CN114958174A - Super-wear-resistant super-hydrophobic coating and preparation method and application thereof - Google Patents
Super-wear-resistant super-hydrophobic coating and preparation method and application thereof Download PDFInfo
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- 238000000576 coating method Methods 0.000 title claims abstract description 88
- 239000011248 coating agent Substances 0.000 title claims abstract description 84
- 230000003075 superhydrophobic effect Effects 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical class O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 94
- 239000002245 particle Substances 0.000 claims abstract description 36
- 239000002105 nanoparticle Substances 0.000 claims abstract description 35
- 239000011859 microparticle Substances 0.000 claims abstract description 28
- 239000003085 diluting agent Substances 0.000 claims abstract description 27
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 23
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 21
- 229920013822 aminosilicone Polymers 0.000 claims abstract description 18
- 239000003921 oil Substances 0.000 claims abstract description 18
- 239000002270 dispersing agent Substances 0.000 claims abstract description 15
- 238000009736 wetting Methods 0.000 claims abstract description 13
- -1 aliphatic isocyanate Chemical class 0.000 claims abstract description 12
- 239000012948 isocyanate Substances 0.000 claims abstract description 8
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 7
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 32
- 239000003795 chemical substances by application Substances 0.000 claims description 24
- 238000005299 abrasion Methods 0.000 claims description 17
- 238000003756 stirring Methods 0.000 claims description 17
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 16
- 239000002518 antifoaming agent Substances 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 13
- 239000000843 powder Substances 0.000 claims description 13
- 238000005507 spraying Methods 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 239000000945 filler Substances 0.000 claims description 11
- FOWDZVNRQHPXDO-UHFFFAOYSA-N propyl hydrogen carbonate Chemical compound CCCOC(O)=O FOWDZVNRQHPXDO-UHFFFAOYSA-N 0.000 claims description 10
- 238000005096 rolling process Methods 0.000 claims description 10
- ZYAASQNKCWTPKI-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propan-1-amine Chemical compound CO[Si](C)(OC)CCCN ZYAASQNKCWTPKI-UHFFFAOYSA-N 0.000 claims description 9
- 239000006229 carbon black Substances 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- 239000004567 concrete Substances 0.000 claims description 8
- 239000011347 resin Substances 0.000 claims description 8
- 229920005989 resin Polymers 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- 239000002244 precipitate Substances 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 238000010276 construction Methods 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 239000000049 pigment Substances 0.000 claims description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 4
- 238000005119 centrifugation Methods 0.000 claims description 4
- 239000000178 monomer Substances 0.000 claims description 4
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 4
- 230000003373 anti-fouling effect Effects 0.000 claims description 3
- 230000001680 brushing effect Effects 0.000 claims description 3
- 229920001577 copolymer Polymers 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- 239000002023 wood Substances 0.000 claims description 3
- YXRKNIZYMIXSAD-UHFFFAOYSA-N 1,6-diisocyanatohexane Chemical compound O=C=NCCCCCCN=C=O.O=C=NCCCCCCN=C=O.O=C=NCCCCCCN=C=O YXRKNIZYMIXSAD-UHFFFAOYSA-N 0.000 claims description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Natural products CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 claims description 2
- UDSFAEKRVUSQDD-UHFFFAOYSA-N Dimethyl adipate Chemical compound COC(=O)CCCCC(=O)OC UDSFAEKRVUSQDD-UHFFFAOYSA-N 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- OHJMTUPIZMNBFR-UHFFFAOYSA-N biuret Chemical compound NC(=O)NC(N)=O OHJMTUPIZMNBFR-UHFFFAOYSA-N 0.000 claims description 2
- DFFDSQBEGQFJJU-UHFFFAOYSA-M butyl carbonate Chemical compound CCCCOC([O-])=O DFFDSQBEGQFJJU-UHFFFAOYSA-M 0.000 claims description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 2
- XTDYIOOONNVFMA-UHFFFAOYSA-N dimethyl pentanedioate Chemical compound COC(=O)CCCC(=O)OC XTDYIOOONNVFMA-UHFFFAOYSA-N 0.000 claims description 2
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 239000002808 molecular sieve Substances 0.000 claims description 2
- CQDGTJPVBWZJAZ-UHFFFAOYSA-N monoethyl carbonate Chemical compound CCOC(O)=O CQDGTJPVBWZJAZ-UHFFFAOYSA-N 0.000 claims description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 2
- 239000007921 spray Substances 0.000 claims description 2
- 239000002344 surface layer Substances 0.000 claims description 2
- 125000000524 functional group Chemical group 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 9
- 238000005260 corrosion Methods 0.000 abstract description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 abstract description 3
- 230000007797 corrosion Effects 0.000 abstract description 2
- 239000011253 protective coating Substances 0.000 abstract description 2
- 239000000126 substance Substances 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 12
