-washing paint, the uniformity of film formation is improved, and the large-sheet structure of the graphene greatly improves the adhesive force and corrosion resistance of the epoxy micaceous iron intermediate paint.

Description

A kind of organic/inorganic hybrid modified graphene water-based epoxy micaceous iron intermediate paint and preparation method and application thereof

technical field

The invention belongs to the technical field of anti-corrosion of steel structures, and in particular relates to an organic/inorganic hybrid modified graphene water-based epoxy micaceous iron intermediate paint and a preparation method and application thereof.

Background technique

Solvent-based two-component epoxy coatings have good corrosion resistance, but traditional epoxy resin coatings are mostly solvent-based, and the amount of organic solvent added is large, even reaching 80% (volume fraction). Volatile organic solvents (VOCs) do not participate in film formation, and will escape from the paint film after the coating dries, which not only pollutes the atmosphere but also causes serious harm to the human body. Due to the increasingly stringent environmental protection requirements, it is an inevitable trend of development for water-based epoxy coatings to replace solvent-based epoxy coatings. Due to the different film-forming mechanism, compared with solvent-based coatings, water-based anti-corrosion coatings are difficult to form high-quality coatings with highly uniform composition and highly complete structure, and their film-forming properties and corrosion resistance are not good; residual in water-based anti-corrosion coatings The water-based group has poor shielding ability against corrosive media such as water and oxygen; due to the large surface tension of water, it is difficult for water-based coatings to achieve high infiltration and dispersion of pigments and fillers. Therefore, improving the corrosion resistance of water-based coatings has become the development of environmentally friendly coatings. focus in.

The current water-based paint system mainly consists of primer, intermediate paint and topcoat. The primer mainly plays the role of electrochemical protection. When the coating is damaged, it contacts with the electrolyte to form a galvanic cell, which can effectively prevent the damaged part from rapidly corroding and causing the coating to fail. The main function of the intermediate paint is to block, and the main function of the top coat is to increase the weather resistance of the coating. The intermediate paint is generally epoxy micaceous iron intermediate paint. Mica iron oxide is a two-dimensional sheet structure, which can effectively increase the penetration distance of water vapor and oxygen ions in the coating. Therefore, the thicker the thickness of the intermediate paint, the better its anti-corrosion performance. However, an excessively thick film thickness will increase the cost and waste resources. Therefore, it is urgent to improve the barrier and penetration performance of the intermediate paint and reduce its dosage.

As a two-dimensional nanomaterial, graphene has a large specific surface area, electrical conductivity, etc. The lamellar structure of graphene is superimposed layer by layer and staggered up and down, which can form dozens to hundreds of dense physical barriers in the coating. layer, greatly improving the penetration resistance of the coating. At the same time, graphene's own electrostatic adsorption can firmly improve the anti-settling performance of water-based coatings with ionic adsorption of pigments and fillers, which brings new ways to improve the compactness, barrier properties, mechanical properties and anti-corrosion properties of water-based coatings.

Although some patents and documents in recent years have disclosed graphene-modified water-based epoxy resin and its preparation process, in order to improve the dispersibility of graphene, the current preparation process is relatively complicated, and a large number of acids, alkalis or toxic reagents are used. At present, the commonly used method is to prepare water-based anti-corrosion coatings by adding graphene dispersion, but graphene is easy to agglomerate, and it is difficult to achieve uniform dispersion in water-based coatings.

SUMMARY OF THE INVENTION

In view of the defects existing in the above-mentioned prior art, the purpose of the present invention is to design and provide an organic/inorganic hybrid modified graphene water-based epoxy micaceous iron intermediate paint and its preparation method and application. In the invention, graphene and silica sol are combined to prepare graphene silica sol, and the silica sol is uniformly mixed with the water-based epoxy resin, thereby solving the problem that graphene is difficult to disperse in the water-based epoxy resin. The organic/inorganic hybrid modified graphene water-based epoxy micaceous iron intermediate paint of the present invention applies organic/inorganic hybrid graphene silica sol to the modification of epoxy resin-based paint, and the electrostatic adsorption of graphene itself It can be strongly adsorbed with pigments and fillers to improve the anti-settling performance of water-based coatings; on the other hand, graphene silica sol has good dispersibility in water-based coatings, improving the uniformity of film formation, and the large lamellar structure of graphene greatly improves epoxy resin. The adhesion and corrosion resistance of the micaceous iron intermediate paint have good application prospects.

