CN114773956A - Organic/inorganic hybrid modified graphene water-based epoxy micaceous iron oxide intermediate paint as well as preparation method and application thereof - Google Patents
Organic/inorganic hybrid modified graphene water-based epoxy micaceous iron oxide intermediate paint as well as preparation method and application thereof Download PDFInfo
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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
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- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
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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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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
Technical Field
The invention belongs to the technical field of steel structure corrosion prevention, and particularly relates to organic/inorganic hybrid modified graphene water-based epoxy micaceous iron oxide intermediate paint and a preparation method and application thereof.
Background
The solvent type two-component epoxy coating has good corrosion resistance, however, the traditional epoxy resin coating mainly adopts a solvent type, and the addition amount of an organic solvent is large and even reaches 80 percent (volume fraction). Volatile organic solvents (VOC) do not participate in film formation, and can escape from a paint film after the coating is dried, so that the coating not only causes pollution to the atmosphere, but also can cause serious harm to human bodies. As the environmental protection requirements become more strict, the water-based epoxy coating is a necessary trend to replace the solvent-based epoxy coating. Due to different film forming mechanisms, compared with a solvent-based coating, the water-based anticorrosive coating is difficult to form a high-quality coating with uniform composition height and complete 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 the surface tension of water is large, the water-based coating is difficult to achieve high infiltration and dispersion of pigments and fillers, so that the improvement of the corrosion resistance of the water-based coating becomes a key point in the development of environment-friendly coatings.
The current water paint system mainly comprises a primer, an intermediate paint and a finish paint. The primer mainly plays an electrochemical protection role, and when the coating is damaged, the primer is contacted with an electrolyte to form a primary battery, so that the failure of the coating caused by rapid corrosion of the damaged part can be effectively prevented. The main function of the intermediate paint is barrier function, and the main function of the finish paint is to increase the weather resistance of the coating. The intermediate paint is generally epoxy micaceous iron intermediate paint. The mica iron oxide is of a two-dimensional lamellar structure, and the penetration distance of water vapor and oxygen ions can be effectively increased in the coating. Therefore, the thicker the intermediate paint is, the better the corrosion resistance is, but the excessively thick film thickness causes cost increase and resource waste, so that the barrier permeability of the intermediate paint needs to be improved and the consumption of the intermediate paint needs to be reduced.
The graphene is used as a two-dimensional nano material, has extremely large specific surface area, electrical conductivity and the like, and the lamellar structures of the graphene are overlapped layer by layer and staggered up and down, so that dozens to hundreds of compact physical barrier layers can be formed in the coating, and the impermeability of the coating is greatly improved. Meanwhile, the electrostatic adsorption of graphene can be firmly adsorbed with pigment and filler ions to improve the anti-settling property of the water-based paint, and a new improvement way is brought for improving the compactness, the barrier property, the mechanical property and the corrosion resistance of the water-based paint.
Although some patents and documents disclose graphene modified waterborne epoxy resins and preparation processes thereof in recent years, the current preparation processes are complicated and employ a large amount of acids, bases or toxic reagents in order to improve the dispersibility of graphene. The existing common method is to prepare the water-based anti-corrosion coating by adding the graphene dispersion liquid, but the graphene is easy to agglomerate and is difficult to realize by uniformly dispersing in the water-based paint.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to design and provide an organic/inorganic hybrid modified graphene water-based epoxy micaceous iron oxide intermediate paint as well as a preparation method and application thereof. According to the invention, graphene and silica sol are combined to prepare graphene silica sol, and the graphene silica sol is uniformly mixed with the aqueous epoxy resin, so that the problem that the graphene is difficult to disperse in the aqueous epoxy resin is solved. According to the organic/inorganic hybrid modified graphene water-based epoxy micaceous iron oxide intermediate paint, organic/inorganic hybrid graphene silica sol is applied to modification of epoxy resin-based paint, and the electrostatic adsorption effect of graphene per se can be firmly adsorbed with pigment and filler ions to improve the anti-settling property of the water-based paint; on the other hand, the graphene silica sol has good dispersibility in the water-based paint, the uniformity of film formation is improved, the large-sheet structure of the graphene greatly improves the adhesive force and corrosion resistance of the epoxy micaceous iron oxide intermediate paint, and the graphene-based epoxy micaceous iron oxide intermediate paint has good application prospect.
