CN106590385A - Self-cleaning antifouling organic-inorganic super-amphiphobic polymer coating - Google Patents
Self-cleaning antifouling organic-inorganic super-amphiphobic polymer coating Download PDFInfo
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- CN106590385A CN106590385A CN201611143545.3A CN201611143545A CN106590385A CN 106590385 A CN106590385 A CN 106590385A CN 201611143545 A CN201611143545 A CN 201611143545A CN 106590385 A CN106590385 A CN 106590385A
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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
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
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- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
- C08G18/3802—Low-molecular-weight compounds having heteroatoms other than oxygen having halogens
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- C08G18/3812—Polyhydroxy compounds having fluorine atoms
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/06—Pretreated ingredients and ingredients covered by the main groups C08K3/00 - C08K7/00
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- 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
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
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- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
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- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
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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
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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
- C09D5/1687—Use of special additives
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- 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
- C08K2003/2241—Titanium dioxide
Abstract
The invention discloses a self-cleaning antifouling organic-inorganic super-amphiphobic polymer coating which is prepared from the following raw materials: perfluoroalkyl ethanol, methyl isobutyl ketone, HDI trimer, methyl methacrylate, styrene, hydroxyethyl methacrylate, perfluorooctyl methacrylate, benzoyl peroxide, 25-28 parts of methanol silica sol, propylene glycol methyl ether acetate, titanium dioxide, sodium hexametaphosphate, ethyl orthosilicate, vinyl triethoxysilane, an appropriate amount of ammonia water, an appropriate amount of silane coupling agent KH570, an appropriate amount of methyl hydroxyl silicone oil, an appropriate amount of 10% dibutyltin dilaurate, a dispersant, a leveling agent, a defoamer, an appropriate amount of butyl acetate, an appropriate amount of anhydrous ethanol, and an appropriate amount of deionized water. The super-amphiphobic polymer coating provided by the invention is simple and feasible in preparation method, can be firmly combined with a variety of substrates, and has universality, good self-cleaning performance, dirt resistance, scrub resistance, corrosion resistance and other performance, and good application prospects.
Description
Technical field
The present invention relates to technical field of coatings, more particularly to a kind of antifouling organic-inorganic super-amphiphobic polymer painting of automatically cleaning
Material.
Background technology
Wettability is a key property of the surface of solids, it is conventionally believed that the microstructure of the surface of solids and chemical group
The in pairs wettability shown by it plays a key effect.The wettability of the surface of solids is risen in daily life and industrial and agricultural production
Critically important effect, such as washing, printing and dyeing, the dispersion of coating, the use of lubricating oil and infiltration of skin care item etc..Current people
Do not get wet this, and the phenomenon that can be tumbled with oneself of water droplet is referred to as super-hydrophobic phenomenon, and the surface with this property is claimed
For super hydrophobic surface, research worker is more for the research of super hydrophobic coating, but the type coating be often easily stained with oil stain and compared with
It is difficult to remove, therefore greatly limit the application and popularization of the type coating.Double open coats are as which is for alienation while water and oil
Effect, simple super-hydrophobic coat of holding one's breath are easier to be applied in the middle of daily life and commercial production.But it is existing at present
Super-hydrophobic oleophobic coating preparation method has the following disadvantages：Need special installation（Plasma, laser ablation）, be unfavorable for large area
Construction, has particular/special requirement, is only applicable to particular surface to ground, and universal complex forming technology, with high costs, therefore seriously
Limit the extensive application of such material.
