CN114479618B - Organic-inorganic hybrid material, preparation method thereof, paint and electronic display device - Google Patents

Organic-inorganic hybrid material, preparation method thereof, paint and electronic display device Download PDF

Info

Publication number
CN114479618B
CN114479618B CN202210066438.4A CN202210066438A CN114479618B CN 114479618 B CN114479618 B CN 114479618B CN 202210066438 A CN202210066438 A CN 202210066438A CN 114479618 B CN114479618 B CN 114479618B
Authority
CN
China
Prior art keywords
parts
product
organic
inorganic hybrid
epoxy resin
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.)
Active
Application number
CN202210066438.4A
Other languages
Chinese (zh)
Other versions
CN114479618A (en
Inventor
彭春燕
任娜娜
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.)
Shenzhen Honghe Innovation Information Technology Co Ltd
Original Assignee
Shenzhen Honghe Innovation Information Technology 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 Shenzhen Honghe Innovation Information Technology Co Ltd filed Critical Shenzhen Honghe Innovation Information Technology Co Ltd
Priority to CN202210066438.4A priority Critical patent/CN114479618B/en
Publication of CN114479618A publication Critical patent/CN114479618A/en
Application granted granted Critical
Publication of CN114479618B publication Critical patent/CN114479618B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

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
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09D133/10—Homopolymers or copolymers of methacrylic acid esters
    • C09D133/12—Homopolymers or copolymers of methyl methacrylate
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/08—Anti-corrosive paints
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • 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
    • G—PHYSICS
    • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2237—Oxides; Hydroxides of metals of titanium
    • C08K2003/2241—Titanium dioxide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • 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
    • C08K2003/2244—Oxides; Hydroxides of metals of zirconium

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Inorganic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Theoretical Computer Science (AREA)
  • Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
  • Laminated Bodies (AREA)
  • Paints Or Removers (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)

Abstract

The invention discloses an organic-inorganic hybrid material, a preparation method thereof and a coating. The preparation method comprises the following steps: taking zirconium n-propoxide as a precursor, isopropanol as a solvent and ethyl acetate as a complexing agent to obtain a product A; mixing epoxy resin and a silane coupling agent, and then sequentially adding tetraethoxysilane and deionized water to obtain a product B; mixing the product A, the product B and a titanium source, adding ethylenediamine after ultrasonic treatment, feeding the mixture into a high-pressure reaction kettle, adding methyl methacrylate and azodiisobutyronitrile, and then performing supercritical CO treatment 2 Carrying out polymerization reaction under high pressure to obtain a product C; cooling the high-pressure reaction kettle and introducing liquid CO 2 And then obtaining a product D, and transferring the product D into a vacuum drying oven for curing to obtain the organic-inorganic hybrid material. The invention can not only provide anticorrosion protection and air purification for the surface of the metal base material, but also firmly bond the photocatalyst and the surface of the metal base material and prevent the photocatalyst from directly contacting the metal base material.

