CN108997876B - Antibacterial antifouling mosquito-repellent insect-preventing water-based wood coating and preparation method thereof - Google Patents

Antibacterial antifouling mosquito-repellent insect-preventing water-based wood coating and preparation method thereof Download PDF

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CN108997876B
CN108997876B CN201811048886.1A CN201811048886A CN108997876B CN 108997876 B CN108997876 B CN 108997876B CN 201811048886 A CN201811048886 A CN 201811048886A CN 108997876 B CN108997876 B CN 108997876B
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CN108997876A (en
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卢超
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Chengdu Polytechnic
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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
    • C09D133/00—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 only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
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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
    • C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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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
    • C09D5/16—Antifouling paints; Underwater paints
    • C09D5/1606—Antifouling paints; Underwater paints characterised by the anti-fouling agent
    • C09D5/1612—Non-macromolecular compounds
    • C09D5/1618—Non-macromolecular compounds inorganic
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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
    • C09D5/16—Antifouling paints; Underwater paints
    • C09D5/1656—Antifouling paints; Underwater paints characterised by the film-forming substance
    • C09D5/1662—Synthetic film-forming substance
    • C09D5/1668—Vinyl-type polymers
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    • 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
    • C09D5/16—Antifouling paints; Underwater paints
    • C09D5/1687—Use of special additives
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    • 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
    • C09D5/18—Fireproof paints including high temperature resistant paints
    • 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
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
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    • C08L2205/00—Polymer mixtures characterised by other features
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Abstract

The invention discloses an antibacterial antifouling mosquito-repellent insect-proof aqueous wood coating and a preparation method thereof, wherein the aqueous wood coating comprises the following components in parts by weight: 24-30 parts of water-based polyacrylate; 7-12 parts of waterborne polyurethane; 1.5-2.5 parts of water-based fluorocarbon resin; 0.5-0.8 part of cosolvent; 3-6 parts of deionized water; 1.0-2.5 parts of silicone oil; 0.1-0.3 part of nano zinc oxide; 0.6-1.0 part of multiple modified nano titanium dioxide; 0.05-0.15 part of surfactant; 0.6-1.8 parts of absolute ethyl alcohol. The water-based wood coating has good effects of resisting bacteria and dirt, preventing insects and repelling mosquitoes and cleaning air, and meanwhile, a coating film of the water-based wood coating also has good performances of adhesion, toughness, water resistance, wear resistance, weather resistance and the like.

Description

Antibacterial antifouling mosquito-repellent insect-preventing water-based wood coating and preparation method thereof
Technical Field
The invention relates to the technical field of coatings, and particularly relates to an antibacterial antifouling mosquito-repellent insect-proof water-based wood coating and a preparation method thereof.
Background
Currently, due to the increasing environmental protection pressure, the state has developed a plurality of emission reduction policies, and the "water-based" of the wood coatings is urgent. In English and Germany countries, the water-based wood coating accounts for 80% -90% of the market share in the whole coating industry, but is less than 20% in China. The water-based wood coating takes water as a medium, basically does not contain toxic and harmful substances such as formaldehyde, benzene series, VOC, heavy metal and the like, can improve the indoor environment and the living comfort, has the advantages of energy conservation, emission reduction, low carbon, environmental protection and the like, and has great market application demand.
In the existing water-based paint, the acrylic paint has lower production cost, better film forming property, adhesive force, weather resistance and stain resistance, but has the defects of low hardness and hot stickiness and cold brittleness; although the waterborne polyurethane coating product has high cost and poor water resistance and chemical resistance of a coating film, the waterborne polyurethane coating has excellent wear resistance and flexibility; the water-based fluorocarbon coating has excellent light and color retention, super weather resistance, water resistance, stain resistance, flame retardance and chemical resistance, and has excellent adhesive force and ageing resistance.
At present, the water-based wood coating gradually develops towards the direction of a composite coating, and with the popularization of the water-based wood coating and the rise of the personalized requirements of consumers, the functional application of the coating shows an increasing trend.
Disclosure of Invention
The invention aims to solve the technical problems in the existing water-based paint, and provides the water-based wood paint with the functions of antibiosis, antifouling, insect prevention, mosquito repelling and air cleaning, and the paint film has good adhesive force, toughness, water resistance, wear resistance, weather resistance and the like.
The invention also aims to provide a preparation method of the water-based wood coating.