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- 238000012360 testing method Methods 0.000 description 9
- MUXOBHXGJLMRAB-UHFFFAOYSA-N Dimethyl succinate Chemical compound COC(=O)CCC(=O)OC MUXOBHXGJLMRAB-UHFFFAOYSA-N 0.000 description 8
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- 239000004408 titanium dioxide Substances 0.000 description 7
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- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 238000002464 physical blending Methods 0.000 description 2
- 229920001228 polyisocyanate Polymers 0.000 description 2
- 239000005056 polyisocyanate Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 229920002545 silicone oil Polymers 0.000 description 2
- 229920005707 BASONAT® HB 175 MP/X Polymers 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 239000013207 UiO-66 Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000007227 biological adhesion Effects 0.000 description 1
- 238000005422 blasting Methods 0.000 description 1
- DUEPRVBVGDRKAG-UHFFFAOYSA-N carbofuran Chemical compound CNC(=O)OC1=CC=CC2=C1OC(C)(C)C2 DUEPRVBVGDRKAG-UHFFFAOYSA-N 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
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- 238000004132 cross linking Methods 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical group FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 239000013183 functionalized metal-organic framework Substances 0.000 description 1
- JYVHOGDBFNJNMR-UHFFFAOYSA-N hexane;hydrate Chemical compound O.CCCCCC JYVHOGDBFNJNMR-UHFFFAOYSA-N 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- AQYSYJUIMQTRMV-UHFFFAOYSA-N hypofluorous acid Chemical compound FO AQYSYJUIMQTRMV-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
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- 230000037452 priming Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
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- C—CHEMISTRY; METALLURGY
- 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
- C09D5/08—Anti-corrosive paints
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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
- 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
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
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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
- 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
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- 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
- C09D7/69—Particle size larger than 1000 nm
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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- C09D7/70—Additives characterised by shape, e.g. fibres, flakes or microspheres
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- C08K2201/00—Specific properties of additives
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Abstract
A super wear-resistant super-hydrophobic coating and a preparation method and application thereof belong to the technical field of waterproof and protective coatings. The super wear-resistant super-hydrophobic coating is a two-component coating and comprises a component A and a component B; the mass ratio of the component A to the component B is 2:1, wherein the component A comprises the following components in percentage by mass: 50-70% of hydroxyl fluororesin, 5-10% of amino silicone oil, 5-15% of modified silica nanoparticles, 5-15% of modified silica microparticles, 0.1-1% of wetting dispersant and the balance of environment-friendly diluent; the component B comprises the following components in percentage by mass: 5-30% of aliphatic isocyanate, 5-10% of an auxiliary agent and the balance of an environment-friendly diluent. The super wear-resistant super-hydrophobic coating is obtained by introducing amino silicone oil and amino functionalized nano/micron silicon dioxide particles into a fluororesin coating, is simple and convenient to prepare, and has the functions of water resistance, corrosion resistance and the like.
Description
Technical Field
The invention relates to the technical field of waterproof and protective coatings, in particular to a super-wear-resistant super-hydrophobic coating and a preparation method and application thereof.
Background
The super-hydrophobic material has wide application prospect due to the functions of oil-water separation, frost prevention, freezing resistance, metal corrosion prevention, water vapor collection, energy conservation, drag reduction, pollution prevention, dust prevention, wood mildew prevention, biological adhesion prevention, self cleaning and the like. However, superhydrophobic surfaces are inevitably affected by external complications (oxidation, corrosive media, mechanical friction, etc.). In particular, mechanical rubbing action can disrupt the microscopic roughness of the superhydrophobic surface, resulting in loss of superhydrophobicity of the material. The poor durability and short service life greatly limit the engineering applications of superhydrophobic materials. Therefore, the method for improving the wear resistance of the super-hydrophobic material has great significance for breaking through the technical bottleneck limiting the application of the super-hydrophobic material, and is also one of the current research hotspots.