Description

Organic-inorganic hybrid material, preparation method thereof, coating and electronic display device
Technical Field
The invention relates to a metal surface protection material, in particular to an organic-inorganic hybrid material for corrosion prevention and purification of a metal substrate surface, a preparation method thereof, a coating containing the organic-inorganic hybrid material and electronic display equipment adopting the coating.
Background
Metal corrosion is the damage of metal materials by the action of surrounding media, and the corrosion of metals is the most common corrosion form. In corrosion, a chemical or electrochemical multiphase reaction occurs at the interface of the metal, which causes the metal to be in an oxidized (ionic) state, which significantly reduces mechanical properties such as strength, plasticity, toughness, etc. of the metal material, and deteriorates physical properties such as electricity and optics, etc. The metal base material is widely applied to various structural parts, and is easy to corrode, so that damage to the metal structural parts is caused, for example, the geometric shape of the metal structural parts is damaged, the abrasion among parts is increased, the service life of equipment is shortened, and when the damage is serious, a major accident can be caused. Therefore, it is necessary to take appropriate and effective corrosion protection measures for the metal substrate, and a protective layer method for preventing corrosion of the metal surface is generally adopted, in which protective layers made of various materials are manufactured on the surface of the metal substrate to isolate the metal substrate from external corrosive media, thereby achieving the purpose of preventing metal corrosion. Thus, the protective layer should have good barrier properties, and adhesion of the protective layer to the surface of the metal substrate is also critical. Generally, the protective layer can be formed on the surface of the metal base material by painting, spraying, electroplating, hot-dipping, spraying, or the like.
In addition, as the environmental requirements are continuously increased, more and more attention is paid to further improving the indoor air quality. The indoor air purifying paint has many kinds, and mainly includes physical adsorption type, chemical reaction type, photocatalytic type, etc. The physical adsorption type mainly depends on adding a physical adsorption material with strong adsorption capacity into the coating to purify air through adsorption, the application is convenient, the cost is low, the chemical reaction type mainly depends on components which can chemically react with pollutants in the coating to achieve the purpose of eliminating harmful gases, but a single type of material often has self defects, such as that micropores on the surface of the adsorption material are easy to block, the dispersibility of part of chemical components is poor and the corrosion resistance is poor, so that the existing part of coating realizes the air purification effect by utilizing a composite material combining two mechanisms of physical adsorption and chemical reaction.
At present, the photocatalyst is widely applied in many industries due to the functions of photocatalytic oxidation of pollutants and the function of optical self-cleaning, and is considered as an ideal material for treating indoor pollution. Wherein, the titanium dioxide is used as an air purifying agent and has the characteristics of high treatment speed, no secondary pollution, good treatment effect and the like. Titanium dioxide in ultravioletUnder irradiation, free radical reaction can be generated, strong oxidizability is achieved, substances such as harmful gas molecules and microorganisms can be decomposed and converted into environment harmless substances such as water and carbon dioxide, titanium dioxide is not lost in the process, secondary pollution is not generated, and the method is suitable for achieving long-term air purification. For example, coating a titanium dioxide film on a building substrate such as exterior wall tiles, exterior wall paint and curtain wall glass can not only play a self-cleaning role, but also remove NO in air through photocatalysis 2 And SO 2 And air pollutants can be effectively removed. If a titanium dioxide film can be coated on the surface of a commonly used metal substrate to improve the sterilization, self-cleaning, purification and corrosion resistance, it is advantageous to promote the application range of the photocatalyst. However, the building substrates are all non-metallic materials or inert materials, the titanium dioxide film has little influence on the surface performance, the surface of the metal substrate is easy to be active, when a layer of titanium dioxide film is coated on the surface of the building substrates, electron transfer action may exist between the building substrates and the titanium dioxide film, and further the surface of the metal substrate is likely to lose electrons and be oxidized, that is, the surface of the metal substrate is corroded, which may cause damage to metal components. In addition, the bonding strength between the photocatalyst and the surface of the metal substrate is weak, and the requirements of long-acting corrosion resistance and purification cannot be met.
Disclosure of Invention
Based on the above situation, the main object of the present invention is to provide an organic-inorganic hybrid material, a preparation method thereof, a coating material and an electronic display device, wherein the coating material containing the organic-inorganic hybrid material obtained based on the preparation method can provide corrosion protection and air purification for the surface of a metal substrate, can firmly bond a photocatalyst and the surface of the metal substrate, and can prevent the photocatalyst from directly contacting the metal substrate.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
according to a first aspect of the present invention, a method for preparing an organic-inorganic hybrid material, comprises the steps of:
mixing isopropanol containing zirconium n-propoxide with ethyl acetate, aging, adjusting the pH value to 0.5-4.0, and performing ultrasonic treatment to obtain a product A;
mixing and stirring epoxy resin and a silane coupling agent, then adding tetraethoxysilane for mixing and stirring, and finally adding deionized water for stirring to obtain a product B;
mixing the product A, the product B and a titanium source, carrying out ultrasonic treatment, adding ethylenediamine, stirring, sending into a high-pressure reaction kettle, simultaneously adding methyl methacrylate and azodiisobutyronitrile, and introducing primary liquid CO into the kettle 2 Then the temperature in the kettle is raised to 60-80 ℃ and secondary liquid CO is continuously introduced into the kettle 2 Stirring the reactants in the kettle until the pressure in the kettle reaches 25-50 MPa to obtain a product C;
cooling the high-pressure reaction kettle and introducing liquid CO for three times into the product C 2 And transferring the product D into a vacuum drying oven, and curing at 50-100 ℃ to obtain the organic-inorganic hybrid material.
Further, in the preparation process of the product A, the raw material components in parts by weight are respectively as follows: 1-10 parts of isopropanol and 1-5 parts of ethyl acetate, wherein the content of zirconium n-propoxide in isopropanol liquid is 50-90%.
Further, in the preparation process of the product B, the raw material components in parts by weight are as follows: 1 to 10 parts of epoxy resin, 0.1 to 2 parts of silane coupling agent, 1 to 10 parts of ethyl orthosilicate and 0.1 to 5 parts of deionized water.