In order to achieve the above object, the present invention adopts the following technical solutions:

An organic/inorganic hybrid modified graphene water-based epoxy micaceous iron intermediate paint, characterized in that the graphene water-based epoxy micaceous iron intermediate paint comprises A component and B component;

The A component includes the following raw materials by mass percentage: 60-80% of water-based epoxy emulsion, 4% of ethylene glycol monobutyl ether, and the balance of organic/inorganic hybrid graphene silica sol;

The B component includes the following raw materials by mass percentage: 25-27% of epoxy curing agent, 30-32% of anti-rust pigment and filler, 15-20% of gray mica iron oxide, 1-2% of dispersant, and 0.5-2% of defoamer. 1.0%, anti-settling agent 0.8-1.2%, thickener 3-3.5%, leveling agent 0.4%, ethylene glycol butyl ether acetate 2%, ethylene glycol monobutyl ether 2%, the balance is deionized water.

The organic/inorganic hybrid modified graphene water-based epoxy micaceous iron intermediate paint is characterized in that the mass ratio of the A component to the B component is 1:0.4～0.5, and the water-based epoxy The emulsion includes Beckopox EP 384w/53WAMP.

Described a kind of organic/inorganic hybrid modified graphene water-based epoxy micaceous iron intermediate paint is characterized in that described organic/inorganic hybrid graphene silica sol comprises X component and Y component;

The X component includes: isopropanol, ethyl orthosilicate, silane coupling agent, graphene oxide, the addition ratio of the isopropanol: ethyl orthosilicate TEOS: silane coupling agent: graphene oxide It is 2～10mL:2～20mL:3～30mL:0.1～1mg, and the preferred addition ratio is 8mL:10mL:10mL:0.5mg;

The Y component includes: deionized water, isopropanol, and the volume ratio of the deionized water and isopropanol is 1:7.

Described a kind of organic/inorganic hybrid modified graphene water-based epoxy micaceous iron intermediate paint is characterized in that described epoxy curing agent comprises Beckopox EH 616w/67WA;

The anti-rust pigments and fillers include one or more mixtures of titanium dioxide, talc, and precipitated barium sulfate;

The mesh number of the gray mica iron oxide is 300-500 mesh;

The dispersant includes Zetasperse 3800;

The defoamer comprises a mixture of one or more of Tego aierx901w and Tego foamex 845;

The anti-settling agent comprises a mixture of one or more of fumed silica and organic bentonite;

Described thickener is the mixed solution of 3060 and water volume ratio 1:1;

The leveling agent includes a mixture of one or more of AF3251 and AF3588.

The organic/inorganic hybrid modified graphene water-based epoxy micaceous iron intermediate paint is characterized in that the film-forming thickness of the graphene water-based epoxy micaceous iron intermediate paint is 100-160 μm.

The preparation method of any described organic/inorganic hybrid modified graphene water-based epoxy micaceous iron intermediate paint, is characterized in that comprising the following steps: preparing A component and B component, and according to A component and B component The mass ratio of component B is 1:0.4~0.5 and evenly mixed to obtain an organic/inorganic hybrid modified graphene water-based epoxy micaceous iron intermediate paint;

The A component contains organic/inorganic hybrid graphene silica sol.

The preparation method of described a kind of organic/inorganic hybrid modified graphene water-based epoxy micaceous iron intermediate paint is characterized in that the preparation method of described A component comprises the following steps:

(1) Weigh the water-based epoxy emulsion, add ethylene glycol monobutyl ether while stirring at a rotating speed of 400～600 rpm, and continue stirring for 15～25min;

(1) adding organic/inorganic hybrid graphene-silica sol and stirring for 15-25min at a rotating speed of 400-600 r/min, then filtering to obtain component A;

The mass percentage of the raw materials in the A component is: 60-80% of the water-based epoxy emulsion, 4% of ethylene glycol monobutyl ether, and the balance of organic/inorganic hybrid graphene silica sol.

