CN107760091B - Bottom surface integrated wear-resistant fluorine-silicon-based super-amphiphobic coating and preparation method and application thereof - Google Patents
Bottom surface integrated wear-resistant fluorine-silicon-based super-amphiphobic coating and preparation method and application thereof Download PDFInfo
- Publication number
- CN107760091B CN107760091B CN201710867187.9A CN201710867187A CN107760091B CN 107760091 B CN107760091 B CN 107760091B CN 201710867187 A CN201710867187 A CN 201710867187A CN 107760091 B CN107760091 B CN 107760091B
- Authority
- CN
- China
- Prior art keywords
- amphiphobic coating
- based super
- particles
- fluorosilicone
- coupling agent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 238000000576 coating method Methods 0.000 title claims abstract description 123
- 239000011248 coating agent Substances 0.000 title claims abstract description 121
- ZHPNWZCWUUJAJC-UHFFFAOYSA-N fluorosilicon Chemical compound [Si]F ZHPNWZCWUUJAJC-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims abstract description 36
- 239000002105 nanoparticle Substances 0.000 claims abstract description 104
- 239000002245 particle Substances 0.000 claims abstract description 86
- 239000007822 coupling agent Substances 0.000 claims abstract description 85
- 238000002156 mixing Methods 0.000 claims abstract description 59
- 239000011347 resin Substances 0.000 claims abstract description 37
- 229920005989 resin Polymers 0.000 claims abstract description 37
- 238000010008 shearing Methods 0.000 claims abstract description 33
- 238000003756 stirring Methods 0.000 claims abstract description 24
- 230000002195 synergetic effect Effects 0.000 claims abstract description 23
- 239000000463 material Substances 0.000 claims abstract description 21
- 239000006185 dispersion Substances 0.000 claims abstract description 20
- 238000010438 heat treatment Methods 0.000 claims abstract description 19
- 239000002904 solvent Substances 0.000 claims abstract description 19
- 239000000758 substrate Substances 0.000 claims abstract description 19
- 239000000839 emulsion Substances 0.000 claims abstract description 18
- WMOVHXAZOJBABW-UHFFFAOYSA-N tert-butyl acetate Chemical compound CC(=O)OC(C)(C)C WMOVHXAZOJBABW-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000000725 suspension Substances 0.000 claims abstract description 13
- 238000001132 ultrasonic dispersion Methods 0.000 claims abstract description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 49
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 43
- 238000000034 method Methods 0.000 claims description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 33
- 239000000377 silicon dioxide Substances 0.000 claims description 31
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 28
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 26
- 238000001035 drying Methods 0.000 claims description 22
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 21
- 238000000498 ball milling Methods 0.000 claims description 20
- 239000004094 surface-active agent Substances 0.000 claims description 19
- 239000002270 dispersing agent Substances 0.000 claims description 16
- 239000011259 mixed solution Substances 0.000 claims description 15
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 13
- 239000002518 antifoaming agent Substances 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 13
- 230000008569 process Effects 0.000 claims description 13
- 238000004140 cleaning Methods 0.000 claims description 10
- 239000000843 powder Substances 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 235000012239 silicon dioxide Nutrition 0.000 claims description 8
- 238000005507 spraying Methods 0.000 claims description 8
- LBTSNEJGMVFUEW-UHFFFAOYSA-N 2,2,3,3,4,4,5,5,6,8,8,8-dodecafluorooctoxy-dimethoxy-propylsilane Chemical group FC(C(C(C(C(F)(F)CO[Si](OC)(OC)CCC)(F)F)(F)F)(F)F)CC(F)(F)F LBTSNEJGMVFUEW-UHFFFAOYSA-N 0.000 claims description 7
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 7
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 claims description 7
- 239000000243 solution Substances 0.000 claims description 7
- 239000007921 spray Substances 0.000 claims description 7
- 238000005303 weighing Methods 0.000 claims description 7
- -1 allyloxy nonyl phenol Chemical compound 0.000 claims description 6
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical group CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- DCQBZYNUSLHVJC-UHFFFAOYSA-N 3-triethoxysilylpropane-1-thiol Chemical compound CCO[Si](OCC)(OCC)CCCS DCQBZYNUSLHVJC-UHFFFAOYSA-N 0.000 claims description 5
- 230000007797 corrosion Effects 0.000 claims description 5
- 238000005260 corrosion Methods 0.000 claims description 5
- 239000004408 titanium dioxide Substances 0.000 claims description 5
- GMEMZXVKMVBEGX-UHFFFAOYSA-N 2-(oxiran-2-ylmethoxymethyl)oxirane;trimethoxy(propyl)silane Chemical compound C1OC1COCC1CO1.CCC[Si](OC)(OC)OC GMEMZXVKMVBEGX-UHFFFAOYSA-N 0.000 claims description 4
- SEKZHGKCVMOJSY-UHFFFAOYSA-N [dimethoxy(propyl)silyl]oxymethyl 2-methylprop-2-enoate Chemical compound CCC[Si](OC)(OC)OCOC(=O)C(C)=C SEKZHGKCVMOJSY-UHFFFAOYSA-N 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 3
- 239000003973 paint Substances 0.000 claims description 3
- QTRSWYWKHYAKEO-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(1,1,2,2,2-pentafluoroethoxy)silane Chemical compound FC(F)(F)C(F)(F)O[Si](OC(F)(F)C(F)(F)F)(OC(F)(F)C(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 QTRSWYWKHYAKEO-UHFFFAOYSA-N 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 2
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 2
- 239000002244 precipitate Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- BPCXHCSZMTWUBW-UHFFFAOYSA-N triethoxy(1,1,2,2,3,3,4,4,5,5,8,8,8-tridecafluorooctyl)silane Chemical compound CCO[Si](OCC)(OCC)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)CCC(F)(F)F BPCXHCSZMTWUBW-UHFFFAOYSA-N 0.000 claims description 2
- RZXLPPRPEOUENN-UHFFFAOYSA-N Chlorfenson Chemical compound C1=CC(Cl)=CC=C1OS(=O)(=O)C1=CC=C(Cl)C=C1 RZXLPPRPEOUENN-UHFFFAOYSA-N 0.000 claims 1
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 claims 1
- 125000000129 anionic group Chemical group 0.000 claims 1
- 230000004048 modification Effects 0.000 abstract description 16
- 238000012986 modification Methods 0.000 abstract description 16
- 239000000126 substance Substances 0.000 abstract description 10
- 238000007334 copolymerization reaction Methods 0.000 abstract description 3
- 238000000227 grinding Methods 0.000 abstract description 2
- 229910052681 coesite Inorganic materials 0.000 description 24
- 229910052906 cristobalite Inorganic materials 0.000 description 24
- 239000011858 nanopowder Substances 0.000 description 24
- 229910052682 stishovite Inorganic materials 0.000 description 24
- 229910052905 tridymite Inorganic materials 0.000 description 24
- 239000010954 inorganic particle Substances 0.000 description 22
- 229910052593 corundum Inorganic materials 0.000 description 21
- 229910001845 yogo sapphire Inorganic materials 0.000 description 21
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 17
- 235000019441 ethanol Nutrition 0.000 description 16
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 15
- 238000006460 hydrolysis reaction Methods 0.000 description 13
- 238000005054 agglomeration Methods 0.000 description 11
- 230000002776 aggregation Effects 0.000 description 11
- 230000000694 effects Effects 0.000 description 10
- 238000010907 mechanical stirring Methods 0.000 description 10
- 230000003075 superhydrophobic effect Effects 0.000 description 9
- 230000007062 hydrolysis Effects 0.000 description 8
- 238000006482 condensation reaction Methods 0.000 description 7
- 238000005096 rolling process Methods 0.000 description 7
- 229910003076 TiO2-Al2O3 Inorganic materials 0.000 description 6
- 229910003082 TiO2-SiO2 Inorganic materials 0.000 description 6
- 230000002209 hydrophobic effect Effects 0.000 description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 150000004645 aluminates Chemical class 0.000 description 4
- 230000006870 function Effects 0.000 description 4
- 238000005299 abrasion Methods 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- 238000012423 maintenance Methods 0.000 description 3
- 239000005543 nano-size silicon particle Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 230000009471 action Effects 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 239000002114 nanocomposite Substances 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 229920000620 organic polymer Polymers 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 230000008439 repair process Effects 0.000 description 2
- 230000003746 surface roughness Effects 0.000 description 2
- PQUCIEFHOVEZAU-UHFFFAOYSA-N Diammonium sulfite Chemical compound [NH4+].[NH4+].[O-]S([O-])=O PQUCIEFHOVEZAU-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000009881 electrostatic interaction Effects 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000005661 hydrophobic surface Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000006011 modification reaction Methods 0.000 description 1
- 239000002052 molecular layer Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 230000037081 physical activity Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- 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
- C09D183/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen, and oxygen
-
- 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
-
- 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
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
-
- 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
-
- 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
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
-
- 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
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
-
- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
Abstract
The invention discloses a bottom surface integrated wear-resistant fluorine-silicon-based super-amphiphobic coating and a preparation method and application thereof, and the preparation method comprises the following steps: 1) carrying out synergistic modification treatment on two or more types of nano particles to obtain modified blended particles; 2) adding the blended modified nano particles into a dispersing solvent, performing ultrasonic dispersion for 1-2 hours, and then mechanically stirring; 3) adding a certain amount of tert-butyl acetate into the fluorosilicone resin, and shearing and dispersing to obtain a substrate material emulsion; 4) mixing the blended modified nano particle suspension obtained in the step (2) and the base material emulsion obtained in the step (3), adding a coupling agent, heating, stirring and dispersing, and then dispersing by adopting a high-speed shearing dispersion machine to obtain the super-amphiphobic coating; 5) the super-amphiphobic coating is uniformly stirred, sprayed on the surface of an object, and dried for 10-30 minutes at room temperature to successfully prepare the wear-resistant integrated super-amphiphobic coating. The super-amphiphobic grinding organic-inorganic hybrid coating is formed by connecting a fluorine-silicon substrate and blending modified particles through a chemical grafting copolymerization reaction.