Xu Runbin exists《The preparation of super-hydrophobic/oleophobic coating and research》Nanometer is prepared for by conventional grinding methods in one text
Aluminium sesquioxide particle, nano-silicon dioxide particle is prepared for using sol-gel process, is distinguished using fluorine-containing silane coupler
Surface grafting process being carried out to both, the nanoparticle and micron particle of surface fluorine modification having been obtained as color stuffing, next is adopted
A kind of fluorine-containing Hydroxylated acrylic resin is prepared as the main resin of binding agent, selection perfluoroalkyl with polytype acrylic monomerss
Ethanol and hexamethylene diisocyanate trimer prepare a kind of fluorine-containing isocyanate curing agent, and as a result paint is matched somebody with somebody by mixing in surface
The acroleic acid polyurethane varnish paint film property of preparation is good, adhesion 1 grade, pliability 1mm, impact 50cm, hardness 2H, for water
Static contact angle reach as high as 104 °, finally obtained nanometer, micron particle are scattered in fluorine-containing Hydroxylated acrylic resin,
Adjustment pigment and nano/micrometre particle ratio, and be equipped with dispersant, anti-settling auxiliary agent and firming agent be obtained it is various super thin
Water-oleophobic coating, testing result show coating there is preferable adhesive force, pliability and paint film intensity, now film for water,
The static contact angle of Oleum Brassicae campestriss and aircraft fluid is respectively 154 °, 100 ° and 94 °, illustrates that the coating is shown to water and oil
Good alienation effect, although the preparation method proposed in this article has certain effect in terms of hydrophobic and oleophobic, but
The contact angle to oil is not reaching to more than 150 °, and the intensity of coating, wearability, durability, stability and mechanical performance one
As, actual use demand is can not meet, the commercial Application of super-amphiphobic coating is limited.
The content of the invention
The object of the invention is exactly for the defect for making up prior art, there is provided a kind of antifouling organic-inorganic super-amphiphobic of automatically cleaning
Polymer coating.
The present invention is achieved by the following technical solutions：
A kind of antifouling organic-inorganic super-amphiphobic polymer coating of automatically cleaning, is made up of the raw material of following weight portion：Perfluor alkane
Base ethanol 32-35, methyl iso-butyl ketone (MIBK) 40-50, HDI trimer 90-100, methyl methacrylate 30-35, styrene 20-
23rd, hydroxyethyl methylacrylate 8.5-9, ten trifluoro monooctyl ester 17-19 of methacrylic acid, benzoyl peroxide 0.6-0.8, methanol silicon
Colloidal sol 25-28, propylene glycol methyl ether acetate 25-26, titanium dioxide 5-6, sodium hexameta phosphate 0.2-0.4, tetraethyl orthosilicate 2.8-
3.3rd, VTES 0.3-0.4, appropriate ammonia, silane coupler KH570 are appropriate, methylhydroxy silicone oil is appropriate,
10% dibutyl tin laurate is appropriate, dispersant 0.6-1, levelling agent 0.6-0.8, defoamer 0.4-0.6, appropriate butyl acetate,
Appropriate dehydrated alcohol, appropriate deionized water.
A kind of antifouling organic-inorganic super-amphiphobic polymer coating of automatically cleaning, is made up of step in detail below：
（1）Perfluoroalkyl ethanol is mixed with the methyl iso-butyl ketone (MIBK) of butyl acetate, 2/3 times of amount, is added in reaction bulb, start to rise
Temperature is simultaneously slowly stirred to perfluoroalkyl ethanol and is completely dissolved, and instills the dibutyl tin laurate of 8-10 drops 10%, and liter high-temperature is extremely
After 70 DEG C, the mixed liquor of Deca HDI trimer and butyl acetate, it is ensured that the completion of dropping in the 1h is stepped up temperature to 90 DEG C,
After insulation 2-3h, cooling down is to room temperature, standby as component A；
（2）Appropriate butyl acetate is added to into vessel in heating to the insulation 20min that flows back, then by methyl methacrylate, benzene second
The mixing of alkene, hydroxyethyl methylacrylate, remaining methyl iso-butyl ketone (MIBK), 80% benzoyl peroxide and butyl acetate, wherein vinegar
Acid butyl ester is 3 with the volume ratio of methyl iso-butyl ketone (MIBK):1, the butyl acetate of above-mentioned backflow insulation is slowly dropped to after stirring and dissolving
In solution, it is ensured that completion of dropping in 1.5h, ten trifluoro monooctyl ester of methacrylic acid is then rapidly added, rises high-temperature and flow back to 95 DEG C
Insulation 2h, is then disposably added to 10% benzoyl peroxide and appropriate butyl acetate mixing in container, insulation reaction 1-
Again remaining benzoyl peroxide and appropriate butyl acetate mixing are disposably added after 1.5h, insulation reaction 1-1.5h, with