Described a kind of preparation method of organic/inorganic hybrid modified graphene water-based epoxy micaceous iron intermediate paint, it is characterized in that the preparation method of described organic/inorganic hybrid graphene silica sol comprises:

(a) weigh graphene oxide and add it to the silane coupling agent, carry out ultrasonic treatment, and disperse for 20 to 120 minutes at a rotating speed of 5000rpm to 10000rpm to obtain a silane-modified graphene oxide dispersion;

The specific surface area of the graphene oxide is 100-200 m ² /g, the proportion of -OH is less than 5%, and the particle size is 0.5-5 μm;

(b) Weigh isopropanol and tetraethyl orthosilicate (TEOS), add them into the silane-modified graphene oxide dispersion obtained in the above step (a), stir for 3 to 5 minutes and mix well, adjust the pH to 9 to 10, to obtain X component;

(c) Weighing deionized water and isopropanol and mixing uniformly to obtain Y component, adding Y component to X component at a dropping rate of 0.3-0.7 mL/h to obtain a mixed solution;

(d) The mixed solution obtained in the above step (c) is placed in a 25-35 ℃ constant temperature water bath with magnetic stirring at a low speed and stirred for 2 hours to fully hydrolyze, and the temperature is raised to 65-75 ℃. After ethyl orthosilicate (TEOS) and silane The modified graphene dispersion undergoes a polycondensation reaction for 5-7 hours to generate organic/inorganic hybrid graphene silica sol.

The preparation method of the described a kind of organic/inorganic hybrid modified graphene water-based epoxy micaceous iron intermediate paint, is characterized in that the preparation method of described B component comprises the following steps:

(i) Weigh the epoxy curing agent, add deionized water, anti-rust pigments and fillers, mica iron oxide, thickener, defoamer, leveling agent, anti-settling agent in turn at a rotating speed of 400 to 600 rpm , continue to stir for 15-25min;

(ii) Add ethylene glycol monobutyl ether and ethylene glycol butyl ether acetate, stir evenly at a rotational speed of 400-600 rpm, and filter to obtain component B.

Any of the described organic/inorganic hybrid modified graphene water-based epoxy micaceous iron intermediate paints are matched with primers and topcoats, and are used as environmental protection coatings.

Compared with the prior art, the present invention has the following beneficial effects:

1. The present invention innovatively prepares graphene into graphene silica sol, realizes good dispersibility of graphene in epoxy resin, greatly improves the shielding performance of the coating, realizes the long-term corrosion resistance of the coating, and coats the coating. The adhesion of the layer is greater than or equal to 5MPa, the resistance to neutral salt spray can reach more than 1000 hours, and the resistance to immersion in 5% H ₂ SO ₄ solution can reach 168 hours. The electrostatic adsorption of graphene itself can firmly improve the anti-settling performance of water-based coatings with ion adsorption of pigments and fillers.

2. In the present invention, after graphene is modified by silane, it is polymerized with TEOS to make graphene silica sol, and its polymer chain has abundant anchoring groups, which can be passed through electrostatic interaction with pigments and fillers such as mica iron oxide, titanium dioxide, etc. It has firm adsorption and improves the anti-settling performance of water-based coatings.

Description of drawings

Fig. 1 is the preparation flow chart of the method of the present invention.

Detailed ways

The present invention will be further described below with reference to the embodiments and accompanying drawings.

Example 1: Preparation of organic-inorganic hybrid modified graphene water-based epoxy micaceous iron intermediate paint

The first step: preparation of organic-inorganic hybrid graphene silica sol

X component includes: isopropanol (8mL) + tetraethyl orthosilicate TEOS (10mL) + silane coupling agent KH-560 (10mL) + graphene oxide (0.5mg);

Y component included: deionized water (1 mL) + isopropanol (7 mL).

(1) Add 0.5 mg of graphene oxide with a specific surface area of 100 to 200 m ² /g, a proportion of -OH less than 5%, and a particle size of 0.5 to 5 μm into 10 ml of silane coupling agent KH560, and cyclic ultrasonic dispersion for 30 minutes to prepare silane Modified graphene dispersion;

(2) 8mL of isopropanol and 10mL of LTEOS were added to the silane-modified graphene dispersion, stirred at room temperature for 3-5min to make it evenly mixed, and NaOH was added to adjust the pH of the solution to pH9-10 to obtain component X;

(3) 1 mL of deionized water and 7 mL of isopropanol are uniformly mixed to prepare component Y; then component Y is added to component X at a drop rate of 0.5 mL/h;

(4) The mixed solution was placed in a water bath with magnetic stirring and stirred at low speed for 2 hours, and the temperature of the water bath was 30 °C to fully hydrolyze TEOS and KH-560; then the solution was heated to 70 °C, and the heating reaction was carried out for 6 hours. The polycondensation reaction of TEOS and silane-modified graphene dispersion liquid occurs to generate organic-inorganic hybrid graphene-silica sol.