Description
Technical Field
The invention belongs to the field of preparation of super-amphiphobic coatings, and particularly relates to a bottom surface integrated wear-resistant fluorine-silicon-based super-amphiphobic coating as well as a preparation method and application thereof.
Background
The super-hydrophobic coating is formed by coating one or more layers of super-hydrophobic materials on the surface of a solid so as to realize the functions of corrosion resistance, water resistance, ice coating resistance and the like by having a high water contact angle (150 degrees) and a low rolling angle (10 degrees). The super-hydrophobic coating has excellent hydrophobicity, so that the coating is coated outside a metal component, the water vapor surrounding is reduced, and the anticorrosion function can be realized; under the condition of freezing rain and snowfall, the super-hydrophobic surface keeps an unfrozen state or reduces the adhesive force of an ice layer to prevent or delay the icing of the power transmission line, and the super-hydrophobic coating with durability and anti-icing performance is prepared on the surface of the wire, so that the technology is economically feasible for realizing active anti-icing. With the gradual improvement of the development requirements of people on novel materials, the materials with single super-hydrophobicity can not meet the requirements of people, so that the multifunctional super-amphiphobic material is produced at the same time. Firstly, fluorine atoms are moved to the surface, so that the surface has extremely low surface energy, and oil stains are not easy to adhere to the surface of the surface; secondly, the organic oil stain is decomposed by means of photocatalytic degradation. The key to preparing the super-amphiphobic surface is a low surface energy substance and a surface rough structure. Super-amphiphobic coating can realize super hydrophobic and super oleophobic function simultaneously, can show the surface free energy that reduces the solid, has characteristics such as anti-pollution, automatically cleaning, hydrophobic, oleophobic, low resistance, low friction, coats super-amphiphobic coating in power transmission and transformation equipment insulator, can effectively reduce filthy adhesion and keep the dry not by the wet state, reinforcing insulating properties prevents the pollution flashover accident. Because most pollutants are oil-soluble, the self-cleaning surface with the super-amphiphobic property has larger market application prospect than the surface with the super-hydrophobic effect.
However, there are still major obstacles to extending super-hydrophobic or super-amphiphobic coatings to practical applications: (1) the existing prepared super-amphiphobic surface rough structure is unstable, has poor fingerprint resistance or abrasion resistance, and can eliminate the hydrophobic phenomenon when being abraded, because the surface abrasion can damage the microstructure and reduce the surface roughness; furthermore, surface abrasion may result in a change in the chemical composition of the low surface energy species of the surface, resulting in a reduction or loss of performance of the super-amphiphobic surface. However, the fundamental reason for the instability of the surface roughness is that the bonding strength between the micro roughness structure and the substrate and between the micro roughness structures is low, and the roughness structure is easily broken. In view of this, no super-amphiphobic coating which has achieved wide practical application is currently available; (2) the super-amphiphobic coating usually needs expensive mechanical equipment, the preparation process is complex, the production cost is high, and the application of the super-hydrophobic coating is greatly limited; (3) the super-amphiphobic coating usually needs the combined use of two layers of paint on the bottom surface, and needs the combined use of a special matched curing agent, so that the repair and maintenance are difficult to realize in practical application; (4) the coating needs to be subjected to heat treatment, the crosslinking curing temperature is high, and the coating curing by utilizing high temperature in practical application undoubtedly increases the construction difficulty.
In summary, an effective solution is not yet available for a series of problems of the prior art in practical application of the super-amphiphobic coating.
Disclosure of Invention
Aiming at the problems of poor wear resistance, complex preparation process, high cost, complex maintenance process and the like of the super-amphiphobic coating in the prior art, the preparation method for the synergetic modified blending particles for the fluorine-silicon-based super-amphiphobic coating is provided, different types of nanoparticles are added into resin in a mode of blending nano modified particles, adverse factors of various nanoparticles can be balanced, respective advantages of the nanoparticles can be exerted, simultaneously the addition amount of the nanoparticles can be greatly increased, the micro-rough structure of the coating is improved, and the performances of hydrophobicity, oleophobicity, chemical stability, weather resistance, corrosion resistance, oxidation resistance and the like of the coating are improved.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
a preparation method of a synergistic modified blending particle for a fluorine-silicon-based super-amphiphobic coating comprises the following steps:
1) weighing two or more particles selected from micron-sized silicon dioxide, nano-sized titanium dioxide and nano-sized aluminum trioxide, uniformly mixing, and performing ball milling treatment to prepare blended ball-milled powder;
2) adding the blended ball-milled powder into an organic solvent, uniformly shearing, adding a surfactant into the mixture, and uniformly mixing;
3) adding a coupling agent subjected to prehydrolysis into the pre-dispersed blending ball-milling powder solution prepared in the step 2), heating, and carrying out grafting reaction to obtain the synergistic modified blending particles.
The blended nano modified particles are modified by the synergy of the surfactant and the coupling agent, so that the modification rate of the inorganic nano powder can be improved, the surface property of the inorganic nano powder can be fully changed, and the compatibility of the inorganic nano powder and an organic matrix can be enhanced.
Preferably, in the step 1), the ball mill used for ball milling is a planetary ball mill, and the ball milling time is 1-3 h.
Preferably, in step 2), the organic solvent is absolute ethyl alcohol.
Preferably, in the step 2), the rotation speed of shearing and uniformly mixing is 6-10 krpm, and the shearing time is 10-30 min.
Further preferably, in the step 2), the stirring speed after the surfactant is added is 500-800 rpm.
In order to ensure the later modification effect, particles with agglomeration tendency need to be pre-dispersed, the agglomerated particles can be well dispersed by utilizing shear dispersion, the reticular inorganic particles are sheared into short chain shapes, then the surfactant is added under the low-speed stirring state, the surfactant can be effectively coated on the surfaces of the micro-nano particles, and the particles adsorbing the surfactant are not easy to approach each other due to the steric hindrance effect of the surfactant chain, so that the particle agglomeration can be effectively prevented; the low speed stirring is adopted to avoid the high speed shearing force from weakening the action of the surface active agent.
Still more preferably, in the step 2), the surfactant is an anionic surfactant, namely allyloxynonylphenol polyoxyethylene ether ammonium sulfonate (DNS-86). The surfactant is easy to adsorb to the surface of the micro-nano powder.
Preferably, in the step 3), the prehydrolyzed coupling agent is prehydrolyzed by dissolving the coupling agent in an aqueous ethanol solution with a pH value of 3-4, and ultrasonically dispersing for 5-10min to sufficiently hydrolyze the coupling agent.
Further preferably, in the step 3), the volume ratio of ethanol to deionized water in the ethanol aqueous solution is 9:1-19: 1.
Preferably, in the step 3), the coupling agent is a silane coupling agent or a fluorosilane coupling agent, and the silane coupling agent is vinyl triethoxysilane, glycidyl ether propyl trimethoxysilane, (methacryloxy) propyl trimethoxysilane or mercaptopropyl triethoxysilane; the fluorosilane coupling agent is dodecafluoroheptyl propyl trimethoxy silane, tridecafluorooctyl triethoxy silane or perfluorodecyl triethoxy silane.
Further preferably, the concentration of the pre-hydrolyzed coupling agent is 3% to 6%. The concentration here is a mass fraction.
Because a certain amount of water is needed for the hydrolysis of the silane coupling agent or the fluorosilane coupling agent, the hydrolysis is insufficient if the water content is insufficient; if the water amount is excessive, silanol generated by hydrolysis of the silane coupling agent or the fluorosilane coupling agent can undergo dehydration condensation under the action of enough water, and finally, the three-dimensional network polysiloxane is generated, and the modification effect on the inorganic micro-nano particles is lost. The concentration of the coupling agent is 3% -6%, the silane coupling agent or the fluorosilane coupling agent is prepared into an alcohol-water solution, so that the silane coupling agent or the fluorosilane coupling agent can be uniformly distributed on the surface of the inorganic micro-nano powder, the purpose of reducing the using amount of the silane coupling agent or the fluorosilane coupling agent can be achieved, the surface of the inorganic micro-nano particles can be coated to form a silane coupling agent or fluorosilane coupling agent molecular layer with proper thickness by proper concentration, and the inorganic micro-nano particles can be effectively coupled with the organic polymer.