Further, in the preparation process of the product C, the raw material components in parts by weight are as follows: 5 to 10 portions of product A, 3 to 5 portions of product B, 1 to 3 portions of titanium source, 1 to 4.8 portions of ethylenediamine, 0.2 to 6 portions of methyl methacrylate and 0.02 to 0.6 portion of azodiisobutyronitrile.
Further, the air conditioner is provided with a fan,
the epoxy resin comprises one or more of bisphenol A epoxy resin, polyphenol glycidyl ether epoxy resin and bisphenol F epoxy resin;
and/or the silane coupling agent comprises one or more of 3-aminopropyltriethoxysilane, alcoholic propyl trimethoxy silane, 3- (methacryloyloxy) propyl trimethoxy silane and gamma-glycidoxypropyl trimethoxy silane;
and/or the titanium source comprises one or more of titanium dioxide, titanium tetrachloride, titanium isopropoxide and titanium sulfate.
Further, the primary liquid CO 2 The introduction amount of (2) is 1/2 of the volume of the high-pressure reaction kettle; the tertiary liquid CO 2 The flow rate of (2) is 10 to 30 ml/min.
According to a second aspect of the present invention, an organic-inorganic hybrid material comprises, by weight, 5 to 10 parts of a first raw material, 3 to 5 parts of a second raw material, and 1 part of a third raw material;
the first raw material comprises the following components in parts by weight: 1-10 parts of isopropanol and 1-5 parts of ethyl acetate, wherein the content of zirconium n-propoxide in isopropanol liquid is 50-90%;
the second raw material comprises the following components in parts by weight: 1-10 parts of epoxy resin, 0.1-2 parts of silane coupling agent, 1-10 parts of ethyl orthosilicate and 0.1-5 parts of deionized water;
the third raw material comprises the following components in parts by weight: 1 to 3 parts of titanium source, 1 to 4.8 parts of ethylenediamine, 0.2 to 6 parts of methyl methacrylate and 0.02 to 0.6 part of azodiisobutyronitrile;
the organic-inorganic hybrid material comprises an epoxy resin/polymethyl methacrylate three-dimensional cross-linked network formed by cross-linking the methyl methacrylate with the epoxy resin through the silane coupling agent, wherein the epoxy resin/polymethyl methacrylate three-dimensional cross-linked network coats zirconium oxide particles, silicon oxide particles and titanium oxide particles.
According to a third aspect of the present invention, a coating material comprises organic-inorganic hybrid materials, a dispersant and a solvent, wherein the components comprise, by weight: 19 to 52 percent of organic-inorganic hybrid material, 0.5 to 2.0 percent of dispersant and 47 to 80 percent of solvent;
the organic-inorganic hybrid material is obtained by the production method described in the above first aspect.
Further, the dispersing agent comprises one or a combination of several of Surfynol CT-231, sodium polyacrylate and sodium carboxymethylcellulose;
and/or the solvent comprises one or more of acrylic emulsion, dichloromethane and ethanol.
According to a fourth aspect of the present invention, an electronic display device comprises a structural member composed of a metal base material, wherein a coating material applied to a surface of the metal base material comprises an organic-inorganic hybrid material obtained by the preparation method of the first aspect.
Firstly, zirconium-normal propoxide is taken as a precursor, isopropanol is taken as a solvent, ethyl acetate is taken as a complexing agent to obtain a zirconium-containing product A, epoxy resin, a silane coupling agent, ethyl orthosilicate and deionized water are mixed to obtain a silicon-containing product B, then the product A, the product B and a titanium source are mixed to obtain a modified compound, methyl Methacrylate Monomer (MMA) is added into the modified compound, and supercritical CO is carried out 2 Under the condition, the organic-inorganic hybrid material with zirconium, silicon and titanium oxide particles coated by an epoxy resin/polymethyl methacrylate (PMMA) three-dimensional cross-linked network is obtained by an in-situ dispersion polymerization method, so that the copolymerization of carbon-carbon double bonds on the surface of the zirconium, silicon and titanium inorganic material and methyl methacrylate is realized by adding the methyl methacrylate, and the cross-linking of the methyl methacrylate surface and the epoxy resin is realized by a silane coupling agent, so that the epoxy resin/polymethyl methacrylate three-dimensional cross-linked network is formed and is used for coating zirconium, silicon and titanium oxide particles to form a core-shell structure, the interface combination of an organic component and an inorganic component is enhanced, and the compatibility, thermal property, rigidity and toughness of the materials are improved. And secondly, zirconium oxide particles and silicon oxide particles are coated by an epoxy resin/polymethyl methacrylate three-dimensional cross-linked network, so that the coating not only can be used as an anti-corrosion protective layer on the surface of a metal base material, but also can firmly adhere photocatalyst titanium dioxide and the surface of the metal base material, thereby avoiding the direct contact between the titanium dioxide and the surface of the metal base material and reducing the corrosion of the metal base material. Moreover, titanium dioxide is used as an air purification factor, so that the metal substrate has long-acting effectThe air purifying capacity is improved, the purifying treatment speed is high, and no secondary pollution is caused.
The coating provided by the invention comprises the organic-inorganic hybrid material, is easy to manufacture and simple in process, can be attached to the surface of a metal base material by conventional methods such as coating, spraying and dip-coating, is convenient to use, can be firmly adhered to the surface of the metal base material, prevents a photocatalyst from directly contacting the surface of the metal base material, can effectively improve the corrosion resistance of the metal base material, prolongs the service life, and can obtain a good air purification effect.
Other advantages of the present invention will be described in the detailed description, and those skilled in the art will understand the technical features and technical solutions presented in the description.
Drawings
Preferred embodiments according to the present invention will be described below with reference to the accompanying drawings. In the figure:
FIG. 1 is a schematic view showing the steps of a preferred embodiment of the method for preparing an organic-inorganic hybrid material according to the present invention.
Detailed Description
Referring to fig. 1, a method for preparing an organic-inorganic hybrid material for manufacturing a surface coating material for a metal substrate, the method comprising the steps of:
preparation of product a: mixing isopropanol containing zirconium n-propoxide and ethyl acetate, aging, adjusting the pH value to 0.5-4.0, and performing ultrasonic treatment to obtain a product A. Wherein, zirconium n-propoxide is a zirconium source and is used as a precursor, isopropanol is used as a solvent, and ethyl acetate is used as a complexing agent. In this step, preferably, the aging treatment time is 10 to 60 minutes, and the ultrasonic treatment time is 60 to 150 minutes.
Preparation of product B: under the anhydrous condition, uniformly mixing the epoxy resin and the silane coupling agent, stirring, adding tetraethoxysilane, uniformly mixing, stirring under the anhydrous condition, adding deionized water, and continuously stirring at room temperature to obtain a product B. It is provided withIn the method, by utilizing the chemical activity of the epoxy resin, a compound containing active hydrogen can be subjected to ring opening to be cured and crosslinked to generate a network structure; the silane coupling agent comprises a silane oxygen group and an organic functional group and is used for functionalizing the epoxy resin, zirconium and titanium so as to improve the compatibility, the thermal stability and the corrosion resistance among materials; tetraethoxysilane is used for providing silicon source and generates hydrolysis condensation reaction to generate SiO 2 . In this step, the stirring time is preferably 1 to 5 hours.