In order to achieve the purpose, the invention adopts the following technical scheme:
an organic/inorganic hybrid modified graphene aqueous epoxy micaceous 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 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.
The organic/inorganic hybrid modified graphene water-based epoxy micaceous iron oxide 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 Beckopox EP 384w/53 WAMP.
The organic/inorganic hybrid modified graphene water-based epoxy micaceous iron oxide 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: isopropanol, ethyl orthosilicate, a silane coupling agent and graphene oxide, wherein the molar ratio of the isopropanol to the silane coupling agent is as follows: tetraethoxysilane TEOS: 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: 7.
The organic/inorganic hybrid modified graphene water-based epoxy micaceous iron intermediate paint is 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.
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 mu m.
The preparation method of the organic/inorganic hybrid modified graphene water-based epoxy micaceous iron oxide intermediate paint 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 organic/inorganic hybrid modified graphene water-based epoxy micaceous iron oxide 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 micaceous iron oxide intermediate paint is characterized in that 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;
(1) adding organic/inorganic hybrid graphene silica sol, stirring at a rotating speed of 400-600 rpm for 15-25 min, 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.
The preparation method of the organic/inorganic hybrid modified graphene water-based epoxy micaceous iron oxide intermediate paint is 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 at the rotating speed of 5000-10000 rpm for 20-120 minutes 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 Tetraethoxysilane (TEOS), adding the isopropanol and the TEOS into the silane modified graphene oxide dispersion liquid obtained in the step (a), stirring for 3-5 min, uniformly mixing, and adjusting 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 speed 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 ℃ and stirring at a low speed for 2 hours for full hydrolysis, heating to 65-75 ℃, and carrying out polycondensation reaction on Tetraethoxysilane (TEOS) and silane modified graphene dispersion liquid for 5-7 hours to generate organic/inorganic hybrid graphene silica sol.
The preparation method of the organic/inorganic hybrid modified graphene water-based epoxy micaceous iron oxide intermediate paint is characterized in that 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, uniformly stirring at the rotating speed of 400-600 r/min, and filtering to obtain a component B.
Any one of the organic/inorganic hybrid modified graphene water-based epoxy micaceous iron oxide intermediate paint is matched with a primer and a topcoat, and is applied to an environment-friendly coating.
Compared with the prior art, the invention has the following beneficial effects:
1. book (notebook)The graphene is innovatively prepared into the graphene silica sol, so that the good dispersibility of the graphene in the epoxy resin is realized, the shielding performance of the coating is greatly improved, the long-acting corrosion resistance of the coating is realized, the adhesive force of the coating is not less than 5MPa, the neutral salt spray resistance of the coating is more than 1000 hours, and the resistance to 5% H is realized2SO4The 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-settling property of the water-based paint is improved.
2. According to the invention, graphene is subjected to silane modification and then polymerized with TEOS to prepare graphene silica sol, and a polymer chain of the graphene silica sol has rich anchoring groups, so that the graphene silica sol can be firmly adsorbed by pigments and fillers such as mica iron oxide, titanium dioxide and the like under the electrostatic action, and the anti-settling property of the water-based paint is improved.
Drawings
FIG. 1 is a flow chart of the preparation method of the present invention.
Detailed Description
The present invention will be further described with reference to the following examples and the accompanying drawings.