Preferably, in the step 3), the temperature of the grafting reaction is 70-100 ℃, the reaction time is 6-12h, and the stirring speed is 600-.
Preferably, in step 3), the prehydrolyzed coupling agent is added dropwise. The dripping process can fully disperse the coupling agent, and the coupling agent is fully contacted with the micro-nano particles, thereby realizing good modification effect.
Preferably, the preparation method further comprises the steps of performing solid-liquid separation, cleaning and drying on the prepared synergistic modified blended particles.
Further preferably, the cleaning step is to clean the centrifugal precipitate for 10-30min by using an ultrasonic cleaning machine, and the cleaning step is repeated for three times.
Further preferably, the drying temperature is 80-105 ℃, and the drying time is 12-24 h.
The preparation mechanism of the synergistic modified blended particles is that the surface physical activity state of the micro-nano particles can be changed by performing ball milling treatment on a plurality of micro-nano particles, and the micro-nano particles are mutually adsorbed, so that two micro-nano particles with different properties are fully and uniformly mixed. For example, light nanometer SiO2With denser TiO2The particles with large density difference can be mixed by fully mixing. The agglomeration force of the micro-nano particles can be broken through by pre-dispersing the blended micro-nano particles, and the micro-nano particles before modification reaction have better dispersibility. The prepared blending modified nano particles are modified on the surfaces of the nano particles by using a coupling agent, so that hydroxyl groups on the surfaces of the nano particles are eliminated, the hydrophilicity of the nano particles is weakened, more importantly, different nano particles are connected by using a silane coupling agent or a fluorosilane coupling agent through chemical bonds of the nano particles, the problem that the nano particles are not uniformly dispersed due to different densities is solved, and the agglomeration phenomenon of the nano particles is greatly reduced.
In addition, the hydrophilic groups on the surface of the silane coupling agent or the fluorosilane coupling agent are utilized, the hydrolyzed hydroxyl on the surface and the hydroxyl on the surface of the nanoparticle are subjected to dehydration condensation reaction to connect two or more kinds of inorganic particles, so that the problem of uneven dispersion of the inorganic particles due to different densities is solved, the oleophilic groups are grafted to the surfaces of the inorganic particles, the hydrophilic characteristic of the inorganic particles is improved, the compatibility of the inorganic particles and an organic environment is improved, the agglomeration among the inorganic nanoparticles is effectively eliminated, and the dispersibility is improved.
Taking the blending modification of the particles 1 and 2 as an example, the modification mechanism is as follows:
firstly, the surface activity states of the nanoparticles of the particles 1 and 2 are changed by ball milling treatment, so that the nanoparticles are attached to each other, and two types of nanoparticles with different properties are fully mixed.
In addition, the silane coupling agent is utilized to carry out synergistic modification treatment on the two, and the silane coupling agent undergoes hydrolysis reaction, which is shown as the following formula:
wherein R is an oleophilic group of the silane coupling agent, and X is a hydrolyzable group.
Then, multi-step dehydration condensation reaction occurs between hydroxyl groups on the surface of the particles and the inorganic particles, and finally the blending modified particles are formed, which are shown as the following formula:
the two can be fully mixed through ball milling treatment, and the adsorption force is certain. Therefore, the whole blending ball-milling powder system can have particles formed by coating large particles with modified small particles and particles formed by chemically grafting particles 1 and 2.
The second purpose of the invention is to provide the synergistic modified blended particles prepared by the preparation method for the fluorine-silicon-based super-amphiphobic coating.
The third purpose of the invention is to provide a fluorine-silicon-based super-amphiphobic coating, which is prepared by reacting the synergistic modified blended particles, fluorine-silicon resin and a coupling agent.
Preferably, the coupling agent is KH550, KH792, KH560 or KH 570.
Further preferably, the mass ratio of the coupling agent to the fluorosilicone resin is 1:20-1: 15.
Preferably, the mass ratio of the synergistic modified blended particles to the fluorosilicone resin is 1:1-1: 3.
The fourth purpose of the invention is to provide a preparation method of the fluorine-silicon-based super-amphiphobic coating, which comprises the following steps:
1) adding the synergistic modified blended particles into a dispersion solvent, adding a dispersing agent into the dispersion solvent, and shearing and dispersing to obtain a suspension;
2) adding tert-butyl acetate into the fluorosilicone resin, and shearing and dispersing to obtain a substrate material emulsion;
3) and mixing the turbid liquid and the substrate material emulsion, adding a coupling agent into the mixed liquid, and adding a defoaming agent in the shearing and dispersing process to obtain the fluorosilicone-based super-amphiphobic coating.
Preferably, in the step 1), the weight ratio of the synergistically modified blended particles to the dispersion solvent is from 1:5 to 1: 3.
More preferably, the dispersing solvent is a mixed solution of butyl acetate, tert-butyl acetate, propylene glycol methyl ether acetate and ethyl acetate, and the weight ratio of the components is 1:1-1.5:1.5-2:1.5-2 in sequence.
Preferably, in the step 1), the weight ratio of the synergistically modified blended particles to the dispersant is 15:1 to 20: 1.
Further preferably, the dispersant is BYK-163.
Preferably, in the step 2), the weight ratio of the fluorosilicone resin to the tert-butyl acetate is 10:1-4: 1.
Preferably, in step 2), the rate of shear dispersion is 4000-7000r/min, the time is 0.5-1h, and the viscosity is adjusted to 15-30 s.
Preferably, in the step 3), the weight ratio of the synergistically modified blended particles to the fluorosilicone resin is 1:3 to 1:1.
Preferably, in step 3), the coupling agent is KH550, KH792, KH560 or KH 570.
Preferably, in step 3), the defoaming agent is a silicone 100 defoaming agent.
Preferably, in step 3), after the coupling agent is added to the mixed solution, the mixture is stirred and dispersed for 1-3h at 40-60 ℃ and then dispersed for 0.5-1.5 h at a shear rate of 7000-10000 rpm.
Because the nonionic surfactant is added in the preparation process of the synergistic modified blended particles, the synergistic modified blended particles can serve as an effective emulsifier in the subsequent coating preparation process, so that the surfaces of F-Si emulsion particles can be charged, and the micro-nano particles and the organic polymer can be compounded mutually through electrostatic interaction; and the oleophilic group of the silane coupling agent can be connected with the F-Si resin through chemical graft copolymerization.
The mixture is stirred and dispersed for 1 to 3 hours at the temperature of between 40 and 60 ℃, the function of the coupling agent can be effectively promoted, and the system can be dispersed more uniformly.
The fifth purpose of the invention is to provide a preparation method of the bottom surface integrated wear-resistant fluorosilicone super-amphiphobic coating, which comprises the following steps: and (3) uniformly stirring the super-amphiphobic coating, spraying the mixture on the surface of an object, and drying to obtain the super-amphiphobic coating.
Preferably, the spraying pressure is 0.3MPa-0.6MPa, and the distance between the spray gun and the surface of the coated object is 10-30 cm.
The sixth purpose of the invention is to provide the bottom surface integrated wear-resistant fluorine-silicon-based super-amphiphobic coating prepared by the preparation method.
A seventh object of the present invention is to provide the use of the above-mentioned super-amphiphobic coating and the above-mentioned super-amphiphobic coating for corrosion protection, water protection, self-cleaning or ice coating protection.
The invention has the beneficial effects that:
(1) the blended nano modified particles are prepared by modifying the surfaces of the nano particles by using the silane coupling agent, so that the hydroxyl groups on the surfaces of the nano particles are eliminated, the hydrophilicity of the nano particles is weakened, more importantly, the silane coupling agent connects different nano particles through chemical bonds of the silane coupling agent, the problem that the nano particles are not uniformly dispersed due to different densities is solved, and the agglomeration phenomenon of the nano particles is greatly reduced. And the powder of the blended nano modified particles has better hydrophobic effect when being coated on the glass sheet.
(2) The nano modified particles are added into the resin emulsion in a blending mode instead of subsequent mechanical mixing, so that adverse factors of various nano particles can be balanced, respective advantages are exerted, the addition of the nano particles is greatly increased, and the formation of a micro rough structure of the nano particles is improved without affecting the film forming performance of the resin.
(3) The blended nano modified particles are modified by the synergy of the surfactant and the silane coupling agent, so that the modification rate of the inorganic nano powder can be improved, the surface property of the inorganic nano powder can be fully changed, and the compatibility of the inorganic nano powder and an organic matrix can be enhanced. The micro-nano particles and the fluorine-silicon substrate have cross-linking polymerization reaction and are connected through chemical grafting copolymerization reaction, so that the organic and inorganic materials have better compatibility, the use of the silane coupling agent improves the adhesive property between the coating and the base material, the defect of poor bonding force of the fluorine-silicon coating is changed, and the bonding force between the super-amphiphobic coating and the substrate can reach 1-2 levels;
(4) the prepared super-amphiphobic coating has excellent super-amphiphobic characteristics, the water contact angle can reach 155-160 degrees, the rolling angle can reach 1-5 degrees or so, and for an alcohol water solution with the concentration of 20%, the contact angle can reach more than 100 degrees, so that the super-amphiphobic coating has good oleophobic property, and the advantages of a micro-nano structure and low-surface-energy fluorine-silicon are effectively combined, so that the performances of hydrophobicity, oleophobicity, chemical stability, weather resistance, corrosion resistance, oxidation resistance and the like of the coating are obviously improved.
