CN116640511A - Super-hydrophobic self-repairing transparent coating, and preparation method and application thereof - Google Patents
Super-hydrophobic self-repairing transparent coating, and preparation method and application thereof Download PDFInfo
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- CN116640511A CN116640511A CN202310672040.XA CN202310672040A CN116640511A CN 116640511 A CN116640511 A CN 116640511A CN 202310672040 A CN202310672040 A CN 202310672040A CN 116640511 A CN116640511 A CN 116640511A
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- cerium oxide
- stirring
- super
- nano cerium
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- 238000000576 coating method Methods 0.000 title claims abstract description 99
- 239000011248 coating agent Substances 0.000 title claims abstract description 95
- 230000003075 superhydrophobic effect Effects 0.000 title claims abstract description 59
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 229910000420 cerium oxide Inorganic materials 0.000 claims abstract description 73
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims abstract description 73
- 238000003756 stirring Methods 0.000 claims abstract description 66
- 229920002635 polyurethane Polymers 0.000 claims abstract description 38
- 239000004814 polyurethane Substances 0.000 claims abstract description 38
- 239000000758 substrate Substances 0.000 claims abstract description 38
- 229920001577 copolymer Polymers 0.000 claims abstract description 32
- 238000004140 cleaning Methods 0.000 claims abstract description 29
- 239000000725 suspension Substances 0.000 claims abstract description 25
- 239000000178 monomer Substances 0.000 claims abstract description 19
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims abstract description 18
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 claims abstract description 13
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 10
- 239000011737 fluorine Substances 0.000 claims abstract description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 8
- 239000012986 chain transfer agent Substances 0.000 claims abstract description 8
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910000077 silane Inorganic materials 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 49
- 238000002156 mixing Methods 0.000 claims description 43
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 42
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 33
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 33
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 26
- 239000011521 glass Substances 0.000 claims description 25
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 22
- 239000003960 organic solvent Substances 0.000 claims description 19
- -1 polytetramethylene Polymers 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 16
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 14
- 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 13
- 238000001816 cooling Methods 0.000 claims description 13
- 238000009210 therapy by ultrasound Methods 0.000 claims description 13
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 11
- 239000011261 inert gas Substances 0.000 claims description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 10
- 238000004528 spin coating Methods 0.000 claims description 10
- 239000004970 Chain extender Substances 0.000 claims description 9
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 9
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 9
- 239000005457 ice water Substances 0.000 claims description 9
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 9
- 229920000151 polyglycol Polymers 0.000 claims description 9
- 239000010695 polyglycol Substances 0.000 claims description 9
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 9
- 239000012498 ultrapure water Substances 0.000 claims description 9
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 claims description 8
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 8
- QTIMEBJTEBWHOB-PMDAXIHYSA-N [3-[(z)-octadec-9-enoyl]oxy-2,2-bis[[(z)-octadec-9-enoyl]oxymethyl]propyl] (z)-octadec-9-enoate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCC(COC(=O)CCCCCCC\C=C/CCCCCCCC)(COC(=O)CCCCCCC\C=C/CCCCCCCC)COC(=O)CCCCCCC\C=C/CCCCCCCC QTIMEBJTEBWHOB-PMDAXIHYSA-N 0.000 claims description 8
- 150000002148 esters Chemical class 0.000 claims description 8
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims description 7
- DEQJNIVTRAWAMD-UHFFFAOYSA-N 1,1,2,4,4,4-hexafluorobutyl prop-2-enoate Chemical compound FC(F)(F)CC(F)C(F)(F)OC(=O)C=C DEQJNIVTRAWAMD-UHFFFAOYSA-N 0.000 claims description 7
- 125000005442 diisocyanate group Chemical group 0.000 claims description 7
- 229920001223 polyethylene glycol Polymers 0.000 claims description 7
- 238000001291 vacuum drying Methods 0.000 claims description 7
- 238000009423 ventilation Methods 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 6
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- 238000007599 discharging Methods 0.000 claims description 6
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 6
- 229920001610 polycaprolactone Polymers 0.000 claims description 6
- 229920000909 polytetrahydrofuran Polymers 0.000 claims description 6
- 238000007789 sealing Methods 0.000 claims description 6
- KYNFOMQIXZUKRK-UHFFFAOYSA-N 2,2'-dithiodiethanol Chemical compound OCCSSCCO KYNFOMQIXZUKRK-UHFFFAOYSA-N 0.000 claims description 5
- YJKHMSPWWGBKTN-UHFFFAOYSA-N 2,2,3,3,4,4,5,5,6,6,7,7-dodecafluoroheptyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)F YJKHMSPWWGBKTN-UHFFFAOYSA-N 0.000 claims description 5
- QSVOWVXHKOQYIP-UHFFFAOYSA-N 2-dodecylsulfanylcarbothioylsulfanyl-2-methylpropanenitrile Chemical compound CCCCCCCCCCCCSC(=S)SC(C)(C)C#N QSVOWVXHKOQYIP-UHFFFAOYSA-N 0.000 claims description 5
- VURAQNQRBLGZAU-UHFFFAOYSA-N 2-methyl-2-tridecanethioylsulfanylpropanoic acid Chemical compound CCCCCCCCCCCCC(=S)SC(C)(C)C(O)=O VURAQNQRBLGZAU-UHFFFAOYSA-N 0.000 claims description 5
- DGMOBVGABMBZSB-UHFFFAOYSA-N 2-methylpropanoyl chloride Chemical compound CC(C)C(Cl)=O DGMOBVGABMBZSB-UHFFFAOYSA-N 0.000 claims description 5
- VWGKEVWFBOUAND-UHFFFAOYSA-N 4,4'-thiodiphenol Chemical compound C1=CC(O)=CC=C1SC1=CC=C(O)C=C1 VWGKEVWFBOUAND-UHFFFAOYSA-N 0.000 claims description 5
- 239000002202 Polyethylene glycol Substances 0.000 claims description 5
- 239000003599 detergent Substances 0.000 claims description 5
- 239000005357 flat glass Substances 0.000 claims description 5
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 5
- 239000004632 polycaprolactone Substances 0.000 claims description 5
- 230000000379 polymerizing effect Effects 0.000 claims description 5
- 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 5
- BDQZGTSZNWENDM-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldisulfanyl)-2-methylpropanenitrile Chemical compound C(C(C)(C)SSC(C#N)(C)C)#N BDQZGTSZNWENDM-UHFFFAOYSA-N 0.000 claims description 3
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 3
- 239000012670 alkaline solution Substances 0.000 claims description 3
- 239000006260 foam Substances 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 229920001451 polypropylene glycol Polymers 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 3
- 229920002554 vinyl polymer Polymers 0.000 claims description 3
- 239000008096 xylene Substances 0.000 claims description 3
- 238000002791 soaking Methods 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 abstract description 20
- 238000002834 transmittance Methods 0.000 abstract description 19
- 230000032683 aging Effects 0.000 abstract description 7
- 238000007334 copolymerization reaction Methods 0.000 abstract description 4
- 239000000853 adhesive Substances 0.000 abstract description 3
- 230000001070 adhesive effect Effects 0.000 abstract description 3
- 238000006116 polymerization reaction Methods 0.000 abstract description 3
- 238000004132 cross linking Methods 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 22
- 238000012360 testing method Methods 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 11
- 230000003068 static effect Effects 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- 239000000428 dust Substances 0.000 description 6
- 239000002086 nanomaterial Substances 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- 238000013467 fragmentation Methods 0.000 description 5
- 238000006062 fragmentation reaction Methods 0.000 description 5
- 238000010526 radical polymerization reaction Methods 0.000 description 5
- 150000003254 radicals Chemical class 0.000 description 5
- 230000002441 reversible effect Effects 0.000 description 5
- 238000012546 transfer Methods 0.000 description 5
- 102100026735 Coagulation factor VIII Human genes 0.000 description 4
- 101000911390 Homo sapiens Coagulation factor VIII Proteins 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 4
- 150000002009 diols Chemical class 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000005227 gel permeation chromatography Methods 0.000 description 3
- 230000008439 repair process Effects 0.000 description 3
- 238000005096 rolling process Methods 0.000 description 3
- 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 description 2
- KMKDABFJLFWNNV-UHFFFAOYSA-N C(=S)(NO)SSC(=S)NO Chemical compound C(=S)(NO)SSC(=S)NO KMKDABFJLFWNNV-UHFFFAOYSA-N 0.000 description 2
