CN114686031A - Corrosion-resistant fluorescent paint and preparation method thereof - Google Patents
Corrosion-resistant fluorescent paint and preparation method thereof Download PDFInfo
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- CN114686031A CN114686031A CN202210462825.XA CN202210462825A CN114686031A CN 114686031 A CN114686031 A CN 114686031A CN 202210462825 A CN202210462825 A CN 202210462825A CN 114686031 A CN114686031 A CN 114686031A
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- benzoin
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- 238000005260 corrosion Methods 0.000 title claims abstract description 41
- 230000007797 corrosion Effects 0.000 title claims abstract description 41
- 239000003973 paint Substances 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 59
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 claims abstract description 52
- 238000000576 coating method Methods 0.000 claims abstract description 36
- 239000000843 powder Substances 0.000 claims abstract description 36
- 239000011248 coating agent Substances 0.000 claims abstract description 35
- -1 europium ions Chemical class 0.000 claims abstract description 30
- 239000003094 microcapsule Substances 0.000 claims abstract description 29
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 27
- OMUADEPNIQXNRG-UHFFFAOYSA-N 5-nitropyridine-3,4-diamine Chemical compound NC1=CN=CC([N+]([O-])=O)=C1N OMUADEPNIQXNRG-UHFFFAOYSA-N 0.000 claims abstract description 26
- 244000028419 Styrax benzoin Species 0.000 claims abstract description 26
- 235000000126 Styrax benzoin Nutrition 0.000 claims abstract description 26
- 235000008411 Sumatra benzointree Nutrition 0.000 claims abstract description 26
- 229960002130 benzoin Drugs 0.000 claims abstract description 26
- 235000019382 gum benzoic Nutrition 0.000 claims abstract description 26
- UXOQQUHZHRSERD-UHFFFAOYSA-N methyl 6-cyano-1h-indole-3-carboxylate Chemical compound N#CC1=CC=C2C(C(=O)OC)=CNC2=C1 UXOQQUHZHRSERD-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000004925 Acrylic resin Substances 0.000 claims abstract description 12
- 229920000178 Acrylic resin Polymers 0.000 claims abstract description 12
- SLIBCJURSADKPV-UHFFFAOYSA-N 1,10-dihydro-1,10-phenanthroline-4,7-dione Chemical compound N1C=CC(=O)C2=CC=C3C(=O)C=CNC3=C21 SLIBCJURSADKPV-UHFFFAOYSA-N 0.000 claims abstract description 11
- HFAUMPWMNPYULN-UHFFFAOYSA-N 2-bromo-3-methylbutanoyl bromide Chemical compound CC(C)C(Br)C(Br)=O HFAUMPWMNPYULN-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000011162 core material Substances 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 70
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 69
- 239000000243 solution Substances 0.000 claims description 68
- 238000003756 stirring Methods 0.000 claims description 59
- 150000001875 compounds Chemical class 0.000 claims description 53
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 48
- 239000008367 deionised water Substances 0.000 claims description 45
- 229910021641 deionized water Inorganic materials 0.000 claims description 45
- 238000002156 mixing Methods 0.000 claims description 42
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 claims description 36
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 32
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 30
- 238000005406 washing Methods 0.000 claims description 30
- 238000007193 benzoin condensation reaction Methods 0.000 claims description 26
- 238000001816 cooling Methods 0.000 claims description 25
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 18
- 235000010288 sodium nitrite Nutrition 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 17
- 238000001035 drying Methods 0.000 claims description 16
- 239000002243 precursor Substances 0.000 claims description 16
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 15
- 229910001940 europium oxide Inorganic materials 0.000 claims description 15
- AEBZCFFCDTZXHP-UHFFFAOYSA-N europium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Eu+3].[Eu+3] AEBZCFFCDTZXHP-UHFFFAOYSA-N 0.000 claims description 15
- 238000001914 filtration Methods 0.000 claims description 15
- 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 12
- 239000007864 aqueous solution Substances 0.000 claims description 12
- NNMXSTWQJRPBJZ-UHFFFAOYSA-K europium(iii) chloride Chemical compound Cl[Eu](Cl)Cl NNMXSTWQJRPBJZ-UHFFFAOYSA-K 0.000 claims description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 10
- HLZKNKRTKFSKGZ-UHFFFAOYSA-N tetradecan-1-ol Chemical compound CCCCCCCCCCCCCCO HLZKNKRTKFSKGZ-UHFFFAOYSA-N 0.000 claims description 10
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 10
- 229920003180 amino resin Polymers 0.000 claims description 8
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 7
- 239000002202 Polyethylene glycol Substances 0.000 claims description 7
- 239000012153 distilled water Substances 0.000 claims description 7
- 229920001223 polyethylene glycol Polymers 0.000 claims description 7
- 239000008096 xylene Substances 0.000 claims description 7
- 239000003960 organic solvent Substances 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 239000012065 filter cake Substances 0.000 claims description 5
- 238000000227 grinding Methods 0.000 claims description 5
- 239000005457 ice water Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 239000003208 petroleum Substances 0.000 claims description 5
- 238000009210 therapy by ultrasound Methods 0.000 claims description 5
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 230000004048 modification Effects 0.000 claims description 4
- 238000012986 modification Methods 0.000 claims description 4
- 238000004321 preservation Methods 0.000 claims description 4
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 239000000839 emulsion Substances 0.000 claims description 2
- GKQPCPXONLDCMU-CCEZHUSRSA-N lacidipine Chemical compound CCOC(=O)C1=C(C)NC(C)=C(C(=O)OCC)C1C1=CC=CC=C1\C=C\C(=O)OC(C)(C)C GKQPCPXONLDCMU-CCEZHUSRSA-N 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 229960001124 trientine Drugs 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 19
