CN113717635A - Preparation method of super-hydrophobic nano porous cobalt blue coating - Google Patents
Preparation method of super-hydrophobic nano porous cobalt blue coating Download PDFInfo
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- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
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- C09D161/00—Coating compositions based on condensation polymers of aldehydes or ketones; Coating compositions based on derivatives of such polymers
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- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
- C09D163/10—Epoxy resins modified by unsaturated compounds
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- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/04—Polysiloxanes
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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
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/70—Additives characterised by shape, e.g. fibres, flakes or microspheres
Abstract
The invention relates to a preparation method of a super-hydrophobic nano porous cobalt blue coating. The polymer microspheres with uniform particle size and active groups or charges on the surface are obtained by emulsion polymerization, dispersion polymerization or suspension polymerization. The polymer microspheres act as templates and knotsThe guiding agent acts to guide metal ions Co2+And Al3+Directionally precipitating and assembling on the surface of the polymer microsphere. After high-temperature calcination, the polymer microspheres are melted and decomposed at high temperature, holes are left, and cobalt aluminum hydroxide is subjected to coprecipitation to be converted into the cobalt blue pigment with the nano hierarchical pore structure. Mixing the nano hierarchical porous cobalt blue pigment with polymer resin, an optional curing agent, an optional catalyst and an optional hydrophobic modifier to prepare the super-hydrophobic nano porous cobalt blue coating. The cobalt blue coating prepared by the invention has bright blue color, high hydrophobicity and high infrared reflectivity, and can be applied to various fields of self-cleaning, antifouling, drag reduction, oil-water separation and the like.
Description
Technical Field
The invention belongs to the technical field of functional materials, and particularly relates to a preparation method of a super-hydrophobic nano porous cobalt blue coating.
Background
The surface water contact angle of the super-hydrophobic coating is more than 150 degrees, and the rolling angle is less than 10 degrees. The micro-nano scale rough structure and the surface tension of the surface of the coating are main factors influencing the super-hydrophobic performance of the coating. Researchers have combined micro-and nano-scale layered structures with low surface energy materials to produce a variety of superhydrophobic coatings. The super-hydrophobic functional coating is widely applied, and plays an important role in the fields of self-cleaning, pollution prevention, ice coating prevention, drag reduction, oil-water separation and the like.
Common white fillers, e.g. nano-ZnO particles, nano-SiO2Granular, nano TiO2Particles, etc. are often combined with resin by researchers to prepare super-hydrophobic functional coatings. The microstructure of the coating surface can be adjusted by adjusting the dispersion state of the nano-scale filler particles, so that a high-roughness surface is constructed. However, the super-hydrophobic coating prepared by the filler has monotonous color and is difficult to meet the aesthetic requirement. In recent years, colored superhydrophobic coatings have attracted attention from researchers. The colored super-hydrophobic coating can meet aesthetic requirements of buildings, fabrics and the like, can realize functions of self-cleaning, antifouling and the like, and improves the weather resistance of the coating.
Disclosure of Invention
The invention aims to provide a super-hydrophobic nano porous cobalt blue coating with simple process, short preparation time, high infrared reflectivity and good hydrophobicity and a preparation method thereof.
The super-hydrophobic nano porous cobalt blue coating provided by the invention is obtained by performing electrostatic adsorption, coprecipitation, high-temperature calcination and resin blending on a polymer template, cobalt salt and aluminum salt, and comprises the following specific steps:
(1) stirring and heating the mixed solution of the polymerization monomer and the deionized water by using an emulsion polymerization, dispersion polymerization or suspension polymerization method, and heating to 50-100 ℃; dissolving 0.1-5 g of initiator by using deionized water, adding the initiator into the polymerization monomer mixed solution, and continuously reacting at 50-100 ℃ for 0.5-48h to obtain polymer microspheres; centrifuging and washing to obtain the polymer microsphere template with uniform particle size and active groups or charges on the surface.