Preparation of product C: uniformly mixing the product A, the product B and a titanium source, carrying out ultrasonic treatment, adding ethylenediamine, stirring at room temperature, feeding into a high-pressure reaction kettle, simultaneously adding Methyl Methacrylate (MMA) and azodiisobutyronitrile, and introducing primary liquid CO into the kettle 2 Then raising the temperature in the kettle to 60-80 ℃ and continuously introducing secondary liquid CO into the kettle 2 Until the pressure in the kettle reaches 25-50 MPa, the reactants in the kettle continue to carry out polymerization reaction under stirring to obtain a product C. Wherein, ethylenediamine is used as an epoxy resin curing agent; methyl methacrylate is used to form an epoxy/polymethyl methacrylate three-dimensional crosslinked network by a silane coupling agent and an epoxy resin; azobisisobutyronitrile (i.e., 2' -azobisisobutyronitrile) is used as an initiator to promote the polymerization of methyl methacrylate. In the step, preferably, the ultrasonic treatment time is 2 to 10 hours, the stirring time at room temperature after the ethylenediamine is added is 0.5 to 5 hours, and the stirring time of the reactants in the kettle is 10 to 20 hours after the pressure in the kettle reaches 25 to 50 MPa.
Preparation of product D and obtaining of organic-inorganic hybrid material: after polymerization, the autoclave was cooled and the product C was fed with liquid CO three times 2 Extracting unreacted methyl methacrylate in the product C to obtain a product D, transferring the product D into a vacuum drying oven, and curing at 50-100 ℃ to obtain an organic-inorganic hybrid material, wherein the organic-inorganic hybrid material comprises an epoxy resin/polymethyl methacrylate three-dimensional cross-linked network formed by crosslinking methyl methacrylate and epoxy resin through a silane coupling agent, and the epoxy resin/polymethyl methacrylate three-dimensional cross-linked network coats zirconium oxideParticles, silicon oxide particles and titanium oxide particles. Wherein, the cooling of the high-pressure reaction kettle can adopt an ice water bath. In this step, preferably, liquid CO is introduced three times 2 The time of (2) is 5 to 30 minutes, and the curing treatment time is 1 to 10 hours.
Thus, through the steps, the ethyl orthosilicate undergoes a hydrolytic condensation reaction to generate SiO 2 In the process of networking, the epoxy resin, zirconium and titanium are modified in situ by a silane coupling agent, the siloxy in the silane coupling agent has reactivity with inorganic matters, and the organic functional group in the silane coupling agent has reactivity or compatibility with organic matters, then methyl methacrylate monomer is added into the modified compound, and supercritical CO is added 2 The organic-inorganic hybrid material is obtained by an in-situ dispersion polymerization method. In the polymerization process, carbon-carbon double bonds (C = C) on the surface of inorganic materials such as zirconium, silicon and titanium oxide are copolymerized with methyl methacrylate, and the surface of the methyl methacrylate is crosslinked with epoxy resin through a silane coupling agent to form an epoxy resin/polymethyl methacrylate three-dimensional crosslinking network which is used for coating zirconium, silicon and titanium oxide particles to form a core-shell structure, so that the interface combination of the organic material and the inorganic material is enhanced, the organic-inorganic hybrid material can have the characteristics of the organic material and the inorganic material, and the anticorrosion performance and the purification effect are improved.
As an optional example, in the preparation process of the product a, the raw material components in parts by weight are respectively: 1-10 parts of isopropanol liquid and 1-5 parts of ethyl acetate, wherein the content of zirconium n-propoxide in the isopropanol liquid is 50-90%.
As an optional example, in the preparation process of the product B, the raw material components in parts by weight are: 1 to 10 parts of epoxy resin, 0.1 to 2 parts of silane coupling agent, 1 to 10 parts of ethyl orthosilicate and 0.1 to 5 parts of deionized water.
As an optional example, in the preparation process of the product C, the raw material components in parts by weight are: 5 to 10 portions of product A, 3 to 5 portions of product B, 1 to 3 portions of titanium source, 1 to 5 portions of ethylenediamine, 0.2 to 6 portions of methyl methacrylate and 0.02 to 0.6 portion of azodiisobutyronitrile.
As an alternative embodiment, the epoxy resin includes one or more of bisphenol a epoxy resin, polyphenol glycidyl ether epoxy resin, and bisphenol F epoxy resin. The epoxy resin has excellent adhesive property for various metal materials, wherein the bisphenol A type epoxy resin has the advantages of easily obtained raw materials, lower cost, higher yield, higher strength and adhesive strength, and higher corrosion resistance and electrical property; the polyphenol glycidyl ether epoxy resin is a multifunctional epoxy resin, has more than two epoxy groups on molecules, and has high crosslinking density, excellent heat resistance, strength, modulus, electrical insulation and corrosion resistance when forming a cured product; compared with bisphenol A type epoxy resin, the bisphenol F type epoxy resin has lower viscosity and also has good heat resistance and electrical properties.
As an alternative example, the silane coupling agent comprises one or more of 3-aminopropyltriethoxysilane, alcoholic propyl-trimethoxysilane, 3- (methacryloyloxy) propyl-trimethoxysilane and gamma-glycidoxypropyltrimethoxysilane. The hydrolysis speed of the silane coupling agent depends on the siloxy group, the reactivity with the organic polymer depends on the organic functional group, therefore, the silane coupling agent is suitable for different processing objects, the silane coupling agent containing CH2CHCH2O and H2N is mostly selected for the epoxy resin, the adhesive strength between different materials is influenced by a series of factors, such as wetting, surface energy, interface layer and polar adsorption, the action of acid and base, interpenetrating network and covalent bond reaction, and the like, therefore, on the basis of the preliminary selection of the test, the composition of the materials and the sensitivity thereof to the silane coupling agent reaction need to be comprehensively considered, and the reactivity of the silane coupling agent is equivalent to the reactivity of a specific curing system used for the epoxy resin.
As an alternative embodiment, the titanium source comprises one or a combination of titanium dioxide, titanium tetrachloride, titanium isopropoxide and titanium sulfate.
As an alternative embodiment, the primary liquid CO 2 The introduction amount of (b) is 1/2 of the volume of the high-pressure reaction kettle. The tertiary liquid CO 2 The flow rate of (A) is 10 to 30 ml/minClock, three times of liquid CO is introduced 2 The time of (2) is preferably 5 to 30 minutes.
The invention also provides an organic-inorganic hybrid material, which comprises 5-10 parts of the first raw material, 3-5 parts of the second raw material and 1 part of the third raw material in parts by weight;
the first raw material comprises the following components in parts by weight: 1-10 parts of isopropanol liquid and 1-5 parts of ethyl acetate, wherein the content of zirconium n-propoxide in the isopropanol liquid is 50-90%;
the second raw material comprises the following components in parts by weight: 1-10 parts of epoxy resin, 0.1-2 parts of silane coupling agent, 1-10 parts of ethyl orthosilicate and 0.1-5 parts of deionized water;
