CN115260899A - Hydrophobic coating and preparation method and application thereof - Google Patents

Hydrophobic coating and preparation method and application thereof Download PDF

Info

Publication number
CN115260899A
CN115260899A CN202210903607.5A CN202210903607A CN115260899A CN 115260899 A CN115260899 A CN 115260899A CN 202210903607 A CN202210903607 A CN 202210903607A CN 115260899 A CN115260899 A CN 115260899A
Authority
CN
China
Prior art keywords
hydrophobic coating
coating
hydrophobic
water
inorganic
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202210903607.5A
Other languages
Chinese (zh)
Inventor
汪英
王立莹
苏云健
姚俊红
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Midea Group Co Ltd
Guangdong Midea White Goods Technology Innovation Center Co Ltd
Original Assignee
Midea Group Co Ltd
Guangdong Midea White Goods Technology Innovation Center Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Midea Group Co Ltd, Guangdong Midea White Goods Technology Innovation Center Co Ltd filed Critical Midea Group Co Ltd
Priority to CN202210903607.5A priority Critical patent/CN115260899A/en
Publication of CN115260899A publication Critical patent/CN115260899A/en
Pending legal-status Critical Current

Links

Images

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
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
    • 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
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
    • 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
    • C09D5/18—Fireproof paints including high temperature resistant 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
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/80—Siloxanes having aromatic substituents, e.g. phenyl side groups
    • 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
    • C08K2003/2217—Oxides; Hydroxides of metals of magnesium
    • C08K2003/222—Magnesia, i.e. magnesium oxide
    • 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
    • C08K2003/2227—Oxides; Hydroxides of metals of aluminium
    • 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
    • C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
    • C08K2003/3045—Sulfates
    • 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
    • C08K3/32—Phosphorus-containing compounds
    • C08K2003/321—Phosphates
    • C08K2003/324—Alkali metal phosphate
    • 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
    • C08K3/32—Phosphorus-containing compounds
    • C08K2003/321—Phosphates
    • C08K2003/327—Aluminium phosphate
    • 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

Abstract

The invention relates to a hydrophobic coating and a preparation method and application thereof. According to the hydrophobic coating, the preparation raw materials comprise an inorganic compound, an inorganic acid ester, an organic silicon precursor, a binder, a catalyst and water, wherein the inorganic compound comprises at least one of magnesium oxide, silicon nitride, aluminum oxide, barium sulfate, zinc oxide and silicon carbide. The coating formed by the hydrophobic coating has good coating performance, and meanwhile has lasting high temperature resistance and stronger hydrophobicity. The invention also provides a preparation method and application of the hydrophobic coating.