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- RNSLCHIAOHUARI-UHFFFAOYSA-N butane-1,4-diol;hexanedioic acid Chemical compound OCCCCO.OC(=O)CCCCC(O)=O RNSLCHIAOHUARI-UHFFFAOYSA-N 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- AMFIBVNSEBYBAM-UHFFFAOYSA-N ethylcarbamothioylsulfanyl n-ethylcarbamodithioate Chemical compound CCNC(=S)SSC(=S)NCC AMFIBVNSEBYBAM-UHFFFAOYSA-N 0.000 description 2
- UFFSXJKVKBQEHC-UHFFFAOYSA-N heptafluorobutyric anhydride Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(=O)OC(=O)C(F)(F)C(F)(F)C(F)(F)F UFFSXJKVKBQEHC-UHFFFAOYSA-N 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 238000005935 nucleophilic addition reaction Methods 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 230000001172 regenerating effect Effects 0.000 description 2
- YEORLXJBCPPSOC-UHFFFAOYSA-N 2-amino-5-(diaminomethylideneazaniumyl)-2-(difluoromethyl)pentanoate Chemical compound NC(N)=NCCCC(N)(C(F)F)C(O)=O YEORLXJBCPPSOC-UHFFFAOYSA-N 0.000 description 1
- DZFGVGDQHQHOKZ-UHFFFAOYSA-N 2-dodecylsulfanylcarbothioylsulfanyl-2-methylpropanoic acid Chemical compound CCCCCCCCCCCCSC(=S)SC(C)(C)C(O)=O DZFGVGDQHQHOKZ-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 229920001688 coating polymer Polymers 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 210000003608 fece Anatomy 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 229910003471 inorganic composite material Inorganic materials 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000004154 testing of material Methods 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- GYTROFMCUJZKNA-UHFFFAOYSA-N triethyl triethoxysilyl silicate Chemical compound CCO[Si](OCC)(OCC)O[Si](OCC)(OCC)OCC GYTROFMCUJZKNA-UHFFFAOYSA-N 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 238000009736 wetting Methods 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
- C09D187/00—Coating compositions based on unspecified macromolecular compounds, obtained otherwise than by polymerisation reactions only involving unsaturated carbon-to-carbon bonds
- C09D187/005—Block or graft polymers not provided for in groups C09D101/00 - C09D185/04
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/001—Macromolecular compounds containing organic and inorganic sequences, e.g. organic polymers grafted onto silica
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Wood Science & Technology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Paints Or Removers (AREA)
Abstract
The invention relates to the technical field of transparent coatings, in particular to a super-hydrophobic self-repairing transparent coating, a preparation method and application thereof. The preparation method comprises the following steps: preparing a modified nano cerium oxide suspension, preparing a double-bond-terminated disulfide bond-containing polyurethane prepolymer solution, stirring the double-bond-terminated disulfide bond-containing polyurethane prepolymer solution, a fluorine-containing acrylate monomer and vinyl-terminated polydimethoxy silane, adding a RAFT chain transfer agent, reacting for a certain time, adding triallyl isocyanurate for cross-linking polymerization, adding the modified nano cerium oxide suspension for continuous copolymerization, finally obtaining a nano cerium oxide/polyurethane acrylate copolymer solution, and coating the nano cerium oxide/polyurethane acrylate copolymer solution on a substrate to obtain the super-hydrophobic self-repairing transparent coating. The super-hydrophobic self-repairing transparent coating provided by the invention has the advantages of reliable product performance, high ultraviolet aging resistance, high light transmittance, excellent adhesive force, strong self-cleaning performance and capability of repairing polymer cracks, and the preparation method and the application thereof.
Description
Technical Field
The invention relates to the technical field of transparent coatings, in particular to a super-hydrophobic self-repairing transparent coating, a preparation method and application thereof.
Background
The solar photovoltaic system is provided with a large number of daylighting glass plates, and because the daylighting glass on the solar photovoltaic cell plates is exposed to outdoor environments (especially desert and humid environments) for a long time, dust and dirt are accumulated on the solar cell assembly in a large amount, so that the absorption of the solar photovoltaic cell to sunlight is reduced, and the photoelectric conversion efficiency of the solar photovoltaic cell is reduced. The solar packaging is commonly used with 3.2mm ultra-white rolled glass, the transmittance is about 92%, and the solar panel energy conversion rate can be reduced by 40% by a small amount of dust (0.005 kg/m < 2 >) through testing, so that the annual energy generation lost due to pollution of the glass panel is considerable.
In order to improve the conversion efficiency of solar cells, currently used cleaning techniques can be classified into manual, automatic and self-cleaning. The manual cleaning needs to rely on a large amount of manpower and material resources to clean the surface of the solar panel glass, and a large amount of water and electricity are consumed in the cleaning process, so that the energy is not saved, and the environment is not protected; the automatic cleaning has large investment in the early stage, high energy consumption in the use process, is limited by terrains, still needs manpower to assist cleaning, and has high maintenance cost in the later stage; the super-hydrophobic self-cleaning coating is a better choice for maintaining the photovoltaic module, dust on a solar cell panel can be easily removed, so that the photoelectric conversion efficiency is improved, but most solar cell panels are in a severe environment, and the super-hydrophobic self-cleaning coating can face the problems of ultraviolet radiation, rain wash, flying sand and stone abrasion, extreme high-low temperature change, corrosion of bird excreta and the like in sunlight, the existing super-hydrophobic self-cleaning coating is a general formula product through compounding, the coating has poor transparency, the coating is not firmly adhered to a base material, the rough micro-nano structure on the surface of the coating is too fragile, and the coating is easy to impact, wear and corrosion, so that the rough surface and the self-cleaning performance are lost. Therefore, it is necessary to develop a superhydrophobic coating having uv aging resistance, good adhesion, light transmittance, and self-healing ability.
Disclosure of Invention
The invention aims to provide a super-hydrophobic self-repairing transparent coating, a preparation method and application thereof, so as to solve the technical problems of poor transparency, weak adhesion of a base material and weak rough micro-nano structure of the surface of the super-hydrophobic self-cleaning coating in the prior art.
The preparation method of the super-hydrophobic self-repairing transparent coating provided by the invention comprises the following steps:
adding 0.5-0.8 part of pentaerythritol tetraoleate and 5-10 parts of organic solvent into a container according to the mass ratio, stirring and mixing uniformly at the temperature of 20-30 ℃, adding 2-5 parts of nano cerium oxide, stirring and mixing uniformly, adding 3-6 parts of gamma-methacryloxypropyl trimethoxysilane and 8-15 parts of organic solvent, stirring and mixing uniformly, and performing ultrasonic treatment for a first preset period of time to obtain modified nano cerium oxide suspension;
adding 17-25 parts of diisocyanate after drying treatment, 21-45 parts of polyglycol monomer and 25-35 parts of organic solvent into another container according to the mass ratio, stirring and mixing uniformly under the protection of inert gas and at the temperature of 80-85 ℃, adding 0.05-0.1 part of dibutyltin dilaurate to react for a second preset time period, cooling to 60-65 ℃, adding 0.8-1.2 parts of chain extender to react for a third preset time period, adding 0.5-1 part of trimethylolpropane to react for a fourth preset time period, adding 65-100 parts of organic solvent, preserving heat to react for a fifth preset time period, and adding 3-7 parts of hydroxyethyl methacrylate to obtain a double-bond capped polyurethane prepolymer solution containing disulfide bonds;
Adding 16-24 parts of double bond capped disulfide bond-containing polyurethane prepolymer solution, 2.2-5.3 parts of fluorine-containing acrylate monomer and 5.1-8.6 parts of vinyl capped polydimethoxy silane into another container according to the mass ratio, stirring and mixing uniformly in an ice water bath under the protection of inert gas, adding 0.2-0.5 part of RAFT chain transfer agent, stirring and reacting for a sixth preset time at 60-70 ℃, adding 0.02-0.05 part of triallyl isocyanurate, stirring and reacting for a seventh preset time, adding 8-13 parts of modified nano cerium oxide suspension, stirring and polymerizing for an eighth preset time to obtain nano cerium oxide/polyurethane acrylate copolymer solution;
and coating the nano cerium oxide/polyurethane acrylic ester copolymer solution on a substrate to obtain the super-hydrophobic self-repairing transparent coating.