Chinese patent application publication No. CN 113896430 a discloses an adhesive composite wear-resistant super-hydrophobic coating and a preparation method thereof, and specifically discloses a fluorine-free super-hydrophobic coating using an adhesive as an auxiliary coating. The hydrophobic nano particles and the substrate can be firmly attached together by the strong bonding effect of the adhesive, so that the wear resistance of the coating is improved. After the coating is subjected to 50 times of peeling tests, although partial areas are seriously damaged, the surface can still enable water drops to easily roll down and the rolling angle<8 degrees. Chinese patent application with publication number CN 112898886A discloses an anti-corrosion, anti-icing and wear-resistant super-hydrophobic coating and a preparation method thereof, and particularly discloses a wear-resistant nano SiO 2 A method for improving the wear resistance of a super-hydrophobic coating by the synergistic effect of particles and an elastic TPU coating. Nano SiO with certain wear resistance 2 The particles are half embedded into the surface of the TPU coating with certain elasticity, so that external objects cannot directly act on the TPU coating, but firstly touch the nano SiO 2 Particles. Therefore, the wear resistance of the coating is significantly improved. However, these conventional preparations are ultraphobicIn the water coating method, nano particles are doped into a resin system in a physical blending method, so that the improvement of the wear resistance of the super-hydrophobic coating is limited.
Chinese patent application with publication number CN 113637401A discloses a preparation method and application of a two-component wear-resistant super-hydrophobic coating, and particularly discloses a wear-resistant super-hydrophobic coating based on a Metal Organic Framework (MOF) material. The functionalized MOF and the aminated silicone oil are firstly pre-grafted on a resin framework through covalent bonds and then are solidified with a curing agent. After the paint is cured, the paint film has rough structure and low surface energy component from top to bottom, and the abraded surface can still expose a new surface to continuously exert the super-hydrophobic effect. After 7.6 m of the abrasive was rubbed with 2000-mesh sandpaper with a weight of 100 g, the contact angle was 150 °, the rolling angle was 8 °, and the abrasion resistance was excellent. However, the particle size of the MOF UiO-66 used is 180 nm, so that only a micro-scale rough structure can be formed after the coating is cured, and a nano-scale rough structure cannot be formed, so that the super-hydrophobicity of the coating is improved to a limited extent.
Disclosure of Invention
The technical problem to be solved is as follows: aiming at the problem that the wear resistance and durability of a super-hydrophobic coating are to be improved in the prior art, the invention provides a super-wear-resistant super-hydrophobic coating, and a preparation method and application thereof.
The technical scheme is as follows: the super wear-resistant super-hydrophobic coating is a two-component coating and comprises a component A and a component B, wherein the mass ratio of the component A to the component B is 2:1, and the component A comprises the following components in percentage by mass: 50-70% of hydroxyl fluororesin, 5-10% of amino silicone oil, 5-15% of modified silica nanoparticles, 5-15% of modified silica microparticles, 0.1-1% of wetting dispersant and the balance of environment-friendly diluent;
the component B comprises the following components in percentage by mass: 5-30% of aliphatic isocyanate, 5-10% of an auxiliary agent and the balance of an environment-friendly diluent;
the preparation method of the modified silicon dioxide nano/micron particles comprises the following steps: firstly, adding silicon dioxide nano/micron particles and acetone into a reaction container, adding gamma-aminopropyl methyl dimethoxy silane into the reaction container after ultrasonic dispersion, centrifuging after electromagnetic stirring, collecting solid precipitate, and finally washing and drying by using acetone to obtain the modified silicon dioxide nano/micron particles.
Preferably, the ratio of the silica nano/micro particles to acetone is 3 g: 100 mL, the ratio of gamma-aminopropylmethyldimethoxysilane to silica nano/micro particles is 1 g: 3g, ultrasonic dispersion is carried out for 30min, centrifugation is carried out for 10min after electromagnetic stirring is carried out for 2h, and the centrifugation rotating speed is 2000 r/min.
Preferably, the environment-friendly diluent is at least one of ethyl carbonate, propyl carbonate, butyl carbonate, dimethyl butyrate, dimethyl adipate and dimethyl glutarate.
Preferably, the hydroxyl fluororesin is a copolymer of a non-functional monomer and a monomer with hydroxyl, has a low molecular weight, can be subjected to a crosslinking reaction with a curing agent such as polyisocyanate to form a polymer network structure, and can be purchased from GK570 (hydroxyl value of 60 +/-5 mgKOH/g) of Dajin fluorine chemical engineering (China) Co., Ltd.), JF-2X (hydroxyl value of 50 +/-5 mgKOH/g) and/or JF-3X (hydroxyl value of 50 +/-5 mgKOH/g) of Sanefuzhonghao chemical new material Co., Ltd.; the silica nanoparticles are silica microspheres, the surface of the silica nanoparticles is hydrophilic, the particle size of the silica nanoparticles is 20-50 nm, the silica nanoparticles are 999121 (particle size-20 nm), 972472 (particle size-40 nm) and/or 952360 (particle size-50 nm) purchased from Beijing Bailingwei science and technology Limited, the silica microparticles are silica microspheres, the surface of the silica microspheres is hydrophilic, the particle size of the silica microparticles is 0.2-0.8 mu m, and the silica nanoparticles are purchased from S5505 (particle size of 0.2-0.3 mu m), 2748684 (particle size of 0.2-0.8 mu m) and/or BD01403879 (particle size-0.5 mu m) of Shanghai Bijie medical science and technology Limited. The amino silicone oil is an amino-terminated polysiloxane which can be purchased from Shanghai Hui research New Material company HY-2300 (viscosity 60-150cp, 25 ℃), Dow chemical OFX-8040A (viscosity 800-. The active ingredient of the wetting and dispersing agent is an acidic group-containing copolymer for stabilizing the pigment and reducing flooding/blooming. The wetting and dispersing agent may be selected from at least one of BYK-111, BYK-163, BYK-220s and BYK-P104s, which are commercially available from Bik chemical company.