Description

Hydrophobic coating and preparation method and application thereof
Technical Field
The invention belongs to the technical field of coatings, and particularly relates to a hydrophobic coating as well as a preparation method and application thereof.
Background
Hydrophobic materials play a very important role in both basic research and industrial applications. The surface hydrophobic modification is carried out on the material, so that the performance of the traditional material is improved, the material is endowed with new additional functions, and the material has wider application prospects in the fields of batteries, buildings and household appliances. Most of the hydrophobic materials are usually polymer materials or hydrophobic organic coatings with low surface energy. Organic materials such as polymers are inferior in thermal stability, chemical stability and durability, and when they are exposed to a high temperature environment, they are easily decomposed chemically and thermally, thereby losing hydrophobic characteristics of the materials. Therefore, the practical application of the hydrophobic material in real life is severely limited.
In the related technology, some methods for preparing the hydrophobic coating are complex in equipment and are not beneficial to large-area preparation; the coating prepared by the method has rough surface, is easy to wear and has non-lasting hydrophobicity; the maximum use temperature of the hydrophobic coating prepared by some methods is lower than 260 ℃, the temperature resistance time is short, and the hydrophobic duration time is short.
In summary, there is a need to develop a new coating material which has a good coating performance, a durable high temperature resistance and a strong hydrophobicity after forming a coating layer.
Disclosure of Invention
The present invention is directed to solving at least one of the above problems in the prior art. Therefore, the invention provides the hydrophobic coating, and the coating formed by the hydrophobic coating has good coating performance, and meanwhile has lasting high-temperature resistance and stronger hydrophobicity.
The invention also provides a preparation method of the hydrophobic coating.
The invention also provides a hydrophobic coating prepared from the hydrophobic coating.
The invention also provides a method for preparing the hydrophobic coating.
The invention also provides application of the hydrophobic coating.
The first aspect of the present invention provides a hydrophobic coating material, the raw materials for preparing the hydrophobic coating material comprise an inorganic compound, an inorganic acid ester, an organic silicon precursor, a binder, a catalyst and water, wherein the inorganic compound comprises at least one of magnesium oxide, silicon nitride, aluminum oxide, barium sulfate, zinc oxide and silicon carbide.
The technical scheme of the hydrophobic coating at least has the following beneficial effects:
in the hydrophobic coating, the preparation raw materials comprise an inorganic compound, an inorganic acid ester, an organic silicon precursor, a binder, a catalyst and water. The inorganic compound includes at least one of magnesium oxide, silicon nitride, aluminum oxide, barium sulfate, zinc oxide, and silicon carbide. Wherein, the inorganic compound has the functions of improving the thermal stability of the system, increasing the surface roughness and making the surface more hydrophobic. The function of the inorganic acid ester is to form an inorganic network structure through hydrolysis and condensation, and simultaneously provide a reaction site for the reaction of the organic silicon precursor. The function of the organosilicon precursor is to reduce the surface free energy, so that the surface of a coating formed by the coating is hydrophobic. The inorganic binder functions to increase the adhesion between the inorganic compound particles. Water acts as a solvent. The catalyst is used for catalyzing inorganic acid ester, inorganic binder and organic silicon precursor to carry out hydrolytic condensation.
According to the hydrophobic coating, under the combined action of an inorganic compound, an inorganic acid ester, an organic silicon precursor, a binder, a catalyst and water, after the coating is formed by the prepared coating, the coating has good performance, the adhesive force can reach 0 grade, and the pencil hardness can reach 9H. Meanwhile, the thermal decomposition temperature of the coating is more than 500 ℃, the water contact angle is more than or equal to 120 degrees, the coating still maintains stronger hydrophobic property after being treated at the high temperature of 250-400 ℃ for 10 hours, and the water contact angle is still more than 120 degrees.
According to some embodiments of the invention, the preparation feedstock comprises the following components in parts by weight:
inorganic compound (b): 2 to 60 portions of the mixture of the components,
inorganic acid ester: 8 to 64 portions of the mixture of the components,
organic silicon precursor: 10 to 20 portions of the raw materials are mixed,
adhesive: 1 to 30 parts of (A) and (B),
catalyst: 0.05 to 3 portions of the stabilizer,
water: 20 to 80 portions.
According to some embodiments of the invention, the preparation feedstock comprises the following components in parts by weight:
inorganic compound (b): 5 to 50 portions of the mixture of the organic acid and the organic acid,
inorganic acid ester: 10 to 55 portions of the mixture of the components,
organosilicon precursor: 12 to 18 portions of the mixture of the components,
adhesive: 5 to 30 parts of (by weight),
catalyst: 0.1 to 3 portions of the raw materials,
water: 20 to 80 portions.
The proportion of the inorganic compound, the inorganic acid ester, the organic silicon precursor, the binder, the catalyst and the water is a proper proportion, and the performance of the coating are affected when the proportion is lower than the proportion range or exceeds the proportion range.
According to some embodiments of the invention, the shape of the inorganic compound comprises at least one of a plate shape, a needle shape, a particle shape, and a whisker shape.
When the shape of the inorganic compound is compounded by more than two shapes, the coating can be more compact, and the coating performance is better.
The inorganic compounds with different shapes can promote the dispersibility of the paint system and the adhesive force of the paint. For example, the flaky compound has a smooth and flat surface, good dispersibility and can promote the adhesion of a coating, and the flaky compound has a special two-dimensional planar structure, has a small thickness-to-large diameter-thickness ratio, can reach a nanometer level in the thickness direction and a micron level in the radial direction, so that the flaky compound has double effects of nanometer powder and micron powder. The adoption of inorganic compounds with different shapes is helpful to ensure that the surface activity of the coating is moderate, the coating can be effectively combined with other active groups, and the coating is not easy to agglomerate and is convenient for effective dispersion. A coating formed by the coating has good adhesive force, obvious shielding effect and light reflection capability, and simultaneously has excellent performances of acid and alkali resistance, high temperature resistance, high hardness, high melting point, high thermal conductivity, high resistivity and the like.
According to some embodiments of the invention, the shape of the inorganic compound comprises a granular shape, the granular shape comprising spherical particles.
When the inorganic compound is compounded by more than two inorganic compounds with different particle sizes, the coating is more compact and the performance of the coating is better.
According to some embodiments of the invention, the inorganic acid ester comprises at least one of tetrabutyl titanate, dimethyl sulfate, methyl hydrogen sulfate, glyceryl trinitrate, tributyl phosphate, and ethyl orthosilicate.
According to some embodiments of the invention, the organosilicon precursor comprises at least one of methyltriethoxysilane, trimethylchlorosilane, dimethyldimethoxysilane, dodecyltrimethoxysilane, hexadecyltrimethoxysilane, methylphenyldimethoxysilane.
Different organosilicon precursors have influence on temperature resistance, and the selection of the organosilicon precursors influences the thermal stability of the system.
According to some embodiments of the invention, the binder comprises at least one of aluminum dihydrogen phosphate, aluminum phosphate, lithium silicate, aluminum silicate, sodium silicate.
According to some embodiments of the invention, the catalyst comprises at least one of sodium hydroxide, ammonia, sodium thiosulfate, sodium dihydrogen phosphate, hydrochloric acid, formic acid, acetic acid.
In a second aspect the present invention provides a process for preparing said hydrophobic coating comprising the steps of:
s1: mixing the inorganic compound with water, and then adding the inorganic acid ester and the binder;
s2: and (2) adding the organic silicon precursor and a catalyst into the mixture obtained in the step (S1) to react to obtain the hydrophobic coating.
The invention relates to a technical scheme for preparing the hydrophobic coating, which at least has the following beneficial effects:
the preparation method of the hydrophobic coating comprises the steps of mixing the inorganic compound with water, adding the inorganic acid ester and the binder, adding the organic silicon precursor and the catalyst into the mixture, and reacting to obtain the hydrophobic coating. The preparation method is simple and easy to operate, does not need expensive equipment or complex process control, is favorable for ensuring the stability of the quality of the coating product, and is easy for large-scale batch production.