In order to solve the technical problems, the invention provides the following technical scheme:
the antibacterial antifouling mosquito-repellent insect-proof aqueous wood coating is characterized by comprising the following components in parts by weight:
24-30 parts of water-based polyacrylate;
7-12 parts of waterborne polyurethane;
1.5-2.5 parts of water-based fluorocarbon resin;
0.5-0.8 part of cosolvent;
3-6 parts of deionized water;
1.0-2.5 parts of silicone oil;
0.1-0.3 part of nano zinc oxide;
0.6-1.0 part of multiple modified nano titanium dioxide;
0.05-0.15 part of surfactant;
0.6-1.8 parts of absolute ethyl alcohol.
In the above technical scheme, further, the preparation process of the multiple modified nano titanium dioxide comprises the following steps:
(1) dissolving 0.8-1.2 parts of titanyl sulfate, 0.005-0.035 part of copper nitrate, 0.01-0.04 part of ammonium molybdate tetrahydrate and 1.5-2.0 parts of ammonium carbonate in 40-50 parts of deionized water according to the parts by weight, placing the mixed solution in a closed reaction kettle, carrying out hydrothermal treatment at the temperature of 120-160 ℃ for 12-24h, centrifugally washing and drying the product obtained after the thermal treatment, and then calcining at the temperature of 500-700 ℃ for 1-3h to obtain the Mo-Cu-N co-doped nano TiO2；
(2) 0.4 to 0.8 portion of hydroxideDissolving sodium in 40-50 parts of deionized water to obtain a sodium hydroxide solution, and then co-doping the Mo-Cu-N obtained in the step (1) with the nano TiO2Adding the mixture into a sodium hydroxide solution, uniformly stirring to obtain a mixed solution, carrying out hydrothermal treatment for 3-6h at 90-120 ℃ in a closed reaction kettle, washing and drying a product obtained after the thermal treatment to obtain the Mo-Cu-N co-doped nano TiO with hydroxylated surface2；
(3) Adding the graphene oxide dispersion liquid, ascorbic acid, ethylene glycol, ethanol and superfine tourmaline powder into deionized water according to the weight parts, uniformly stirring to obtain turbid liquid, and then carrying out surface hydroxylation Mo-Cu-N co-doping on the nano TiO obtained in the step (2)2Adding the suspension into a closed reaction kettle, carrying out hydrothermal treatment at 140-180 ℃ for 4-8h, carrying out centrifugal washing on a product obtained after the thermal treatment, and carrying out vacuum drying at 40-60 ℃ to obtain multiple modified nano titanium dioxide;
in the step (3), the graphene oxide dispersion liquid, ascorbic acid, ethylene glycol, ethanol, ultrafine tourmaline powder, deionized water and surface hydroxylated Mo-Cu-N co-doped nano TiO2The weight ratio of (2-5): 0.3-0.8: 0.1-0.3: 4-8: 0.1-0.2: 35-45: 1; the concentration of the graphene oxide dispersion liquid is 1-10 mg/ml; the particle size of the tourmaline powder is not less than 2000 meshes.
In the above technical solution, further, the cosolvent is a mixture of alcohol amine and ammonia water.
In the above technical scheme, further, the silicone oil is one or more of methyl silicone oil, ethyl silicone oil, phenyl silicone oil, methylphenyl silicone oil, methyl ethoxy silicone oil and methyl vinyl silicone oil.
In the above technical solution, further, the surfactant is one or more of span 60, span 80, and glyceryl monostearate.
In the technical scheme, the waterborne wood coating further comprises 2-4 parts by weight of wood wax oil.
In the technical scheme, the waterborne wood coating further comprises 2-5 parts by weight of natural plant essential oil, wherein the natural plant essential oil is at least two of eucalyptus oil, camphor oil and litsea cubeba oil.
In the technical scheme, further, 0.1-0.4 part of nano diatomite is also included in the aqueous wood coating according to the parts by weight.
The preparation method of the antibacterial antifouling mosquito-repellent insect-preventing water-based wood coating comprises the following steps:
(1) preparing an aqueous composite emulsion: mixing and stirring the water-based polyacrylate and the cosolvent, then adding the water-based polyurethane, the water-based fluorocarbon resin, the natural plant essential oil, the deionized water, the wood wax oil and the silicone oil, and uniformly stirring to obtain a water-based composite emulsion;
(2) preparing inorganic nano composite slurry: mixing a surfactant and absolute ethyl alcohol, heating to 50-60 ℃, stirring to form a transparent solution, adding nano zinc oxide, multiple modified nano titanium dioxide and nano kieselguhr into the transparent solution, and uniformly grinding the obtained mixture in a sand mill to obtain inorganic nano composite slurry;
(3) preparing the water-based wood coating: adding the inorganic nano composite slurry prepared in the step (2) into the aqueous composite emulsion prepared in the step 1), and uniformly stirring to obtain a finished product.
