CN116179004B - 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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- 230000003075 superhydrophobic effect Effects 0.000 title claims abstract description 71
- 238000000034 method Methods 0.000 title claims abstract description 49
- 238000001338 self-assembly Methods 0.000 title claims abstract description 32
- 230000003373 anti-fouling effect Effects 0.000 title claims abstract description 21
- 239000003973 paint Substances 0.000 title claims abstract description 17
- 229910004298 SiO 2 Inorganic materials 0.000 claims abstract description 77
- 239000002070 nanowire Substances 0.000 claims abstract description 62
- 238000000576 coating method Methods 0.000 claims abstract description 51
- 239000011248 coating agent Substances 0.000 claims abstract description 50
- 238000001556 precipitation Methods 0.000 claims abstract description 11
- 238000005507 spraying Methods 0.000 claims abstract description 10
- 238000002360 preparation method Methods 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 62
- 229910010413 TiO 2 Inorganic materials 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
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 36
- 238000003756 stirring Methods 0.000 claims description 34
- 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 21
- 239000006185 dispersion Substances 0.000 claims description 18
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 16
- 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
- 239000007788 liquid Substances 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
- 238000000967 suction filtration Methods 0.000 claims description 8
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 8
- 238000005303 weighing Methods 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000004848 polyfunctional curative Substances 0.000 claims description 3
- 238000007711 solidification Methods 0.000 claims description 3
- 230000008023 solidification Effects 0.000 claims description 3
- 239000011148 porous material Substances 0.000 claims description 2
- 238000004140 cleaning Methods 0.000 abstract description 6
- 239000004005 microsphere Substances 0.000 abstract description 4
- 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
- 238000003760 magnetic stirring Methods 0.000 description 5
- 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
- 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
- 238000002386 leaching Methods 0.000 description 2
- 239000000203 mixture Substances 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
- 125000004122 cyclic group Chemical group 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
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- 231100000719 pollutant Toxicity 0.000 description 1
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- 235000012045 salad Nutrition 0.000 description 1
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Classifications
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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
- 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, wherein SiO 2 nano wire with high mechanical strength is selected to replace common SiO 2 microsphere, tiO 2 is wrapped on the surface of the microsphere, a preparation mode of spraying solvent on primer and inducing self-assembly precipitation method is adopted on the basis of inorganic-organic hybridization to form an array SiO 2 nano wire@Ti 2 super-hydrophobic coating, super-hydrophobicity, wear resistance and weather resistance are enhanced, and the function of degrading organic pollutants on the surface under the action of illumination is endowed. 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, wherein SiO 2 nano wires with high mechanical strength are selected to replace common SiO 2 microspheres, tiO 2 is wrapped on the surfaces of the nano wires, an array SiO 2 nano wire@TiO 2 super-hydrophobic coating , is formed by adopting a preparation mode of a solvent-induced self-assembly precipitation method on the basis of inorganic-organic hybridization, the super-hydrophobicity and wear-resistance and weather resistance are enhanced, organic pollutants on the surfaces are degraded under the action of illumination, natural rainwater or common tap water is used for leaching, and dust stained on the surfaces can be carried away by water to realize a self-cleaning function.
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 a TiO 2 shell structure: dispersing SiO 2 nanowire powder in an organic solution in an ultrasonic manner, and marking the solution as A; butyl titanate is dissolved in an organic solution and is marked as liquid B; dropwise adding the solution B into the solution A under the stirring condition, and stirring and reacting to obtain a dispersion liquid of SiO 2 nanowire@Ti 2;
Step two, preparing SiO 2 nanowire @ TiO 2 super-hydrophobic particles: heating the dispersion liquid of SiO 2 nanowire@TiO 2 to 40-60 ℃, adding a cross-linking agent, magnetically stirring for 10-40 min, performing ultrasonic dispersion, 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: the SiO 2 nanowire@TiO 2 super-hydrophobic particles are uniformly sieved and dropped on a primer coated with dichloroethane solution by a self-assembly precipitation method by using a standard sample classifying screen, and the dichloroethane is slowly volatilized to induce the SiO 2 nanowire@TiO 2 super-hydrophobic particles to be deposited on the surface of the primer near a solid-liquid-gas three-phase contact line to form regular stripes. And after the solidification is finished, removing particles which are not combined with the primer, so as to prepare the SiO 2 nanowire @ TiO 2 array-shaped super-hydrophobic coating.
Further improved, the diameter of the SiO 2 nanowire is 20-100 nm, and the length is more than 10 mu m.