Preferably, the mass ratio of the modified silica nanoparticles to the modified silica microparticles is 3:1 to 1: 3.
Preferably, the aliphatic isocyanate is at least one of N3390, HDI biuret, and HDI trimer. More preferably, it is at least one of N3390 and HDI.
Preferably, the auxiliary agent comprises the following components in parts by weight: 5-20 parts of a leveling agent, 0.5-3 parts of a defoaming agent, 10-50 parts of a pigment and 10-50 parts of a powder filler, wherein the pigment is at least one of rutile titanium dioxide (such as commercially available R-103, R-902 and R-960) and carbon black, and the powder filler is at least one of calcium carbonate with the fineness of 800-2000 meshes, talcum powder and molecular sieve activated powder. The effective component of the leveling agent is a surface auxiliary agent containing organic silicon and used for reducing the surface tension of the coating. The leveling agent may be selected from at least one of BYK300, BYK306, and BYK333, which are commercially available from bick chemical company. The defoaming agent is a commercially available organic silicon defoaming agent; the defoaming agent may be selected from at least one of AF-8014, BYK-085 and BYK-088, commercially available from Dow chemical company.
The preparation method of the super wear-resistant super-hydrophobic coating comprises the following steps:
step one, preparation of component A modified fluororesin: uniformly mixing hydroxyl fluororesin, amino silicone oil, modified silica nanoparticles, modified silica microparticles, a wetting dispersant and an environment-friendly diluent to obtain modified fluororesin;
step two, preparation of the component B curing agent: mixing and dispersing the aliphatic isocyanate and the auxiliary agent uniformly by using an environment-friendly diluent to obtain an active hydrogen-containing resin component;
and step three, uniformly mixing the component A and the component B according to the mass ratio and then constructing. And uniformly coating the coating on the treated base surface, wherein the treated base surface is a concrete or metal base surface treated by surface cleaning, shot blasting, pit hole repairing, priming paint brushing and other processes.
The super wear-resistant super-hydrophobic coating is applied to preparing waterproof, anticorrosive and antifouling coatings on the surface layers of concrete, metal and wood.
Preferably, the coating construction mode is spraying, brushing or rolling construction, the coating thickness is 1.5-3.0 mm, the single-pass coating thickness is 0.5-1 mm, the construction is carried out more than two times, and the spraying process conditions are as follows: the air pressure is 0.6MPa, the distance between the spray gun and the base surface is 15cm, the spraying time is 10s, and the coating is uniform.
Has the beneficial effects that: the invention provides a simple and convenient super wear-resistant super-hydrophobic coating, which is prepared by forming amino functionalized modified silicon dioxide nano/micron particles through YDH-660 modified silicon dioxide nano/micron particles; the modified silicon dioxide nano particles and the modified silicon dioxide micro particles are used for respectively forming rough structures with the surface in a nano scale and a micro scale, and the polysiloxane chain segment in the silicone oil and the fluorocarbon chain segment in the fluororesin are used for reducing the surface tension to form a coating with super-hydrophobicity, so that the super-hydrophobicity and anti-fouling effects are achieved; the modified silicon dioxide nano/micron particles and amino silicone oil are covalently grafted to a resin matrix by utilizing the chemical reaction of amino and curing agent polyisocyanate to form the super-wear-resistant super-hydrophobic coating surface. The method is different from the traditional physical blending method, the modified silicon dioxide nano particles, the modified silicon dioxide micro particles and the amino silicone oil are connected to the resin matrix in a covalent bond mode, the wear resistance and durability of the super-hydrophobic coating are greatly improved, and the method has the advantages of simplicity and convenience in preparation, water resistance, corrosion resistance and the like.
Drawings
Fig. 1 is a graph showing the tendency of abrasion resistance change of the superhydrophobic coating of example 1.