Step 2: Prepare the A component

Prepare the following raw materials according to the parts by mass: 80% water-based epoxy resin, 4% ethylene glycol monobutyl ether, 16% organic-inorganic hybrid graphene silica sol, and the prepared raw materials are added to the reactor according to the following steps to prepare:

(1) Add water-based epoxy resin;

(2) adding organic-inorganic hybrid graphene silica sol and ethylene glycol monobutyl ether successively under 400 rev/min stirring state, and continued stirring for 15 minutes;

(3) Filtration.

Step 3: Prepare the B component

Prepare the following raw materials according to the parts by mass: epoxy curing agent 26%, anti-rust pigment and filler 30%, gray mica iron oxide 17.5%, dispersant 2%, defoamer 1.0%, anti-settling agent 1.2%, thickener 3%, leveling agent 0.4%, ethylene glycol butyl ether acetate 2%, ethylene glycol monobutyl ether 2%, deionized water 14.9%. The prepared raw materials are added to the reactor according to the following steps to prepare:

(1) Add water-based epoxy curing agent;

(2) Add deionized water, dispersant, defoamer, anti-settling agent, thickener and leveling agent in turn under stirring at 400 r/min. After stirring evenly, the rotational speed rises to 1,500 r/min and disperses for 20 minutes. ;

(3) reduce the rotating speed to 300 rpm, add anti-rust pigments and fillers and 325 mesh gray mica iron oxide, and increase the rotating speed to 1000 rpm and disperse for 20 minutes;

(4) rotating speed is reduced to 500 rev/min, adds ethylene glycol butyl ether acetate and ethylene glycol monobutyl ether and stirs for 10 minutes;

(5) Filtration.

Step 4: Mixing and Spraying

Mix the A component and the B component according to the mass ratio of 1:0.46, stir for 15 minutes, and spray according to the conventional method. The preparation flow chart of the method of the present invention is shown in FIG. 1 .

Example 2: Preparation of organic-inorganic hybrid modified graphene water-based epoxy micaceous iron intermediate paint

The first step: preparation of organic-inorganic hybrid graphene silica sol

X component includes: isopropanol (8mL) + tetraethyl orthosilicate TEOS (10mL) + silane coupling agent KH-560 (10mL) + graphene oxide (0.5mg);

Y component includes: deionized water (1mL) + isopropanol (7mL)

(1) Add 0.5 mg of graphene oxide with a specific surface area of 100 to 200 m ² /g, a proportion of -OH less than 5%, and a particle size of 0.5 to 5 μm into 10 ml of silane coupling agent KH560, and cyclic ultrasonic dispersion for 30 minutes to prepare silane Modified graphene dispersion;

(2) 8mL of isopropanol and 10mL of TEOS are added to the silane-modified graphene dispersion, stirred at room temperature for 3-5min to make it evenly mixed, and NaOH is added to adjust the pH of the solution to pH9-10 to obtain component X;

(3) 1 mL of deionized water and 7 mL of isopropanol are uniformly mixed to prepare component Y; then component Y is added to component X at a drop rate of 0.5 mL/h;

(4) The mixed solution was placed in a water bath with magnetic stirring and stirred at low speed for 2h, and the temperature of the water bath was 30°C to fully hydrolyze TEOS and KH-560;

The solution was then heated to 70 °C for 6 h. During heating, TEOS and the silane-modified graphene dispersion underwent a polycondensation reaction to generate organic-inorganic hybrid graphene-silica sol.

Step 2: Prepare the A component

Prepare the following raw materials according to parts by mass: 60% of water-based epoxy resin, 4% of ethylene glycol monobutyl ether, 36% of organic-inorganic hybrid graphene silica sol, and the prepared raw materials are added to the reactor according to the following steps to prepare:

(1) Add water-based epoxy resin;

(2) adding organic-inorganic hybrid graphene silica sol and ethylene glycol monobutyl ether successively under 400 rev/min stirring state, and continued stirring for 15 minutes;

(3) Filtration.

Step 3: Prepare the B component

Prepare the following raw materials according to the parts by mass: epoxy curing agent 26%, anti-rust pigment and filler 30%, gray mica iron oxide 17.5%, dispersant 2%, defoamer 1.0%, anti-settling agent 1.2%, thickener 3%, leveling agent 0.4%, ethylene glycol butyl ether acetate 2%, ethylene glycol monobutyl ether 2%, deionized water 14.9%. The prepared raw materials are added to the reactor according to the following steps to prepare:

(1) Add water-based epoxy curing agent;

(2) Add deionized water, dispersant, defoamer, anti-settling agent, thickener and leveling agent in turn under stirring at 400 r/min. After stirring evenly, the rotational speed rises to 1,500 r/min and disperses for 20 minutes. ;

(3) reduce the rotating speed to 300 rpm, add anti-rust pigments and fillers and 325 mesh gray mica iron oxide, and increase the rotating speed to 1000 rpm and disperse for 20 minutes;

(4) rotating speed is reduced to 500 rev/min, adds ethylene glycol butyl ether acetate and ethylene glycol monobutyl ether and stirs for 10 minutes;

(5) Filtration.

