CN116179004A - Method for preparing super-hydrophobic anti-fouling paint by self-assembly method and application - Google Patents
Method for preparing super-hydrophobic anti-fouling paint by self-assembly method and application Download PDFInfo
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- CN116179004A CN116179004A CN202310284787.8A CN202310284787A CN116179004A CN 116179004 A CN116179004 A CN 116179004A CN 202310284787 A CN202310284787 A CN 202310284787A CN 116179004 A CN116179004 A CN 116179004A
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- 230000003075 superhydrophobic effect Effects 0.000 title claims abstract description 80
- 238000000034 method Methods 0.000 title claims abstract description 48
- 230000003373 anti-fouling effect Effects 0.000 title claims abstract description 28
- 238000001338 self-assembly Methods 0.000 title claims abstract description 28
- 239000003973 paint Substances 0.000 title claims abstract description 24
- 229910010413 TiO 2 Inorganic materials 0.000 claims abstract description 69
- 238000000576 coating method Methods 0.000 claims abstract description 50
- 239000011248 coating agent Substances 0.000 claims abstract description 49
- 229910004298 SiO 2 Inorganic materials 0.000 claims abstract description 47
- 239000002070 nanowire Substances 0.000 claims abstract description 23
- 238000001556 precipitation Methods 0.000 claims abstract description 11
- 238000002360 preparation method Methods 0.000 claims abstract description 10
- 238000005507 spraying Methods 0.000 claims abstract description 10
- 239000000243 solution Substances 0.000 claims description 60
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 54
- 239000002245 particle Substances 0.000 claims description 42
- 238000003756 stirring Methods 0.000 claims description 38
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 36
- 239000004593 Epoxy Substances 0.000 claims description 26
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 25
- 239000011259 mixed solution Substances 0.000 claims description 17
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 16
- 239000007788 liquid Substances 0.000 claims description 16
- 239000006185 dispersion Substances 0.000 claims description 14
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 13
- 239000003431 cross linking reagent Substances 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 13
- 239000000839 emulsion Substances 0.000 claims description 13
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 13
- VBGGLSWSRVDWHB-UHFFFAOYSA-N 1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-henicosafluorodecyl-tris(trifluoromethoxy)silane Chemical compound FC(F)(F)O[Si](OC(F)(F)F)(OC(F)(F)F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F VBGGLSWSRVDWHB-UHFFFAOYSA-N 0.000 claims description 11
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 11
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- 230000002209 hydrophobic effect Effects 0.000 claims description 10
- 239000000843 powder Substances 0.000 claims description 9
- 230000001680 brushing effect Effects 0.000 claims description 8
- 239000003822 epoxy resin Substances 0.000 claims description 8
- 229920000647 polyepoxide Polymers 0.000 claims description 8
- 238000005303 weighing Methods 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 4
- 239000004848 polyfunctional curative Substances 0.000 claims description 3
- 239000011148 porous material Substances 0.000 claims description 2
- 230000008569 process Effects 0.000 claims description 2
- 238000000967 suction filtration Methods 0.000 claims description 2
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 2
- 239000011253 protective coating Substances 0.000 claims 1
- 238000004140 cleaning Methods 0.000 abstract description 6
- 239000004005 microsphere Substances 0.000 abstract description 3
- 239000002957 persistent organic pollutant Substances 0.000 abstract description 3
- 239000008399 tap water Substances 0.000 abstract description 3
- 235000020679 tap water Nutrition 0.000 abstract description 3
- 230000009471 action Effects 0.000 abstract description 2
- 239000000428 dust Substances 0.000 abstract description 2
- 238000009396 hybridization Methods 0.000 abstract description 2
- 238000005286 illumination Methods 0.000 abstract description 2
- 239000002904 solvent Substances 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 2
- 230000000593 degrading effect Effects 0.000 abstract 1
- 230000001939 inductive effect Effects 0.000 abstract 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 230000032683 aging Effects 0.000 description 3
- 229910052681 coesite Inorganic materials 0.000 description 3
- 229910052906 cristobalite Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- 229910052682 stishovite Inorganic materials 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910052905 tridymite Inorganic materials 0.000 description 3
- 230000008859 change Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000002386 leaching Methods 0.000 description 2
- 240000008415 Lactuca sativa Species 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000002519 antifouling agent Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 230000037452 priming Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 235000012045 salad Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
Classifications
-
- 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
- C09D5/16—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
-
- 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
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
-
- 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
- C08K2003/2241—Titanium dioxide
-
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
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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)
- Inorganic Chemistry (AREA)
- Paints Or Removers (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
Abstract
The invention discloses a method for preparing super-hydrophobic anti-fouling paint by self-assembly method and application thereof, which selects SiO with high mechanical strength 2 Nanowires replace common SiO 2 Microsphere, and coating TiO on its surface 2 Forming array-shaped SiO by spraying solvent on primer and adopting a preparation mode of inducing self-assembly precipitation method on the basis of inorganic-organic hybridization 2 Nanowire @ TiO 2 The super-hydrophobic coating enhances the super-hydrophobic, wear-resistant and weather-resistant properties and endows the coating with the function of degrading organic pollutants on the surface under the action of illumination. The invention is rinsed by natural rainwater or common tap water, and dust stained on the surface can be carried by water to realize the self-cleaning function.