Fig. 2 is a graph showing a change tendency of abrasion resistance of the superhydrophobic coating of comparative example 1.
Fig. 3 is a graph showing the tendency of abrasion resistance change of the superhydrophobic coating of example 2.
Fig. 4 is a graph showing a change tendency of abrasion resistance of the superhydrophobic coating of comparative example 2.
Detailed Description
The invention is further described with reference to the following drawings and specific examples, which do not represent a limitation to the technical solution of the invention.
In the examples of the present invention, the raw materials and reagents are all of industrial grade and commercially available.
The manufacturers and the models of part of raw materials in the embodiment are as follows:
1. silica nanoparticles
(1) The particle size is 999121, Beijing Bailingwei science and technology Limited, and the particle size is 20 nm;
(2) the particle size is 972472, Beijing Bailingwei science and technology Limited, and the particle size is 40 nm;
2. silica microparticles
(1) The particle size of the product is 0.2-0.3 mu m, model S5505, Beijing Bailingwei science and technology Limited;
(2) the size of the particle is 2748684, and the particle size is 0.2-0.8 mu m in Beijing Bailingwei science and technology limited;
3. hydroxy fluorine resin
(1) GK570, Dai-Fluorochemical (China) Co., Ltd., hydroxyl value 60. + -. 5 mgKOH/g;
(2) JF-2X, Sanai Fuzhonghao chemical new material Co., Ltd, hydroxyl value is 50 +/-5 mgKOH/g;
4. amino silicone oil
(1) HY-2300, Shanghai Hui research New Material Co., Ltd., viscosity 60-150cp, 25 deg.C;
(2) OFX-8040A, Dow chemical, viscosity 800-;
5. aliphatic isocyanates
(1) HDI (high Density interconnection), produced by BASF (China) Limited, and having an industrial name of Basonat HB 175MP/X CN and an NCO content of 16-17%;
(2) n3390, produced by Bayer (China) Limited, named Desmodur N3390, and having NCO content of (19.6 +/-0.3)%;
6. wetting and dispersing agent:
(1) BYK-163 (hereinafter "BYK-163") manufactured by Bick chemical company;
(2) BYK-P104s (hereinafter "BYK-P104 s") manufactured by Bick chemical company;
7. an environment-friendly diluent:
(1) propyl carbonate, industrial grade, produced by welfare technologies ltd;
(2) dimethyl succinate, produced by carbofuran technologies ltd, industrial grade;
8. leveling agent:
(1) BYK-306 (hereinafter "BYK-495"), manufactured by Bick chemical company;
(2) BYK-333 (hereinafter referred to as "BYK-333") manufactured by Bick chemical company;
9. defoaming agent:
(1) model AF-80144 (hereinafter referred to as "AF-8014") manufactured by Dow chemical company;
(2) BYK-088 (hereinafter referred to as "BYK-088") is available from Bick chemical company.
Example 1
The preparation method of the super wear-resistant super-hydrophobic coating in the embodiment is as follows:
3g silica nanoparticles (model 999121)/microparticles (model S5505) and acetone (100 mL) were added to a 250 mL round bottom flask and ultrasonically dispersed for 30 min. Then, γ -aminopropylmethyldimethoxysilane (YDH-660, 1g) was added to the reaction flask, magnetically stirred for 2h and centrifuged (2000 r/min, 10 min) and the solid precipitate was collected. Finally, washing and drying the mixture by using acetone to obtain the modified silicon dioxide nano/micron particles.
Sequentially adding 10g of environment-friendly diluent dimethyl succinate, 65g of hydroxyl fluororesin GK570, 1g of wetting dispersant BYK-163, 9g of modified silica nano particles, 3g of modified silica micro particles and 12g of amino silicone oil HY-2300 under the condition that a mechanical dispersion stirrer is started for 1000r/min, and continuously stirring for 30min to obtain component A modified fluororesin; adding 12g of HDI curing agent, 16g of propyl carbonate environment-friendly diluent, 15.5g of titanium dioxide R-902, 0.5g of carbon black, 5g of powder filler, 0.5g of BYK-306 flatting agent and 0.5g of defoaming agent AF-8014 into a beaker in sequence, and stirring for 1h at room temperature at 2000R/min to obtain a B component curing system; and uniformly mixing the component A and the component B according to the mass ratio of 2:1, and spraying the mixture on the treated concrete base surface to obtain the super wear-resistant super-hydrophobic coating. The abrasion resistance of the coating was then characterized by peel testing and measuring the contact and rolling angles.