Step 4: Mixing and Spraying

Mix the A component and the B component according to the mass ratio of 1:0.4, stir for 15 minutes, and spray according to the conventional method.

Example 3: Preparation of organic-inorganic hybrid modified graphene water-based epoxy micaceous iron intermediate paint

The first step: preparation of organic-inorganic hybrid graphene silica sol

X component includes: isopropanol (8mL) + tetraethyl orthosilicate TEOS (10mL) + silane coupling agent KH-560 (10mL) + graphene oxide (0.5mg);

Y component includes: deionized water (1mL) + isopropanol (7mL)

(1) Add 0.5 mg of graphene oxide with a specific surface area of 100 to 200 m ² /g, a proportion of -OH less than 5%, and a particle size of 0.5 to 5 μm into 10 ml of silane coupling agent KH560, and cyclic ultrasonic dispersion for 30 minutes to prepare silane Modified graphene dispersion;

(2) 8mL of isopropanol and 10mL of LTEOS were added to the silane-modified graphene dispersion, stirred at room temperature for 3-5min to make it evenly mixed, and NaOH was added to adjust the pH of the solution to pH9-10 to obtain component X;

(3) 1 mL of deionized water and 7 mL of isopropanol are uniformly mixed to prepare component Y; then component Y is added to component X at a drop rate of 0.5 mL/h;

(4) The mixed solution was placed in a water bath with magnetic stirring and stirred at low speed for 2h, and the temperature of the water bath was 30°C, so that TEOS and KH-560 were fully hydrolyzed;

The solution was then heated to 70 °C for 6 h. During heating, TEOS and the silane-modified graphene dispersion underwent a polycondensation reaction to generate organic-inorganic hybrid graphene-silica sol.

Step 2: Prepare the A component

Prepare the following raw materials according to parts by mass: 80% water-based epoxy resin, 4% ethylene glycol monobutyl ether, 16% organic-inorganic hybrid graphene silica sol, and the prepared raw materials are added to the reactor according to the following steps to prepare:

(1) Add water-based epoxy resin;

(2) adding organic-inorganic hybrid graphene silica sol and ethylene glycol monobutyl ether successively under 400 rev/min stirring state, and continued stirring for 15 minutes;

(3) Filtration.

Step 3: Prepare the B component

Prepare the following raw materials in parts by mass: epoxy curing agent 26%, anti-rust pigments and fillers 30%, gray mica iron oxide 17.5%, dispersant 2%, defoamer 1.0%, anti-settling agent 1.2%, thickener 3%, leveling agent 0.4%, ethylene glycol butyl ether acetate 2%, ethylene glycol monobutyl ether 2%, deionized water 14.9%. The prepared raw materials are added to the reactor according to the following steps to prepare:

(1) Add water-based epoxy curing agent;

(2) Add deionized water, dispersant, defoamer, anti-settling agent, thickener and leveling agent in turn under stirring at 400 r/min. After stirring evenly, the rotational speed rises to 1,500 r/min and disperses for 20 minutes. ;

(3) reduce the rotating speed to 300 rpm, add anti-rust pigments and fillers and 325 mesh gray mica iron oxide, and increase the rotating speed to 1000 rpm for 20 minutes;

(4) rotating speed is reduced to 500 rev/min, adds ethylene glycol butyl ether acetate and ethylene glycol monobutyl ether and stirs for 10 minutes;

(5) Filtration.

Step 4: Mixing and Spraying

Mix the A component and the B component according to the mass ratio of 1:0.5, stir for 15 minutes, and spray according to the conventional method.

Comparative Example 1:

The difference from Example 1 is that pure water is used instead of organic-inorganic hybrid graphene-silica sol.

Comparative Example 2:

The difference from Example 1 is that pure water is used instead of organic-inorganic hybrid graphene silica sol, A component and B component are mixed according to a mass ratio of 1:1, stirred for 15 minutes, and sprayed by conventional methods.

