CN113292876B - Super-hydrophobic coating and preparation method and application thereof - Google Patents

Super-hydrophobic coating and preparation method and application thereof Download PDF

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CN113292876B
CN113292876B CN202110600013.2A CN202110600013A CN113292876B CN 113292876 B CN113292876 B CN 113292876B CN 202110600013 A CN202110600013 A CN 202110600013A CN 113292876 B CN113292876 B CN 113292876B
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coating
super
micro
nano particles
solvent
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CN113292876A (en
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汪黎明
杨金婵
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Guangzhou University
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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
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • 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
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/66—Additives characterised by particle size
    • C09D7/67—Particle size smaller than 100 nm
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/0056—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the compounding ingredients of the macro-molecular coating
    • D06N3/0063—Inorganic compounding ingredients, e.g. metals, carbon fibres, Na2CO3, metal layers; Post-treatment with inorganic compounds
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/04—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06N3/042—Acrylic polymers
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
    • D06N3/128—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with silicon polymers
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00—Coated paper; Coating material
    • D21H19/10—Coatings without pigments
    • D21H19/14—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00—Coated paper; Coating material
    • D21H19/10—Coatings without pigments
    • D21H19/14—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12
    • D21H19/20—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12 comprising macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00—Coated paper; Coating material
    • D21H19/10—Coatings without pigments
    • D21H19/14—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12
    • D21H19/24—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12 comprising macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H19/32—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12 comprising macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds obtained by reactions forming a linkage containing silicon in the main chain of the macromolecule
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N2209/00—Properties of the materials
    • D06N2209/14—Properties of the materials having chemical properties
    • D06N2209/142—Hydrophobic

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  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Textile Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Nanotechnology (AREA)
  • Dispersion Chemistry (AREA)
  • Paints Or Removers (AREA)

Abstract

The invention provides a super-hydrophobic coating and a preparation method and application thereof. The coating can be coated on the surface of a flexible or rigid material, and also can be coated on a flat or rough plastic, metal and other material substrates, can realize the functions of self-cleaning, water resistance, freeze prevention, fog prevention, fluid drag reduction and corrosion prevention, and can be widely applied to the fields of buildings, household appliances, transportation, clothes, electronic devices, liquid transportation and the like.

Description

Super-hydrophobic coating and preparation method and application thereof
Technical Field
The invention belongs to the technical field of functional materials, and particularly relates to a super-hydrophobic coating as well as a preparation method and application thereof.
Background
The preparation of the super-hydrophobic coating starts from the understanding and research of people on the extreme wetting phenomenon of the natural world such as lotus leaves, rose petals, desert beetles and the like, and the super-hydrophobic coating has excellent performances such as self-cleaning, ice coating prevention, corrosion prevention, bacteria resistance and the like, so the super-hydrophobic coating has wide application value on the coating of the base materials such as glass, ceramic tile cement, textiles, metal and the like. The preparation of superhydrophobic surfaces is generally motivated by the use of low surface energy materials such as polydimethylsiloxanes, fluorochemicals, etc.; and secondly, constructing a micro-nano composite coarse structure.
In the related art, the process for preparing the super-hydrophobic surface is generally complex and time-consuming, for example, in some processes, a substrate needs to be polished and then soaked in acid solution for etching to form a certain micro-nano structure. In some processes, glass is first frosted to obtain a rough structure and then treated with silane at high temperature. In addition, the lowest surface energy of the fluorine-containing compound can be as low as 15.0 mN/m, so that the fluorine-containing compound is used in many existing super-hydrophobic technologies, and the fluorine-containing silane modified acrylate emulsion is used for preparing the super-hydrophobic surface, but fluorine monomers and compounds thereof are high in price and difficult to apply to common industrial products.