(2) Ultrasonically dispersing 1g of polymer microsphere template in deionized water, weighing 0.5-10g of cobalt salt and 0.5-30 parts of aluminum salt, and dissolving with 30-50 g of deionized water; uniformly mixing the two dispersions, and dropwise adding a pH regulator at room temperature while stirring until the pH value of the solution is 2-11; continuously stirring and reacting for 0.5-48h, loading cobalt ions and aluminum ions on the surface of the polymer microspheres through hydrogen bond action, electrostatic adsorption and chemical bonding, enabling the polymer microspheres to play a role of a template and a structure directing agent to obtain coprecipitation, filtering, washing and drying the precipitate to obtain a cobalt blue pigment precursor; calcining the cobalt blue pigment precursor at 600-1200 ℃ for 2-50h to obtain the nano hierarchical porous cobalt blue pigment; wherein: the mass ratio of the polymer microsphere template to the cobalt salt is 1: 0.2-1: 20, the molar ratio of the cobalt salt to the aluminum salt is 1: 1 to 1: 10.
(3) uniformly dispersing 10-95 parts of nano hierarchical pore cobalt blue pigment, 5-90 parts of polymer resin, 0-20 parts of unnecessary curing agent, 0-5 parts of unnecessary catalyst and 0-50 parts of unnecessary hydrophobic modifier in 0-50 parts of unnecessary solvent and 0-10 parts of unnecessary auxiliary agent to obtain a mixture, coating the mixture on the surface of a base material such as metal, plastic, glass, concrete and the like, curing for 0.1-48 hours, and obtaining a super-hydrophobic nano porous cobalt blue coating with high infrared reflectivity under the synergistic action of a nano micropore and protrusion structure formed by the accumulation of cobalt blue pigment aggregates on the surface of the coating and a nano pore structure of the nano hierarchical pore cobalt blue pigment; wherein the mass fraction of the nano hierarchical pore cobalt blue pigment in the coating is 10-95%.
In the invention, the polymerized monomer in the step (1) is one or more selected from vinyl monomers such as styrene, methyl styrene, divinylbenzene, methyl methacrylate, ethyl methacrylate, butyl acrylate, hydroxyethyl methacrylate, acrylic acid, methacrylic acid, 2-acetaminoacrylic acid, acrylamide, vinyl methyl siloxane, and allyl alcohol.
In the invention, the initiator in the step (1) is one or more selected from ammonium persulfate or potassium persulfate, azobisisobutyronitrile, azobisisoheptonitrile, azobisisobutylamidine hydrochloride, hydrogen peroxide, benzoyl peroxide tert-butyl peroxide, methyl ethyl ketone peroxide, N-dimethyl-p-toluidine, methyl ethyl ketone peroxide, dibenzophthalide peroxide and naphthenic acid amine.
In the invention, the cobalt salt in the step (2) is a substance formed by cobalt ions and acid radicals, and can also contain other ions in a certain proportion; aluminum salt refers to a salt of a trivalent aluminum ion and an acid anion, and is generally white or colorless crystal. The cobalt salt is selected from any one or more of cobalt nitrate, cobalt carbonate, cobalt sulfate, cobalt acetate, cobalt chloride, cobalt bromide, cobalt fluoride or cobalt iodide; the aluminum salt is selected from one or more of aluminum nitrate, aluminum sulfate, aluminum trichloride, aluminum silicate or aluminum sulfide.
In the present invention, the pH adjuster in step (2) is a compound capable of reacting with an acid or a base, and is generally an acid, an acid oxide, a strong base and weak acid salt, a base, a basic oxide, a strong acid and weak base salt, and is one or more selected from sulfuric acid, nitric acid, acetic acid, hydrochloric acid, ammonia water, sodium hydroxide, potassium hydroxide, and urea.
In the invention, the polymer resin in the step (3) is an organic polymer which has a softening or melting range after being heated, has a flowing tendency under the action of external force during softening, is solid or semi-solid at normal temperature, and can also be liquid, and is not limited to one or more of acrylic resin, polyurethane resin, phenolic resin, epoxy resin, alkyd resin, polyester resin, organic silicon resin, fluorocarbon resin, siloxane resin, polyaspartic acid ester resin and silicone oil.
In the present invention, the optional curing agent in step (3) refers to a substance that promotes or controls the curing reaction, and examples thereof include, but are not limited to, one or more of an epoxy curing agent, a polyurethane curing agent, an amino resin curing agent, a silane coupling agent, a phthalate coupling agent, and a zirconate coupling agent.
In the present invention, the optional catalyst in step (3) is a substance capable of changing the chemical reaction rate of the reactants, and is not limited to one or more of naphthenate, amine naphthenate, dibutyltin dilaurate and platinum catalyst.
In the present invention, the non-essential hydrophobic modifier in step (3) refers to a chemical substance added into the coating material to form a special water-resistant structure on the film-forming surface of the coating material, such as, but not limited to, one or more of methyltrimethoxysilane, ethyltrimethoxysilane, octadecyltrimethoxysilane, perfluorooctyltrimethoxysilane, dodecyltrimethoxysilane, tridecafluorooctyltrimethoxysilane, polysiloxane, and polysilazane.
In the present invention, the optional solvent in step (3) is selected from solvents commonly used in paints, such as any one or more of xylene, butyl acetate, methyl ethyl ketone, acetone, ethanol, n-butanol, propylene glycol methyl ether, propylene glycol butyl ether, propylene glycol methyl ether acetate, propylene glycol butyl ether acetate, and pyrrolidone, by way of non-limiting examples.
In the invention, the optional auxiliary agent in the step (3) is a common auxiliary agent for the coating, and is selected from one or more of a dispersing agent, a thickening agent, a defoaming agent, a leveling agent, a wetting agent and an anti-settling agent.
The super-hydrophobic nano porous cobalt blue coating obtained by the preparation method disclosed by the invention is applied to the fields of self-cleaning, pollution prevention, drag reduction, oil-water separation, infrared reflection, cooling or heat insulation.
In the present invention, the adsorption-coprecipitation technique is used to obtain metallic cobalt ion (Co)2+) And aluminum ion (Al)3+) Through hydrogen bond action, electrostatic adsorption, chemical bonding and combination with polymer microsphere, through regulating and controlling reaction pH, Al3+And Co2+And forming metal hydroxide precipitate, and loading the metal hydroxide precipitate on the surface of the polymer microsphere to obtain a cobalt blue pigment precursor.
In the invention, the mass ratio of the polymer microsphere template to the cobalt salt is 1: 0.2-1: 20, the molar ratio of the cobalt salt to the aluminum salt is 1: 1 to 1: 10.
in the invention, the cobalt blue pigment precursor is calcined at 600-1200 ℃ for 2-50h to obtain the nano hierarchical porous cobalt blue pigment
In the invention, the nano hierarchical pore structure of the cobalt blue pigment is that in the high-temperature calcination process, the polymer microspheres are melted and decomposed at high temperature, and nano holes are left; and (3) coprecipitating and dehydrating the cobalt aluminum hydroxide, and converting the cobalt aluminum hydroxide into the cobalt blue pigment with the nano hierarchical pore structure.
In the invention, the super-hydrophobic coating is prepared by directly blending a nano hierarchical pore cobalt blue pigment, a polymer resin, an optional curing agent, an optional catalyst, an optional hydrophobic modifier and an optional solvent.
In the invention, the super-hydrophobic property of the coating is realized by the synergistic effect of the nano-scale micropores and the bulge structures formed by the accumulation of the cobalt blue pigment aggregates on the surface of the coating and the nano-pore structures of the nano-scale multi-pore cobalt blue pigment, and the surface roughness of the coating is improved.
According to the super-hydrophobic nano porous cobalt blue coating, the mass fraction of the nano multi-level porous cobalt blue pigment in the coating is 10-95%.
The super-hydrophobic nano porous cobalt blue coating prepared by the invention has bright blue color, ultrahigh hydrophobic angle and high infrared reflectivity, and can be applied to the fields of self-cleaning, antifouling, drag reduction, oil-water separation, infrared reflection, temperature reduction, heat insulation and the like.
The super-hydrophobic coating prepared by the method can be directly constructed by a blending method through a micro-nano multilevel structure of the nano multilevel pore cobalt blue pigment without adding a hydrophobic agent or modifying the surface of the pigment.
The invention uses polymer microsphere as template, metal cobalt ion (Co)2+) And aluminum ion (Al)3+) The polymer microspheres are enriched on the surfaces of the polymer microspheres through electrostatic adsorption, hydrogen bond action and chemical combination. Regulating and controlling reaction pH and Al by adding a pH regulator3+And Co2+And forming metal hydroxide precipitate which is enriched on the surface of the polymer microsphere. The polymer microspheres play the role of a template and a structure directing agent and guide metal ions Co2+And Al3+Directional precipitation and assembly, and simultaneously, the aggregation of the precipitate is limited, and the function of controlling the particle size is achieved. After high-temperature calcination, the polymer microspheres are melted and decomposed at high temperature, holes are left, and cobalt-aluminum hydroxide is subjected to coprecipitation and dehydration to be converted into the cobalt blue pigment with the nano hierarchical pore structure.Mixing the nano hierarchical porous cobalt blue pigment with polymer resin, an optional curing agent, an optional catalyst and an optional hydrophobic modifier to prepare the super-hydrophobic nano porous cobalt blue coating. The method directly constructs the super-hydrophobic coating by a blending method through the synergistic effect of the nano-scale micropores and the bulge structures formed by the accumulation of the cobalt blue pigment aggregates on the surface of the coating and the nano-scale hole structures of the nano-scale porous cobalt blue pigment. The cobalt blue coating prepared by the invention has bright blue color and high hydrophobicity, and can be applied to various fields of self-cleaning, pollution prevention, resistance reduction, oil-water separation, infrared reflection, temperature reduction, heat insulation and the like.
The super-hydrophobic nano porous cobalt blue coating provided by the invention has the advantages that: the super-hydrophobic nano-porous cobalt blue coating is bright in color, good in hydrophobic property and good in infrared reflection property, so that the super-hydrophobic nano-porous cobalt blue coating becomes an excellent material in the fields of self-cleaning, heat insulation and cooling coatings. The nano hierarchical pore cobalt blue pigment not only endows the coating with bright blue color, but also improves the roughness of the surface of the coating, so that the coating has higher water contact angle. The cobalt blue pigment with bright blue color and nano porous structure is obtained by using the polymer microspheres as a template and adopting an adsorption-coprecipitation technology, and the nano multi-level pore cobalt blue pigment is directly mixed with resin to directly construct a super-hydrophobic coating. The method has simple process and easy implementation.
All percentages and ratios used herein are by weight unless otherwise indicated.
Drawings
FIG. 1 is a schematic diagram of a synthesis mechanism of a nano hierarchical pore cobalt blue pigment. As can be seen from the figure, metallic cobalt ion (Co)2 +) And aluminum ion (Al)3+) The polymer microspheres are enriched on the surfaces of the polymer microspheres through electrostatic adsorption, hydrogen bond action and chemical combination. Regulating and controlling reaction pH and Al by adding a pH regulator3+And Co2+And forming metal hydroxide precipitate which is enriched on the surface of the polymer microsphere. The polymer microspheres play the role of a template and a structure directing agent and guide metal ions Co2+And Al3+Directed precipitation and assembly ofThe aggregation of the precipitate is limited, and the function of controlling the particle size is achieved. After high-temperature calcination, the polymer microspheres are melted and decomposed at high temperature, holes are left, and cobalt-aluminum hydroxide is subjected to coprecipitation and dehydration to be converted into the cobalt blue pigment with the nano hierarchical pore structure.
FIG. 2 is a photograph of a nano-sized hierarchical pore cobalt blue pigment obtained in example 5 of the present invention. As can be seen from the figure, the prepared cobalt blue pigment has very excellent hue. Wherein: a is a photo of the nano hierarchical pore cobalt blue pigment; and B is the microscopic morphology of the nano hierarchical pore cobalt blue pigment.
FIG. 3 is a photograph of water contact angle of the super-hydrophobic nano-porous cobalt blue coating obtained in example 9 of the present invention. As can be seen from the figure, the prepared coating has very excellent hydrophobicity. Wherein: A-D are dynamic demonstration that water drops fall on the surface of the super-hydrophobic nano porous cobalt blue coating; and E is a surface contact angle photo of the super-hydrophobic nano porous cobalt blue coating.
FIG. 4 is an ultraviolet-visible spectrum of the super-hydrophobic nano-porous cobalt blue coating obtained in examples 9 to 12 of the present invention. As can be seen from the figure, the prepared coating has good infrared reflection performance.
FIG. 5 shows the oil-water separation application of the super-hydrophobic nano-porous cobalt blue coating obtained in example 9 of the present invention. As can be seen from the figure, the prepared coating has high oil-water separation efficiency. Wherein: a is a photo before a mixture of water and oil (normal hexane) is separated by common gauze; c is a photograph of the common gauze after water and oil are separated; b is a photo before the mixture of water and oil (normal hexane) is separated by the gauze coated with the nano-porous cobalt blue composite coating; and D is a photo of the mixture of water and oil (n-hexane) separated by the gauze coated with the nano-porous cobalt blue composite coating.
Detailed Description
The following examples further describe and demonstrate preferred methods of practice within the scope of the present invention. These examples are given for illustrative purposes only and are not to be construed as limiting the invention.
The steps of preparing the superhydrophobic nanoporous cobalt blue coating in each of the following examples were performed at atmospheric pressure unless otherwise indicated.
The super-hydrophobic nano porous cobalt blue coating prepared by the invention has the following performance characteristics:
the microstructure of the nano hierarchical pore cobalt blue pigment is obtained by a German Zeiss company Gemini SEM500 field emission scanning electron microscope test.
The hydrophobicity of the super-hydrophobic nano hierarchical pore cobalt blue coating is measured by a German Data Physics company OCA15 contact angle tester.
The infrared reflectivity of the super-hydrophobic nano-porous cobalt blue coating is measured by a UV-4100 ultraviolet-visible spectrophotometer of Hitachi, Japan.
Examples 1 to 4: synthesis of Polymer templates
Example 1: using emulsion polymerization techniques, 10g of styrene and 180g of deionized water were added to a 500mL three-necked flask, and the mixed solution was stirred and heated at 500rpm to bring it to 80 ℃. 0.5g of ammonium persulfate initiator is dispersed in 200g of deionized water, and the solution is added into a three-necked bottle and reacted for 24 hours at 80 ℃ to obtain the polystyrene emulsion. Centrifuging and washing to obtain the polystyrene microsphere.
Example 2: using emulsion polymerization techniques, 8g of styrene and 2g of acrylic acid were dispersed in 90g of deionized water, and the mixed solution was stirred and heated at 500rpm to bring it to 75 ℃. 0.5g of ammonium persulfate initiator is dispersed in 10g of deionized water, and the solution is added into a three-necked bottle and reacted for 12 hours at 75 ℃ to obtain the polystyrene-acrylic emulsion. Centrifuging and washing to obtain the polystyrene-acrylic acid microspheres.
Example 3: using the suspension polymerization technique, 2g of polyvinyl alcohol, 5g of sodium dodecyl sulfate and 2g of cetyl alcohol were dispersed in a 500mL three-necked flask and the temperature was raised to 80 ℃. 3g of azobisisobutyronitrile is dissolved in 150g of methyl methacrylate, the solution is added into a three-necked bottle in several times, after being stirred and dispersed evenly at the speed of 700rpm, nitrogen is introduced for 30min, and the reaction is carried out for 24h at the temperature of 80 ℃, thus obtaining the polymethyl methacrylate emulsion. Centrifuging and washing to obtain the polymethyl methacrylate microspheres.
Example 4: by using a dispersion polymerization technology, 10g of acrylamide monomer, 2g of cross-linking agent N, N-methylene bisacrylamide and 1g of dispersion stabilizer polyvinylpyrrolidone are dissolved in 300g of ethanol, the solution is placed in a 500mL three-necked bottle, nitrogen is introduced into the bottle, the temperature is slowly raised to 60 ℃, and then initiator ammonium persulfate is dropwise added into the bottle. The reaction was carried out at 60 ℃ for 12h to give a milky white dispersion. Centrifuging and washing to obtain the polyacrylamide microspheres.
Examples 5 to 8: synthesis of nano hierarchical pore cobalt blue pigment
Example 5: 5.82g of polystyrene microspheres are ultrasonically dispersed in 100g of deionized water, and 5.82g of Co (NO) is weighed3)2·6H2O and 15gAl (NO)3)3·9H2O, dissolved with 100g of deionized water. The two dispersions were mixed uniformly and a 5% aqueous solution of ammonia was added dropwise at room temperature with stirring until the solution had a pH of 8. And continuously stirring for reaction for 2 hours, collecting reaction liquid, centrifuging, washing and drying to obtain the cobalt blue precursor. And heating the precursor to 1000 ℃ in a muffle furnace, and calcining for 2h to obtain the nano cobalt blue pigment.
Example 6: 2.5g of polystyrene-acrylic acid microspheres are ultrasonically dispersed in 30g of deionized water, and 0.5g of CoCl is weighed2·6H2O and 1.0gAlCl3And dissolved with 10g of deionized water. The two dispersions were mixed uniformly and an aqueous sodium hydroxide solution was added dropwise at room temperature while stirring until the solution had a pH of 10. And continuously stirring for reaction for 4 hours, collecting reaction liquid, centrifuging, washing and drying to obtain the cobalt blue precursor. And heating the precursor to 1200 ℃ in a muffle furnace, and calcining for 3h to obtain the nano cobalt blue pigment.
Example 7: ultrasonically dispersing 10g of polymethyl methacrylate microspheres in 50g of deionized water, and weighing 5g of cobalt acetate (C)4H6CoO4) And 19g of Al2(SO4)3Dissolved with 80g of deionized water. The two dispersions were mixed uniformly and an aqueous urea solution was added dropwise at room temperature with stirring until the solution pH was 9. And continuously stirring for reaction for 4 hours, collecting reaction liquid, centrifuging, washing and drying to obtain the cobalt blue precursor. And heating the precursor in a muffle furnace to 800 ℃ and calcining for 6h to obtain the nano cobalt blue pigment.
Example 8: ultrasonically dispersing 8g of polyacrylamide microspheres in 50g of deionized water, and weighing 5g of polyacrylamide microspheresCobalt acetate (C)4H6CoO4) And 15g Al (NO)3)3·9H2O, dissolved with 60g of deionized water. The two dispersions were mixed uniformly and the aqueous solution of potassium oxide was added dropwise with stirring at room temperature until the solution pH was 10. And continuously stirring for reaction for 4 hours, collecting reaction liquid, centrifuging, washing and drying to obtain the cobalt blue precursor. And heating the precursor to 900 ℃ in a muffle furnace, and calcining for 5h to obtain the nano cobalt blue pigment.
Examples 9 to 12: preparation of super-hydrophobic nano hierarchical pore cobalt blue coating
Example 9: uniformly dispersing 20g of multi-level porous cobalt blue pigment particles and 5g of polydimethylsiloxane resin in 20g of butyl acetate solvent, coating the mixture on the surface of a clean glass substrate by using a wire rod, and curing at room temperature for 24 hours to obtain the nano porous cobalt blue super-hydrophobic coating.
Example 10: uniformly dispersing 10g of multi-level porous cobalt blue pigment particles, 5g of acrylic silicon resin, 0.8g of dibutyltin dilaurate and 0.1g of perfluorooctyl trimethoxysilane in 5g of acetone solvent, coating the mixture on the surface of a steel plate by using a wire rod, and curing at room temperature for 48 hours to obtain the nano porous cobalt blue super-hydrophobic coating.
Example 11: and spraying the mixture on a metal aluminum plate at 200 ℃ in 8g of multi-level porous cobalt blue pigment particles, 3g of epoxy acrylate resin and 2g of polyamide resin to obtain the nano porous cobalt blue super-hydrophobic coating.
Example 12: uniformly dispersing 10g of multi-level porous cobalt blue pigment particles, 2g of methyltrimethoxysilane, 2g of phenolic resin, 1g of siloxane resin and 2g of hexamethylenetetramine in 3g of dimethylbenzene and 2g of n-butyl alcohol, coating the mixture on the surface of tinplate by using a wire rod, and curing for 4 hours at 200 ℃ to obtain the nano-porous cobalt blue super-hydrophobic coating.
Table 1 shows the water contact angles of the superhydrophobic nanoporous cobalt blue coatings obtained in examples 9-12, from which it can be seen that all the superhydrophobic nanoporous cobalt blue coatings have hydrophobicity.
TABLE 1
| Numbering | Water contact Angle (°) |
| Example 9 | 153 |
| Example 10 | 150 |
| Example 11 | 148 |
| Example 12 | 154 |
Claims (12)
1. A preparation method of a super-hydrophobic nano porous cobalt blue coating is characterized by comprising the following specific steps:
(1) stirring and heating the mixed solution of the polymerization monomer and the deionized water by using an emulsion polymerization, dispersion polymerization or suspension polymerization method, and heating to 50-100 ℃; dissolving 0.1-5 g of initiator by using deionized water, adding the initiator into the polymerization monomer mixed solution, and continuously reacting for 0.5-48h at 50-100 ℃ to obtain polymer microspheres with uniform particle size and active groups or charges on the surfaces; centrifuging and washing to obtain a polymer microsphere template;
(2) ultrasonically dispersing 1g of the polymer microsphere template obtained in the step (1) in deionized water, weighing 0.5-10g of cobalt salt and 0.5-30 parts of aluminum salt, and dissolving with 30-50 g of deionized water; uniformly mixing the two dispersions, and dropwise adding a pH regulator at room temperature while stirring until the pH value of the solution is 2-11; continuously stirring and reacting for 0.5-48h, loading cobalt ions and aluminum ions on the surface of the polymer microsphere through the combination of hydrogen bond action, electrostatic adsorption and chemical bonding with the polymer microsphere, enabling the polymer microsphere to play the roles of a template and a structure directing agent to obtain coprecipitation, filtering, washing and drying the precipitate to obtain a cobalt blue pigment precursor; calcining the cobalt blue pigment precursor at 600-1200 ℃ for 2-50h to obtain the nano hierarchical porous cobalt blue pigment; wherein: the mass ratio of the polymer microsphere template to the cobalt salt is 1: 0.2-1: 20, the molar ratio of the cobalt salt to the aluminum salt is 1: 1 to 1: 10;
(3) uniformly dispersing 10-95 parts of the nano hierarchical pore cobalt blue pigment obtained in the step (2), 5-90 parts of polymer resin, 0-20 parts of an unnecessary curing agent, 0-5 parts of an unnecessary catalyst and 0-50 parts of an unnecessary hydrophobic modifier in 0-50 parts of an unnecessary solvent and 0-10 parts of an unnecessary auxiliary agent to obtain a mixture, coating the mixture on the surface of a metal, plastic, glass or concrete substrate, curing for 0.1-48 hours, and performing synergistic action of nano micropores and protrusion structures formed by the cobalt blue pigment aggregates stacked on the surface of the coating and a nano pore structure of the nano hierarchical pore cobalt blue pigment to improve the surface roughness of the coating so as to obtain the super-hydrophobic nano porous cobalt blue coating with high infrared reflectivity; wherein the mass fraction of the nano hierarchical pore cobalt blue pigment in the coating is 10-95%.
2. The method according to claim 1, wherein the polymerized monomer in step (1) is selected from one or more of styrene, methyl styrene, divinylbenzene, methyl methacrylate, ethyl methacrylate, butyl acrylate, hydroxyethyl methacrylate, acrylic acid, methacrylic acid, 2-acetaminoacrylic acid, acrylamide, vinyl methyl siloxane and allyl alcohol monomers.
3. The method according to claim 1, wherein the initiator in step (1) is one or more selected from the group consisting of ammonium persulfate, potassium persulfate, azobisisobutyronitrile, azobisisoheptonitrile, azobisisobutylamidine hydrochloride, hydrogen peroxide, benzoyl peroxide t-butyl peroxide, methyl ethyl ketone peroxide, N-dimethyl-p-toluidine, methyl ethyl ketone peroxide, dibenzophthalide peroxide and ammonium naphthenate.
4. The method according to claim 1, wherein the cobalt salt in step (2) is one or more selected from cobalt nitrate, cobalt carbonate, cobalt sulfate, cobalt acetate, cobalt chloride, cobalt bromide, cobalt fluoride and cobalt iodide.
5. The method according to claim 1, wherein the aluminum salt in step (2) is selected from any one or more of aluminum nitrate, aluminum sulfate, aluminum trichloride, aluminum silicate and aluminum sulfide.
6. The method according to claim 1, wherein the pH regulator in step (2) is selected from one or more of sulfuric acid, nitric acid, acetic acid, hydrochloric acid, ammonia water, sodium hydroxide, potassium hydroxide and urea.
7. The method according to claim 1, wherein the polymer resin in step (3) is one or more selected from acrylic resin, polyurethane resin, phenolic resin, epoxy resin, alkyd resin, polyester resin, silicone resin, fluorocarbon resin, silicone resin, polyaspartic acid ester resin, and silicone oil.
8. The preparation method according to claim 1, wherein the optional curing agent in step (3) is one or more selected from epoxy curing agent, polyurethane curing agent, amino resin curing agent, silane coupling agent, phthalate coupling agent or zirconate coupling agent.
9. The method according to claim 1, wherein the optional catalyst in step (3) is one or more selected from cobalt naphthenate, amine naphthenate and dibutyltin dilaurate.
10. The method according to claim 1, wherein the optional hydrophobic modifier in step (3) is selected from one or more of methyltrimethoxysilane, ethyltrimethoxysilane, octadecyltrimethoxysilane, perfluorooctyltrimethoxysilane, dodecyltrimethoxysilane, tridecafluorooctyltrimethoxysilane, polysiloxane or polysilazane.
11. The method according to claim 1, wherein the non-essential solvent in the step (3) is one or more selected from xylene, butyl acetate, butanone, acetone, ethanol, n-butanol, propylene glycol methyl ether, propylene glycol butyl ether, propylene glycol methyl ether acetate, propylene glycol butyl ether acetate, and pyrrolidone; the non-essential auxiliary agent is a common auxiliary agent for the coating and is selected from one or more of a dispersing agent, a thickening agent, a defoaming agent, a leveling agent, a wetting agent and an anti-settling agent.