(5) The wear resistance of the super-amphiphobic coating is obviously improved, the nano modified particles have hydrophobicity, and are stacked into a multi-nano composite structure through chemical bonding of fluorine-silicon resin and non-single nano particles, so that the wear resistance and the long-acting property of the coating are ensured.
(6) The method realizes the integration of the bottom surface coating, has simple preparation process and simple and feasible maintenance and repair, greatly reduces the application cost of the super-amphiphobic coating, can effectively form the super-amphiphobic coating on various matrixes, has simple use method, does not need harsh conditions and is suitable for large-scale industrial production.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this application, illustrate embodiments of the application and, together with the description, serve to explain the application and are not intended to limit the application.
FIG. 1 is a fluorine-silicon-based super-amphiphobic coating AFM profile, wherein (a) is a plan view, and (b) is a 3D profile view, and micron-scale and nano-scale protrusions can be seen.
FIG. 2 is a hydrophobic effect diagram of modified blended ball-milled micro-nano powder.
FIG. 3 is a picture of the contact angle between the surface of the fluorosilicone-based super-amphiphobic coating of the present invention and water and 20% alcohol, wherein 1-water drop and 2-20% alcohol drop.
FIG. 4 shows the water contact angle of the fluorosilicone-based super-amphiphobic coating of the present invention.
Detailed Description
It should be noted that the following detailed description is exemplary and is intended to provide further explanation of the disclosure. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of example embodiments according to the present application. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise.
Example 1: bottom surface integrated wear-resistant fluorine silicon-based-micro nano SiO2Preparation process of super-amphiphobic coating
1. Synergistically modifying the micron silicon dioxide and the nano silicon dioxide to obtain modified blended micro-nano SiO2Particles.
(1) Preparing blending ball-milling micro-nano powder: weighing a certain amount of micron-sized SiO2With nano-SiO2And placing the two types of particles into a mixer to be uniformly mixed, and then placing the mixture into a planetary ball mill to be subjected to ball milling treatment for 2 hours to prepare the blended ball-milled micro-nano powder.
(2) Pre-dispersing the blended micro-nano particles: dissolving the blended ball-milled micro-nano powder in absolute ethyl alcohol, shearing and dispersing at the speed of 6krpm for 20min, converting to a low-speed mechanical stirring speed of 500rpm, adding a small amount of surfactant DNS-86, and stirring for 20 min.
(3) Pre-hydrolysis of the coupling agent: dissolving dodecafluoroheptyl propyl trimethoxy silane in a mixed solution of ethanol and deionized water in a ratio of 9:1, adjusting the pH value to 3 by using acetic acid, and performing ultrasonic dispersion for 5min to ensure that the coupling agent is fully hydrolyzed.
(4) Preparation of synergistically modified blended particles: dripping the prehydrolyzed dodecafluoroheptyl propyl trimethoxy silane into the pre-dispersed blended micro-nano particles, stirring and heating to promote the grafting reaction of the dodecafluoroheptyl propyl trimethoxy silane and the pre-dispersed blended micro-nano particles, wherein the heating temperature is 80 ℃, the speed is 600r/min, and the time is 6 hours.
(5) Centrifugal treatment and drying: and (4) centrifuging the suspension obtained in the step (4), washing with absolute ethyl alcohol for multiple times, centrifuging again, and finally drying in a drying oven at 80 ℃ for 20 hours.
The hydrophobic effect diagram of the prepared modified blended ball-milling micro-nano powder is shown in fig. 2, water drops are dropped on the powder to show the effect of dropping water to form balls, and the powder has a better hydrophobic effect after being modified.
2. Adding the blended modified micro-nano silicon dioxide particles into a dispersion solvent in a weight ratio of 1:5, adding a dispersant BYK-163, performing ultrasonic dispersion for 1.5 hours, and then performing mechanical stirring for 1 hour. The dispersing solvent is a mixed solution of butyl acetate, tert-butyl acetate, propylene glycol methyl ether acetate and ethyl acetate in a weight ratio of 1:1:2: 1.5. The weight ratio of the blended modified nano particles to the dispersant BYK-163 is 15: 1.
3. Adding a certain amount of tert-butyl acetate into the fluorosilicone resin according to the weight ratio of 10:1, and carrying out shear dispersion at the shear rate of 7000r/min for 1h, wherein the viscosity is adjusted to 30s, so as to obtain the base material emulsion.
4. And (3) mixing the blending modified micro-nano silicon dioxide particle suspension obtained in the step (2) with the substrate material emulsion obtained in the step (3), wherein the weight ratio of the blending modified nano particles to the fluorosilicone resin is 1: 3. Adding a coupling agent KH792, heating to 40 ℃, stirring for dispersing for 3h, then adopting a high-speed shearing dispersion machine for dispersing at the speed of 10000rpm for 1.5h, and adding a defoaming agent in the shearing process to obtain the super-amphiphobic coating. The weight ratio of KH792 to resin is 1: 20. The defoaming agent is an organic silicon 100 defoaming agent.
5. Preparing a super-amphiphobic coating: the super-amphiphobic coating is uniformly stirred, sprayed on the surface of an object, and dried for 30 minutes at room temperature to successfully prepare the wear-resistant bottom surface integrated wear-resistant fluorine-silicon-based-micro-nano-silica super-amphiphobic coating. The spraying pressure is 0.3MPa-0.4MPa, and the distance between the spray gun and the surface of the coated object is 15 cm.
In the embodiment, fluorosilane coupling agent dodecafluoroheptyl propyl trimethoxy silane is utilized for hydrolysis and micro-nano SiO2The mixed modified micro-nano SiO is formed by condensation reaction2Particles prepared by mixing micro-nano SiO with two different sizes2The connection solves the problem of uneven dispersion due to different densities, and the oleophylic group is grafted to the surface of the inorganic particles, thereby improving the hydrophilicity of the inorganic particles, improving the compatibility of the inorganic particles and an organic environment, powerfully eliminating the agglomeration among the inorganic nano particles and improving the dispersibility. Wherein the blending modified particles have the following formula:
wherein R is a lipophilic group of dodecafluoroheptyl propyl trimethoxy silane.
The AFM appearance of the fluorosilicone-based super-amphiphobic coating prepared in the embodiment is shown in fig. 1, wherein (a) is a plan view, and (b) is a 3D appearance view, so that the coating has a regular micro-nano coarse structure and is in convex-concave order, and small convex structures are distributed on a larger convex structure. Due to the fact that the micro-nano composite binary structure on the solid surface can form a large number of grooves, air can be effectively trapped, and structural roughness is provided for the formation of the hydrophobic surface.
The bottom surface integrated wear-resistant fluorosilicone-micro nano silica super-amphiphobic coating prepared by the embodiment has excellent super-amphiphobic characteristics, the water contact angle can reach 152 degrees, the rolling angle is about 2 degrees, and for a 20% alcohol solution, the contact angle can reach 100 degrees, as shown in fig. 3 and fig. 4. The binding force between the super-amphiphobic resin and the substrate can reach 2 grades, and the super-amphiphobic performance can still be continuously maintained after the friction of fingers or abrasive paper.
Example 2: bottom surface integrated wear-resistant fluorine silicon-based-nano TiO2-SiO2Preparation process of super-amphiphobic coating
1. Nano TiO 22With nano SiO2To obtain modified TiO2-SiO2Nanoparticles
(1) Preparing blending ball-milling micro-nano powder: weighing a certain amount of nano-scale silicon dioxide and nano-scale titanium dioxide particles, placing the particles into a mixer to be uniformly mixed, and then placing the mixture into a planetary ball mill to be ball-milled for 2 hours to prepare the blending ball-milled micro-nano powder. Nano-sized TiO 22With nano-SiO2The weight ratio between the particles was 1: 2.
(2) Pre-dispersing the blended micro-nano particles: dispersing the blended ball-milled micro-nano powder in absolute ethyl alcohol, shearing and dispersing at the speed of 8krpm for 30min, converting to a low-speed mechanical stirring speed of 600rpm, adding a small amount of surfactant DNS-86, and stirring for 25 min.
(3) Prehydrolysis of vinyltriethoxysilane coupling agent: dissolving a vinyltriethoxysilane coupling agent in a mixed solution of ethanol and deionized water at a ratio of 19:1, using acetic acid to adjust the pH value to 4, and performing ultrasonic dispersion for 10min to fully hydrolyze the coupling agent.
(4) Synergistically modified TiO2-SiO2Preparing nano particles: and (3) dropwise adding the pre-hydrolyzed coupling agent into the pre-dispersed blended micro-nano particles, stirring and heating to promote the grafting reaction of the pre-hydrolyzed coupling agent and the blended micro-nano particles, wherein the heating temperature is 80 ℃, the speed is 700r/min, and the time is 8 h. The dripping process can fully disperse the coupling agent, and the coupling agent is fully contacted with the micro-nano particles, thereby realizing good modification effect.
(5) Centrifugal treatment and drying: and (4) centrifuging the suspension obtained in the step (4), washing with absolute ethyl alcohol for multiple times, centrifuging again, and finally drying in a drying oven at 105 ℃ for 12 hours.