Example 1: preparation of organic-inorganic hybrid modified graphene water-based epoxy micaceous iron oxide intermediate paint
The first step is as follows: preparation of organic-inorganic hybrid graphene silica sol
The X component comprises: isopropanol (8mL) + tetraethoxysilane TEOS (10mL) + silane coupling agent KH-560(10mL) + graphene oxide (0.5 mg);
the Y component comprises: deionized water (1mL) + isopropanol (7 mL).
(1) The specific surface area is 100 to 200m2Per gram, adding 0.5mg of graphene oxide with the-OH content of less than 5% and the particle size of 0.5-5 mu m into 10ml of silane coupling agent KH560, and performing circulating ultrasonic dispersion for 30 minutes to prepare a silane modified graphene dispersion solution;
(2) adding 8mL of isopropanol and 10mL of TEOS into the silane modified graphene dispersion liquid, stirring at room temperature for 3-5 min to uniformly mix the mixture, and adding NaOH to adjust the pH value of the solution to 9-10 to obtain an X component;
(3) 1mL of deionized water and 7mL of isopropanol are uniformly mixed to prepare a component Y; then 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, stirring at low speed for 2h, wherein the water bath temperature is 30 ℃, and fully hydrolyzing TEOS and KH-560; and heating the solution to 70 ℃, and carrying out heating reaction for 6h, wherein during heating, TEOS and silane modified graphene dispersion liquid are subjected to polycondensation reaction to generate organic-inorganic hybrid graphene silica sol.
The second step is that: preparation of component A
The following raw materials are prepared according to the parts by weight: the preparation method comprises the following steps of adding 80% of waterborne epoxy resin, 4% of ethylene glycol monobutyl ether and 16% of organic-inorganic hybrid graphene silica sol into a reaction kettle according to the following steps:
(1) adding water-based epoxy resin;
(2) sequentially adding organic-inorganic hybrid graphene silica sol and ethylene glycol monobutyl ether under the stirring state of 400 revolutions per minute, and continuing stirring for 15 minutes;
(3) and (5) filtering.
The third step: preparation of component B
The following raw materials are prepared according to the parts by weight: 26% of epoxy curing agent, 30% of antirust pigment filler, 17.5% of gray mica iron oxide, 2% of dispersant, 1.0% of defoaming agent, 1.2% of anti-settling agent, 3% of thickening agent, 0.4% of flatting agent, 2% of ethylene glycol butyl ether acetate, 2% of ethylene glycol monobutyl ether and 14.9% of deionized water. Adding the prepared raw materials into a reaction kettle according to the following steps:
(1) adding a water-based epoxy curing agent;
(2) sequentially adding deionized water, a dispersing agent, a defoaming agent, an anti-settling agent, a thickening agent and a flatting agent under the stirring state of 400 revolutions per minute, uniformly stirring, increasing the rotating speed to 1500 revolutions per minute, and dispersing for 20 minutes;
(3) reducing the rotating speed to 300 r/min, adding the antirust pigment filler and 325-mesh gray mica iron oxide, and increasing the rotating speed to 1000 r/min for dispersing for 20 min;
(4) reducing the rotating speed to 500 revolutions per minute, adding ethylene glycol monobutyl ether acetate and ethylene glycol monobutyl ether, and stirring for 10 minutes;
(5) and (4) filtering.