Silicones can exhibit good hydrophobic properties in coatings, such as polydimethylsiloxane, which has a soft molecular chain segment, low surface energy and high spreadability, which properties enable it to be used for surface modification and control, but polydimethylsiloxane has weak intermolecular forces, poor adhesion to substrates, low mechanical strength, susceptibility to scratching and damage, and short lifetime. The process flow of the method for constructing the template method with high roughness, the electrostatic weaving method, the plasma etching method and the like is relatively complex, and the requirement on production equipment is high. Although inorganic powder materials (generally, silicon dioxide, titanium dioxide, zinc oxide, modifiers thereof and the like) are added into the polymer, the hydrophobic property of the high-altitude coating can be improved by utilizing the hydrophobic property and the surface roughness of the powder materials, and finally the super-hydrophobic composite material is obtained. However, the high content of inorganic powder additive causes poor adhesion between the polymer emulsion and the base material, affects the film forming property of the original polymer emulsion, causes the problems of too high system viscosity and limited coating processes such as spraying, dip coating and the like, and reduces the transparency of the coating, so that the application places of the coating are greatly reduced, and therefore, when the super-hydrophobic composite material is prepared, the balance between the roughness and the transparency is required.
Disclosure of Invention
The present invention is directed to solving at least one of the above problems in the prior art. Therefore, the invention provides a super-hydrophobic coating which can be coated on the surface of a flexible or rigid material, can also be coated on flat or rough plastic, metal and other material substrates, can realize the functions of self-cleaning, water resistance, freeze prevention, fog prevention, fluid drag reduction and corrosion prevention, and can be widely applied to the fields of buildings, household appliances, transportation, clothes, electronic devices, liquid transportation and the like.
The invention also provides a preparation method of the super-hydrophobic coating.
The invention also provides application of the super-hydrophobic coating.
The invention provides a super-hydrophobic coating, which is prepared from silane compounds, micro-nano particles and an auxiliary agent, wherein the mass ratio of the silane compounds to the micro-nano particles is (0.01 to 100): 1, the particle size of the micro-nano particles is between 1 nm and 100 mu m.
In the invention, the term "superhydrophobic" refers to a state that water drops fall on the surface and are not adhered to the surface, and the water drops can quickly bounce or slide in a spherical shape, similar to the water drops on the surface of lotus leaves.
In the present invention, "super-hydrophobic" can be generally considered as the material having a static contact angle of more than 150 ° and a rolling angle of less than 10 °.
The super-hydrophobic coating disclosed by the invention at least has the following beneficial effects:
in the formula of the super-hydrophobic coating, the silane compound provides hydrophobicity, the micro-nano particles provide a coarse structure and system strength, and the auxiliary agent provides enhanced coating strength. Specifically, based on the low surface energy characteristic provided by the silane compound and the surface rough structure provided by the micro-nano particles, under the combined action of the auxiliary agent, the main body component in the coating can quickly form chemical bonds on the surfaces of various substrates, and the super-hydrophobic performance can be realized on the surfaces of various substrates.
The super-hydrophobic coating disclosed by the invention can spontaneously generate a stable multi-scale low-surface-energy molecular structure on the surface of a substrate by utilizing the chemical action between micromolecular silane or linear macromolecular silane, and meanwhile, a silane system can also react with the surface of micro-nano particles, so that the whole super-hydrophobic coating is stably attached to the surface of a solid substrate, and the super-hydrophobic coating can be super-hydrophobic regardless of the substrates such as rough fabrics, woods and the like or flat substrates such as glass, plastics and the like.
The super-hydrophobic coating does not need to use a super-hydrophobic fabric finishing agent containing long-chain alkyl and a silane coupling agent, so thatThe micro-nano particles are not limited to nano SiO 2 Other inorganic and organic nanoparticles are also possible.
The super-hydrophobic coating mainly utilizes micromolecular silane or linear silane as a low surface energy substance source, does not need to use tetraethoxysilane as a silicon source, does not need to use a component containing amino as a catalyst, does not need to be heated, and does not need to add a curing agent.
The superhydrophobic coating of the invention can react with the surface of a plurality of base materials through chemical crosslinking so as to be firmly attached to the surface of a substrate, so that the substrate treated by the superhydrophobic coating of the invention is not limited to a fabric, can be a plurality of other solid materials, and can be suitable for active metal surfaces.
The super-hydrophobic coating can quickly generate stable super-hydrophobic coatings on the surfaces of various rough or flat solid substrates.
The super-hydrophobic coating disclosed by the invention is low in raw material cost, small in temperature influence and good in transparency.
The super-hydrophobic coating has good adhesive force and wide application range, and is particularly suitable for various pipelines and electronic components.