Comparative example 1
Sequentially adding 10g of environment-friendly diluent dimethyl succinate, 65g of hydroxyl fluororesin GK570, 1g of wetting dispersant BYK-163, 9g of unmodified silica nanoparticles (model 999121), 3g of unmodified silica microparticles (model S5505) and 12g of amino silicone oil HY-2300 under the condition that a mechanical dispersion stirrer is started for 1000r/min, and continuously stirring for 30min to obtain component A modified fluororesin; adding 12g of curing agent HDI, 16g of environment-friendly diluent propyl carbonate, 15.5g of titanium dioxide R-902, 0.5g of carbon black, 5g of powder filler, 0.5g of flatting agent BYK-306 and 0.5g of defoaming agent AF-8014 into a beaker in sequence, and stirring at room temperature for 1h at 2000R/min to obtain a B component curing system; and uniformly mixing the component A and the component B according to the mass ratio of 2:1, and spraying the mixture on the treated concrete base surface to obtain the super wear-resistant super-hydrophobic coating. The abrasion resistance of the coating was then characterized by peel testing and measuring the contact and rolling angles.
Example 2
3g silica nanoparticles (model 972472)/microparticles (model 2748684) and acetone (100 mL) were added to a 250 mL round bottom flask and ultrasonically dispersed for 30 min. Then, γ -aminopropylmethyldimethoxysilane (YDH-660, 1g) was added to the reaction flask, magnetically stirred for 2h and centrifuged (2000 r/min, 10 min) and the solid precipitate was collected. Finally, washing and drying the mixture by using acetone to obtain the modified silicon dioxide nano/micron particles.
Sequentially adding 10g of environment-friendly diluent dimethyl succinate, 65g of hydroxyl fluororesin JF-2X, 1g of dispersant BYK-P104s, 3g of modified silica nanoparticles, 9g of modified silica microparticles and 12g of amino silicone oil OFX-8040A under the condition that a mechanical dispersing stirrer is started for 1000r/min, and continuously stirring for 30min to obtain component A modified fluororesin; adding 8g of curing agent N3390, 20g of environment-friendly diluent propyl carbonate, 15.5g of titanium dioxide R-902, 0.5g of carbon black, 5g of powder filler, 0.5g of flatting agent BYK-333 and 0.5g of defoaming agent BYK-088 into a beaker in sequence, and stirring at the room temperature of 2000R/min for 1h to obtain a component B curing system; and uniformly mixing the component A and the component B according to the mass ratio of 2:1, and spraying the mixture on the treated metal base surface to obtain the super wear-resistant super-hydrophobic coating. The abrasion resistance of the coating was then characterized by peel testing and measuring the contact and rolling angles.
Comparative example 2
Sequentially adding 10g of environment-friendly diluent dimethyl succinate, 65g of hydroxyl fluororesin JF-2X, 1g of dispersant BYK-P104s, 3g of unmodified silica nanoparticles, 9g of unmodified silica microparticles and 12g of amino silicone oil OFX-8040A under the condition that a mechanical dispersing stirrer is started for 1000r/min, and continuously stirring for 30min to obtain component A modified fluororesin; adding 8g of curing agent N3390, 20g of environment-friendly diluent propyl carbonate, 15.5g of titanium dioxide R-902, 0.5g of carbon black, 5g of powder filler, 0.5g of flatting agent BYK-333 and 0.5g of defoaming agent BYK-088 into a beaker in sequence, and stirring at the room temperature of 2000R/min for 1h to obtain a component B curing system; and uniformly mixing the component A and the component B according to the mass ratio of 2:1, and spraying the mixture on the treated metal base surface to obtain the super wear-resistant super-hydrophobic coating. The abrasion resistance of the coating was then characterized by peel testing and measuring the contact and sliding angles.
Comparative example 3
3g of silica nanoparticles (model 999121) and acetone (100 mL) were added to a 250 mL round bottom flask and ultrasonically dispersed for 30 min. Then, γ -aminopropylmethyldimethoxysilane (YDH-660, 1g) was added to the reaction flask, magnetically stirred for 2h and centrifuged (2000 r/min, 10 min) and the solid precipitate was collected. Finally, washing and drying the nano particles by using acetone to obtain the modified silicon dioxide nano particles.
Sequentially adding 13 g of environment-friendly diluent dimethyl succinate, 65g of hydroxyl fluororesin GK570, 1g of wetting dispersant BYK-163, 9g of modified silica nanoparticles and 12g of amino silicone oil HY-2300 under the condition that a mechanical dispersion stirrer is started for 1000r/min, and continuously stirring for 30min to obtain component A modified fluororesin; adding 12g of curing agent HDI, 16g of environment-friendly diluent propyl carbonate, 15.5g of titanium dioxide R-902, 0.5g of carbon black, 5g of powder filler, 0.5g of flatting agent BYK-306 and 0.5g of defoaming agent AF-8014 into a beaker in sequence, and stirring at room temperature for 1h at 2000R/min to obtain a B component curing system; and uniformly mixing the component A and the component B according to the mass ratio of 2:1, and spraying the mixture on the treated concrete base surface to obtain the super wear-resistant super-hydrophobic coating. The abrasion resistance of the coating was then characterized by peel testing and measuring the contact and rolling angles.
