CN116200114A - Super-hydrophobic self-cleaning thermochromic multifunctional coating as well as preparation and application thereof - Google Patents
Super-hydrophobic self-cleaning thermochromic multifunctional coating as well as preparation and application thereof Download PDFInfo
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- CN116200114A CN116200114A CN202310123558.8A CN202310123558A CN116200114A CN 116200114 A CN116200114 A CN 116200114A CN 202310123558 A CN202310123558 A CN 202310123558A CN 116200114 A CN116200114 A CN 116200114A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 20
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 17
- 239000002904 solvent Substances 0.000 claims abstract description 17
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- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000000758 substrate Substances 0.000 claims abstract description 12
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- 239000011521 glass Substances 0.000 claims description 21
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- 238000000034 method Methods 0.000 claims description 8
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- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical group O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 5
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 4
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- 229910052618 mica group Inorganic materials 0.000 claims description 4
- 239000010453 quartz Substances 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 2
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 claims description 2
- -1 aliphatic isocyanate Chemical class 0.000 claims description 2
- 239000012948 isocyanate Substances 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
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- 239000002103 nanocoating Substances 0.000 claims 2
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- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims 1
- 238000002845 discoloration Methods 0.000 abstract 1
- 239000000463 material Substances 0.000 description 41
- 230000008859 change Effects 0.000 description 22
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 16
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- 238000005507 spraying Methods 0.000 description 5
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 4
- 230000003373 anti-fouling effect Effects 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- MCPLVIGCWWTHFH-UHFFFAOYSA-L methyl blue Chemical compound [Na+].[Na+].C1=CC(S(=O)(=O)[O-])=CC=C1NC1=CC=C(C(=C2C=CC(C=C2)=[NH+]C=2C=CC(=CC=2)S([O-])(=O)=O)C=2C=CC(NC=3C=CC(=CC=3)S([O-])(=O)=O)=CC=2)C=C1 MCPLVIGCWWTHFH-UHFFFAOYSA-L 0.000 description 4
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- 239000000377 silicon dioxide Substances 0.000 description 4
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- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
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Images
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/26—Thermosensitive paints
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/65—Additives macromolecular
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/70—Additives characterised by shape, e.g. fibres, flakes or microspheres
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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Abstract
The invention discloses a super-hydrophobic self-cleaning thermochromic multifunctional paint and preparation and application thereof, wherein the preparation method of the paint comprises the following steps: dispersing 15-25 parts of hydroxy acrylic resin and 2-3 parts of fluorocarbon resin in 20-30 parts of solvent A, adding 6-15 parts of filler and 0.5-1 part of chain extender, stirring and reacting for 0.5-2 hours, and aging for 12-24 hours to obtain modified resin dispersion; adding 3-8 parts of super-hydrophobic nano particles into 40-50 parts of solvent B, adding 1-4 parts of silane coupling agent, and uniformly mixing to obtain super-hydrophobic dispersion liquid; mixing the modified resin dispersion liquid with the super-hydrophobic dispersion liquid, and adding 1-3 parts of thermochromic powder to uniformly mix to obtain the modified resin dispersion liquid. After the curing agent is added into the coating, the coating obtained by coating the coating on the surface of the substrate not only can realize reversible and irreversible discoloration under temperature sensing, but also has excellent superhydrophobic self-cleaning performance, has a contact angle of more than 150 degrees, and has important application value and significance in electrical and mechanical equipment.
Description
Technical Field
The invention belongs to the technical field of functional coatings, and particularly relates to a super-hydrophobic self-cleaning thermochromic multifunctional coating, and preparation and application thereof.
Background
Generally, a superhydrophobic material surface is defined as a superhydrophobic surface when a static contact angle between the superhydrophobic material surface and water is greater than 150 ° and a rolling angle is less than 10 °, and lotus leaves are the earliest superhydrophobic material found by human in nature, so the superhydrophobic effect is also called a "lotus leaf effect". Surface wettability is an important factor affecting the superhydrophobic properties of an object surface. According to the wettability theory, two key requirements for preparing the super-hydrophobic coating are that the surface of the material has the roughness of a micro/nano structure and low surface energy. The current methods for preparing superhydrophobic coatings can be broadly divided into two types: (1) Constructing a rough surface of a micro/nano structure on the surface of a base material, then adopting a low-surface-energy substance to modify to obtain a super-hydrophobic coating, and (2) modifying a low-surface-energy material on the surface of the base material, and then constructing a rough surface of the micro/nano structure on the low-surface-energy material to obtain the super-hydrophobic coating. At present, the super-hydrophobic material has been widely focused, and has wide application in the aspects of chemical industry, food, medical treatment, ships and the like because the super-hydrophobic material has the characteristics of excellent antifouling property, corrosion resistance, adhesion resistance, self-cleaning property, resistance reduction and the like.