The super-hydrophobic coating can realize the super-hydrophobic effect on the surface of the base material within seconds or minutes.
The super-hydrophobic coating can be prepared at room temperature without adding tetraethoxysilane and heating treatment.
According to some embodiments of the invention, the mass ratio of the silane compound to the micro-nano particles is (0.1 to 10): 1.
according to some embodiments of the invention, the mass ratio of the silane compound to the micro-nano particles is (0.3 to 3): 1.
according to some embodiments of the invention, the silane compound comprises a linear, branched R 2 -Si-(OR) 2 、Si 2 R'(OR) 2 R 4 Cyclic or linear [ SiR ] 2 O] m Polysiloxane, modified polysiloxane, R n -Si-(OR) 4-n 、Si 2 R'(OR 2 ) 6-n R n 、Si 3 R' 2 (OR) 8-n R n 、Si 4 R' 3 (OR) 10-n R n 、Si(ON=CR 2 ) 4 Wherein R is C 1 -C 20 Straight or branched chain alkyl, cycloalkyl, aralkenyl and derivatives thereof;
m is 1 to 100000;
n can be 0 to 8;
OR comprises NR 2 An ester group;
r' comprises O and CH 2 NR, S, NR-R-NR and R-O-R.
According to some embodiments of the invention, the silane compound comprises at least one of dimethyldimethoxysilane, dimethyldichlorosilane, methyltrimethoxysilane, hydrogen-containing silicone oil, diethyldimethoxysilane, diethyldiethoxysilane, dipropyldimethoxysilane, dipropyldiethoxysilane, dimethyldiethoxysilane, polymethylalkylsiloxane, polydimethylsiloxane, hydrogen-containing silicone oil, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, tetramethoxysilane, tetraethoxysilane, bis (triethoxysilyl) methane, 1, 2-bis (triethoxysilyl) ethane, methyltributanioximosilane, γ -aminopropyl-triethoxysilane, and γ -glycidoxypropyl-propyltrimethoxysilane.
According to some embodiments of the present invention, the micro-nano particles include inorganic micro-nano particles and organic micro-nano particles.
According to some embodiments of the invention, the inorganic micro-nano particles comprise silica, silicate, carbonate, carbide, sulfate, sulfide, titanate, hydroxide, quartz powder, wollastonite, barite powder, white rose powder, crystalline calcium carbonate, dolomite powder, kaolin, fibrous talc, calcium carbonate-containing talc, mica powder, diatomaceous earth, flaky talc, natural graphite, barium sulfate, white carbon black, alumina, zirconia, zinc oxide, titanium oxide and aluminum powder.
According to some embodiments of the present invention, the organic micro-nano particles include regenerated cellulose, synthetic resin, and rubber particles.
According to some embodiments of the invention, the micro-nano particles comprise titanium dioxide particles and silicon dioxide particles.
According to some embodiments of the present invention, the micro-nano particles have a particle size of 1 nm to 100 μm.
According to some embodiments of the invention, the micro-nano particles have a particle size of between 10 nm and 5 μm.
According to some embodiments of the invention, the micro-nano particles have a particle size of between 60 nm and 1 μm.
According to some embodiments of the invention, the adjuvant comprises ethyl cyanoacrylate, epoxy acrylate, 3-aminopropyltriethoxysilane, gamma-methacryloxypropyltrimethoxysilane, and a cyclic ethyl acrylate.
According to some embodiments of the invention, the preparation feedstock further comprises a solvent.
The solvent provides good dispersibility and coatability of the components.
The second aspect of the invention provides a method for preparing the super-hydrophobic coating, wherein the silane compound, the micro-nano particles and the auxiliary agent are uniformly mixed in a solvent.
According to some embodiments of the invention, the stirring and dispersing time for uniformly mixing the silane compound, the micro-nano particles and the auxiliary agent in the solvent can be 0.01 to 100 hours.
The method for preparing the super-hydrophobic coating has at least the following beneficial effects:
the super-hydrophobic coating can be prepared at room temperature without heating treatment.
The super-hydrophobic coating is easy to construct and can be constructed on the surfaces of various base materials such as metal, plastic and the like.