Preferably, as an implementation manner, the first preset duration is 0.5 to 1h, and/or the second preset duration is 0.5 to 1h, and/or the third preset duration is 0.5 to 1h, and/or the fourth preset duration is 0.5 to 1h, and/or the fifth preset duration is 2 to 3h, and/or the sixth preset duration is 1 to 2h, and/or the seventh preset duration is 1 to 2h, and/or the eighth preset duration is 4 to 6h.
Preferably, as an implementation manner, in the step of stirring and mixing uniformly for the first time at the temperature of 20-30 ℃, the duration of stirring and mixing is 0.5-1 h; and/or in the step of stirring and uniformly mixing in an ice water bath under the protection of inert gas, the stirring and mixing time is 0.3-0.5 h.
Preferably, as an embodiment, after the preparing of the modified nano cerium oxide suspension, the method further comprises: sealing and preserving the modified nano cerium oxide suspension; and/or, after the nano cerium oxide/polyurethane acrylate copolymer solution is obtained, the method further comprises the steps of preserving heat for 1.5-2.5 hours, cooling to room temperature and discharging.
Preferably, as an embodiment, the step of applying the nano cerium oxide/polyurethane acrylate copolymer solution to a substrate includes:
and cleaning the transparent substrate, vacuum drying the cleaned transparent substrate at the temperature of 70-80 ℃, placing the transparent substrate on a spin coater for spin coating, spin coating the nano cerium oxide/polyurethane acrylate copolymer solution on the surface of the transparent substrate at the preset rotating speed for a tenth preset time period, and then carrying out ventilation drying at normal temperature.
Preferably, as an implementation manner, the preset rotating speed is 3000-4000 rpm, and the tenth preset time period is 2-3 s.
Preferably, as an embodiment, the step of cleaning the transparent substrate includes: putting the transparent substrate into an ultrasonic cleaning tank, adding ultrapure water and a detergent, and performing ultrasonic treatment for 0.5-1 h; washing foam with ultrapure water, soaking in alkaline solution for 0.8-1.2 hr, washing with ultrapure water, and ultrasonic treating with acetone for 0.5-1 hr.
Preferably, as one embodiment, the diisocyanate includes one, two or more of toluene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, and hexamethylene diisocyanate;
and/or the polyglycol monomer comprises one, two or more of polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polycaprolactone glycol, polytetrahydrofuran ether glycol, poly adipic acid-1 and 4-butanediol ester glycol, and the number average molecular weight is 500-1000;
and/or the chain extender comprises one of dihydroxydiethylthiuram disulfide, bis (2-hydroxyethyl) disulfide, bis (4-hydroxyphenyl) sulfide;
And/or the fluorine-containing acrylate monomer comprises one of perfluoroalkyl ethyl acrylate, hexafluorobutyl acrylate and dodecafluoroheptyl methacrylate;
and/or the RAFT chain transfer agent comprises one of 2- (dodecylthiocarbonylthio) -2-methylpropanoic acid, bis (dimethylacetyl chloride) trithiocarbonyl ester, 2-cyano-2-propyldisulfide, 2-cyano-2-propyldodecyl trithiocarbonate;
and/or the organic solvent comprises one of chloroform, ethyl acetate, toluene, xylene, acetone, dimethyl sulfoxide and tetrahydrofuran;
and/or the inert gas comprises nitrogen.
The invention also provides a super-hydrophobic self-repairing transparent coating, which is prepared by adopting the preparation method of the super-hydrophobic self-repairing transparent coating.
The invention also provides application of the super-hydrophobic self-repairing transparent coating, which is used for a daylighting glass plate, a glass curtain wall or vehicle window glass of a solar photovoltaic cell panel.
Compared with the prior art, the invention has the beneficial effects that:
the invention firstly utilizes isocyanate monomer to carry out nucleophilic addition reaction with hydroxyl-containing polyglycol monomer and hydroxyl-containing disulfide to obtain double-bond capped polyurethane prepolymer containing disulfide bonds, then carries out reversible addition-fragmentation chain transfer free radical polymerization (RAFT) with fluorine-containing acrylic ester and double-bond capped polydimethoxysilane to carry out graft copolymerization on modified nano cerium oxide to obtain nano cerium oxide/polyurethane acrylic ester copolymer solution, and finally coats the nano cerium oxide/polyurethane acrylic ester copolymer solution on the surface of a substrate to obtain the super-hydrophobic self-repairing transparent coating.
By utilizing the reversible addition-fragmentation chain transfer free radical polymerization (RAFT) technology, the molecular mass distribution of the polymer can be more balanced, and the product performance can be outputted reliably and continuously. Firstly, the super-hydrophobic coating is constructed to form a necessary rough micro-nano structure by introducing nano cerium oxide, and has excellent ultraviolet absorption performance and shielding effect on ultraviolet rays (with the wavelength of 200-400 nm), so that the ultraviolet aging resistance of the polymer can be improved, the polymer has no characteristic absorption on visible light, the transmittance is good, and the light transmittance of the coating can be ensured; secondly, introducing low-surface energy substances such as fluorosilicone into polyurethane to endow the coating with low surface energy, forming a coating firmly adhered to the surface of the substrate under the combined action of the low-surface energy substances and a rough micro-nano structure constructed by a nano cerium oxide material, and endowing the coating with excellent self-cleaning performance, wherein the static water contact angle of the surface of the coating reaches more than 150.0 degrees, and the rolling angle is less than 5 degrees; in addition, disulfide bonds (dynamic covalent bonds) are introduced into the polymer, the disulfide bonds can be uniformly broken into sulfur free radicals under the irradiation of visible light, and the recombination of chain segments is realized in the process of regenerating the disulfide bonds by the sulfur free radicals, so that the repair of polymer cracks is realized, and the polymer cracks can be automatically repaired when the polymer cracks are impacted, abraded and corroded, so that the good performance of the coating is maintained.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are required to be used in the embodiments or the description of the prior art will be briefly described below, and it is obvious that the drawings in the following description are only embodiments of the present invention, and that other drawings can be obtained according to the provided drawings without inventive effort for a person skilled in the art.
FIG. 1 is a micro-nano rough structure morphology diagram of the super-hydrophobic self-repairing transparent coating obtained in the embodiment 1 of the invention on the lower surface of a scanning electron microscope;
FIG. 2 shows the surface static contact angle of the super-hydrophobic self-repairing transparent coating obtained in example 1 of the present invention;
FIG. 3 is a surface static contact angle of the super-hydrophobic self-repairing transparent coating obtained in example 2 of the present invention;
FIG. 4 shows the surface static contact angle of the super-hydrophobic self-repairing transparent coating obtained in example 3 of the present invention;
FIG. 5 shows the surface static contact angle of the super-hydrophobic self-repairing transparent coating obtained in example 4 of the present invention;
FIG. 6 is a front-to-back comparison of the shape of water drops on the surface of the treated glass with the super-hydrophobic self-repairing transparent coating obtained in example 1 of the present invention.
Detailed Description
The following description of the embodiments of the present invention will be made apparent and fully in view of the accompanying drawings, in which some, but not all embodiments of the invention are shown. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The invention will now be described in further detail by way of specific examples of embodiments in connection with the accompanying drawings.