Heat is often associated with the long-term operation of electrical equipment. When heat is accumulated to a certain degree, safety accidents are easy to occur, so that temperature detection is an important part of equipment inspection. Compared with the traditional temperature measuring modes such as infrared, thermocouple, optical fiber and the like, the thermochromic material can directly display the temperature change of the object surface through the change of color, and has the advantages of quick color change, low cost, intuitiveness and rapidness. Therefore, nutrition of thermochromic materials in an electric power system is gradually paid attention to at home and abroad.
The thermochromic material can reflect the change of the temperature of the equipment in real time, and the super-hydrophobic material can promote the self-cleaning effect of the surface of the equipment and prevent the surface from being corroded due to long-term humidity, so that the combination of super-hydrophobic and thermochromic is expected to realize the combination of overheat detection and insulation protection of the power equipment, and has important value and significance for the operation safety management of the power equipment.
Disclosure of Invention
The super-hydrophobic material can show super-strong hydrophobic performance, on one hand, due to the fact that substances with low surface free energy exist in the material, water drops can easily roll off on the surface of the material; on the other hand, due to the construction of the mastoid micro-nano coarse structure, air is trapped between the water drops and the solid surface, so that the solid-liquid contact surface is reduced. The two functions can be combined to endow the surface of the super-hydrophobic material with functions of antifouling, self-cleaning, ice coating prevention, corrosion prevention and the like.
The thermochromic material can repeatedly change color when the ambient temperature changes, and has environmental responsiveness. Thermochromic pigments are prepared from electron-transfer organic compound systems. Electron transfer organic compounds are a class of organic chromophoric systems with specific chemical structures. The principle is that when the specific temperature is reached, the molecular structure of the organic matter is changed due to electron transfer, so that the color conversion is realized. When the temperature-variable pigment changes color, the color change can be rapidly and sensitively displayed in a short time. The color contrast before and after color change is clear and easy to identify. Because of the advantages of free color change, reversible color change, sensitive color change and the like, the thermochromic material is widely applied to various fields such as temperature indicating materials, anti-counterfeiting marks, mechanical equipment and the like. The temperature-changing material has wide application, but can only realize the single function of thermochromic after all, and if the super-hydrophobic function can be endowed to the temperature-changing material to prepare the temperature-thermochromic super-hydrophobic composite functional material, the multifunctional composite coating with the self-cleaning function and the thermochromic function can be realized.
In view of the above, the invention aims to provide a super-hydrophobic self-cleaning thermochromic multifunctional coating, which is prepared by mixing a solvent, resin, super-hydrophobic nano particles, a filler, a chain extender, a curing agent, a silane coupling agent and thermochromic powder. The high-performance high-temperature self-cleaning agent has the advantages of quick reversible thermochromic response, good self-cleaning effect, good mechanical strength, friction resistance, acid and alkali corrosion resistance, and can be applied to various aspects of electrical and mechanical equipment surfaces, wall waterproofing, indoor temperature characterization and the like. The preparation method is simple, easy to operate, low in cost, capable of realizing mass preparation and suitable for popularization and application.
The technical scheme of the invention is as follows:
the invention provides a super-hydrophobic self-cleaning thermochromic multifunctional coating, which comprises, by weight, 15-25 parts of hydroxy acrylic resin, 2-3 parts of fluorocarbon resin, 20-30 parts of solvent A, 6-15 parts of filler, 0.5-1 part of chain extender, 3-8 parts of super-hydrophobic nano particles, 40-50 parts of solvent B, 1-4 parts of silane coupling agent and 1-3 parts of thermochromic powder per 100 parts of coating; and the preparation process comprises the following steps:
dispersing 15-25 parts of hydroxy acrylic resin and 2-3 parts of fluorocarbon resin in 20-30 parts of solvent A, adding 6-15 parts of filler and 0.5-1 part of chain extender, stirring and reacting for 0.5-2 hours, and aging for 12-24 hours to obtain modified resin dispersion;
adding 3-8 parts of super-hydrophobic nano particles into 45-50 parts of solvent B, adding 1-4 parts of silane coupling agent, and uniformly mixing to obtain super-hydrophobic dispersion liquid;
mixing the modified resin dispersion liquid with the super-hydrophobic dispersion liquid, and adding 1-3 parts of thermochromic powder to uniformly mix to obtain the modified resin dispersion liquid.
In the paint, the solvent A is one or more of methyl acetate, ethyl acetate and butyl acetate.
In the paint, the filler comprises fumed silica and one or more of glass powder, mica powder, nylon powder and quartz powder, and the mass ratio of the fumed silica to the glass powder to the mica powder is (1-2) to 1; wherein the particle size of the glass powder, the mica powder, the nylon powder and the quartz powder is 25-30 microns.
In the coating, the chain extender is one or more of trimethylolpropane, diglycol, triethylene glycol, polyethylene glycol and glycerol.
In the coating, the super-hydrophobic nano particles are super-hydrophobic nano silicon dioxide, and the solvent B is methanol or ethanol; the preparation method of the super-hydrophobic nano silicon dioxide comprises the following steps: adding a catalyst and TEOS into the solvent B for reaction, and aging to obtain SiO 2 Evaporating the solvent to dryness to obtain the nano dispersion; wherein the volume ratio of the solvent B to the Tetraethoxysilane (TEOS) is 100:15-25, the catalyst is sodium hydroxide aqueous solution or ammonia water, and when the mass concentration of the ammonia water is 25-29% or the concentration of the sodium hydroxide aqueous solution is 1-2 mol/L, the volume ratio of the TEOS to the catalyst is 20:3-5; reaction of TEOS in alcohol solvent and catalyst at normal temperatureThe reaction time is 10-12 h, and the aging time is 100-120 h.
In the coating, the silane coupling agent is one or more of KH550, KH560, KH570 and KH 792.
In the coating, the thermochromic powder comprises reversible thermochromic powder at 31-80 ℃ and/or irreversible thermochromic powder at more than 80 ℃.
The invention also provides application of the super-hydrophobic self-cleaning thermochromic multifunctional paint in preparing an indicating and self-cleaning composite functional coating with temperature response, which comprises the following specific steps: and adding a curing agent into the coating, uniformly stirring, then coating the coating on a substrate, and drying to obtain the coating. It is understood that the coating may be by spraying, dipping, brushing, etc.
In the above application, the curing agent is hexamethylene diisocyanate or aliphatic isocyanate, and the molar ratio of the curing agent to the hydroxyl groups of the hydroxyl acrylic resin in the coating is 1: (0.9-1). According to the different usage amounts of the curing agents, the construction time after the curing agents are added is more than 30 minutes.
Compared with the prior art, the invention has the beneficial effects that:
(1) The invention provides a super-hydrophobic self-cleaning thermochromic multifunctional coating material, which not only can improve the mechanical and other physical properties of thermochromic coating, but also can endow the coating with super-hydrophobic properties, so that the coating has a self-cleaning antifouling function, and the application field and range of the thermochromic material are greatly expanded;
(2) The preparation method adopts a one-pot method to prepare the super-hydrophobic thermochromic coating, and adopts single-layer coating, so that the preparation process is simple, the reaction is mild, the operation is convenient, and the preparation can be carried out in large quantities;
(3) The super-hydrophobic thermochromic coating prepared by the invention can be applied to the surfaces of electrical and mechanical equipment and the like, can not only warn the temperature of key parts in the running process of the equipment, but also endow the surface of the equipment with self-cleaning and antifouling functions, thereby reducing the occurrence of accidents and prolonging the service life of the equipment.
Drawings
FIG. 1 is an SEM image of a superhydrophobic thermochromic coating coated on a glass surface prepared in example 1 of the present invention;
FIG. 2 is a graph showing the color change of the super-hydrophobic thermochromic coating coated on the surfaces of glass and aluminum materials prepared in example 1 of the present invention;
FIG. 3 is a photograph of the surface contact angle of the superhydrophobic thermochromic coating coated on the surfaces of glass and aluminum materials prepared in example 1 of the present invention;
FIG. 4 is a graph showing the color change of the super-hydrophobic thermochromic coating coated on the surfaces of glass and aluminum materials prepared in example 2 of the present invention;
FIG. 5 is a photograph of the surface contact angle of the super-hydrophobic thermochromic coating coated on the surfaces of glass and aluminum materials prepared in example 2 of the present invention;
FIG. 6 is a graph showing the color change of the super-hydrophobic thermochromic coating coated on the surfaces of glass and aluminum materials prepared in example 3 of the present invention;
FIG. 7 is a photograph of the surface contact angle of the super-hydrophobic thermochromic coating coated on the surfaces of glass and aluminum materials prepared in example 3 of the present invention;
FIG. 8 is a graph showing the color change of the super-hydrophobic thermochromic coating coated on the surfaces of glass and aluminum materials prepared in example 4 of the present invention;
FIG. 9 is a photograph of the surface contact angle of the superhydrophobic thermochromic coating coated on the surfaces of glass and aluminum materials prepared in example 4 of the present invention.
Detailed Description
For a better understanding of the present invention, the following description will further illustrate the present invention with reference to specific examples, but the present invention is not limited to the following examples.
In the following examples, unless otherwise specified, the methods are conventional; the reagents and materials described, unless otherwise specified, are commercially available.
Example 1
The example provides a super-hydrophobic thermochromic composite functional paint and coating capable of changing color at 31 ℃, and the preparation method comprises the following steps:
1) 45g of hydroxy acrylic resin is added into 45g of butyl acetate under the magnetic stirring condition, 5g of fluorocarbon resin is slowly added after stirring for 5min, and stirring is continued for 1h, so as to obtain the fluorocarbon resin modified hydroxy acrylic resin.
2) 10g of fumed silica and 15g of nylon powder are added into the mixed solution obtained in the step 1) under the magnetic stirring condition, 1.5g of polyethylene glycol 400 is slowly added, and the mixture is aged for 24 hours after stirring reaction for 1 hour.
3) While stirring, 8g of superhydrophobic silica was added to 79g of ethanol solution, and 1.5mL of KH550 solution (KH 550: etOH: h 2 O=40:60:10), for 30min, to obtain a super-hydrophobic dispersion.
4) Adding the super-hydrophobic dispersion liquid obtained in the step 3) into the modified resin dispersion liquid obtained in the step 2), and stirring for 20min.
5) To the dispersion obtained in step 4), 2g of a thermochromic powder (black/yellow) at 31℃was added, and uniformly dispersed in the mixed solution obtained in step 4) under magnetic stirring.
6) Adding 50 mu L of hexamethylene diisocyanate into the coating system obtained in the step 5), continuously stirring for 10min, and respectively spraying the obtained material on a glass substrate and an aluminum substrate to obtain the thermochromic super-hydrophobic coating at 31 ℃.
The morphology of the sample is shown in fig. 1 by using a Scanning Electron Microscope (SEM), and the surface of the sample has a rough structure, which is helpful for realizing super-hydrophobic performance. The prepared coating sample rises along with the ambient temperature, the optical digital photos before and after color change at about 31 ℃ are shown in fig. 2, wherein the coating is black (a) at room temperature, turns yellow (b) at the temperature above 31 ℃, and can be recovered to black after being transferred to the room temperature; the water drops dyed by the methyl blue can be well standing on the surface of the coating before and after color change, and show good hydrophobic performance. The contact angle pictures of water and the coating obtained in the embodiment are shown in fig. 3, and the contact angles of water on the surfaces of the coatings coated on the glass substrate (left) and the aluminum material (right) reach 156.6 degrees and 162.5 degrees, which shows that the prepared film has superhydrophobic performance.
Example 2
The example provides a super-hydrophobic thermochromic composite functional paint and coating capable of changing color at 45 ℃, and the preparation method comprises the following steps:
1) Under the magnetic stirring condition, 45g of hydroxy acrylic resin is added into 45g of butyl acetate, 5g of fluorocarbon resin is slowly added after stirring for 5min, and stirring is continued for 1h, so as to obtain fluorocarbon resin modified hydroxy acrylic resin;
2) Adding 15g of fumed silica and 10g of nylon powder into the mixed solution obtained in the step 1) under the magnetic stirring condition, slowly adding 2.5g of polyethylene glycol 400, stirring and reacting for 1h, and aging for 24h;
3) 10g of super-hydrophobic silica was added to 79g of ethanol solution with stirring, and 1.5mL of KH550 solution (KH 550: etOH: h 2 O=40:60:10), for 30min, to obtain a super-hydrophobic dispersion.
4) Adding the super-hydrophobic dispersion liquid obtained in the step 3) into the modified resin dispersion liquid obtained in the step 2), and stirring for 20min.
5) 2g of thermochromic powder (black/red) at 45 ℃ is added into the mixed solution obtained in the step 4), and the thermochromic powder is uniformly dispersed in the mixed solution in the step 4) under the magnetic stirring state.
6) Adding 50 mu L of hexamethylene diisocyanate into the coating system obtained in the step 5), stirring for 10min, and respectively spraying the obtained material liquid on glass and an aluminum substrate to obtain the 45 ℃ thermochromic super-hydrophobic coating.
The prepared coating sample increases with the ambient temperature, and the optical digital photos before and after color change at about 45 ℃ are shown in fig. 4: wherein the coating layer is brown (a) at room temperature, turns to light red (b) at the temperature of more than 45 ℃, and can be recovered to brown after being transferred to room temperature; the water drops dyed by the methyl blue can be well standing on the surface of the coating before and after color change, and show good hydrophobic performance. The contact angle pictures of water and the coating obtained in the embodiment are shown in fig. 5, and the contact angles of water on the surfaces of the coatings coated on the glass substrate (left) and the aluminum material (right) reach 156.6 degrees and 162.5 degrees, which shows that the prepared film has superhydrophobic performance.
Example 3
The example provides a super-hydrophobic thermochromic composite functional paint and coating capable of changing color at 65 ℃, and the preparation method comprises the following steps:
1) 45g of hydroxy acrylic resin is added into 45g of butyl acetate under the magnetic stirring condition, 5g of fluorocarbon resin is slowly added after stirring for 5min, and stirring is continued for 1h, so as to obtain the fluorocarbon resin modified hydroxy acrylic resin.
2) 15g of fumed silica and 10g of nylon powder are added into the mixed solution obtained in the step 1) under the magnetic stirring condition, 2.0mL of polyethylene glycol 400 is slowly added, and the mixture is aged for 24 hours after stirring reaction for 1 hour.
3) While stirring, 15g of superhydrophobic silica was added to 79g of ethanol solution, and 1.5mL of KH550 solution (KH 550: etOH: h 2 O=40:60:10), for 30min, to obtain a super-hydrophobic dispersion.
4) Adding the super-hydrophobic dispersion liquid obtained in the step 3) into the modified resin dispersion liquid obtained in the step 2), and stirring for 20min.
5) 2.5g of 65 ℃ thermochromic powder (green/yellow) is added into the mixed solution obtained in the step 4), and the mixture is uniformly dispersed in the mixed solution in the step 4) under the magnetic stirring state.
6) Adding 50 mu L of hexamethylene diisocyanate into the coating system obtained in the step 5), continuously stirring for 10min, and respectively spraying the obtained dispersion liquid on glass and an aluminum substrate to obtain the 65 ℃ thermochromic super-hydrophobic coating.
The prepared optical digital photo before and after the color change of the coating sample at about 65 ℃ along with the increase of the ambient temperature is shown in fig. 6: the coating is green at room temperature, turns yellow at the temperature of more than 65 ℃, and can be recovered to be green after being transferred to room temperature; the water drops dyed by the methyl blue can be well standing on the surface of the coating before and after color change, and show good hydrophobic performance. The contact angle pictures of water and the coating obtained in the embodiment are shown in fig. 7, and the contact angles of water on the surfaces of the coatings coated on the glass substrate (left) and the aluminum material (right) reach 157.7 degrees and 158.4 degrees, which shows that the prepared film has super-hydrophobic performance.
Example 4
The example provides a super-hydrophobic thermochromic composite functional paint and coating capable of changing color at 80 ℃, and the preparation method comprises the following steps:
1) Under the magnetic stirring condition, 50g of hydroxy acrylic resin is added into 53g of butyl acetate, 5g of fluorocarbon resin is slowly added after stirring for 5min, and stirring is continued for 1h, so as to obtain fluorocarbon resin modified hydroxy acrylic resin.
2) 15g of fumed silica and 10g of nylon powder are added into the mixed solution obtained in the step 1) under the magnetic stirring condition, 2.0mL of polyethylene glycol 400 is slowly added, and the mixture is aged for 24 hours after stirring reaction for 1 hour.
3) While stirring, 15g of superhydrophobic silica was added to 79g of ethanol solution, and 1.5mL of KH550 solution (KH 550: etOH: h 2 O=40: 60:10 And reacting for 30min to obtain the super-hydrophobic dispersion liquid.
4) Adding the super-hydrophobic dispersion liquid obtained in the step 3) into the modified resin dispersion liquid obtained in the step 2), and stirring for 20min.
5) Adding 2.5g of 80 ℃ thermochromic powder (blue/white) into the mixed solution obtained in the step 4), uniformly dispersing the powder in the dispersion solution in the step 4) under the magnetic stirring state, then adding 60 mu L of hexamethylene diisocyanate, continuously stirring for 10min, and respectively spraying the obtained dispersion solution on glass and an aluminum substrate to obtain the 80 ℃ thermochromic super-hydrophobic coating.
The prepared coating sample increases with the ambient temperature, and the optical digital photos before and after color change at about 80 ℃ are shown in fig. 8: the coating appears blue at room temperature, turns white at 80 ℃ or above, and remains white at room temperature after cooling below 80 ℃; the water drops dyed by the methyl blue can be well standing on the surface of the coating before and after color change, and show good hydrophobic performance. The contact angle pictures of water and the coating obtained in the embodiment are shown in fig. 9, and the contact angles of water on the surfaces of the coatings coated on the glass substrate (left) and the aluminum material (right) reach 159.3 degrees and 159.5 degrees, which shows that the prepared film has super-hydrophobic performance.
The raw materials listed in the present invention, the upper and lower limits and interval values of the raw materials, and the upper and lower limits and interval values of the process parameters can all realize the present invention, and examples are not listed here.
The invention takes hydroxy acrylic resin as a main raw material, adopts fluorocarbon resin for fluoridation modification, and further refers to the toughness and hardness of the coating through a chain extender; according to the invention, the modified resin dispersion liquid and the super-hydrophobic dispersion liquid are prepared respectively, and can be well mixed and dissolved, and the modified resin dispersion liquid and the super-hydrophobic dispersion liquid still have excellent hydrophobic effect after being directly coated and cured into a film, so that layered coating is avoided, and the operation is simplified; according to the invention, the thermochromic powder is added into the coating system to endow the coating with thermochromic performance, and the coating system has good compatibility with the thermochromic powder.
In conclusion, the super-hydrophobic thermochromic composite functional coating and coating provided by the invention have quick reversible thermochromic response and good self-cleaning effect, can be used for surfaces of electrical and mechanical equipment and has important value.
The above examples are presented for clarity of illustration only and are not limiting of the embodiments. Other variations and modifications of the above description will be apparent to those of ordinary skill in the art, and it is not necessary or exhaustive of all embodiments, and thus all obvious variations or modifications that come within the scope of the invention are desired to be protected.
Claims (10)
1. The preparation method of the super-hydrophobic self-cleaning thermochromic multifunctional paint is characterized by comprising the following steps of:
dispersing 15-25 parts of hydroxy acrylic resin and 2-3 parts of fluorocarbon resin in 20-30 parts of solvent A, adding 6-15 parts of filler and 0.5-1 part of chain extender, stirring and reacting for 0.5-2 hours, and aging for 12-24 hours to obtain modified resin dispersion;
adding 3-8 parts of super-hydrophobic nano particles into 40-50 parts of solvent B, adding 1-4 parts of silane coupling agent, and uniformly mixing to obtain super-hydrophobic dispersion liquid;
mixing the modified resin dispersion liquid with the super-hydrophobic dispersion liquid, and adding 1-3 parts of thermochromic powder to uniformly mix to obtain the modified resin dispersion liquid.
2. The preparation method according to claim 1, wherein the solvent A is one or more of methyl acetate, ethyl acetate and butyl acetate.
3. The method of claim 1, wherein the filler comprises fumed silica and one or more of glass frit, mica powder, nylon powder, quartz powder.
4. The method according to claim 1, wherein the chain extender is one or more of trimethylolpropane, diethylene glycol, triethylene glycol, polyethylene glycol, and glycerin.
5. The preparation method according to claim 1, wherein the superhydrophobic nanoparticle is superhydrophobic nanosilica, and the solvent B is methanol or ethanol.
6. The preparation method according to claim 1, wherein the silane coupling agent is one or more of KH550, KH560, KH570, KH 792.
7. The method according to claim 1, wherein the thermochromic powder comprises a reversible thermochromic powder at 31 to 80 ℃ and/or an irreversible thermochromic powder at 80 ℃ or higher.
8. A superhydrophobic self-cleaning thermochromic multifunctional coating prepared according to any one of claims 1-7.
9. A super-hydrophobic self-cleaning thermochromic multifunctional nano-coating is characterized in that a curing agent is added into the coating according to claim 8, and the coating is coated on a substrate after being uniformly stirred.
10. The super-hydrophobic self-cleaning thermochromic multifunctional nano-coating according to claim 9, wherein the curing agent is hexamethylene diisocyanate or aliphatic isocyanate, and the molar ratio of the curing agent to hydroxyl groups of the hydroxyl acrylic resin in the coating is 1: (0.9-1).
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