CN117050563B - Preparation method of super-hydrophobic coating with high wear resistance and water impact resistance - Google Patents
Preparation method of super-hydrophobic coating with high wear resistance and water impact resistance Download PDFInfo
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- CN117050563B CN117050563B CN202311312130.4A CN202311312130A CN117050563B CN 117050563 B CN117050563 B CN 117050563B CN 202311312130 A CN202311312130 A CN 202311312130A CN 117050563 B CN117050563 B CN 117050563B
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- 238000000576 coating method Methods 0.000 title claims abstract description 52
- 239000011248 coating agent Substances 0.000 title claims abstract description 49
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 230000003075 superhydrophobic effect Effects 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 61
- 239000004925 Acrylic resin Substances 0.000 claims abstract description 38
- 229920000178 Acrylic resin Polymers 0.000 claims abstract description 38
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 37
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 25
- 239000005543 nano-size silicon particle Substances 0.000 claims abstract description 24
- 239000006185 dispersion Substances 0.000 claims abstract description 22
- 239000002245 particle Substances 0.000 claims abstract description 22
- 239000007788 liquid Substances 0.000 claims abstract description 18
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 12
- 239000002904 solvent Substances 0.000 claims abstract description 9
- 239000002253 acid Substances 0.000 claims abstract description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 7
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 52
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical group COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 claims description 24
- 235000019441 ethanol Nutrition 0.000 claims description 13
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 11
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 9
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 8
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims description 8
- -1 tridecyl fluorine octyl triethoxysilane Chemical compound 0.000 claims description 7
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 claims description 7
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 6
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 6
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 6
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 6
- MTEZSDOQASFMDI-UHFFFAOYSA-N 1-trimethoxysilylpropan-1-ol Chemical compound CCC(O)[Si](OC)(OC)OC MTEZSDOQASFMDI-UHFFFAOYSA-N 0.000 claims description 4
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 4
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 4
- 239000011164 primary particle Substances 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- MSRJTTSHWYDFIU-UHFFFAOYSA-N octyltriethoxysilane Chemical compound CCCCCCCC[Si](OCC)(OCC)OCC MSRJTTSHWYDFIU-UHFFFAOYSA-N 0.000 claims description 3
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 claims description 2
- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-UHFFFAOYSA-N 0.000 claims description 2
- 238000010276 construction Methods 0.000 abstract description 9
- 238000007761 roller coating Methods 0.000 abstract description 8
- 238000005507 spraying Methods 0.000 abstract description 8
- 238000009863 impact test Methods 0.000 abstract description 6
- 229910000831 Steel Inorganic materials 0.000 abstract description 4
- 239000010959 steel Substances 0.000 abstract description 4
- 210000002268 wool Anatomy 0.000 abstract description 4
- 230000001680 brushing effect Effects 0.000 abstract description 2
- 239000002356 single layer Substances 0.000 abstract description 2
- 239000003973 paint Substances 0.000 abstract 2
- 238000006243 chemical reaction Methods 0.000 description 19
- 238000003756 stirring Methods 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 8
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 6
- 238000005299 abrasion Methods 0.000 description 5
- 125000003277 amino group Chemical group 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 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 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 150000001343 alkyl silanes Chemical class 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000004205 dimethyl polysiloxane Substances 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 2
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical class O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 description 1
- CUDYYMUUJHLCGZ-UHFFFAOYSA-N 2-(2-methoxypropoxy)propan-1-ol Chemical compound COC(C)COC(C)CO CUDYYMUUJHLCGZ-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920001709 polysilazane Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- OYGYKEULCAINCL-UHFFFAOYSA-N triethoxy(hexadecyl)silane Chemical compound CCCCCCCCCCCCCCCC[Si](OCC)(OCC)OCC OYGYKEULCAINCL-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
-
- 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
- C09D7/63—Additives non-macromolecular organic
-
- 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
- C09D7/65—Additives macromolecular
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Paints Or Removers (AREA)
Abstract
The invention relates to the technical field of paint, in particular to a preparation method of a super-hydrophobic paint with high wear resistance and water impact resistance, which is prepared from 25-40 parts of hydrophobic modified nano silicon dioxide particle dispersion liquid, 1-3 parts of modified acrylic resin, 0.1-2 parts of silane coupling agent and 50-70 parts of solvent system; the molecular weight of the modified acrylic resin is 40000-55000, the hydroxyl content is 0.01-0.08, and the acid value is 5-10. The super-hydrophobic coating prepared by the preparation method provided by the invention is tested for wear resistance by a steel wool friction tester, the load is 100g, and the hydrophobic angle is still more than 150 degrees after friction is carried out 3000 times; the water impact resistance of the water impact test can be carried out for more than 10 times by using the water impact test with the height of 1.2m and the water impact of 300 mL. In addition, the construction mode only needs single-layer spraying, brushing or roller coating, and the construction is simple and convenient.
