CN116218320B - Preparation method of super-hydrophobic self-cleaning aluminum alloy coating - Google Patents
Preparation method of super-hydrophobic self-cleaning aluminum alloy coating Download PDFInfo
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- 238000000576 coating method Methods 0.000 title claims abstract description 51
- 239000011248 coating agent Substances 0.000 title claims abstract description 49
- 229910000838 Al alloy Inorganic materials 0.000 title claims abstract description 47
- 230000003075 superhydrophobic effect Effects 0.000 title claims abstract description 30
- 238000004140 cleaning Methods 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 229910004298 SiO 2 Inorganic materials 0.000 claims abstract description 53
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 17
- 239000011737 fluorine Substances 0.000 claims abstract description 17
- 239000003822 epoxy resin Substances 0.000 claims abstract description 16
- 229920001558 organosilicon polymer Polymers 0.000 claims abstract description 16
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 16
- -1 polysiloxane Polymers 0.000 claims abstract description 16
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- STYXVTBFUKQEKM-UHFFFAOYSA-N 1,1,1,2,3,3,4,4,5,5,6,6,7,7,8,8,8-heptadecafluorooctan-2-yl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(F)(C(F)(F)F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F STYXVTBFUKQEKM-UHFFFAOYSA-N 0.000 claims abstract description 10
- XHIRWEVPYCTARV-UHFFFAOYSA-N n-(3-aminopropyl)-2-methylprop-2-enamide;hydrochloride Chemical compound Cl.CC(=C)C(=O)NCCCN XHIRWEVPYCTARV-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 10
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 10
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 10
- FSAJWMJJORKPKS-UHFFFAOYSA-N octadecyl prop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C=C FSAJWMJJORKPKS-UHFFFAOYSA-N 0.000 claims abstract description 8
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims abstract description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 26
- 239000002904 solvent Substances 0.000 claims description 19
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 238000001723 curing Methods 0.000 claims description 17
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 16
- 239000000839 emulsion Substances 0.000 claims description 16
- 238000001914 filtration Methods 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 13
- 238000005406 washing Methods 0.000 claims description 13
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 9
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 9
- AHDSRXYHVZECER-UHFFFAOYSA-N 2,4,6-tris[(dimethylamino)methyl]phenol Chemical compound CN(C)CC1=CC(CN(C)C)=C(O)C(CN(C)C)=C1 AHDSRXYHVZECER-UHFFFAOYSA-N 0.000 claims description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- VYKXQOYUCMREIS-UHFFFAOYSA-N methylhexahydrophthalic anhydride Chemical compound C1CCCC2C(=O)OC(=O)C21C VYKXQOYUCMREIS-UHFFFAOYSA-N 0.000 claims description 8
- 125000001261 isocyanato group Chemical group *N=C=O 0.000 claims description 7
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 7
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 7
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 6
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims description 6
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 claims description 6
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- 239000012153 distilled water Substances 0.000 claims description 6
- 230000001804 emulsifying effect Effects 0.000 claims description 6
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 5
- 239000007810 chemical reaction solvent Substances 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- JTHZUSWLNCPZLX-UHFFFAOYSA-N 6-fluoro-3-methyl-2h-indazole Chemical compound FC1=CC=C2C(C)=NNC2=C1 JTHZUSWLNCPZLX-UHFFFAOYSA-N 0.000 claims 1
- 238000005260 corrosion Methods 0.000 abstract description 9
- 230000007797 corrosion Effects 0.000 abstract description 8
- 230000002209 hydrophobic effect Effects 0.000 abstract description 4
- 238000007334 copolymerization reaction Methods 0.000 abstract description 2
- 239000006260 foam Substances 0.000 abstract description 2
- 238000013007 heat curing Methods 0.000 abstract description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 abstract description 2
- 239000012948 isocyanate Substances 0.000 abstract 1
- 150000002513 isocyanates Chemical class 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 8
- 238000005303 weighing Methods 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 230000035939 shock Effects 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- WCCVMVPVUAVUFI-UHFFFAOYSA-N 2-methylprop-2-enamide;hydrochloride Chemical compound Cl.CC(=C)C(N)=O WCCVMVPVUAVUFI-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 230000003373 anti-fouling effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002221 fluorine Chemical class 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002952 polymeric resin Substances 0.000 description 1
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical group CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
-
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Paints Or Removers (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
Abstract
The invention relates to the technical field of aluminum alloy coatings, and discloses a preparation method of a super-hydrophobic self-cleaning aluminum alloy coating, which utilizes amino and isocyanate SiO of N- (3-aminopropyl) methacrylamide hydrochloride 2 Reacting the isocyanate groups on the surface to obtain acrylamide SiO 2 The introduced acrylamide group and perfluorohexyl ethyl methacrylate, octadecyl acrylate and double-end vinyl polysiloxane are subjected to copolymerization reaction, so that the fluorine-containing organosilicon polymer is grafted to the nano SiO 2 The surface is obtained to obtain the hydrophobic modified nano SiO 2 Finally, the nano SiO is compounded with epoxy resin and coated on the surface of aluminum alloy, and the nano SiO is obtained after heat curing 2 The super-hydrophobic coating compounded with the epoxy resin has a water contact angle of 153.6 degrees at most, and the impact strength of the aluminum alloy coating reaches 15.4kJ/m 2 The coating is not pulverized, does not crack, does not foam, and has excellent corrosion resistance.
Description
Technical Field
The invention relates to the technical field of aluminum alloy coatings, in particular to a preparation method of a super-hydrophobic self-cleaning aluminum alloy coating.
Background
The aluminum alloy has the advantages of low density, light weight, high strength, good electric conduction and thermal conductivity, excellent casting performance and weldability, is widely applied to the fields of transportation, aerospace, mechanical manufacturing and the like, adopts high polymer resin to form a coating on the surface of the aluminum alloy, can endow the aluminum alloy with excellent surface properties such as corrosion resistance, superhydrophobic and the like, and reports on fluorine-containing polyurethane and nano SiO (silicon dioxide) in the literature, namely the preparation of the superhydrophobic coating on the surface of the aluminum alloy and the corrosion resistance of the superhydrophobic coating 2 Under the synergistic effect, a layer of super-hydrophobic coating is successfully prepared on the surface of the aluminum alloy, and the aluminum alloy has excellent corrosion resistance.
The super-hydrophobic coating has a unique super-hydrophobic self-cleaning effect, and has wide application prospects in the fields of metal surface water resistance, rust resistance, outdoor building antifouling and corrosion resistance and the like, for example, patent 202010695661.6, a preparation method of an aluminum alloy surface super-hydrophobic composite coating, discloses that phosphoric acid anodic oxidation treatment is carried out on the aluminum alloy surface; for SiO 2 Carrying out hydrophobic modification treatment, preparing a coating with epoxy resin, fluorine-containing polyurethane and the like, then spraying on the surface of the aluminum alloy, and curing at room temperature to obtain the super-hydrophobic composite coating. The invention aims at preparing hydrophobically modified fluorine-containing organosilicon polymer-based SiO 2 And the super-hydrophobic coating is formed on the surface of the aluminum alloy by compounding the super-hydrophobic coating with epoxy resin, so that the performances of super-hydrophobic self-cleaning, corrosion resistance, shock resistance and the like of the surface of the aluminum alloy are improved.
Disclosure of Invention
(one) solving the technical problems
The invention provides a super-hydrophobic self-cleaning aluminum alloy coating, which endows the aluminum alloy coating with excellent super-hydrophobic self-cleaning, corrosion resistance, shock resistance and other properties.
(II) technical scheme
The preparation method of the super-hydrophobic self-cleaning aluminum alloy coating comprises the following steps:
(1) Nano SiO 2 And 2, 4-toluene diisocyanate in toluene solvent to obtain isocyanato SiO 2 Redispersing in a reaction solvent and then adding N- (3-aminopropyl)Stirring and dissolving methacrylamide hydrochloride, dropwise adding dibutyltin dilaurate, filtering a solvent after reaction, and washing a product with ethanol to obtain acrylamide SiO 2 。
(2) Acrylic amide group SiO 2 Dispersing into methyl isobutyl ketone solvent, adding perfluorohexyl ethyl methacrylate, octadecyl acrylate, double-end vinyl polysiloxane, sodium dodecyl sulfate and OP-10, stirring and emulsifying uniformly, adding azodiisobutyronitrile in nitrogen atmosphere, filtering solvent after reaction, washing the product with distilled water and ethanol to obtain fluorine-containing organosilicon polymer base SiO 2 。
(3) To the fluorine-containing organosilicon polymer base SiO 2 Adding into emulsion of epoxy resin, ultrasonic dispersing, adding into curing agent methyl hexahydrophthalic anhydride and accelerator 2,4, 6-tri (dimethylamino methyl) phenol, uniformly coating the emulsion on the surface of aluminum alloy, and heating for curing to obtain the super-hydrophobic self-cleaning aluminum alloy coating.
Preferably, the reaction solvent in (1) comprises tetrahydrofuran, acetone, toluene, N-dimethylformamide or ethyl acetate.
Preferably, the isocyanate group SiO in the above (1) 2 The weight ratio of N- (3-aminopropyl) methacrylamide hydrochloride to dibutyltin dilaurate is 1:2-8:0.002-0.006.
Preferably, the reaction temperature is controlled to be 60-80 ℃ and the reaction time is controlled to be 6-18h in the step (1).
Preferably, the acrylamide group SiO in the step (2) 2 The weight ratio of the perfluorohexyl ethyl methacrylate to the octadecyl acrylate to the double-end vinyl polysiloxane is 1:2-10:1.5-6:3-15.
Preferably, the reaction temperature is controlled to be 65-80 ℃ and the reaction time is controlled to be 4-6h in the step (2).
Preferably, the fluorine-containing organosilicon polymer-based SiO in the step (3) 2 And the weight ratio of the epoxy resin is 0.01-0.05:1.
(III) beneficial technical effects
Amino and isocyanato SiO using N- (3-aminopropyl) methacrylamide hydrochloride 2 Surface of the bodyIs reacted with an isocyanate group to give acrylamido SiO 2 The introduced acrylamide group is subjected to copolymerization reaction with perfluorohexyl ethyl methacrylate, octadecyl acrylate and double-end vinyl polysiloxane, so that the hydrophobic fluorine-containing organosilicon polymer is grafted to the nano SiO 2 The surface is obtained to obtain the hydrophobic modified nano SiO 2 Finally, the nano SiO is compounded with epoxy resin and coated on the surface of aluminum alloy, and the nano SiO is obtained after heat curing 2 Super-hydrophobic coating compounded with epoxy resin and hydrophobically modified nano SiO 2 Uniformly dispersed in the coating to form a micro-nano protruding structure, the water contact angle is up to 153.6 degrees, and the impact strength of the aluminum alloy coating is up to 15.4kJ/m 2 The coating is not pulverized, does not crack, does not foam, and has excellent corrosion resistance.
Detailed Description
Example 1
(1) 0.1g of nano SiO 2 And 0.2g of 2, 4-toluene diisocyanate in a toluene solvent to give an isocyanato SiO 2 Weighing 0.1g, dispersing into acetone, adding 0.2g of N- (3-aminopropyl) methacrylamide hydrochloride, stirring and dissolving, dripping 0.2mg of dibutyltin dilaurate, reacting at 60 ℃ for 12 hours, filtering the solvent after the reaction, washing the product with ethanol to obtain acrylamide-based SiO 2 。
(2) 0.1g of acrylamido SiO 2 Dispersing into methyl isobutyl ketone solvent, adding 0.2g of perfluorohexyl ethyl methacrylate, 0.15g of octadecyl acrylate, 0.3g of double-end vinyl polysiloxane, 0.05g of sodium dodecyl sulfate and 0.1g of OP-10, stirring and emulsifying uniformly, adding 6mg of azodiisobutyronitrile in nitrogen atmosphere, reacting at 70 ℃ for 5h, filtering the solvent after the reaction, washing the product with distilled water and ethanol to obtain fluorine-containing organosilicon polymer base SiO 2 。
(3) 0.2g of fluorine-containing organosilicon polymer-based SiO 2 Adding into emulsion containing 20g of epoxy resin, adding 10g of curing agent methyl hexahydrophthalic anhydride and 0.12g of accelerator 2,4, 6-tris (dimethylaminomethyl) phenol after ultrasonic dispersion, uniformly coating the emulsion on the surface of aluminum alloy, heating for curing,obtaining the super-hydrophobic self-cleaning aluminum alloy coating.
Example 2
(1) 0.1g of nano SiO 2 And 0.2g of 2, 4-toluene diisocyanate in a toluene solvent to give an isocyanato SiO 2 Weighing 0.1g of the mixture, redispersing the mixture into N, N-dimethylformamide, adding 0.4g of N- (3-aminopropyl) methacrylamide hydrochloride, stirring and dissolving the mixture, dropwise adding 0.3mg of dibutyltin dilaurate, reacting the mixture at 60 ℃ for 18 hours, filtering the solvent after the reaction, and washing the product by ethanol to obtain acrylamide SiO 2 。
(2) 0.1g of acrylamido SiO 2 Dispersing into methyl isobutyl ketone solvent, adding 0.4g of perfluorohexyl ethyl methacrylate, 0.2g of octadecyl acrylate, 0.6g of double-end vinyl polysiloxane, 0.05g of sodium dodecyl sulfate and 0.1g of OP-10, stirring and emulsifying uniformly, adding 15mg of azodiisobutyronitrile in nitrogen atmosphere, reacting at 70 ℃ for 6 hours, filtering the solvent after the reaction, washing the product with distilled water and ethanol to obtain fluorine-containing organosilicon polymer base SiO 2 。
(3) 0.4g of fluorine-containing organosilicon polymer-based SiO 2 Adding into emulsion containing 20g of epoxy resin, adding 10g of curing agent methyl hexahydrophthalic anhydride and 0.12g of accelerator 2,4, 6-tris (dimethylaminomethyl) phenol after ultrasonic dispersion, uniformly coating the emulsion on the surface of the aluminum alloy, and heating and curing to obtain the super-hydrophobic self-cleaning aluminum alloy coating.
Example 3
(1) 0.1g of nano SiO 2 And 0.2g of 2, 4-toluene diisocyanate in a toluene solvent to give an isocyanato SiO 2 Weighing 0.1g, redispersing into ethyl acetate, adding 0.6g of N- (3-aminopropyl) methacrylamide hydrochloride, stirring and dissolving, dripping 0.4mg of dibutyltin dilaurate, reacting at 60 ℃ for 18h, filtering the solvent after the reaction, washing the product with ethanol to obtain acrylamide SiO 2 。
(2) 0.1g of acrylamido SiO 2 Dispersed in methyl isobutyl ketone solvent, then 0.8g of perfluorohexyl ethyl methacrylate, 0.4g of acrylic acid are addedOctadecyl ester, 1.2g of double-end vinyl polysiloxane, 0.05g of sodium dodecyl sulfate and 0.1g of OP-10, adding 35mg of azodiisobutyronitrile in a nitrogen atmosphere after stirring and emulsifying uniformly, reacting for 4 hours at 70 ℃, filtering the solvent after the reaction, and washing the product with distilled water and ethanol to obtain the fluorine-containing organosilicon polymer-based SiO 2 。
(3) 0.8g of fluorine-containing organosilicon polymer-based SiO 2 Adding into emulsion containing 20g of epoxy resin, adding 10g of curing agent methyl hexahydrophthalic anhydride and 0.12g of accelerator 2,4, 6-tris (dimethylaminomethyl) phenol after ultrasonic dispersion, uniformly coating the emulsion on the surface of the aluminum alloy, and heating and curing to obtain the super-hydrophobic self-cleaning aluminum alloy coating.
Example 4
(1) 0.1g of nano SiO 2 And 0.2g of 2, 4-toluene diisocyanate in a toluene solvent to give an isocyanato SiO 2 Weighing 0.1g, dispersing into toluene, adding 0.8g of N- (3-aminopropyl) methacrylamide hydrochloride, stirring and dissolving, dripping 0.6mg of dibutyltin dilaurate, reacting at 70 ℃ for 18h, filtering the solvent after the reaction, washing the product with ethanol to obtain acrylamide-based SiO 2 。
(2) 0.1g of acrylamido SiO 2 Dispersing into methyl isobutyl ketone solvent, adding 1g of perfluorohexyl ethyl methacrylate, 0.6g of octadecyl acrylate, 1.5g of double-end vinyl polysiloxane, 0.05g of sodium dodecyl sulfate and 0.1g of OP-10, stirring and emulsifying uniformly, adding 50mg of azodiisobutyronitrile in nitrogen atmosphere, reacting at 75 ℃ for 6 hours, filtering the solvent after the reaction, washing the product with distilled water and ethanol to obtain the fluorine-containing organosilicon polymer base SiO 2 。
(3) 1g of a fluorosilicone polymer-based SiO 2 Adding into emulsion containing 20g of epoxy resin, adding 10g of curing agent methyl hexahydrophthalic anhydride and 0.12g of accelerator 2,4, 6-tris (dimethylaminomethyl) phenol after ultrasonic dispersion, uniformly coating the emulsion on the surface of the aluminum alloy, and heating and curing to obtain the super-hydrophobic self-cleaning aluminum alloy coating.
Comparative example 1
(1) 0.2g of nano SiO 2 Adding into emulsion containing 20g of epoxy resin, adding 10g of curing agent methyl hexahydrophthalic anhydride and 0.12g of accelerator 2,4, 6-tris (dimethylaminomethyl) phenol after ultrasonic dispersion, uniformly coating the emulsion on the surface of aluminum alloy, and heating and curing to obtain the aluminum alloy coating.
Comparative example 2
(1) 0.1g of nano SiO 2 And 0.2g of 2, 4-toluene diisocyanate in a toluene solvent to give an isocyanato SiO 2 Weighing 0.1g of the mixture, dispersing the mixture into tetrahydrofuran, adding 0.2g of N- (3-aminopropyl) methacrylamide hydrochloride, stirring and dissolving the mixture, dropwise adding 0.2mg of dibutyltin dilaurate, reacting the mixture at 70 ℃ for 12 hours, filtering the solvent after the reaction, and washing the product by ethanol to obtain acrylamide SiO 2 。
(2) 0.2g of acrylamido SiO 2 Adding into emulsion containing 20g of epoxy resin, adding 10g of curing agent methyl hexahydrophthalic anhydride and 0.12g of accelerator 2,4, 6-tris (dimethylaminomethyl) phenol after ultrasonic dispersion, uniformly coating the emulsion on the surface of aluminum alloy, and heating and curing to obtain the aluminum alloy coating.
With reference to the method of GB/T30693-2014, a water contact angle tester is used to determine the water contact angle of an aluminum alloy coating.
With reference to the method of GB/T1843-2008, a cantilever beam impact strength tester is adopted to test the impact resistance of the aluminum alloy coating.
The performance of the aluminum alloy media resistance was rated with reference to the method of GB/T1766-2008. The comprehensive grade of the coating film is rated according to the single damage grade in the medium-resistant process of the coating, and is divided into six grades: grade 0 (excellent), grade 1 (good), grade 2 (medium), grade 3 (bad), grade 4 (poor), grade 5 (bad).
The maximum water contact angle of the super-hydrophobic self-cleaning aluminum alloy coating reaches 152.2 degrees, and the maximum impact strength reaches 15.4kJ/m 2 The coating is not pulverized, bubble-free and cracking-freeAnd has excellent anti-corrosion performance.
Claims (3)
1. A preparation method of a super-hydrophobic self-cleaning aluminum alloy coating is characterized by comprising the following steps of: the preparation method comprises the following steps:
(1) Nano SiO 2 And 2, 4-toluene diisocyanate in toluene solvent to obtain isocyanato SiO 2 Dispersing in reaction solvent, adding N- (3-aminopropyl) methacrylamide hydrochloride, stirring to dissolve, and dripping dibutyl tin dilaurate, wherein isocyanate group SiO 2 The weight ratio of the N- (3-aminopropyl) methacrylamide hydrochloride to the dibutyltin dilaurate is 1:2-8:0.002-0.006; controlling the reaction temperature to be 60-80 ℃ and the reaction time to be 6-18h, filtering the solvent after the reaction, and washing the product with ethanol to obtain the acrylamide SiO 2 ；
(2) Acrylic amide group SiO 2 Dispersing into methyl isobutyl ketone solvent, adding perfluorohexyl ethyl methacrylate, stearyl acrylate, double-end vinyl polysiloxane, sodium dodecyl sulfate and OP-10, wherein acrylamide SiO 2 The weight ratio of the perfluorohexyl ethyl methacrylate to the octadecyl acrylate to the double-end vinyl polysiloxane is 1:2-10:1.5-6:3-15; stirring and emulsifying uniformly, adding azodiisobutyronitrile in nitrogen atmosphere, filtering solvent after reaction, washing the product with distilled water and ethanol to obtain fluorine-containing organosilicon polymer-based SiO 2 ；
(3) To the fluorine-containing organosilicon polymer base SiO 2 Added into an emulsion of epoxy resin, wherein the fluorine-containing organosilicon polymer base SiO 2 And epoxy resin in a weight ratio of 0.01-0.05:1; adding a curing agent methyl hexahydrophthalic anhydride and an accelerator 2,4, 6-tris (dimethylaminomethyl) phenol after ultrasonic dispersion, uniformly coating the emulsion on the surface of the aluminum alloy, and heating and curing to obtain the super-hydrophobic self-cleaning aluminum alloy coating.
2. The method for preparing the superhydrophobic self-cleaning aluminum alloy coating according to claim 1, wherein the method comprises the following steps: the reaction solvent in the step (1) comprises tetrahydrofuran, acetone, toluene, N-dimethylformamide or ethyl acetate.
3. The method for preparing the superhydrophobic self-cleaning aluminum alloy coating according to claim 1, wherein the method comprises the following steps: the reaction temperature is controlled to be 65-80 ℃ and the reaction time is controlled to be 4-6h in the step (2).
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