Comparative example 4
3g of silica microparticles (model S5505) and acetone (100 mL) were added to a 250 mL round bottom flask and ultrasonically dispersed for 30 min. Then, γ -aminopropylmethyldimethoxysilane (YDH-660, 1g) was added to the reaction flask, magnetically stirred for 2h and centrifuged (2000 r/min, 10 min) and the solid precipitate was collected. Finally, washing and drying the mixture by using acetone to obtain the modified silicon dioxide micron particles.
Under the condition that a mechanical dispersion stirrer is started for 1000r/min, 19 g of environment-friendly diluent dimethyl succinate, 65g of hydroxyl fluororesin GK570, 1g of wetting dispersant BYK-163, 3g of modified silicon dioxide microparticles and 12g of amino silicone oil HY-2300 are sequentially added, and stirring is continued for 30min to obtain component A modified fluororesin; adding 12g of curing agent HDI, 16g of environment-friendly diluent propyl carbonate, 15.5g of titanium dioxide R-902, 0.5g of carbon black, 5g of powder filler, 0.5g of flatting agent BYK-306 and 0.5g of defoaming agent AF-8014 into a beaker in sequence, and stirring at room temperature for 1h at 2000R/min to obtain a B component curing system; and uniformly mixing the component A and the component B according to the mass ratio of 2:1, and spraying the mixture on the treated concrete base surface to obtain the super wear-resistant super-hydrophobic coating. The abrasion resistance of the coating was then characterized by peel testing and measuring the contact and rolling angles.
Comparative example 5
3g silica nanoparticles (model 999121)/microparticles (model S5505) and acetone (100 mL) were added to a 250 mL round bottom flask and ultrasonically dispersed for 30 min. Then, γ -aminopropylmethyldimethoxysilane (YDH-660, 1g) was added to the reaction flask, magnetically stirred for 2h and centrifuged (2000 r/min, 10 min) and the solid precipitate was collected. Finally, washing and drying the mixture by using acetone to obtain the modified silicon dioxide nano/micron particles.
Under the condition that a mechanical dispersion stirrer is started for 1000r/min, 22 g of environment-friendly diluent dimethyl succinate, 65g of hydroxyl fluororesin GK570, 1g of wetting dispersant BYK-163, 9g of modified silica nano particles and 3g of modified silica micro particles are sequentially added, and the mixture is continuously stirred for 30min to obtain component A modified fluororesin; adding 12g of curing agent HDI, 16g of environment-friendly diluent propyl carbonate, 15.5g of titanium dioxide R-902, 0.5g of carbon black, 5g of powder filler, 0.5g of flatting agent BYK-306 and 0.5g of defoaming agent AF-8014 into a beaker in sequence, and stirring at room temperature for 1h at 2000R/min to obtain a B component curing system; and uniformly mixing the component A and the component B according to the mass ratio of 2:1, and spraying the mixture on the treated concrete base surface to obtain the super wear-resistant super-hydrophobic coating. The abrasion resistance of the coating was then characterized by peel testing and measuring the contact and rolling angles.
After the component A and the component B obtained in the above examples and comparative examples are uniformly mixed, the component A and the component B are coated on a base surface to form a super-hydrophobic coating;
the abrasion resistance of the coating is characterized by measuring the contact angle of the coating to water through a stripping test and a contact angle measuring instrument of SDC-100 model. During measurement, 10 mu L of water or n-hexane is dripped on the surface of the material by using a contact angle measuring instrument, the contact angles of 5 points in the total of 4 angles and the center of the substrate are measured, and the average value is taken as the contact angle value of the substrate; to judge the superhydrophobic performance of the following examples and comparative examples. And (3) drawing a change trend graph according to the change of the contact angle value along with the stripping times, and judging the wear resistance of the super-hydrophobic coating.
TABLE 1 contact angles of examples and comparative examples
As can be seen from the above examples 1-2, the static water contact angle of the obtained super wear-resistant super hydrophobic coating can be increased to163.5 o . Referring to the attached drawings 1-4, compared with comparative examples 1 and 2, the abrasion resistance of the coatings in examples 1 and 2 can be improved to more than 180 times of peeling experiments, which shows that the abrasion resistance of the super-hydrophobic coating can be remarkably improved by grafting the modified silica nano/micron particles and the amino silicone oil into the resin matrix through a covalent bond strategy.