In the step (2), in the preparation process of the multiple modified nano titanium dioxide, Mo-Cu and N are firstly adopted to respectively react with TiO2The Ti and O sites of the titanium dioxide are doped to reduce TiO2The forbidden band width of TiO is enlarged2Light response range of (2), TiO2The ultraviolet light-catalyzed antibacterial agent not only has ultraviolet light catalytic activity, but also has a certain photocatalytic sterilization function in a visible light region; ascorbic acid and ethylene glycol are used as a composite reducing agent of graphene oxide, and the graphene oxide can be fully reduced into high-conductivity graphene through high-temperature and high-pressure hydrothermal treatment; for co-doped TiO2After surface hydroxylation modification treatment, the TiO is effectively enhanced2The prepared graphene with high conductivity and the superfine tourmaline powder pass through TiO2Rich active bond and TiO on surface2A stable complex is formed. The multiple modified nano titanium dioxide utilizes the high conductivity of graphene and the superfine tourmaline powderHowever, the permanent polarization electric field can effectively inhibit the recombination of titanium dioxide photo-generated electron-hole pairs and improve the carrier concentration and the electron transmission rate. Mo-Cu-N co-doping and graphene-tourmaline powder co-composite multiple modification are carried out on the nano titanium dioxide, and the performance of the nano titanium dioxide for photocatalytic degradation of formaldehyde and other pollutants is synergistically enhanced, so that the effects of antibiosis, decontamination and air purification of the coating are improved.
The invention has the following beneficial effects:
(1) the aqueous fluorocarbon resin adopted by the invention has excellent water resistance, stain resistance, weather resistance and chemical resistance (3-8 times of the performances of other common resins), also has the advantages of high film-forming transparency, strong adhesive force and good flame retardance (the flame-retardant temperature reaches 300 ℃), has good intermiscibility with aqueous polyacrylate and aqueous polyurethane, can promote the curing and molding of a paint film of the coating, and improves the surface molding quality of the paint film;
(2) according to the invention, inorganic nano composite particles such as nano zinc oxide, multiple modified nano titanium dioxide and nano kieselguhr are hybridized and crosslinked with the polyacrylate/polyurethane/fluorocarbon resin composite emulsion, so that the hardness, wear resistance, scratch resistance and ultraviolet aging resistance of the coating film can be effectively improved;
(3) Mo-Cu-N co-doping modification and high-conductivity graphene-permanent spontaneous electric polarization superfine tourmaline powder co-compounding modification are carried out on nano titanium dioxide, so that TiO is reduced2The forbidden band width of the TiO is enhanced2Electron transport rate of (3), promoting TiO2Separation of photogenerated electron-hole pairs, increased carrier concentration, and broadened TiO2The light response range of the nano TiO material is ensured to be photocatalytic in an ultraviolet light area and a partial visible light area, and the nano TiO is improved2The performance of photocatalytic degradation of pollutants improves the effects of antibiosis, decontamination and air purification of the coating;
(4) the special faint scent emitted by the pure natural plant essential oil added in the coating has the functions of insect prevention, mosquito repelling, antibiosis and deodorization, and can improve the indoor air quality; meanwhile, porous diatomite with large porosity and strong absorbability is used as an adsorption carrier of the plant essential oil, so that the fragrance is slowly released, and the effects of repelling mosquitoes, preventing insects, resisting bacteria and deodorizing are prolonged;
(5) the paint adopts nontoxic, environment-friendly and good-permeability natural wood wax oil to be tightly combined with wood fibers, so that deep moistening and maintenance are provided for wood, the surface hardness of the wood is enhanced, and the wood has water resistance, stain resistance, cracking resistance, wear resistance and scuffing resistance.
Detailed Description
The following will explain the specific embodiments and beneficial effects of the aqueous wood coating of the present invention in detail with reference to specific examples and comparative examples. In the following examples and comparative examples, the respective raw material ratios are by weight.
Example 1
The antibacterial antifouling, mosquito-repellent and insect-proof waterborne wood coating in the embodiment is prepared by the following preparation process:
(1) preparing an aqueous composite emulsion: mixing 25 parts of waterborne polyacrylate and 0.6 part of cosolvent, stirring, adding 7 parts of waterborne polyurethane, 1.5 parts of waterborne fluorocarbon resin, 2 parts of natural plant essential oil, 3 parts of deionized water, 2 parts of wood wax oil and 1 part of silicone oil, and uniformly stirring to obtain a waterborne composite emulsion;
in the embodiment, the cosolvent comprises 0.1 part of alcohol amine and 0.5 part of ammonia water; the natural plant essential oil comprises 1 part of eucalyptus oil and 1 part of litsea cubeba oil; the silicone oil comprises 0.5 part of methyl silicone oil and 0.5 part of ethyl silicone oil;
(2) preparing inorganic nano composite slurry: mixing 0.05 part of surfactant and 1.2 parts of absolute ethyl alcohol, heating to 50 ℃, stirring to form a transparent solution, adding 0.25 part of nano zinc oxide, 0.6 part of multiple modified nano titanium dioxide and 0.2 part of nano kieselguhr into the transparent solution, and uniformly grinding the obtained mixture in a sand mill to obtain inorganic nano composite slurry;
in the embodiment, the surfactant comprises 0.03 part of span 60 and 0.02 part of span 80;
(3) preparing the water-based wood coating: and (3) adding the inorganic nano composite slurry prepared in the step (2) into the aqueous composite emulsion prepared in the step (1), and uniformly stirring to obtain a finished product.
Wherein the preparation process of the multiple modified nano titanium dioxide in the step (2) is as follows:
① mixing 1 part of titanyl sulfate (TiOSO)4) 0.01 part of copper nitrate (Cu (NO)3)2) 0.02 part of ammonium molybdate tetrahydrate ((NH)4)6Mo7O24·4H2O) and 1.5 parts of ammonium carbonate are dissolved in 45 parts of deionized water, the mixed solution is placed in a closed reaction kettle and subjected to hydrothermal treatment at 130 ℃ for 24 hours, the product is centrifugally washed and dried, and then calcined at 700 ℃ for 1.5 hours to obtain the Mo-Cu-N co-doped nano TiO2；
② dissolving 0.5 part of sodium hydroxide in 40 parts of deionized water to obtain sodium hydroxide solution, and then adding the co-doped nano TiO obtained in the step 1) to the solution2Adding the mixture into a sodium hydroxide solution, placing the obtained mixed solution into a closed reaction kettle, carrying out hydrothermal treatment at 110 ℃ for 3 hours, washing and drying the obtained product to obtain the surface hydroxylated Mo-Cu-N co-doped nano TiO2；
③ adding the graphene oxide dispersion liquid, ascorbic acid, ethylene glycol, ethanol and ultrafine tourmaline powder into deionized water, stirring uniformly to obtain a suspension, and then adding the surface hydroxylated Mo-Cu-N co-doped nano TiO obtained in step ②2Adding the turbid liquid, placing the turbid liquid in a closed reaction kettle, carrying out hydrothermal treatment for 6 hours at 160 ℃, centrifugally washing a product, and drying the product in vacuum at 45 ℃ to obtain the Mo-Cu-N/graphene/tourmaline multiple modified nano TiO2。
In the step ③, the graphene oxide dispersion liquid, ascorbic acid, ethylene glycol, ethanol, ultrafine tourmaline powder, deionized water, and surface-hydroxylated Mo-Cu-N co-doped nano TiO2The weight ratio is 4: 0.6: 0.1: 6: 0.12: 45: 1; the concentration of the graphene oxide dispersion liquid is 1-10 mg/ml; the particle size of the superfine tourmaline powder is 2500 meshes.
Example 2
The antibacterial antifouling, mosquito-repellent and insect-proof waterborne wood coating in the embodiment is prepared by the following preparation process:
(1) preparing an aqueous composite emulsion: mixing 24 parts of waterborne polyacrylate and 0.5 part of cosolvent, stirring, adding 10 parts of waterborne polyurethane, 2.5 parts of waterborne fluorocarbon resin, 4 parts of natural plant essential oil, 4 parts of deionized water, 3 parts of wood wax oil and 2 parts of silicone oil, and uniformly stirring to obtain a waterborne composite emulsion;
in the embodiment, the cosolvent comprises 0.2 part of alcohol amine and 0.3 part of ammonia water; the natural plant essential oil comprises 2 parts of eucalyptus oil and 2 parts of camphor oil; the silicone oil comprises 0.5 part of methyl silicone oil, 0.5 part of ethyl silicone oil and 1 part of phenyl silicone oil;
(2) preparing inorganic nano composite slurry: mixing 0.1 part of surfactant and 1 part of absolute ethyl alcohol, heating to 60 ℃, stirring to form a transparent solution, adding 0.2 part of nano zinc oxide, 0.8 part of multiple modified nano titanium dioxide and 0.3 part of nano kieselguhr into the transparent solution, and uniformly grinding the obtained mixture in a sand mill to obtain inorganic nano composite slurry;
in this embodiment, the surfactant comprises 0.05 parts of span 60 and 0.05 parts of glyceryl monostearate;
(3) preparing the water-based wood coating: and (3) adding the inorganic nano composite slurry prepared in the step (2) into the aqueous composite emulsion prepared in the step (1), and uniformly stirring to obtain a finished product.
Wherein, the preparation process of the multiple modified nano titanium dioxide in the step (2) is as follows:
① dissolving 1 part of titanyl sulfate, 0.015 part of copper nitrate, 0.04 part of ammonium molybdate tetrahydrate and 1.8 parts of ammonium carbonate in 48 parts of deionized water, placing the mixed solution in a closed reaction kettle, carrying out hydrothermal treatment at 150 ℃ for 13h, centrifugally washing and drying the product, and calcining at 600 ℃ for 3h to obtain the Mo-Cu-N co-doped nano TiO2；
② dissolving 0.6 part of sodium hydroxide in 45 parts of deionized water to obtain sodium hydroxide solution, and then adding the co-doped nano TiO obtained in the step 1) to the solution2Adding the mixture into a sodium hydroxide solution, placing the obtained mixed solution into a closed reaction kettle, carrying out hydrothermal treatment for 4 hours at 105 ℃, washing and drying the obtained product to obtain the surface hydroxylated Mo-Cu-N co-doped nano TiO2；
③ adding the graphene oxide dispersion liquid, ascorbic acid, ethylene glycol, ethanol and ultrafine tourmaline powder into deionized water, stirring uniformly to obtain a suspension, and then adding the surface hydroxylated Mo-Cu-N co-doped nano TiO obtained in step ②2Adding the suspension, and sealingCarrying out hydrothermal treatment for 8h at 150 ℃ in a reaction kettle, centrifugally washing the product, and drying the product in vacuum at 50 ℃ to obtain the Mo-Cu-N/graphene/tourmaline multiple modified nano TiO2。
In the step ③, the graphene oxide dispersion liquid, ascorbic acid, ethylene glycol, ethanol, ultrafine tourmaline powder, deionized water, and surface-hydroxylated Mo-Cu-N co-doped nano TiO2The weight ratio is 4: 0.7: 0.2: 7: 0.16: 42: 1; the concentration of the graphene oxide dispersion liquid is 1-10 mg/ml; the granularity of the superfine tourmaline powder is 3000 meshes.
Example 3
The antibacterial antifouling, mosquito-repellent and insect-proof waterborne wood coating in the embodiment is prepared by the following preparation process:
(1) preparing an aqueous composite emulsion: mixing 30 parts of waterborne polyacrylate and 0.8 part of cosolvent, stirring, adding 12 parts of waterborne polyurethane, 2 parts of waterborne fluorocarbon resin, 5 parts of natural plant essential oil, 6 parts of deionized water, 4 parts of wood wax oil and 2.5 parts of silicone oil, and uniformly stirring to obtain a waterborne composite emulsion;
in the embodiment, the cosolvent comprises 0.3 part of alcohol amine and 0.5 part of ammonia water; the natural plant essential oil comprises 2 parts of eucalyptus oil, 2 parts of camphor oil and 1 part of litsea cubeba oil; the silicone oil comprises 1 part of ethyl silicone oil, 1 part of phenyl silicone oil and 0.5 part of methyl vinyl silicone oil;
(2) preparing inorganic nano composite slurry: mixing 0.12 part of surfactant and 1.8 parts of absolute ethyl alcohol, heating to 55 ℃, stirring to form a transparent solution, adding 0.1 part of nano zinc oxide, 1.4 parts of multiple modified nano titanium dioxide and 0.4 part of nano kieselguhr into the transparent solution, and uniformly grinding the obtained mixture in a sand mill to obtain inorganic nano composite slurry;
in this embodiment, the surfactant comprises 0.04 parts of span 60, 0.04 parts of span 80, and 0.04 parts of glyceryl monostearate;
(3) preparing the water-based wood coating: and (3) adding the inorganic nano composite slurry prepared in the step (2) into the aqueous composite emulsion prepared in the step (1), and uniformly stirring to obtain a finished product.
Wherein, the preparation process of the multiple modified nano titanium dioxide in the step (2) is as follows:
① dissolving 0.8-1.2 parts of titanyl sulfate, 0.03 part of copper nitrate, 0.01 part of ammonium molybdate tetrahydrate and 2 parts of ammonium carbonate in 42 parts of deionized water, placing the mixed solution in a closed reaction kettle, carrying out hydrothermal treatment at 140 ℃ for 18h, centrifugally washing and drying the product, and calcining at 650 ℃ for 2h to obtain the Mo-Cu-N co-doped nano TiO2；
② dissolving 0.8 part of sodium hydroxide in 48 parts of deionized water to obtain sodium hydroxide solution, and then adding the co-doped nano TiO obtained in the step 1) to the solution2Adding the mixture into a sodium hydroxide solution, placing the obtained mixed solution into a closed reaction kettle, carrying out hydrothermal treatment for 6 hours at the temperature of 100 ℃, washing and drying the obtained product to obtain the surface hydroxylated Mo-Cu-N co-doped nano TiO2；
③ adding the graphene oxide dispersion liquid, ascorbic acid, ethylene glycol, ethanol and ultrafine tourmaline powder into deionized water, stirring uniformly to obtain a suspension, and then adding the surface hydroxylated Mo-Cu-N co-doped nano TiO obtained in step ②2Adding the suspension, placing the suspension in a closed reaction kettle, carrying out hydrothermal treatment at 170 ℃ for 5 hours, centrifugally washing the product, and drying the product in vacuum at 52 ℃ to obtain the Mo-Cu-N/graphene/tourmaline multiple modified nano TiO2。
In the step ③, the graphene oxide dispersion liquid, ascorbic acid, ethylene glycol, ethanol, ultrafine tourmaline powder, deionized water, and surface-hydroxylated Mo-Cu-N co-doped nano TiO2The weight ratio is 3: 0.4: 0.2: 5: 0.15: 40: 1; the concentration of the graphene oxide dispersion liquid is 1-10 mg/ml; the granularity of the superfine tourmaline powder is 3500 meshes.
Comparative example 1
The difference between the comparative example and the above example 3 is that the multiple modified nano titanium dioxide in the step (2) of the above example is replaced by a simple mixture of nano titanium dioxide, nano graphene and ultrafine tourmaline powder, and other preparation processes are kept unchanged, and the specific preparation process of the aqueous wood coating is as follows:
(1) preparing an aqueous composite emulsion: mixing 30 parts of waterborne polyacrylate and 0.8 part of cosolvent, stirring, adding 12 parts of waterborne polyurethane, 2 parts of waterborne fluorocarbon resin, 5 parts of natural plant essential oil, 6 parts of deionized water, 4 parts of wood wax oil and 2.5 parts of silicone oil, and uniformly stirring to obtain a waterborne composite emulsion;
in the comparative example, the cosolvent comprises 0.3 part of alcohol amine and 0.5 part of ammonia water; the natural plant essential oil comprises 2 parts of eucalyptus oil, 2 parts of camphor oil and 1 part of litsea cubeba oil; the silicone oil comprises 1 part of ethyl silicone oil, 1 part of phenyl silicone oil and 0.5 part of methyl vinyl silicone oil;
(2) preparing inorganic nano composite slurry: mixing 0.12 part of surfactant and 1.8 parts of absolute ethyl alcohol, heating to 55 ℃, stirring to form a transparent solution, adding 0.1 part of nano zinc oxide, 0.08 part of nano graphene, 0.7 part of nano titanium dioxide, 0.1 part of superfine tourmaline powder and 0.4 part of nano diatomite into the transparent solution, and uniformly grinding the mixture in a sand mill to obtain inorganic nano composite slurry;
in this comparative example, the surfactant included 0.04 parts span 60, 0.04 parts span 80, 0.04 parts glyceryl monostearate;
(3) preparing the water-based wood coating: and (3) adding the inorganic nano composite slurry prepared in the step (2) into the aqueous composite emulsion prepared in the step (1), and uniformly stirring to obtain a finished product.
The performance test data of the waterborne wood coatings prepared in the embodiments 1-3 and the comparative example 1 of the invention are shown in the following table:
Figure BDA0001793996730000111
as can be seen from the performance data in the above examples and comparative examples, the coating of the present invention has good antibacterial and sterilizing properties, lasting formaldehyde and toluene purification and purification effects, low VOC and formaldehyde content, good environmental protection properties and good service properties. Simultaneously, through adopting multiple modified nanometer titanium dioxide in the coating of this application, utilize the performance that multiple modified nanometer titanium dioxide has and with the coating in between the good mating reaction of other components, compare in the current conventional mixture that directly adds nanometer titanium dioxide, nanometer graphite alkene, superfine tourmaline powder the wooden furniture coating that obtains, it has better effect on antibiotic, sterilization performance, and formaldehyde, toluene purification and purifying effect persistence.
The present invention has been described in an illustrative rather than a restrictive sense, and it is within the scope of the present invention that certain changes and modifications may be effected therein without departing from the spirit and scope of the invention by one of ordinary skill in the art in light of the teachings of the disclosure.

Claims (8)

1. The antibacterial antifouling mosquito-repellent insect-proof aqueous wood coating is characterized by comprising the following components in parts by weight:
24-30 parts of water-based polyacrylate;
7-12 parts of waterborne polyurethane;
1.5-2.5 parts of water-based fluorocarbon resin;
0.5-0.8 part of cosolvent;
3-6 parts of deionized water;
1.0-2.5 parts of silicone oil;
0.1-0.3 part of nano zinc oxide;
0.6-1.0 part of multiple modified nano titanium dioxide;
0.05-0.15 part of surfactant;
0.6-1.8 parts of absolute ethyl alcohol;
the preparation process of the multiple modified nano titanium dioxide comprises the following steps:
(1) dissolving 0.8-1.2 parts of titanyl sulfate, 0.005-0.035 part of copper nitrate, 0.01-0.04 part of ammonium molybdate tetrahydrate and 1.5-2.0 parts of ammonium carbonate in 40-50 parts of deionized water according to the parts by weight, placing the mixed solution in a closed reaction kettle, carrying out hydrothermal treatment at the temperature of 120-160 ℃ for 12-24h, centrifugally washing and drying the product obtained after the thermal treatment, and then calcining at the temperature of 500-700 ℃ for 1-3h to obtain the Mo-Cu-N co-doped nano TiO2；
(2) Dissolving 0.4-0.8 part of sodium hydroxide in 40-50 parts of deionized water according to parts by weight to obtain a sodium hydroxide solution, and then co-doping the Mo-Cu-N obtained in the step (1) with nano TiO2Adding into sodium hydroxide solution, stirring to obtain mixed solution, performing hydrothermal treatment at 90-120 deg.C for 3-6 hr in a sealed reaction kettle, and performing thermal treatmentWashing and drying the obtained product to obtain the Mo-Cu-N co-doped nano TiO with hydroxylated surface2；
(3) Adding the graphene oxide dispersion liquid, ascorbic acid, ethylene glycol, ethanol and superfine tourmaline powder into deionized water, stirring uniformly to obtain a suspension, and then doping the surface hydroxylated Mo-Cu-N co-doped nano TiO obtained in the step (2)2Adding the suspension into a closed reaction kettle, carrying out hydrothermal treatment at 140-180 ℃ for 4-8h, carrying out centrifugal washing on a product obtained after the thermal treatment, and carrying out vacuum drying at 40-60 ℃ to obtain multiple modified nano titanium dioxide;
in the step (3), the graphene oxide dispersion liquid, ascorbic acid, ethylene glycol, ethanol, ultrafine tourmaline powder, deionized water and surface hydroxylated Mo-Cu-N co-doped nano TiO2The weight ratio of (2-5): 0.3-0.8: 0.1-0.3: 4-8: 0.1-0.2: 35-45: 1; the concentration of the graphene oxide dispersion liquid is 1-10 mg/ml; the particle size of the tourmaline powder is not less than 2000 meshes.
2. The antibacterial antifouling mosquito-repellent insect-proof aqueous wood coating as claimed in claim 1, which is characterized in that: the cosolvent is a mixture of alcohol amine and ammonia water.
3. The antibacterial antifouling mosquito-repellent insect-proof aqueous wood coating as claimed in claim 1, which is characterized in that: the silicone oil is one or more of methyl silicone oil, ethyl silicone oil, phenyl silicone oil, methyl ethoxy silicone oil and methyl vinyl silicone oil.
4. The antibacterial antifouling mosquito-repellent insect-proof aqueous wood coating as claimed in claim 1, which is characterized in that: the surfactant is one or more of span 60, span 80 and glyceryl monostearate.
5. The antibacterial antifouling mosquito-repellent insect-proof aqueous wood coating as claimed in claim 1, which is characterized in that: the waterborne wood coating also comprises 2-4 parts of wood wax oil according to parts by weight.
6. The antibacterial antifouling mosquito-repellent insect-proof aqueous wood coating as claimed in claim 1, which is characterized in that: the water-based wood coating further comprises 2-5 parts of natural plant essential oil in parts by weight, wherein the natural plant essential oil is at least two of eucalyptus oil, camphor oil and litsea cubeba oil.
7. The antibacterial antifouling mosquito-repellent insect-proof aqueous wood coating as claimed in claim 1, which is characterized in that: the waterborne wood coating also comprises 0.1 to 0.4 part of nano diatomite by weight.
8. A preparation method of an antibacterial antifouling mosquito-repellent insect-proof water-based wood paint is characterized by comprising the following steps:
(1) preparing an aqueous composite emulsion: mixing and stirring the water-based polyacrylate and the cosolvent, then adding the water-based polyurethane, the water-based fluorocarbon resin, the natural plant essential oil, the deionized water, the wood wax oil and the silicone oil, and uniformly stirring to obtain a water-based composite emulsion;
(2) preparing inorganic nano composite slurry: mixing a surfactant and absolute ethyl alcohol, heating to 50-60 ℃, stirring to form a transparent solution, adding nano zinc oxide, multiple modified nano titanium dioxide and nano kieselguhr into the transparent solution, and uniformly grinding the obtained mixture in a sand mill to obtain inorganic nano composite slurry;
(3) preparing the water-based wood coating: adding the inorganic nano composite slurry prepared in the step (2) into the aqueous composite emulsion prepared in the step (1), and uniformly stirring to obtain a finished product;
the preparation process of the multiple modified nano titanium dioxide comprises the following steps:
(21) dissolving 0.8-1.2 parts of titanyl sulfate, 0.005-0.035 part of copper nitrate, 0.01-0.04 part of ammonium molybdate tetrahydrate and 1.5-2.0 parts of ammonium carbonate in 40-50 parts of deionized water according to the parts by weight, placing the mixed solution in a closed reaction kettle, carrying out hydrothermal treatment at the temperature of 120-160 ℃ for 12-24h, centrifugally washing and drying the product obtained after the thermal treatment, and then calcining at the temperature of 500-700 ℃ for 1-3h to obtain the Mo-Cu-N co-doped titanium dioxideHetero-nano TiO2；
(22) Dissolving 0.4-0.8 part of sodium hydroxide in 40-50 parts of deionized water according to parts by weight to obtain a sodium hydroxide solution, and then carrying out Mo-Cu-N co-doping on the nano TiO obtained in the step (21)2Adding the mixture into a sodium hydroxide solution, uniformly stirring to obtain a mixed solution, carrying out hydrothermal treatment for 3-6h at 90-120 ℃ in a closed reaction kettle, washing and drying a product obtained after the thermal treatment to obtain the Mo-Cu-N co-doped nano TiO with hydroxylated surface2；
(23) Adding the graphene oxide dispersion liquid, ascorbic acid, ethylene glycol, ethanol and superfine tourmaline powder into deionized water, stirring uniformly to obtain a suspension, and then adding the surface-hydroxylated Mo-Cu-N co-doped nano TiO obtained in the step (22)2Adding the suspension into a closed reaction kettle, carrying out hydrothermal treatment at 140-180 ℃ for 4-8h, carrying out centrifugal washing on a product obtained after the thermal treatment, and carrying out vacuum drying at 40-60 ℃ to obtain multiple modified nano titanium dioxide;
in the step (23), the graphene oxide dispersion liquid, ascorbic acid, ethylene glycol, ethanol, ultrafine tourmaline powder, deionized water, and surface-hydroxylated Mo-Cu-N co-doped nano TiO2The weight ratio of (2-5): 0.3-0.8: 0.1-0.3: 4-8: 0.1-0.2: 35-45: 1; the concentration of the graphene oxide dispersion liquid is 1-10 mg/ml; the particle size of the tourmaline powder is not less than 2000 meshes.
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