Description
Technical field:
the invention belongs to the technical field of super-hydrophobic anti-fouling paint, and particularly relates to a method for preparing super-hydrophobic anti-fouling paint by a self-assembly method and application thereof.
The background technology is as follows:
the surface of the bridge and tunnel facility is corroded by wind and rain and various pollutants are adhered throughout the year, so that the quality of the bridge and tunnel facility is seriously influenced, the degradation and corrosion of the facility are accelerated, and the safety and the service life of the bridge and tunnel structure are influenced. With the enhancement of environmental awareness and the increase of labor cost, the application of the super-hydrophobic anti-fouling paint on bridge and tunnel facilities is increasingly wide. The key to superhydrophobic materials is the chemical nature of the material surface and its roughness, which tends to exhibit hydrophobicity when the surface energy of the solid surface is low and the surface is rough. To obtain superhydrophobic surfaces, there are two methods: firstly, constructing a micro-nano coarse structure required by superhydrophobic on the surface of a substance with low surface energy; secondly, grafting low surface energy substances or groups on the surface of the micro-nano coarse structure to enable the particles to be hydrophobic due to grafting of organic long chains on the surface of the particles. However, there are two problems in practical use: (1) The preparation method is complex, often requires special equipment, has complex process, has selectivity to the base material, and is not suitable for preparing the super-hydrophobic coating in a large area; (2) The super-hydrophobic durability of the coating is poor, the actual service time is too short, and the combination property and the air permeability of the single-component inorganic/organic coating and the matrix are required to be improved.
The invention comprises the following steps:
the invention aims to provide a method for preparing super-hydrophobic anti-fouling paint by a self-assembly method, which selects SiO with high mechanical strength 2 Nanowires replace common SiO 2 Microsphere, and coating TiO on its surface 2 On the basis of inorganic-organic hybridization, the array-shaped SiO is formed by adopting a preparation mode of a solvent-induced self-assembly precipitation method 2 Nanowire @ TiO 2 Super-hydrophobic coating ， The super-hydrophobic, wear-resistant and weather-resistant performance is enhanced, organic pollutants on the surface are degraded under the action of illumination, and the dust stained on the surface can be carried by water to realize the self-cleaning function through leaching by natural rainwater or common tap water.