2. Blended TiO2-SiO2Adding the nano particles into a dispersing solvent according to the weight ratio of 1:3, adding a dispersing agent BYK-163 to perform ultrasonic dispersion for 2 hours, and then performing mechanical stirring for 2 hours. The dispersing solvent is butyl acetate,The weight ratio of the mixed solution of the tert-butyl acetate, the propylene glycol methyl ether acetate and the ethyl acetate is 1:1.5:2: 1.5. The weight ratio of the blended modified nano particles to the dispersant BYK-163 is 18: 1.
3. Adding a certain amount of tert-butyl acetate into the fluorosilicone resin according to the weight ratio of 10:1, and carrying out shear dispersion at the shear rate of 5000r/min for 0.7h, wherein the viscosity is adjusted to 20s, so as to obtain the substrate material emulsion.
4. Blending modified TiO of step 22-SiO2And (3) mixing the nano particle suspension with the base material emulsion obtained in the step (3), wherein the weight ratio of the blended modified nano particles to the fluorosilicone resin is 4: 5. Adding a coupling agent KH560, heating to 50 ℃, stirring and dispersing for 2h, then dispersing by adopting a high-speed shearing dispersion machine, wherein the speed is 8000rpm, the shearing time is 1.5h, and adding a defoaming agent organosilicon 100 in the shearing process to obtain the super-amphiphobic coating. The weight ratio of KH560 to resin is 1: 20.
5. Preparing a super-amphiphobic coating: the super-amphiphobic coating is stirred uniformly, sprayed on the surface of an object and dried for 10 minutes at room temperature to successfully prepare the wear-resistant bottom surface integrated wear-resistant fluorine-silicon-based-nano TiO2-SiO2A super-amphiphobic coating. The spraying pressure is 0.4MPa, and the distance between the spray gun and the surface of the coated object is 13 cm.
In the embodiment, the hydrolysis of the silane coupling agent vinyltriethoxysilane coupling agent and the nano SiO are utilized2With nano TiO2The mixed modified nano TiO is formed by condensation reaction2-SiO2Mixing two kinds of TiO2-SiO2The nanoparticles are connected, so that the problem of uneven dispersion due to different densities is solved, oleophylic groups are grafted to the surfaces of the inorganic particles, the hydrophilic characteristic of the inorganic particles is improved, the compatibility of the inorganic particles and an organic environment is improved, the agglomeration among the inorganic nanoparticles is powerfully eliminated, and the dispersibility is improved. Wherein the blending modified particles have the following formula:
wherein R is the oleophilic group of the vinyltriethoxysilane coupling agent.
Bottom surface integrated wear-resistant fluorine silicon-based micro-nano TiO prepared by the embodiment2-SiO2The super-amphiphobic coating has excellent super-amphiphobic characteristics, the water contact angle can reach 151 degrees, the rolling angle is about 2 degrees, and for 20% alcohol, the contact angle can reach 100 degrees. The binding force between the super-amphiphobic resin and the substrate can reach 2 grades, and the super-amphiphobic performance can still be continuously maintained after the friction of fingers or abrasive paper.
Example 3: bottom surface integrated wear-resistant fluorine silicon-based-nano Al2O3-SiO2Preparation process of super-amphiphobic coating
1. Nano Al2O3With nano SiO2To obtain modified Al2O3-SiO2Nanoparticles
(1) Preparing blending ball-milling micro-nano powder: weighing a certain amount of nano-scale silicon dioxide and nano-scale aluminum trioxide particles, placing the particles into a mixer, uniformly mixing, placing the mixture into the mixer, uniformly mixing, and then placing the mixture into a planetary ball mill for ball milling treatment for 2 hours to prepare the blended ball-milled micro-nano powder. Nanoscale Al2O3With nano-SiO2The weight ratio between the particles was 3: 1.
(2) Pre-dispersing the blended micro-nano particles: dispersing the blended ball-milled micro-nano powder in absolute ethyl alcohol, shearing and dispersing at the speed of 8krpm for 30min, converting to a low-speed mechanical stirring speed of 600rpm, adding a small amount of surfactant DNS-86, and stirring for 25 min.
(3) Pre-hydrolysis of the coupling agent: dissolving (methacryloxy) propyl trimethoxy silane coupling agent in a mixed solution of ethanol and deionized water at a ratio of 9:1, and ultrasonically dispersing for 7min by using acetic acid to ensure that the coupling agent is fully hydrolyzed. .
(4) Synergistically modified Al2O3-SiO2Preparing nano particles: and (3) dropwise adding the pre-hydrolyzed coupling agent into the pre-dispersed blended micro-nano particles, stirring and heating to promote the grafting reaction of the pre-hydrolyzed coupling agent and the blended micro-nano particles, wherein the heating temperature is 70 ℃, the speed is 800r/min, and the time is 9 h. The dripping process can fully disperse the coupling agent, and the coupling agent is fully contacted with the micro-nano particles, thereby realizing good modification effect.
(5) Centrifugal treatment and drying: and (4) centrifuging the suspension obtained in the step (4), washing with absolute ethyl alcohol for multiple times, centrifuging again, and finally drying in a drying oven at 100 ℃ for 20 hours.
2. Blended Al2O3-SiO2Adding the nano particles into a dispersing solvent according to the weight ratio of 1:4, adding a dispersing agent BYK-163 to perform ultrasonic dispersion for 1 hour, and then performing mechanical stirring for 2 hours. The dispersing solvent is a mixed solution of butyl acetate, tert-butyl acetate, propylene glycol methyl ether acetate and ethyl acetate, and the weight ratio is 1:1.5:1: 1.5. The weight ratio of the blended modified nano particles to the dispersant BYK-163 is 16: 1.
3. Adding a certain amount of tert-butyl acetate into the fluorosilicone resin according to the weight ratio of 10:1, and carrying out shear dispersion at the shear rate of 6000r/min for 0.7h, wherein the viscosity is adjusted to 20s, so as to obtain the substrate material emulsion.
4. Modifying the blending of the step (2) with modified Al2O3-SiO2And (4) mixing the nano particle suspension with the base material emulsion obtained in the step (3), wherein the weight ratio of the blended modified nano particles to the fluorosilicone resin is 4: 5. Adding a coupling agent of aluminate coupling agent, heating to 50 ℃, stirring and dispersing for 3h, then dispersing by adopting a high-speed shearing disperser at the speed of 8000rpm for 1h, and adding defoaming agent organosilicon 100 in the shearing process to obtain the super-amphiphobic coating. The weight ratio of the aluminate coupling agent to the resin is 1: 20.
5. Preparing a super-amphiphobic coating: the super-amphiphobic coating is stirred uniformly, sprayed on the surface of an object and dried for 25 minutes at room temperature to successfully prepare the wear-resistant bottom surface integrated wear-resistant fluorine-silicon-based-nano Al2O3-SiO2A super-amphiphobic coating. The spraying pressure is 0.4MPa, and the distance between the spray gun and the surface of the coated object is 15 cm.
In this example, silane coupling agent (methacryloyloxy) propyl trimethoxy hydrolysis and nano SiO were used2And nano Al2O3The mixed modified nano Al is formed by condensation reaction2O3-SiO2Two kinds of Al2O3-SiO2Connecting nano particles, grafting oleophylic groups to the surface of inorganic particles,improves the hydrophilicity of the inorganic particles, improves the compatibility of the inorganic particles with organic environment, powerfully eliminates the agglomeration among the inorganic nano particles, and improves the dispersibility. Wherein the blending modified particles have the following formula:
wherein R is the oleophilic group of the (methacryloyloxy) propyltrimethoxysilane coupling agent: gamma-methacryloxy.
Bottom surface integrated wear-resistant fluorosilicone-nano Al prepared in the embodiment2O3-SiO2The super-amphiphobic coating has excellent super-amphiphobic characteristics, the water contact angle can reach 150 degrees, the rolling angle is about 3 degrees, and for 20% alcohol, the contact angle can reach 100 degrees. The binding force between the super-amphiphobic resin and the substrate can reach 2 grades, and the super-amphiphobic performance can still be continuously maintained after the friction of fingers or abrasive paper.
Example 4: bottom surface integrated wear-resistant fluorine silicon-based-nano TiO2-Al2O3Preparation process of super-amphiphobic coating
1. Nano TiO 22And nano Al2O3To obtain modified TiO2-Al2O3Nanoparticles
(1) Preparing blending ball-milling micro-nano powder: weighing a certain amount of nano-scale titanium dioxide and nano-scale aluminum trioxide particles, placing the particles into a mixer, uniformly mixing, placing the mixture into the mixer, uniformly mixing, and then placing the mixture into a planetary ball mill for ball milling treatment for 2 hours to prepare the blended ball-milled micro-nano powder. Nanoscale Al2O3With nanoscale TiO2The weight ratio between the particles was 1: 2.
(2) Pre-dispersing the blended micro-nano particles: dispersing the blended ball-milled micro-nano powder in absolute ethyl alcohol, shearing and dispersing at the speed of 8krpm for 30min, converting to a low-speed mechanical stirring speed of 600rpm, adding a small amount of surfactant DNS-86, and stirring for 20 min.