In the preparation process, the surface roughness is improved by adding the micro-nano particles, a cross-linking reaction is carried out, a stable super-hydrophobic three-dimensional structure is formed, the super-hydrophobic coating can be obtained in a very short time (within seconds or minutes), and the preparation process is convenient and rapid.
According to some embodiments of the invention, the solvent comprises an alcohol solvent, a ketone solvent, an ether solvent and an ester solvent.
According to some embodiments of the invention, the solvent may be a water-miscible solvent.
According to some embodiments of the invention, the solvent comprises at least one of methanol, ethanol, isopropanol, acetone, methyl ethyl ketone, diethyl ether, diisopropyl ether, tetrahydrofuran, ethyl acetate, methyl acetate, propylene oxide, acetone, methyl butanone, methyl isobutyl ketone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and ethylene glycol monobutyl ether.
According to some embodiments of the invention, the solvent may be a water-insoluble solvent.
According to some embodiments of the invention, the solvent comprises at least one of benzene, toluene, xylene, styrene, butyltoluene, vinyltoluene, trichloroethylene, dichloromethane, chlorobenzene, dichlorobenzene, carbon disulfide, carbon tetrachloride, n-pentane, n-hexane, cyclohexane, octane, hexadecane, liquid paraffin, and the like.
According to some embodiments of the invention, the mass ratio of the solvent to the silane compound is (0.01 to 1000): 1.
according to some embodiments of the invention, the mass ratio of the solvent to the silane compound is (0.01 to 100): 1.
according to some embodiments of the invention, the mass ratio of the solvent to the silane compound is (0.05 to 20): 1.
in a third aspect of the invention, a super-hydrophobic coating is provided, which is prepared from the super-hydrophobic coating.
According to some embodiments of the invention, the superhydrophobic coating has a static contact angle of greater than 150 ° and a sliding angle of less than 10 °.
The super-hydrophobic coating has good wear-resisting and durable performances.
The super-hydrophobic coating can further enhance various performances by modifying inorganic powder, and can meet different application requirements.
The super-hydrophobic coating is coated on the surface of a substrate, and the substrate can be made of metal or nonmetal materials.
The super-hydrophobic coating is coated on the surface of a base material, and the base material can be metal, including aluminum, iron, copper, zinc, titanium, magnesium, tin, nickel, silver and alloys and oxides thereof.
The super-hydrophobic coating is coated on the surface of a base material, and the base material can be plastic.
The super-hydrophobic coating is coated on the surface of a substrate, and the substrate can be ceramic, including conventional and functional ceramics such as glass ceramic, oxide ceramic, nitride ceramic, carbide ceramic, boride ceramic, alumina ceramic, zirconia ceramic, magnesia ceramic, silicon nitride ceramic, boron nitride ceramic, aluminum nitride ceramic, titanium nitride ceramic, silicon carbide ceramic, boron carbide ceramic, titanium carbide ceramic, zirconium carbide ceramic and the like.
The super-hydrophobic coating is coated on the surface of a base material, and the base material can be a composite material.
The super-hydrophobic coating is coated on the surface of a base material, and the base material can be a rigid base material.
The super-hydrophobic coating is coated on the surface of a base material, and the base material can be a flexible base material.
The super-hydrophobic coating of the present invention is coated on the surface of a substrate, which may be a polymer substrate including polyolefins (polyethylene, polypropylene, polystyrene, ABS resin, polyisobutylene, etc.), polyhalogenated olefins (polytetrafluoroethylene, polyvinylidene fluoride, polyvinyl chloride hydrocarbon, etc.), polyethers (polyoxymethylene, polyphenylene oxide, chlorinated polyether, polyphenylene sulfide, polyether ether ketone, etc.), polyesters (polycarbonate, polybutylene terephthalate, dimethyl terephthalate, polyarylate, etc.), polyacrylic acids and derivatives thereof (polyacrylonitrile, polymethyl methacrylate, polyethyl methacrylate, polybutyl methacrylate, etc.), polyurethanes, polysulfones (polysulfone, polyarylsulfone, and polyethersulfone), polyamides (aliphatic polyamides and aromatic polyamides, polybutyrolactam, polycaprolactam, poly 7-aminoheptanoic acid, polycapryllactam, poly 11-aminoundecanoic acid, polydodecalactam, polyhexamethyleneadipamidehexanediaminebacic acid, polyhexamethylenediaminodecanedioic acid, polyisophthaloylamide, isophthalamide, metaphenylenediamine, polyterephthalamide, polyepoxy resins (polyglycidyl oils, the former including glycidyl ethers, glycidol esters, the latter including aliphatic resins, epoxyolefins, and derivatives thereof), and derivatives thereof.