In order to solve the problems, the technical scheme of the invention is as follows:
a method for preparing super-hydrophobic anti-fouling paint by a self-assembly method comprises the following steps:
step one, wrapping TiO 2 Shell structure: siO is made of 2 The nanowire powder is ultrasonically dispersed in an organic solution and is marked as A liquid; butyl titanate is dissolved in an organic solution and is marked as liquid B; dropwise adding the solution B into the solution A under stirring, and stirring for reacting to obtain SiO 2 Nanowire @ TiO 2 Is a dispersion of (a);
step two, preparing SiO 2 Nanowire @ TiO 2 Super-hydrophobic particles: siO is made of 2 Nanowire @ TiO 2 Heating the dispersion liquid of (2) to 40-60 ℃, adding a cross-linking agent, magnetically stirring for 10-40 min, performing ultrasonic dispersion, performing suction filtration, and drying to obtain SiO 2 Nanowire @ TiO 2 Super-hydrophobic particles;
brushing primer and spraying dichloroethane solution on the primer;
step four, preparing a hydrophobic coating by a self-assembly method: siO was isolated by self-assembled precipitation using standard sample sieves 2 Nanowire @ TiO 2 The super-hydrophobic particles are evenly sieved and dropped on the primer coated with dichloroethane solution, and the dichloroethane solution is preparedSlow volatilization induced SiO 2 Nanowire @ TiO 2 The superhydrophobic particles deposit near the solid-liquid-gas three-phase contact line to the primer surface forming regular stripes. After the curing is completed, the particles which are not combined with the primer are removed, thereby preparing the SiO 2 Nanowire @ TiO 2 Array super-hydrophobic coating.
Further improvements, the SiO 2 The diameter of the nanowire is 20-100 nm, and the length is more than 10 mu m.
Further improvement, in step one, siO 2 The mass volume ratio of the nanowire to the butyl titanate is 2-8 g: 0.5-4 ml; the organic solution is a mixed solution of ethanol and acetonitrile, and the volume ratio of the ethanol to the acetonitrile is 2:1.
in the first step, the solution B is slowly injected into the solution A, and then stirred and reacted at 20-50 ℃ for 2-30 h.
In the first step, the dropping speed of the liquid B slowly injected into the liquid A is controlled to be 30-60 drops/min, and each drop is added for 5-10 min at intervals of 5-mL, and stirring is kept during the period.
In the second step, the cross-linking agent comprises tetraethyl silicate and perfluoro decyl trimethoxy silane, wherein the mass ratio of the tetraethyl silicate to the perfluoro decyl trimethoxy silane is 5-8: 1, a step of; crosslinking agent and SiO 2 Nanowire @ TiO 2 The mass volume ratio of the dispersion liquid of (2) is 1g:4ml.
In the third step, the primer is prepared by the following steps: weighing waterborne epoxy putty A, butyl acetate B and waterborne epoxy curing agent emulsion C with preset mass, magnetically stirring, vacuumizing for 2-3 min to remove bubbles, and uniformly coating the waterborne epoxy putty A, butyl acetate B and waterborne epoxy curing agent emulsion C on an epoxy resin plate to serve as a primer; wherein, the volume ratio of the aqueous epoxy putty A to the butyl acetate B to the aqueous epoxy hardener emulsion C is 1:0.2 to 0.6:1, and magnetically stirring for 5-30 min.
In the fourth step, the curing time is 24-72 h; the pore diameter of the standard sample separating sieve is 100 meshes.
The super-hydrophobic anti-fouling paint prepared by the method for preparing the super-hydrophobic anti-fouling paint by the self-assembly method.
The super-hydrophobic anti-fouling paint prepared by the method for preparing the super-hydrophobic anti-fouling paint by the self-assembly method is used as a protective paint on the surface of tunnel facilities
The invention has the advantages that:
(1) The super-hydrophobic anti-fouling paint has super-hydrophobic anti-fouling, wear-resistant and weather-resistant properties, can degrade organic pollutants on the surface, and realizes a self-cleaning function through leaching by natural rainwater or common tap water;
(2) In the invention, siO with high mechanical strength is selected 2 Nanowires replace common SiO 2 The microspheres not only can enhance the compressive strength of the coating, but also can enhance the bonding strength of the coating;
(3) In the invention, siO is used for preparing 2 TiO coated outside nano wire 2 The surface of the modified paint is modified to ensure that the modified paint has super-hydrophobic performance, and simultaneously endows the modified paint with ultraviolet aging resistance, acid and alkali resistance and the like, so that the paint has excellent durability.
(4) The SiO with regular arrangement is prepared by spraying dichloroethane solution on the priming paint, which is volatile, induces self-assembly precipitation 2 Nanowire @ TiO 2 The super-hydrophobic coating is firmer and has better hydrophobic performance.