(3) Pre-hydrolysis of the coupling agent: dissolving the glycidyl ether propyl trimethoxy silane coupling agent in a mixed solution of ethanol and deionized water in a ratio of 9:1, and ultrasonically dispersing for 7min by using acetic acid to ensure that the coupling agent is fully hydrolyzed.
(4) Synergistically modified TiO2-Al2O3Preparing nano particles: and (3) dropwise adding the pre-hydrolyzed coupling agent into the pre-dispersed blended micro-nano particles, stirring and heating to promote the grafting reaction of the pre-hydrolyzed coupling agent and the blended micro-nano particles, wherein the heating temperature is 70 ℃, the speed is 700r/min, and the time is 10 hours. The dripping process can fully disperse the coupling agent, and the coupling agent is fully contacted with the micro-nano particles, thereby realizing good modification effect.
(5) Centrifugal treatment and drying: and (4) centrifuging the suspension obtained in the step (4), washing with absolute ethyl alcohol for multiple times, centrifuging again, and finally drying in a drying oven at the temperature of 80-105 ℃ for 12-24 hours.
2. Blended TiO2-Al2O3The nano particles are added into a dispersing solvent in a weight ratio of 1:4, a dispersing agent BYK-163 is added for ultrasonic dispersion for 1.5 hours, and then mechanical stirring is carried out for 2 hours. The dispersing solvent is a mixed solution of butyl acetate, tert-butyl acetate, propylene glycol methyl ether acetate and ethyl acetate, and the weight ratio is 1:1.5:2: 1.5. The weight ratio of the blended modified nano particles to the dispersant BYK-163 is 17: 1.
3. Adding a certain amount of tert-butyl acetate into the fluorosilicone resin according to the weight ratio of 10:1, and carrying out shear dispersion at the shear rate of 5000r/min for 0.7h, wherein the viscosity is adjusted to 20s, so as to obtain the substrate material emulsion.
4. Blending the modified TiO of the step (2)2-Al2O3And (4) mixing the nano particle suspension with the base material emulsion obtained in the step (3), wherein the weight ratio of the blended modified nano particles to the fluorosilicone resin is 4: 5. Adding a coupling agent KH560, heating to 50 ℃, stirring and dispersing for 3h, then dispersing by adopting a high-speed shearing dispersion machine at the speed of 10000rpm for 1.5h, and adding defoaming agent organosilicon 100 in the shearing process to obtain the super-amphiphobic coating. The weight ratio of KH560 to resin is 1: 20.
5. Preparing a super-amphiphobic coating: the super-amphiphobic coating is stirred uniformly, sprayed on the surface of an object and dried for 20 minutes at room temperature to successfully prepare the wear-resistant bottom surface integrated wear-resistant fluorine-silicon-based-nano TiO2-Al2O3A super-amphiphobic coating. The spraying pressure is 0.4MPa, and the distance between the spray gun and the surface of the coated object is 10 cm.
In this example, the glycidyl ether group propyl trimethoxy hydrolysis of silane coupling agent and nano TiO are utilized2And nano Al2O3The mixed modified nano TiO is formed by condensation reaction2-Al2O3Mixing two kinds of TiO2-Al2O3The nanoparticles are connected, and oleophilic groups are grafted to the surfaces of the inorganic particles, so that the hydrophilicity of the inorganic particles is improved, the compatibility of the inorganic particles and an organic environment is improved, the agglomeration among the inorganic nanoparticles is powerfully eliminated, and the dispersibility is improved. Wherein the blending modified particles have the following formula:
wherein R is the oleophilic group of the glycidyl ether propyl trimethoxy silane coupling agent.
Bottom surface integrated wear-resistant fluorine silicon-based micro-nano TiO prepared by the embodiment2-Al2O3The super-amphiphobic coating has excellent super-amphiphobic characteristics, the water contact angle can reach 151 degrees, the rolling angle is about 4 degrees, and for 20% alcohol, the contact angle can reach 96 degrees. The binding force between the super-amphiphobic resin and the substrate can reach 2 grades, and the super-amphiphobic performance can still be continuously maintained after the friction of fingers or abrasive paper.
Example 5: bottom surface integrated wear-resistant fluorine silicon-based-nano TiO2-SiO2-Al2O3Preparation process of super-amphiphobic coating
1. Nano TiO 22Nano SiO2And nano Al2O3And the modified TiO is obtained by synergistic modification treatment2-SiO2-Al2O3Nanoparticles
(1) Preparing blending ball-milling micro-nano powder: weighing a certain amount of nano-scale titanium dioxide and nano-scale aluminum trioxide particles, uniformly mixing the particles in a mixer, uniformly mixing the particles in the mixer, then placing the mixture in a planetary ball mill for ball milling treatment for 2 hours to prepare blended ball-milled micro-nano powderAnd (3) grinding. Nano-sized TiO 22nano-SiO 22With nanoscale Al2O3The weight ratio between the particles was 1:1.5: 1.
(2) Pre-dispersing the blended micro-nano particles: dispersing the blended ball-milled micro-nano powder in absolute ethyl alcohol, shearing and dispersing at the speed of 8krpm for 30min, converting to a low-speed mechanical stirring speed of 600rpm, adding a small amount of surfactant DNS-86, and stirring for 20 min.
(3) Pre-hydrolysis of the coupling agent: dissolving the mercaptopropyltriethoxysilane coupling agent in a mixed solution of ethanol and deionized water in a ratio of 9:1, and ultrasonically dispersing for 10min by using acetic acid to ensure that the coupling agent is fully hydrolyzed.
(4) Synergistically modified TiO2-SiO2-Al2O3Preparing nano particles: and (3) dropwise adding the pre-hydrolyzed coupling agent into the pre-dispersed blended micro-nano particles, stirring and heating to promote the grafting reaction of the pre-hydrolyzed coupling agent and the blended micro-nano particles, wherein the heating temperature is 70 ℃, the speed is 800r/min, and the time is 8 h. The dripping process can fully disperse the coupling agent, and the coupling agent is fully contacted with the micro-nano particles, thereby realizing good modification effect.
(5) Centrifugal treatment and drying: and (4) centrifuging the suspension obtained in the step (4), washing with absolute ethyl alcohol for multiple times, centrifuging again, and finally drying in a drying oven at 105 ℃ for 12 hours.
2. Blended TiO2-SiO2-Al2O3Adding the nano particles into a dispersing solvent according to the weight ratio of 1:4, adding a dispersing agent BYK-163 to perform ultrasonic dispersion for 1 hour, and then performing mechanical stirring for 3 hours. The dispersing solvent is a mixed solution of butyl acetate, tert-butyl acetate, propylene glycol methyl ether acetate and ethyl acetate in a weight ratio of 1:1:1.5: 1. The weight ratio of the blended modified nano particles to the dispersant BYK-163 is 18: 1.
3. Adding a certain amount of tert-butyl acetate into the fluorosilicone resin according to the weight ratio of 10:1, and carrying out shear dispersion at the shear rate of 5000r/min for 0.7h, wherein the viscosity is adjusted to 25s, so as to obtain the substrate material emulsion.
4. Blending modified TiO of step 22-SiO2-Al2O3Nanoparticle suspension and base material emulsion of step 3And mixing, wherein the weight ratio of the blended modified nano particles to the fluorosilicone resin is 3: 5. Adding a coupling agent of aluminate coupling agent, heating to 50 ℃, stirring and dispersing for 2h, then dispersing by adopting a high-speed shearing disperser, adding defoaming agent organosilicon 100 in the shearing process at a speed of 9000rpm for 1.5h to obtain the super-amphiphobic coating. The weight ratio of the aluminate coupling agent to the resin is 1: 20.
5. Preparing a super-amphiphobic coating: the super-amphiphobic coating is stirred uniformly, sprayed on the surface of an object and dried for 10 minutes at room temperature to successfully prepare the wear-resistant bottom surface integrated wear-resistant fluorine-silicon-based-nano TiO2-SiO2-Al2O3A super-amphiphobic coating. The spraying pressure is 0.5MPa, and the distance between the spray gun and the surface of the coated object is 15 cm.
In the embodiment, silane coupling agent mercaptopropyltriethoxysilane hydrolysis and nano TiO are utilized2Nano SiO2Nano Al2O3The mixed modified nano TiO is formed by condensation reaction2-SiO2-Al2O3Mixing three kinds of TiO2-SiO2-Al2O3The nanoparticles are connected, and oleophilic groups are grafted to the surfaces of the inorganic particles, so that the hydrophilicity of the inorganic particles is improved, the compatibility of the inorganic particles and an organic environment is improved, the agglomeration among the inorganic nanoparticles is powerfully eliminated, and the dispersibility is improved. Wherein the blending modified particles have the following formula:
wherein R is lipophilic group of mercaptopropyltriethoxysilane.
The bottom surface integrated wear-resistant fluorosilicone-nano TiO prepared by the embodiment2-SiO2-Al2O3The super-amphiphobic coating has excellent super-amphiphobic characteristics, the water contact angle can reach 153 degrees, the rolling angle is about 1 degree, and for 20% alcohol, the contact angle can reach 100 degrees. The binding force between the super-amphiphobic resin and the substrate can reach 1 grade, and the super-amphiphobic performance can still be continuously maintained after the friction of fingers or abrasive paper.
