CN116640482A - Water-based graphene antibacterial building coating - Google Patents

Water-based graphene antibacterial building coating Download PDF

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CN116640482A
CN116640482A CN202310819175.4A CN202310819175A CN116640482A CN 116640482 A CN116640482 A CN 116640482A CN 202310819175 A CN202310819175 A CN 202310819175A CN 116640482 A CN116640482 A CN 116640482A
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graphene
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李晶
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D125/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Coating compositions based on derivatives of such polymers
    • C09D125/02—Homopolymers or copolymers of hydrocarbons
    • C09D125/04—Homopolymers or copolymers of styrene
    • C09D125/08—Copolymers of styrene
    • C09D125/14—Copolymers of styrene with unsaturated esters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C08K2003/0806—Silver
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/221—Oxides; Hydroxides of metals of rare earth metal
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2237—Oxides; Hydroxides of metals of titanium
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/30—Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Plant Pathology (AREA)
  • Paints Or Removers (AREA)

Abstract

The invention provides an aqueous graphene antibacterial building coating, wherein the surface of a fluorine-containing styrene-acrylic emulsion coating has super-hydrophobic and self-cleaning properties, and is excellent in abrasion resistance and mechanical strength properties, and the sterilization and sterilization stability of the coating is particularly excellent.

Description

Water-based graphene antibacterial building coating
Technical Field
The invention relates to a preparation method of a water-based paint, in particular to a water-based antibacterial paint filler and a preparation method of a paint for the building field.
Background
Currently, three main categories of water-based paint are water-based building paint, water-based industrial paint and water-based furniture paint. With the vigorous development of the building field in China, the proportion of the water-based building paint in the building cost is continuously increased and is about 50%, so that the water-based building paint is the main body of the current paint. The water-based building coating mainly comprises four resins, namely water-based polyurethane, water-based acrylic ester, water-based alkyd resin and water-based epoxy resin.
The styrene-acrylic emulsion is a copolymer of styrene and acrylic acid monomer, and has the advantages of heat resistance, corrosion resistance, weather resistance, stain resistance, good glossiness, good color retention and the like. Styrene-acrylic emulsion is one of ten non-crosslinking emulsions, and has high industrial application value, so that the styrene-acrylic emulsion is more researched in emulsion polymerization systems. The styrene-acrylic emulsion is an important intermediate chemical product, has very wide application, and the emulsion paint serving as a main film forming material has the advantages of high bonding strength, good adhesive force, simple construction, low cost and the like, and most importantly, the emulsion paint serving as an aqueous system accords with the environmental protection concept. However, the styrene-acrylic emulsion also has the defects of poor compactness, high oxygen and water vapor transmission rate and the like, so that the application of the styrene-acrylic emulsion is limited, and therefore, how to improve the performance of the styrene-acrylic emulsion becomes a research hot spot.
The traditional preparation method of the styrene-acrylic emulsion cannot meet the current application requirements, so researchers develop different preparation methods to improve the performance of the styrene-acrylic emulsion. At present, three preparation methods of styrene-acrylic emulsion are mainly adopted, one is microemulsion polymerization, and emulsion coating film with high performance and stability can be obtained by adopting the method mainly pursuing ultra-micronization of emulsion particles. It has been reported that polystyrene-acrylic acid (St/AA) sub-microcapsules are prepared by a microemulsion polymerization method, and AA is introduced into the microemulsion polymerization of St to improve the Zeta potential and electrostatic stability of St/AA sub-microcapsules. The second is to use core-shell particle design to enhance the latex function, and to reduce the lowest film forming temperature of the emulsion to synthesize a novel core-shell polymer containing styrene (St) and Butyl Acrylate (BA) in both the core and shell layers of the polymer particles, and to use the novel core-shell polymer in pigment printing paste. The third method is to use a crosslinking technology to improve the compactness of emulsion, such as a semi-batch seed emulsion polymerization method, to synthesize Divinylbenzene (DVB) crosslinked styrene (St)/Butyl Acrylate (BA)/acrylic acid (AAc) copolymer (SAC) emulsion particles, and the existence of DVB fragments of the emulsion particles in the capsule leads to the increase of thermal stability. And then, the hydroxy phosphate is used as an antirust functional monomer and the hydroxypropyl acrylate is used as a crosslinking monomer to synthesize the styrene-acrylic acid copolymer emulsion, so that the adhesive force and the flashing resistance of the styrene-acrylic acid emulsion to a metal substrate can be effectively improved.
In addition to improvements in the preparation methods, the modification of styrene-acrylic emulsions with epoxy resins, silicones, organofluorine, nanomaterials, and the like is also a direction of efforts by researchers. The mechanism of epoxy modification mainly comprises a graft copolymerization method and an esterification copolymerization method, the modified emulsion has the excellent characteristics of styrene-acrylic emulsion and the characteristics of high strength and high adhesiveness of epoxy resin, wherein fluorine-containing groups are introduced into acrylic ester by organic fluorine, stable C-F bonds are generated by utilizing the advantage of great electronegativity of fluorine, the stability of the styrene-acrylic emulsion can be effectively improved, for example, nano silicon dioxide modified fluorine-containing polyacrylate emulsifier-free emulsion is synthesized by a sol-gel method, and experimental results prove that the nano SiO2 modified fluorine-containing polyacrylate emulsifier-free emulsion has good water resistance and solvent resistance, and an organic fluorine segment can migrate to a film-air interface.
The nano materials such as carbon nano tubes and graphene with excellent mechanical property and electrical property are added into the styrene-acrylic emulsion as the reinforcing phase, so that the mechanical property, the electrical property and the thermodynamic property of the styrene-acrylic emulsion can be greatly improved, for example, the styrene-acrylic emulsion/graphene aerogel supporting microencapsulated phase change composite material with an oriented porous network is prepared by a hydrothermal method, a vacuum impregnation method and a freeze drying method, a connected heat transfer network is provided for the styrene-acrylic emulsion/graphene composite material, and when the graphene content is 14.7 wt%, the thermal conductivity reaches 0.92W/m.K, which is 265% higher than that of pure paraffin.