The fourth step: mixing and spraying
And (3) 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 water-based epoxy micaceous iron oxide intermediate paint
The first step is as follows: preparation of organic-inorganic hybrid graphene silica sol
The X component comprises: isopropanol (8mL) + tetraethylorthosilicate TEOS (10mL) + silane coupling agent KH-560(10mL) + graphene oxide (0.5 mg);
the Y component comprises: deionized water (1mL) + isopropyl alcohol (7mL)
(1) The specific surface area is 100 to 200m2Per gram, adding 0.5mg of graphene oxide with the-OH content of less than 5% and the particle size of 0.5-5 mu m into 10ml of silane coupling agent KH560, and performing circulating ultrasonic dispersion for 30 minutes to prepare a silane modified graphene dispersion solution;
(2) adding 8mL of isopropanol and 10mL of TEOS into the silane modified graphene dispersion, stirring at room temperature for 3-5 min to uniformly mix, adding NaOH to adjust the pH value of the solution to 9-10, and obtaining an X component;
(3) 1mL of deionized water and 7mL of isopropanol are uniformly mixed to prepare a component Y; then adding the component Y into the component X at the dropping rate of 0.5 mL/h;
(4) placing the mixed solution in a water bath kettle with magnetic stirring, stirring at low speed for 2h, wherein the water bath temperature is 30 ℃, and fully hydrolyzing TEOS and KH-560;
and heating the solution to 70 ℃, and carrying out heating reaction for 6h, wherein during heating, TEOS and silane modified graphene dispersion liquid are subjected to polycondensation reaction to generate organic-inorganic hybrid graphene silica sol.
The second step: preparation of component A
The following raw materials are prepared according to the parts by mass: 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 according to the following steps:
(1) adding waterborne epoxy resin;
(2) sequentially adding organic-inorganic hybrid graphene silica sol and ethylene glycol monobutyl ether under the stirring state of 400 revolutions per minute, and continuing stirring for 15 minutes;
(3) and (4) filtering.
The third step: preparation of component B
The following raw materials are prepared according to the parts by weight: 26% of epoxy curing agent, 30% of antirust pigment filler, 17.5% of gray mica iron oxide, 2% of dispersant, 1.0% of defoaming agent, 1.2% of anti-settling agent, 3% of thickening agent, 0.4% of flatting agent, 2% of ethylene glycol butyl ether acetate, 2% of ethylene glycol monobutyl ether and 14.9% of deionized water. Adding the prepared raw materials into a reaction kettle according to the following steps:
(1) adding a waterborne epoxy curing agent;
(2) sequentially adding deionized water, a dispersing agent, a defoaming agent, an anti-settling agent, a thickening agent and a flatting agent under the stirring state of 400 revolutions per minute, uniformly stirring, increasing the rotating speed to 1500 revolutions per minute, and dispersing for 20 minutes;
(3) reducing the rotating speed to 300 r/min, adding the antirust pigment filler and 325-mesh gray mica iron oxide, and increasing the rotating speed to 1000 r/min for dispersing for 20 min;
(4) reducing the rotating speed to 500 revolutions per minute, adding ethylene glycol monobutyl ether acetate and ethylene glycol monobutyl ether, and stirring for 10 minutes;
(5) and (4) filtering.
The fourth step: mixing and spraying
And (3) 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 water-based epoxy micaceous iron oxide intermediate paint
The first step is as follows: preparation of organic-inorganic hybrid graphene silica sol
The X component comprises: isopropanol (8mL) + tetraethylorthosilicate TEOS (10mL) + silane coupling agent KH-560(10mL) + graphene oxide (0.5 mg);
the Y component comprises: deionized water (1mL) + isopropyl alcohol (7mL)
(1) The specific surface area is 100 to 200m2Per gram, adding 0.5mg of graphene oxide with-OH content less than 5% and particle size of 0.5-5 mu m into 10ml of silane coupling agent KH560, and performing circulating ultrasonic separationDispersing for 30 minutes to prepare a silane modified graphene dispersion liquid;
(2) adding 8mL of isopropanol and 10mL of TEOS into the silane modified graphene dispersion liquid, stirring at room temperature for 3-5 min to uniformly mix the mixture, and adding NaOH to adjust the pH value of the solution to 9-10 to obtain an X component;
(3) uniformly mixing 1mL of deionized water and 7mL of isopropanol to prepare a component Y; then 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, stirring at low speed for 2h, and performing water bath at 30 deg.C to fully hydrolyze TEOS and KH-560;
and heating the solution to 70 ℃, and carrying out heating reaction for 6h, wherein during heating, TEOS and silane modified graphene dispersion liquid are subjected to polycondensation reaction to generate organic-inorganic hybrid graphene silica sol.