- 229910052693 Europium Inorganic materials 0.000 abstract description 7
- 230000002209 hydrophobic effect Effects 0.000 abstract description 3
- 238000010382 chemical cross-linking Methods 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract description 2
- 239000012528 membrane Substances 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 15
- 230000004888 barrier function Effects 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 230000000087 stabilizing effect Effects 0.000 description 3
- 206010070834 Sensitisation Diseases 0.000 description 2
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 2
- 239000004568 cement Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 230000001678 irradiating effect Effects 0.000 description 2
- 238000004020 luminiscence type Methods 0.000 description 2
- LKPFBGKZCCBZDK-UHFFFAOYSA-N n-hydroxypiperidine Chemical compound ON1CCCCC1 LKPFBGKZCCBZDK-UHFFFAOYSA-N 0.000 description 2
- 238000005424 photoluminescence Methods 0.000 description 2
- 230000008313 sensitization Effects 0.000 description 2
- 238000007873 sieving Methods 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 230000005923 long-lasting effect Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
- 238000002604 ultrasonography 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/22—Luminous paints
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/003—Compounds containing elements of Groups 3 or 13 of the Periodic Table without C-Metal linkages
-
- 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
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
-
- 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
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/18—Metal complexes
- C09K2211/182—Metal complexes of the rare earth metals, i.e. Sc, Y or lanthanide
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Paints Or Removers (AREA)
- Nitrogen Condensed Heterocyclic Rings (AREA)
Abstract
The invention discloses a corrosion-resistant fluorescent paint and a preparation method thereof, and relates to the technical field of paints. According to the invention, 5-nitropyridine-3, 4-diamine, 6-cyanoindole-3-carboxylic acid methyl ester, 2,6, 6-tetramethyl piperidinol and benzoin are firstly utilized to prepare a benzoin condensate, so that the coating has a photostable effect, and is coordinated with 4, 7-dihydroxy-1, 10-phenanthroline on europium ions to obtain photoluminescent self-made fluorescent powder, so that the coating has long-acting fluorescence; then, taking acrylic resin as a wall material and self-made fluorescent powder as a core material to obtain microcapsules, and sequentially coating the modified graphene and the hydrophobic membrane through chemical crosslinking to effectively isolate the permeation of corrosive media; the modified graphene is prepared from graphene, 2-bromoisopentanoyl bromide and 5-mercapto-4-p-chlorophenyl-4-hydro-3-hydroxy-1, 2, 4-triazole, and the dispersibility of the graphene oxide is improved. The corrosion-resistant fluorescent paint prepared by the invention has the effects of corrosion resistance and long-acting fluorescence.
Description
Technical Field
The invention relates to the technical field of coatings, in particular to a corrosion-resistant fluorescent coating and a preparation method thereof.
Background
The current methods for preparing fluorescent paint include: (1) synthesizing resin with a fluorescent effect, and utilizing the fluorescent property of the resin to emit light; (2) and adding fluorescent powder as a filler to prepare the fluorescent paint. The first method has complex preparation process and strict requirements on process conditions, and uses a large amount of organic solvent, and the residual organic solvent can cause environmental pollution. The second method has relatively simple process, but the dispersion of the fluorescent powder has problems, which can cause uneven luminescence and local fluorescence quenching, and the two methods have poor light resistance and are easy to age under multiple times of illumination.
The fluorescent paint is usually coated on tunnels, building outer walls, billboards and the like and is exposed for a long time, and polyester resin is adopted as a matrix in the fluorescent paint, so that the fluorescent paint is easy to hydrolyze in a humid environment and also easy to react with an acidic medium, and therefore, the fluorescent paint is often corroded, aged, fallen and the like. Based on this, how to prepare a corrosion-resistant fluorescent paint is very important.
Disclosure of Invention
The invention aims to provide a corrosion-resistant fluorescent paint and a preparation method thereof, and aims to solve the problems in the prior art.
In order to solve the technical problems, the invention provides the following technical scheme: the preparation method of the corrosion-resistant fluorescent paint comprises the following steps of mixing self-made fluorescent powder and polyethylene glycol in distilled water, stirring at a high speed and under ultrasound to form a core material emulsion, then adding acrylic resin, stirring to obtain microcapsules, and then carrying out modification treatment.
Further, the self-made fluorescent powder is prepared from 5-nitropyridine-3, 4-diamine, 6-cyanoindole-3-carboxylic acid methyl ester, 2,6, 6-tetramethylpiperidinol, benzoin, 4, 7-dihydroxy-1, 10-phenanthroline and europium oxide.
Further, the modification treatment comprises the following steps of mixing the modified graphene, the azobisisobutyronitrile and the methanol, adding the microcapsule, placing the microcapsule in a water bath, reacting for a preset time, adding the 1-hydroxytetradecane, stirring the mixture for reaction, washing and distilling the reaction product.
Further, the modified graphene is prepared from graphene oxide, 2-bromoisopentanoyl bromide and 5-mercapto-4-p-chlorophenyl-4H-3-hydroxy-1, 2, 4-triazole.