Carbon nanomaterial can be classified into zero-dimensional (0D) fullerene, one-dimensional (1D) carbon nanotube, and two-dimensional (2D) graphene, and it is generally known that two-dimensional graphene is a basic unit constituting a carbon nanomaterial. The graphene sheets are wrapped and curled from the edges to obtain spherical fullerene, carbon nanotubes are curled from two sides in parallel, and the graphene sheets are stacked in a large amount to form graphite. Among them, applications in the paint field include flame retardant paints, heat conductive paints, anticorrosive paints, electrically conductive paints, functional paints, and the like. In the graphene, electrons are less affected by atoms, and the electrons can freely move on the track in the graphene, so that the graphene has higher conductivity. In recent years, the shielding performance of graphene is gradually discovered, and the graphene has a very wide development space for preparing building coatings with electromagnetic shielding effect. However, due to the characteristic of large specific surface area of graphene, graphene is easy to agglomerate in a solution, the agglomerated graphene can influence the exertion of the excellent performance of the graphene, the adsorption capacity of the graphene is reduced, and the electromagnetic shielding performance of the prepared coating is also greatly influenced. The agglomeration is irreversible under the action of no external force, and needs to be uniformly dispersed under the condition of ultrasonic or strong stirring, so that the influence can be eliminated. Accordingly, researchers have made a great deal of research effort in overcoming the problem of graphene agglomeration.
Disclosure of Invention
Based on the above, the invention provides the water-based graphene antibacterial building coating, and the water-based graphene antibacterial building coating is used in the building water-based coating, and the prepared coating has good physicochemical properties and antibacterial and mildew-proof properties, and specifically:
the water-based graphene antibacterial building coating comprises the following raw materials in parts by weight:
40-70 parts of fluorine-containing styrene-acrylic emulsion;
2-10 parts of rod-shaped (Ag-Ti-Sc) Ox-graphene antibacterial composite filler;
0.2-0.5 part of defoaming agent;
0.5-8 parts of film forming auxiliary agent;
1.0 to 3.0 portions of flatting agent;
0.3-0.6 part of dispersing agent;
60-80 parts of deionized water;
the rod-shaped (Ag-Ti-Sc) Ox-graphene antibacterial composite filler is prepared by the following steps:
(1) Sequentially adding 40-50mM scandium nitrate solution, 7-8mM tetrabutyl titanate, 4-5mM sodium citrate and 1-2g polyvinylpyrrolidone into a container, magnetically stirring for 20-40min, and then adding 20-50mL 2M NaOH in 5-7min at 200-300rpm to obtain solution A;
(2) Preparing a graphene glycol aqueous solution containing silver nitrate: the product is named as liquid B;
(3) Introducing the solution B into the solution A, then placing the solution B into a stainless steel water heating reaction kettle, sealing the water heating reaction kettle, heating to 200-220 ℃ by a program, keeping the temperature for 24-26 hours, naturally cooling to room temperature, and repeatedly washing and filtering with deionized water and propanol;
(4) And freeze-drying to obtain the rod-shaped (Ag-Ti-Sc) Ox-graphene antibacterial composite filler.
The preparation method of the fluorine-containing styrene-acrylic emulsion comprises the following steps:
(a) Adding acrylic ester monomers and styrene into an aqueous solution containing an emulsifier, and performing ultrasonic dispersion for 20-30min to obtain a pre-emulsion, wherein the addition amount of the emulsifier accounts for 30-50% of the total mass of the emulsifier;
(b) Heating a three-neck flask to 75-80 ℃, adding an initiator, wherein the addition amount of the initiator accounts for 1/3-1/2 of the total mass of the initiator, stirring for 10-20min, then dropwise adding a pre-emulsion of 1/3-1/2, continuously adding for 50-70min, and keeping the temperature at 75-80 ℃ until blue fluorescence appears, and then keeping the temperature to obtain a pre-polymerization solution;
(c) Adding fluoromonomer, residual initiator, residual emulsifier and residual pre-emulsion into the pre-polymerization solution, and stirring at 75-80 ℃ for 1-3 hours;
(d) Adding ammonia water to regulate pH value to 7-7.5, cooling to room temperature, filtering and discharging to obtain the fluorine-containing styrene-acrylic emulsion.
The acrylic ester monomer comprises at least one of methyl acrylate, ethyl acrylate, butyl acrylate, hydroxyethyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate and hydroxyethyl methacrylate.
The fluorine monomer is at least one selected from trifluoroethyl acrylate, trifluoroethyl methacrylate, hexafluorobutyl acrylate, dodecafluoroheptyl methacrylate and hexafluorobutyl methacrylate.
The emulsifier is at least one selected from sodium dodecyl sulfate and sodium dodecyl benzene sulfonate.
The initiator is at least one selected from ammonium persulfate, potassium persulfate, sodium persulfate and azodiisobutyronitrile.
The preparation method of the graphene antibacterial water-based paint comprises the following steps:
(1) Mixing deionized water, a defoaming agent, a dispersing agent and a film forming additive, and then adding a rod-shaped (Ag-Ti-Sc) Ox-graphene antibacterial composite filler for uniform dispersion for 30-60min;
(2) Grinding the uniformly dispersed material in the step (1) to 20-40 mu m, adding the fluorine-containing styrene-acrylic emulsion, the flatting agent and the residual 1/2 defoamer while stirring, uniformly stirring, adjusting the pH value to 7-8, standing, filtering, and packaging to obtain the water-based paint, wherein the paint is sprayed on the surface of a building material under high pressure.