After be cooled to 50 DEG C, seal it is standby；
（3）Titanium dioxide is added in deionized water the solution for making that concentration is 0.6-0.8wt%, adds sodium hexameta phosphate to carry out
Ultrasonic disperse obtains titanium oxide dispersion, is 3% by ammonia content（v/v）Ethanol solution be slowly dropped to titanium dioxide
In dispersion liquid, 5% tetraethyl orthosilicate ethanol solution is added dropwise over after magnetic agitation 15-20min again, at room temperature with 3000r/
Mixed liquor is put after completion of dropwise addition and be aged at room temperature 5h by the rotating speed stirring of min, and centrifugation, precipitate with deionized water are rinsed
Clean and dry for standby；
（4）By step（3）The product of preparation and 10%（v/v）VTES ethanol solution mixes, and starts stirring,
Rotating speed is controlled to 400-600r/min, adds appropriate ammonia, and bath temperature is controlled at 40 DEG C in whipping process, reaction
After 10-13h, filter, product absolute ethanol washing, be dried at being subsequently placed in 60 DEG C in vacuum drying oven, after being cooled to room temperature
Grinding is standby；
（5）Methanol Ludox is placed in the container that bath temperature is 60 DEG C, total system quality is slowly added under agitation
Fraction is 12% silane coupler KH570, isothermal reaction 1h, add total system mass fraction for 3% methylhydroxy silicone oil after
Continuous reaction 1h, is transferred to after being subsequently adding propylene glycol methyl ether acetate mix homogeneously in rotary evaporator, and vacuum distillation is except nor-
Alcohol, obtains the scattered hydrophobically modified Ludox of propylene glycol methyl ether acetate；
（6）By step（4）The product of preparation is added to step（5）In, being placed in fully shaking in ultrasonator uniformly, then will be mixed
Compound is added to step（2）It is slowly stirred in the product of preparation to being uniformly dispersed, adds dispersant, levelling agent and defoamer at a high speed
Stirring 30-50min, rotating speed are controlled to 1000-1200r/min, and then ultrasonic disperse 30-40min, then continues to high-speed stirred
20-30min, rotating speed are controlled to 700r/min, obtain component B, then by component A and component B according to mass ratio 1：3.2 mixing,
Room temperature is placed 10-15min and carries out ripening, is adjusted to suitable viscosity with ethyl acetate and sprays or brush after surface of the work, surface drying
The baking-curing at 80 DEG C.
It is an advantage of the invention that：Polyurethane resin has good adhesive force, mechanical endurance and toughness, and film is acidproof
Alkali, chemical-resistant resistance, saline solution etc., film can in -50 DEG C of -120 DEG C of life-time service, acrylic resin have weatherability it is good, protect
Light colour retention is excellent, heat-resist, has certain decay resistance, and the acrylic resin of hydroxyl can with polyisocyanates reaction
The acroleic acid polyurethane film of prepared function admirable, it is of many uses, in order to reach double open coats for the requirement of low-surface-energy,
Acrylic acid fluorochemical monomer is introduced during synthesis of hydroxy acrylic resin, fluorine is introduced by perfluoroalkyl ethanol in isocyanate component
Element, resin system of the synthesis with low-surface-energy, and further increase the chemical-resistant of coating, anticorrosive property, resistance to
The cold performance such as heat-resisting, also hydrolyzes the silanol and silica particle surface in Ludox for producing using silane coupler KH570
There is intermolecular dehydration in a part of hydroxyl, add methylhydroxy silicone oil, the silanol produced after hydrolysis and silicon dioxide granule
The hydroxyl of surface residual continues intermolecular dehydration, obtains modified hydrophobic Ludox, coats two in titanium dioxide surface
Silicon oxide, reduces its photocatalytic activity and the uv absorption property not changed substantially, makes up titanium dioxide as anti-purple
There is during external additive the defect of highlight catalytic active, and titanium dioxide is coated on after hydrolyzing using VTES
The surface of silicon cladding titanium dioxide composite, improves the compatibility with hydrophobic sol and hydrophobicity, constructs super-amphiphobic painting
Roughness in layer so as to meet the requirement of double open coats on the whole in microstructure and surface composition, improve paint film
It is hydrophobic, be difficult stain and ageing resistace, the present invention preparation method simple possible, can with various base material strong bondeds, have
There is a universality, gained super-amphiphobic coating has good automatically cleaning, stain resistance, scrubbing resistance and the performance such as corrosion-resistant, application prospect
Well.