The second step is that: preparation of component A
The following raw materials are prepared according to the parts by mass: 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 according to the following steps:
(1) adding waterborne epoxy resin;
(2) sequentially adding organic-inorganic hybrid graphene silica sol and ethylene glycol monobutyl ether under the stirring state of 400 revolutions per minute, and continuing stirring for 15 minutes;
(3) and (5) filtering.
The third step: preparation of component B
The following raw materials are prepared according to the parts by mass: 26% of epoxy curing agent, 30% of antirust pigment filler, 17.5% of gray mica iron oxide, 2% of dispersant, 1.0% of defoaming agent, 1.2% of anti-settling agent, 3% of thickening agent, 0.4% of flatting agent, 2% of ethylene glycol butyl ether acetate, 2% of ethylene glycol monobutyl ether and 14.9% of deionized water. Adding the prepared raw materials into a reaction kettle according to the following steps:
(1) adding a water-based epoxy curing agent;
(2) sequentially adding deionized water, a dispersing agent, a defoaming agent, an anti-settling agent, a thickening agent and a flatting agent under the stirring state of 400 revolutions per minute, uniformly stirring, increasing the rotating speed to 1500 revolutions per minute, and dispersing for 20 minutes;
(3) reducing the rotating speed to 300 r/min, adding the anti-rust pigment and the 325-mesh gray mica iron oxide, and increasing the rotating speed to 1000 r/min for dispersing for 20 min;
(4) reducing the rotating speed to 500 revolutions per minute, adding ethylene glycol monobutyl ether acetate and ethylene glycol monobutyl ether, and stirring for 10 minutes;
(5) and (4) filtering.
The fourth step: mixing and spraying
And (3) 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:
different from the embodiment 1, pure water is used for replacing inorganic hybrid graphene silica sol, the component A and the component B are mixed according to the mass ratio of 1:1, stirred for 15 minutes and sprayed according to a conventional method.
The major raw material manufacturers and technical parameters in the examples of the present invention are shown in Table 1.
TABLE 1 Main raw Material manufacturers and technical parameters in the examples of the present invention
And (3) performance detection:
the primers prepared in the above examples 1-3 and comparative examples 1-2 were sprayed on a white iron plate according to a thickness of 75-100 μm, dried and left for 14 days to obtain a coating having an adhesion and a 5% H resistance2SO4And (3) detecting the soaking and neutral salt spray resistance of the solution, wherein the test conditions of the neutral salt spray resistance are as follows:
concentration of the settled salt solution: (50. + -.10) g/LNaCl
Temperature of the test chamber: (35+2) deg.C
Salt spray lifting rate: (1.0-2.0) ml/(80 cm)2 h)
pH of the settled salt solution (25 ℃): 6.5 to 7.2
The results of the performance tests 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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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN116179055A (en) * | 2022-12-26 | 2023-05-30 | 山东韩师傅新材料有限公司 | Graphene modified ship heavy-duty anti-corrosion polymer coating and preparation method thereof |
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| CN107779052A (en) * | 2017-11-21 | 2018-03-09 | 马鞍山天宇船舶制造有限公司 | A kind of anti-corrosion type epoxy ribbons of the disperse modified color stuffing containing coupling embroider the preparation method of coating |
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| CN107779052A (en) * | 2017-11-21 | 2018-03-09 | 马鞍山天宇船舶制造有限公司 | A kind of anti-corrosion type epoxy ribbons of the disperse modified color stuffing containing coupling embroider the preparation method of coating |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116179055A (en) * | 2022-12-26 | 2023-05-30 | 山东韩师傅新材料有限公司 | Graphene modified ship heavy-duty anti-corrosion polymer coating and preparation method thereof |
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