The manufacturers 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 manufacturers and technical parameters in the embodiment of the present invention

Performance check:

The primers prepared in the above Examples 1-3 and Comparative Examples 1-2 were sprayed on a white iron plate according to 75 to 100 microns, dried and placed for 14 days, and then the coating adhesion, resistance to 5% H ₂ SO ₄ were tested. Test for solution immersion and neutral salt spray resistance. The test conditions for neutral salt spray performance are as follows:

Sedimentation salt solution concentration: (50±10)g/LNaCl

Test chamber temperature: (35+2)℃

Salt spray lift rate: (1.0～2.0)ml/(80cm ² h)

pH value of sedimentation salt solution (25℃): 6.5～7.2

The performance test results are shown in Table 2 below:

Table 2 Performance test results

Claims (10)

1. An organic/inorganic hybrid modified graphene water-based epoxy micaceous iron oxide 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 anti-rust pigment filler, 15-20% of gray mica iron 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.

2. The organic/inorganic hybrid modified graphene aqueous epoxy micaceous iron oxide intermediate paint as claimed in 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 Beckopox EP 384w/53 WAMP.

3. The organic/inorganic hybrid modified graphene aqueous epoxy micaceous iron oxide intermediate paint as claimed in claim 1, wherein the organic/inorganic hybrid graphene silica sol comprises an X component and a Y component;

the X component comprises: isopropanol, ethyl orthosilicate, a silane coupling agent, graphene oxide, wherein the isopropanol: ethyl orthosilicate: silane coupling agent: the addition ratio of the graphene oxide is 2-10 mL, 2-20 mL, 3-30 mL and 0.1-1 mg, and the preferable addition ratio is 8mL, 10mL and 0.5 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.

4. An organic/inorganic hybrid modified graphene aqueous epoxy micaceous iron oxide intermediate paint as claimed in claim 1, characterized in that the epoxy curing agent comprises Beckopox EH 616w/67 WA;

the anti-rust pigment 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 antifoaming agent comprises a mixture of one or more of Tego aierx901w, Tego foamex 845;

the anti-settling agent comprises one or more of fumed silica and organic bentonite;

the thickening agent is mixed liquid of 3060 and water in a volume ratio of 1: 1;

the leveling agent comprises one or more of AF3251 and AF 3588.

5. The organic/inorganic hybrid modified graphene aqueous epoxy micaceous iron oxide intermediate paint as claimed in claim 1, wherein the film-forming thickness of the graphene aqueous epoxy micaceous iron oxide intermediate paint is 100-160 μm.

6. The preparation method of the organic/inorganic hybrid modified graphene water-based epoxy micaceous iron oxide intermediate paint as claimed in any one of claims 1 to 5, 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 organic/inorganic hybrid modified graphene water-based epoxy micaceous iron oxide 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 micaceous iron oxide intermediate paint as claimed in claim 6, wherein the preparation method of the component A comprises the following steps:

(1) weighing the water-based epoxy emulsion, adding ethylene glycol monobutyl ether while stirring at the rotating speed of 400-600 rpm, and continuously stirring for 15-25 min;

(2) adding organic/inorganic hybrid graphene silica sol, stirring for 15-25 min at the rotating 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 water-based 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 water-based epoxy micaceous iron oxide intermediate paint as claimed in claim 6 or 7, characterized in that 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 for 20-120 minutes at a rotating speed of 5000-10000 rpm to obtain a silane modified graphene oxide dispersion liquid;

the specific surface area of the graphene oxide is 100-200 m²(iv) g, wherein the-OH content is less than 5%, and the particle size is 0.5-5 μm;

(b) weighing isopropanol and ethyl orthosilicate, adding the isopropanol and ethyl orthosilicate into the silane modified graphene oxide dispersion liquid obtained in the step (a), stirring for 3-5 min, uniformly mixing, and adjusting the pH value to 9-10 to obtain a component X;

(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 for sufficient hydrolysis, heating to 65-75 ℃, and then carrying out polycondensation reaction for 5-7 hours to generate organic/inorganic hybrid graphene silica sol.

9. The preparation method of the organic/inorganic hybrid modified graphene water-based epoxy micaceous iron oxide 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, an anti-rust 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;

and (ii) adding ethylene glycol monobutyl ether and ethylene glycol monobutyl ether acetate, stirring uniformly at the rotating speed of 400-600 r/min, and filtering to obtain a component B.

10. The organic/inorganic hybrid modified graphene water-based epoxy micaceous iron oxide intermediate paint as claimed in any one of claims 1 to 5 is matched with a primer and a topcoat and is applied to being used as an environment-friendly coating.

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