The super-hydrophobic coating can be applied by spin coating, drop coating, dip coating, brush coating, blade coating and spray coating.
After the super-hydrophobic coating is coated, the drying temperature is 0-200 ℃, and the drying time is 0.01-1000 h.
Drawings
FIG. 1 is a schematic view of the application of the coating of example 1 to a wood surface with optical droplets added.
FIG. 2 is a schematic view of the application of the coating of example 1 to a glass surface with optical droplets dropped.
FIG. 3 is a schematic view of the optical droplets dropped on the surface of polytetrafluoroethylene coated with the coating of example 1.
FIG. 4 is a schematic view of the application of the coating of example 1 to a paper surface with optical droplets dropped.
FIG. 5 is a schematic of a water column wash test for a coating prepared from the coating of example 1.
FIG. 6 is a schematic view of an oil-water separation test in which the coating material of example 1 was applied to cotton cloth.
FIG. 7 is a schematic representation of a continuous boiling water test of a coating prepared from the coating of example 1.
Fig. 8 is a graph of the results of the coating contact angle test of example 2.
Fig. 9 is a graph of the coating contact angle test results of example 3.
Fig. 10 is a graph of the results of the coating contact angle test of example 4.
FIG. 11 is a graph of the coating contact angle test results of example 5.
Fig. 12 is a graph of the coating contact angle test results of example 6.
FIG. 13 is a graph of the coating contact angle test results of example 7.
FIG. 14 is a graph of the coating contact angle test results of example 8.
FIG. 15 is a graphical representation of the low temperature test results for the coating of example 3.
FIG. 16 is the contact angle test results of the coating of example 4 before rubbing.
Fig. 17 is the contact angle test results after rubbing of the coating of example 4.
Detailed Description
The following are specific examples of the present invention, and the technical solutions of the present invention will be further described with reference to the examples, but the present invention is not limited to the examples.
Example 1
The embodiment prepares the super-amphiphobic coating, and the specific preparation process comprises the following steps:
20ml of isopropyl alcohol, 0.3g of titanium dioxide (100 nm), and 3ml of ethyl cyanoacrylate were sequentially added to 5g of dimethyldimethoxysilane, and the mixture was dispersed for 3 min with stirring.
When the superhydrophobic coating of the present embodiment is used, the uniformly mixed liquid may be applied to the surface of the substrate by spin coating.
70. Air drying at deg.C for 2 min, washing the coating surface with distilled water and ethanol, and air drying at room temperature for 5 min to obtain the final product.
Example 2
The embodiment prepares the super-hydrophobic coating, and the specific preparation process comprises the following steps:
20ml of isopropanol, 2g of methyltrimethoxysilane, 0.5g of silicon dioxide (100 nm) and 5ml of ethyl cyanoacrylate are sequentially added into 5g of dimethyldichlorosilane, stirred and dispersed for 3 min, and the uniformly mixed liquid is coated on the surface of the glass substrate in a spraying mode.
50. Air drying at deg.C for 5 min, washing the coating surface with distilled water and ethanol, and air drying at 20 deg.C for 3 min to obtain super-hydrophobic coating.
Example 3
The embodiment prepares the super-hydrophobic coating, and the specific preparation process comprises the following steps:
10ml of toluene, 0.6g of silicon dioxide (100 nanometers) and 1.2g of epoxy acrylate are sequentially added into 5g of dimethyldichlorosilane, stirred and dispersed for 3 min, and the uniformly mixed liquid is coated on the surface of a base material in a dip-coating mode.
25. Air drying at deg.C for 5 min, washing the coating surface with distilled water and ethanol, and air drying at 20 deg.C for 10 min to obtain super-hydrophobic coating.