Detailed Description
The invention will now be described in further detail with reference to specific examples, which are intended to illustrate, but not to limit, the invention.
The invention relates to a method and a process for preparing super-hydrophobic anti-fouling paint by a self-assembly method, which comprises the following steps:
(1) Wrapping TiO 2 Shell structure: siO is made of 2 The nanowire powder is ultrasonically dispersed in a mixed solution of ethanol and acetonitrile and is marked as solution A; dissolving butyl titanate into a mixed solution of ethanol and acetonitrile, and marking the mixed solution as solution B; under the stirring condition, slowly injecting the solution B into the solution A, and stirring for reaction to obtain SiO 2 Nanowire @ TiO 2 Is a dispersion of (a);
(2) Preparation of SiO 2 Nanowire @ TiO 2 Super-hydrophobic particles: siO is made of 2 Nanowire @ TiO 2 Heating the dispersion liquid of (2) to 40-60 ℃, and adding a cross-linking agent tetraethyl silicate and perfluorodecylTrimethoxysilane, magnetically stirring for 10-40 min, ultrasonic dispersing, suction filtering, and drying to obtain SiO 2 Nanowire @ TiO 2 Super-hydrophobic particles;
(3) Brushing primer: weighing a certain mass of aqueous epoxy putty A, butyl acetate B and aqueous epoxy curing agent emulsion C, magnetically stirring, vacuumizing for 2-3 min to remove bubbles, uniformly coating the mixture on an epoxy resin plate to serve as a primer, and spraying dichloroethane solution on the primer after the mixture is dried;
(4) Preparing a hydrophobic coating by a self-assembly method: siO was isolated by self-assembled precipitation using a 100 target quasi-sample sieve 2 Nanowire @ TiO 2 The super-hydrophobic particles are evenly sieved and fall on paint coated with dichloroethane solution, and the dichloroethane slowly volatilizes to induce SiO 2 Nanowire @ TiO 2 The superhydrophobic particles deposit near the solid-liquid-gas three-phase contact line to the primer surface forming regular stripes. After the curing is completed, the particles which are not combined with the primer are removed, thereby preparing the SiO 2 Nanowire @ TiO 2 Array super-hydrophobic coating.
In the above method, in step (1), siO 2 White powder with diameter of 20-100 nm and length of more than 10 mu m of nano wire, and after liquid B is injected into liquid A, siO 2 The ratio of the nanowire to the butyl titanate is (2-8) g: (0.5-4 ml), slowly injecting the solution B into the solution A, reacting for 2-30 h at 20-50 ℃, controlling the dripping speed of the solution B into the solution A to be 30-60 drops/min, and keeping stirring during the period of 5-10 min of each drop of 5 mL; the volume ratio of ethanol to acetonitrile in the ethanol and acetonitrile mixed solution is 2: in the step (2), the proportion of the cross-linking agent tetraethyl silicate and the perfluoro decyl trimethoxy silane is (5-8): 1, a step of; in the step (3), the proportion of the aqueous epoxy putty A, the butyl acetate B and the aqueous epoxy hardener emulsion C is 1: (0.2 to 0.6): 1, magnetically stirring for 5-30 min; in the step (4), the curing time is 24-72 h.