Further, the preparation method of the corrosion-resistant fluorescent paint comprises the following preparation steps:
(1) mixing deionized water, 6-cyanoindole-3-carboxylic acid methyl ester and sodium hydroxide according to a mass ratio of 4:1: 1-7: 1:2, stirring at 50-100 rpm for 44-56 min, cooling to 0-5 ℃, adding a 5-nitropyridine-3, 4-diamine solution which is 1-3 times of the mass of 6-cyanoindole-3-carboxylic acid methyl ester at 0.2-0.5 mL/min, reacting for 2-4 h under heat preservation, adding 10% hydrochloric acid by mass until the pH of the solution is 6-7, filtering, and washing a filter cake with deionized water for 2-4 times to obtain an azo compound;
(2) mixing an azo compound, 2,6, 6-tetramethyl piperidinol and tetraisopropyl titanate according to a mass ratio of 1:1: 0.001-1: 3:0.003, reacting at 146-160 ℃ for 6-10 hours, adding xylene 2-4 times of the mass of the azo compound, cooling to 50-60 ℃, adding methanol 3-6 times of the mass of the azo compound, cooling to 0-5 ℃, filtering, and drying at 70-90 ℃ for 3-5 hours to obtain a light-stabilized compound;
(3) dissolving benzoin in absolute ethyl alcohol with the mass 4-8 times of that of the benzoin, adding a light-stabilizing compound solution with the mass 1.5-3.7 times of that of the benzoin, reacting at 50-100 rpm for 4-8 h, distilling at 50-64 ℃ and under the vacuum degree of 20-40 kPa for 46-62 min, adding petroleum ether with the mass 3-5 times of that of the benzoin, cooling to 0-5 ℃, filtering, and washing with distilled water for 3-5 times to obtain a benzoin condensation compound;
(4) dissolving a benzoin condensation compound in absolute ethyl alcohol with the mass 4-7 times of that of the benzoin condensation compound in a water bath at 50-60 ℃, stirring and dissolving, adding a europium chloride solution with the mass 1-3 times of that of the benzoin condensation compound, adding a sodium hydroxide solution with the mass fraction of 10% until the pH of the solution is 7-8, reacting at 100-200 rpm for 1-4 h, adding 4, 7-dihydroxy-1, 10-phenanthroline and absolute ethyl alcohol with the mass 1-3 times of that of the benzoin condensation compound 0.1-0.4, reacting for 1-3 h, heating to 80-90 ℃, distilling for 1.5-4 h, drying at 70-80 ℃ and under the vacuum degree of 10-30 kPa for 2-5 h to obtain fluorescent powder;
(5) mixing the self-made fluorescent powder, polyethylene glycol and deionized water according to a mass ratio of 1:0.1: 14-1: 0.1:16, stirring at 1000-1500 rpm for 20-30 min, performing ultrasonic treatment at 25-35 kHz for 10-22 min, adding acrylic resin which is 0.5-1 times of the mass of the self-made fluorescent powder, uniformly stirring, adding a 10% hydrochloric acid solution to a solution pH of 2-4, heating to 60-70 ℃, stirring at the same rotation speed for 1.5-3.5 h, adding a 20% sodium hydroxide solution to a solution pH of 6-7, and washing with deionized water for 3-5 times to obtain microcapsules;
(6) mixing modified graphene, azodiisobutyronitrile and methanol according to the mass ratio of 1:0.005: 55-1: 0.008:62, adding microcapsules 2-4 times of the mass of the modified graphene, placing the microcapsules in a water bath kettle at 50-60 ℃, reacting for 24-28 h, adding 1-hydroxytetradecane 0.4-0.7 times of the mass of the modified graphene at room temperature, stirring for 4-8 h at 50-100 rpm, washing for 3-5 times with methanol and deionized water in sequence, and distilling for 1-3 h at 65-72 ℃ and a vacuum degree of 20-40 kPa to obtain a coating precursor; and uniformly mixing the coating precursor, the organic solvent and the curing agent according to the mass ratio of 1:1.2: 0.3-1: 2.6:0.5 to obtain the corrosion-resistant fluorescent coating.
Further, the preparation method of the 5-nitropyridine-3, 4-diamine solution in the step (1) comprises the following steps: after stirring and dissolving 98% concentrated sulfuric acid, deionized water and 5-nitropyridine-3, 4-diamine according to the mass ratio of 1.5:2.0: 1-1.5: 5.0:1, cooling to 0-5 ℃, stirring at 50-100 rpm for 20-32 min, adding a sodium nitrite aqueous solution with the mass of 1.0-1.5 times that of the 5-nitropyridine-3, 4-diamine, wherein the mass ratio of sodium nitrite to deionized water in the sodium nitrite aqueous solution is 2:3, and reacting for 55-67 min.
Further, the light-stabilizing compound solution in the step (3) is prepared by mixing a light-stabilizing compound and absolute ethyl alcohol according to a mass ratio of 1: 2.0-1: 2.7.
Further, the preparation method of the europium chloride solution in the step (4) comprises the following steps: dissolving europium oxide in concentrated hydrochloric acid with the mass fraction of 38% and the mass of 15-18 times of that of the europium oxide, heating to 35-42 ℃, and preserving heat for 58-70 min.
Further, the preparation method of the modified graphene in the step (6) comprises the following steps: mixing graphene oxide, triethylamine and N, N-dimethylformamide according to a mass ratio of 1:3: 44-1: 5:48, ultrasonically dispersing for 30-42 min at 25-35 kHz, adding 2-bromoisovaleryl bromide 1-3 times the mass of the graphene oxide into an ice water bath, stirring for 16-20 h at 200-300 rpm, adding 5-mercapto-4-p-chlorophenyl-4-hydrogen-3-hydroxy-1, 2, 4-triazole 1-3 times the mass of the graphene oxide, stirring for 4-7 h at the same speed, washing for 3-5 times with N, N-dimethylformamide and deionized water, centrifuging for 7-18 min at 5000-7000 rpm, drying for 2-4 h at 60-70 ℃, and grinding to pass through a 400-600-mesh sieve.
Further, the organic solvent in the step (6) is one or more of propylene glycol methyl ether, xylene, ethyl acetate and tetrahydrofuran; the curing agent is one or a mixture of amino resin, triethylene tetramine and dipropylene triamine.
Compared with the prior art, the invention has the following beneficial effects:
the invention adopts the self-made fluorescent powder and the modified resin as raw materials to prepare the fluorescent paint, so as to realize the effects of long-acting fluorescence and corrosion resistance.
Firstly, 5-nitropyridine-3, 4-diamine and 6-cyanoindole-3-carboxylic acid methyl ester are connected by azo group, and the azo group and the adjacent nitro group form a ring; then, reacting the ester group of the 6-cyanoindole-3-carboxylic acid methyl ester with the hydroxyl group of the piperidinol to form a light-stabilizing compound, so that the self-made fluorescent powder has light resistance and still has a fluorescent effect under multiple times of illumination, the service life of the self-made fluorescent powder is prolonged, and the coating has a long-acting fluorescent effect; condensing the light-stabilizing compound with benzoin, and coordinating with 4, 7-dihydroxy-1, 10-phenanthroline to be located in europium ions to obtain photoluminescent self-made fluorescent powder; the complex has sensitization effect on europium ions to excite the europium ions to emit light, has a conjugated long chain, effectively improves the luminous efficiency, expands a conjugated system by amino, hydroxyl and cyano at the tail end, enhances the luminous effect, and improves the long-acting fluorescent effect of the self-made fluorescent powder.