From the results of comparative examples 3 to 5, it can be seen that, compared to example 1, the modified silica nanoparticles and the modified silica microparticles act synergistically to form a micro/nano rough structure on the surface of the coating; the introduction of the amino silicone oil can reduce the surface energy of the coating through siloxane; the micro/nano-roughness structure and low surface energy characteristics of the coating surface are important factors for the super-hydrophobicity of the coating.
Claims (10)
1. The super wear-resistant super-hydrophobic coating is characterized by being a two-component coating and comprising a component A and a component B, wherein the mass ratio of the component A to the component B is 2:1, and the component A comprises the following components in percentage by mass: 50-70% of hydroxyl fluororesin, 5-10% of amino silicone oil, 5-15% of modified silica nanoparticles, 5-15% of modified silica microparticles, 0.1-1% of wetting dispersant and the balance of environment-friendly diluent;
the component B comprises the following components in percentage by mass: 5-30% of aliphatic isocyanate, 5-10% of an auxiliary agent and the balance of an environment-friendly diluent;
the preparation method of the modified silicon dioxide nano/micron particles comprises the following steps: firstly, adding silicon dioxide nano/micron particles and acetone into a reaction container, adding gamma-aminopropyl methyl dimethoxy silane into the reaction container after ultrasonic dispersion, centrifuging after electromagnetic stirring, collecting solid precipitate, and finally washing and drying by using acetone to obtain the modified silicon dioxide nano/micron particles.
2. The super wear-resistant super hydrophobic coating according to claim 1, wherein the ratio of silica nano/micro particles to acetone is 3 g: 100 mL, the ratio of gamma-aminopropylmethyldimethoxysilane to silica nano/micro particles is 1 g: 3g, ultrasonic dispersion is carried out for 30min, centrifugation is carried out for 10min after electromagnetic stirring is carried out for 2h, and the centrifugation rotating speed is 2000 r/min.
3. The super abrasion-resistant super hydrophobic coating according to claim 1, wherein the environment friendly diluent is at least one of ethyl carbonate, propyl carbonate, butyl carbonate, dimethyl butyrate, dimethyl adipate and dimethyl glutarate.
4. The super-wear-resistant super-hydrophobic coating according to claim 1, wherein the hydroxyl fluororesin is a copolymer of a non-functional group monomer and a monomer with hydroxyl, the particle size of the silica nanoparticles is 20-50 nm, and the particle size of the silica microparticles is 0.2-0.8 μm.
5. The super wear-resistant super-hydrophobic coating as claimed in claim 1, wherein the mass ratio of the modified silica nanoparticles to the modified silica microparticles is 3: 1-1: 3.
6. The super abrasion-resistant and super-hydrophobic coating according to claim 1, wherein the aliphatic isocyanate is at least one of N3390, HDI biuret and HDI trimer.
7. The super wear-resistant super-hydrophobic coating as claimed in claim 1, wherein the auxiliary comprises the following components in parts by weight: 5-20 parts of a leveling agent, 0.5-3 parts of a defoaming agent, 10-50 parts of a pigment and 10-50 parts of a powder filler, wherein the pigment is at least one of rutile titanium dioxide and carbon black, and the powder filler is at least one of calcium carbonate, talcum powder and molecular sieve activated powder with the fineness of 800-2000 meshes.
8. The preparation method of the super wear-resistant super-hydrophobic coating based on claim 1 is characterized by comprising the following steps:
step one, preparation of component A modified fluororesin: uniformly mixing hydroxyl fluororesin, amino silicone oil, modified silica nanoparticles, modified silica microparticles, a wetting dispersant and an environment-friendly diluent to obtain modified fluororesin;
step two, preparation of the component B curing agent: mixing and dispersing the aliphatic isocyanate and the auxiliary agent uniformly by using an environment-friendly diluent to obtain an active hydrogen-containing resin component;
and step three, uniformly mixing the component A and the component B according to the mass ratio and then constructing.
9. The use of the super wear-resistant super-hydrophobic coating material according to claim 1 in the preparation of waterproof, anticorrosive and antifouling coatings for concrete, metal and wood surface layers.
10. The application of claim 9, wherein the coating construction mode is spraying, brushing or rolling construction, the coating thickness is 1.5-3.0 mm, the single-pass coating thickness is 0.5-1 mm, the two-pass construction is carried out, and the spraying process conditions are as follows: the air pressure is 0.6MPa, the distance between the spray gun and the base surface is 15cm, the spraying time is 10s, and the coating is uniform.
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