Description
Technical Field
The invention relates to the technical field of coatings, in particular to a preparation method of a super-hydrophobic coating with high wear resistance and water impact resistance.
Background
The surface of the super-hydrophobic material has excellent hydrophobic performance and self-cleaning performance, so that the super-hydrophobic material has good application prospects in the fields of water resistance, corrosion resistance, ice resistance, dust resistance and the like. However, the application of the super-hydrophobic coating is limited at present, and the reason is mainly due to the following problems:
(1) The surface of the super-hydrophobic coating needs a rough micro-nano structure, so that the wear resistance is poor, and when the rough surface is subjected to mechanical actions such as impact, friction and the like, the rough surface is easily damaged to lose the super-hydrophobic performance.
(2) In outdoor environmental applications, it is desirable to be able to withstand the impact of rainfall while maintaining superhydrophobicity, and the water impact resistance of existing superhydrophobic materials is still to be further improved.
(3) The construction process is complex, most of super-hydrophobic coatings with better performances are double-layer construction, and some of the super-hydrophobic coatings are required to be heated and cured.
CN116285666A discloses a micro-nano structure super-hydrophobic coating and a preparation method thereofThe composition of the super-hydrophobic coating comprises a bottom coating and a top coating, wherein the bottom coating comprises polydimethylsiloxane, micron/submicron silicon dioxide particles and a curing agent, and the top coating comprises polydimethylsiloxane, hydrophobic nano silicon dioxide particles and a curing agent. The coating is at 1250N/m 2 The coating still has superhydrophobicity after being worn for 50 times under the load, however, the wear resistance of the coating still needs to be improved, and the superhydrophobicity performance of the coating can be influenced under the conditions of high friction and severe environment.
CN116622288A discloses a double coating system, the organo polysilazane, polymethyl methacrylate based polymer particles and thermoplastic acrylic resin in the primer layer provide good adhesion and toughness to the coating, making it better resistant to external friction and scratches. The polymethyl methacrylate polymer particles are spherical micron particles with the particle size of 25-31 mu m, and uniform spherical micron structures are formed in the bottom coating. This structure allows the modified nano alpha-alumina in the topcoat to "hide" therein, thereby enhancing the wear resistance of the coating. Meanwhile, the modified nano alpha-alumina in the surface coating provides additional hardness and wear resistance for the coating, and further improves the stability and durability of the coating in severe environments. The coating of this patent was tested with a linear abrasion tester and as a result, was excellent in abrasion resistance. According to the manufacturing method of the patent, the rough structure formed by polymethyl methacrylate polymer particles is mainly relied on to ensure high wear resistance. However, such a coarse structure performs poorly in water impact resistance tests, which limits its practical application outdoors.
Disclosure of Invention
Aiming at the defects of the existing superhydrophobic coating in the aspects of wear resistance, water impact resistance, complex construction and the like in practical application, the invention provides a preparation method of the superhydrophobic coating with high wear resistance, water impact resistance and convenient construction, and the coating prepared by the method can be constructed in a spray coating, roller coating or brush coating mode and the like and can be solidified at normal temperature.
In order to solve the technical problems, the application provides the following technical scheme:
a preparation method of a super-hydrophobic coating with high wear resistance and water impact resistance comprises the following steps: is prepared from 25-40 parts of hydrophobic modified nano silicon dioxide particle dispersion liquid, 1-3 parts of modified acrylic resin, 0.1-2 parts of silane coupling agent and 50-70 parts of solvent system.