Example 1:
(1) Wrapping TiO 2 Shell structure: siO with diameter of 20 nm and length of > 10 μm 2 The nanowire powder 20g is ultrasonically dispersed in a mixed solution of 100 ml ethanol and acetonitrile, and is marked as solution A; 5g of butyl titanate was dissolved in 100The mixture of ethanol and acetonitrile is marked as liquid B; wherein SiO is 2 The ratio of nanowires to butyl titanate was 2 g:0.5 ml, slowly injecting the solution B into the solution A under stirring, controlling the dripping speed at 30 drops/min, adding 5-mL each for 5 min, stirring, and reacting at 20deg.C for 30-h to obtain SiO 2 Nanowire @ TiO 2 Is a dispersion of (a);
(2) Preparation of SiO 2 Nanowire @ TiO 2 Super-hydrophobic particles: siO is made of 2 Nanowire @ TiO 2 50g of the cross-linking agents tetraethyl silicate and perfluorodecyl trimethoxysilane were added in a ratio of 5:1 magnetically stirring for 40 min, ultrasonic dispersing, suction filtering, and drying to obtain SiO 2 Nanowire @ TiO 2 Super-hydrophobic particles;
(3) Brushing primer: weighing a certain mass of aqueous epoxy putty A, butyl acetate B and aqueous epoxy curing agent emulsion C, and ensuring A: b: the mass ratio of C is 1:0.2:1, magnetically stirring for 5 min, vacuumizing for 2-3 min to remove bubbles, uniformly coating the bubbles on an epoxy resin plate to serve as a primer, and spraying dichloroethane solution on the primer after drying;
(4) Preparing a hydrophobic coating by a self-assembly method: siO was isolated by self-assembled precipitation using a 100 target quasi-sample sieve 2 Nanowire @ TiO 2 The super-hydrophobic particles are evenly sieved and placed on a primer coated with dichloroethane solution, and the dichloroethane is slowly volatilized to induce SiO 2 Nanowire @ TiO 2 The superhydrophobic particles deposit near the solid-liquid-gas three-phase contact line to the primer surface forming regular stripes. After curing 24 h, the particles not bonded to the primer are removed, thereby preparing SiO 2 Nanowire @ TiO 2 Array super-hydrophobic coating.
Example 2:
(1) Wrapping TiO 2 Shell structure: dispersing SiO2 nanowire powder 40g with the diameter of 20 nm and the length of more than 10 mu m in a mixed solution of 200ml ethanol and acetonitrile by ultrasonic, and marking as A solution; 10g of butyl titanate is dissolved in 200ml of mixed solution of ethanol and acetonitrile and is marked as solution B; wherein SiO is 2 The ratio of nanowires to butyl titanate was 4 g:1 ml, slowly injecting solution B into solution A under stirringIn the solution, the dropping speed is controlled at 40 drops/min, each drop is added at intervals of 5 mL for 6 min, stirring is kept, and the reaction is carried out at 30 ℃ for 20 h, thus obtaining SiO 2 Nanowire @ TiO 2 Is a dispersion of (a);
(2) Preparation of SiO 2 Nanowire @ TiO 2 Super-hydrophobic particles: siO is made of 2 Nanowire @ TiO 2 100g of the cross-linking agents tetraethyl silicate and perfluorodecyl trimethoxysilane were added in a ratio of 6:1 magnetically stirring for 30 min, ultrasonic dispersing, suction filtering, and drying to obtain SiO 2 Nanowire @ TiO 2 Super-hydrophobic particles;
(3) Brushing primer: weighing a certain mass of aqueous epoxy putty A, butyl acetate B and aqueous epoxy curing agent emulsion C, and ensuring A: b: the mass ratio of C is 1:0.3:1, magnetically stirring for 10 min, vacuumizing for 2-3 min to remove bubbles, uniformly coating the bubbles on an epoxy resin plate to serve as a primer, and spraying dichloroethane solution on the primer after drying;
(4) Preparing a hydrophobic coating by a self-assembly method: siO was isolated by self-assembled precipitation using a 100 target quasi-sample sieve 2 Nanowire @ TiO 2 The super-hydrophobic particles are evenly sieved and placed on a primer coated with dichloroethane solution, and the dichloroethane is slowly volatilized to induce SiO 2 Nanowire @ TiO 2 The superhydrophobic particles deposit near the solid-liquid-gas three-phase contact line to the primer surface forming regular stripes. After curing 36 h, the particles not bonded to the primer are removed to prepare SiO 2 Nanowire @ TiO 2 And (3) a super-hydrophobic coating.