The above description is only a preferred embodiment of the present application and is not intended to limit the present application, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, improvement and the like made within the spirit and principle of the present application shall be included in the protection scope of the present application.
Claims (29)
1. A preparation method of synergistic modified blending particles for a fluorine-silicon-based super-amphiphobic coating is characterized by comprising the following steps: the method comprises the following steps:
1) weighing two or more particles selected from micron-sized silicon dioxide, nano-sized titanium dioxide and nano-sized aluminum trioxide, uniformly mixing, and performing ball milling treatment to prepare blended ball-milled powder;
2) adding the blended ball-milled powder into an organic solvent, uniformly shearing, adding a surfactant into the mixture, and uniformly mixing;
3) adding a coupling agent subjected to prehydrolysis into the pre-dispersed blending ball-milling powder solution prepared in the step 2), heating, and carrying out a grafting reaction to obtain synergistic modified blending particles;
in the step 3), the concentration of the coupling agent for prehydrolysis is 3% -6%, and the concentration is the mass fraction.
2. The preparation method of the synergistically modified blended particles for the fluorosilicone-based super-amphiphobic coating according to claim 1, characterized in that: in the step 2), the rotating speed of shearing and uniformly mixing is 6-10 krpm, and the shearing time is 10-30 min.
3. The preparation method of the synergistically modified blended particles for the fluorosilicone-based super-amphiphobic coating according to claim 1, characterized in that: in the step 2), the stirring speed after the surfactant is added is 500-800 rpm.
4. The preparation method of the synergistically modified blended particles for the fluorosilicone-based super-amphiphobic coating according to claim 1, characterized in that: in the step 2), the surfactant is anionic surfactant-ammonium allyloxy nonyl phenol polyoxyethylene ether sulfonate.
5. The preparation method of the synergistically modified blended particles for the fluorosilicone-based super-amphiphobic coating according to claim 1, characterized in that: in the step 3), the prehydrolysis method of the coupling agent comprises the steps of dissolving the coupling agent in an ethanol aqueous solution with the pH value of 3-4, and performing ultrasonic dispersion for 5-10min to fully hydrolyze the coupling agent.
6. The method for preparing the synergistically modified blended particles for the fluorosilicone-based super-amphiphobic coating according to claim 5, wherein the step of: in the step 3), the volume ratio of the ethanol to the deionized water in the ethanol aqueous solution is 9:1-19: 1.
7. The method for preparing the synergistically modified blended particles for the fluorosilicone-based super-amphiphobic coating according to claim 5, wherein the step of: in the step 3), the coupling agent is a silane coupling agent or a fluorosilane coupling agent, and the silane coupling agent is vinyl triethoxysilane, glycidyl ether propyl trimethoxysilane, (methacryloyloxy) propyl trimethoxysilane or mercaptopropyl triethoxysilane; the fluorosilane coupling agent is dodecafluoroheptyl propyl trimethoxy silane, tridecafluorooctyl triethoxy silane or perfluorodecyl triethoxy silane.
8. The preparation method of the synergistically modified blended particles for the fluorosilicone-based super-amphiphobic coating according to claim 1, characterized in that: in the step 3), the temperature of the grafting reaction is 70-100 ℃, the reaction time is 6-12h, and the stirring speed is 600-1000 r/min.
9. The preparation method of the synergistically modified blended particles for the fluorosilicone-based super-amphiphobic coating according to claim 1, characterized in that: in the step 3), the adding mode of the coupling agent for prehydrolysis is dropwise adding.
10. The preparation method of the synergistically modified blended particles for the fluorosilicone-based super-amphiphobic coating according to claim 1, characterized in that: the method also comprises the steps of carrying out solid-liquid separation, cleaning and drying on the prepared synergistic modified blended particles.
11. The method for preparing the synergistically modified blended particles for the fluorosilicone-based super-amphiphobic coating according to claim 10, wherein the method comprises the following steps: the cleaning step is to clean the centrifugal precipitate for 10-30min by using an ultrasonic cleaner, and the cleaning is repeated for three times.
12. The method for preparing the synergistically modified blended particles for the fluorosilicone-based super-amphiphobic coating according to claim 10, wherein the method comprises the following steps: the drying temperature is 80-105 ℃, and the drying time is 12-24 h.
13. The synergistically modified blended particles obtained by the process for preparing synergistically modified blended particles for use in a fluorosilicone-based superamphiphobic coating according to any one of claims 1 to 12.
14. A fluorine-silicon-based super-amphiphobic coating is characterized in that: the coating is prepared by reacting the synergistic modified blended particles prepared by the preparation method for the synergistic modified blended particles of the fluorosilicone-based super-amphiphobic coating, the fluorosilicone resin and the coupling agent according to claim 13;
the mass ratio of the synergistic modified blended particles to the fluorosilicone resin is 1:1-1: 3.
15. The fluoro-silicon based super-amphiphobic coating of claim 14, wherein: the coupling agent is KH550, KH792, KH560 or KH 570.
16. The fluoro-silicon based super-amphiphobic coating of claim 14, wherein: the mass ratio of the coupling agent to the fluorosilicone resin is 1:20-1: 15.
17. The method for preparing the fluorosilicone-based super-amphiphobic coating of any one of claims 14 to 16, wherein: the method comprises the following steps:
1) adding the synergistic modified blended particles into a dispersion solvent, adding a dispersing agent into the dispersion solvent, and shearing and dispersing to obtain a suspension;
2) adding tert-butyl acetate into the fluorosilicone resin, and shearing and dispersing to obtain a substrate material emulsion;
3) and mixing the turbid liquid and the substrate material emulsion, adding a coupling agent into the mixed liquid, and adding a defoaming agent in the shearing and dispersing process to obtain the fluorosilicone-based super-amphiphobic coating.
18. The method for preparing the fluorine-silicon-based super-amphiphobic coating according to claim 17, which is characterized by comprising the following steps: in the step 1), the weight ratio of the synergistic modified blending particles to the dispersing solvent is 1:5-1: 3.
19. The method for preparing the fluorine-silicon-based super-amphiphobic coating according to claim 17, which is characterized by comprising the following steps: the dispersing solvent is a mixed solution of butyl acetate, tert-butyl acetate, propylene glycol methyl ether acetate and ethyl acetate, and the weight ratio of the components is 1:1-1.5:1.5-2:1.5-2 in sequence.
20. The method for preparing the fluorine-silicon-based super-amphiphobic coating according to claim 17, which is characterized by comprising the following steps: in the step 1), the weight ratio of the synergistic modified blending particles to the dispersing agent is 15:1-20: 1.
21. The method for preparing the fluorine-silicon-based super-amphiphobic coating according to claim 17, which is characterized by comprising the following steps: the dispersant is BYK-163.
22. The method for preparing the fluorine-silicon-based super-amphiphobic coating according to claim 17, which is characterized by comprising the following steps: in the step 2), the weight ratio of the fluorine-silicon resin to the tert-butyl acetate is 10:1-4: 1.
23. The method for preparing the fluorine-silicon-based super-amphiphobic coating according to claim 17, which is characterized by comprising the following steps: in the step 2), the shearing and dispersing speed is 4000-7000r/min, the time is 0.5-1h, and the viscosity is adjusted to be 15-30 Pa.s.
24. The method for preparing the fluorine-silicon-based super-amphiphobic coating according to claim 17, which is characterized by comprising the following steps: in the step 3), the defoaming agent is an organic silicon 100 defoaming agent.
25. The method for preparing the fluorine-silicon-based super-amphiphobic coating according to claim 17, which is characterized by comprising the following steps: in the step 3), after the coupling agent is added into the mixed solution, the mixed solution is stirred and dispersed for 1 to 3 hours at the temperature of between 40 and 60 ℃ and then dispersed for 0.5 to 1.5 hours at the shearing rate of 7000 plus 10000 rpm.
26. A preparation method of a bottom surface integrated wear-resistant fluorine-silicon-based super-amphiphobic coating is characterized by comprising the following steps of: the method comprises the following steps: the fluorosilicone-based super-amphiphobic paint of any one of claims 14 to 16 is uniformly stirred, sprayed on the surface of an object and dried to obtain the paint.
27. The preparation method of the bottom surface integrated wear-resistant fluorosilicone-based super-amphiphobic coating according to claim 26, which is characterized in that: the spraying pressure is 0.3MPa-0.6MPa, and the distance between the spray gun and the surface of the object to be coated is 10-30 cm.
28. The bottom-surface-integrated wear-resistant fluorosilicone-based super-amphiphobic coating prepared by the method for preparing the bottom-surface-integrated wear-resistant fluorosilicone-based super-amphiphobic coating of claim 26 or 27.