Example 4
The embodiment prepares the super-hydrophobic coating, and the specific preparation process comprises the following steps:
10ml of toluene, 1.4g of methyltrimethoxysilane, 0.5g of silica (100 nm) and 1.2g of epoxy acrylate were added to 0.5g of dimethyldichlorosilane, stirred and dispersed for 3 min, and the mixed solution was applied to the surface of the substrate by brush coating.
20. And (3) drying in air at the temperature of 3 ℃ for 3 min, then washing the surface of the coating with distilled water, and drying in air at the temperature of 20 ℃ for 10 min to obtain the super-hydrophobic coating.
Example 5
The embodiment prepares the super-hydrophobic coating, and the specific preparation process comprises the following steps:
10ml of toluene, 0.5g of silica (100 nm) and 3g of ethyl cyanoacrylate were added to 2g of methyltrimethoxysilane, and the mixture was stirred and dispersed for 3 min, and the mixed solution was applied to the surface of the substrate by brush coating.
20. Air drying at temperature of 5 deg.C for 5 min, washing the coating surface with distilled water, and air drying at 20 deg.C for 10 min to obtain the final product.
Example 6
The embodiment prepares the super-hydrophobic coating, and the specific preparation process comprises the following steps:
10ml of toluene, 0.3g of silica (100 nm), 3g of ethyl cyanoacrylate and 1g of methyltrimethoxysilane were added to 1g of methyltrimethoxysilane, and the mixture was dispersed for 3 min with stirring, and the mixed solution was applied to the surface of the substrate by brush coating.
25. And (3) drying in air at the temperature of 5 ℃ for 5 min, then washing the surface of the coating with distilled water, and drying in air at the temperature of 20 ℃ for 10 min to obtain the super-hydrophobic coating.
Example 7
The embodiment prepares the super-hydrophobic coating, and the specific preparation process comprises the following steps:
10ml of toluene, 0.5g of silicon dioxide (100 nm) and 5g of ethyl cyanoacrylate are added into 0.5g of hydrogen-containing silicone oil, stirred and dispersed for 3 min, and the uniformly mixed liquid is coated on the surface of a base material by brushing.
25. Air drying at temperature of 5 deg.C for 5 min, washing the coating surface with distilled water, and air drying at 20 deg.C for 10 min to obtain the final product.
Example 8
The embodiment prepares the super-hydrophobic coating, and the specific preparation process comprises the following steps:
firstly, 15ml of hexane, 1.2g of silicon dioxide (100 nm) and 5g of ethyl cyanoacrylate are sequentially added into 0.5g of hydrogen-containing silicone oil, stirred and dispersed for 3 min, and the uniformly mixed liquid is coated on the surface of a base material by a brush coating mode.
25. And (3) drying in air at the temperature of 5 ℃ for 5 min, then washing the surface of the coating with distilled water, and drying in air at the temperature of 20 ℃ for 10 min to obtain the super-hydrophobic coating.
Example 9
The embodiment prepares the super-hydrophobic coating, and the specific preparation process comprises the following steps:
10ml of toluene, 0.2g of silica (100 nm) and 4g of ethyl cyanoacrylate were added to 1g of diethyldiethoxysilane, and the mixture was stirred and dispersed for 3 min, and the mixed solution was applied to the surface of the substrate by brush coating.
20. Air drying at 20 deg.C for 5 min, washing the coating surface with distilled water, and air drying at 20 deg.C for 8 min to obtain the final product.
Example 10
The embodiment prepares the super-hydrophobic coating, and the specific preparation process comprises the following steps:
105ml of toluene, 0.15g of silicon dioxide (100 nm) and 4g of ethyl cyanoacrylate were added to 0.5g of gamma-aminopropyl-triethoxysilane, stirred and dispersed for 3 min, and the uniformly mixed solution was applied to the surface of the substrate by brushing.
20. Air drying at 20 deg.C for 5 min, washing the coating surface with distilled water, and air drying at 20 deg.C for 8 min to obtain the final product.
Detection example 1
The super-amphiphobic performance of the coating of example 1 was shown in fig. 1 to 4 after applying the coating to the surfaces of wood, glass, teflon and paper and dropping optical droplets.