In the first step, the mass-volume ratio of the SiO 2 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 at intervals of 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; the mass volume ratio of the cross-linking agent to the SiO 2 nanowire@Ti 2 dispersion 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 2 nano wires with high mechanical strength are selected to replace common SiO 2 microspheres, so that the compressive strength of the coating can be enhanced, and the bonding strength of the coating can be enhanced;
(3) According to the invention, the SiO 2 nanowire is coated with the TiO 2, and the surface of the coating is modified, so that the coating has super-hydrophobic performance, and simultaneously is endowed with ultraviolet ageing resistance, acid and alkali resistance and the like, and finally has excellent durability.
(4) Through spraying dichloroethane solution on the primer, the primer is easy to volatilize, self-assembly precipitation is induced, and the SiO 2 nanowire@Ti 2 super-hydrophobic coating with regular arrangement is prepared, so that the 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) Coating TiO 2 shell structure: dispersing SiO 2 nanowire powder in a mixed solution of ethanol and acetonitrile by ultrasonic waves, and marking the mixed solution as solution A; dissolving butyl titanate into a mixed solution of ethanol and acetonitrile, and marking the mixed solution as solution B; slowly injecting the solution B into the solution A under the stirring condition, and stirring and reacting to obtain a dispersion liquid of SiO 2 nanowire @ TiO 2;
(2) Preparing SiO 2 nanowire @ TiO 2 super-hydrophobic particles: heating the dispersion liquid of SiO 2 nanowire@TiO 2 to 40-60 ℃, adding cross-linking agents of tetraethyl silicate and perfluoro decyl trimethoxy silane, magnetically stirring 10-40 min, performing ultrasonic dispersion, performing suction filtration, 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: through a self-assembly precipitation method, siO 2 nanowire@TiO 2 super-hydrophobic particles are uniformly sieved and dropped on paint coated with dichloroethane solution by a 100-target quasi-sample sieve, and the dichloroethane is slowly volatilized to induce the SiO 2 nanowire@TiO 2 super-hydrophobic particles to be deposited on the surface of the primer near a solid-liquid-gas three-phase contact line to form regular stripes. And after the solidification is finished, removing particles which are not combined with the primer, so as to prepare the SiO 2 nanowire @ TiO 2 array-shaped super-hydrophobic coating.
In the method, in the step (1), white powder with the diameter of the SiO 2 nanowire being 20-100 nm and the length being more than 10 mu m is injected into the solution A, and the ratio of the SiO 2 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) Coating TiO 2 shell structure: ultrasonically dispersing SiO 2 nanowire powder 20g with the diameter of 20 nm and the length of more than 10 mu m in a mixed solution of 100ml ethanol and acetonitrile, and marking the mixed solution as solution A; 5g of butyl titanate is dissolved in 100ml of mixed solution of ethanol and acetonitrile and is marked as solution B; wherein the ratio of SiO 2 nanowire to butyl titanate is 2 g:0.5 Slowly injecting the solution B into the solution A under the stirring condition, controlling the dripping speed to be 30 drops/min, adding 5mL drops at intervals of 5min, keeping stirring, and reacting at 20 ℃ for 30 h to obtain a dispersion of SiO 2 nanowire @ TiO 2;
(2) Preparing SiO 2 nanowire @ TiO 2 super-hydrophobic particles: the dispersion of SiO 2 nanowire @ TiO 2 is heated to 40 ℃, 50g of cross-linking agents tetraethyl silicate and perfluorodecyl trimethoxysilane are added, and the ratio of the two is 5:1 magnetically stirring 40 min, performing ultrasonic dispersion, performing suction filtration 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, after magnetic stirring for 5min min, vacuumizing for 2-3 min to remove bubbles, uniformly coating the bubbles on an epoxy resin plate to serve as a primer, and after drying, spraying an dichloroethane solution on the primer;
(4) Preparing a hydrophobic coating by a self-assembly method: through a self-assembly precipitation method, siO 2 nanowire@TiO 2 super-hydrophobic particles are uniformly sieved and dropped on a primer coated with dichloroethane solution by a 100-target quasi-sample sieve, and the dichloroethane is slowly volatilized to induce the SiO 2 nanowire@TiO 2 super-hydrophobic particles to be deposited on the surface of the primer near a solid-liquid-gas three-phase contact line to form regular stripes. After 24h is solidified, particles which are not combined with the primer are removed, so that the SiO 2 nanowire@TiO 2 array-shaped super-hydrophobic coating is prepared.