Secondly, under the action of an emulsifier, the acrylic resin coats the self-made fluorescent powder to form a microcapsule; after graphene is oxidized, hydroxyl on the surface of the graphene is used as an active site to be covalently connected with 2-bromoisopentanoyl bromide, the remaining bromide ions are used for reacting with 5-mercapto-4-p-chlorophenyl-4-hydrogen-3-hydroxy-1, 2, 4-triazole, and then mercapto groups and acrylic resin undergo free radical polymerization, so that graphene is deposited on the surface of a microcapsule to form a barrier layer, the permeation of corrosive media is effectively isolated, the coating has a corrosion resistance effect, and then 1-hydroxytetradecane is introduced by using chloride ions in a graphene molecular chain to form a hydrophobic film on the surface of the graphene, so that the barrier effect of the barrier layer is further enhanced, and the corrosion resistance of the coating is improved.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In order to more clearly illustrate the method provided by the present invention, the following examples are used to illustrate the method for testing each index of the corrosion-resistant fluorescent paint prepared in the following examples as follows:
long-lasting fluorescence: coating the embodiment and the comparative example with the same mass on a cement board, and carrying out photoluminescence and light stability effect tests;
photoluminescence: irradiating the substrate by using an ultraviolet lamp with the wavelength of 200-400 nm, and observing whether the surface has a luminous phenomenon or not;
light stabilization: continuously irradiating for 18d by using an ultraviolet lamp with the wavelength of 200-400 nm, and observing the fluorescence intensity.
Corrosion resistance: coating the cement boards with the embodiment and the comparative example to the same thickness, and performing salt spray effect and water contact angle tests;
testing the salt spray effect: and (5) placing the sample in a salt fog box at 35 ℃, corroding for 300h, and observing whether the surface has corrosion stains.
Example 1
The preparation method of the corrosion-resistant fluorescent paint comprises the following preparation steps:
(1) after stirring and dissolving 98% concentrated sulfuric acid, deionized water and 5-nitropyridine-3, 4-diamine according to the mass ratio of 1.5:2.0:1, cooling to 0 ℃, stirring at 50rpm for 20min, adding a sodium nitrite aqueous solution 1.0 time of the mass of the 5-nitropyridine-3, 4-diamine, wherein the mass ratio of sodium nitrite in the sodium nitrite aqueous solution to deionized water is 2:3, and reacting for 55min to obtain a 5-nitropyridine-3, 4-diamine solution; mixing deionized water, 6-cyanoindole-3-carboxylic acid methyl ester and sodium hydroxide according to a mass ratio of 4:1:1, stirring for 56min at 50rpm, cooling to 0 ℃, adding 5-nitropyridine-3, 4-diamine solution which is 1 time of the mass of 6-cyanoindole-3-carboxylic acid methyl ester at 0.2mL/min, reacting for 2h under heat preservation, adding hydrochloric acid with a mass fraction of 10% until the pH of the solution is 6, filtering, and washing a filter cake with deionized water for 2 times to obtain an azo compound;
(2) mixing an azo compound, 2,6, 6-tetramethyl piperidinol and tetraisopropyl titanate according to a mass ratio of 1:1:0.001, reacting at 146 ℃ for 10 hours, adding xylene 2 times the mass of the azo compound, cooling to 50 ℃, adding methanol 3 times the mass of the azo compound, cooling to 0 ℃, filtering, and drying at 70 ℃ for 5 hours to obtain a light-stabilized compound;
(3) dissolving benzoin in absolute ethyl alcohol with the mass 4 times that of the benzoin, adding a light-stabilizing compound solution with the mass 1.5 times that of the benzoin, reacting the light-stabilizing compound and the absolute ethyl alcohol at the mass ratio of 1:2.0 and 50rpm for 8 hours, distilling at 50 ℃ and the vacuum degree of 20kPa for 46min, adding petroleum ether with the mass 3 times that of the benzoin, cooling to 0 ℃, filtering, and washing with distilled water for 3 times to obtain a benzoin condensation compound;
(4) dissolving europium oxide in concentrated hydrochloric acid with the mass fraction of 38% and the mass of the europium oxide being 15 times that of the europium oxide, heating to 35 ℃, and preserving heat for 70min to obtain a europium chloride solution; dissolving a benzoin condensation compound in absolute ethyl alcohol with the mass 4 times that of the benzoin condensation compound in a water bath at 50 ℃, stirring and dissolving, adding a europium chloride solution with the mass 1 time that of the benzoin condensation compound, adding a sodium hydroxide solution with the mass fraction of 10% until the pH of the solution is 7, reacting for 4 hours at 100rpm, adding 4, 7-dihydroxy-1, 10-phenanthroline with the mass 0.1 time that of the benzoin condensation compound, reacting for 4 hours, heating to 80 ℃, distilling for 4 hours, drying for 2 hours at 70 ℃ and under the vacuum degree of 10kPa to obtain fluorescent powder;
(5) mixing the self-made fluorescent powder, polyethylene glycol and deionized water according to the mass ratio of 1:0.1:14, stirring for 30min at 1000rpm, performing ultrasonic treatment for 22min at 25kHz, adding acrylic resin which is 0.5 times of the mass of the self-made fluorescent powder, stirring uniformly, adding a hydrochloric acid solution with the mass fraction of 10% until the pH of the solution is 2, heating to 60 ℃, stirring for 3.5h at the same rotating speed, adding a sodium hydroxide solution with the mass fraction of 20% until the pH of the solution is 6, and washing for 3 times by using the deionized water to obtain microcapsules;
(6) mixing graphene oxide, triethylamine and N, N-dimethylformamide according to a mass ratio of 1:3:44, ultrasonically dispersing for 42min at 25kHz, adding 2-bromoisopentanoyl bromide 1 time as much as the mass of the graphene oxide into an ice-water bath, stirring for 20h at 200rpm, adding 5-mercapto-4-p-chlorophenyl-4-hydro-3-hydroxy-1, 2, 4-triazole 1 time as much as the mass of the graphene oxide, stirring for 7h at the same speed, washing for 3 times with the N, N-dimethylformamide and deionized water, centrifuging for 18min at 5000rpm, drying for 4h at 60 ℃, and grinding through a 400-mesh sieve to obtain modified graphene;
(7) mixing modified graphene, azodiisobutyronitrile and methanol according to the mass ratio of 1:0.005:55, adding microcapsules 2 times the mass of the modified graphene, placing the microcapsules in a water bath kettle at 50 ℃, reacting for 28 hours, adding 1-hydroxytetradecane 0.4 times the mass of the modified graphene at room temperature, stirring for 8 hours at 50rpm, washing for 3 times by using methanol and deionized water in sequence, and distilling for 1 hour at 65 ℃ and under the vacuum degree of 20kPa to obtain a coating precursor; and uniformly mixing the coating precursor, ethyl acetate and amino resin according to the mass ratio of 1:1.2:0.3 to obtain the corrosion-resistant fluorescent coating.
Example 2
The preparation method of the corrosion-resistant fluorescent paint comprises the following preparation steps:
(1) after stirring and dissolving 98% concentrated sulfuric acid, deionized water and 5-nitropyridine-3, 4-diamine according to the mass ratio of 1.5:3.5:1, cooling to 2 ℃, stirring at 70rpm for 26min, adding a sodium nitrite aqueous solution with the mass of 1.25 times that of the 5-nitropyridine-3, 4-diamine, wherein the mass ratio of sodium nitrite in the sodium nitrite aqueous solution to deionized water is 2:3, and reacting for 61min to obtain a 5-nitropyridine-3, 4-diamine solution; mixing deionized water, 6-cyanoindole-3-carboxylic acid methyl ester and sodium hydroxide according to the mass ratio of 5.5:1:1.5, stirring for 50min at 80rpm, cooling to 3 ℃, adding 5-nitropyridine-3, 4-diamine solution which is 2 times of the mass of the 6-cyanoindole-3-carboxylic acid methyl ester at 0.3mL/min, reacting for 3h under heat preservation, adding hydrochloric acid with the mass fraction of 10% until the pH of the solution is 6.5, filtering, and washing a filter cake for 3 times by using the deionized water to obtain an azo compound;
(2) mixing an azo compound, 2,6, 6-tetramethyl piperidinol and tetraisopropyl titanate according to a mass ratio of 1:2:0.002, reacting at 153 ℃ for 8 hours, adding xylene with the mass of 3 times that of the azo compound, cooling to 55 ℃, adding methanol with the mass of 4.5 times that of the azo compound, cooling to 2 ℃, filtering, and drying at 80 ℃ for 4 hours to obtain a light-stabilized compound;
(3) dissolving benzoin in absolute ethyl alcohol with the mass 6 times of that of the benzoin, adding a light stabilizing compound solution with the mass 2.6 times of that of the benzoin, reacting the light stabilizing compound and the absolute ethyl alcohol in the light stabilizing compound solution at the mass ratio of 1:2.35 at 80rpm for 6h, distilling at 57 ℃ and the vacuum degree of 30kPa for 54min, then adding petroleum ether with the mass 4 times of that of the benzoin, cooling to 3 ℃, filtering, and washing with distilled water for 4 times to obtain a benzoin condensation compound;
(4) dissolving europium oxide in concentrated hydrochloric acid with the mass fraction of 38% and the mass of 16.5 times of that of the europium oxide, heating to 39 ℃, and preserving heat for 64min to obtain a europium chloride solution; dissolving a benzoin condensation compound in absolute ethyl alcohol with the mass 5.5 times that of the benzoin condensation compound in water bath at 55 ℃, stirring and dissolving, adding a europium chloride solution with the mass 2 times that of the benzoin condensation compound, adding a sodium hydroxide solution with the mass fraction of 10% until the pH of the solution is 7.5, reacting for 2.5h at 150rpm, adding 4, 7-dihydroxy-1, 10-phenanthroline with the mass 0.25 time that of the benzoin condensation compound, and absolute ethyl alcohol with the mass 2 times that of the benzoin condensation compound, continuously reacting for 2h, heating to 85 ℃, distilling for 2.7h, drying for 3.5h at 75 ℃ and the vacuum degree of 20kPa to obtain fluorescent powder;
(5) mixing the self-made fluorescent powder, polyethylene glycol and deionized water according to the mass ratio of 1:0.1:15, stirring for 25min at 1300rpm, performing ultrasonic treatment for 16min at 30kHz, adding acrylic resin with the mass of 0.75 time of that of the self-made fluorescent powder, stirring uniformly, adding a hydrochloric acid solution with the mass fraction of 10% until the pH of the solution is 3, heating to 65 ℃, stirring for 2.5h at the same rotation speed, adding a sodium hydroxide solution with the mass fraction of 20% until the pH of the solution is 6.5, and washing for 4 times with the deionized water to obtain microcapsules;
(6) mixing graphene oxide, triethylamine and N, N-dimethylformamide according to a mass ratio of 1:4:46, performing ultrasonic dispersion for 36min at 30kHz, adding 2-bromoisopentanoyl bromide 2 times the mass of the graphene oxide into ice water bath, stirring for 18h at 250rpm, adding 5-mercapto-4-p-chlorophenyl-4-hydro-3-hydroxy-1, 2, 4-triazole 2 times the mass of the graphene oxide, stirring for 5.5h at the same speed, washing for 4 times with N, N-dimethylformamide and deionized water, centrifuging for 12min at 6000rpm, drying for 3h at 65 ℃, and grinding and sieving with a 500-mesh sieve to obtain modified graphene;
(7) mixing modified graphene, azodiisobutyronitrile and methanol according to the mass ratio of 1:0.006:58.5, adding microcapsules of which the mass is 3 times that of the modified graphene, placing the microcapsules in a water bath kettle at 55 ℃, reacting for 26 hours, adding 1-hydroxytetradecane of which the mass is 0.55 times that of the modified graphene at room temperature, stirring for 6 hours at 80rpm, washing for 4 times by using methanol and deionized water in sequence, and distilling for 2 hours at 69 ℃ and the vacuum degree of 30kPa to obtain a coating precursor; and uniformly mixing the coating precursor, ethyl acetate and amino resin according to the mass ratio of 1:1.9:0.4 to obtain the corrosion-resistant fluorescent coating.
Example 3
The preparation method of the corrosion-resistant fluorescent paint comprises the following preparation steps:
(1) dissolving 98% concentrated sulfuric acid, deionized water and 5-nitropyridine-3, 4-diamine in a mass ratio of 1.5:5.0:1, stirring, cooling to 5 ℃, stirring at 100rpm for 32min, adding a sodium nitrite aqueous solution 1.5 times the mass of the 5-nitropyridine-3, 4-diamine, wherein the mass ratio of sodium nitrite to deionized water in the sodium nitrite aqueous solution is 2:3, and reacting for 67min to obtain a 5-nitropyridine-3, 4-diamine solution; mixing deionized water, 6-cyanoindole-3-carboxylic acid methyl ester and sodium hydroxide according to the mass ratio of 7:1:2, stirring for 44min at 100rpm, cooling to 5 ℃, adding 5-nitropyridine-3, 4-diamine solution which is 3 times of the mass of the 6-cyanoindole-3-carboxylic acid methyl ester at 0.5mL/min, keeping the temperature for reacting for 4h, adding hydrochloric acid with the mass fraction of 10% until the pH of the solution is 7, filtering, and washing a filter cake with the deionized water for 4 times to obtain an azo compound;
(2) mixing an azo compound, 2,6, 6-tetramethyl piperidinol and tetraisopropyl titanate according to a mass ratio of 1:3:0.003, reacting at 160 ℃ for 6 hours, adding xylene with the mass of 4 times that of the azo compound, cooling to 60 ℃, adding methanol with the mass of 6 times that of the azo compound, cooling to 5 ℃, filtering, and drying at 90 ℃ for 3 hours to obtain a light-stabilized compound;
(3) dissolving benzoin in absolute ethyl alcohol with the mass 8 times that of the benzoin, adding a light-stabilizing compound solution with the mass 3.7 times that of the benzoin, reacting at 100rpm for 4 hours with the mass ratio of the light-stabilizing compound to the absolute ethyl alcohol being 1:2.7, distilling at 64 ℃ and the vacuum degree of 40kPa for 62 minutes, then adding petroleum ether with the mass 5 times that of the benzoin, cooling to 5 ℃, filtering, and washing with distilled water for 5 times to obtain a benzoin condensation compound;
(4) dissolving europium oxide in concentrated hydrochloric acid with the mass fraction of 38 percent, which is 18 times of the mass of the europium oxide, heating to 42 ℃, and preserving heat for 58min to obtain a europium chloride solution; dissolving a benzoin condensation compound in absolute ethyl alcohol 7 times of the mass of the benzoin condensation compound in a water bath at 60 ℃, stirring and dissolving, adding a europium chloride solution 3 times of the mass of the benzoin condensation compound, adding a sodium hydroxide solution with the mass fraction of 10% until the pH of the solution is 8, reacting at 200rpm for 1h, adding 4, 7-dihydroxy-1, 10-phenanthroline and absolute ethyl alcohol 3 times of the mass of the benzoin condensation compound, reacting at 0.4 time for 3h, heating to 90 ℃, distilling for 1.5h, drying at 80 ℃ for 5h under the vacuum degree of 30kPa to obtain fluorescent powder;
(5) mixing the self-made fluorescent powder, polyethylene glycol and deionized water according to a mass ratio of 1:0.1:16, stirring for 20min at 1500rpm, performing ultrasonic treatment for 10min at 35kHz, adding acrylic resin which is 1 time of the mass of the self-made fluorescent powder, stirring uniformly, adding a hydrochloric acid solution with the mass fraction of 10% until the pH of the solution is 4, heating to 70 ℃, stirring for 1.5h at the same rotating speed, adding a sodium hydroxide solution with the mass fraction of 20% until the pH of the solution is 7, and washing for 5 times with the deionized water to obtain microcapsules;
(6) mixing graphene oxide, triethylamine and N, N-dimethylformamide according to a mass ratio of 1:5:48, ultrasonically dispersing for 30min at 35kHz, adding 2-bromoisopentanoyl bromide 3 times as much as the mass of the graphene oxide into an ice-water bath, stirring for 16h at 300rpm, adding 5-mercapto-4-p-chlorophenyl-4-hydro-3-hydroxy-1, 2, 4-triazole 3 times as much as the mass of the graphene oxide, stirring for 4h at the same speed, washing for 5 times with the N, N-dimethylformamide and deionized water, centrifuging for 7min at 7000rpm, drying for 2h at 70 ℃, and grinding and sieving with a 600-mesh sieve to obtain modified graphene;
(7) mixing modified graphene, azodiisobutyronitrile and methanol according to the mass ratio of 1:0.008:62, adding microcapsules 4 times the mass of the modified graphene, placing the microcapsules in a water bath kettle at 60 ℃, reacting for 24 hours, adding 1-hydroxytetradecane 0.7 times the mass of the modified graphene at room temperature, stirring for 4 hours at 100rpm, washing for 5 times by using methanol and deionized water in sequence, and distilling for 13 hours at 72 ℃ and under the vacuum degree of 40kPa to obtain a coating precursor; and uniformly mixing the coating precursor, ethyl acetate and amino resin according to the mass ratio of 1:2.6:0.5 to obtain the corrosion-resistant fluorescent coating.
Comparative example 1
Comparative example 1 differs from example 2 in that step (1) is different, step (1) being changed to: after being stirred and dissolved, concentrated sulfuric acid with the mass fraction of 98%, deionized water and 5-nitropyridine-3, 4-diamine are cooled to 2 ℃ and stirred for 26min at 70rpm, a sodium nitrite aqueous solution with the mass of 1.25 times that of the 5-nitropyridine-3, 4-diamine is added, the mass ratio of sodium nitrite to deionized water in the sodium nitrite aqueous solution is 2:3, and the azo compound is obtained after 61min of reaction. The rest of the procedure was the same as in example 2.
Comparative example 2
Comparative example 2 differs from example 2 in that step (3) is not present and step (4) is changed to: dissolving europium oxide in concentrated hydrochloric acid with the mass fraction of 38% and the mass of 16.5 times of that of the europium oxide, heating to 39 ℃, and preserving heat for 64min to obtain a europium chloride solution; dissolving a light-stabilizing compound in absolute ethyl alcohol with the mass 5.5 times that of the light-stabilizing compound in water bath at 55 ℃, stirring and dissolving, adding a europium chloride solution with the mass 2 times that of the light-stabilizing compound, adding a sodium hydroxide solution with the mass fraction of 10% until the pH of the solution is 7.5, reacting for 2.5h at 150rpm, adding 4, 7-dihydroxy-1, 10-phenanthroline with the mass 0.25 time that of the light-stabilizing compound and absolute ethyl alcohol with the mass 2 times that of the light-stabilizing compound, heating to 85 ℃, distilling for 2.7h, drying for 3.5h at 75 ℃ and the vacuum degree of 20kPa to obtain the fluorescent powder. The rest of the procedure was the same as in example 2.
Comparative example 3
Comparative example 3 differs from example 2 in that step (5) is not present and step (7) is changed to: mixing modified graphene, azodiisobutyronitrile and methanol according to the mass ratio of 1:0.006:58.5, adding acrylic resin with the mass 3 times that of the modified graphene, placing the mixture in a water bath kettle at 55 ℃, reacting for 26 hours, adding 1-hydroxytetradecane with the mass 0.55 time that of the modified graphene at room temperature, stirring for 6 hours at 80rpm, washing for 4 times with methanol and deionized water in sequence, and distilling for 2 hours at 69 ℃ and the vacuum degree of 30kPa to obtain a coating precursor; and uniformly mixing the coating precursor, the self-made fluorescent powder, ethyl acetate and amino resin according to the mass ratio of 1:0.3:1.9:0.4 to obtain the corrosion-resistant fluorescent coating. The rest of the procedure was the same as in example 2.
Comparative example 4
Comparative example 4 differs from example 2 in that step (6) is not present and step (7) is changed to: mixing graphene oxide, azodiisobutyronitrile and methanol according to the mass ratio of 1:0.006:58.5, adding microcapsules of which the mass is 3 times that of the graphene oxide, placing the microcapsules in a water bath kettle at 55 ℃, reacting for 26 hours, adding 1-hydroxytetradecane of which the mass is 0.55 times that of the graphene oxide at room temperature, stirring for 6 hours at 80rpm, washing for 4 times by using methanol and deionized water in sequence, and distilling for 2 hours at 69 ℃ and the vacuum degree of 30kPa to obtain a coating precursor; and uniformly mixing the coating precursor, ethyl acetate and amino resin according to the mass ratio of 1:1.9:0.4 to obtain the corrosion-resistant fluorescent coating. The rest of the procedure was the same as in example 2.
Comparative example 5
Comparative example 5 differs from example 2 in the step (7), which is changed to: mixing modified graphene, azodiisobutyronitrile and methanol according to the mass ratio of 1:0.006:58.5, adding microcapsules with the mass 3 times that of the modified graphene, placing the microcapsules in a water bath kettle at 55 ℃, reacting for 26 hours, washing for 4 times by using methanol and deionized water in sequence, and distilling for 2 hours at 69 ℃ and the vacuum degree of 30kPa to obtain a coating precursor; and uniformly mixing the coating precursor, ethyl acetate and amino resin according to the mass ratio of 1:1.9:0.4 to obtain the corrosion-resistant fluorescent coating. The rest of the procedure was the same as in example 2.
Examples of effects
The following table 1 shows the results of performance analysis of the corrosion-resistant fluorescent paint using examples 1 to 3 of the present invention and comparative examples 1 to 5.
TABLE 1
From the comparison of experimental data of luminescence phenomenon and fluorescence intensity of examples and comparative examples, it can be found that the product uses 2, 6-diamino-3-nitrosopyrimidine, 6-cyanoindole-3-carboxylic acid methyl ester, piperidinol and benzoin, 4, 7-dihydroxy-1, 10-phenanthroline to form a coordination compound, and absorbs europium ions to obtain photoluminescent self-made fluorescent powder; the complex has a sensitization effect on europium ions, excites the europium ions to emit light, conjugates long-chain and a plurality of electron-assisted groups, and improves the long-acting fluorescence effect of the self-made fluorescent powder, and the light stability effect of the coordination compound enables the coating to have light resistance and improves the fluorescence of the self-made fluorescent powder; the experimental data comparison of the water contact angle and the corrosion condition of the embodiment and the comparative example shows that the microcapsules are prepared by taking the acrylic resin as the wall material and the self-made fluorescent powder as the core material, the self-made fluorescent powder is protected, and the modified graphene and the hydrophobic film are sequentially coated through the chemical crosslinking reaction to form the barrier layer, so that the penetration of a corrosion medium is effectively isolated, and the coating has the corrosion resistance effect.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Any reference sign in a claim should not be construed as limiting the claim concerned.
Claims (10)
1. The preparation method of the corrosion-resistant fluorescent paint is characterized by comprising the following steps of mixing self-made fluorescent powder and polyethylene glycol in distilled water, stirring at a high speed, forming a core material emulsion under ultrasonic waves, adding acrylic resin, stirring to obtain microcapsules, and then carrying out modification treatment.
2. The corrosion-resistant fluorescent paint of claim 1, wherein the self-made fluorescent powder is prepared from 5-nitropyridine-3, 4-diamine, 6-cyanoindole-3-carboxylic acid methyl ester, 2,6, 6-tetramethylpiperidinol, benzoin, 4, 7-dihydroxy-1, 10-phenanthroline and europium oxide.
3. The corrosion-resistant fluorescent paint according to claim 1, wherein the modification treatment comprises the steps of mixing the modified graphene, the azobisisobutyronitrile and the methanol, adding the microcapsule, placing the microcapsule in a water bath, reacting for a predetermined time, adding the 1-hydroxytetradecane, stirring the mixture for reaction, washing and distilling the reaction product.
4. The corrosion-resistant fluorescent paint of claim 3, wherein the modified graphene is prepared from graphene oxide, 2-bromoisopentanoyl bromide, and 5-mercapto-4-p-chlorophenyl-4-hydro-3-hydroxy-1, 2, 4-triazole.
5. The preparation method of the corrosion-resistant fluorescent paint is characterized by comprising the following preparation steps of:
(1) mixing deionized water, 6-cyanoindole-3-carboxylic acid methyl ester and sodium hydroxide according to a mass ratio of 4:1: 1-7: 1:2, stirring at 50-100 rpm for 44-56 min, cooling to 0-5 ℃, adding a 5-nitropyridine-3, 4-diamine solution which is 1-3 times of the mass of 6-cyanoindole-3-carboxylic acid methyl ester at 0.2-0.5 mL/min, reacting for 2-4 h under heat preservation, adding 10% hydrochloric acid by mass until the pH of the solution is 6-7, filtering, and washing a filter cake with deionized water for 2-4 times to obtain an azo compound;
(2) mixing an azo compound, 2,6, 6-tetramethyl piperidinol and tetraisopropyl titanate according to a mass ratio of 1:1: 0.001-1: 3:0.003, reacting at 146-160 ℃ for 6-10 hours, adding xylene 2-4 times of the mass of the azo compound, cooling to 50-60 ℃, adding methanol 3-6 times of the mass of the azo compound, cooling to 0-5 ℃, filtering, and drying at 70-90 ℃ for 3-5 hours to obtain a light-stabilized compound;
(3) dissolving benzoin in absolute ethyl alcohol with the mass 4-8 times of that of the benzoin, adding a light-stabilizing compound solution with the mass 1.5-3.7 times of that of the benzoin, reacting at 50-100 rpm for 4-8 h, distilling at 50-64 ℃ and under the vacuum degree of 20-40 kPa for 46-62 min, adding petroleum ether with the mass 3-5 times of that of the benzoin, cooling to 0-5 ℃, filtering, and washing with distilled water for 3-5 times to obtain a benzoin condensation compound;
(4) dissolving a benzoin condensation compound in absolute ethyl alcohol with the mass 4-7 times of that of the benzoin condensation compound in a water bath at 50-60 ℃, stirring and dissolving, adding a europium chloride solution with the mass 1-3 times of that of the benzoin condensation compound, adding a sodium hydroxide solution with the mass fraction of 10% until the pH of the solution is 7-8, reacting at 100-200 rpm for 1-4 h, adding 4, 7-dihydroxy-1, 10-phenanthroline and absolute ethyl alcohol with the mass 1-3 times of that of the benzoin condensation compound 0.1-0.4, reacting for 1-3 h, heating to 80-90 ℃, distilling for 1.5-4 h, drying at 70-80 ℃ and under the vacuum degree of 10-30 kPa for 2-5 h to obtain fluorescent powder;
(5) mixing self-made fluorescent powder, polyethylene glycol and deionized water according to a mass ratio of 1:0.1: 14-1: 0.1:16, stirring at 1000-1500 rpm for 20-30 min, performing ultrasonic treatment at 25-35 kHz for 10-22 min, adding acrylic resin which is 0.5-1 time of the mass of the self-made fluorescent powder, uniformly stirring, adding 10% hydrochloric acid solution to a solution pH of 2-4, heating to 60-70 ℃, stirring at the same rotating speed for 1.5-3.5 h, adding 20% sodium hydroxide solution to a solution pH of 6-7, and washing with deionized water for 3-5 times to obtain microcapsules;
(6) mixing modified graphene, azodiisobutyronitrile and methanol according to the mass ratio of 1:0.005: 55-1: 0.008:62, adding microcapsules 2-4 times of the mass of the modified graphene, placing the microcapsules in a water bath kettle at 50-60 ℃, reacting for 24-28 h, adding 1-hydroxytetradecane 0.4-0.7 times of the mass of the modified graphene at room temperature, stirring for 4-8 h at 50-100 rpm, washing for 3-5 times with methanol and deionized water in sequence, and distilling for 1-3 h at 65-72 ℃ and a vacuum degree of 20-40 kPa to obtain a coating precursor; and uniformly mixing the coating precursor, the organic solvent and the curing agent according to the mass ratio of 1:1.2: 0.3-1: 2.6:0.5 to obtain the corrosion-resistant fluorescent coating.
6. The method for preparing a corrosion-resistant fluorescent paint according to claim 5, wherein the preparation method of the 5-nitropyridine-3, 4-diamine solution in the step (1) comprises the following steps: after stirring and dissolving 98% concentrated sulfuric acid, deionized water and 5-nitropyridine-3, 4-diamine according to the mass ratio of 1.5:2.0: 1-1.5: 5.0:1, cooling to 0-5 ℃, stirring at 50-100 rpm for 20-32 min, adding a sodium nitrite aqueous solution with the mass of 1.0-1.5 times that of the 5-nitropyridine-3, 4-diamine, wherein the mass ratio of sodium nitrite to deionized water in the sodium nitrite aqueous solution is 2:3, and reacting for 55-67 min.
7. The method for preparing the corrosion-resistant fluorescent paint according to claim 5, wherein the light-stabilizing compound solution in the step (3) is prepared by mixing a light-stabilizing compound and absolute ethyl alcohol according to a mass ratio of 1: 2.0-1: 2.7.
8. The method for preparing a corrosion-resistant fluorescent paint according to claim 5, wherein the preparation method of the europium chloride solution in the step (4) comprises the following steps: dissolving europium oxide in concentrated hydrochloric acid with the mass fraction of 38% and the mass of 15-18 times of that of the europium oxide, heating to 35-42 ℃, and preserving heat for 58-70 min.
9. The method for preparing the corrosion-resistant fluorescent paint according to claim 5, wherein the modified graphene prepared in the step (6) is prepared by: mixing graphene oxide, triethylamine and N, N-dimethylformamide according to a mass ratio of 1:3: 44-1: 5:48, ultrasonically dispersing for 30-42 min at 25-35 kHz, adding 2-bromoisovaleryl bromide 1-3 times the mass of the graphene oxide into an ice water bath, stirring for 16-20 h at 200-300 rpm, adding 5-mercapto-4-p-chlorophenyl-4-hydrogen-3-hydroxy-1, 2, 4-triazole 1-3 times the mass of the graphene oxide, stirring for 4-7 h at the same speed, washing for 3-5 times with N, N-dimethylformamide and deionized water, centrifuging for 7-18 min at 5000-7000 rpm, drying for 2-4 h at 60-70 ℃, and grinding to pass through a 400-600-mesh sieve.
10. The method for preparing a corrosion-resistant fluorescent paint according to claim 5, wherein the organic solvent in step (6) is one or more of propylene glycol methyl ether, xylene, ethyl acetate and tetrahydrofuran; the curing agent is one or a mixture of amino resin, triethylene tetramine and dipropylene triamine.
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