the third raw material comprises the following components in parts by weight: 1 to 3 parts of titanium source, 1 to 4.8 parts of ethylenediamine, 0.2 to 6 parts of methyl methacrylate and 0.02 to 0.6 part of azodiisobutyronitrile;
the organic-inorganic hybrid material comprises an epoxy resin/polymethyl methacrylate three-dimensional cross-linked network formed by cross-linking the methyl methacrylate with the epoxy resin through the silane coupling agent, wherein the epoxy resin/polymethyl methacrylate three-dimensional cross-linked network coats zirconium oxide particles, silicon oxide particles and titanium oxide particles.
Therefore, the organic-inorganic hybrid material obtained by the preparation method of the organic-inorganic hybrid material is coated with zirconium, silicon and titanium oxide particles by the formed epoxy resin/polymethyl methacrylate (PMMA) three-dimensional cross-linked network, so that the interface combination of an organic component and an inorganic component is enhanced, and the compatibility, thermal property, rigidity and toughness of the materials are improved.
The invention also provides a coating for corrosion prevention and purification of the surface of a metal base material, which comprises the following components in percentage by weight: 19 to 52 percent of organic-inorganic hybrid material, 0.5 to 2.0 percent of dispersant and 47 to 80 percent of solvent.
The organic-inorganic hybrid material is obtained by the preparation method.
Therefore, the coating coats zirconium oxide particles and silicon oxide particles through an epoxy resin/polymethyl methacrylate three-dimensional cross-linked network, can be used as an anti-corrosion protective layer on the surface of a metal base material, can firmly adhere photocatalyst titanium dioxide and the surface of the metal base material, avoids direct contact between the titanium dioxide and the surface of the metal base material, and reduces corrosion of the metal base material. Meanwhile, the coating can be attached to the surface of a reduced metal base material by a conventional process method, and is suitable for being applied to various occasions containing the metal base material in a large scale.
As an alternative embodiment, the dispersing agent comprises one or a combination of Surfynol CT-231, polyacrylic acid sodium salt and sodium carboxymethyl cellulose.
As an alternative embodiment, the solvent comprises one or a combination of acrylic emulsion, dichloromethane and ethanol.
The preparation method of the coating specifically comprises the following steps: the organic-inorganic hybrid material, the dispersant and the solvent are uniformly mixed according to the weight percentage to prepare the coating, and the specific weight percentage is as follows: 19 to 52 percent of organic-inorganic hybrid material, 0.5 to 2.0 percent of dispersant and 47 to 80 percent of solvent. Therefore, the preparation method of the coating is simple in process, easy to realize and suitable for large-scale preparation and application.
The invention also provides electronic display equipment which comprises a structural member formed by the metal base material, wherein the coating adopted on the surface of the metal base material comprises an organic-inorganic hybrid material, and the organic-inorganic hybrid material is obtained by the preparation method.
Example 1
Isopropyl alcohol liquid containing 70% zirconium n-propoxide and ethyl acetate liquid were mixed in a ratio of 2:1 to obtain mixed liquid, aging the mixed liquid for 30 minutes, adjusting the pH value of the mixed liquid to 1.0, and carrying out ultrasonic treatment for 120 minutes to obtain a product A.
8 parts of bisphenol A type epoxy resin, 0.3 part of 3-aminopropyltriethoxysilane and 0.5 part of gamma-glycidoxypropyltrimethoxysilane are uniformly mixed and stirred for 2.5 hours under anhydrous conditions, 5 parts of tetraethoxysilane is added, the mixture is uniformly mixed and stirred for 2 hours under anhydrous conditions, and then 3 parts of deionized water is added and stirred for 5 hours at room temperature to obtain a product B.
Uniformly mixing 20 parts of the product A, 10 parts of the product B and 3 parts of titanium dioxide, carrying out ultrasonic treatment for 5 hours, adding 5 parts of ethylenediamine, stirring at room temperature for 3 hours, feeding into a high-pressure reaction kettle, simultaneously adding 5 parts of methyl methacrylate and 0.05 part of azobisisobutyronitrile, and introducing 1/2 volume of liquid CO into the kettle 2 Then the temperature of the high-pressure reaction kettle is raised to 60 ℃ and liquid CO is continuously introduced into the kettle 2 And (3) continuously carrying out polymerization reaction for 12 hours under stirring on reactants in the kettle until the pressure in the kettle reaches 30MPa to obtain a product C.
After the polymerization reaction, the autoclave was cooled and charged with liquid CO at a flow rate of 20 ml/min 2 And extracting unreacted methyl methacrylate in the product C to obtain a product D after 20 minutes, transferring the product D into a vacuum drying oven, and curing for 5 hours at the temperature of 80 ℃ to obtain the organic-inorganic hybrid material.
According to the weight percentage, the content of the organic-inorganic hybrid material is 30 percent, the content of the polyacrylic acid sodium salt is 1.0 percent, and the content of the acrylic emulsion is 69 percent, and the coating is prepared by uniformly mixing.
Example 2
Isopropanol liquid containing 70% zirconium n-propoxide and ethyl acetate liquid were mixed in a ratio of 1:1 to obtain mixed liquid, aging the mixed liquid for 30 minutes, adjusting the pH value of the mixed liquid to 1.0, and carrying out ultrasonic treatment for 120 minutes to obtain a product A.
2 parts of bisphenol A epoxy resin, 0.05 part of 3-aminopropyltriethoxysilane and 0.1 part of gamma-glycidoxypropyltrimethoxysilane are uniformly mixed and stirred for 2.5 hours under the anhydrous condition, 5 parts of tetraethoxysilane is added, the mixture is uniformly mixed and stirred for 2 hours under the anhydrous condition, and then 3 parts of deionized water is added and stirred for 5 hours at room temperature to obtain a product B.
Uniformly mixing 40 parts of product A, 15 parts of product B and 5 parts of titanium dioxide, carrying out ultrasonic treatment for 5 hours, adding 5 parts of ethylenediamine, stirring at room temperature for 3 hours, feeding into a high-pressure reaction kettle, simultaneously adding 5 parts of methyl methacrylate and 0.1 part of azobisisobutyronitrile, and adding into the kettleThe liquid CO with the volume of 1/2 is introduced 2 Then the temperature of the high-pressure reaction kettle is raised to 60 ℃ and liquid CO is continuously introduced into the kettle 2 And (4) continuing the polymerization reaction of the reactants in the kettle for 12 hours under stirring until the pressure in the kettle reaches 30MPa to obtain a product C.
After the polymerization reaction, the autoclave was cooled and charged with liquid CO at a flow rate of 20 ml/min 2 And extracting unreacted methyl methacrylate in the product C to obtain a product D after 20 minutes, transferring the product D into a vacuum drying oven, and curing for 5 hours at the temperature of 80 ℃ to obtain the organic-inorganic hybrid material.
According to the weight percentage, the content of the organic-inorganic hybrid material is 30 percent, the content of the sodium polyacrylate is 1.0 percent, and the content of the acrylic emulsion is 69 percent, and the materials are evenly mixed to prepare the coating.
Example 3
Isopropyl alcohol liquid containing 70% zirconium n-propoxide and ethyl acetate liquid were mixed in a ratio of 3:1 to obtain mixed liquid, aging the mixed liquid for 30 minutes, adjusting the pH value of the mixed liquid to 1.0, and carrying out ultrasonic treatment for 120 minutes to obtain a product A.