Example 2:
(1) Coating 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 the mixed solution as solution A; 10g of butyl titanate is dissolved in 200ml of mixed solution of ethanol and acetonitrile and is marked as solution B; wherein the ratio of SiO 2 nanowire to butyl titanate is 4 g:1 ml, slowly injecting the solution B into the solution A under the stirring condition, controlling the dripping speed at 40 drops/min, adding 5 mL drops at intervals of 6 min, keeping stirring, and reacting at 30 ℃ for 20h to obtain a dispersion of SiO 2 nanowire@Ti 2;
(2) Preparing SiO 2 nanowire @ TiO 2 super-hydrophobic particles: the dispersion of SiO 2 nanowire @ TiO 2 is heated to 45 ℃, and 100g of cross-linking agents tetraethyl silicate and perfluorodecyl trimethoxysilane are added in a ratio of 6:1, magnetically stirring 30min, performing ultrasonic dispersion, performing suction filtration 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, after magnetic 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 an dichloroethane solution on the primer after drying;
(4) Preparing a hydrophobic coating by a self-assembly method: through a self-assembly precipitation method, siO 2 nanowire@TiO 2 super-hydrophobic particles are uniformly sieved and dropped on a primer coated with dichloroethane solution by a 100-target quasi-sample sieve, and the dichloroethane is slowly volatilized to induce the SiO 2 nanowire@TiO 2 super-hydrophobic particles to be deposited on the surface of the primer near a solid-liquid-gas three-phase contact line to form regular stripes. After curing 36 h, the particles which are not combined with the primer are removed, so that the SiO 2 nanowire@TiO 2 super-hydrophobic coating is prepared.
Example 3:
(1) Coating TiO 2 shell structure: the SiO 2 nanowire powder 60g with the diameter of 20 nm and the length of more than 10 mu m is dispersed in a mixed solution of 300ml ethanol and acetonitrile by ultrasonic, 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 the ratio of SiO 2 nanowire to butyl titanate is 6 g:2 ml, slowly injecting the solution B into the solution A under the stirring condition, controlling the dripping speed at 45 drops/min, adding 5mL drops at intervals of 7 min each, keeping stirring, and reacting at 40 ℃ for 10 h to obtain a dispersion of SiO 2 nanowire@Ti 2;
(2) Preparing SiO 2 nanowire @ TiO 2 super-hydrophobic particles: the dispersion of SiO 2 nanowire @ TiO 2 is heated to 50 ℃, 150g of cross-linking agents tetraethyl silicate and perfluorodecyl trimethoxysilane are added, and the ratio of the two is 7:1, magnetically stirring 20min, performing ultrasonic dispersion, performing suction filtration 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, after magnetic 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 an dichloroethane solution on the primer after drying;
(4) Preparing a hydrophobic coating by a self-assembly method: through a self-assembly precipitation method, siO 2 nanowire@TiO 2 super-hydrophobic particles are uniformly sieved and dropped on a primer coated with dichloroethane solution by a 100-target quasi-sample sieve, and the dichloroethane is slowly volatilized to induce the SiO 2 nanowire@TiO 2 super-hydrophobic particles to be deposited on the surface of the primer near a solid-liquid-gas three-phase contact line to form regular stripes. After curing 48 h, removing particles which are not combined with the primer, thereby preparing the SiO 2 nanowire@TiO 2 super-hydrophobic coating.
Example 4:
(1) Coating TiO 2 shell structure: dispersing SiO2 nanowire powder 80 g with the diameter of 20nm 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 solution A; 40g of butyl titanate is dissolved in 400ml of mixed solution of ethanol and acetonitrile and is marked as solution B; wherein the ratio of SiO 2 nanowire to butyl titanate is 8 g:4 ml, slowly injecting the solution B into the solution A under the stirring condition, controlling the dripping speed at 50 drops/min, adding 5mL drops at intervals of 8 min, keeping stirring, and reacting at 45 ℃ for 3 h to obtain a dispersion of SiO 2 nanowire@Ti 2;
(2) Preparing SiO 2 nanowire @ TiO 2 super-hydrophobic particles: the dispersion of SiO 2 nanowire @ TiO 2 is heated to 55 ℃, 200g of cross-linking agents tetraethyl silicate and perfluorodecyl trimethoxysilane are added, and the ratio of the two is 7.5:1, magnetically stirring 15 min, performing ultrasonic dispersion, performing suction filtration 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, after magnetic 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 an dichloroethane solution on the primer after drying;
(4) Preparing a hydrophobic coating by a self-assembly method: through a self-assembly precipitation method, siO 2 nanowire@TiO 2 super-hydrophobic particles are uniformly sieved and dropped on a primer coated with dichloroethane solution by a 100-target quasi-sample sieve, and the dichloroethane is slowly volatilized to induce the SiO 2 nanowire@TiO 2 super-hydrophobic particles to be deposited on the surface of the primer near a solid-liquid-gas three-phase contact line to form regular stripes. After curing 60 h, the particles which are not combined with the primer are removed, so that the SiO 2 nanowire@TiO 2 super-hydrophobic coating is prepared.