29. Use of the fluorosilicone-based super-amphiphobic coating of any one of claims 14 to 16 or the bottom-side integrated wear-resistant fluorosilicone-based super-amphiphobic coating of claim 28 for corrosion protection, water protection, self-cleaning, or ice protection.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710867187.9A CN107760091B (en) | 2017-09-22 | 2017-09-22 | Bottom surface integrated wear-resistant fluorine-silicon-based super-amphiphobic coating and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710867187.9A CN107760091B (en) | 2017-09-22 | 2017-09-22 | Bottom surface integrated wear-resistant fluorine-silicon-based super-amphiphobic coating and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107760091A CN107760091A (en) | 2018-03-06 |
| CN107760091B true CN107760091B (en) | 2020-10-16 |
Family
ID=61266243
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710867187.9A Active CN107760091B (en) | 2017-09-22 | 2017-09-22 | Bottom surface integrated wear-resistant fluorine-silicon-based super-amphiphobic coating and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107760091B (en) |
Families Citing this family (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109232946B (en) * | 2018-08-15 | 2022-03-25 | 杭州联通管业有限公司 | Anti-fouling plastic drain pipe and preparation method thereof |
| CN109306243A (en) * | 2018-08-23 | 2019-02-05 | 国网湖南省电力有限公司 | A kind of super hydrophobic coating and its preparation method and application of resistance to greasy dirt |
| CN110079181A (en) * | 2019-04-12 | 2019-08-02 | 西安理工大学 | A kind of preparation method of environmental response type super-amphiphobic coating |
| CN110128894A (en) * | 2019-05-14 | 2019-08-16 | 尚蒙科技无锡有限公司 | A kind of super-hydrophobic self-cleaning nano paint and preparation method thereof |
| CN110272707B (en) * | 2019-06-24 | 2021-03-09 | 万华化学集团股份有限公司 | Isocyanate adhesive composite material and routing fiberboard manufactured by same |
| CN111180147B (en) * | 2020-01-03 | 2021-12-24 | 西北核技术研究院 | Ceramic insulator with microgrooves and self-assembled molecular film on surface and preparation method thereof |
| CN113122081B (en) * | 2020-01-10 | 2022-05-06 | 中国科学院化学研究所 | Transparent high-hardness multifunctional integrated self-repairing coating and preparation method and application thereof |
| CN111440488A (en) * | 2020-05-11 | 2020-07-24 | 杭州传化唯迅新材料有限公司 | Building coating with self-cleaning function and preparation method thereof |
| CN111716931A (en) * | 2020-05-26 | 2020-09-29 | 湖南天琪智慧印刷有限公司 | Heat-sensitive paper with improved sun-proof and antibacterial performance and manufacturing method thereof |
| CN111825840B (en) * | 2020-06-23 | 2022-04-22 | 湖北航天化学技术研究所 | Sulfydryl-containing fluorosilicone resin, UV (ultraviolet) photocuring super-hydrophobic protective coating and preparation method |
| CN112094494B (en) * | 2020-08-28 | 2022-07-19 | 东莞市吉鑫高分子科技有限公司 | Super-barrier thermoplastic polyurethane elastomer and preparation method thereof |
| CN112226135B (en) * | 2020-09-23 | 2022-03-18 | 深圳市艾比森光电股份有限公司 | Waterproof heat dissipation coating material and LED display screen |
| CN114573986B (en) * | 2020-12-01 | 2023-04-07 | 中国科学院化学研究所 | 3D printing part capable of being completely degraded and recycled, and preparation method and application thereof |
| CN113698809B (en) * | 2021-08-06 | 2022-12-02 | 叶向东 | Super-amphiphobic coating with adjustable transparency and preparation method thereof |
| CN113952949A (en) * | 2021-09-14 | 2022-01-21 | 青岛创启迈沃环境科技有限公司 | Preparation method of hydrophobic normal-temperature decomposition ozone catalyst |
| CN114345311B (en) * | 2021-12-30 | 2023-09-05 | 浙江工业大学 | Super-hydrophobic fluorocarbon chain modified titanium dioxide and preparation method and application thereof |
| CN115216221A (en) * | 2022-06-21 | 2022-10-21 | 山东中实易通集团有限公司 | Anti-pollution flashover coating with surface layer self-cleaning function and preparation method thereof |
| CN115806755A (en) * | 2022-11-16 | 2023-03-17 | 国网山东省电力公司电力科学研究院 | Super-hydrophobic coating designed based on compact accumulation theory and preparation method thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001106978A (en) * | 1999-10-08 | 2001-04-17 | Sk Kaken Co Ltd | Aqueous low-stain coating composition |
| CN101195717A (en) * | 2007-12-28 | 2008-06-11 | 江苏南大紫金科技集团有限公司 | Organic surface modifying method of attapulgite |
| CN103468047A (en) * | 2013-09-20 | 2013-12-25 | 云南银峰新材料有限公司 | Preparation method of composite nanometer SiO2 double-hydrophobic coating |
| CN103724558A (en) * | 2013-12-13 | 2014-04-16 | 中科院广州化学有限公司 | Inorganic/organic fluorine-containing microspheres with strawberry-shaped structures as well as preparation method and application thereof |
| CN106752425A (en) * | 2016-11-29 | 2017-05-31 | 国网山东省电力公司电力科学研究院 | A kind of integrated wear-resisting super-amphiphobic coating and preparation method thereof |
| CN106752819A (en) * | 2016-12-13 | 2017-05-31 | 天长市银狐漆业有限公司 | A kind of organic-inorganic hybrid polymer coating of modified particle modification |
-
2017
- 2017-09-22 CN CN201710867187.9A patent/CN107760091B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001106978A (en) * | 1999-10-08 | 2001-04-17 | Sk Kaken Co Ltd | Aqueous low-stain coating composition |
| CN101195717A (en) * | 2007-12-28 | 2008-06-11 | 江苏南大紫金科技集团有限公司 | Organic surface modifying method of attapulgite |
| CN103468047A (en) * | 2013-09-20 | 2013-12-25 | 云南银峰新材料有限公司 | Preparation method of composite nanometer SiO2 double-hydrophobic coating |
| CN103724558A (en) * | 2013-12-13 | 2014-04-16 | 中科院广州化学有限公司 | Inorganic/organic fluorine-containing microspheres with strawberry-shaped structures as well as preparation method and application thereof |
| CN106752425A (en) * | 2016-11-29 | 2017-05-31 | 国网山东省电力公司电力科学研究院 | A kind of integrated wear-resisting super-amphiphobic coating and preparation method thereof |
| CN106752819A (en) * | 2016-12-13 | 2017-05-31 | 天长市银狐漆业有限公司 | A kind of organic-inorganic hybrid polymer coating of modified particle modification |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107760091A (en) | 2018-03-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107760091B (en) | Bottom surface integrated wear-resistant fluorine-silicon-based super-amphiphobic coating and preparation method and application thereof | |
| CN107722827B (en) | Fluorosilicone resin/composite modified nano material hybrid super-amphiphobic coating and preparation process thereof | |
| CN107418266B (en) | Super-hydrophobic coating and preparation method thereof | |
| CN102408757B (en) | Solvent-based nano silicon oxide concentrated pulp and preparation method thereof | |
| CN108517154A (en) | A kind of aqueous, floride-free super hydrophobic coating and preparation method | |
| CN109370418A (en) | A kind of super hydrophobic coating, coating and its preparation method and application | |
| CN104910656B (en) | A kind of method that super-hydrophobic silica powder and super-hydrophobic coat are prepared with compound silicon source | |
| CN107746676B (en) | A kind of self demixing gradient fluorine silicon substrate super-hydrophobic coat and its preparation process | |
| CN104910779A (en) | Super-hydrophobic acrylic polyurethane coating and preparation method thereof | |
| CN111534162B (en) | Montmorillonite-based photocatalytic super-hydrophobic coating and preparation method thereof | |
| CN104250498A (en) | Water-based weather-proof stain-proof thermal reflective insulation coating and preparation method thereof | |
| CN111607283A (en) | Modified halloysite, composite coating based on modified halloysite and preparation method of composite coating | |
| CN115322597B (en) | Self-cleaning ceramic coating with lotus leaf-like structure and preparation and application methods thereof | |
| CN113088123A (en) | Micro-nano composite SiO2Particle, micro-nano composite structure super-hydrophobic coating, preparation method and application thereof | |
| CN115960496B (en) | Weather-resistant corrosion-resistant metal fluorocarbon coating and preparation method thereof | |
| CN112300648A (en) | Transparent super-hydrophobic coating and preparation method thereof | |
| KR101406116B1 (en) | Forming method of superhydrophobic coating layer using inorganic oxide supraparticles and the superhydrophobic coating layer formed thereby | |
| CN111040527A (en) | Heat-reflecting super-hydrophobic PVDF coating and preparation method thereof | |
| WO2023129058A2 (en) | A superhydrophobic coating method | |
| KR102296571B1 (en) | Method for controlling aggregation of sol-gel nanoparticles by solvent relative permittivity, and fabrication of superhydrophobic surfaces using thereof | |
| CN109535865A (en) | A kind of nano combined stone protectant and preparation method thereof | |
| CN109627978B (en) | Water-impact-resistant super-hydrophobic coating and preparation method thereof | |
| CN106833043A (en) | A kind of transparent durable super-hydrophobic new material coating and preparation method thereof | |
| CN110105838B (en) | Micron/nano cross-linked composite super-hydrophobic coating and preparation method thereof | |
| CN107903667A (en) | A kind of multi-functional super-hydrophilic coating and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |