CN112143299A - Long-acting self-cleaning high-weatherability fluorocarbon coating and preparation method thereof - Google Patents
Long-acting self-cleaning high-weatherability fluorocarbon coating and preparation method thereof Download PDFInfo
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- CN112143299A CN112143299A CN202011015610.0A CN202011015610A CN112143299A CN 112143299 A CN112143299 A CN 112143299A CN 202011015610 A CN202011015610 A CN 202011015610A CN 112143299 A CN112143299 A CN 112143299A
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- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 title claims abstract description 73
- 238000000576 coating method Methods 0.000 title claims abstract description 42
- 239000011248 coating agent Substances 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 238000004140 cleaning Methods 0.000 title claims abstract description 28
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 54
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000003973 paint Substances 0.000 claims abstract description 38
- 239000002904 solvent Substances 0.000 claims abstract description 36
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims abstract description 35
- 230000005496 eutectics Effects 0.000 claims abstract description 32
- 239000002994 raw material Substances 0.000 claims abstract description 30
- 239000011347 resin Substances 0.000 claims abstract description 24
- 229920005989 resin Polymers 0.000 claims abstract description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 20
- 239000001763 2-hydroxyethyl(trimethyl)azanium Substances 0.000 claims abstract description 15
- 235000019743 Choline chloride Nutrition 0.000 claims abstract description 15
- 229960003178 choline chloride Drugs 0.000 claims abstract description 15
- SGMZJAMFUVOLNK-UHFFFAOYSA-M choline chloride Chemical compound [Cl-].C[N+](C)(C)CCO SGMZJAMFUVOLNK-UHFFFAOYSA-M 0.000 claims abstract description 15
- 239000002518 antifoaming agent Substances 0.000 claims abstract description 14
- 239000002270 dispersing agent Substances 0.000 claims abstract description 14
- 239000000126 substance Substances 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 7
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 36
- 238000003756 stirring Methods 0.000 claims description 35
- 238000005303 weighing Methods 0.000 claims description 22
- 239000000945 filler Substances 0.000 claims description 19
- 238000002156 mixing Methods 0.000 claims description 17
- 239000000049 pigment Substances 0.000 claims description 16
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 15
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 15
- 238000001914 filtration Methods 0.000 claims description 14
- 238000004806 packaging method and process Methods 0.000 claims description 14
- 239000002002 slurry Substances 0.000 claims description 14
- 239000000243 solution Substances 0.000 claims description 12
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 10
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 10
- 238000005507 spraying Methods 0.000 claims description 10
- 239000012295 chemical reaction liquid Substances 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 7
- 239000003085 diluting agent Substances 0.000 claims description 7
- 238000000227 grinding Methods 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 239000012948 isocyanate Substances 0.000 claims description 7
- 150000002513 isocyanates Chemical class 0.000 claims description 7
- 239000004952 Polyamide Substances 0.000 claims description 6
- 229920002647 polyamide Polymers 0.000 claims description 6
- 238000005516 engineering process Methods 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 238000010276 construction Methods 0.000 claims description 4
- 238000010790 dilution Methods 0.000 claims description 4
- 239000012895 dilution Substances 0.000 claims description 4
- 239000008096 xylene Substances 0.000 claims description 4
- 239000004698 Polyethylene Substances 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- GXDVEXJTVGRLNW-UHFFFAOYSA-N [Cr].[Cu] Chemical compound [Cr].[Cu] GXDVEXJTVGRLNW-UHFFFAOYSA-N 0.000 claims description 3
- 229910021485 fumed silica Inorganic materials 0.000 claims description 3
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 claims description 3
- -1 polyethylene Polymers 0.000 claims description 3
- 229920000573 polyethylene Polymers 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 241001428214 Polyides Species 0.000 claims 2
- KRQUFUKTQHISJB-YYADALCUSA-N 2-[(E)-N-[2-(4-chlorophenoxy)propoxy]-C-propylcarbonimidoyl]-3-hydroxy-5-(thian-3-yl)cyclohex-2-en-1-one Chemical compound CCC\C(=N/OCC(C)OC1=CC=C(Cl)C=C1)C1=C(O)CC(CC1=O)C1CCCSC1 KRQUFUKTQHISJB-YYADALCUSA-N 0.000 claims 1
- 241000544076 Whipplea modesta Species 0.000 claims 1
- 239000002105 nanoparticle Substances 0.000 abstract description 6
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical class ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 abstract description 4
- 125000001931 aliphatic group Chemical group 0.000 abstract description 4
- 239000007788 liquid Substances 0.000 abstract description 4
- 230000001699 photocatalysis Effects 0.000 abstract description 4
- 229920001228 polyisocyanate Polymers 0.000 abstract description 4
- 239000005056 polyisocyanate Substances 0.000 abstract description 4
- 230000015556 catabolic process Effects 0.000 abstract description 3
- 239000003054 catalyst Substances 0.000 abstract description 3
- 238000006731 degradation reaction Methods 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 3
- 230000008569 process Effects 0.000 abstract description 2
- 239000002699 waste material Substances 0.000 abstract description 2
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 abstract 1
- 239000003365 glass fiber Substances 0.000 abstract 1
- 239000002932 luster Substances 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 230000032683 aging Effects 0.000 description 6
- 229910000831 Steel Inorganic materials 0.000 description 5
- 238000011109 contamination Methods 0.000 description 5
- 239000010959 steel Substances 0.000 description 5
- 238000005260 corrosion Methods 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 238000007865 diluting Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000002519 antifouling agent Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000011253 protective coating Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000003796 beauty Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000001132 ultrasonic dispersion 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
- C09D127/00—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 a halogen; Coating compositions based on derivatives of such polymers
- C09D127/02—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 a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
- C09D127/12—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 a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- 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
- 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
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1687—Use of special additives
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/20—Diluents or solvents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Paints Or Removers (AREA)
Abstract
The invention discloses a long-acting self-cleaning high-weatherability fluorocarbon coating and a preparation method thereof, wherein the coating is two components, and the component A comprises the following components: the coating comprises Asahi nitroxide LF-200 fluorocarbon resin, a solvent, a dispersant, self-made modified nano-scale titanium dioxide liquid, silicon-aluminum coated titanium dioxide, an anti-settling agent, a leveling agent and an antifoaming agent. The component B comprises: aliphatic polyisocyanate and elastic curing agent. The film is characterized in that firstly, the Asahi glass fiber LF-200 fluorocarbon resin is used as a main film forming substance, so that a paint film has ultrahigh weather resistance; secondly, the choline chloride/alcohol eutectic solvent has the characteristics of solvent property, catalyst, degradation and the like, the raw materials are easy to obtain and low in cost, the nano titanium dioxide is modified, the nano particles are dispersed more uniformly and have better stability, and pollution and resource waste are not generated in the whole process; thirdly, the choline chloride/alcohol eutectic solvent modified nano titanium dioxide is added into the fluorocarbon coating, so that a paint film has stronger photocatalytic property, the contact angle of the paint film can be reduced, the hydrophilicity of the paint film is improved, the self-cleaning effect of the fluorocarbon coating is improved, the luster, the stability and the ultrahigh weather resistance of the fluorocarbon coating are not influenced, and the characteristics of long-acting self-cleaning and high weather resistance are really achieved.
Description
Technical Field
The invention relates to the technical field of steel surface heavy-duty anticorrosive, self-cleaning and high-weatherability coating chemical industry, in particular to a long-acting self-cleaning high-weatherability fluorocarbon coating and a preparation method thereof.
Background
The fluorine atom in the fluorocarbon resin has high electronegativity (4.0) and C-F bond energy (451-485) multiplied by 103Larger J/mol, larger bond distance (136X 10)-10) m is short and fluorine atoms densely surround the C-C main bond to form a spiral structure, thereby protecting C-C from impact and damage by chemical media. The fluororesin has the characteristics of good adhesive force, super-long weather resistance, stain resistance, corrosion resistance and the like, is widely applied to the fields of buildings, transportation and the like at present, becomes a substitute term of high-performance coating, and is one of three high-performance finishing paints in the bridge manufacturing industry. With the rapid development of modern science and technology and economy, the requirement on the service life of a large bridge is longer and longer, and the requirement is generally more than 100 years, even up to 120 years. Therefore, the salt spray resistance and the artificial weather aging resistance of 3000 h of the cross-sea bridge in a severe corrosion environment, such as a typical HongZhu Australia bridge and the like, cannot meet the requirements. Therefore, research and development of the high-performance fluorocarbon finish paint are certainly a future development trend, and particularly, the fluorocarbon finish paint with salt spray resistance and artificial weather aging resistance (QUV test) of more than 6000h meets the requirements is researched and applied more.
Disclosure of Invention
For coatings used for outdoor buildings such as large steel structure bridges and the like, the coatings are characterized by long-acting corrosion resistance and certain self-cleaning capability so as to meet the requirements of practicality, cleanness and beauty, reduce the heavy loss of building corrosion and reduce the higher investment for cleaning the outer surfaces of polluted buildings. The nano titanium dioxide has photocatalytic property and can improve the stain resistance of a paint film, but the nano titanium dioxide is nano particles (nano TiO)2) The nano-particles are very tiny and have very large specific surface area, so that extremely high interfacial force can be generated among the particles, the particles are aggregated into aggregates and are difficult to be soaked and dispersed, and the phenomenon of agglomeration of the nano-particles can occur even if the traditional dispersion methods such as ultrasonic dispersion, high-speed shear dispersion and the like are limited and the time is too long, so that the invention utilizes choline chloride (molecular formula: the solvent property, catalyst property, degradation property and other properties of the HOC2H4N + (CH3)3 Cl-)/alcohol eutectic solvent modify the nano titanium dioxide, so that the nano particles are dispersed more uniformly and have better stability, and the choline chloride/alcohol eutectic solvent modified nano titanium dioxide added into the fluorocarbon coating can ensure that a paint film not only has stronger photocatalysis property, but also can reduce the contact angle of the paint film, improve the hydrophilicity of the paint film, improve the self-cleaning effect of the fluorocarbon coating, and does not influence the ultrahigh weather resistance of the fluorocarbon coating.
The purpose of the invention can be realized by the following technical scheme:
a preparation method of a long-acting self-cleaning high-weatherability fluorocarbon coating comprises the following five steps:
(1) preparation of eutectic solvent: adding the two raw materials into a sealed container, and stirring at 50-90 ℃ until the reaction liquid is transparent to obtain a eutectic solvent;
wherein: the two raw materials in the step (1) are specifically: the first raw material is choline chloride, and the second raw material is one or more of glycerol, ethylene glycol or ethanol;
(2) preparing a self-made modified nano titanium dioxide solution: adding nano titanium dioxide into the eutectic solvent obtained in the step (1), fully stirring, heating to 50-100 ℃, keeping the temperature for 0.1-1 h until the nano titanium dioxide is uniformly dispersed to obtain a modified nano titanium dioxide solution, namely a low-surface-energy filler, and cooling to room temperature for later use;
(3) preparation of the component A:
the first step is as follows: uniformly mixing 30-50 parts of fluorocarbon resin and 2-15 parts of dimethylbenzene, sequentially adding 0.1-1 part of dispersing agent, 8-50 parts of pigment and 0.1-1 part of anti-settling agent in a stirring state, uniformly mixing, and grinding the slurry to the fineness of less than 20 mu m to obtain fluorocarbon finish paint color paste for later use;
the second step is that: weighing 10-50 parts of fluorocarbon finish paint color paste, adding 10-50 parts of fluorocarbon resin, 0.1-1 part of anti-settling agent, 0.1-1 part of flatting agent, 0.1-0.5 part of defoaming agent, 1-5 parts of low-surface-energy filler and 2-10 parts of dimethylbenzene into the partial paste, uniformly stirring, and filtering and packaging to obtain the component A.
(4) Preparation of the component B: and (3) uniformly mixing 40-70 parts of isocyanate curing agent, 10-30 parts of elastic curing agent and 10-30 parts of butyl acetate, filtering and packaging to obtain the component B.
(5) Preparation of a paint film: the components A are as follows by mass ratio: component B is (100): (6.5-12.5), adding a high-energy diluent for dilution, and performing spraying construction to obtain the long-acting self-cleaning high-weather-resistance fluorocarbon coating film.
The long-acting self-cleaning high-weatherability fluorocarbon coating is prepared by the following method:
(1) preparation of eutectic solvent: adding the two raw materials into a sealed container, and stirring at 50-90 ℃ until the reaction liquid is transparent to obtain a eutectic solvent;
wherein: the two raw materials in the step (1) are specifically: the first raw material is choline chloride, and the second raw material is one or more of glycerol, ethylene glycol or ethanol;
(2) preparing a self-made modified nano titanium dioxide solution: adding nano titanium dioxide into the eutectic solvent obtained in the step (1), fully stirring, heating to 50-100 ℃, keeping the temperature for 0.1-1 h until the nano titanium dioxide is uniformly dispersed to obtain a modified nano titanium dioxide solution, namely a low-surface-energy filler, and cooling to room temperature for later use;
(3) preparation of the component A:
the first step is as follows: uniformly mixing 30-50 parts of fluorocarbon resin and 2-15 parts of dimethylbenzene, sequentially adding 0.1-1 part of dispersing agent, 8-50 parts of pigment and 0.1-1 part of anti-settling agent in a stirring state, uniformly mixing, and grinding the slurry to the fineness of less than 20 mu m to obtain fluorocarbon finish paint color paste for later use;
the second step is that: weighing 10-50 parts of fluorocarbon finish paint color paste, adding 10-50 parts of fluorocarbon resin, 0.1-1 part of anti-settling agent, 0.1-1 part of flatting agent, 0.1-0.5 part of defoaming agent, 1-5 parts of low-surface-energy filler and 2-10 parts of dimethylbenzene into the partial paste, uniformly stirring, and filtering and packaging to obtain the component A.
(4) Preparation of the component B: and (3) uniformly mixing 40-70 parts of isocyanate curing agent, 10-30 parts of elastic curing agent and 10-30 parts of butyl acetate, filtering and packaging to obtain the component B.
(5) Preparation of a paint film: the components A are as follows by mass ratio: component B is (100): (6.5-12.5), adding a high-energy diluent for dilution, and performing spraying construction to obtain the long-acting self-cleaning high-weather-resistance fluorocarbon coating film.
In some specific embodiments: in the first step of the component A: the fluorocarbon resin, the dimethylbenzene, the dispersing agent, the pigment and the anti-settling agent are respectively 35-45 parts, 8-12 parts, 0.3-0.8 part, 10-50 parts and 0.3-0.8 part by weight;
in the second step: the fluorocarbon finishing paint color paste, the fluorocarbon resin, the anti-settling agent, the flatting agent, the defoaming agent, the low-surface-energy filler and the xylene are respectively 30-50 parts, 40-50 parts, 0.3-0.8 part, 0.1-0.5 part, 1-5 parts and 2-10 parts by weight.
The isocyanate curing agent, the elastic curing agent and the butyl acetate in the component B are respectively 55-65 parts, 15-25 parts and 20-30 parts by weight.
In some specific technical schemes, the molar ratio of the first raw material to the second raw material in the step (1) is 1: 0.5 to 10; preferably, the method comprises the following steps: the molar ratio of the first raw material to the second raw material is 1: 2 to 6.
In some specific embodiments: in the step (2), the mass percent of the nano titanium dioxide in the eutectic solvent in the step (1) is 10-50%. Preferably: in the step (2), the mass percent of the nano titanium dioxide in the eutectic solvent in the step (1) is 20-50%.
In some specific embodiments: in the step (3), the dispersant is one or more of BYK-2025, BYK-180, Digao 670 and Digao 671.
In some specific embodiments: the pigment in the step (3) is one or more of DuPont R960 titanium dioxide, Hunan Megaku science and technology Co., Ltd JF-B2852 copper chromium black powder, Jiangsu Zhengxin New pigment GmbH, Phthalocyanin blue BGS, and Nantong war new material science and technology Co., Ltd pigment Red GL.
In some specific embodiments: the anti-settling agent in the step (3) is one or more of Japanese Disparlon6900-HV polyamide wax, Degussa fumed silica R972 and Changzhou Roro chemical polyethylene wax slurry 201P anti-settling agent.
In some specific embodiments: the leveling agent in the step (3) is one or more of Digao 300, BYK-300 and BYK-331.
In some specific embodiments: the defoaming agent in the step (3) is one or more of BYK-066N, BYK141 and D.E. 3500.
In some specific embodiments: in the step (4), the elastic curing agent is one or two of Polydand E402-90T and Polydand E405-80T.
The invention has the beneficial effects that:
(1) the use of Asahi nitroxide LF-200 fluorocarbon resin as the main film-forming substance can make the paint film have ultrahigh weather resistance.
(2) The choline chloride/alcohol eutectic solvent has the characteristics of solvent property, catalyst, degradation and the like, the raw materials are easy to obtain and low in cost, the nano titanium dioxide is modified, the nano particles are dispersed more uniformly and have better stability, and pollution and resource waste are avoided in the whole process.
(3) The choline chloride/alcohol eutectic solvent modified nano titanium dioxide added into the fluorocarbon coating can enable a paint film to have stronger photocatalytic property, reduce the contact angle of the paint film, improve the hydrophilicity of the paint film, improve the self-cleaning effect of the fluorocarbon coating, and does not influence the ultrahigh weather resistance of the fluorocarbon coating.
Detailed Description
The invention is further illustrated by the following examples, without limiting the scope of the invention:
example 1
Weighing 1 mol of choline chloride and 2 mol of glycerol, adding into a sealed container, and stirring at 80 ℃ for 20min until reaction liquid is transparent, thereby obtaining a eutectic solvent; weighing nano-scale titanium dioxide which accounts for 20% of the mass of the eutectic solvent, adding the nano-scale titanium dioxide into a container, fully stirring, heating to 50 ℃, preserving heat for 0.5h, reacting until the nano-scale titanium dioxide is uniformly dispersed to obtain a self-made modified nano-scale titanium dioxide liquid, namely a low-surface-energy filler, and cooling to room temperature for later use;
weighing 35 parts of Asahi glass LF200 fluorocarbon resin and 9 parts of dimethylbenzene by mass, uniformly stirring, sequentially adding 0.5 part of BYK-2025 dispersing agent, 30 parts of DuPont R960 titanium dioxide and 0.5 part of Desogosace R972 anti-settling agent under a stirring state, uniformly mixing, and grinding the slurry in a grinder until the fineness is less than 20 mu m; namely LF200 fluorocarbon finish white slurry, and is taken out for later use.
Weighing 40 parts of LF200 fluorocarbon finish white slurry by mass, adding 47 parts of Asahi nitroxide LF200 fluorocarbon resin, 0.3 part of Japan Disparlon6900-HV polyamide wax, 0.1 part of BYK-331 leveling agent, 0.3 part of BYK-066N defoaming agent, 5 parts of low surface energy filler (example 1) and 3 parts of dimethylbenzene, uniformly stirring at high speed, filtering and packaging to obtain the component A.
Weighing 55 parts of German Bayer N3390 aliphatic polyisocyanate, 15 parts of Polynaiad E405-80T and 20 parts of butyl acetate by mass, uniformly stirring at high speed, filtering and packaging to obtain the component B.
Weighing 10 parts of component A and 1 part of component B by mass, uniformly mixing, adding a high-energy diluent for diluting to spraying viscosity, spraying by using air, and testing the mechanical property, the chemical resistance, the industrial weather aging resistance and other properties according to the standard requirements of Q/CR (railway bridge steel structure and member protective coating and paint), and testing the contamination resistance according to the standard requirements of GB/T9780-2013 (Experimental method for contamination resistance of building coating).
Example 2
Weighing 1 mol of choline chloride and 2 mol of ethylene glycol, adding into a sealed container, and stirring at 80 ℃ for 20min until reaction liquid is transparent, thereby obtaining a eutectic solvent; weighing nano-scale titanium dioxide accounting for 30% of the mass of the eutectic solvent, adding the nano-scale titanium dioxide into a container, fully stirring, heating to 65 ℃, preserving heat for 0.5h, reacting until the nano-scale titanium dioxide is uniformly dispersed to obtain a self-made modified nano-scale titanium dioxide liquid, namely a low-surface-energy filler, and cooling to room temperature for later use;
weighing 40 parts of Asahi glass LF200 fluorocarbon resin and 10 parts of dimethylbenzene by mass, uniformly stirring, sequentially adding 0.3 part of Digao 670 dispersant, 40 parts of DuPont R960 titanium dioxide and 0.3 part of Degussa R972 anti-settling agent under the stirring state, uniformly mixing, and grinding the slurry in a grinder until the fineness is less than 20 mu m; namely LF200 fluorocarbon finish white slurry, and is taken out for later use.
Weighing 50 parts of LF200 fluorocarbon finish white slurry by mass, adding 45 parts of Asahi nitroxide LF200 fluorocarbon resin, 0.5 part of Japan Disparlon6900-HV polyamide wax, 0.3 part of BYK-300 flatting agent, 0.1 part of BYK141 defoaming agent, 4 parts of low surface energy filler (example 2) and 4 parts of dimethylbenzene, uniformly stirring at high speed, filtering and packaging to obtain the component A.
Weighing 60 parts of German Bayer N3390 aliphatic polyisocyanate, 20 parts of Polynaide E402-90T and 25 parts of butyl acetate by mass, uniformly stirring at high speed, filtering and packaging to obtain the component B.
Weighing 10 parts of component A and 1 part of component B by mass, uniformly mixing, adding a high-energy diluent for diluting to spraying viscosity, spraying by using air, and testing the mechanical property, the chemical resistance, the industrial weather aging resistance and other properties according to the standard requirements of Q/CR (railway bridge steel structure and member protective coating and paint), and testing the contamination resistance according to the standard requirements of GB/T9780-2013 (Experimental method for contamination resistance of building coating).
Example 3
Weighing 1 mol of choline chloride and 6 mol of ethanol, adding into a sealed container, and stirring at 50 ℃ for 10min until reaction liquid is transparent, thereby obtaining a eutectic solvent; weighing nano-scale titanium dioxide accounting for 50% of the mass of the eutectic solvent, adding the nano-scale titanium dioxide into a container, fully stirring, heating to 80 ℃, preserving heat for 0.5h, reacting until the nano-scale titanium dioxide is uniformly dispersed to obtain a self-made modified nano-scale titanium dioxide liquid, namely a low-surface-energy filler, and cooling to room temperature for later use;
weighing 45 parts of Asahi glass LF200 fluorocarbon resin and 12 parts of dimethylbenzene by mass, uniformly stirring, sequentially adding 0.8 part of BYK-180 dispersing agent, 50 parts of DuPont R960 titanium dioxide and 0.8 part of Desogosace R972 anti-settling agent under a stirring state, then increasing the rotating speed for stirring, and feeding the slurry into a grinder for grinding until the fineness is less than 20 mu m; namely LF200 fluorocarbon finish white slurry, and is taken out for later use.
Weighing 43 parts of LF200 fluorocarbon finish white slurry by mass, adding 40 parts of Asahi glass LF200 fluorocarbon resin, 0.8 part of Japan Disparlon6900-HV polyamide wax, 0.5 part of Digao 300 leveling agent, 0.5 part of moderate 3500 defoaming agent, 2 parts of low surface energy filler (example 3) and 7 parts of xylene, stirring uniformly at high speed, filtering and packaging to obtain the component A.
Weighing 65 parts of German Bayer N3390 aliphatic polyisocyanate, 25 parts of Polynaide E405-80T and 30 parts of butyl acetate by mass, uniformly stirring at high speed, filtering and packaging to obtain the component B.
Weighing 10 parts of component A and 1 part of component B by mass, uniformly mixing, adding a high-energy diluent for diluting to spraying viscosity, using air for spraying, and testing the mechanical property, the chemical resistance, the industrial climate aging resistance and other properties according to the standard requirements of Q/CR & lt & gt railway bridge steel structure and member protection coating and paint & gt, and testing the stain resistance according to the standard requirements of GB/T9780 plus 2013 & lt & gt experimental method for stain resistance of building coating coatings & gt.
Comparative example 1
The conditions were otherwise the same as in example 1 except that no low surface energy filler was added to component A.
Comparative example 2
The conditions were otherwise the same as in example 2 except that the low surface energy filler in component A was replaced with mechanically dispersed nano-titanium dioxide.
TABLE 1 Properties of examples and comparative examples
From the data results of table 1, it can be seen that:
(1) in comparative example 1, namely, the choline chloride/alcohol eutectic solvent modified nano titanium dioxide solution is not added, the contamination resistance grade is 3 grade after the nano titanium dioxide solution is exposed to the sun for 1a, and obvious color difference exists; while the nano titanium dioxide is added in the comparative example 2, although the stain resistance of the paint film after being exposed to 1a is 2 grades, and the paint film has obvious color difference, the glossiness is lower than that of the comparative example 1.
(2) The nano titanium dioxide solution modified by different choline chloride/alcohol eutectic solvents is added in the embodiments 1, 2 and 3, the stain resistance grade of the paint film is 0 grade after the paint film is exposed to the sun for 1a, no color difference is perceptible, and the gloss of the paint film is not affected; and other properties are not influenced, and the color change, the light loss and the chalking of a paint film are less than or equal to 1 grade after the paint film resists artificial accelerated aging (QUV. B light source) for 6000 hours; and has no bubbling, falling off and cracking; the light-retaining rate is higher than 80%, and the coating has the characteristics of long-acting self-cleaning property, high weather resistance and the like.
Finally, it should be noted that the above-mentioned embodiments are only preferred embodiments and comparative examples, and are not intended to limit the present invention, and although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that modifications and equivalents can be made in the technical solutions described in the foregoing embodiments, or some technical features thereof can be replaced. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A preparation method of a long-acting self-cleaning high-weatherability fluorocarbon coating is characterized by comprising the following steps: the method comprises the following five steps:
(1) preparation of eutectic solvent: adding the two raw materials into a sealed container, and stirring at 50-90 ℃ until the reaction liquid is transparent to obtain a eutectic solvent;
wherein: the two raw materials in the step (1) are specifically: the first raw material is choline chloride, and the second raw material is one or more of glycerol, ethylene glycol or ethanol;
(2) preparing a self-made modified nano titanium dioxide solution: adding nano titanium dioxide into the eutectic solvent obtained in the step (1), fully stirring, heating to 50-100 ℃, keeping the temperature for 0.1-1 h until the nano titanium dioxide is uniformly dispersed to obtain a modified nano titanium dioxide solution, namely a low-surface-energy filler, and cooling to room temperature for later use;
(3) preparation of the component A:
the first step is as follows: uniformly mixing 30-50 parts of fluorocarbon resin and 2-15 parts of dimethylbenzene, sequentially adding 0.1-1 part of dispersing agent, 8-50 parts of pigment and 0.1-1 part of anti-settling agent in a stirring state, uniformly mixing, and grinding the slurry to the fineness of less than 20 mu m to obtain fluorocarbon finish paint color paste for later use;
the second step is that: weighing 10-50 parts of fluorocarbon finish paint color paste, adding 10-50 parts of fluorocarbon resin, 0.1-1 part of anti-settling agent, 0.1-1 part of flatting agent, 0.1-0.5 part of defoaming agent, 1-5 parts of low-surface-energy filler and 2-10 parts of dimethylbenzene into the partial paste, uniformly stirring, and filtering and packaging to obtain the component A.
(4) Preparation of the component B: and (3) uniformly mixing 40-70 parts of isocyanate curing agent, 10-30 parts of elastic curing agent and 10-30 parts of butyl acetate, filtering and packaging to obtain the component B.
(5) Preparation of a paint film: the components A are as follows by mass ratio: component B is (100): (6.5-12.5), adding a high-energy diluent for dilution, and performing spraying construction to obtain the long-acting self-cleaning high-weather-resistance fluorocarbon coating film.
2. The preparation method of the long-acting self-cleaning high-weatherability fluorocarbon coating according to claim 1, characterized in that: in the first step of the component A: the fluorocarbon resin, the dimethylbenzene, the dispersing agent, the pigment and the anti-settling agent are respectively 35-45 parts, 8-12 parts, 0.3-0.8 part, 10-50 parts and 0.3-0.8 part by weight;
in the second step: the fluorocarbon finishing paint color paste, the fluorocarbon resin, the anti-settling agent, the flatting agent, the defoaming agent, the low-surface-energy filler and the xylene are respectively 30-50 parts, 40-50 parts, 0.3-0.8 part, 0.1-0.5 part, 1-5 parts and 2-10 parts by weight.
The isocyanate curing agent, the elastic curing agent and the butyl acetate in the component B are respectively 55-65 parts, 15-25 parts and 20-30 parts by weight.
3. The preparation method of the long-acting self-cleaning high-weatherability fluorocarbon coating according to claim 1, wherein the molar ratio of the first raw material to the second raw material in the step (1) is 1: 0.5 to 10; preferably: the molar ratio of the first raw material to the second raw material is 1: 2 to 6.
4. The preparation method of the long-acting self-cleaning high-weatherability fluorocarbon coating according to claim 1, characterized in that the mass percentage of the nano titanium dioxide in the step (2) to the eutectic solvent in the step (1) is 10-50%; preferably: in the step (2), the mass percent of the nano titanium dioxide in the eutectic solvent in the step (1) is 20-50%.
5. The preparation method of the long-acting self-cleaning high weather resistance fluorocarbon coating as claimed in claim 1, wherein in the first step of step (3), the dispersant is one or more of BYK-2025, BYK-180, Digao 670 and Digao 671;
the pigment in the first step of the step (3) is one or more of DuPont R960 titanium dioxide, Hunan Megaku science and technology Limited JF-B2852 copper chromium black powder, Jiangsu Zhengxin New pigment GmbH Phthalocyanin blue BGS, and Nantong war new material science and technology Limited pigment red GL.
6. The preparation method of the long-acting self-cleaning high weather resistance fluorocarbon coating as claimed in claim 1, wherein the anti-settling agent in the first and second steps of step (3) is one or more of japanese Tetris Disparlon6900-HV polyamide wax, Degussa fumed silica R972, and polyethylene wax 201P of Chang Zhong Rong chemical New materials Ltd;
and (3) in the second step, the flatting agent is one or more of Digao 300, BYK-300 and BYK-331.
7. The preparation method of the long-acting self-cleaning high-weatherability fluorocarbon coating according to claim 1, wherein the antifoaming agent in step (3) is one or more of BYK-066N, BYK141 and modesty 3500.
8. The preparation method of the long-acting self-cleaning high-weatherability fluorocarbon coating according to claim 1, wherein the elastic curing agent in step (4) is one or two of PolyId E402-90T and PolyId E405-80T.
9. A long-acting self-cleaning high-weatherability fluorocarbon coating is characterized in that: the fluorocarbon coating is prepared by the following method:
(1) preparation of eutectic solvent: adding the two raw materials into a sealed container, and stirring at 50-90 ℃ until the reaction liquid is transparent to obtain a eutectic solvent;
wherein: the two raw materials in the step (1) are specifically: the first raw material is choline chloride, and the second raw material is one or more of glycerol, ethylene glycol or ethanol;
(2) preparing a self-made modified nano titanium dioxide solution: adding nano titanium dioxide into the eutectic solvent obtained in the step (1), fully stirring, heating to 50-100 ℃, keeping the temperature for 0.1-1 h until the nano titanium dioxide is uniformly dispersed to obtain a modified nano titanium dioxide solution, namely a low-surface-energy filler, and cooling to room temperature for later use;
(3) preparation of the component A:
the first step is as follows: uniformly mixing 30-50 parts of fluorocarbon resin and 2-15 parts of dimethylbenzene, sequentially adding 0.1-1 part of dispersing agent, 8-50 parts of pigment and 0.1-1 part of anti-settling agent in a stirring state, uniformly mixing, and grinding the slurry to the fineness of less than 20 mu m to obtain fluorocarbon finish paint color paste for later use;
the second step is that: weighing 10-50 parts of fluorocarbon finish paint color paste, adding 10-50 parts of fluorocarbon resin, 0.1-1 part of anti-settling agent, 0.1-1 part of flatting agent, 0.1-0.5 part of defoaming agent, 1-5 parts of low-surface-energy filler and 2-10 parts of dimethylbenzene into the partial paste, uniformly stirring, and filtering and packaging to obtain the component A.
(4) Preparation of the component B: and (3) uniformly mixing 40-70 parts of isocyanate curing agent, 10-30 parts of elastic curing agent and 10-30 parts of butyl acetate, filtering and packaging to obtain the component B.
(5) Preparation of a paint film: the components A are as follows by mass ratio: component B is (100): (6.5-12.5), adding a high-energy diluent for dilution, and performing spraying construction to obtain the long-acting self-cleaning high-weather-resistance fluorocarbon coating film.
10. The long-acting self-cleaning highly weatherable fluorocarbon coating of claim 9, wherein: in the first step of the component A: the fluorocarbon resin, the dimethylbenzene, the dispersing agent, the pigment and the anti-settling agent are respectively 35-45 parts, 8-12 parts, 0.3-0.8 part, 10-50 parts and 0.3-0.8 part by weight;
in the second step: the fluorocarbon finishing paint color paste, the fluorocarbon resin, the anti-settling agent, the flatting agent, the defoaming agent, the low-surface-energy filler and the xylene are respectively 30-50 parts, 40-50 parts, 0.3-0.8 part, 0.1-0.5 part, 1-5 parts and 2-10 parts by weight.
The isocyanate curing agent, the elastic curing agent and the butyl acetate in the component B are respectively 55-65 parts, 15-25 parts and 20-30 parts by weight;
preferably: the mol ratio of the first raw material to the second raw material in the step (1) is 1: 0.5 to 10; further preferably: the molar ratio of the first raw material to the second raw material is 1: 2-6;
preferably: in the step (2), the mass percent of the nano titanium dioxide in the eutectic solvent in the step (1) is 10-50%; further preferably: in the step (2), the mass percent of the nano titanium dioxide in the eutectic solvent in the step (1) is 20-50%;
preferably: in the first step of the step (3), the dispersant is one or more of BYK-2025, BYK-180, Digao 670 and Digao 671;
the pigment in the first step of the step (3) is one or more of DuPont R960 titanium dioxide, Hunan Megaku science and technology Limited JF-B2852 copper chromium black powder, Jiangsu Zhengxin New pigment GmbH Phthalocyanin blue BGS, and Nantong war new material science and technology Limited pigment red GL;
preferably: the anti-settling agent in the first step and the second step of the step (3) is one or more of Japanese Disparlon6900-HV polyamide wax, Degussa fumed silica R972, and polyethylene wax 201P of Changzhou Roro chemical new material company Limited;
the leveling agent in the second step of the step (3) is one or more of Digao 300, BYK-300 and BYK-331;
preferably: the defoaming agent in the step (3) is one or more of BYK-066N, BYK141 and a D.E. 3500;
preferably: in the step (4), the elastic curing agent is one or two of Polydand E402-90T and Polydand E405-80T.
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