Example 3:
(1) Wrapping TiO 2 Shell structure: siO with diameter of 20 nm and length of > 10 μm 2 The nanowire powder 60 g is ultrasonically dispersed in a mixed solution of 300ml ethanol and acetonitrile, and is marked as solution A; dissolving 20g of butyl titanate in 300ml of a mixed solution of ethanol and acetonitrile, and marking as solution B; wherein SiO is 2 The ratio of nanowires to butyl titanate was 6 g:2 ml slowly injecting the solution B into the solution A under stirring, controlling the dripping speed at 45 drops/min, adding 5 mL drops each for 7 min, stirring, and reacting at 40deg.C for 10 h to obtain SiO 2 Nanowire @ TiO 2 Is a dispersion of (2)；
(2) Preparation of SiO 2 Nanowire @ TiO 2 Super-hydrophobic particles: siO is made of 2 Nanowire @ TiO 2 150g of the cross-linking agents tetraethyl silicate and perfluorodecyl trimethoxysilane were added in a ratio of 7:1 magnetically stirring for 20 min, ultrasonic dispersing, suction filtering, and drying to obtain SiO 2 Nanowire @ TiO 2 Super-hydrophobic particles;
(3) Brushing primer: weighing a certain mass of aqueous epoxy putty A, butyl acetate B and aqueous epoxy curing agent emulsion C, and ensuring A: b: the mass ratio of C is 1:0.4:1, magnetically stirring for 15 min, vacuumizing for 2-3 min to remove bubbles, uniformly coating the bubbles on an epoxy resin plate to serve as a primer, and spraying dichloroethane solution on the primer after drying;
(4) Preparing a hydrophobic coating by a self-assembly method: siO was isolated by self-assembled precipitation using a 100 target quasi-sample sieve 2 Nanowire @ TiO 2 The super-hydrophobic particles are evenly sieved and placed on a primer coated with dichloroethane solution, and the dichloroethane is slowly volatilized to induce SiO 2 Nanowire @ TiO 2 The superhydrophobic particles deposit near the solid-liquid-gas three-phase contact line to the primer surface forming regular stripes. After curing 48 h, the particles not bonded to the primer are removed, thereby preparing SiO 2 Nanowire @ TiO 2 And (3) a super-hydrophobic coating.
Example 4:
(1) Wrapping TiO 2 Shell structure: dispersing SiO2 nanowire powder 80 g with the diameter of 20 nm and the length of more than 10 mu m in a mixed solution of 400ml ethanol and acetonitrile in an ultrasonic manner, and marking the mixed solution as A solution; 40g of butyl titanate is dissolved in 400ml of mixed solution of ethanol and acetonitrile and is marked as solution B; wherein SiO is 2 The ratio of nanowires to butyl titanate was 8g: 4ml slowly injecting the solution B into the solution A under stirring, controlling the dripping speed at 50 drops/min, adding 5-mL of each drop for 8 min, stirring, and reacting at 45deg.C for 3 h to obtain SiO 2 Nanowire @ TiO 2 Is a dispersion of (a);
(2) Preparation of SiO 2 Nanowire @ TiO 2 Super-hydrophobic particles: siO is made of 2 Nanowire @ TiO 2 Heating the dispersion of (2) to 55200g of cross-linking agents tetraethyl silicate and perfluorodecyl trimethoxysilane were added at a ratio of 7.5:1 magnetically stirring for 15 min, ultrasonic dispersing, suction filtering, and drying to obtain SiO 2 Nanowire @ TiO 2 Super-hydrophobic particles;
(3) Brushing primer: weighing a certain mass of aqueous epoxy putty A, butyl acetate B and aqueous epoxy curing agent emulsion C, and ensuring A: b: the mass ratio of C is 1:0.5:1, magnetically stirring for 20 min, vacuumizing for 2-3 min to remove bubbles, uniformly coating the bubbles on an epoxy resin plate to serve as a primer, and spraying dichloroethane solution on the primer after drying;
(4) Preparing a hydrophobic coating by a self-assembly method: siO was isolated by self-assembled precipitation using a 100 target quasi-sample sieve 2 Nanowire @ TiO 2 The super-hydrophobic particles are evenly sieved and placed on a primer coated with dichloroethane solution, and the dichloroethane is slowly volatilized to induce SiO 2 Nanowire @ TiO 2 The superhydrophobic particles deposit near the solid-liquid-gas three-phase contact line to the primer surface forming regular stripes. After curing 60 h, the particles not bonded to the primer are removed to prepare SiO 2 Nanowire @ TiO 2 And (3) a super-hydrophobic coating.
Example 5:
(1) Wrapping TiO 2 Shell structure: dispersing SiO2 nanowire powder 80 g with the diameter of 20 nm and the length of more than 10 mu m in a mixed solution of 400ml ethanol and acetonitrile in an ultrasonic manner, and marking the mixed solution as A solution; 40g of butyl titanate is dissolved in 400ml of mixed solution of ethanol and acetonitrile and is marked as solution B; wherein SiO is 2 The ratio of nanowires to butyl titanate was 8g: 4ml slowly injecting the solution B into the solution A under stirring, controlling the dripping speed at 60 drops/min, adding 5: 5 mL of each drop for 10 min, stirring, and reacting at 50deg.C for 2: 2 h to obtain SiO 2 Nanowire @ TiO 2 Is a dispersion of (a);
(2) Preparation of SiO 2 Nanowire @ TiO 2 Super-hydrophobic particles: siO is made of 2 Nanowire @ TiO 2 200g of the cross-linking agents tetraethyl silicate and perfluorodecyl trimethoxysilane were added in a ratio of 8:1 magnetically stirring for 10 min, ultrasonic dispersing, suction filtering, and drying to obtain SiO 2 Nanowire @ TiO 2 Super-hydrophobic particles;
(3) Brushing primer: weighing a certain mass of aqueous epoxy putty A, butyl acetate B and aqueous epoxy curing agent emulsion C, and ensuring A: b: the mass ratio of C is 1:0.6:1, magnetically stirring for 30 min, vacuumizing for 2-3 min to remove bubbles, uniformly coating the bubbles on an epoxy resin plate to serve as a primer, and spraying dichloroethane solution on the primer after drying;
(4) Preparing a hydrophobic coating by a self-assembly method: siO was isolated by self-assembled precipitation using a 100 target quasi-sample sieve 2 Nanowire @ TiO 2 The super-hydrophobic particles are evenly sieved and placed on a primer coated with dichloroethane solution, and the dichloroethane is slowly volatilized to induce SiO 2 Nanowire @ TiO 2 The superhydrophobic particles deposit near the solid-liquid-gas three-phase contact line to the primer surface forming regular stripes. After curing 72 h, the particles not bonded to the primer are removed, thereby preparing SiO 2 Nanowire @ TiO 2 And (3) a super-hydrophobic coating.
Performance detection
(1) Superhydrophobicity: the contact angle was measured with a DataPhysics OCA35 (with temperature control accessory accurate temperature control range of-30 ℃ C. To 160 ℃ C.) in Germany, the drop quantity was 4 [ mu ] L, and the static contact angle was the average of 5 contact angles measured.
(2) Weather resistance: QUV/Se artificial aging device of Q-panel company in U.S.A.: test conditions: wavelength 340 nm, radiation power 0.68W/m 2 Cycling the program: ultraviolet irradiation for 8 h at 50 ℃, condensation for 4 h and aging for 1440 h at 40 ℃; the weather resistance of the coating is reflected by measuring the change in the contact angle of the coating.
(3) Self-cleaning: gasoline is used as a pollution source. By applying a layer of salad oil to the surface of the superhydrophobic coating, and then placing the coating under an ultraviolet lamp (365 nm, 20 mW/cm 2 ) The self-cleaning properties of the coating are characterized by measuring the change in contact angle of the surface of the coating.
The performance of examples 1-5 and commercially available superhydrophobic anti-fouling coatings was tested for superhydrophobicity, weatherability and self-cleaning properties and the test results are shown in table 1.
TABLE 1 Performance test results
The foregoing description is only a preferred embodiment of the invention and is not intended to limit the invention to the particular form disclosed, but on the contrary, the intention is to cover all modifications, equivalents, and alternatives falling within the spirit and scope of the invention.