The embodiment provides a preparation method of a super-hydrophobic self-repairing transparent coating, which comprises the following steps:
preparation of modified nano cerium oxide suspension: adding 0.5-0.8 part of pentaerythritol tetraoleate and 5-10 parts of organic solvent into a container according to the mass ratio, stirring and mixing uniformly at the temperature of 20-30 ℃, adding 2-5 parts of nano cerium oxide, stirring and mixing uniformly, adding 3-6 parts of gamma-methacryloxypropyl trimethoxysilane and 8-15 parts of organic solvent, stirring and mixing uniformly, and performing ultrasonic treatment for a first preset period of time to obtain the modified nano cerium oxide suspension.
Preparation of double-bond-terminated disulfide bond-containing polyurethane prepolymer solution: adding 17-25 parts of diisocyanate after drying treatment, 21-45 parts of polyglycol monomer and 25-35 parts of organic solvent into another container according to the mass ratio, stirring and mixing uniformly under the protection of inert gas and at the temperature of 80-85 ℃, adding 0.05-0.1 part of dibutyltin dilaurate to react for a second preset time period, cooling to 60-65 ℃, adding 0.8-1.2 parts of chain extender to react for a third preset time period, adding 0.5-1 part of trimethylolpropane to react for a fourth preset time period, adding 65-100 parts of organic solvent, preserving heat to react for a fifth preset time period, and adding 3-7 parts of hydroxyethyl methacrylate to obtain the polyurethane prepolymer solution containing disulfide bonds with double-bond end caps. Wherein dibutyl tin dilaurate is used as a catalyst.
Preparation of a nano cerium oxide/polyurethane acrylate copolymer solution: adding 16-24 parts of double bond end capped polyurethane prepolymer solution containing disulfide bonds, 2.2-5.3 parts of fluorine-containing acrylate monomer and 5.1-8.6 parts of vinyl end capped polydimethoxy silane into another container according to the mass ratio, stirring and mixing uniformly in an ice water bath under the protection of inert gas, adding 0.2-0.5 part of RAFT chain transfer agent, stirring and reacting for a sixth preset time at the temperature of 60-70 ℃, adding 0.02-0.05 part of triallyl isocyanurate, stirring and reacting for a seventh preset time, adding 8-13 parts of modified nano cerium oxide suspension, stirring and polymerizing for an eighth preset time, and obtaining the nano cerium oxide/polyurethane acrylate copolymer solution.
Preparation of the coating: and coating the nano cerium oxide/polyurethane acrylic ester copolymer solution on a substrate to obtain the super-hydrophobic self-repairing transparent coating.
According to the embodiment, firstly, isocyanate monomers can be subjected to nucleophilic addition reaction with hydroxyl-containing polyglycol monomers and hydroxyl-containing disulfide to obtain double-bond-terminated polyurethane prepolymer containing disulfide bonds, then, the polyurethane prepolymer is subjected to reversible addition-fragmentation chain transfer free radical polymerization (RAFT) technology with fluorine-containing acrylic ester and double-bond-terminated polydimethoxysilane to carry out graft copolymerization on modified nano cerium oxide to obtain nano cerium oxide/polyurethane acrylic ester copolymer solution, and finally, the nano cerium oxide/polyurethane acrylic ester copolymer solution is coated on the surface of a substrate to obtain the super-hydrophobic self-repairing transparent coating.
By utilizing the reversible addition-fragmentation chain transfer free radical polymerization (RAFT) technology, the molecular mass distribution of the polymer can be more balanced, and the product performance can be outputted reliably and continuously. Firstly, the super-hydrophobic coating is constructed to form a necessary rough micro-nano structure by introducing nano cerium oxide, and has excellent ultraviolet absorption performance and shielding effect on ultraviolet rays (with the wavelength of 200-400 nm), so that the ultraviolet aging resistance of the polymer can be improved, the polymer has no characteristic absorption on visible light, the transmittance is good, and the light transmittance of the coating can be ensured; secondly, introducing low-surface energy substances such as fluorosilicone into polyurethane to endow the coating with low surface energy, forming a coating firmly adhered to the surface of the substrate under the combined action of the low-surface energy substances and a rough micro-nano structure constructed by a nano cerium oxide material, and endowing the coating with excellent self-cleaning performance, wherein the static water contact angle of the surface of the coating reaches more than 150.0 degrees, and the rolling angle is less than 5 degrees; in addition, disulfide bonds (dynamic covalent bonds) are introduced into the polymer, the disulfide bonds can be uniformly broken into sulfur free radicals under the irradiation of visible light, and the recombination of chain segments is realized in the process of regenerating the disulfide bonds by the sulfur free radicals, so that the repair of polymer cracks is realized, and the polymer cracks can be automatically repaired when the polymer cracks are impacted, abraded and corroded, so that the good performance of the coating is maintained.
Specifically, in the preparation step of the modified nano cerium oxide suspension, the mass parts of pentaerythritol tetraoleate can be selected as follows: 0.6 part, 0.7 part, 0.72 part, 0.75 part, and any mass fraction value between the two mass fraction value points; the types and the parts by weight of the organic solvent added for the first time can be selected as follows: 6 parts of acetone, 8 parts of ethyl acetate, 9 parts of dimethyl sulfoxide and 9.6 parts of toluene; the temperature of the first stirring can be selected as follows: 24 ℃, 26 ℃ and 27 ℃; the time length of the first stirring can be 0.5-1 h, and concretely can be 0.6h, 0.7h, 0.8h and 0.9h; the gamma-methacryloxypropyl trimethoxysilane is prepared from the following components in parts by weight: 3.5 parts, 4 parts, 5 parts, 5.8 parts, and any mass fraction value between the two mass fraction values; the types and the mass parts of the organic solvents added for the second time can be selected as follows: 9 parts of acetone, 11 parts of ethyl acetate, 13 parts of dimethyl sulfoxide and 14 parts of toluene; the mass portions of the nano cerium oxide can be selected as follows: 3 parts, 3.8 parts, 4.2 parts, 4.8 parts, and any mass fraction value between the two mass fraction values; the particle size of the nano cerium oxide can be 40nm, 60nm, 75nm and 95nm, and any particle size value between two particle size values.
In the preparation step of the double-bond-blocked disulfide bond-containing polyurethane prepolymer solution, the types and the mass parts of diisocyanate can be selected as follows: 18.5 parts of toluene diisocyanate, 19.7 parts of isophorone diisocyanate, 23.2 parts of isophorone diisocyanate, 24.3 parts of hexamethylene diisocyanate; the types and the mass parts of the polyglycol monomers can be selected as follows: 23.5 parts of polytetrahydrofuran ether glycol, 28 parts of polyethylene glycol, 36.4 parts of polycaprolactone diol and 43.8 parts of poly (1, 4-butanediol adipate) diol; the types and the parts by weight of the organic solvent added for the first time can be selected as follows: 28 parts of acetone, 30 parts of ethyl acetate, 32 parts of dimethyl sulfoxide and 34 parts of toluene; the temperature conditions for the first stirring are: 82 ℃, 83 ℃, 84 ℃ and any temperature value between two temperature value points; the mass parts of the dibutyl tin dilaurate can be selected as follows: 0.06 part, 0.07 part, 0.08 part, 0.09 part, and any part by mass value between the two parts by mass values; the temperature of the chain extender before and after the addition of the chain extender is reduced can be: 61 ℃, 62 ℃, 63 ℃, 64 ℃ and any temperature value between two temperature value points; the chain extender is selected from the following types in parts by mass: 0.9 parts of dihydroxythiuram disulfide, 1 part of bis (2-hydroxyethyl) disulfide, 1.1 parts of dihydroxythiuram disulfide or 1.17 parts of bis (4-hydroxyphenyl) sulfide; the weight parts of the trimethylolpropane can be selected as follows: 0.73 part, 0.65 part, 0.78 part, 0.95 part, and any mass fraction value between the two mass fraction value points; the types and the mass parts of the secondary added organic solvent can be selected as follows: 80.6 parts of acetone, 78 parts of ethyl acetate, 92 parts of dimethyl sulfoxide and 95 parts of toluene; the mass parts of the hydroxyethyl methacrylate can be selected as follows: 3.7 parts, 4.7 parts, 5.9 parts, 5.4 parts, and any mass fraction value between the two mass fraction values.
In the preparation step of the nano cerium oxide/polyurethane acrylate copolymer solution, the double bond end capped disulfide bond-containing polyurethane prepolymer solution is added in the following parts by weight: 16.5 parts, 21.4 parts, 23.8 parts, and any mass fraction value between the two mass fraction values; the fluorine-containing acrylic ester monomer is prepared from the following components in parts by weight: 2.4 parts of perfluoroalkyl ethyl acrylate, 3.6 parts of hexafluorobutyl acrylate, 4.5 parts of dodecafluoroheptyl methacrylate and 5 parts of hexafluorobutyl acrylate; the mass parts of the vinyl-terminated polydimethoxysilane can be selected as follows: 5.4 parts, 6.7 parts, 7.3 parts, 8.3 parts, and any mass fraction value between the two mass fraction values; the time length of the first stirring can be 0.3-0.5 h, and specifically can be 0.35h, 0.4h, 0.45h and 0.46h, and any time length value between two time length value points; the RAFT chain transfer agent is selected from the following materials in parts by weight: 0.25 part of 2- (dodecylthiocarbonylthio) -2-methylpropionic acid, 0.37 part of bis (dimethylacetyl chloride) trithiocarbonyl ester, 0.42 part of 2-cyano-2-propyldodecyl trithiocarbonate, 0.48 part of 2-cyano-2-propyldithio; the temperature conditions of the secondary stirring can be selected as follows: 65 ℃, 67 ℃, 68 ℃ and any temperature value between two temperature value points; the weight parts of triallyl isocyanurate can be selected as follows: 0.03 part, 0.035 part, 0.043 part, 0.047 part, and any mass fraction value between the two mass fraction value points; in the preparation step of the nano cerium oxide/polyurethane acrylate copolymer solution, the mass part of the modified nano cerium oxide suspension is added, and the mass part is selected as follows: 15.5 parts, 17.4 parts, 18.5 parts, 19.8 parts, and any mass fraction value between the two mass fraction values.
In addition, the value range of the first preset time period can be set to 0.5-1 h, and specific values can be 0.6h, 0.7h, 0.8h and 0.9h, and any time period value between two time period value points. The value range of the second preset time period can be set to be 0.5-1 h, and specific value can be 0.6h, 0.7h, 0.8h and 0.9h, and any time period value between two time period value points. The value range of the third preset time period can be set to be 0.5-1 h, and specific value can be 0.6h, 0.7h, 0.8h and 0.9h, and any time period value between two time period value points. The value range of the fourth preset time length can be set to be 0.5-1 h, and specific value can be 0.6h, 0.7h, 0.8h and 0.9h, and any time length value between two time length value points. The value range of the fifth preset duration may be set to 2-3 h, and specific values may be 2.2h, 2.4h, 2.5h, 2.8h, and any duration value between two duration value points. The value range of the sixth preset duration may be set to 1-2 h, and specific values may be 1.2h, 1.4h, 1.6h, 1.8h, and any duration value between two duration value points. The value range of the seventh preset duration may be set to 1-2 h, and specific values may be 1.3h, 1.4h, 1.6h, 1.8h, and any duration value between two duration value points. The value range of the eighth preset duration may be set to 4-6 h, and specific values may be 4.5h, 5.2h, 5.5h, 5.7h, and any duration value between two duration value points.
Specifically, after the modified nano cerium oxide suspension is prepared, the modified nano cerium oxide suspension is stored in a sealed manner.
After the nano cerium oxide/polyurethane acrylic ester copolymer solution is obtained, the temperature is kept for 1.5 to 2.5 hours (1.7 hours, 2 hours and 2.3 hours can be selected as well as any time length value between two time length value taking points), and then the mixture is cooled to room temperature and discharged.
The step of coating the nano cerium oxide/polyurethane acrylate copolymer solution on a substrate comprises the following steps:
cleaning a transparent substrate, vacuum drying the cleaned transparent substrate at the temperature of 70-80 ℃ (75 ℃, 76 ℃, 78 ℃, 79 ℃ and any temperature value between two temperature values), placing the transparent substrate on a spin coater for spin coating, spin coating a nano cerium oxide/polyurethane acrylate copolymer solution on the surface of the transparent substrate at the preset rotating speed and the tenth preset time period, and then carrying out ventilation drying at normal temperature. The preset rotating speed range can be set to 3000-4000 rpm, and can be particularly 3400rpm, 3500rpm, 3700rpm and 3900rpm, and any rotating speed value between two rotating speed value points; the value range of the tenth preset time period can be set to 2-3 s, and specifically can be 2.2s, 2.4s, 2.6s and 2.8s, and any time period value between two time period value points.
The step of cleaning the transparent substrate comprises the following steps: putting the transparent substrate into an ultrasonic cleaning tank, adding ultrapure water and a detergent, and performing ultrasonic treatment for 0.5-1 h (specifically, 0.6h, 0.7h, 0.8h and 0.9h and any time length value between two time length value points are selected); washing foam with ultrapure water, immersing in alkaline solution for 0.8-1.2 h (specifically, 0.9h, 1h, 1.1h and any time length between two time length value points), washing with ultrapure water, adding acetone, and performing ultrasonic treatment for 0.5-1 h (specifically, 0.6h, 0.7h, 0.8h and 0.9h and any time length between two time length value points). Wherein the detergent can be washing powder, detergent, cleaning powder, etc.
The diisocyanate may include one, two or more of toluene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, and hexamethylene diisocyanate.
The polyglycol monomer may include one, two or more of polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polycaprolactone glycol, polytetrahydrofuran ether glycol, poly adipic acid-1, 4-butanediol ester glycol, and has a number average molecular weight of 500-1000, specifically 600, 700, 800, 900, and any number average molecular weight value between two number average molecular weight values.
The chain extender may comprise one of dihydroxydiethylthiuram disulfide, bis (2-hydroxyethyl) disulfide, bis (4-hydroxyphenyl) sulfide.
The above-mentioned fluorine-containing acrylate monomer may include one of perfluoroalkyl ethyl acrylate, hexafluorobutyl acrylate and dodecafluoroheptyl methacrylate.
The RAFT chain transfer agent may comprise one of 2- (dodecylthiocarbonylthio) -2-methylpropanoic acid, bis (dimethylacetyl chloride) trithiocarbonyl ester, 2-cyano-2-propyldithio, 2-cyano-2-propyldodecyltrithiocarbonate.
The organic solvent may include one of chloroform, ethyl acetate, toluene, xylene, acetone, dimethyl sulfoxide, and tetrahydrofuran.
The inert gas may be nitrogen.
The embodiment also provides a super-hydrophobic self-repairing transparent coating, which is prepared by adopting the preparation method of the super-hydrophobic self-repairing transparent coating.
The super-hydrophobic self-repairing transparent coating provided by the embodiment is reliable in product performance due to the adoption of the method, the ultraviolet aging resistance of the polymer can be improved, the light transmittance of the coating is ensured, the adhesive force is excellent, the self-cleaning performance is excellent, in addition, the repair of polymer cracks can be realized, and good performance is maintained.
The embodiment also provides an application of the super-hydrophobic self-repairing transparent coating, wherein the super-hydrophobic self-repairing transparent coating is used for a daylighting glass plate, a glass curtain wall or window glass of a solar photovoltaic cell panel.
The lighting glass plate coated with the super-hydrophobic self-repairing transparent coating has the advantages that dust is not easy to accumulate on the surface, the lighting effect is good, the lost generated energy is less, and the high energy conversion rate can be kept for a long time.
The glass curtain wall coated with the super-hydrophobic self-repairing transparent coating has the advantages that dust is not easy to accumulate on the surface, the cleaning time is saved, the cleaning cost is reduced, the light transmittance is good, and ultraviolet rays can be shielded.
The window glass coated with the super-hydrophobic self-repairing transparent coating has the advantages that dust is not easy to accumulate on the surface of the window glass, the cleaning time is saved, the light transmittance is good, and ultraviolet rays can be shielded.
Example 1
Mixing 0.6g of pentaerythritol tetraoleate and 6g of acetone for 0.6h at 24 ℃ in advance, adding 3g of nano cerium oxide with the particle size of 40nm, stirring and mixing uniformly, adding 3.5g of gamma-methacryloxypropyl trimethoxysilane and 9g of acetone, stirring and mixing uniformly, performing ultrasonic treatment for 0.6h, and sealing and preserving to obtain modified nano cerium oxide suspension MNCS;
18.5g of toluene diisocyanate TDI after drying, 23.5g of polytetrahydrofuran ether glycol PTMEG and 28g of acetone are reacted in N 2 Stirring and mixing uniformly under the protection of 82 ℃, adding 0.06g of dibutyl tin dilaurate DBTDL for reaction for 0.6h, cooling to 61 ℃, adding 0.9g of dihydroxyl diethyl thiuram disulfide TDS for reaction for 0.7h, adding 0.73g of trimethylolpropane TMP for reaction for 0.7h, adding 80.6g of acetone, preserving heat for reaction for 2.5h, and adding 3.7g of hydroxyethyl methacrylate HEMA to obtain a double-bond capped polyurethane SSPU solution containing disulfide bonds;
16.5g of double bond-terminated disulfide bond-containing polyurethane prepolymer SSPU solution, 2.4g of perfluoroalkyl ethyl acrylate PFEA and 5.4g of vinyl-terminated polydimethoxysilane VPDMS were reacted under N 2 Stirring in an ice-water bath under protection for 0.35h, uniformly mixing, adding 0.25g of 2- (dodecylthio-thiocarbonylthio) -2-methylpropanoic acid DTMPA, stirring at 65 ℃ for reacting for 1.2h, then adding 0.03g of triallyl isocyanurate TAIC, continuously stirring for reacting for 1.3h, finally adding 15.5g of modified nano cerium oxide suspension MNCS, stirring for polymerizing for 4.5h, preserving heat for 2h, cooling to room temperature, and discharging to obtain nano cerium oxide/polyurethane acrylate copolymer solution CSPUA;
And (3) vacuum drying the cleaned glass substrate at 75 ℃, placing the glass substrate on a spin coater, coating the nano cerium oxide/polyurethane acrylate copolymer solution CSPUA, setting the rotating speed to 3400rpm, spin-coating for 2.2s, and performing normal-temperature ventilation drying to obtain the self-cleaning super-hydrophobic transparent coating.
Example 2
Mixing 0.7g of pentaerythritol tetraoleate and 8g of ethyl acetate for 0.7h at 26 ℃ in advance, then adding 3.8g of nano cerium oxide with the particle size of 60nm, stirring and mixing uniformly, then adding 4.0g of gamma-methacryloxypropyl trimethoxysilane and 11g of ethyl acetate, stirring and mixing uniformly, performing ultrasonic treatment for 0.7h, and sealing and preserving to obtain modified nano cerium oxide suspension MNCS;
19.7g of isophorone diisocyanate IPDI after drying, 28g of polyethylene glycol PEG and 30g of ethyl acetate are reacted in N 2 Stirring and mixing uniformly under the protection of 82 ℃, adding 0.07g of dibutyl tin dilaurate DBTDL for reaction for 0.7h, cooling to 62 ℃, adding 1.0g of bis (2-hydroxyethyl) disulfide HEDS for reaction for 0.6h, adding 0.65g of trimethylolpropane TMP for reaction for 0.7h, adding 78g of ethyl acetate, preserving heat for reaction for 2.5h, and adding 4.7g of hydroxyethyl methacrylate HEMA to obtain a double-bond-capped polyurethane SSPU solution containing disulfide bonds;
Step 3) 21.4g of double bond-terminated disulfide bond-containing polyurethane prepolymer SSPU solution, 3.6g of hexafluorobutyl acrylate HFBA and 6.7g of vinyl-terminated polydimethoxysilane VPDMS were reacted in N 2 Stirring in an ice-water bath under protection for 0.4h, uniformly mixing, adding 0.37g of bis (dimethyl acetyl chloride) trithiocarbonyl ester BDACT, stirring at 67 ℃ for reaction for 1.4h, then adding 0.035g of triallyl isocyanurate TAIC, continuously stirring for reaction for 1.4h, finally adding 17.4g of modified nano cerium oxide suspension MNCS, stirring for polymerization for 5.2h, preserving heat for 2h, cooling to room temperature, and discharging to obtain nano cerium oxide/polyurethane acrylate copolymer solution CSPUA;
and (3) vacuum drying the cleaned glass substrate at 76 ℃, placing the glass substrate on a spin coater, coating the nano cerium oxide/polyurethane acrylate copolymer solution CSPUA, setting the rotating speed to 3500rpm, spin-coating for 2.4s, and performing normal-temperature ventilation drying to obtain the self-cleaning super-hydrophobic transparent coating.
Example 3
Mixing 0.72g of pentaerythritol tetraoleate and 9g of dimethyl sulfoxide for 0.8h at the temperature of 27 ℃ in advance, then adding 4.2g of nano cerium oxide with the particle size of 75nm, stirring and mixing uniformly, then adding 5.0g of gamma-methacryloxypropyl trimethoxysilane and 13g of dimethyl sulfoxide, stirring and mixing uniformly, performing ultrasonic treatment for 0.8h, and sealing and preserving to obtain modified nano cerium oxide suspension MNCS;
23.2g of isophorone diisocyanate IPDI after drying, 36.4g of polycaprolactone diol PCL and 32g of dimethyl sulfoxide are reacted in N 2 Stirring and mixing uniformly at 83 ℃ under the protection, adding 008g of dibutyl tin dilaurate DBTDL is reacted for 0.8h, the temperature is reduced to 63 ℃, 1.1g of dihydroxyl diethyl thiuram disulfide TDS is added for 0.8h, 0.78g of trimethylolpropane TMP is added for 0.8h, 92g of dimethyl sulfoxide is added for 2.8h of heat preservation reaction, and 5.9g of hydroxyethyl methacrylate HEMA is added to obtain double-bond-capped disulfide-bond-containing polyurethane SSPU solution;
23.8g of double bond-terminated disulfide bond-containing polyurethane prepolymer SSPU solution, 4.5g of dodecafluoroheptyl methacrylate DFMA and 7.3g of vinyl-terminated polydimethoxysilane VPDMS were reacted in N 2 Stirring in an ice-water bath under protection for 0.45h, uniformly mixing, adding 0.42g of 2-cyano-2-propyldodecyl trithiocarbonate CPDTC, stirring at 68 ℃ for reaction for 1.6h, then adding 0.043g of triallyl isocyanurate TAIC, continuously stirring for reaction for 1.6h, finally adding 18.5g of modified nano cerium oxide suspension MNCS, stirring for polymerization for 5.5h, preserving heat for 2h, cooling to room temperature, and discharging to obtain nano cerium oxide/polyurethane acrylate copolymer solution CSPUA;
And (3) vacuum drying the cleaned glass substrate at 78 ℃, placing the glass substrate on a spin coater, coating a nano cerium oxide/polyurethane acrylate copolymer solution CSPUA, setting the rotating speed to 3700rpm, spin-coating for 2.6s, and performing normal-temperature ventilation drying to obtain the self-cleaning super-hydrophobic transparent coating.
Example 4
Mixing 0.75g of pentaerythritol tetraoleate and 9.6g of toluene for 0.9h at 27 ℃ in advance, then adding 4.8g of nano cerium oxide with the particle size of 95nm, stirring and mixing uniformly, then adding 5.8g of gamma-methacryloxypropyl trimethoxysilane and 14g of toluene, stirring and mixing uniformly, performing ultrasonic treatment for 0.9h, and sealing and preserving to obtain modified nano cerium oxide suspension MNCS;
24.3g of hexamethylene diisocyanate HDI after drying, 43.8g of poly (1, 4-butylene glycol) adipate PBA and 34g of toluene were reacted in N 2 Stirring and mixing uniformly under the protection at 84 ℃, adding 0.09g of dibutyl tin dilaurate DBTDL for reaction for 0.9h, cooling to 64 ℃, adding 1.17g of bis (4-hydroxyphenyl) thioether TDP for reaction for 0.9h, adding 0.95g of trimethylolpropane TMP for reaction for 0.9h, adding 95g of toluene, preserving heat for reaction for 2.8h, and adding 5.4g of methylpropaneHydroxyethyl acrylate HEMA is used for obtaining double-bond-terminated disulfide bond-containing polyurethane SSPU solution;
23.8g of double bond-terminated disulfide bond-containing polyurethane prepolymer SSPU solution, 5.0g of hexafluorobutyl acrylate HFBA and 8.3g of vinyl-terminated polydimethoxysilane VPDMS were reacted in N 2 Stirring in an ice-water bath under protection for 0.46h, uniformly mixing, adding 0.48g of 2-cyano-2-propyl disulfide CYBCB, stirring at 68 ℃ for reacting for 1.8h, then adding 0.047g of triallyl isocyanurate TAIC, continuously stirring for reacting for 1.8h, finally adding 19.8g of modified nano cerium oxide suspension MNCS, stirring for polymerizing for 5.7h, preserving heat for 2h, cooling to room temperature, and discharging to obtain nano cerium oxide/polyurethane acrylate copolymer solution CSPUA;
and (3) vacuum drying the cleaned glass substrate at 79 ℃, placing the glass substrate on a spin coater, coating a nano cerium oxide/polyurethane acrylate copolymer solution CSPUA, setting the rotating speed to 3900rpm, spin-coating for 2.8s, and performing normal-temperature ventilation drying to obtain the self-cleaning super-hydrophobic transparent coating.
Comparative example 1
The procedure is the same as in example 1, except that modified nano-ceria is not prepared and added, and detailed steps are not repeated here.
Comparative example 2
The procedure is the same as in example 1 except that no dihydroxy diethylthiuram disulfide is added, and detailed steps are not repeated here.
Comparative example 3
The procedure is the same as in example 1 except that no perfluoroalkyl ethyl acrylate and vinyl-terminated polydimethoxysilane are added, and detailed steps are not repeated here.
Comparative example 4
The procedure of example 1 was followed except that the equivalent amount of the oily initiator azobisisobutyronitrile was used in place of 2- (dodecylthiocarbonylthio) -2-methylpropanoic acid.
The items tested in the examples and comparative examples of the present invention include: 1) molecular weight test, 2) wettability test, 3) transmittance test, 4) coating adhesion test, 5) self-repairing performance test, 6) weather resistance test.
1) Molecular weight testing: the relative molecular mass and PDI were measured by aqueous Gel Permeation Chromatography (GPC). GPC instruments were calibrated with PEG standard polymers and the weight average molecular weight and PDI of the polymers were determined using a calibration curve.
2) Wetting property test: the surface wettability of the coating was tested using a video optical contact angle tester, the size of the test drop was 10 μl, and the static contact angle and the roll angle were tested.
3) Light transmittance performance test: the transparency of the glass slide is tested by using an ultraviolet-visible spectrophotometer, the tested light wave range is adjusted to be 340-800 nm, and the wavelength interval is 2nm.
4) Adhesion test: (1) the adhesion of the paint films was determined according to ISO2409-1992 Standard of color paint and varnish-cross-hatch test. (2) The prepared transparent super-hydrophobic coated glass is placed in a beaker containing absolute ethyl alcohol, ultrasonic treatment is carried out for 48 hours under 60KHz and 100W by using an ultrasonic cleaner, and the wettability and the light transmittance of the coating obtained by ultrasonic treatment are tested.
5) Self-repairing performance test: pouring the organic-inorganic composite material solution into a tetrafluoroethylene plate groove for leveling, enabling the surface to be flat and bubble-free, drying for 3 days at room temperature, drying for 24 hours at 50 ℃ in vacuum, cooling, taking out the prepared membrane, and putting the membrane into a dryer for standby. And (3) adopting an electronic universal material testing machine to test the temperature at 25 ℃ and the stretching speed at 500mm/min, cutting off the stretching sample bars from the middle part by using a blade, then tightly butting, testing at least 5 sample bars in each group, and taking the average value of the stretching strength of each group of test sample bars. And (3) performing self-repairing on the cut sample strips by using room temperature visible light irradiation for 16h, and representing corresponding self-repairing efficiency by adopting a ratio of tensile strength before and after self-repairing.
6) Weather resistance test: and placing the prepared transparent super-hydrophobic coating in an ultraviolet curing machine, and testing the tensile strength reduction rate, wettability and light transmittance of the coating after ultraviolet irradiation for 148 hours at the wavelength of 200-400 nm.
The molecular weight, wettability, transmittance, adhesion, self-repairing property and weather resistance of the coatings prepared in examples 1 to 4 and the coatings prepared in comparative examples 1 to 4 were measured, and the results are shown in the following table.
Test results of examples and comparative examples
As can be seen from the performance test results of examples 1 to 4 in Table 1, the molecular weight of the coating polymers prepared in examples 1 to 4 is 6500 to 7500, the static water contact angle is more than 150 degrees, as shown in FIGS. 2 to 5, the water drops are spherical on the surface of the glass substrate, as shown in FIG. 6, and the rolling angle is less than 5 degrees; the visible light transmittance reaches more than 83%; the coating can reach self-repairing efficiency of 85-90% after being irradiated for 24 hours under room temperature visible light; the ISO adhesive force reaches 0 level, and has excellent mechanical strength and ultraviolet aging resistance.
As can be seen from examples 1-4 and comparative example 1, the super-hydrophobic transparent coating provided by the invention is introduced with nano cerium oxide, so that the ultraviolet aging resistance of the coating is effectively improved while the light transmittance is ensured, and a micro-nano rough structure is constructed for the surface of the coating, as shown in figure 1; as can be seen from examples 1 to 4 and comparative example 2, the introduction of disulfide bonds (dynamic covalent bonds) into the superhydrophobic transparent coating is a key element for achieving self-repair of the coating; as can be seen from examples 1 to 4 and comparative example 3, the introduction of the fluorosilicone material into the superhydrophobic transparent coating can effectively construct the surface of the low surface energy coating and promote the hydrophobicity of the coating; it can be seen from examples 1 to 4 and comparative example 4 that the polymer obtained by the reversible addition-fragmentation chain transfer radical polymerization (RAFT) technique has a narrower molecular weight distribution than that by conventional radical copolymerization, and that the light transmittance of the coating layer is related to the molecular weight by the previous studies, and when the molecular weight exceeds a certain range, the light transmittance is significantly reduced.
Finally, it is also noted that in this document, terms such as "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to the embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. The preparation method of the super-hydrophobic self-repairing transparent coating is characterized by comprising the following steps of:
adding 0.5-0.8 part of pentaerythritol tetraoleate and 5-10 parts of organic solvent into a container according to the mass ratio, stirring and mixing uniformly at the temperature of 20-30 ℃, adding 2-5 parts of nano cerium oxide, stirring and mixing uniformly, adding 3-6 parts of gamma-methacryloxypropyl trimethoxysilane and 8-15 parts of organic solvent, stirring and mixing uniformly, and performing ultrasonic treatment for a first preset period of time to obtain modified nano cerium oxide suspension;
Adding 17-25 parts of diisocyanate after drying treatment, 21-45 parts of polyglycol monomer and 25-35 parts of organic solvent into another container according to the mass ratio, stirring and mixing uniformly under the protection of inert gas and at the temperature of 80-85 ℃, adding 0.05-0.1 part of dibutyltin dilaurate to react for a second preset time period, cooling to 60-65 ℃, adding 0.8-1.2 parts of chain extender to react for a third preset time period, adding 0.5-1 part of trimethylolpropane to react for a fourth preset time period, adding 65-100 parts of organic solvent, preserving heat to react for a fifth preset time period, and adding 3-7 parts of hydroxyethyl methacrylate to obtain a double-bond capped polyurethane prepolymer solution containing disulfide bonds;
adding 16-24 parts of double bond capped disulfide bond-containing polyurethane prepolymer solution, 2.2-5.3 parts of fluorine-containing acrylate monomer and 5.1-8.6 parts of vinyl capped polydimethoxy silane into another container according to the mass ratio, stirring and mixing uniformly in an ice water bath under the protection of inert gas, adding 0.2-0.5 part of RAFT chain transfer agent, stirring and reacting for a sixth preset time at 60-70 ℃, adding 0.02-0.05 part of triallyl isocyanurate, stirring and reacting for a seventh preset time, adding 8-13 parts of modified nano cerium oxide suspension, stirring and polymerizing for an eighth preset time to obtain nano cerium oxide/polyurethane acrylate copolymer solution;
And coating the nano cerium oxide/polyurethane acrylic ester copolymer solution on a substrate to obtain the super-hydrophobic self-repairing transparent coating.
2. The method for preparing the super-hydrophobic self-repairing transparent coating according to claim 1, wherein the first preset duration is 0.5-1 h, and/or the second preset duration is 0.5-1 h, and/or the third preset duration is 0.5-1 h, and/or the fourth preset duration is 0.5-1 h, and/or the fifth preset duration is 2-3 h, and/or the sixth preset duration is 1-2 h, and/or the seventh preset duration is 1-2 h, and/or the eighth preset duration is 4-6 h.
3. The method for preparing the super-hydrophobic self-repairing transparent coating according to claim 1, wherein in the step of stirring and mixing uniformly for the first time at the temperature of 20-30 ℃, the duration of stirring and mixing is 0.5-1 h;
and/or in the step of stirring and uniformly mixing in an ice water bath under the protection of inert gas, the stirring and mixing time is 0.3-0.5 h.
4. The method for preparing a superhydrophobic self-healing transparent coating according to claim 1, wherein after preparing the modified nano cerium oxide suspension, the method further comprises: sealing and preserving the modified nano cerium oxide suspension;
And/or, after the nano cerium oxide/polyurethane acrylate copolymer solution is obtained, the method further comprises the steps of preserving heat for 1.5-2.5 hours, cooling to room temperature and discharging.
5. The method of preparing a superhydrophobic self-healing transparent coating according to claim 1, wherein the step of applying the nano cerium oxide/polyurethane acrylate copolymer solution to a substrate comprises:
and cleaning the transparent substrate, vacuum drying the cleaned transparent substrate at the temperature of 70-80 ℃, placing the transparent substrate on a spin coater for spin coating, spin coating the nano cerium oxide/polyurethane acrylate copolymer solution on the surface of the transparent substrate at the preset rotating speed for a tenth preset time period, and then carrying out ventilation drying at normal temperature.
6. The method for preparing a super-hydrophobic self-repairing transparent coating according to claim 5, wherein the preset rotating speed is 3000-4000 rpm, and the tenth preset time period is 2-3 s.
7. The method for preparing a superhydrophobic self-healing transparent coating according to claim 5, wherein the step of cleaning the transparent substrate comprises: putting the transparent substrate into an ultrasonic cleaning tank, adding ultrapure water and a detergent, and performing ultrasonic treatment for 0.5-1 h; washing foam with ultrapure water, soaking in alkaline solution for 0.8-1.2 hr, washing with ultrapure water, and ultrasonic treating with acetone for 0.5-1 hr.
8. The method for preparing the super-hydrophobic self-repairing transparent coating according to claim 1, wherein the diisocyanate comprises one, two or more of toluene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate and hexamethylene diisocyanate;
and/or the polyglycol monomer comprises one, two or more of polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polycaprolactone glycol, polytetrahydrofuran ether glycol, poly adipic acid-1 and 4-butanediol ester glycol, and the number average molecular weight is 500-1000;
and/or the chain extender comprises one of dihydroxydiethylthiuram disulfide, bis (2-hydroxyethyl) disulfide, bis (4-hydroxyphenyl) sulfide;
and/or the fluorine-containing acrylate monomer comprises one of perfluoroalkyl ethyl acrylate, hexafluorobutyl acrylate and dodecafluoroheptyl methacrylate;
and/or the RAFT chain transfer agent comprises one of 2- (dodecylthiocarbonylthio) -2-methylpropanoic acid, bis (dimethylacetyl chloride) trithiocarbonyl ester, 2-cyano-2-propyldisulfide, 2-cyano-2-propyldodecyl trithiocarbonate;
And/or the organic solvent comprises one of chloroform, ethyl acetate, toluene, xylene, acetone, dimethyl sulfoxide and tetrahydrofuran;
and/or the inert gas comprises nitrogen.
9. The super-hydrophobic self-repairing transparent coating is characterized by being prepared by adopting the preparation method of the super-hydrophobic self-repairing transparent coating in any one of claims 1-8.
10. The use of the superhydrophobic self-healing transparent coating of claim 9, wherein the superhydrophobic self-healing transparent coating is used for daylighting glass panels, glass curtain walls or window glass of solar photovoltaic panels.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101824273A (en) * | 2010-03-31 | 2010-09-08 | 中科院广州化学有限公司 | Fluoropolymer/inorganic nano-hybrid particle modified ultraviolet photocured paint and preparation method thereof |
| KR20170041928A (en) * | 2015-10-07 | 2017-04-18 | 한국생산기술연구원 | Organic-inorganic composite particle material having water repellent and antibiotic, and preparation method thereof |
| CN110845952A (en) * | 2019-12-02 | 2020-02-28 | 西北工业大学 | Fluorinated polyurethane coating and preparation method of super-hydrophobic coating |
| CN112778905A (en) * | 2019-11-07 | 2021-05-11 | 香港城市大学深圳研究院 | Self-repairing super-hydrophobic coating and preparation method thereof |
| CN115262231A (en) * | 2022-08-24 | 2022-11-01 | 江南大学 | Self-repairing self-cleaning electromagnetic shielding fabric coating and preparation method and application thereof |
| CN116120827A (en) * | 2023-02-08 | 2023-05-16 | 国网山西省电力公司超高压输电分公司 | Polyurethane-based self-repairing super-hydrophobic coating and preparation method thereof |
-
2023
- 2023-06-07 CN CN202310672040.XA patent/CN116640511B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101824273A (en) * | 2010-03-31 | 2010-09-08 | 中科院广州化学有限公司 | Fluoropolymer/inorganic nano-hybrid particle modified ultraviolet photocured paint and preparation method thereof |
| KR20170041928A (en) * | 2015-10-07 | 2017-04-18 | 한국생산기술연구원 | Organic-inorganic composite particle material having water repellent and antibiotic, and preparation method thereof |
| CN112778905A (en) * | 2019-11-07 | 2021-05-11 | 香港城市大学深圳研究院 | Self-repairing super-hydrophobic coating and preparation method thereof |
| CN110845952A (en) * | 2019-12-02 | 2020-02-28 | 西北工业大学 | Fluorinated polyurethane coating and preparation method of super-hydrophobic coating |
| CN115262231A (en) * | 2022-08-24 | 2022-11-01 | 江南大学 | Self-repairing self-cleaning electromagnetic shielding fabric coating and preparation method and application thereof |
| CN116120827A (en) * | 2023-02-08 | 2023-05-16 | 国网山西省电力公司超高压输电分公司 | Polyurethane-based self-repairing super-hydrophobic coating and preparation method thereof |
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