12. The application of the super-hydrophobic nano-porous cobalt blue coating obtained by the preparation method of claim 1 in the fields of self-cleaning, pollution prevention, drag reduction, oil-water separation, infrared reflection, temperature reduction or heat insulation.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114700242A (en) * | 2022-04-12 | 2022-07-05 | 江苏中基复合材料有限公司 | Aluminum foil for ultraviolet reflecting material and preparation method thereof |
| CN115746638A (en) * | 2022-09-28 | 2023-03-07 | 欧利生东邦涂料（东莞）有限公司 | Low-reflectivity coating and preparation method and application thereof |
| CN116040654A (en) * | 2022-12-13 | 2023-05-02 | 深圳华钠新材有限责任公司 | Super-hydrophobic Prussian blue material and preparation method and application thereof |
| CN117070112A (en) * | 2023-10-16 | 2023-11-17 | 上海沪正实业有限公司 | Paint containing heat-insulating anti-corrosion composite functional pigment |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030119668A1 (en) * | 2000-05-19 | 2003-06-26 | Johnson Matthey Plc | Catalysts with high cobalt surface area |
| KR100827296B1 (en) * | 2007-10-08 | 2008-05-06 | 공주대학교 산학협력단 | Porous waterproof coating for using nano calcium carbonate |
| CN104212277A (en) * | 2014-08-26 | 2014-12-17 | 中国建筑股份有限公司 | Colored solar heat reflective cooling coating and preparation method thereof |
| CN106809885A (en) * | 2017-01-10 | 2017-06-09 | 上海印钞有限公司 | A kind of preparation method of nanometer cobalt blue dye |
| CN109337573A (en) * | 2018-09-10 | 2019-02-15 | 东北石油大学 | A kind of no fluorine-type polyphenylene sulfide super-hydrophobic coat and preparation method thereof |
| CN110433806A (en) * | 2019-07-19 | 2019-11-12 | 福州大学 | A kind of cobalt-aluminium composite oxide catalyst and its preparation method and application |
-
2021
- 2021-08-27 CN CN202110992969.1A patent/CN113717635A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030119668A1 (en) * | 2000-05-19 | 2003-06-26 | Johnson Matthey Plc | Catalysts with high cobalt surface area |
| KR100827296B1 (en) * | 2007-10-08 | 2008-05-06 | 공주대학교 산학협력단 | Porous waterproof coating for using nano calcium carbonate |
| CN104212277A (en) * | 2014-08-26 | 2014-12-17 | 中国建筑股份有限公司 | Colored solar heat reflective cooling coating and preparation method thereof |
| CN106809885A (en) * | 2017-01-10 | 2017-06-09 | 上海印钞有限公司 | A kind of preparation method of nanometer cobalt blue dye |
| CN109337573A (en) * | 2018-09-10 | 2019-02-15 | 东北石油大学 | A kind of no fluorine-type polyphenylene sulfide super-hydrophobic coat and preparation method thereof |
| CN110433806A (en) * | 2019-07-19 | 2019-11-12 | 福州大学 | A kind of cobalt-aluminium composite oxide catalyst and its preparation method and application |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114700242A (en) * | 2022-04-12 | 2022-07-05 | 江苏中基复合材料有限公司 | Aluminum foil for ultraviolet reflecting material and preparation method thereof |
| CN115746638A (en) * | 2022-09-28 | 2023-03-07 | 欧利生东邦涂料（东莞）有限公司 | Low-reflectivity coating and preparation method and application thereof |
| CN115746638B (en) * | 2022-09-28 | 2023-08-18 | 欧利生东邦涂料（东莞）有限公司 | Low-reflectivity coating and preparation method and application thereof |
| CN116040654A (en) * | 2022-12-13 | 2023-05-02 | 深圳华钠新材有限责任公司 | Super-hydrophobic Prussian blue material and preparation method and application thereof |
| CN117070112A (en) * | 2023-10-16 | 2023-11-17 | 上海沪正实业有限公司 | Paint containing heat-insulating anti-corrosion composite functional pigment |
| CN117070112B (en) * | 2023-10-16 | 2024-02-23 | 上海沪正实业有限公司 | Paint containing heat-insulating anti-corrosion composite functional pigment |
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