Claims (10)
1. The method for preparing the super-hydrophobic anti-fouling paint by a self-assembly method is characterized by comprising the following steps of:
step one, wrapping TiO 2 Shell structure: siO is made of 2 The nanowire powder is ultrasonically dispersed in an organic solution and is marked as A liquid; butyl titanate is dissolved in an organic solution and is marked as liquid B; dropwise adding the solution B into the solution A under stirring, and stirring for reacting to obtain SiO 2 Nanowire @ TiO 2 Is a dispersion of (a);
step two, preparing SiO 2 Nanowire @ TiO 2 Super-hydrophobic particles: siO is made of 2 Nanowire @ TiO 2 Heating the dispersion liquid of (2) to 40-60 ℃, adding a cross-linking agent, magnetically stirring for 10-40 min, performing ultrasonic dispersion, performing suction filtration, and drying to obtain SiO 2 Nanowire @ TiO 2 Super-hydrophobic particles;
brushing primer and spraying dichloroethane solution on the primer;
step four, preparing a hydrophobic coating by a self-assembly method: siO was isolated by self-assembled precipitation using standard sample sieves 2 Nanowire @ TiO 2 The super-hydrophobic particles are evenly sieved and placed on a primer coated with dichloroethane solution, and the dichloroethane is slowly volatilized to induce SiO 2 Nanowire @ TiO 2 The super-hydrophobic particles are deposited on the surface of the primer near the solid-liquid-gas three-phase contact line to form regular stripes; after the curing is completed, the particles which are not combined with the primer are removed, thereby preparing the SiO 2 Nanowire @ TiO 2 Array super-hydrophobic coating.
2. The self-assembly of claim 1The method for preparing the super-hydrophobic anti-fouling coating is characterized in that the SiO 2 The diameter of the nanowire is 20-100 nm, and the length is more than 10 mu m.
3. The method for preparing the super-hydrophobic and anti-fouling coating by a self-assembly method according to claim 1, wherein in the first step, siO 2 The mass volume ratio of the nanowire to the butyl titanate is 2-8 g: 0.5-4 ml; the organic solution is a mixed solution of ethanol and acetonitrile, and the volume ratio of the ethanol to the acetonitrile is 2:1.
4. the method for preparing the super-hydrophobic anti-fouling paint by the self-assembly method according to claim 1, wherein in the first step, after the solution B is slowly injected into the solution A, stirring and reacting at 20-50 ℃ for 2-30 h.
5. The method for preparing a super-hydrophobic anti-fouling coating according to claim 4, wherein in the first step, the dripping speed of the liquid B slowly injected into the liquid A is controlled to be 30-60 drops/min, and each drop is added for 5-10 min at intervals of 5-mL, and stirring is kept during the period.
6. The method for preparing the super-hydrophobic anti-fouling paint by the self-assembly method according to claim 1, wherein in the second step, the cross-linking agent comprises tetraethyl silicate and perfluoro decyl trimethoxy silane, and the mass ratio of the tetraethyl silicate to the perfluoro decyl trimethoxy silane is 5-8: 1, a step of; crosslinking agent and SiO 2 Nanowire @ TiO 2 The mass volume ratio of the dispersion liquid of (2) is 1g:4ml.
7. The method for preparing the super-hydrophobic anti-fouling paint by a self-assembly method according to claim 1, wherein in the third step, the preparation method of the primer is as follows: weighing waterborne epoxy putty A, butyl acetate B and waterborne epoxy curing agent emulsion C with preset mass, magnetically stirring, vacuumizing for 2-3 min to remove bubbles, and uniformly coating the waterborne epoxy putty A, butyl acetate B and waterborne epoxy curing agent emulsion C on an epoxy resin plate to serve as a primer; wherein, the volume ratio of the aqueous epoxy putty A to the butyl acetate B to the aqueous epoxy hardener emulsion C is 1:0.2 to 0.6:1, and magnetically stirring for 5-30 min.
8. The method for preparing the super-hydrophobic anti-fouling coating by using the self-assembly method according to claim 1, wherein in the fourth step, the curing time is 24-72 hours; the pore diameter of the standard sample separating sieve is 100 meshes.
9. A superhydrophobic anti-fouling coating prepared by the method for preparing a superhydrophobic anti-fouling coating according to any one of claims 1-8.
10. A superhydrophobic anti-fouling coating prepared by the method for preparing a superhydrophobic anti-fouling coating by the self-assembly process according to any one of claims 1-8, which is used as a protective coating on tunnel facility surfaces.
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