10 parts of bisphenol A epoxy resin and 2 parts of 3-aminopropyltriethoxysilane are uniformly mixed and stirred for 2.5 hours under the anhydrous condition, 5 parts of tetraethoxysilane is added, the mixture is uniformly mixed and stirred for 2 hours under the anhydrous condition, and then 3 parts of deionized water is added and stirred for 5 hours at room temperature to obtain a product B.
Uniformly mixing 10 parts of product A, 5 parts of product B and 1 part of titanium dioxide, carrying out ultrasonic treatment for 5 hours, adding 5 parts of ethylenediamine, stirring at room temperature for 3 hours, feeding into a high-pressure reaction kettle, simultaneously adding 5 parts of methyl methacrylate and 0.05 part of azobisisobutyronitrile, and introducing 1/2 volume of liquid CO into the kettle 2 Then the temperature of the high-pressure reaction kettle is raised to 60 ℃ and liquid CO is continuously introduced into the kettle 2 And (4) continuing the polymerization reaction of the reactants in the kettle for 12 hours under stirring until the pressure in the kettle reaches 30MPa to obtain a product C.
After the polymerization reaction, the autoclave was cooled and charged with a solution having a flow rate of 20 ml/minState CO 2 And extracting unreacted methyl methacrylate in the product C to obtain a product D after 20 minutes, transferring the product D into a vacuum drying oven, and curing for 5 hours at the temperature of 80 ℃ to obtain the organic-inorganic hybrid material.
According to the weight percentage, the content of the organic-inorganic hybrid material is 30 percent, the content of the sodium polyacrylate is 1.0 percent, and the content of the acrylic emulsion is 69 percent, and the materials are evenly mixed to prepare the coating.
Comparative example 1
The isopropyl alcohol liquid containing 70% zirconium n-propoxide was directly used as product a, and the rest of the procedure and the ratio of the other components were the same as in example 1, and product C was obtained.
According to the weight percentage, the content of the product C is 30 percent, the content of the sodium polyacrylate is 1.0 percent, and the content of the acrylic emulsion is 69 percent, and the mixture is evenly mixed to prepare the coating.
Comparative example 2
Isopropanol liquid containing 70% zirconium n-propoxide and ethyl acetate liquid were mixed in a ratio of 1:1 to obtain mixed liquid, aging the mixed liquid for 30 minutes, adjusting the pH value of the mixed liquid to 1.0, and performing ultrasonic treatment for 120 minutes to obtain a product A.
8 parts of bisphenol A epoxy resin and 5 parts of tetraethoxysilane are uniformly mixed under anhydrous condition and stirred for 2 hours, and then 3 parts of deionized water is added and stirred for 5 hours at room temperature to obtain a product B.
Uniformly mixing 30 parts of the product A, 10 parts of the product B and 1 part of titanium dioxide, carrying out ultrasonic treatment for 5 hours, adding 5 parts of ethylenediamine, stirring at room temperature for 3 hours, feeding into a high-pressure reaction kettle, simultaneously adding 5 parts of methyl methacrylate and 0.05 part of azobisisobutyronitrile, and introducing 1/2 volume of liquid CO into the kettle 2 Then the temperature of the high-pressure reaction kettle is raised to 60 ℃ and liquid CO is continuously introduced into the kettle 2 Until the pressure in the kettle reaches 30MPa, the reactants in the kettle continue to carry out polymerization reaction for 12 hours under the stirring condition.
After polymerization, the autoclave was cooled and charged with liquid CO at a flow rate of 20 ml/min 2 To extract unreacted methyl methacrylate, after 20 minutesThe reaction product in the kettle is transferred into a vacuum drying oven and is solidified for 5 hours at the temperature of 80 ℃ to obtain a product D.
According to the weight percentage, the content of the product D is 30 percent, the content of the polyacrylic acid sodium salt is 1.0 percent, and the content of the acrylic emulsion is 69 percent, and the coating is prepared by uniformly mixing.
The coatings obtained in examples 1 to 3 and comparative examples 1 to 2 were applied to a metal substrate on which a front surface finish layer was formed, and the metal substrate was sampled and cut into a sample plate of a standard size and subjected to a performance test, thereby obtaining test data of various performances thereof, respectively, and specific test items and test methods were as follows:
1. weather resistance
And (3) carrying out an accelerated aging test on the sample plate, namely placing the sample plate in an ultraviolet aging test box (UVB-313 lamp tube) for 8 hours, wherein the cycle period is as follows: ultraviolet illumination is carried out for 4 hours, and the temperature of a blackboard is 60 +/-3 ℃; 4 hours is condensation, the temperature of the blackboard is 50 +/-3 ℃. The appearance of the above-described panels was observed after 1000 hours and evaluated based on CIE 1976.
2. Corrosion resistance
The sample is subjected to a neutral salt spray test, is subjected to the standard ASTMB117 for 1000 hours, and is judged according to the rust point (spot) quantity grade shown in Table 12 in GB/T1766 rating method for the aging of paint and varnish coatings.
3. Air purification performance
The test is carried out according to QB/T2761-2006 method for measuring the purification effect of indoor air purification products, and the time is 24 hours.
The results of the test of weather resistance, corrosion resistance and air cleaning performance of examples 1 to 3 and comparative examples 1 to 2 are shown in Table 1.
TABLE 1
Description of the preferred embodiment Color difference in weather resistance Corrosion resistance Formaldehyde removal rate (%)
Example 1 0.15 No corrosion 93.32
Example 2 0.20 No corrosion 90.36
Example 3 0.35 No corrosion 90.67
Comparative example 1 0.40 Few, several rust spots 85.33
Comparative example 2 1.20 With moderate rust 89.86
The test results show that the colorimetric value change delta E of the examples 1 to 3 in the weather resistance test is less than 1, the surface of the metal base material is rustless, and the formaldehyde gas elimination rate in 24 hours reaches more than 90%, so that the coatings prepared by the examples 1 to 3 based on the organic-inorganic hybrid material have excellent weather resistance, corrosion resistance and air purification performance, while the product A of the comparative example 1 does not have the complexation of ethyl acetate, so that the corrosion resistance is lower, and the epoxy resin and the zirconium source of the comparative example 2 do not adopt a silane coupling agent, so that the epoxy resin and the zirconium source of the comparative example are not modified in situ, and a core-shell structure can not be formed to coat silicon, zirconium and titanium compounds, so that the titanium compounds directly contact the surface of the metal base material, and the weather resistance and the corrosion resistance of the titanium compounds are the worst. Therefore, the paint prepared based on the organic-inorganic hybrid material has good corrosion resistance and aging resistance, can effectively purify air pollutants, has a simple preparation method, and is suitable for continuous large-scale production.
It will be appreciated by those skilled in the art that the above-described preferred embodiments may be freely combined, superimposed, without conflict.
It will be understood that the embodiments described above are illustrative only and not restrictive, and that various obvious and equivalent modifications and substitutions for details described herein may be made by those skilled in the art without departing from the basic principles of the invention.

Claims (7)

1. A preparation method of an organic-inorganic hybrid material is characterized by comprising the following steps:
mixing isopropanol containing zirconium n-propoxide and ethyl acetate, aging, adjusting the pH value to 0.5-4.0, and performing ultrasonic treatment to obtain a product A, wherein the raw material components comprise 1-10 parts by weight of isopropanol liquid and 1-5 parts by weight of ethyl acetate respectively, and the content of the zirconium n-propoxide in the isopropanol liquid is 50-90%;
mixing and stirring epoxy resin and a silane coupling agent, adding tetraethoxysilane for mixing and stirring, and finally adding deionized water for stirring to obtain a product B, wherein the raw material components comprise 1-10 parts by weight of epoxy resin, 0.1-2 parts by weight of silane coupling agent, 1-10 parts by weight of tetraethoxysilane and 0.1-5 parts by weight of deionized water;
mixing the product A, the product B and a titanium source, carrying out ultrasonic treatment, adding ethylenediamine, stirring, sending into a high-pressure reaction kettle, simultaneously adding methyl methacrylate and azodiisobutyronitrile, and introducing primary liquid CO into the kettle 2 Then raising the temperature in the kettle to 60-80 ℃ and continuously introducing secondary liquid CO into the kettle 2 Until the pressure in the kettle reaches 25-50 MPa, stirring the reactants in the kettle to obtain a product C, wherein the raw materials comprise the following components in parts by weight: 5 to 10 portions of product A, 3 to 5 portions of product B, 1 to 3 portions of titanium source, 1 to 5 portions of ethylenediamine, 0.2 to 6 portions of methyl methacrylate and 0.02 to 0.6 portion of azodiisobutyronitrile;
cooling the high-pressure reaction kettle and introducing liquid CO for three times into the product C 2 And (3) obtaining a product D, transferring the product D into a vacuum drying oven, and curing at 50-100 ℃ to obtain the organic-inorganic hybrid material.
2. The method for producing an organic-inorganic hybrid material according to claim 1,
the epoxy resin comprises one or a combination of bisphenol A epoxy resin, polyphenol glycidyl ether epoxy resin and bisphenol F epoxy resin;
and/or the silane coupling agent comprises one or more of 3-aminopropyltriethoxysilane, alcoholic propyl trimethoxy silane, 3- (methacryloyloxy) propyl trimethoxy silane and gamma-glycidoxypropyl trimethoxy silane;
and/or the titanium source comprises one or more of titanium dioxide, titanium tetrachloride, titanium isopropoxide and titanium sulfate.
3. The method for producing an organic-inorganic hybrid material according to claim 1, wherein the primary liquid CO is 2 The introduction amount of (2) is 1/2 of the volume of the high-pressure reaction kettle; the tertiary liquid CO 2 The flow rate of (2) is 10 to 30 ml/min.
4. An organic-inorganic hybrid material is characterized by comprising 5-10 parts by weight of a first raw material, 3-5 parts by weight of a second raw material and 1 part by weight of a third raw material;
the first raw material comprises the following components in parts by weight: 1-10 parts of isopropanol and 1-5 parts of ethyl acetate, wherein the content of zirconium n-propoxide in the isopropanol is 50-90%;
the second raw material comprises the following components in parts by weight: 1-10 parts of epoxy resin, 0.1-2 parts of silane coupling agent, 1-10 parts of ethyl orthosilicate and 0.1-5 parts of deionized water;
the third raw material comprises the following components in parts by weight: 1 to 3 parts of titanium source, 1 to 4.8 parts of ethylenediamine, 0.2 to 6 parts of methyl methacrylate and 0.02 to 0.6 part of azodiisobutyronitrile;
the organic-inorganic hybrid material comprises an epoxy resin/polymethyl methacrylate three-dimensional cross-linked network formed by cross-linking the methyl methacrylate with the epoxy resin through the silane coupling agent, wherein the epoxy resin/polymethyl methacrylate three-dimensional cross-linked network coats zirconium oxide particles, silicon oxide particles and titanium oxide particles;
the organic-inorganic hybrid material is obtained by the production method as set forth in any one of claims 1 to 3.
5. A coating, characterized by: the coating comprises the following components in percentage by weight: 30% of organic-inorganic hybrid material, 1% of dispersant and 69% of acrylic emulsion;
the organic-inorganic hybrid material is obtained by the production method according to any one of claims 1 to 3.
6. The coating of claim 5, wherein the dispersant comprises one or more of Surfynol CT-231, sodium polyacrylate, and sodium carboxymethylcellulose.
7. An electronic display device comprising a structural member composed of a metal base material, wherein a coating material applied to a surface of the metal base material comprises an organic-inorganic hybrid material obtained by the production method according to any one of claims 1 to 3.
CN202210066438.4A 2022-01-20 2022-01-20 Organic-inorganic hybrid material, preparation method thereof, paint and electronic display device Active CN114479618B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202210066438.4A CN114479618B (en) 2022-01-20 2022-01-20 Organic-inorganic hybrid material, preparation method thereof, paint and electronic display device

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202210066438.4A CN114479618B (en) 2022-01-20 2022-01-20 Organic-inorganic hybrid material, preparation method thereof, paint and electronic display device

Publications (2)

Publication Number Publication Date
CN114479618A CN114479618A (en) 2022-05-13
CN114479618B true CN114479618B (en) 2023-02-17

Family

ID=81472542

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202210066438.4A Active CN114479618B (en) 2022-01-20 2022-01-20 Organic-inorganic hybrid material, preparation method thereof, paint and electronic display device

Country Status (1)

Country Link
CN (1) CN114479618B (en)

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05148453A (en) * 1991-03-08 1993-06-15 Armstrong World Ind Inc Epoxy/glass coating composition
JP2001200202A (en) * 2000-01-21 2001-07-24 Yamaha Livingtec Corp Method of forming inorganic film
CA2339053A1 (en) * 2001-03-02 2002-09-02 Zenastra Photonics Inc. Organic-inorganic hybrids surface adhesion promotor
JP4000448B2 (en) * 2002-02-19 2007-10-31 Ｊｓｒ株式会社 Coating composition for sliding member and sliding member
JP5255270B2 (en) * 2007-12-27 2013-08-07 日揮触媒化成株式会社 Inorganic oxide fine particles having a core-shell structure, dispersed sol containing the fine particles, and coating solution for optical substrate
CN103709747B (en) * 2013-12-27 2017-01-04 广东生益科技股份有限公司 A kind of compositions of thermosetting resin and application thereof
CN104987808B (en) * 2015-08-07 2016-06-29 深圳市世家丽科技发展有限公司 A kind of environmental protection conch meal functional coating and its production and use
CN110776706A (en) * 2019-10-29 2020-02-11 追信数字科技有限公司 Method for manufacturing CPU heat dissipation material by heat absorption, heat transfer and radiation combined mechanism
CN111686311B (en) * 2020-06-16 2021-05-11 四川大学 Super-lubricating coating for interventional valve delivery system and preparation method thereof

Also Published As

Publication number Publication date
CN114479618A (en) 2022-05-13

Similar Documents

Publication Publication Date Title
CN109370408B (en) Method for preparing super-hydrophobic coating by compounding waterborne polyurethane and hydrophobic modified inorganic nanoparticles
Zandi-Zand et al. Silica based organic–inorganic hybrid nanocomposite coatings for corrosion protection
CN100473469C (en) Corrosion protection on metals
EP3006526B1 (en) Hot-dip aluminum-zinc coated steel sheet with excellent weatherability, corrosion resistance, and alkali resistance, and preparation method and surface treatment agent therefor
CN106906462B (en) A kind of metal surface pretreating reagent and preparation method thereof, application
CN111534162A (en) Montmorillonite-based photocatalytic super-hydrophobic coating and preparation method thereof
CN105885611A (en) Polymer metallic copper anticorrosive coating and preparation method thereof
CN106835093B (en) A kind of Q type POSS modified metal surface pretreating reagent and preparation method thereof, application
CN108727961A (en) Heat insulating and corrosion coating and preparation method thereof
CN113881292B (en) Anti-permeability anticorrosive paint with good stability and strong adhesiveness and preparation method thereof
Seok et al. Preparation of corrosion protective coatings on galvanized iron from aqueous inorganic–organic hybrid sols by sol–gel method
CN114479618B (en) Organic-inorganic hybrid material, preparation method thereof, paint and electronic display device
CN106894009B (en) A kind of epoxy group POSS modified metal surface pretreating reagent and preparation method thereof, application
CN108102434B (en) Nano toughened inorganic zinc-rich coating and preparation method thereof
CN113337210A (en) Corrosion inhibitor-loaded pH-responsive silicon dioxide nano container composite silane film and preparation and application thereof
CN115477893B (en) Preparation method of water-based alkyd anticorrosive paint
CN114163848B (en) Preparation method of environment-friendly anticorrosive paint for neodymium iron boron magnet
JP4223138B2 (en) Precoated steel sheet excellent in workability, weather resistance and photocatalytic activity, and method for producing the same
CN115233203A (en) Aluminum plate pre-color-coating chromium-free passivation solution for improving paint binding force and coating process thereof
CN115261842A (en) Organic composite passivation treating fluid for hot-dip galvanized sheet and use method thereof
Zhang et al. Effect of Sol-Gel Film on the Corrosion Resistance of Low Carbon Steel Plate
CN111704822B (en) Hydrophobic modified diatom shell material, preparation method and application thereof, and hydrophobic component containing hydrophobic modified diatom shell material
JP5238934B2 (en) Aqueous zirconium anticorrosive, metal corrosion prevention method using the same, and aqueous zirconium anticorrosive
CN114479583B (en) Preparation method of coating composition
CN112979921B (en) In-situ response corrosion inhibition type epoxy resin and preparation method and application 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
GR01 Patent grant
GR01 Patent grant