Wherein the molecular weight of the modified acrylic resin is 40000-55000, the hydroxyl content is 0.01-0.08, and the acid value is 5-10. The modified acrylic resin has poor compatibility in an ethanol solvent system by controlling the molecular weight, the hydroxyl content and the acid value. Epoxy functional groups are introduced into the hydrophobically modified nano silica particles, and carboxyl groups in the modified acrylic resin can be combined with epoxy groups of the modified nano silica through reaction. Because the modified nano silicon dioxide has good compatibility with ethanol, and the modified acrylic resin has poor compatibility with ethanol, the composition of the modified nano silicon dioxide and the ethanol is in a state that the modified nano silicon dioxide is uniformly dispersed on the outer layer of the modified acrylic resin colloidal particles in an ethanol solvent, and the state ensures that hydrophobic modified silicon dioxide particles and the resin are uniformly distributed in the upper and lower directions of a film layer in the drying and curing process of the coating, has strong bonding force, and can realize very high wear resistance.
Wherein the hydrophobic modified nano silicon dioxide particle dispersion liquid is prepared from 1 to 5 parts of nano silicon dioxide, 0.1 to 2 parts of long-chain alkyl silane or fluorine-containing long-chain alkyl alkoxy silane, 0.05 to 0.1 part of gamma-glycidyl ether oxypropyl trimethoxy silane, 0.005 to 0.01 part of ammonia water and 85 to 95 parts of absolute ethyl alcohol.
Wherein the nano silicon dioxide is hydrophilic nano silicon dioxide, and the primary particle size is 5-50nm.
Wherein the primary particle size of the nano silicon dioxide is preferably 7-12nm.
Wherein the long-chain alkyl silane is n-octyl triethoxy silane or hexadecyl triethoxy silane.
Wherein the fluorine-containing long-chain alkyl alkoxy silane is tridecyl fluorine octyl triethoxy silane or heptadecyl fluorine decyl triethoxy silane.
Wherein the modified acrylic resin is prepared from 4-8 parts of butyl acrylate, 0.9-1.3 parts of methacrylic acid, 10-15 parts of methyl methacrylate, 20-40 parts of butyl methacrylate, 0.1-0.6 part of hydroxyethyl acrylate, 0.3-0.5 part of benzoyl peroxide and 30-50 parts of butyl acetate.
Wherein the silane coupling agent comprises gamma-aminopropyl triethoxysilane or N- (beta-aminoethyl) -gamma-aminopropyl trimethoxysilane, gamma-glycidoxypropyl trimethoxysilane or gamma-glycidoxypropyl triethoxysilane.
Wherein the solvent system is one or more of propylene glycol methyl ether, dipropylene glycol methyl ether, diethylene glycol butyl ether and butanol and absolute ethyl alcohol.
Compared with the prior art, the preparation method of the super-hydrophobic coating with high wear resistance and water impact resistance has at least the following beneficial effects:
the super-hydrophobic coating prepared by the preparation method provided by the invention is tested for wear resistance by a steel wool friction tester, the load is 100g, and the hydrophobic angle is still more than 150 degrees after friction is carried out 3000 times; the water impact resistance of the water impact test can be carried out for more than 10 times by using the water impact test with the height of 1.2m and the water impact of 300 mL. In addition, the construction mode only needs single-layer spraying, brushing or roller coating, and the construction is simple and convenient.
The preparation method of the super-hydrophobic coating with high wear resistance and water impact resistance is further described below.
Detailed Description
EXAMPLE 1 preparation of hydrophobically modified nanosilica particle Dispersion A
According to the mass parts, 94.422 parts of absolute ethyl alcohol and 5 parts of nano silicon dioxide are respectively added into a reaction kettle, and the mixture is stirred for 1h at a rotating speed of 3000 r/min; then adding 0.5 part of tridecafluorooctyl triethoxysilane, setting the reaction temperature to 60 ℃, adding 0.008 part of ammonia water, and continuously stirring for reaction for 1.5 hours; then adding 0.07 part of gamma-glycidol ether oxypropyl trimethoxy silane, stirring and reacting for 1h, cooling and taking out to obtain absolute ethyl alcohol dispersion liquid A of hydrophobically modified silicon dioxide particles.
EXAMPLE 2 preparation of modified acrylic resin A
Adding 40 parts of butyl acetate into a reaction kettle according to parts by mass, and heating to 110 ℃; 6 parts of butyl acrylate, 1.1 parts of methacrylic acid, 0.4 part of hydroxyethyl acrylate, 12.5 parts of methyl methacrylate, 30 parts of butyl methacrylate and 0.4 part of benzoyl peroxide are mixed in advance, uniformly dropwise added into a reaction system for 2.5 hours, after the dropwise addition is finished, the reaction temperature is adjusted to be in a reflux state, and the temperature is kept at the reflux temperature for 2 hours; 10 parts of butyl acetate and 0.15 part of benzoyl peroxide are mixed in advance, and then added into a reaction kettle in a dropwise manner at a constant speed for 1.5 hours. And cooling and discharging when the conversion rate reaches more than 95%, and removing butyl acetate to obtain the solid modified acrylic resin A. The molecular weight of the prepared modified propionic acid resin is 45000, the acid value is 7, and the hydroxyl content is 0.06.
Example 3 configuration of super hydrophobic coating
Adding 2 parts by mass of the modified acrylic resin A described in the example 2 into 18 parts by mass of propylene glycol methyl ether, stirring and dissolving; 35 parts of the modified nano silica particle ethanol dispersion liquid A described in the example 1 and the propylene glycol methyl ether solution of the modified acrylic resin A are mixed and stirred, so that amino groups on the hydrophobic modified nano silica particles and carboxyl groups on the modified acrylic resin are fully reacted and combined. Then 44 parts of absolute ethyl alcohol, 0.5 part of gamma-aminopropyl triethoxysilane and 0.5 part of gamma-glycidoxypropyl trimethoxysilane are added and stirred uniformly to form slightly turbid emulsion.
The dispersion liquid can be applied by roller coating, brush coating or spray coating, and is naturally dried for 24 hours or dried for 10 minutes below 120 ℃ to prepare the super-hydrophobic coating.
Example 4
The ethanol dispersion B of hydrophobically modified nano silica particles was prepared by changing 0.5 part of tridecafluorooctyltriethoxysilane in example 1 to 0.5 part of n-octyltriethoxysilane, and the remaining materials and preparation process were the same.
Adding 2 parts by mass of the modified acrylic resin A described in the example 2 into 18 parts by mass of propylene glycol methyl ether, stirring and dissolving; and mixing 35 parts of modified nano silicon dioxide particle ethanol dispersion liquid B with propylene glycol methyl ether solution of modified acrylic resin A, and stirring to enable amino groups on the modified nano silicon dioxide particles and carboxyl groups on the modified acrylic resin to fully react and combine. Then 44 parts of absolute ethyl alcohol, 0.5 part of gamma-aminopropyl triethoxysilane and 0.5 part of gamma-glycidoxypropyl trimethoxysilane are added and stirred uniformly to form slightly turbid emulsion.
The dispersion liquid can be applied by roller coating, brush coating or spray coating, and is naturally dried for 24 hours or dried for 10 minutes below 120 ℃ to prepare the super-hydrophobic coating.
Example 5
By changing 1.1 part of methacrylic acid in example 2 to 0.8 part of methacrylic acid, 0.4 part of hydroxyethyl acrylate to 0.54 part of hydroxyethyl acrylate, the acid value of the modified acrylic resin was adjusted to 5, and the hydroxyl group content was adjusted to 0.08, a solid modified acrylic resin B was obtained.
Adding 2 parts of the modified acrylic resin B into 18 parts of propylene glycol methyl ether according to parts by mass, stirring and dissolving; 35 parts of the ethanol dispersion liquid A of the modified nano-silica particles described in the example 1 and the propylene glycol methyl ether solution of the modified acrylic resin B were mixed and stirred to fully react and bond the amino groups on the modified nano-silica particles and the carboxyl groups on the modified acrylic resin. Then 44 parts of absolute ethyl alcohol, 0.5 part of gamma-aminopropyl triethoxysilane and 0.5 part of gamma-glycidoxypropyl trimethoxysilane are added and stirred uniformly to form slightly turbid emulsion.
The dispersion liquid can be applied by roller coating, brush coating or spray coating, and is naturally dried for 24 hours or dried for 10 minutes below 120 ℃ to prepare the super-hydrophobic coating.
To highlight the beneficial effects of the present invention, the following comparative experiments are exemplified.
Comparative example 1
This comparative example describes the effect of hydrophobically modified silica particles made using a process different from the present invention.
Respectively adding 94.49 parts of absolute ethyl alcohol and 5 parts of nano silicon dioxide into a reaction kettle according to parts by mass, and stirring for 1h at a rotating speed of 3000 r/min; then 0.5 part of tridecafluorooctyl triethoxysilane is added, the reaction temperature is set to 60 ℃, 0.01 part of oxalic acid is added, and the reaction is continued to be carried out for 3 hours, thus completing the reaction. And cooling and taking out to obtain an absolute ethyl alcohol dispersion liquid C of the hydrophobically modified silica particles.
Adding 2 parts by mass of the modified acrylic resin A described in the example 2 into 18 parts by mass of propylene glycol methyl ether, stirring and dissolving; 35 parts of modified nano silicon dioxide particle ethanol dispersion liquid C and propylene glycol methyl ether solution of modified acrylic resin A are mixed and stirred. Then 44 parts of absolute ethyl alcohol, 0.5 part of gamma-aminopropyl triethoxysilane and 0.5 part of gamma-glycidoxypropyl trimethoxysilane are added, and uneven white precipitate is formed after stirring, so that the subsequent construction cannot be carried out.
Comparative example 2
This comparative example describes the effect of modified acrylic resins made using a different process than the present invention.
Adding 50 parts by mass of butyl acetate into a reaction kettle, and heating to 90 ℃; 5 parts of butyl acrylate, 2.1 parts of methacrylic acid, 1.2 parts of hydroxyethyl acrylate, 10 parts of methyl methacrylate, 25 parts of butyl methacrylate and 0.3 part of benzoyl peroxide are mixed in advance, uniformly dropwise added into a reaction system for 2 hours, after the dropwise addition is finished, the reaction temperature is adjusted to be in a reflux state, and the reaction is kept at the reflux temperature for 1 hour; 6.3 parts of butyl acetate and 0.1 part of benzoyl peroxide are mixed in advance, and then added into the reaction kettle in a dropwise manner at a constant speed for 1 hour. And cooling and discharging when the conversion rate reaches more than 95%, and removing butyl acetate to obtain the solid modified acrylic resin C. The prepared modified propionic acid resin has a molecular weight of 10000, an acid value of 15 and a hydroxyl content of 0.2.
Adding 2 parts of modified acrylic resin C into 18 parts of propylene glycol methyl ether according to parts by mass, stirring and dissolving; 35 parts of the ethanol dispersion liquid A of the modified nano-silica particles described in the example 1 and the propylene glycol methyl ether solution of the modified acrylic resin C were mixed and stirred to sufficiently react and bond the amino groups on the modified nano-silica particles with the carboxyl groups on the modified acrylic resin. Then 44 parts of absolute ethyl alcohol, 0.5 part of gamma-aminopropyl triethoxysilane and 0.5 part of gamma-glycidol ether oxypropyl trimethoxysilane are added and stirred uniformly to form a slightly white uniform dispersion.
The dispersion liquid can be applied by roller coating, brush coating or spray coating, and is naturally dried for 24 hours or dried for 10 minutes below 120 ℃ to prepare the super-hydrophobic coating.
Comparative example 3
This comparative example describes the effect of using a different solvent system than the present invention.
Adding 2 parts of modified acrylic resin C into 18 parts of butyl acetate according to parts by mass, stirring and dissolving; 35 parts of the ethanol dispersion liquid A of the modified nano-silica particles described in example 1 and the butyl acetate solution of the modified acrylic resin C were mixed and stirred to allow the amino groups on the modified nano-silica particles to react and bond with the carboxyl groups on the modified acrylic resin. Then 44 parts of butyl acetate, 0.5 part of gamma-aminopropyl triethoxysilane and 0.5 part of gamma-glycidoxypropyl trimethoxysilane are added and stirred uniformly to form a slightly white uniform dispersion.
The dispersion liquid can be applied by roller coating, brush coating or spray coating, and is naturally dried for 24 hours or dried for 10 minutes below 120 ℃ to prepare the super-hydrophobic coating.
The products of examples 3-5 and comparative examples 2-3 were tested for abrasion resistance and water resistance, respectively.
Abrasion resistance test: the test is carried out by adopting a steel wool abrasion resistance tester, 0000# steel wool is adopted, the area is 10 multiplied by 10mm, the stroke is 40 times/min, the load is 100g, the water contact angle of a test sample piece is rubbed 100 times each time, when the water contact angle is smaller than 150 degrees, the test is stopped, and the final times are recorded.
Water impact resistance test: adding 1mL of red ink into 1L of distilled water or water conforming to GB/T6682-2008, fully stirring to uniformly mix, wherein the red ink is commercially available red ink conforming to QB/T1745.1-2011, using a funnel with a capacity of 300mL, connecting a plastic pipe with a length of 15cm and an inner diameter of 2cm below, and placing a sample plate to be tested at a position of 1.2m below the plastic pipe. 300ml of test water was poured into the funnel. The test water is allowed to fall freely under the action of gravity to impact the surface of the test plate, and after 300ml of water is completely drained, the surface of the test plate is inspected. If the condition that the surface of the test board is not stained with the color is regarded as qualified, the next water impact resistance test can be continued. And when the surface of the test board is stained with water drops with color, stopping detection, and recording the final times.
The test results are shown in the following table:
from the above results, it can be seen that the hydrophobic angle of the coating prepared by the method is still above 150 degrees after 3000 times of friction; the water impact resistance of the water impact test can be carried out for more than 10 times by using the water impact test with the height of 1.2m and the water impact of 300 mL.
The above examples are only illustrative of the preferred embodiments of the present invention and are not intended to limit the scope of the present invention, and various modifications and improvements made by those skilled in the art to the technical solution of the present invention should fall within the scope of protection defined by the claims of the present invention without departing from the spirit of the present invention.
Claims (4)
1. A preparation method of a super-hydrophobic coating with high wear resistance and water impact resistance is characterized by comprising the following steps: is prepared from 25-40 parts of hydrophobic modified nano silicon dioxide particle dispersion liquid, 1-3 parts of modified acrylic resin, 0.1-2 parts of silane coupling agent and 50-70 parts of solvent system;
the molecular weight of the modified acrylic resin is 40000-55000, the hydroxyl content is 0.01-0.08, and the acid value is 5-10;
the hydrophobic modified nano silicon dioxide particle dispersion liquid is prepared from 1 to 5 parts of nano silicon dioxide, 0.1 to 2 parts of n-octyl triethoxysilane or tridecyl fluorine octyl triethoxysilane, 0.05 to 0.1 part of gamma-glycidyl ether oxypropyl trimethoxy silane, 0.005 to 0.01 part of ammonia water and 85 to 95 parts of absolute ethyl alcohol;
the modified acrylic resin is prepared from 4-8 parts of butyl acrylate, 0.9-1.3 parts of methacrylic acid, 10-15 parts of methyl methacrylate, 20-40 parts of butyl methacrylate, 0.1-0.6 part of hydroxyethyl acrylate, 0.3-0.5 part of benzoyl peroxide and 30-50 parts of butyl acetate;
the solvent system is propylene glycol methyl ether and absolute ethyl alcohol;
wherein, the modified acrylic resin and the modified nano silicon dioxide particles are in a state that the modified nano silicon dioxide is uniformly dispersed on the outer layer of the modified acrylic resin colloidal particle in the ethanol solvent.
2. The method for preparing the super-hydrophobic coating with high wear resistance and water impact resistance according to claim 1, which is characterized in that: the nano silicon dioxide is hydrophilic nano silicon dioxide, and the primary particle size is 5-50nm.
3. The method for preparing the super-hydrophobic coating with high wear resistance and water impact resistance according to claim 2, which is characterized in that: the primary particle size of the nano silicon dioxide is 7-12nm.
4. The method for preparing the super-hydrophobic coating with high wear resistance and water impact resistance according to claim 1, which is characterized in that: the silane coupling agent comprises gamma-aminopropyl triethoxysilane or N- (beta-aminoethyl) -gamma-aminopropyl trimethoxysilane, gamma-glycidoxypropyl trimethoxysilane or gamma-glycidoxypropyl triethoxysilane.
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