A preparation method of a water-based antibacterial paint filler comprises the following steps:
(1) Sequentially adding 40-50mM scandium nitrate solution, 7-8mM tetrabutyl titanate, 4-5mM sodium citrate and 1-2g polyvinylpyrrolidone into a container, magnetically stirring for 20-40min, and then adding 20-50mL 2M NaOH in 5-7min at 200-300rpm to obtain solution A;
(2) Preparing a graphene glycol aqueous solution containing silver nitrate: the product is named as liquid B;
(3) Introducing the solution B into the solution A, then placing the solution B into a stainless steel water heating reaction kettle, sealing the water heating reaction kettle, heating to 200-220 ℃ by a program, keeping the temperature for 24-26 hours, naturally cooling to room temperature, and repeatedly washing and filtering with deionized water and propanol;
(4) And freeze-drying to obtain the rod-shaped (Ag-Ti-Sc) Ox-graphene antibacterial composite filler.
The graphene is prepared by a hummer method, the mass dispersion of the obtained graphene aqueous solution is 10-30wt.%, and then 10-15g/L silver nitrate solution and 100-200mL ethylene glycol are added into the graphene aqueous solution.
The volume ratio of the liquid A to the liquid B is 2: (1-1.5).
The temperature-programmed heating rate is 2-4 ℃/min.
The process for preparing graphene by the hummer method comprises the following steps:
firstly, adding 2g of 200-mesh natural crystalline flake graphite and 0.67g of sodium nitrate into a flask, adding 40mL of 99wt.% concentrated sulfuric acid, stirring in an ice-water bath, adding 10g of potassium permanganate, and reacting for 2 hours, wherein; then heating to 35 ℃ and reacting for 1.5h;
and adding 80mL of deionized water, heating to 80 ℃ after the dropwise addition is finished, maintaining the temperature for 15min, cooling the reaction liquid to room temperature, adding 100mL of 35w.% hydrogen peroxide, diluting to 500mL by using deionized water, standing for 24h, and filtering and washing to neutrality to obtain the graphene aqueous solution.
The main antibacterial materials of the invention are three types, including titanium oxide, silver and graphene, wherein the titanium oxide is formed in a hydrothermal stripUnder the condition of the component, tetrabutyl titanate is obtained by hydrothermal method, and titanium oxide can generate hydroxyl radical under the excitation of light energy . OH and superoxide radical . O 2 - And (3) the active oxygen with strong oxidizing property can cause oxidative damage to the bacterial cell structure, silver is the reducing property of glycol under the high-temperature and high-pressure condition, silver oxide is reduced into silver heavy metal, and the silver ions destroy the bacterial cell structure by dissolving out metal ions, so that the effects of inhibiting bacterial growth and reproduction or killing bacteria are exerted. The graphene is a carbon-based antibacterial material, and the carbon-based antibacterial material achieves an antibacterial effect mainly through physical damage to cell membranes of bacteria, mechanical constraint of the bacteria, destruction of a bacterial structure by oxidative stress and the like.
The scandium oxide is added in the hydrothermal process, so that the active site of the Ti oxide can be effectively exposed, the electronic structure of the titanium oxide material is regulated, the light sterilization effect of titanium oxide is further improved, the Sc modified sterilization filler can be obviously obtained through a sterilization test, the better technical effect is shown, in addition, the rod-shaped material prepared through the hydrothermal process is water-containing (Ag-Ti-Sc) Ox, through a mapping test, each element is uniformly distributed in the rod-shaped material, the uniform doping state is shown, the sterilization stability of the antibacterial filler is good, the appearance is shown as shown in figure 2, and the mapping result is shown as figure 3.
The styrene-acrylic emulsion has the advantages of good film forming property, flexible film forming, high elasticity, high stiffness, excellent light resistance, aging resistance, wet rubbing resistance, wide raw material sources, low cost and the like, and is a polymer film forming material widely applied at present. However, the traditional styrene-acrylic emulsion has higher surface energy on the surface of the emulsion film due to the existence of polar groups in the structure, which provides possibility for adhesion and fixation of bacteria, mold and other microorganisms on the surface of the coating, rapid propagation, formation of bacteria or mold biofilms and erosion of the coating.
According to the invention, the styrene-acrylic emulsion is subjected to organic fluorine modification through molecular structure design, and the fluorine-containing styrene-acrylic emulsion with low surface energy for film formation is prepared by utilizing the low surface energy characteristic of an organic fluorine monomer. The introduction of the fluorine-containing functional monomer with low surface energy can effectively overcome the defect that the surface of the traditional styrene-acrylic emulsion film is easy to adhere and breed bacteria, mould and other microorganisms, improve the hygienic property of the styrene-acrylic emulsion film coating product and improve the grade of the substrate film coating product.
Antibacterial test: the coating prepared by the invention is sprayed on the surface of a smooth substrate (such as aluminum alloy or glass) at high pressure, after solidification, the coating is peeled off from the surface of the substrate to obtain a coating film, the coating film is subjected to disinfection, sterilization and cleaning treatment, and then the coating film is placed in a culture dish containing escherichia coli or staphylococcus aureus bacterial liquid, and is cultured in a constant temperature and humidity incubator with the temperature of 37+/-1 ℃ and the relative humidity of 80% +/-2 percent for 24-48 hours.
Beneficial technical effects
(1) According to the invention, the (Ag-Ti-Sc) Ox-graphene antibacterial filler is prepared by a hydrothermal method, has high antibacterial performance, is a rod-shaped material, is easy to disperse in a coating emulsion, and particularly Sc in the antibacterial filler can improve the photo-sterilization effect of titanium oxide and has a very strong stabilizing effect on the sterilization stability of the coating.
(2) The surface of the fluorine-containing styrene-acrylic emulsion coating has super-hydrophobic and self-cleaning properties, and has excellent abrasion resistance and mechanical strength.
Drawings
The test of the inhibition zone of the examples and comparative examples of figure 1.
FIG. 2 is a topography of an Ox-graphene filler of the present invention (Ag-Ti-Sc).
FIG. 3 (TEM-Mapping diagram of Ag-Ti-Sc) Ox-graphene filler.
Figure 4 example and comparative example absorption test.
Fig. 5 example and comparative example absorption test.
Detailed Description
Example 1
The embodiment and the comparative example mainly relate to the preparation of filler, and the filler is used in the coating and is prepared by the following steps and methods:
the water-based graphene antibacterial building coating comprises the following raw materials in parts by weight:
55 parts of fluorine-containing styrene-acrylic emulsion;
6 parts of rod-shaped (Ag-Ti-Sc) Ox-graphene antibacterial composite filler;
0.35 parts of defoamer;
3 parts of film forming auxiliary agent;
2 parts of flatting agent;
0.45 parts of dispersing agent;
70 parts of deionized water;
the preparation method of the fluorine-containing styrene-acrylic emulsion comprises the following steps:
(a) Adding acrylic ester monomers and styrene into an aqueous solution containing an emulsifier, and performing ultrasonic dispersion for 25min to obtain a pre-emulsion, wherein the addition amount of the emulsifier is 40% of the total mass of the emulsifier;
(b) Heating a three-neck flask to 77.5 ℃, adding an initiator, wherein the addition amount of the initiator is 0.4 of the total mass of the initiator, stirring for 15min, then dropwise adding a 0.4 pre-emulsion, continuously dropwise adding for 60min, and continuously preserving heat at 77.5 ℃ until blue fluorescence appears, thus obtaining a pre-polymerization solution;
(c) Adding fluoromonomer, residual initiator, residual emulsifier and residual pre-emulsion into the pre-polymerization solution, and keeping the temperature at 77.5 ℃ and stirring for 2 hours;
(d) Adding ammonia water to regulate pH value to 7.25, cooling to room temperature, filtering and discharging to obtain the fluorine-containing styrene-acrylic emulsion.
The acrylic monomer is butyl acrylate.
The fluoromonomer is selected from trifluoroethyl methacrylate.
The emulsifier is selected from sodium dodecyl benzene sulfonate.
The initiator is selected from potassium persulfate.
A preparation method of a graphene antibacterial water-based paint comprises the following steps:
(1) Mixing deionized water, a defoaming agent, a dispersing agent and a film forming additive, and then adding a rod-shaped (Ag-Ti-Sc) Ox-graphene antibacterial composite filler for uniformly dispersing for 45min;
(2) Grinding the uniformly dispersed material in the step (1) to the fineness of 30 mu m, adding the fluorine-containing styrene-acrylic emulsion, the flatting agent and the residual 1/2 defoamer while stirring, uniformly stirring, adjusting the pH value to 7.5, standing, filtering and packaging to obtain the water-based paint;
(3) The coating is sprayed on the surface of the substrate under high pressure.
A preparation method of a water-based antibacterial paint filler comprises the following steps:
(1) Sequentially adding 40mM scandium nitrate solution, 7mM tetrabutyl titanate, 4mM sodium citrate and 1g polyvinylpyrrolidone into a container, magnetically stirring for 20min, and then adding 20mL 2M NaOH in 5min at 200rpm to obtain solution A;
(2) Preparing a graphene glycol aqueous solution containing silver nitrate: the product is named as liquid B;
(3) Introducing the solution B into the solution A, then placing the solution B into a stainless steel water heating reaction kettle, sealing the water heating reaction kettle, heating to 200 ℃ by a program, naturally cooling to room temperature after keeping for 24 hours, and repeatedly washing and filtering deionized water and propanol;
(4) And freeze-drying to obtain the rod-shaped (Ag-Ti-Sc) Ox-graphene antibacterial composite filler.
The graphene is prepared by a hummer method, the mass dispersion of the obtained graphene aqueous solution is 10 wt%, and then 10g/L silver nitrate solution and 100mL ethylene glycol are added into the graphene aqueous solution.
The volume ratio of the liquid A to the liquid B is 2: (1).
The temperature-programmed temperature-rising rate is 2 ℃/min.
The process for preparing graphene by the hummer method comprises the following steps: firstly, adding 2g of 200-mesh natural crystalline flake graphite and 0.67g of sodium nitrate into a flask, adding 40mL of 99wt.% concentrated sulfuric acid, stirring in an ice-water bath, adding 10g of potassium permanganate, and reacting for 2 hours, wherein; then heating to 35 ℃ and reacting for 1.5h; and adding 80mL of deionized water, heating to 80 ℃ after the dropwise addition is finished, maintaining the temperature for 15min, cooling the reaction liquid to room temperature, adding 100mL of 35w.% hydrogen peroxide, diluting to 500mL by using deionized water, standing for 24h, and filtering and washing to neutrality to obtain the graphene aqueous solution.
The filler obtained by the preparation of example 1 was designated S-1.
Example 2
A preparation method of a water-based antibacterial paint filler comprises the following steps:
(1) Sequentially adding 40mM scandium nitrate solution, 7.5mM tetrabutyl titanate, 4.5mM sodium citrate and 1.5g polyvinylpyrrolidone into a container, magnetically stirring for 30min, and then adding 35mL 2M NaOH at 250rpm for 6min to obtain solution A;
(2) Preparing a graphene glycol aqueous solution containing silver nitrate: the product is named as liquid B;
(3) Introducing the solution B into the solution A, then placing the solution B into a stainless steel water heating reaction kettle, sealing the water heating reaction kettle, heating to 210 ℃ by a program, naturally cooling to room temperature after keeping for 25 hours, and repeatedly washing and filtering with deionized water and propanol;
(4) And freeze-drying to obtain the rod-shaped (Ag-Ti-Sc) Ox-graphene antibacterial composite filler.
The graphene is prepared by a hummer method, the mass dispersion of the obtained graphene aqueous solution is 20 wt%, and then 12.5g/L silver nitrate solution and 150mL ethylene glycol are added into the graphene aqueous solution.
The volume ratio of the liquid A to the liquid B is 2: (1.25).
The temperature-programmed temperature-rising rate is 3 ℃/min.
The process for preparing graphene by the hummer method comprises the following steps: firstly, adding 2g of 200-mesh natural crystalline flake graphite and 0.67g of sodium nitrate into a flask, adding 40mL of 99wt.% concentrated sulfuric acid, stirring in an ice-water bath, adding 10g of potassium permanganate, and reacting for 2 hours, wherein; then heating to 35 ℃ and reacting for 1.5h; and adding 80mL of deionized water, heating to 80 ℃ after the dropwise addition is finished, maintaining the temperature for 15min, cooling the reaction liquid to room temperature, adding 100mL of 35w.% hydrogen peroxide, diluting to 500mL by using deionized water, standing for 24h, and filtering and washing to neutrality to obtain the graphene aqueous solution.
The filler obtained by the preparation of example 1 was designated S-2.
Example 3
A preparation method of a water-based antibacterial paint filler comprises the following steps:
(1) 43mM scandium nitrate solution, 7.5mM tetrabutyl titanate, 4.5mM sodium citrate and 1.5g polyvinylpyrrolidone are sequentially added into a container, magnetically stirred for 30min, and then 35mL 2M NaOH is added in 6min at the rotation speed of 250rpm to obtain solution A;
(2) Preparing a graphene glycol aqueous solution containing silver nitrate: the product is named as liquid B;
(3) Introducing the solution B into the solution A, then placing the solution B into a stainless steel water heating reaction kettle, sealing the water heating reaction kettle, heating to 210 ℃ by a program, naturally cooling to room temperature after keeping for 25 hours, and repeatedly washing and filtering with deionized water and propanol;
(4) And freeze-drying to obtain the rod-shaped (Ag-Ti-Sc) Ox-graphene antibacterial composite filler.
The graphene is prepared by a hummer method, the mass dispersion of the obtained graphene aqueous solution is 20 wt%, and then 12.5g/L silver nitrate solution and 150mL ethylene glycol are added into the graphene aqueous solution.
The volume ratio of the liquid A to the liquid B is 2: (1.25).
The temperature-programmed temperature-rising rate is 3 ℃/min.
The process for preparing graphene by the hummer method comprises the following steps: firstly, adding 2g of 200-mesh natural crystalline flake graphite and 0.67g of sodium nitrate into a flask, adding 40mL of 99wt.% concentrated sulfuric acid, stirring in an ice-water bath, adding 10g of potassium permanganate, and reacting for 2 hours, wherein; then heating to 35 ℃ and reacting for 1.5h; and adding 80mL of deionized water, heating to 80 ℃ after the dropwise addition is finished, maintaining the temperature for 15min, cooling the reaction liquid to room temperature, adding 100mL of 35w.% hydrogen peroxide, diluting to 500mL by using deionized water, standing for 24h, and filtering and washing to neutrality to obtain the graphene aqueous solution.
The filler obtained by the preparation of example 1 was designated S-3.
Example 4
A preparation method of a water-based antibacterial paint filler comprises the following steps:
(1) 45mM scandium nitrate solution, 7.5mM tetrabutyl titanate, 4.5mM sodium citrate and 1.5g polyvinylpyrrolidone are sequentially added into a container, magnetically stirred for 30min, and then 35mL 2M NaOH is added in 6min at the rotation speed of 250rpm to obtain solution A;
(2) Preparing a graphene glycol aqueous solution containing silver nitrate: the product is named as liquid B;
(3) Introducing the solution B into the solution A, then placing the solution B into a stainless steel water heating reaction kettle, sealing the water heating reaction kettle, heating to 210 ℃ by a program, naturally cooling to room temperature after keeping for 25 hours, and repeatedly washing and filtering with deionized water and propanol;
(4) And freeze-drying to obtain the rod-shaped (Ag-Ti-Sc) Ox-graphene antibacterial composite filler.
The graphene is prepared by a hummer method, the mass dispersion of the obtained graphene aqueous solution is 20 wt%, and then 12.5g/L silver nitrate solution and 150mL ethylene glycol are added into the graphene aqueous solution.
The volume ratio of the liquid A to the liquid B is 2: (1.25).
The temperature-programmed temperature-rising rate is 3 ℃/min.
The process for preparing graphene by the hummer method comprises the following steps: firstly, adding 2g of 200-mesh natural crystalline flake graphite and 0.67g of sodium nitrate into a flask, adding 40mL of 99wt.% concentrated sulfuric acid, stirring in an ice-water bath, adding 10g of potassium permanganate, and reacting for 2 hours, wherein; then heating to 35 ℃ and reacting for 1.5h; and adding 80mL of deionized water, heating to 80 ℃ after the dropwise addition is finished, maintaining the temperature for 15min, cooling the reaction liquid to room temperature, adding 100mL of 35w.% hydrogen peroxide, diluting to 500mL by using deionized water, standing for 24h, and filtering and washing to neutrality to obtain the graphene aqueous solution.
The filler obtained by the preparation of example 1 was designated S-4.
Example 5
A preparation method of a water-based antibacterial paint filler comprises the following steps:
(1) 49mM scandium nitrate solution, 7.5mM tetrabutyl titanate, 4.5mM sodium citrate and 1.5g polyvinylpyrrolidone are sequentially added into a container, magnetically stirred for 30min, and then 35mL 2M NaOH is added in 6min at the rotation speed of 250rpm to obtain solution A;
(2) Preparing a graphene glycol aqueous solution containing silver nitrate: the product is named as liquid B;
(3) Introducing the solution B into the solution A, then placing the solution B into a stainless steel water heating reaction kettle, sealing the water heating reaction kettle, heating to 210 ℃ by a program, naturally cooling to room temperature after keeping for 25 hours, and repeatedly washing and filtering with deionized water and propanol;
(4) And freeze-drying to obtain the rod-shaped (Ag-Ti-Sc) Ox-graphene antibacterial composite filler.
The graphene is prepared by a hummer method, the mass dispersion of the obtained graphene aqueous solution is 20 wt%, and then 12.5g/L silver nitrate solution and 150mL ethylene glycol are added into the graphene aqueous solution.
The volume ratio of the liquid A to the liquid B is 2: (1.25).
The temperature-programmed temperature-rising rate is 3 ℃/min.
The process for preparing graphene by the hummer method comprises the following steps: firstly, adding 2g of 200-mesh natural crystalline flake graphite and 0.67g of sodium nitrate into a flask, adding 40mL of 99wt.% concentrated sulfuric acid, stirring in an ice-water bath, adding 10g of potassium permanganate, and reacting for 2 hours, wherein; then heating to 35 ℃ and reacting for 1.5h; and adding 80mL of deionized water, heating to 80 ℃ after the dropwise addition is finished, maintaining the temperature for 15min, cooling the reaction liquid to room temperature, adding 100mL of 35w.% hydrogen peroxide, diluting to 500mL by using deionized water, standing for 24h, and filtering and washing to neutrality to obtain the graphene aqueous solution.
The filler obtained by the preparation of example 1 was designated S-5.
Example 6
A preparation method of a water-based antibacterial paint filler comprises the following steps:
(1) Sequentially adding 50mM scandium nitrate solution, 8mM tetrabutyl titanate, 5mM sodium citrate and 2g polyvinylpyrrolidone into a container, magnetically stirring for 40min, and then adding 50mL 2M NaOH in 7min at a rotation speed of 300rpm to obtain solution A;
(2) Preparing a graphene glycol aqueous solution containing silver nitrate: the product is named as liquid B;
(3) Introducing the solution B into the solution A, then placing the solution B into a stainless steel water heating reaction kettle, sealing the water heating reaction kettle, heating to 220 ℃ by a program, keeping for 26 hours, naturally cooling to room temperature, and repeatedly washing and filtering with deionized water and propanol;
(4) And freeze-drying to obtain the rod-shaped (Ag-Ti-Sc) Ox-graphene antibacterial composite filler.
The graphene is prepared by a hummer method, the mass dispersion of the obtained graphene aqueous solution is 30 wt%, and then 15g/L silver nitrate solution and 200mL ethylene glycol are added into the graphene aqueous solution.
The volume ratio of the liquid A to the liquid B is 2: (1.5).
The temperature-programmed temperature-rising rate is 4 ℃/min.
The process for preparing graphene by the hummer method comprises the following steps: firstly, adding 2g of 200-mesh natural crystalline flake graphite and 0.67g of sodium nitrate into a flask, adding 40mL of 99wt.% concentrated sulfuric acid, stirring in an ice-water bath, adding 10g of potassium permanganate, and reacting for 2 hours, wherein; then heating to 35 ℃ and reacting for 1.5h; and adding 80mL of deionized water, heating to 80 ℃ after the dropwise addition is finished, maintaining the temperature for 15min, cooling the reaction liquid to room temperature, adding 100mL of 35w.% hydrogen peroxide, diluting to 500mL by using deionized water, standing for 24h, and filtering and washing to neutrality to obtain the graphene aqueous solution.
The filler obtained by the preparation of example 1 was designated S-6.
Comparative example 1
A preparation method of a water-based antibacterial paint filler comprises the following steps:
(1) Sequentially adding 7.5mM tetrabutyl titanate, 4.5mM sodium citrate and 1.5g polyvinylpyrrolidone into a container, magnetically stirring for 30min, and then adding 35mL 2M NaOH in 6min at the rotation speed of 250rpm to obtain solution A;
(2) Preparing an aqueous solution containing graphene glycol: the product is named as liquid B;
(3) Introducing the solution B into the solution A, then placing the solution B into a stainless steel water heating reaction kettle, sealing the water heating reaction kettle, heating to 210 ℃ by a program, naturally cooling to room temperature after keeping for 25 hours, and repeatedly washing and filtering with deionized water and propanol;
(4) And freeze-drying to obtain the rod-shaped (Ti-) Ox-graphene antibacterial composite filler.
The graphene is prepared and obtained through a hummer method, the mass dispersion of the obtained graphene aqueous solution is 20 wt%, and then 150mL of ethylene glycol is added into the graphene aqueous solution.
The volume ratio of the liquid A to the liquid B is 2: (1.25).
The temperature-programmed temperature-rising rate is 3 ℃/min.
The process for preparing graphene by the hummer method comprises the following steps: firstly, adding 2g of 200-mesh natural crystalline flake graphite and 0.67g of sodium nitrate into a flask, adding 40mL of 99wt.% concentrated sulfuric acid, stirring in an ice-water bath, adding 10g of potassium permanganate, and reacting for 2 hours, wherein; then heating to 35 ℃ and reacting for 1.5h; and adding 80mL of deionized water, heating to 80 ℃ after the dropwise addition is finished, maintaining the temperature for 15min, cooling the reaction liquid to room temperature, adding 100mL of 35w.% hydrogen peroxide, diluting to 500mL by using deionized water, standing for 24h, and filtering and washing to neutrality to obtain the graphene aqueous solution.
The filler obtained by the preparation of example 1 was designated D-1.
Comparative example 2.
A preparation method of a water-based antibacterial paint filler comprises the following steps:
(1) 7.5mM tetrabutyl titanate, 4.5mM sodium citrate and 1.5g polyvinylpyrrolidone are sequentially added into a container, magnetically stirred for 30min, and then 35mL 2M NaOH is added into the container for 6min at the rotation speed of 250rpm to obtain solution A;
(2) Preparing a graphene glycol aqueous solution containing silver nitrate: the product is named as liquid B;
(3) Introducing the solution B into the solution A, then placing the solution B into a stainless steel water heating reaction kettle, sealing the water heating reaction kettle, heating to 210 ℃ by a program, naturally cooling to room temperature after keeping for 25 hours, and repeatedly washing and filtering with deionized water and propanol;
(4) And freeze-drying to obtain the rod-shaped (Ag-Ti) Ox-graphene antibacterial composite filler.
The graphene is prepared by a hummer method, the mass dispersion of the obtained graphene aqueous solution is 20 wt%, and then 12.5g/L silver nitrate solution and 150mL ethylene glycol are added into the graphene aqueous solution.
The volume ratio of the liquid A to the liquid B is 2: (1.25).
The temperature-programmed temperature-rising rate is 3 ℃/min.
The process for preparing graphene by the hummer method comprises the following steps: firstly, adding 2g of 200-mesh natural crystalline flake graphite and 0.67g of sodium nitrate into a flask, adding 40mL of 99wt.% concentrated sulfuric acid, stirring in an ice-water bath, adding 10g of potassium permanganate, and reacting for 2 hours, wherein; then heating to 35 ℃ and reacting for 1.5h; and adding 80mL of deionized water, heating to 80 ℃ after the dropwise addition is finished, maintaining the temperature for 15min, cooling the reaction liquid to room temperature, adding 100mL of 35w.% hydrogen peroxide, diluting to 500mL by using deionized water, standing for 24h, and filtering and washing to neutrality to obtain the graphene aqueous solution.
The filler obtained by the preparation of example 1 was designated D-2.
Comparative example 3.
A preparation method of a water-based antibacterial paint filler comprises the following steps:
(1) 45mM scandium nitrate solution, 7.5mM tetrabutyl titanate, 4.5mM sodium citrate and 1.5g polyvinylpyrrolidone are sequentially added into a container, magnetically stirred for 30min, and then 35mL 2M NaOH is added in 6min at the rotation speed of 250rpm to obtain solution A;
(2) Preparing an aqueous solution containing graphene glycol: the product is named as liquid B;
(3) Introducing the solution B into the solution A, then placing the solution B into a stainless steel water heating reaction kettle, sealing the water heating reaction kettle, heating to 210 ℃ by a program, naturally cooling to room temperature after keeping for 25 hours, and repeatedly washing and filtering with deionized water and propanol;
(4) And freeze-drying to obtain the rod-shaped (Ti-Sc) Ox-graphene antibacterial composite filler.
The graphene is prepared by a hummer method, the mass dispersion of the obtained graphene aqueous solution is 20 wt%, and then 12.5g/L silver nitrate solution and 150mL ethylene glycol are added into the graphene aqueous solution.
The volume ratio of the liquid A to the liquid B is 2: (1.25).
The temperature-programmed temperature-rising rate is 3 ℃/min.
The process for preparing graphene by the hummer method comprises the following steps: firstly, adding 2g of 200-mesh natural crystalline flake graphite and 0.67g of sodium nitrate into a flask, adding 40mL of 99wt.% concentrated sulfuric acid, stirring in an ice-water bath, adding 10g of potassium permanganate, and reacting for 2 hours, wherein; then heating to 35 ℃ and reacting for 1.5h; and adding 80mL of deionized water, heating to 80 ℃ after the dropwise addition is finished, maintaining the temperature for 15min, cooling the reaction liquid to room temperature, adding 100mL of 35w.% hydrogen peroxide, diluting to 500mL by using deionized water, standing for 24h, and filtering and washing to neutrality to obtain the graphene aqueous solution.
The filler obtained by the preparation of example 1 was designated D-3.
Examples 1-6 above are prepared by preparing filler, wherein examples 1 and 6 are the end points, examples 2-5 are the concentrations of Sc doped respectively corresponding to different concentrations, and testing their UV-Vis, see FIG. 4, compared to D-1, with increasing Sc, the light absorption curve is red-coated, the absorbance and absorption wavelength are both significantly increased, wherein the Sc doped amount of S-4 is most suitable, which is probably due to Sc ions entering TiO by diffusion and migration during hydrothermal process 2 Lattice and partially substitute for Ti 4+ And thus generates lattice defects, while TiO 2 Forming a hybrid energy band in the band gap and combining with TiO 2 The conduction bands of the photon-generated electrons are overlapped, so that the energy required by the transition of the photon-generated electrons to the conduction bands is smaller than that of the intrinsic absorption band, photons with smaller energy can excite the photon-generated electrons to generate transition, namely waves with longer wavelength can be absorbed, the spectrum is red shifted, the photoresponse range of the photon-generated electrons is widened, and the sterilization efficiency is further improved. In addition, the D-1~D-3 filler corresponds to Ti-graphene, (Ag-Ti) Ox-graphene, (Ti-Sc) Ox-graphene respectively, and the absorption spectrum of the filler is shown in figure 5. Then, the fillers prepared in S-1, S-6, S-4 and comparative examples 1-3 were used as raw materials and added into fluorine-containing paint for sterilization test, the inhibition zone is shown in figure 1, wherein the paint prepared in example 4 has more excellent sterilization effect.
To test the effect of Sc on stability, full spectrum low pressure ammonia arc lamps were used to simulate sunlight, wherein the coatings prepared from S-4, D-1, D-2, and D-3 had sterilization rates of 98.3%, 26.3%, 56.5%, and 48.3%, respectively, and the coatings prepared from S-4, D-1, D-2, and D-3 had sterilization rates of 98.1%, 22.3%, 54.2%, and 46.9%, respectively, for E.coli, and it was apparent that silver was superior to Sc in that Ag acted on the cell membrane to directly destroy the bacterial cell membrane, resulting in exudation of cell contents, and also could be associated with nuclei in cytoplasmAcid binding, inactivation of the cells, and slow release of Ag during use + Since the cell membrane of the microorganism is often negatively charged, ag+ can be firmly adsorbed on the cell membrane by means of coulomb attraction, and Ag + The bacterial protein can further penetrate through the cell wall to enter the bacteria and react with sulfhydryl groups in the bacteria to solidify the bacterial protein, and destroy the activity of cell synthetase of the bacteria, so that the cells lose the division and proliferation capacity and die. And then testing the sterilization stability of S-4, D-1, D-2 and D-3, wherein the sterilization effect is not obviously changed after the S-4 and the D-3 are irradiated for 100 hours, the change rate is lower than 3.2 percent, and the sterilization effect is obviously changed and the change rate is more than 12.2 percent after the D-1 and the D-2 are irradiated for 100 hours.
Although the present invention has been described by way of example with reference to the preferred embodiments, the present invention is not limited to the specific embodiments, and may be modified appropriately within the scope of the present invention.

Claims (9)

1. The water-based graphene antibacterial building coating is characterized by comprising the following raw materials in parts by weight:
40-70 parts of fluorine-containing styrene-acrylic emulsion;
2-10 parts of rod-shaped (Ag-Ti-Sc) Ox-graphene antibacterial composite filler;
0.2-0.5 part of defoaming agent;
0.5-8 parts of film forming auxiliary agent;
1.0 to 3.0 portions of flatting agent;
0.3-0.6 part of dispersing agent;
60-80 parts of deionized water;
the rod-shaped (Ag-Ti-Sc) Ox-graphene antibacterial composite filler is prepared by the following steps:
(1) Sequentially adding 40-50mM scandium nitrate solution, 7-8mM tetrabutyl titanate, 4-5mM sodium citrate and 1-2g polyvinylpyrrolidone into a container, magnetically stirring for 20-40min, and then adding 20-50mL 2M NaOH in 5-7min at 200-300rpm to obtain solution A;
(2) Preparing a graphene glycol aqueous solution containing silver nitrate: the product is named as liquid B;
(3) Introducing the solution B into the solution A, then placing the solution B into a stainless steel water heating reaction kettle, sealing the water heating reaction kettle, heating to 200-220 ℃ by a program, keeping the temperature for 24-26 hours, naturally cooling to room temperature, and repeatedly washing and filtering with deionized water and propanol;
(4) And freeze-drying to obtain the rod-shaped (Ag-Ti-Sc) Ox-graphene antibacterial composite filler.
2. The aqueous graphene antibacterial building coating according to claim 1, wherein the preparation method of the fluorine-containing styrene-acrylic emulsion is as follows:
(a) Adding acrylic ester monomers and styrene into an aqueous solution containing an emulsifier, and performing ultrasonic dispersion for 20-30min to obtain a pre-emulsion, wherein the addition amount of the emulsifier accounts for 30-50% of the total mass of the emulsifier;
(b) Heating a three-neck flask to 75-80 ℃, adding an initiator, wherein the addition amount of the initiator accounts for 1/3-1/2 of the total mass of the initiator, stirring for 10-20min, then dropwise adding a pre-emulsion of 1/3-1/2, continuously adding for 50-70min, and keeping the temperature at 75-80 ℃ until blue fluorescence appears, and then keeping the temperature to obtain a pre-polymerization solution;
(c) Adding fluoromonomer, residual initiator, residual emulsifier and residual pre-emulsion into the pre-polymerization solution, and stirring at 75-80 ℃ for 1-3 hours;
(d) Adding ammonia water to regulate pH value to 7-7.5, cooling to room temperature, filtering and discharging to obtain the fluorine-containing styrene-acrylic emulsion.
3. The aqueous graphene antibacterial building coating according to claim 2, wherein the acrylic monomer comprises at least one of methyl acrylate, ethyl acrylate, butyl acrylate, hydroxyethyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate and hydroxyethyl methacrylate.
4. The aqueous graphene antibacterial building coating according to claim 2, wherein the fluoromonomer is at least one selected from trifluoroethyl acrylate, trifluoroethyl methacrylate, hexafluorobutyl acrylate, dodecafluoroheptyl methacrylate and hexafluorobutyl methacrylate.
5. An aqueous graphene antibacterial architectural coating according to claim 2, wherein the emulsifier is selected from at least one of sodium dodecyl sulphate and sodium dodecyl benzene sulfonate.
6. An aqueous graphene antibacterial architectural coating according to claim 2, wherein the initiator is selected from at least one of ammonium persulfate, potassium persulfate, sodium persulfate, and azobisisobutyronitrile.
7. The aqueous graphene antibacterial building coating according to claim 1, wherein the graphene is prepared by a hummer method, the mass dispersion of the obtained graphene aqueous solution is 10-30wt.%, and then 10-15g/L silver nitrate solution and 100-200mL ethylene glycol are added to the graphene aqueous solution.
8. The aqueous graphene antibacterial building coating as claimed in claim 1, wherein the volume ratio of the liquid a to the liquid B is 2: (1-1.5).
9. The aqueous graphene antibacterial architectural coating of claim 1, wherein the temperature programming rate is 2-4 ℃/min.
CN202310819175.4A 2023-07-05 2023-07-05 Water-based graphene antibacterial building coating Pending CN116640482A (en)

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Publication number Priority date Publication date Assignee Title
CN103263904A (en) * 2013-05-08 2013-08-28 上海纳米技术及应用国家工程研究中心有限公司 Preparation method of scandium doped titanium dioxide nano-belts for photocatalysis
WO2016095358A1 (en) * 2014-12-18 2016-06-23 中山大学 Method for preparing graphene/silver/titanium dioxide composite
US20190311861A1 (en) * 2017-03-18 2019-10-10 The King Abdulaziz City For Science And Technology TiO2-GRAPHENE-SILVER HYBRID NANOCOMPOSITE AND A METHOD OF PREPARATION THEREOF
CN115044256A (en) * 2022-05-20 2022-09-13 浙江衢州巨塑化工有限公司 Modified fluorocarbon coating

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103263904A (en) * 2013-05-08 2013-08-28 上海纳米技术及应用国家工程研究中心有限公司 Preparation method of scandium doped titanium dioxide nano-belts for photocatalysis
WO2016095358A1 (en) * 2014-12-18 2016-06-23 中山大学 Method for preparing graphene/silver/titanium dioxide composite
US20190311861A1 (en) * 2017-03-18 2019-10-10 The King Abdulaziz City For Science And Technology TiO2-GRAPHENE-SILVER HYBRID NANOCOMPOSITE AND A METHOD OF PREPARATION THEREOF
CN115044256A (en) * 2022-05-20 2022-09-13 浙江衢州巨塑化工有限公司 Modified fluorocarbon coating

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