Specific embodiment
The antifouling organic-inorganic super-amphiphobic polymer coating of a kind of automatically cleaning, by following weight portion（Kilogram）Raw material prepare system
Into：Perfluoroalkyl ethanol 32, methyl iso-butyl ketone (MIBK) 40, HDI trimer 90, methyl methacrylate 30, styrene 20, methyl-prop
Olefin(e) acid hydroxyl ethyl ester 8.5, ten trifluoro monooctyl ester 17 of methacrylic acid, benzoyl peroxide 0.6, methanol Ludox 25, propylene glycol monomethyl ether
Acetate 25, titanium dioxide 5, sodium hexameta phosphate 0.2, tetraethyl orthosilicate 2.8, VTES 0.3, ammonia are fitted
Amount, silane coupler KH570 are appropriate, methylhydroxy silicone oil is appropriate, 10% dibutyl tin laurate is appropriate, dispersant 0.6, stream
Flat agent 0.6, defoamer 0.4, appropriate butyl acetate, appropriate dehydrated alcohol, appropriate deionized water.
A kind of antifouling organic-inorganic super-amphiphobic polymer coating of automatically cleaning, is made up of step in detail below：
（1）Perfluoroalkyl ethanol is mixed with the methyl iso-butyl ketone (MIBK) of butyl acetate, 2/3 times of amount, is added in reaction bulb, start to rise
Temperature is simultaneously slowly stirred to perfluoroalkyl ethanol and is completely dissolved, and instills the dibutyl tin laurates of 8 drops 10%, rises high-temperature to 70
After DEG C, the mixed liquor of Deca HDI trimer and butyl acetate, it is ensured that the completion of dropping in the 1h is stepped up temperature to 90 DEG C, protects
After warm 2h, cooling down is to room temperature, standby as component A；
（2）Appropriate butyl acetate is added to into vessel in heating to the insulation 20min that flows back, then by methyl methacrylate, benzene second
The mixing of alkene, hydroxyethyl methylacrylate, remaining methyl iso-butyl ketone (MIBK), 80% benzoyl peroxide and butyl acetate, wherein vinegar
Acid butyl ester is 3 with the volume ratio of methyl iso-butyl ketone (MIBK):1, the butyl acetate of above-mentioned backflow insulation is slowly dropped to after stirring and dissolving
In solution, it is ensured that completion of dropping in 1.5h, ten trifluoro monooctyl ester of methacrylic acid is then rapidly added, rises high-temperature and flow back to 95 DEG C
Insulation 2h, is then disposably added to 10% benzoyl peroxide and appropriate butyl acetate mixing in container, insulation reaction 1h
Afterwards again by remaining benzoyl peroxide and the appropriate disposable addition of butyl acetate mixing, insulation reaction 1h is subsequently cooled to
50 DEG C, seal standby；
（3）Titanium dioxide is added in deionized water the solution for making that concentration is 0.6wt%, adds sodium hexameta phosphate to carry out ultrasound
Disperse to obtain titanium oxide dispersion, be 3% by ammonia content（v/v）Ethanol solution be slowly dropped to titanium dioxide dispersion
In liquid, 5% tetraethyl orthosilicate ethanol solution after magnetic agitation 15min, is added dropwise over again, at room temperature turning with 3000r/min
Mixed liquor is put after completion of dropwise addition and be aged at room temperature 5h, centrifugation by speed stirring, and precipitate with deionized water is rinsed well and dried
It is dry standby；
（4）By step（3）The product of preparation and 10%（v/v）VTES ethanol solution mixes, and starts stirring,
Rotating speed is controlled to 400r/min, adds appropriate ammonia, and bath temperature is controlled at 40 DEG C in whipping process, after reaction 10h,
Filter, product absolute ethanol washing, be dried at being subsequently placed in 60 DEG C in vacuum drying oven, after being cooled to room temperature, grind standby；
（5）Methanol Ludox is placed in the container that bath temperature is 60 DEG C, total system quality is slowly added under agitation
Fraction is 12% silane coupler KH570, isothermal reaction 1h, add total system mass fraction for 3% methylhydroxy silicone oil after
Continuous reaction 1h, is transferred to after being subsequently adding propylene glycol methyl ether acetate mix homogeneously in rotary evaporator, and vacuum distillation is except nor-
Alcohol, obtains the scattered hydrophobically modified Ludox of propylene glycol methyl ether acetate；
（6）By step（4）The product of preparation is added to step（5）In, being placed in fully shaking in ultrasonator uniformly, then will be mixed
Compound is added to step（2）It is slowly stirred in the product of preparation to being uniformly dispersed, adds dispersant, levelling agent and defoamer at a high speed
Stirring 30min, rotating speed are controlled to 1000r/min, and then ultrasonic disperse 30min, then continues to high-speed stirred 20min, rotating speed control
700r/min is made as, component B is obtained, then by component A and component B according to mass ratio 1：3.2 mixing, room temperature are placed 10min and are entered
Row ripening, is adjusted to suitable viscosity with ethyl acetate and sprays or brush in surface of the work, and surface drying baking-curing at 80 DEG C is
Can.
Preparation method according to embodiment carries out performance test to its coating, as a result as follows：
Adhesive force:1 grade；Pliability：1mm；Hardness：5H；Impact strength：50mm；Contact angle with deionized water is 154-160 °；
It it is 153-156 ° with Oleum Arachidis hypogaeae semen contact angle；5 ° of roll angle ＜.
Claims (2)
1. the antifouling organic-inorganic super-amphiphobic polymer coating of a kind of automatically cleaning, it is characterised in that by the raw material system of following weight portion
Prepare into：Perfluoroalkyl ethanol 32-35, methyl iso-butyl ketone (MIBK) 40-50, HDI trimer 90-100, methyl methacrylate 30-
35th, styrene 20-23, hydroxyethyl methylacrylate 8.5-9, ten trifluoro monooctyl ester 17-19 of methacrylic acid, benzoyl peroxide
0.6-0.8, methanol Ludox 25-28, propylene glycol methyl ether acetate 25-26, titanium dioxide 5-6, sodium hexameta phosphate 0.2-0.4,
Tetraethyl orthosilicate 2.8-3.3, VTES 0.3-0.4, appropriate ammonia, silane coupler KH570 are appropriate, methyl
Appropriate hydroxy silicon oil, 10% dibutyl tin laurate are appropriate, dispersant 0.6-1, levelling agent 0.6-0.8, defoamer 0.4-0.6,
Appropriate butyl acetate, appropriate dehydrated alcohol, appropriate deionized water.
2. the antifouling organic-inorganic super-amphiphobic polymer coating of a kind of automatically cleaning according to claim 1, it is characterised in that by with
Lower concrete steps are made：
（1）Perfluoroalkyl ethanol is mixed with the methyl iso-butyl ketone (MIBK) of butyl acetate, 2/3 times of amount, is added in reaction bulb, start to rise
Temperature is simultaneously slowly stirred to perfluoroalkyl ethanol and is completely dissolved, and instills the dibutyl tin laurate of 8-10 drops 10%, and liter high-temperature is extremely
After 70 DEG C, the mixed liquor of Deca HDI trimer and butyl acetate, it is ensured that the completion of dropping in the 1h is stepped up temperature to 90 DEG C,
After insulation 2-3h, cooling down is to room temperature, standby as component A；
（2）Appropriate butyl acetate is added to into vessel in heating to the insulation 20min that flows back, then by methyl methacrylate, benzene second
The mixing of alkene, hydroxyethyl methylacrylate, remaining methyl iso-butyl ketone (MIBK), 80% benzoyl peroxide and butyl acetate, wherein vinegar
Acid butyl ester is 3 with the volume ratio of methyl iso-butyl ketone (MIBK):1, the butyl acetate of above-mentioned backflow insulation is slowly dropped to after stirring and dissolving
In solution, it is ensured that completion of dropping in 1.5h, ten trifluoro monooctyl ester of methacrylic acid is then rapidly added, rises high-temperature and flow back to 95 DEG C
Insulation 2h, is then disposably added to 10% benzoyl peroxide and appropriate butyl acetate mixing in container, insulation reaction 1-
Again remaining benzoyl peroxide and appropriate butyl acetate mixing are disposably added after 1.5h, insulation reaction 1-1.5h, with
After be cooled to 50 DEG C, seal it is standby；
（3）Titanium dioxide is added in deionized water the solution for making that concentration is 0.6-0.8wt%, adds sodium hexameta phosphate to carry out
Ultrasonic disperse obtains titanium oxide dispersion, is 3% by ammonia content（v/v）Ethanol solution be slowly dropped to titanium dioxide
In dispersion liquid, 5% tetraethyl orthosilicate ethanol solution is added dropwise over after magnetic agitation 15-20min again, at room temperature with 3000r/
Mixed liquor is put after completion of dropwise addition and be aged at room temperature 5h by the rotating speed stirring of min, and centrifugation, precipitate with deionized water are rinsed
Clean and dry for standby；
（4）By step（3）The product of preparation and 10%（v/v）VTES ethanol solution mixes, and starts stirring,
Rotating speed is controlled to 400-600r/min, adds appropriate ammonia, and bath temperature is controlled at 40 DEG C in whipping process, reaction
After 10-13h, filter, product absolute ethanol washing, be dried at being subsequently placed in 60 DEG C in vacuum drying oven, after being cooled to room temperature
Grinding is standby；
（5）Methanol Ludox is placed in the container that bath temperature is 60 DEG C, total system quality is slowly added under agitation
Fraction is 12% silane coupler KH570, isothermal reaction 1h, add total system mass fraction for 3% methylhydroxy silicone oil after
Continuous reaction 1h, is transferred to after being subsequently adding propylene glycol methyl ether acetate mix homogeneously in rotary evaporator, and vacuum distillation is except nor-
Alcohol, obtains the scattered hydrophobically modified Ludox of propylene glycol methyl ether acetate；
（6）By step（4）The product of preparation is added to step（5）In, being placed in fully shaking in ultrasonator uniformly, then will be mixed
Compound is added to step（2）It is slowly stirred in the product of preparation to being uniformly dispersed, adds dispersant, levelling agent and defoamer at a high speed
Stirring 30-50min, rotating speed are controlled to 1000-1200r/min, and then ultrasonic disperse 30-40min, then continues to high-speed stirred
20-30min, rotating speed are controlled to 700r/min, obtain component B, then by component A and component B according to mass ratio 1：3.2 mixing,
Room temperature is placed 10-15min and carries out ripening, is adjusted to suitable viscosity with ethyl acetate and sprays or brush after surface of the work, surface drying
The baking-curing at 80 DEG C.
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