Example 5:
(1) Coating 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 solution A; 40g of butyl titanate is dissolved in 400ml of mixed solution of ethanol and acetonitrile and is marked as solution B; wherein the ratio of SiO 2 nanowire to butyl titanate is 8 g:4 ml, slowly injecting the solution B into the solution A under the stirring condition, controlling the dripping speed to be 60 drops/min, adding 5 drops mL each time at intervals of 10 min, keeping stirring, and reacting at 50 ℃ for 2h to obtain a dispersion liquid of SiO 2 nanowire@Ti 2;
(2) Preparing SiO 2 nanowire @ TiO 2 super-hydrophobic particles: the dispersion of SiO 2 nanowire @ TiO 2 is heated to 60 ℃,200 g of cross-linking agents tetraethyl silicate and perfluorodecyl trimethoxysilane are added, and the ratio of the two is 8:1, magnetically stirring 10min, performing ultrasonic dispersion, performing suction filtration 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, after magnetic 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 an dichloroethane solution on the primer after drying;
(4) Preparing a hydrophobic coating by a self-assembly method: through a self-assembly precipitation method, siO 2 nanowire@TiO 2 super-hydrophobic particles are uniformly sieved and dropped on a primer coated with dichloroethane solution by a 100-target quasi-sample sieve, and the dichloroethane is slowly volatilized to induce the SiO 2 nanowire@TiO 2 super-hydrophobic particles to be deposited on the surface of the primer near a solid-liquid-gas three-phase contact line to form regular stripes. After curing 72 h, the particles which are not combined with the primer are removed, so that the SiO 2 nanowire@TiO 2 super-hydrophobic coating is prepared.
Performance detection
(1) Superhydrophobicity: the contact angle was measured with German DATAPHYSICS OCA (with temperature control accessory accurate temperature control range of-30 ℃ C. To 160 ℃ C.) and the drop quantity was 4 [ mu ] L, 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, radiant power 0.68W/m 2, cyclic procedure: ultraviolet irradiation for 8 h at 50 ℃, condensation for 4h, 40 ℃ and aging time 1440 h; 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. The self-cleaning properties of the coating were characterized by measuring the change in contact angle of the coating surface 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 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 (5)
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 a TiO 2 shell structure: dispersing SiO 2 nanowire powder in an organic solution in an ultrasonic manner, and marking the solution as A; butyl titanate is dissolved in an organic solution and is marked as liquid B; dropwise adding the solution B into the solution A under the stirring condition, and stirring and reacting to obtain a dispersion liquid of SiO 2 nanowire@Ti 2; the mass volume ratio of the SiO 2 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, a step of;
Step two, preparing SiO 2 nanowire @ TiO 2 super-hydrophobic particles: heating the dispersion liquid of SiO 2 nanowire@TiO 2 to 40-60 ℃, adding a cross-linking agent, magnetically stirring for 10-40 min, performing ultrasonic dispersion, suction filtration and drying to obtain SiO 2 nanowire@TiO 2 super-hydrophobic particles; 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; the mass volume ratio of the cross-linking agent to the SiO 2 nanowire@Ti 2 dispersion is 1g:4ml;
Brushing primer and spraying dichloroethane solution on the primer; the preparation method of the primer comprises 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
Step four, preparing a hydrophobic coating by a self-assembly method: the SiO 2 nanowire@TiO 2 super-hydrophobic particles are uniformly sieved and dropped on a primer coated with dichloroethane solution by a self-assembly precipitation method by using a standard sample sieve, and the dichloroethane is slowly volatilized to induce the SiO 2 nanowire@TiO 2 super-hydrophobic particles to be deposited on the surface of the primer near a solid-liquid-gas three-phase contact line to form regular stripes; and after the solidification is finished, removing particles which are not combined with the primer, so as to prepare the SiO 2 nanowire @ TiO 2 array-shaped super-hydrophobic coating.
2. The method for preparing the super-hydrophobic and anti-fouling coating by using the self-assembly method according to claim 1, wherein the diameter of the SiO 2 nanowire is 20-100 nm, and the length is more than 10 μm.
3. The method for preparing the super-hydrophobic anti-fouling coating 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.
4. The method for preparing the super-hydrophobic anti-fouling paint by using the self-assembly method according to claim 3, wherein 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 at intervals of 5-10 min at intervals of 5 mL, and stirring is kept during the period.
5. 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.
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