Wherein, fig. 1 is a schematic view of a wood surface, fig. 2 is a schematic view of a glass surface, fig. 3 is a schematic view of a polytetrafluoroethylene surface, and fig. 4 is a schematic view of a paper surface.
In addition, the dynamic contact angle of the coating of example 1 was further tested, wherein the advancing angle was 165.43 ° and the receding angle was 164.97 °.
Detection example 2
The coating of example 1 was applied to the surface of a glass substrate, and a water jet erosion test was performed, and the results are shown in fig. 5, and it can be seen from fig. 5 that no water droplets adhered to the surface of the coating after the coating was water jet eroded.
Detection example 3
The effect of the oil-water separation test performed by applying the coating material of example 1 to cotton cloth with the coating material of example 1 as the test object is shown in fig. 6. In FIG. 6, water is on the left and n-hexadecane is on the right. As can be seen from fig. 6, the oil-water separation effect is excellent.
Detection example 4
The results of a continuous boiling water test performed by applying the coating material to the glass surface using the coating layer of example 1 as a test object are shown in fig. 7. As can be seen from fig. 7, the stability of the coating is good.
Detection example 5
The contact angles of the coatings prepared in examples 2 to 8 were tested. The results are shown in fig. 8 to 14. As can be seen from FIGS. 8 to 14, the coatings prepared in the examples can achieve the super-hydrophobic effect.
Detection example 6
The contact angle of the coating of example 3 was tested after 5 days of freezing at-80 ℃ and the results are shown in figure 15. As can be seen from fig. 15, the coating still has good superhydrophobic performance after being frozen at low temperature for a long time.
Detection example 7
The contact angle of the coating of example 4 was tested after rubbing by the following method: the coating is coated on a glass substrate, one surface with the glass sheet coating is coated on 1500-mesh sand paper, a 100 g weight is placed on the glass sheet, and the glass sheet is pushed by 10 cm (once) along the horizontal direction and the vertical direction respectively under the action of external force.
The results of the contact angle test before rubbing are shown in fig. 16.
The contact angle test results after rubbing are shown in fig. 17.
As can be seen by comparing FIG. 16 with FIG. 17, the change of the contact angle before and after the friction is small, and the coating has better wear resistance.
The present invention has been described in detail with reference to the embodiments, but the present invention is not limited to the embodiments described above, and various changes can be made within the knowledge of those skilled in the art without departing from the gist of the present invention.

Claims (6)

1. The super-hydrophobic coating is characterized in that raw materials for preparation comprise a silane compound, micro-nano particles, an auxiliary agent and a solvent, wherein the mass ratio of the silane compound to the micro-nano particles is 0.01 to 100:1, the particle size of the micro-nano particles is between 1 nm and 100 mu m;
the silane compound includes at least one of dimethyldimethoxysilane, dimethyldichlorosilane, methyltrimethoxysilane, hydrosilicone oil, diethyldimethoxysilane, diethyldiethoxysilane, dipropyldimethoxysilane, dipropyldiethoxysilane, dimethyldiethoxysilane, polydimethylsiloxane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, tetramethoxysilane, tetraethoxysilane, bis (triethoxysilyl) methane, 1, 2-bis (triethoxysilyl) ethane, methyltributanioximinosilane, gamma-aminopropyl-triethoxysilane, and gamma-glycidoxypropyl-propyltrimethoxysilane;
the auxiliary agent comprises epoxy acrylate;
the micro-nano particles comprise inorganic micro-nano particles and organic micro-nano particles;
the mass ratio of the solvent to the silane compound is 0.05-20: 1.
2. the superhydrophobic coating of claim 1, wherein the inorganic micro-nano particles comprise at least one of silica particles and titanium dioxide particles.
3. A method for preparing the superhydrophobic coating according to claim 1 or 2, wherein the silane compound, the micro-nano particles and the auxiliary agent are uniformly mixed in a solvent.
4. The method according to claim 3, wherein the solvent comprises at least one of an alcohol solvent, a ketone solvent, an ether solvent, and an ester solvent.
5. A superhydrophobic coating prepared from the superhydrophobic coating of claim 1 or 2.
6. The superhydrophobic coating of claim 5, wherein the superhydrophobic coating has a static contact angle greater than 150 ° and a sliding angle less than 10 °.
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