The preparation method of the hydrophobic coating comprises the steps of mixing the inorganic compound with water, adding the inorganic acid ester and the adhesive, wherein the inorganic acid ester and the adhesive are partially decomposed when meeting water, then adding the organic silicon precursor and the catalyst, fully decomposing the inorganic acid ester and the adhesive under the action of the catalyst, and simultaneously hydrolyzing the organic silicon precursor, so that active groups generated among the inorganic acid ester, the adhesive and the organic silicon precursor are subjected to condensation reaction to form an inorganic network structure with a nonpolar molecular chain.
According to some embodiments of the present invention, in the step S1, during the process of mixing the inorganic compound with water, ultrasound may be added, and the ultrasound may promote the inorganic compound to be more sufficiently dispersed in water.
According to some embodiments of the invention, the reaction time is between 2h and 8h.
According to some embodiments of the invention, the reaction time is between 4h and 6h.
In a third aspect of the invention, a hydrophobic coating is provided, which is prepared from the hydrophobic coating.
The invention relates to one of the technical schemes of the hydrophobic coating, which at least has the following beneficial effects:
in the hydrophobic coating, the raw materials for preparing the hydrophobic coating comprise an inorganic compound, an inorganic acid ester, an organic silicon precursor, a binder, a catalyst and water, and under the combined action of the inorganic compound, the inorganic acid ester, the organic silicon precursor, the binder, the catalyst and the water, the coating formed by the prepared coating has good performance, the adhesive force can reach 0 grade, and the pencil hardness can reach 9H. Meanwhile, the thermal decomposition temperature of the coating is more than 500 ℃, the water contact angle is more than or equal to 120 degrees, the water contact angle is still more than 120 degrees after the coating is treated at the high temperature of 250-400 ℃ for 10 hours, and the strong hydrophobic property is still maintained between 120 degrees and 130 degrees.
In the hydrophobic coating, a high-temperature resistant inorganic compound and a low-surface-energy organic silicon precursor with good thermal stability are used as raw materials, inorganic acid ester is hydrolyzed and condensed to form an inorganic network structure, reaction sites are provided for the reaction of the organic silicon precursor, and the high-temperature resistant hydrophobic coating is designed and prepared. The coating is coated and cured, and the surface of the coating is partially shrunk to form a porous rough structure, so that a suspended air layer can be formed on the surface of water drops after high-temperature treatment, and a hydrophobic state is kept.
In the hydrophobic coating, the high-temperature resistant hydrophobic porous coating is obtained by synthesizing and controlling the coating, and the surface of the coating has an irregular porous structure of 0.2-2 mu m. The surface of the coating is rough and compact and has no cracks, the organosilicon precursor is polymerized to form a nonpolar polymer chain with higher thermal stability, the nonpolar polymer chain wraps part of the inorganic compound and generates certain phase separation with a coating system (the whole coating composition except the organosilicon precursor), after the coating is coated and cured, the coating is partially shrunk, so that the surface presents an irregular porous structure, and the porous structure combines with the organosilicon precursor with low surface energy component, so that the surface presents a good hydrophobic state.
According to some embodiments of the invention, the hydrophobic coating has a thermal decomposition temperature > 500 ℃.
According to some embodiments of the invention, the hydrophobic coating has a water contact angle >120 ° after 10h of treatment at 250 ℃ to 400 ℃.
According to some embodiments of the invention, the hydrophobic coating has a thickness of 10 μm to 20 μm.
A fourth aspect of the invention provides a method of preparing a hydrophobic coating, the method comprising: and (3) after the hydrophobic coating is constructed on the surface of the base material, carrying out thermosetting treatment.
According to some embodiments of the invention, the hydrophobic coating application method comprises spray coating, dip coating, roll coating or spin coating.
According to some embodiments of the invention, the temperature of the thermal curing process is 60 ℃ to 300 ℃.
According to some embodiments of the invention, the temperature of the thermal curing process is from 200 ℃ to 300 ℃.
According to some embodiments of the invention, the heat curing process is performed for a time period of 10min to 60min.
According to a fifth aspect of the invention, a household appliance is provided, and the surface of the household appliance is provided with the hydrophobic coating.
The invention relates to one of the technical schemes of the household appliances, which at least has the following beneficial effects:
the hydrophobic coating has good performance, so that the adhesive force can reach 0 grade, and the pencil hardness can reach 9H. The thermal decomposition temperature of the hydrophobic coating is more than 500 ℃, the water contact angle is more than or equal to 120 ℃, the coating still maintains stronger hydrophobic property after being treated at the high temperature of 250-400 ℃ for 10 hours, and the water contact angle is still more than 120 ℃. After the hydrophobic coating is coated on the surface of the household appliance by spraying, dip coating, roll coating, spin coating or other methods, the surface performance of the household appliance can be improved, so that the surface of the household appliance can have high temperature resistance and excellent hydrophobic performance besides the conventional performance of the coating.
According to some embodiments of the invention, the household appliance comprises a frying pan, a wall breaking machine, a rice cooker, a microwave oven and an oven.
Drawings
FIG. 1 is the results of the microtopography testing of the hydrophobic coating prepared in example 1.
FIG. 2 shows the results of thermogravimetric analysis of the hydrophobic coating prepared in example 1.
FIG. 3 is the result of water contact angle test after high temperature treatment of the hydrophobic coating prepared in example 1.
Detailed Description
The following are specific examples of the present invention, and the technical solutions of the present invention will be further described with reference to the examples, but the present invention is not limited to the examples.
In some embodiments of the present invention, the present invention provides a hydrophobic coating prepared from raw materials including an inorganic compound, an inorganic acid ester, an organosilicon precursor, a binder, a catalyst, and water, the inorganic compound including at least one of magnesium oxide, silicon nitride, aluminum oxide, barium sulfate, zinc oxide, and silicon carbide.
It is understood that in the hydrophobic coating material of the present invention, the preparation raw materials include an inorganic compound, an inorganic acid ester, an organosilicon precursor, a binder, a catalyst and water. The inorganic compound includes at least one of magnesium oxide, silicon nitride, aluminum oxide, barium sulfate, zinc oxide, and silicon carbide. The inorganic compound has the functions of improving the thermal stability of a system, increasing the surface roughness and enabling the surface of a coating formed by the coating to be more hydrophobic. The function of the inorganic acid ester is to form an inorganic network structure through hydrolysis and condensation, and simultaneously provide a reaction site for the reaction of the organic silicon precursor. The function of the organosilicon precursor is to reduce the surface free energy, so that the surface of a coating formed by the coating is hydrophobic. The inorganic binder functions to increase the adhesion between the inorganic compound particles. Water acts as a solvent. The catalyst is used for catalyzing inorganic acid ester, inorganic binder and organic silicon precursor to carry out hydrolytic condensation.
It can be understood that, under the combined action of the inorganic compound, the inorganic acid ester, the organic silicon precursor, the binder, the catalyst and the water, the coating formed by the prepared coating has good performance, specifically, the adhesive force of the coating can reach 0 grade, and the pencil hardness can reach 9H. Meanwhile, the thermal decomposition temperature of the coating is more than 500 ℃, the water contact angle is more than or equal to 120 degrees, the coating still maintains stronger hydrophobic property after being treated at the high temperature of 250-400 ℃ for 10 hours, and the water contact angle is still more than 120 degrees.
In some embodiments of the present invention, the raw materials for preparing the hydrophobic coating comprise the following components in parts by weight:
inorganic compound (b): 2 to 60 portions of the mixture of the components,
inorganic acid ester: 8 to 64 portions of the raw materials are mixed,
organic silicon precursor: 10 to 20 portions of the raw materials are mixed,
adhesive: 1 to 30 parts of (A) and (B),
catalyst: 0.05 to 3 portions of the raw materials,
water: 20 to 80 portions.
The mixture ratio of the inorganic compound, the inorganic acid ester, the organic silicon precursor, the binder, the catalyst and the water is a proper mixture ratio, and the performance of the coating are affected when the mixture ratio is lower than the mixture ratio range or exceeds the mixture ratio range.
In some embodiments of the present invention, the shape of the inorganic compound includes at least one of a plate shape, a needle shape, a particle shape, and a whisker shape.
Specifically, when the shape of the inorganic compound is composed of two or more shapes, the coating layer can be made more dense and the coating layer performance can be improved.
It will be appreciated that the use of inorganic compounds of different shapes promotes the dispersion of the coating system, and thus the adhesion of the coating.
For example, the flaky compound has a smooth and flat surface, has good dispersibility, can promote the adhesion of the coating, and has a small thickness and a large diameter-thickness ratio due to the special two-dimensional planar structure, can reach a nanometer level in the thickness direction and a micron level in the radial direction, so the flaky compound has double effects of nanometer and micron powder.
Therefore, inorganic compounds with different shapes are adopted, which is beneficial to ensuring that the surface activity of the coating is moderate, can be effectively combined with other active groups, and is not easy to agglomerate so as to be convenient for effective dispersion. A coating formed by the coating has good adhesive force, obvious shielding effect and light reflection capability, and simultaneously has excellent performances of acid and alkali resistance, high temperature resistance, high hardness, high melting point, high thermal conductivity, high resistivity and the like.
In addition, when the inorganic compound is compounded by more than two inorganic compounds with different sizes and particle diameters, the coating can be more compact, and the coating performance is better.
In some embodiments of the invention, the inorganic acid ester comprises at least one of tetrabutyl titanate, dimethyl sulfate, methyl hydrogen sulfate, glyceryl trinitrate, tributyl phosphate, and ethyl orthosilicate.
Tetrabutyl titanate is an organic compound with a molecular formula of C16H36O4Ti, used for the transesterification reaction. When applied to paint, the heat resistance of the paint can be improved, and the paint, rubber and plastic pairs can be improvedAdhesion to metal surfaces also acts as a condensation catalyst, a crosslinking agent.
The structural formula of dimethyl sulfate is (CH)3O)2SO2. Is colorless or yellowish oily flammable liquid with slight onion smell. Is slightly soluble in water at low temperature, is easily soluble in water at normal temperature, and is easily soluble in organic solvents such as diethyl ether, ethanol, chloroform, etc. Is often used as a methylating agent. It has wide application in pesticide manufacturing industry, organic chemical raw material manufacturing industry, dye manufacturing industry, catalyst and additive manufacturing industry, plastic manufacturing industry, daily chemical product manufacturing industry, medicine industry and the like, and can also be used as a solvent for extracting aromatic hydrocarbons.
Methyl hydrogen sulfate reacts with sodium carbonate and the like to generate sodium methyl sulfate.
Tributyl phosphate is mainly used as a solvent, and is also commonly used as a plasticizer for nitrocellulose, cellulose acetate, chlorinated rubber and polyvinyl chloride, an extractant for rare metals, and the like, as a heat exchange medium. Because of its low surface tension and slightly water-soluble physical properties, it can be used as an industrial defoaming agent,
in some embodiments of the invention, the organosilicon precursor comprises at least one of methyltriethoxysilane, trimethylchlorosilane, dimethyldimethoxysilane, dodecyltrimethoxysilane, hexadecyltrimethoxysilane, methylphenyldimethoxysilane.
Different organosilicon precursors have influence on temperature resistance, and the selection of the organosilicon precursors influences the thermal stability of the system.
The methyl triethoxysilane is commonly used in rubber and medicine industry, can be used as an organic silicon polymer raw material, and is an important raw material for producing silicone resin, benzyl silicone oil and a waterproof agent. And meanwhile, the silicon alkoxide is easy to hydrolyze and can generate alkali metal silicon alkoxide with alkali metal hydroxide.
Trimethylchlorosilane is colorless transparent liquid, has pungent odor, and is mainly used as an intermediate for producing silicone oil, a water repellent and an analytical reagent.
The dimethyl dimethoxy silane is mainly used as a modifier for organic silicon resin, a structural control agent for organic silicon rubber compound and a chain extender. Can be widely used for the treatment of organic silica gel and white carbon black.
The molecular formula of the dodecyl trimethoxy silane is C15H34O3Si, CAS number 3069-21-4.
Hexadecyl trimethoxy silane is colorless to light yellow transparent liquid, is solid at low temperature, and is easily dissolved in common polar or non-polar organic solvents such as hydrocarbon, ether, ketone and the like. Is easy to hydrolyze and condense to form polysiloxane. Mainly for processing inorganic materials.
The molecular formula of the methyl phenyl dimethoxy silane is C9H14O2Si, colorless or light yellow transparent liquid, CAS number 3027-21-2.
In some embodiments of the invention, the binder comprises at least one of aluminum dihydrogen phosphate, aluminum phosphate, lithium silicate, aluminum silicate, sodium silicate.
The aluminum dihydrogen phosphate is colorless, odorless and highly viscous liquid or white powder, and is easily soluble in water. The adhesive is used as a binder of refractory materials, and is mainly used for electrical industry, high-temperature kilns, heat treatment resistance furnaces and electrical insulation. It is also used in petroleum, chemical industry, shipbuilding, space technology and other fields. Can also be used as an inorganic coating to be matched with an organic coating.
Aluminum phosphate is generally insoluble in water, soluble in concentrated hydrochloric acid and nitric acid, alkali, and slightly soluble in alcohol. The glass flux can be used as a fluxing agent in the glass production process, can be used as a binding agent for ceramics or teeth, and can be used as an additive to be added into materials such as an emollient, a fireproof coating, conductive cement and the like.
Lithium silicate is mainly used in glass systems, molten salt systems and high-temperature ceramic glazes, and is also used as surface antirust coating for steel and the like. It can also be used as binder for inorganic zinc-rich coating and high-grade welding rod.
When the aluminum silicate is used for the coating, the aluminum silicate has better covering power and can improve the whiteness of the coating. In addition, the superfine and grid structure of the aluminum silicate can thicken the coating, has good suspension property, and prevents the phenomena of bottom sinking and surface water distribution of solid parts. Aluminium silicate also has a matting effect.
In some embodiments of the invention, the catalyst comprises at least one of sodium hydroxide, ammonia, sodium thiosulfate, sodium dihydrogen phosphate, hydrochloric acid, formic acid, acetic acid.
The hydrophobic coating can be directly constructed on the surface of a base material without primer and intermediate coating.
In still other embodiments of the present invention, the present invention provides a method of preparing a hydrophobic coating comprising the steps of:
s1: mixing an inorganic compound with water, and adding an inorganic acid ester and a binder;
s2: and (2) adding an organic silicon precursor and a catalyst into the mixture obtained in the step (S1) to react to obtain the hydrophobic coating.
It can be understood that the preparation method of the hydrophobic coating of the present invention is to mix the inorganic compound with water, add the inorganic acid ester and the binder, add the organosilicon precursor and the catalyst into the mixture, and react to obtain the hydrophobic coating. The preparation method is simple and easy to operate, does not need expensive equipment or complex process control, is favorable for ensuring the stability of the quality of the coating product, and is easy for large-scale batch production.
The hydrophobic coating is prepared by mixing an inorganic compound with water, adding inorganic acid ester and a binder, wherein the inorganic acid ester and the binder are partially decomposed when meeting water, then adding an organic silicon precursor and a catalyst, fully decomposing the inorganic acid ester and the binder under the action of the catalyst, and simultaneously hydrolyzing the organic silicon precursor, so that active groups generated among the inorganic acid ester, the binder and the organic silicon precursor are subjected to condensation reaction to form an inorganic network structure with a nonpolar molecular chain.
Specifically, in the step S1, ultrasound may be applied during the process of mixing the inorganic compound with water, and the application of ultrasound can promote the inorganic compound to be more sufficiently dispersed in water.
In some embodiments of the invention, the reaction time is between 2h and 8h.
In some embodiments of the invention, the reaction time is 4h to 6h.
In other embodiments of the present invention, the present invention provides a hydrophobic coating prepared from the hydrophobic coating described above.
It can be understood that in the hydrophobic coating of the invention, the raw materials for preparing the hydrophobic coating comprise inorganic compound, inorganic acid ester, organic silicon precursor, binder, catalyst and water, and under the combined action of the inorganic compound, the inorganic acid ester, the organic silicon precursor, the binder, the catalyst and the water, after the coating is formed by the prepared coating, the coating has good performance, the adhesive force can reach 0 grade, and the pencil hardness can reach 9H. Meanwhile, the thermal decomposition temperature of the coating is more than 500 ℃, the water contact angle is more than or equal to 120 degrees, the coating still maintains stronger hydrophobic property after being treated at the high temperature of 250-400 ℃ for 10 hours, and the water contact angle is still more than 120 degrees.
It can also be understood that in the hydrophobic coating, the high-temperature-resistant hydrophobic coating is designed and prepared by taking a high-heat-resistant inorganic compound and a low-surface-energy organosilicon precursor with good thermal stability as raw materials and combining a surface porous structure. The porous rough structure can enable the surface of water drops after high-temperature treatment to form a suspended air layer, so that the hydrophobic state is maintained.
In the hydrophobic coating, the synthesis and control of the coating are carried out to obtain the high-temperature-resistant hydrophobic porous coating, and the surface of the coating has an irregular porous structure of 0.2-2 mu m. The surface of the coating is rough and compact and has no cracks, an organic silicon precursor is polymerized to form a nonpolar polymer chain with higher thermal stability, the nonpolar polymer chain wraps part of inorganic compounds and generates certain phase separation with a coating system, and after the coating is coated and cured, the coating is partially shrunk to enable the surface to present an irregular porous structure, and the porous structure is combined with a low surface energy component to enable the surface to present a good hydrophobic state.
In some embodiments of the invention, the hydrophobic coating has a thickness of 10 μm to 20 μm.
In some embodiments of the invention, the hydrophobic coating is prepared by: after the hydrophobic coating is constructed on the surface of the base material, thermosetting treatment is carried out.
In some embodiments of the invention, the hydrophobic coating application method comprises spray coating, dip coating, roll coating, or spin coating.
In some embodiments of the present invention, the temperature of the thermal curing process is 60 ℃ to 300 ℃.
In some embodiments of the present invention, the temperature of the thermal curing process is from 200 ℃ to 300 ℃.
The temperature of the specific thermal curing process is determined by the silicone precursor used.
In some embodiments of the present invention, the substrate may be a high temperature resistant substrate such as stainless steel, galvanized sheet, aluminized sheet, aluminum alloy, and the like.
In further embodiments of the present invention, the present invention provides a household appliance, the surface of which is provided with the hydrophobic coating described above.
It can be understood that the adhesion can reach 0 grade and the pencil hardness can reach 9H due to the good performance of the hydrophobic coating. The thermal decomposition temperature of the hydrophobic coating is more than 500 ℃, the water contact angle is more than or equal to 120 ℃, the coating still maintains stronger hydrophobic property after being treated at the high temperature of 250-400 ℃ for 10 hours, and the water contact angle is still more than 120 ℃. After the hydrophobic coating is coated on the surface of the household appliance through spraying, dip coating, roll coating, spin coating or other methods, the surface performance of the household appliance can be improved, so that the surface of the household appliance can have high temperature resistance and excellent hydrophobic performance besides the conventional performance of the coating.
It is also understood that the home appliances include a frying pan, a wall breaking machine, a rice cooker, a microwave oven, and an oven.
The technical solution of the present invention will be better understood with reference to the following specific examples.
Example 1
The embodiment firstly prepares the hydrophobic coating, and the specific steps are as follows:
according to the mass percentage, 8 percent of spherical nano silicon oxide, 10 percent of sheet aluminum oxide and 55 percent of deionized water are ultrasonically mixed for 20 min-30 min (with the power of 400 Hz);
adding 10% of ethyl orthosilicate and 5% of aluminum silicate, stirring for 1h at the speed of 600rpm under the condition of 15-35 ℃, adding 11% of dimethyl dimethoxy silane and 1% of ammonia water, and continuing stirring for 4h to obtain the hydrophobic coating.
Wherein the particle size of the spherical nano silicon oxide is 50 nm-100 nm.
The size of the flake alumina is 3-6 μm.
Then, preparing a hydrophobic coating by using the prepared hydrophobic coating, which comprises the following specific steps:
spraying the hydrophobic coating on the surface of the substrate, and thermally curing the coated substrate at 280 ℃.
In this example, the base material was stainless steel.
The coating thickness was 20 μm.
Example 2
The embodiment firstly prepares the hydrophobic coating, and the specific steps are as follows:
ultrasonically mixing 10% of flake alumina, 12% of barium sulfate and 50% of deionized water (power 400 Hz) for 20-30min;
adding 10% of ethyl orthosilicate and 5% of aluminum dihydrogen phosphate, stirring for 1h at the speed of 600rpm under the condition of 15-35 ℃, adding 12.5% of dimethyldimethoxysilane and 0.5% of hydrochloric acid, and continuously stirring for 6h to prepare the hydrophobic coating.
Wherein the size of the flaky alumina is 3-6 μm.
The barium sulfate is irregular particles of 3 to 5 μm in shape.
Then, preparing a hydrophobic coating by using the prepared hydrophobic coating, which comprises the following specific steps:
spraying the hydrophobic coating on the surface of the substrate, and thermally curing the coated substrate at 200 ℃.
In this example, the base material was an aluminum plate.
The coating thickness was 12 μm.
Example 3
The embodiment firstly prepares the hydrophobic coating, and the specific steps are as follows:
mixing 5% of silicon oxide whisker, 5% of needle-like zinc oxide and 60% of deionized water by ultrasonic (power 400 Hz) for 20-30min;
adding 10% of ethyl orthosilicate and 5% of aluminum silicate, stirring at the speed of 600rpm for 1h at the temperature of 15-35 ℃, adding 14% of methyl phenyl dimethoxy silane and 1% of sodium dihydrogen phosphate, and continuously stirring for 2h to obtain the hydrophobic coating.
Wherein the size of the silicon oxide whisker is 1-2 μm.
The size of the zinc oxide is 0.5-5 μm.
Then, preparing a hydrophobic coating by using the prepared hydrophobic coating, which comprises the following specific steps:
spraying the hydrophobic coating on the surface of the substrate, and thermally curing the coated substrate at 200 ℃.
In this embodiment, the base material is an aluminum alloy.
The coating thickness was 16 μm.
Example 4
The embodiment firstly prepares the hydrophobic coating, and the specific steps are as follows:
mixing 15% barium sulfate particles, 8% nano silicon oxide and 41% deionized water by ultrasonic (power 400 Hz) for 20-30min;
adding 15% of tetrabutyl titanate and 10% of aluminum phosphate, stirring at the speed of 600rpm for 1h at the temperature of 15-35 ℃, adding 10% of hexadecyl trimethoxy silane and 1% of formic acid, and continuing stirring for 2h to prepare the hydrophobic coating.
Wherein the particle size of the barium sulfate particles is 3-5 μm.
The size of the nano silicon oxide is 50 nm-100 nm
Then, preparing a hydrophobic coating by using the prepared hydrophobic coating, which comprises the following specific steps:
spraying the hydrophobic coating on the surface of the substrate, and thermally curing the coated substrate at 200 ℃.
In this example, the base material was a galvanized sheet.
The coating thickness was 10 μm.
Example 5
The embodiment firstly prepares the hydrophobic coating, and the specific steps are as follows:
mixing 20% of silicon nitride irregular particles, 12% of flake alumina and 21% of deionized water by ultrasonic (power is 400 Hz) for 20-30min;
adding 20% dimethyl sulfate and 6% sodium silicate, stirring at the speed of 600rpm for 1h at the temperature of 15-35 ℃, adding 20% methyltriethoxysilane and 1% sodium thiosulfate, and continuing stirring for 2h to obtain the hydrophobic coating.
Wherein the particle diameter of the silicon nitride irregular particles is 0.5-1 μm.
The size of the flake alumina is 3-6 μm.
Then, preparing a hydrophobic coating by using the prepared hydrophobic coating, which comprises the following specific steps:
spraying the hydrophobic coating on the surface of the substrate, and thermally curing the coated substrate at 200 ℃.
In this example, the base material was stainless steel.
The coating thickness was 15 μm.
Example 6
The embodiment firstly prepares the hydrophobic coating, and the specific steps are as follows:
mixing 10% of spherical silicon oxide, 15% of silicon carbide whisker and 38% of deionized water ultrasonically (power 400 Hz) for 20-30min;
adding 16% of glyceryl trinitrate and 8% of lithium silicate, stirring at the speed of 600rpm for 1h at the temperature of 15-35 ℃, adding 12.95% of trimethylchlorosilane and 0.05% of acetic acid, and continuously stirring for 2h to obtain the hydrophobic coating.
Wherein the particle size of the spherical silicon oxide is 50 nm-100 nm.
The size of the silicon carbide crystal whisker is 2-4 μm.
Then, preparing a hydrophobic coating by using the prepared hydrophobic coating, which comprises the following specific steps:
spraying the hydrophobic coating on the surface of the substrate, and thermally curing the coated substrate at 200 ℃.
In this example, the base material was stainless steel.
The coating thickness was 18 μm.
Example 7
The embodiment firstly prepares the hydrophobic coating, and the specific steps are as follows:
mixing 15% of silicon oxide whiskers, 25% of magnesium oxide irregular particles and 22% of deionized water by ultrasonic waves (power is 400 Hz) for 20-30min;
adding 18 percent of tributyl phosphate and 10 percent of aluminum silicate, stirring for 1 hour at the speed of 600rpm under the condition of 15-35 ℃, adding 9.99 percent of dodecyl trimethoxy silane and 0.01 percent of sodium hydroxide, and continuously stirring for 2 hours to prepare the hydrophobic coating.
Wherein the size of the silicon oxide whisker is 1-2 μm.
The size of the magnesium oxide irregular particles is 0.5-1 mu m.
Then, preparing a hydrophobic coating by using the prepared hydrophobic coating, which comprises the following specific steps:
spraying the hydrophobic coating on the surface of the substrate, and thermally curing the coated substrate at 200 ℃.
In this example, the substrate was a galvanized sheet
The coating thickness was 20 μm.
Comparative example 1
This comparative example prepared a hydrophobic coating, which differs from example 1 in that no inorganic acid ester and no binder were added and in that a silicone resin was added. The method comprises the following specific steps:
mixing 8% spherical nanometer silicon oxide, 10% sheet aluminum oxide and 55% deionized water by ultrasonic (power 400 Hz) for 20-30min;
adding 15 percent of organic silicon resin, stirring for 1 hour at the speed of 600rpm under the condition of 15-35 ℃, adding 11 percent of dimethyl dimethoxy silane and 1 percent of ammonia water, and continuing stirring for 4 hours to prepare the hydrophobic coating.
Note that the silicone resin in this comparative example is not a silicone precursor. The silicone resin in this comparative example may be fluorocarbon resin, epoxy silicone resin, methyl phenyl silicone resin, and the like. In this comparative example, methyl silicone resin (CAS No. 67763-03-5) was specified.
Wherein the size of the spherical nano silicon oxide is 50 nm-100 nm
The size of the flake alumina is 3-6 μm.
Then, preparing a hydrophobic coating by using the prepared hydrophobic coating, which comprises the following specific steps:
spraying the hydrophobic coating on the surface of the substrate, and thermally curing the coated substrate at 200 ℃.
In this comparative example, the substrate was stainless steel.
The coating thickness was 20 μm.
Comparative example 2
This comparative example, in which a hydrophobic coating was prepared, is different from example 1 in that the inorganic compound was a single spherical nano-silica. The method comprises the following specific steps:
mixing 18% of spherical nano silicon oxide and 55% of deionized water by mass percentage for 20-30min in an ultrasonic way (with the power of 400 Hz);
adding 10% of ethyl orthosilicate and 5% of aluminum silicate, stirring at the speed of 600rpm for 1h at the temperature of 1-35 ℃, adding 11% of dimethyldimethoxysilane and 1% of ammonia water, and continuing stirring for 4h to obtain the hydrophobic coating.
Wherein the particle size of the spherical nano silicon oxide is 50 nm-100 nm.
Then, preparing a hydrophobic coating by using the prepared hydrophobic coating, which comprises the following specific steps:
spraying the hydrophobic coating on the surface of the substrate, and thermally curing the coated substrate at 280 ℃.
In this example, the base material was stainless steel.
The coating thickness was 20 μm.
Cracks were observed on the surface of the obtained coating.
Test example 1
The microscopic morphology of the hydrophobic coating prepared in example 1 was observed by 3D depth of field microscopy, as shown in figure 1. As can be seen from FIG. 1, the hydrophobic coating prepared in example 1 has a flat and dense surface without cracks.
The surface roughness Rq (root mean square roughness) of the hydrophobic coating of example 1 was found to be 30nm by atomic force microscopy.
The surface roughness Rq (root mean square roughness) of the coating of comparative example 1 was 16nm.
The surface roughness Rq (root mean square roughness) of the coating of comparative example 2 is greater than 30nm, in particular 33nm.
The hydrophobic coating prepared in example 1 was tested for adhesion according to the standard GB/T9286-2021 and found to be grade 0. The adhesion of the coating prepared in comparative example 1 was of grade 0. The adhesion of the coating prepared in comparative example 2 was grade 1.
The pencil hardness of the hydrophobic coating prepared in example 1 was tested according to standard GB/T6739-2006, resulting in 9H. The hardness of the coating prepared in comparative example 1 was 2H. The hardness of the coating prepared in comparative example 2 was 3H.
The sample plate to be tested is fixed on a test board of the wear resistance tester, the industrial scouring pad is tested by a 3kg weight, and the scouring pad is replaced every 500 times. The test shows that the hydrophobic coating prepared in example 1 has good wear resistance, and the powder does not fall off after 5000 times. The coating prepared in comparative example 1 broke out after 2000 rubs. The abrasion resistance of the coating prepared in comparative example 2 was < 500 times.
Test example 2
The water contact angle of the prepared hydrophobic coating is tested by adopting a contact angle tester, the volume of a water drop is set to be 4 mu L, each sample is tested for more than three times, and an average value is taken. The water contact angle of the coating of example 1 was measured to be 120 deg. or more, indicating that the coating had good hydrophobic properties. The coating prepared in comparative example 1 had a water contact angle of less than 100 °. The water contact angle of the coating prepared in comparative example 2 was 110 °.
Test example 3
The thermal decomposition temperature of the hydrophobic coating prepared in example 1 was tested by thermogravimetric analysis and the results are shown in figure 2. As can be seen from the test results of fig. 2, the thermal decomposition temperature of the coating is greater than 500 ℃, indicating that the coating has excellent high temperature resistance.
Test example 4
Further, the coating prepared in example 1 was tested for hydrophobic properties after being treated at 250-400 ℃ for 10 h. The results are shown in FIG. 3. As can be seen from FIG. 3, after the coating is treated at the high temperature of 250-400 ℃ for 10h, the water contact angles are all larger than 120 degrees, thereby showing that the coating has durable high-temperature resistance and stronger hydrophobicity.
Test example 5
The water contact angle and temperature resistance of the hydrophobic coatings prepared in example 1 and comparative examples 1 and 2 were compared. The results are shown in Table 1.
Table 1 comparison of coating properties of example 1 and comparative examples 1 and 2
Example 1 Comparative example 1 Comparative example 2
Water contact Angle (°) ≥120 ＜100 110
Temperature resistance (. Degree. C.) 400 ＜300 300
According to the test results in table 1, the prepared hydrophobic coating can tolerate higher temperature, the water contact angle is still greater than 120 degrees after the coating is treated at 400 ℃ for 10 hours, the surface is maintained in a hydrophobic state, and the surface has no obvious change compared with a comparative example.
The initial contact angle of the coating prepared in comparative example 1 (without addition of mineral acid ester and binder) was < 100 deg., the surface yellowed at temperatures > 300 deg.C and thermal decomposition occurred. Comparative example 1 used a methyl silicone resin of silicone resins that, although it could act as a binder, had poor temperature resistance, less than 300 ℃. Since comparative example 1 does not add an inorganic acid ester, the inorganic acid ester functions to form an inorganic network structure by hydrolytic condensation while providing a reaction site for the reaction of the organosilicon precursor. Therefore, although the organic silicon precursor is added in the comparative example 1, since there is no reaction site, the molecular chain formed by hydrolysis and condensation of the organic silicon precursor is dissociated in the system, and the coating is easily decomposed at high temperature after being formed, and the coating has poor hydrophobicity.
The initial water contact angle of the coating prepared in comparative example 2 (only using inorganic compounds with single shape) is 110 degrees, the temperature resistance is about 300 ℃, and the surface of the prepared initial coating has cracks, is easy to fall off, and is difficult to maintain the long-term hydrophobic property.
When the hydrophobic coating is used for household appliances such as a frying pan, a wall breaking machine, an electric cooker, a microwave oven and an oven, the surface performance of the household appliances can be improved, so that the surface of the household appliances has high temperature resistance and good hydrophobic performance.
The present invention has been described in detail with reference to the embodiments, but the present invention is not limited to the embodiments described above, and various changes can be made within the knowledge of those skilled in the art without departing from the gist of the present invention.

Claims (15)

1. The hydrophobic coating is characterized in that preparation raw materials comprise an inorganic compound, an inorganic acid ester, an organic silicon precursor, a binder, a catalyst and water, wherein the inorganic compound comprises at least one of magnesium oxide, silicon nitride, aluminum oxide, barium sulfate, zinc oxide and silicon carbide.
2. The hydrophobic coating of claim 1, wherein the raw materials for preparation comprise the following components in parts by weight:
inorganic compound (b): 2 to 60 portions of the raw materials are mixed,
inorganic acid ester: 8 to 64 portions of the mixture of the components,
organic silicon precursor: 10 to 20 portions of the raw materials are mixed,
adhesive: 1 to 30 parts of (A) and (B),
catalyst: 0.05 to 3 portions of the raw materials,
water: 20 to 80 portions.
3. The hydrophobic coating of claim 1 or 2, wherein the inorganic compound has a shape comprising at least one of a flake, a needle, a granule, and a whisker.
4. The hydrophobic coating of claim 1 or 2, wherein the inorganic acid ester comprises at least one of tetrabutyl titanate, dimethyl sulfate, methyl hydrogen sulfate, glycerol trinitrate, tributyl phosphate and ethyl orthosilicate.
5. The hydrophobic coating of claim 1 or 2, wherein the organosilicon precursor comprises at least one of methyltriethoxysilane, trimethylchlorosilane, dimethyldimethoxysilane, dodecyltrimethoxysilane, hexadecyltrimethoxysilane, methylphenyldimethoxysilane.
6. Hydrophobic coating according to claim 1 or 2, characterized in that the binder comprises at least one of aluminium dihydrogen phosphate, aluminium phosphate, lithium silicate, aluminium silicate, sodium silicate.
7. The hydrophobic coating of claim 1 or 2, wherein the catalyst comprises at least one of sodium hydroxide, ammonia, sodium thiosulfate, sodium dihydrogen phosphate, hydrochloric acid, formic acid, acetic acid.
8. A process for preparing the hydrophobic coating according to any one of claims 1 to 7, comprising the steps of:
s1: mixing the inorganic compound with water, and then adding the inorganic acid ester and the binder;
s2: and (2) adding the organic silicon precursor and a catalyst into the mixture obtained in the step (S1) to react to obtain the hydrophobic coating.
9. The method according to claim 8, wherein the reaction time is 2 to 8 hours.
10. A hydrophobic coating, characterized by being prepared from the hydrophobic coating material according to any one of claims 1 to 7.
11. The hydrophobic coating according to claim 10, wherein the hydrophobic coating has a water contact angle >120 ° after 10h of treatment at 250 ℃ to 400 ℃.
12. A method of preparing the hydrophobic coating of claim 10 or 11, wherein the method is: and (3) after the hydrophobic coating is constructed on the surface of the base material, carrying out thermosetting treatment.
13. The method according to claim 12, wherein the temperature of the heat curing process is 60 ℃ to 300 ℃.
14. A household appliance, characterized in that the surface of the household appliance is provided with a hydrophobic coating as claimed in claim 10 or 11.
15. The household appliance of claim 14, wherein the household appliance comprises a wok, a wall breaking machine, a rice cooker, a microwave oven, and an oven.
CN202210903607.5A 2022-07-28 2022-07-28 Hydrophobic coating and preparation method and application thereof Pending CN115260899A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202210903607.5A CN115260899A (en) 2022-07-28 2022-07-28 Hydrophobic coating and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202210903607.5A CN115260899A (en) 2022-07-28 2022-07-28 Hydrophobic coating and preparation method and application thereof

Publications (1)

Publication Number Publication Date
CN115260899A true CN115260899A (en) 2022-11-01

Family

ID=83770943

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202210903607.5A Pending CN115260899A (en) 2022-07-28 2022-07-28 Hydrophobic coating and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN115260899A (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115820112A (en) * 2022-12-01 2023-03-21 广东美的白色家电技术创新中心有限公司 Coating composition and preparation method and application thereof
CN115975408A (en) * 2022-12-26 2023-04-18 杭州老板电器股份有限公司 High-temperature-resistant easy-to-clean inorganic coating, high-temperature-resistant easy-to-clean inorganic coating and application
CN115975408B (en) * 2022-12-26 2024-04-26 杭州老板电器股份有限公司 High-temperature-resistant easy-to-clean inorganic coating, high-temperature-resistant easy-to-clean inorganic coating and application

Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5091468A (en) * 1989-07-03 1992-02-25 T.S.B. Ltd. Organosilane coating composition
WO2010118667A1 (en) * 2009-04-17 2010-10-21 信义汽车玻璃(深圳)有限公司 Hydrophobic solution, hydrophobic glass for vehicle and production method thereof
CN102675938A (en) * 2012-05-10 2012-09-19 中南林业科技大学 Hydrophobic silicate fireproof coating and preparation method thereof
CN103627271A (en) * 2012-08-28 2014-03-12 比亚迪股份有限公司 Heat conductive coating
CN106147441A (en) * 2015-04-27 2016-11-23 广东华润涂料有限公司 Resistance to soiling water-based paint compositions
CN106752255A (en) * 2017-01-20 2017-05-31 兰州交通大学 A kind of material surface protection super-hydrophobic coat spray and its preparation and application
CN109337573A (en) * 2018-09-10 2019-02-15 东北石油大学 A kind of no fluorine-type polyphenylene sulfide super-hydrophobic coat and preparation method thereof
CN109694210A (en) * 2018-11-22 2019-04-30 深圳陶金材料科技有限公司 A kind of modified Portland compound binding agent and the preparation method and application thereof
CN111763438A (en) * 2020-07-16 2020-10-13 广东绿色大地化工有限公司 Water-based nano material modified fireproof coating and preparation method thereof
CN111909616A (en) * 2020-09-03 2020-11-10 无锡米克新材料有限公司 Water-based polysiloxane porcelain-like coating
CN113817392A (en) * 2021-08-20 2021-12-21 南通崇安环保科技有限公司 Long-acting self-cleaning coating, preparation method and application
CN113881253A (en) * 2021-09-22 2022-01-04 兰州交通大学 Fluoride-free self-repairing super-hydrophobic spray enhanced by inorganic binder and preparation and use methods thereof

Patent Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5091468A (en) * 1989-07-03 1992-02-25 T.S.B. Ltd. Organosilane coating composition
WO2010118667A1 (en) * 2009-04-17 2010-10-21 信义汽车玻璃(深圳)有限公司 Hydrophobic solution, hydrophobic glass for vehicle and production method thereof
CN102675938A (en) * 2012-05-10 2012-09-19 中南林业科技大学 Hydrophobic silicate fireproof coating and preparation method thereof
CN103627271A (en) * 2012-08-28 2014-03-12 比亚迪股份有限公司 Heat conductive coating
CN106147441A (en) * 2015-04-27 2016-11-23 广东华润涂料有限公司 Resistance to soiling water-based paint compositions
CN106752255A (en) * 2017-01-20 2017-05-31 兰州交通大学 A kind of material surface protection super-hydrophobic coat spray and its preparation and application
CN109337573A (en) * 2018-09-10 2019-02-15 东北石油大学 A kind of no fluorine-type polyphenylene sulfide super-hydrophobic coat and preparation method thereof
CN109694210A (en) * 2018-11-22 2019-04-30 深圳陶金材料科技有限公司 A kind of modified Portland compound binding agent and the preparation method and application thereof
CN111763438A (en) * 2020-07-16 2020-10-13 广东绿色大地化工有限公司 Water-based nano material modified fireproof coating and preparation method thereof
CN111909616A (en) * 2020-09-03 2020-11-10 无锡米克新材料有限公司 Water-based polysiloxane porcelain-like coating
CN113817392A (en) * 2021-08-20 2021-12-21 南通崇安环保科技有限公司 Long-acting self-cleaning coating, preparation method and application
CN113881253A (en) * 2021-09-22 2022-01-04 兰州交通大学 Fluoride-free self-repairing super-hydrophobic spray enhanced by inorganic binder and preparation and use methods thereof

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115820112A (en) * 2022-12-01 2023-03-21 广东美的白色家电技术创新中心有限公司 Coating composition and preparation method and application thereof
CN115820112B (en) * 2022-12-01 2023-09-19 广东美的白色家电技术创新中心有限公司 Coating composition and preparation method and application thereof
CN115975408A (en) * 2022-12-26 2023-04-18 杭州老板电器股份有限公司 High-temperature-resistant easy-to-clean inorganic coating, high-temperature-resistant easy-to-clean inorganic coating and application
CN115975408B (en) * 2022-12-26 2024-04-26 杭州老板电器股份有限公司 High-temperature-resistant easy-to-clean inorganic coating, high-temperature-resistant easy-to-clean inorganic coating and application

Similar Documents

Publication Publication Date Title
CN103589281B (en) A kind of fire-resistant anticorrosion paint based on Graphene and preparation method thereof
Bagherzadeh et al. Novel water-based nanosiloxane epoxy coating for corrosion protection of carbon steel
AU2020411746A1 (en) Method for preparing aqueous non-stick coating modified with carbon nanotube composite ceramic network
CN110305559B (en) Corrosion-resistant heat-conducting coating and preparation method thereof
Supplit et al. Corrosion protection of aluminum pigments by sol–gel coatings
CN1171962C (en) Process for preparing antirust refractory multifunctional paint
CN107325686A (en) Binary polymerization graphene nano anticorrosive paint and technology of preparing
Balgude et al. Synthesis and characterization of sol–gel derived CNSL based hybrid anti-corrosive coatings
CN115260899A (en) Hydrophobic coating and preparation method and application thereof
CN105778638A (en) Anticorrosion antistatic coating and preparation method thereof
CN113493619A (en) Graphene surface-coated silicon dioxide composite material and preparation method and application thereof
CN110358413A (en) Graphene fire resistant anticorrosive conductive ethylene base ester cold coating and preparation method
CN113388231A (en) Anti-rust carbonyl iron powder wave-absorbing material and preparation method thereof
CN108611631A (en) The processing technology of anticorrosion easy processing galvanized steel plain sheet
CN114316366B (en) Preparation method and application of phosphorus-grafted titanium hydroxide/graphene flame retardant
JPH0218463A (en) Surface-modifying agent for copper powder and production thereof
Li et al. Epoxy/nano-sio2 anticorrosion coatings synthesized by different molar ratio of tetraethyl orthosilicate (TEOS) and tetramethyl orthosilicate (TMOS)
CN108441066B (en) Flame-retardant high-temperature graphene electrothermal coating and preparation method thereof
KR101220679B1 (en) Compositie resin composition for coating galvanized steel sheet and galvanized steel sheet coated with the composition
CN110982385B (en) Special temperature-resistant coating for corrosion prevention in heat storage tank
CN115233203A (en) Aluminum plate pre-color-coating chromium-free passivation solution for improving paint binding force and coating process thereof
CN115247019A (en) Coating structure with anti-corrosion function for bridge steel structure
CN115011202A (en) Water-based epoxy resin coating based on modified graphite and preparation method thereof
JPH0437862B2 (en)
CN115232492A (en) Water-based phosphate ceramic coating and preparation method thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination