CN118495827A - Preparation method of super-hydrophilic self-cleaning anti-fog glass - Google Patents

Preparation method of super-hydrophilic self-cleaning anti-fog glass Download PDF

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CN118495827A
CN118495827A CN202410431383.1A CN202410431383A CN118495827A CN 118495827 A CN118495827 A CN 118495827A CN 202410431383 A CN202410431383 A CN 202410431383A CN 118495827 A CN118495827 A CN 118495827A
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mass
stirring
fog
glass
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杨梅梅
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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/28—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material
    • C03C17/32—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material with synthetic or natural resins
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
    • C07F5/02—Boron compounds
    • C07F5/025—Boronic and borinic acid compounds
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00—Coatings on glass
    • C03C2217/70—Properties of coatings
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2218/00—Methods for coating glass
    • C03C2218/10—Deposition methods
    • C03C2218/11—Deposition methods from solutions or suspensions
    • C03C2218/114—Deposition methods from solutions or suspensions by brushing, pouring or doctorblading
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2218/00—Methods for coating glass
    • C03C2218/30—Aspects of methods for coating glass not covered above
    • C03C2218/32—After-treatment
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Materials Engineering (AREA)
  • Surface Treatment Of Glass (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention discloses a preparation method of super-hydrophilic self-cleaning anti-fog glass, and relates to the technical field of glass. The super-hydrophilic self-cleaning anti-fog glass prepared by the invention comprises a glass base layer and an anti-fog layer from inside to outside; firstly, mixing trivinyl alcohol-based triamino triphenylamine and acrylonitrile-based perylene tetracarboxylic acid hydrazine hydrochloride to form perylene imide, a large amount of hydrophilic group quaternary ammonium salt and carboxyl, and preparing an anti-fog layer; and then, the acrylic acid group chloropropyl phenylboronic acid is used for wrapping the glass base layer by the anti-fog layer through a supercritical ammonia auxiliary knife coating process, so that a three-dimensional network structure is formed between the glass base layer and the anti-fog layer while hindered amine is formed, and the super-hydrophilic self-cleaning anti-fog glass is prepared. The super-hydrophilic self-cleaning anti-fog glass prepared by the invention has good anti-fog property, self-cleaning property, impact resistance and light stability.

Description

Preparation method of super-hydrophilic self-cleaning anti-fog glass
Technical Field
The invention relates to the technical field of glass, in particular to a preparation method of super-hydrophilic self-cleaning anti-fog glass.
Background
Glass is the most common material in our daily life, is closely related to the production activities of people, and along with the development of modern scientific technology and glass technology and the improvement of the living standard of people, the function of the building glass is not only to meet the lighting requirement, but also to have the characteristics of light adjustment, heat preservation, heat insulation, bulletproof, self cleaning and the like. Self-cleaning glass is therefore widely favored in the marketplace.
The self-cleaning glass is glass which is characterized in that after the common glass is treated by a special physical or chemical method, the surface of the common glass has unique physical and chemical characteristics, so that the glass can achieve a cleaning effect without a traditional manual scrubbing method; at present, the super-hydrophilic self-cleaning glass and the super-hydrophobic self-cleaning glass are divided into two main types. In autumn and winter, moisture or steam is extremely easy to condense to form tiny water drops on the surface of a glass product, so that the sight of people is greatly influenced, the super-hydrophilic self-cleaning glass is hydrophilic on the surface of the glass product, when water contacts the surface of the glass, the super-hydrophilic self-cleaning glass spreads on the surface of the glass product rapidly to form a uniform water film, mirror imaging cannot be influenced, meanwhile, the influence of water layer thinness on light transmittance is greatly reduced, stains are taken away through the gravity falling of the uniform water film, and the super-hydrophilic self-cleaning glass is widely applied to the fields of automobiles and buildings, so that the super-hydrophilic self-cleaning glass is required to have good light stability and impact strength.
The present invention addresses this problem by preparing ultra-hydrophilic self-cleaning anti-fog glass.
Disclosure of Invention
The invention aims to provide super-hydrophilic self-cleaning anti-fog glass and a preparation method thereof, which are used for solving the problems in the prior art.
In order to solve the technical problems, the invention provides the following technical scheme:
The super-hydrophilic self-cleaning anti-fog glass comprises a glass base layer and an anti-fog layer from inside to outside, wherein the super-hydrophilic self-cleaning anti-fog glass is prepared by wrapping the glass base layer with the anti-fog layer by utilizing acrylic acid group chloropropyl phenylboronic acid through a supercritical ammonia auxiliary knife coating process.
Further, the anti-fog layer is prepared by mixing trivinyl alcohol-based triamino triphenylamine and acrylonitrile-based perylene tetracarboxylic acid hydrazine hydrochloride.
Further, the glass base layer is toughened glass with the thickness of 6-10 mm.
Further, the preparation method of the super-hydrophilic self-cleaning anti-fog glass comprises the following steps: placing the glass substrate into a reaction kettle with the pressure of 12-13 MPa at room temperature, introducing ammonia gas with the mass of 2-4 times of that of the glass substrate at the speed of 3-5 m 3/min, heating to 158-159 ℃ at the speed of 9-11 ℃/min, preserving heat for 30-50 min, taking out, then scraping and coating anti-fog film liquid with the thickness of 60-80 nm on the surface of the glass substrate at the temperature of 200-260 ℃ by using a scraper, naturally cooling to the room temperature, and then placing into a baking oven with the temperature of 70-90 ℃ for baking for 2-4 h to prepare the anti-fog glass; then under the protection of argon, immersing the anti-fog glass in acrylic acid chloropropyl phenylboric acid with the mass of 1.2-1.6 times of that of the anti-fog glass, standing for 2-3 h after fishing out, baking for 0.5-1 h at the temperature of 30-40 ℃, treating for 20-40 min under the microwave conditions of 2300-2500 MHz and 700-900W after ultrasonic treatment for 10-20 min at the temperature of 30-40 kHz, dropwise adding concentrated sulfuric acid with the mass fraction of 98% which is 0.2-0.4 times of that of the anti-fog glass at the temperature of 40-60 drops/min, continuing ultrasonic treatment for 30-40 min, immersing in aluminum trichloride solution with the mass fraction of 5-7% which is 0.3-0.5 times of that of the anti-fog glass, ultrasonic treatment for 40-60 min at the temperature of 0-4 ℃, and baking for 2-4 h in a baking oven at the temperature of 30-50 ℃, then dripping concentrated hydrochloric acid with the mass fraction of 38-42% at the speed of 40-60 drops/min and with the mass fraction of 0.3-0.5 times of that of the anti-fog glass, putting the anti-fog glass into a reaction kettle with the mass fraction of 12-13 MPa, introducing ammonia gas with the mass of 2-4 times of that of the anti-fog glass at the speed of 3-5 m 3/min, heating to 158-159 ℃ at the speed of 9-11 ℃/min, continuing to carry out ultrasonic treatment for 40-60 min, heating to 180-190 ℃ at the speed of 9-11 ℃/min, cooling to 40-60 ℃ at the speed of 9-11 ℃/min, continuing to carry out ultrasonic treatment for 40-60 min, adding sodium ethoxide with the mass of 0.2-0.4 times of that of the anti-fog glass, continuing to carry out ultrasonic treatment for 40-50 min at the speed of 100-120 ℃, then carrying out ultrasonic treatment at the speed of 2300-250 MHz and 700-900W microwave conditions, naturally cooling to room temperature, and putting the anti-fog glass into an oven with the temperature of 30-50 ℃ for 2-4 h, thus obtaining the anti-ultraviolet glass base layer.
Further, the preparation method of the acrylic acid group chloropropyl phenylboronic acid comprises the following steps: under the protection of argon at the temperature, dichloropropane and (2E) -3- [4- (boric acid group) phenyl ] acrylic acid are mixed according to the mass ratio of 1: 0.2-1: mixing 0.4, stirring for 20-30 min at 300-500 r/min, then adding aluminum trichloride with the mass of 0.03-0.05 times of that of the chlorformaldehyde, cooling to 0-4 ℃ at 4-6 ℃ per min, and stirring for 7-9 h at 500-700 r/min to obtain the acrylic acid chloropropyl phenylboronic acid.
Further, the preparation method of the anti-fog layer film liquid comprises the following steps: dropwise adding 0.3-0.5 times of acrylonitrile-based perylene tetracarboxylic acid hydrazine hydrochloride into the trivinyl alcohol-based triamino triphenylamine at the temperature of 60-80 ℃ under the protection of 3-5 MPa and argon at the temperature of 40-60 drops/min, stirring for 20-30 min at the temperature of 300-500 r/min, dropwise adding 0.1-0.3 times of dibenzoyl peroxide at the temperature of 40-60 drops/min, stirring for 2-4 h at the temperature of 500-700 r/min, naturally cooling to room temperature, adding a sulfuric acid solution with the mass fraction of 70-90% of 3-5 times of the mass fraction of the trivinyl alcohol-based triamino triphenylamine, continuously stirring and refluxing for 2-4 h at the temperature of 100-120 ℃, steaming for 1-3 h at the temperature of 1400-160 r/min and 100-120 ℃, then adding 3-5 times of N, N-dimethylformamide at the temperature of the trivinyl alcohol-based triamino triphenylamine, stirring for 30-40 min at the temperature of 300-500 r/min, heating for 4-154 ℃ to 152 ℃ for 4-300 h, and continuously heating to 400 h to obtain an anti-fog film.
Further, the preparation method of the trivinyl alcohol-based triamino triphenylamine comprises the following steps: under the protection of argon at the temperature, chlorovinyl alcohol and 4, 4'' -triamino triphenylamine are mixed according to the mass ratio of 1: 0.3-1: mixing 0.5, stirring for 20-30 min at 300-500 r/min, then adding aluminum trichloride with the mass of 0.02-0.04 times of that of the chlorformaldehyde, cooling to 0-4 ℃ at 4-6 ℃ per min, and stirring for 7-9 h at 500-700 r/min to obtain the trivinyl alcohol-based triamino triphenylamine.
Further, the preparation method of the acrylonitrile-based perylene tetracarboxylic acid hydrazine hydrochloride comprises the following steps: under the protection of argon at the temperature, the mass ratio of the chloroacrylonitrile to the tetracyano-perylene hydrazine hydrochloride is 1: 0.1-1: mixing 0.3, stirring for 20-30 min at 300-500 r/min, then adding aluminum trichloride with the mass of 0.03-0.05 times that of chloroacrylonitrile, cooling to 0-4 ℃ at 4-6 ℃ per min, and stirring for 7-9 h at 500-700 r/min to obtain the acrylonitrile-based perylene tetracarboxylic acid hydrazine hydrochloride.
Further, the preparation method of the tetracyano perylene hydrazine hydrochloride comprises the following steps: adding amino-tetracyano perylene into hydrochloric acid solution with the mass fraction of 39-45% which is 5-7 times of that of the amino-tetracyano perylene under the protection of argon at the temperature of 0-4 ℃ and stirring for 10-30 min at the speed of 300-500 r/min, then adding the amino-tetracyano perylene into sodium nitrite with the mass of 0.2-0.4 times of that of the amino-tetracyano perylene, and continuously stirring for 1-3 h to prepare the tetracyano perylene hydrazine hydrochloride.
Further, the preparation method of the aminotetracyano perylene comprises the following steps: under the conditions of 50-60 ℃ and argon protection, the mass fraction of the concentrated nitric acid is 68% and the mass fraction of the concentrated sulfuric acid is 98% according to the mass ratio of 1: 0.8-1: 1.2, mixing, stirring for 10-30 min at 300-500 r/min, then dripping 3,4,9, 10-tetracyano perylene with the mass of 1.2-1.4 times of concentrated nitric acid at 40-60 r/min, stirring for 1-3 h at 600-800 r/min, continuously dripping sodium hydroxide solution with the mass fraction of 20-30% to adjust the pH value to 6-8, adding palladium-carbon catalyst with the mass of 0.06-0.08 times of concentrated nitric acid, introducing hydrogen with the mass of 2-3 times of concentrated nitric acid at 2-3 m/min at 1-3 MPa and 79-81 ℃, stirring for 1-3 h at 600-800 r/min, then adding sodium hydroxide solution with the mass fraction of 20-30% of concentrated nitric acid, heating to 95-105 ℃ at 9-11 ℃/min, and continuously stirring for 6-8 h to prepare the aminotetracyano perylene.
Compared with the prior art, the invention has the following beneficial effects:
The super-hydrophilic self-cleaning anti-fog glass prepared by the invention comprises a glass base layer and an anti-fog layer from inside to outside; firstly, mixing trivinyl alcohol-based triamino triphenylamine and acrylonitrile-based perylene tetracarboxylic acid hydrazine hydrochloride to prepare an anti-fog layer; and then coating the glass substrate with the anti-fog layer by using acrylic acid group chloropropyl phenylboronic acid through a supercritical ammonia auxiliary knife coating process, so as to prepare the super-hydrophilic self-cleaning anti-fog glass.
Firstly, polymerizing styrene on trivinyl alcohol-based triamino triphenylamine and acrylonitrile on acrylonitrile-based perylene tetracarboxylic acid hydrazine hydrochloride to form polystyrene acrylonitrile, forming quaternary ammonium salt by trivinyl alcohol-based triamino triphenylamine under the action of acrylonitrile-based perylene tetracarboxylic acid hydrazine hydrochloride, hydrolyzing nitrile to form carboxyl and perylene tetracarboxylic acid, enhancing the hydrophilicity of an anti-fog layer, highly spreading water vapor when condensing on the anti-fog layer, forming a uniform water film, eliminating diffuse reflection of light, and enhancing the anti-fog performance of the anti-fog layer; the perylene tetracarboxylic acid on the acrylonitrile group tetracyano perylene and the amino group on the aminostyrene react and crosslink to form perylene imide with a conjugated microporous structure, and when the perylene imide is irradiated by light, pollutants adsorbed on the anti-fog layer are degraded under the catalysis of the perylene imide to form carbon dioxide and water, so that the self-cleaning performance of the anti-fog layer is enhanced.
Secondly, the surface of the glass substrate is activated to form a large number of free radicals such as hydroxyl, amino and the like, acrylic acid-based chloropropyl phenylboronic acid is deposited on the contact surface of the glass substrate and the antifogging layer through a pore canal on the antifogging layer, boric acid at one end of the acrylic acid-based chloropropyl phenylboronic acid is crosslinked with amino on the glass substrate in a reaction manner, acrylic acid at one end of the acrylic acid-based chloropropyl phenylboronic acid is crosslinked with hydroxyethyl on the antifogging layer in a reaction manner to form ethyl acrylate, the glass substrate and the antifogging layer are firmly connected together, the ethyl acrylate is added and cyclized with ammonia gas to form dimethylpiperidone, chloropropyl and dimethylpiperidone on adjacent acrylic acid-based chloropropyl phenylboronic acid molecular chains are reacted to form hindered amine, a three-dimensional network structure is formed between the glass substrate and the antifogging layer, and the light stability of the superhydrophilic self-cleaning antifogging glass is enhanced while the shock resistance of the superhydrophilic self-cleaning antifogging glass is enhanced.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
In order to more clearly illustrate the method provided by the invention, the following examples are used for describing the detailed description, and the test method of each index of the super-hydrophilic self-cleaning anti-fog glass prepared in the following examples is as follows:
Antifogging properties: the ultra-hydrophilic self-cleaning anti-fog glass prepared by taking the examples and comparative examples with the same length and width was measured for anti-fog property by measuring the contact angle of water using a hydrophobic angle measuring instrument.
Self-cleaning: the super-hydrophilic self-cleaning anti-fog glass surface prepared by the example and the comparative example with the same area is taken, soy sauce with the mass of 0.4 times is dripped, 365nm ultraviolet light is used for continuous irradiation for 8 hours, the interval is 10 hours, after 5 times of circulation, the mass before and after illumination is weighed, and the self-cleaning property is determined by measuring the mass change rate, wherein the mass change rate=100% (mass before illumination-mass after illumination)/mass before illumination.
Impact resistance: the ultra-hydrophilic self-cleaning anti-fog glass prepared by the example and the comparative example with the same quality is used for measuring the breaking number of a sample according to the GB/T9963 standard to measure the impact resistance.
Light stability: the ultraviolet-proof glass substrates prepared in the examples and comparative examples with the same length and width are continuously irradiated with 365nm ultraviolet light for 8 hours at intervals of 10 hours, and after 5 times of circulation, the compressive strength after ultraviolet aging is measured according to the GB/T6552 standard to measure the light stability.
Example 1
The preparation method of the super-hydrophilic self-cleaning anti-fog glass comprises the following preparation steps:
(1) Under the protection of argon at 50 ℃, 68 mass percent of concentrated nitric acid and 98 mass percent of concentrated sulfuric acid are mixed according to the mass ratio of 1:0.8, mixing, stirring for 10min at 300r/min, then dripping 3,4,9, 10-tetracyanopylene with the mass of 1.2 times of concentrated nitric acid at 40 r/min, stirring for 1h at 600r/min, continuously dripping sodium hydroxide solution with the mass fraction of 20% to adjust the pH value to 6, adding palladium-carbon catalyst with the mass of 0.06 times of concentrated nitric acid, introducing hydrogen with the mass of 2 times of concentrated nitric acid at 2 m/min at 1MPa and 79 ℃ and stirring for 1h at 600r/min, then adding sodium hydroxide solution with the mass fraction of 20% with the mass of 2 times of concentrated nitric acid, heating to 95 ℃ at 9 ℃/min, and continuously stirring for 6h to prepare the aminotetracyano perylene; adding amino-tetracyano perylene into hydrochloric acid solution with the mass fraction of 39% which is 5 times of that of the amino-tetracyano perylene at the temperature of 0 ℃ under the protection of argon, stirring for 10min at 300r/min, then adding the amino-tetracyano perylene into sodium nitrite with the mass of 0.2 times of that of the amino-tetracyano perylene, and continuously stirring for 1h to prepare tetracyano perylene hydrazine hydrochloride; under the protection of argon at the temperature, the mass ratio of the chloroacrylonitrile to the tetracyano-perylene hydrazine hydrochloride is 1:0.1, mixing, stirring for 20min at 300r/min, then adding aluminum trichloride with the mass of 0.03 times that of the acrylonitrile, cooling to 0 ℃ at 4 ℃/min, and stirring for 7h at 500r/min to prepare acrylonitrile-based perylene tetracarboxylic acid hydrazine hydrochloride;
(2) Under the protection of argon at the temperature, chlorovinyl alcohol and 4, 4'' -triamino triphenylamine are mixed according to the mass ratio of 1: mixing at a speed of 300r/min for 20min, adding aluminum trichloride with a mass which is 0.02 times that of the formaldehyde chloride, cooling to 0 ℃ at a speed of 4 ℃/min, and stirring at a speed of 500r/min for 7h to prepare the trivinyl alcohol-based triamino triphenylamine; dropwise adding 0.3 times of acrylonitrile-perylene tetracarboxylic acid hydrazine hydrochloride into trivinyl alcohol-based triaminobilide at 60 ℃ under the protection of 3MPa and argon at 40 drops/min, stirring for 20min at 300r/min, then dropwise adding 0.1 times of dibenzoyl peroxide into trivinyl alcohol-based triaminobilide at 40 drops/min, stirring for 2h at 500r/min, naturally cooling to room temperature, adding 70% sulfuric acid solution with 3 times of trivinyl alcohol-based triaminobilide at 100 ℃, continuously stirring and refluxing for 2h at 100 ℃, steaming for 1h at 1400r/min and 100 ℃, then adding 3 times of N, N-dimethylformamide into trivinyl alcohol-based triaminobilide, stirring for 30min at 300r/min, heating to 152 ℃ at 4 ℃/min, stirring and refluxing for 4h at 800r/min, continuously heating to 300 ℃ and preserving heat for 1h, thus obtaining anti-fog film liquid;
(3) Under the protection of argon at the temperature, dichloropropane and (2E) -3- [4- (boric acid group) phenyl ] acrylic acid are mixed according to the mass ratio of 1: mixing 0.2, stirring at 300r/min for 20min, then adding aluminum trichloride with the mass of 0.03 times of that of the formaldehyde chloride, cooling to 0 ℃ at 4 ℃/min, and stirring at 500r/min for 7h to prepare the acrylic acid-based chloropropyl phenylboronic acid;
(4) Placing a glass substrate into a reaction kettle with the temperature of 12MPa, introducing ammonia gas with the mass of 2 times of that of the glass substrate at the speed of 3m 3/min, heating to 158 ℃ at the speed of 9 ℃/min, preserving heat for 30min, taking out, then scraping and coating an anti-fog layer film liquid with the thickness of 60nm on the surface of the glass substrate at the temperature of 200 ℃, naturally cooling to the room temperature, and then placing into a baking oven with the temperature of 70 ℃ for baking for 2h to prepare the anti-fog glass; then under the protection of argon, immersing the anti-fog glass in acrylic chloropropyl phenylboric acid with the mass of 1.2 times of the anti-fog glass, taking out, standing for 2 hours, baking at 30 ℃ for 0.5 hours, processing at 2300MHz and 700W microwave conditions for 20 minutes after ultrasonic treatment at 30kHz for 10 minutes, dropwise adding concentrated sulfuric acid with the mass of 0.2 times of the anti-fog glass at 98% at 40 ℃/min, continuing ultrasonic treatment for 30 minutes, immersing in aluminum trichloride solution with the mass of 5% at 0.3 times of the anti-fog glass at 0 ℃ for 40 minutes, taking out, putting into a baking oven at 30 ℃ for 2 hours, dropwise adding concentrated hydrochloric acid with the mass of 0.3 times of the anti-fog glass at 40 ℃/min into a reaction kettle with the mass of 38% at 12MPa, introducing ammonia gas with the mass of 2 times of the anti-fog glass at 3m 3/min, heating up to 158 ℃ at 9 ℃/min, continuing ultrasonic treatment for 40 minutes after 9 ℃/min to 180 ℃, continuing ultrasonic treatment at 9 ℃/min to 40 ℃ and ultrasonic treatment for 40 minutes, adding sodium trichloride with the mass of the anti-fog glass at 0.3 times of the mass of the anti-fog glass at 40 ℃ for 2 MHz, continuously cooling at 100 ℃ for 20 hours, and then cooling at 100 ℃ for 20 hours under the baking oven at 30 ℃ for the temperature, and preparing the anti-ultraviolet glass, and then, carrying out the anti-fog glass, and carrying out natural treatment, and carrying out the ultraviolet proof treatment under the conditions.
Example 2
The preparation method of the super-hydrophilic self-cleaning anti-fog glass comprises the following preparation steps:
(1) Under the conditions of 55 ℃ and argon protection, the mass fraction of the concentrated nitric acid is 68% and the mass fraction of the concentrated sulfuric acid is 98% according to the mass ratio of 1:1, mixing, stirring for 20min at 400r/min, then dripping 3,4,9, 10-tetracyanopylene with the mass of 1.3 times of concentrated nitric acid at 50 r/min, stirring for 2h at 700r/min, continuously dripping sodium hydroxide solution with the mass fraction of 25% to adjust the pH value to 7, adding palladium-carbon catalyst with the mass fraction of 0.07 times of concentrated nitric acid, introducing hydrogen with the mass of 2.5 times of concentrated nitric acid at 2.5 m/min at 2MPa and 80 ℃, stirring for 2h at 700r/min, then adding sodium hydroxide solution with the mass fraction of 25% with the mass fraction of 2.5 times of concentrated nitric acid, heating to 100 ℃ at 10 ℃/min, and continuously stirring for 7h to prepare the amino tetracyanopylene; adding amino-tetracyano perylene into hydrochloric acid solution with the mass fraction of 42% which is 6 times of that of the amino-tetracyano perylene at the temperature of 2 ℃ under the protection of argon, stirring for 20min at 400r/min, then adding the amino-tetracyano perylene into sodium nitrite with the mass of 0.3 times of that of the amino-tetracyano perylene, and continuously stirring for 2h to prepare tetracyano perylene hydrazine hydrochloride; under the protection of argon at the temperature, the mass ratio of the chloroacrylonitrile to the tetracyano-perylene hydrazine hydrochloride is 1:0.2, mixing, stirring for 25min at 400r/min, then adding aluminum trichloride with the mass of 0.04 times that of the acrylonitrile, cooling to 2 ℃ at 5 ℃/min, and stirring for 8h at 600r/min to prepare acrylonitrile-based perylene tetracarboxylic acid hydrazine hydrochloride;
(2) Under the protection of argon at the temperature, chlorovinyl alcohol and 4, 4'' -triamino triphenylamine are mixed according to the mass ratio of 1:0.4, mixing, stirring for 25min at 400r/min, then adding aluminum trichloride with the mass of 0.03 times of that of the formaldehyde chloride, cooling to 2 ℃ at 5 ℃/min, and stirring for 8h at 600r/min to prepare the trivinyl alcohol-based triamino triphenylamine; dropwise adding 0.4 times of acrylonitrile-perylene tetracarboxylic acid hydrazine hydrochloride into trivinyl alcohol-based triaminobenzidine at 70 ℃ under the protection of 4MPa and argon at 50 drops/min, stirring for 25min at 400r/min, then dropwise adding 0.2 times of dibenzoyl peroxide into the trivinyl alcohol-based triaminobenzidine at 50 drops/min, stirring for 3h at 600r/min, naturally cooling to room temperature, adding 80% sulfuric acid solution with the mass fraction of 4 times of the trivinyl alcohol-based triaminobenzidine, continuously stirring and refluxing for 3h at 110 ℃, steaming for 2h at 1500r/min and 110 ℃, then adding 4 times of N, N-dimethylformamide into the trivinyl alcohol-based triaminobenzidine, stirring for 35min at 400r/min, heating to 153 ℃ at 5 r/min, stirring and refluxing for 5h at 900r/min, continuously heating to 350 ℃ and preserving heat for 2h to prepare anti-fog film liquid;
(3) Under the protection of argon at the temperature, dichloropropane and (2E) -3- [4- (boric acid group) phenyl ] acrylic acid are mixed according to the mass ratio of 1:0.3 mixing, stirring for 25min at 400r/min, then adding aluminum trichloride with the mass of 0.04 times of that of the chlorformaldehyde, cooling to 2 ℃ at 5 ℃/min, stirring for 8h at 600r/min, naturally heating to room temperature, adding formamide with the mass of 0.9 times of that of the dichloropropane, continuously stirring for 25min, then adding nano titanium dioxide with the mass of 0.08 times of that of the dichloropropane, heating to 90 ℃ at 9.5 ℃/min, and continuously stirring for 3h to obtain acrylic acid chloropropyl phenylboronic acid;
(4) Placing a glass substrate into a reaction kettle with the pressure of 12.5MPa at room temperature, introducing ammonia gas with the mass of 3 times of that of the glass substrate at the speed of 4m 3/min, heating to 158.5 ℃ at the speed of 10 ℃/min, preserving heat for 40min, taking out, then scraping a 70nm thick anti-fog layer film liquid on the surface of the glass substrate at the temperature of 230 ℃, naturally cooling to the room temperature, and then placing into an oven with the temperature of 80 ℃ for baking for 3 hours to prepare the anti-fog glass; then under the protection of argon, immersing the anti-fog glass in acrylic acid-based chloropropyl phenylboric acid with the mass of 1.4 times of the anti-fog glass, taking out the anti-fog glass, standing for 2.5h, baking at 35 ℃ for 0.75h, processing at 2400MHz and 800W microwave conditions for 30min after ultrasonic treatment at 35kHz for 15min, dropwise adding concentrated sulfuric acid with the mass fraction of 0.3 times of the anti-fog glass at 50 ℃/min for 98%, continuing to ultrasonically process for 35min, immersing the anti-fog glass in aluminum trichloride solution with the mass fraction of 0.4 times of the anti-fog glass for 6% at 2 ℃ for 50min, taking out the anti-fog glass, then placing the anti-fog glass into a baking oven for 3h at 40 ℃, dropwise adding concentrated hydrochloric acid with the mass fraction of 0.4 times of the anti-fog glass into a reaction kettle of 12.5MPa, introducing ammonia gas with the mass of 3 times of 4m 3 MPa, heating to 158.5 ℃ at 10 ℃/min, continuing to ultrasonically heat for 50min, then continuously heating to 185 ℃ at 10 ℃/min, continuously heating to 50 ℃ for 50min, ultrasonic treatment at 50 ℃ for 50min, continuously cooling to 50 ℃ for 40 MHz, continuously heating to 40 MHz, and cooling the anti-fog glass at 40 ℃ for 40 MHz, continuously cooling at 40 ℃ for 20 h, and continuously carrying out ultrasonic treatment at 40 ℃ for 20 h, and then carrying out ultrasonic treatment to prepare the anti-fog glass.
Example 3
The preparation method of the super-hydrophilic self-cleaning anti-fog glass comprises the following preparation steps:
(1) Under the conditions of 60 ℃ and argon protection, 68 mass percent of concentrated nitric acid and 98 mass percent of concentrated sulfuric acid are mixed according to the mass ratio of 1:1.2, mixing, stirring for 30min at 500r/min, then dripping 3,4,9, 10-tetracyanopylene with the mass of 1.4 times of concentrated nitric acid at 60 drops/min, stirring for 3h at 800r/min, continuously dripping 30% sodium hydroxide solution with the mass fraction of 30% to adjust the pH value to 8, adding a palladium-carbon catalyst with the mass fraction of 0.08 times of concentrated nitric acid, introducing 3 times of hydrogen with the mass of 3m of concentrated nitric acid at 3MPa and 81 ℃, stirring for 3h at 800r/min, then adding 30% sodium hydroxide solution with the mass fraction of 3 times of concentrated nitric acid, heating to 105 ℃ at 11 ℃/min, and continuously stirring for 8h to prepare the aminotetracyano perylene; adding amino-tetracyano perylene into hydrochloric acid solution with mass fraction of 45% which is 7 times of that of the amino-tetracyano perylene at the temperature of 4 ℃ under the protection of argon, stirring for 30min at 500r/min, then adding the amino-tetracyano perylene into sodium nitrite with mass of 0.4 times of that of the amino-tetracyano perylene, and continuously stirring for 3h to prepare tetracyano perylene hydrazine hydrochloride; under the protection of argon at the temperature, the mass ratio of the chloroacrylonitrile to the tetracyano-perylene hydrazine hydrochloride is 1:0.3, mixing, stirring for 30min at 500r/min, then adding aluminum trichloride with the mass of 0.05 times that of the acrylonitrile, cooling to 4 ℃ at 6 ℃/min, and stirring for 9h at 700r/min to prepare acrylonitrile-based perylene tetracarboxylic acid hydrazine hydrochloride;
(2) Under the protection of argon at the temperature, chlorovinyl alcohol and 4, 4'' -triamino triphenylamine are mixed according to the mass ratio of 1: mixing 0.5, stirring at 500r/min for 30min, then adding aluminum trichloride with the mass of 0.04 times of that of the formaldehyde chloride, cooling to 4 ℃ at 6 ℃/min, and stirring at 700r/min for 9h to prepare the trivinyl alcohol-based triamino triphenylamine; dropwise adding 0.5 times of acrylonitrile-perylene tetracarboxylic acid hydrazine hydrochloride into trivinyl alcohol-based triaminobilide at the temperature of 80 ℃ under the protection of 5MPa and argon gas at the speed of 60 drops/min, stirring for 30min at the speed of 500r/min, then dropwise adding 0.3 times of dibenzoyl peroxide into the trivinyl alcohol-based triaminobilide at the speed of 60 drops/min, stirring for 4h at the speed of 700r/min, naturally cooling to room temperature, adding a 90% sulfuric acid solution with the mass fraction of 5 times of the trivinyl alcohol-based triaminobilide, continuously stirring and refluxing at the temperature of 120 ℃ for 4h, steaming at the temperature of 1600r/min and 120 ℃ for 3h, then adding 5 times of N, N-dimethylformamide into the trivinyl alcohol-based triaminobilide, stirring for 40min at the speed of 500r/min, heating to 154 ℃ at the speed of 1000r/min, stirring and refluxing for 6h at the speed of 1000r/min, and continuously heating to 400 ℃ for 3h, so as to prepare anti-fog film liquid;
(3) Under the protection of argon at the temperature, dichloropropane and (2E) -3- [4- (boric acid group) phenyl ] acrylic acid are mixed according to the mass ratio of 1:0.4, mixing, stirring for 30min at 500r/min, then adding aluminum trichloride with the mass of 0.05 times of that of the formaldehyde chloride, cooling to 4 ℃ at 6 ℃/min, and stirring for 9h at 700r/min to obtain acrylic acid chloropropyl phenylboronic acid;
(4) Placing a glass substrate into a 13MPa reaction kettle at room temperature, introducing ammonia gas with the mass of 4 times of that of the glass substrate at the speed of 5m 3/min, heating to 159 ℃ at the speed of 11 ℃/min, preserving heat for 50min, taking out, then scraping and coating an anti-fog film liquid with the thickness of 80nm on the surface of the glass substrate at 260 ℃, naturally cooling to room temperature, and then placing into a 90 ℃ oven for baking for 4h to prepare the anti-fog glass; then under the protection of argon, immersing the anti-fog glass in acrylic chloropropyl phenylboric acid with the mass of 1.6 times of that of the anti-fog glass, taking out the anti-fog glass, standing for 3 hours, baking at 40 ℃ for 1 hour, processing at 2500MHz and 900W microwave for 40 minutes after ultrasonic treatment at 40kHz for 20 minutes, dropwise adding concentrated sulfuric acid with the mass of 0.4 times of that of the anti-fog glass at 60 ℃/min and 98% for 40 minutes, continuing ultrasonic treatment at 11 ℃/min to 60 ℃ after dropwise adding concentrated hydrochloric acid with the mass of 0.5 times of that of the anti-fog glass and 7% for 60 minutes into aluminum trichloride solution with the mass of 0.5 times of that of the anti-fog glass, taking out the anti-fog glass, putting the anti-fog glass into a reaction kettle with the mass of 60 droplets/min and 42% for 4 hours, putting the anti-fog glass into a reaction kettle with the mass of 13MPa for 5m 3/min, continuously heating at 11 ℃/min to 159 ℃, continuously ultrasonic treatment at 11 ℃/min to 190 ℃, continuously ultrasonic treatment at 11 ℃/min and 60 ℃ for 60 minutes, adding sodium trichloride for 60 minutes, and continuously heating at 0.4 MHz to the temperature of the anti-fog glass, continuously cooling at 40 MHz to the temperature of the temperature, and cooling at 50 MHz for 50 hours, and then preparing the anti-fog glass, and cooling at the base layer under the conditions of microwave condition.
Comparative example 1
Comparative example 1 differs from example 2 only in the difference of step (2), the step (2) was modified as: dropwise adding 0.2 times of trivinyl alcohol-triamino triphenylamine peroxide into acrylonitrile-perylene tetracarboxylic acid hydrazine hydrochloride at the temperature of 70 ℃ under the protection of 4MPa and argon gas, stirring for 3 hours at the speed of 600r/min, naturally cooling to room temperature, adding a sulfuric acid solution with the mass fraction of 80% and the mass of 4 times of the acrylonitrile-perylene tetracarboxylic acid hydrazine hydrochloride, continuously stirring and refluxing for 3 hours at the temperature of 110 ℃, steaming for 2 hours at the temperature of 1500r/min and 110 ℃, then adding N, N-dimethylformamide with the mass of 4 times of the acrylonitrile-perylene tetracarboxylic acid hydrazine hydrochloride, stirring for 35 minutes at the speed of 400r/min, heating to 153 ℃ at the speed of 900r/min, stirring and refluxing for 5 hours at the speed of 900r/min, continuously heating to 350 ℃, and preserving heat for 2 hours to prepare the anti-fog film liquid. The remaining preparation steps were the same as in example 2.
Comparative example 2
(1) Under the protection of argon at the temperature, chlorovinyl alcohol and 4, 4'' -triamino triphenylamine are mixed according to the mass ratio of 1:0.4, mixing, stirring for 25min at 400r/min, then adding aluminum trichloride with the mass of 0.03 times of that of the formaldehyde chloride, cooling to 2 ℃ at 5 ℃/min, and stirring for 8h at 600r/min to prepare the trivinyl alcohol-based triamino triphenylamine; dropwise adding dibenzoyl peroxide with the mass of 0.2 times of that of trivinyl alcohol-based triamino-triphenylamine into trivinyl alcohol-based triamino-triphenylamine at the temperature of 70 ℃ under the protection of 4MPa and argon, stirring for 3 hours at the speed of 600r/min, naturally cooling to room temperature, adding sulfuric acid solution with the mass fraction of 80% with the mass of 4 times of that of trivinyl alcohol-based triamino-triphenylamine, continuously stirring and refluxing for 3 hours at the temperature of 110 ℃, steaming for 2 hours at the temperature of 1500r/min and 110 ℃, then adding N, N-dimethylformamide with the mass of 4 times of that of trivinyl alcohol-based triamino-triphenylamine, stirring for 35 minutes at the speed of 400r/min, heating to 153 ℃ at the speed of 5 ℃/min, stirring and refluxing for 5 hours at the speed of 900r/min, continuously heating to 350 ℃, and preserving heat for 2 hours to prepare the anti-fog film liquid;
(2) Under the protection of argon at the temperature, dichloropropane and (2E) -3- [4- (boric acid group) phenyl ] acrylic acid are mixed according to the mass ratio of 1:0.3 mixing, stirring for 25min at 400r/min, then adding aluminum trichloride with the mass of 0.04 times of that of the chlorformaldehyde, cooling to 2 ℃ at 5 ℃/min, stirring for 8h at 600r/min, naturally heating to room temperature, adding formamide with the mass of 0.9 times of that of the dichloropropane, continuously stirring for 25min, then adding nano titanium dioxide with the mass of 0.08 times of that of the dichloropropane, heating to 90 ℃ at 9.5 ℃/min, and continuously stirring for 3h to obtain acrylic acid chloropropyl phenylboronic acid;
(3) Placing a glass substrate into a reaction kettle with the pressure of 12.5MPa at room temperature, introducing ammonia gas with the mass of 3 times of that of the glass substrate at the speed of 4m 3/min, heating to 158.5 ℃ at the speed of 10 ℃/min, preserving heat for 40min, taking out, then scraping a 70nm thick anti-fog layer film liquid on the surface of the glass substrate at the temperature of 230 ℃, naturally cooling to the room temperature, and then placing into an oven with the temperature of 80 ℃ for baking for 3 hours to prepare the anti-fog glass; then under the protection of argon, immersing the anti-fog glass in acrylic acid-based chloropropyl phenylboric acid with the mass of 1.4 times of the anti-fog glass, taking out the anti-fog glass, standing for 2.5h, baking at 35 ℃ for 0.75h, processing at 2400MHz and 800W microwave conditions for 30min after ultrasonic treatment at 35kHz for 15min, dropwise adding concentrated sulfuric acid with the mass fraction of 0.3 times of the anti-fog glass at 50 ℃/min for 98%, continuing to ultrasonically process for 35min, immersing the anti-fog glass in aluminum trichloride solution with the mass fraction of 0.4 times of the anti-fog glass for 6% at 2 ℃ for 50min, taking out the anti-fog glass, then placing the anti-fog glass into a baking oven for 3h at 40 ℃, dropwise adding concentrated hydrochloric acid with the mass fraction of 0.4 times of the anti-fog glass into a reaction kettle of 12.5MPa, introducing ammonia gas with the mass of 3 times of 4m 3 MPa, heating to 158.5 ℃ at 10 ℃/min, continuing to ultrasonically heat for 50min, then continuously heating to 185 ℃ at 10 ℃/min, continuously heating to 50 ℃ for 50min, ultrasonic treatment at 50 ℃ for 50min, continuously cooling to 50 ℃ for 40 MHz, continuously heating to 40 MHz, and cooling the anti-fog glass at 40 ℃ for 40 MHz, continuously cooling at 40 ℃ for 20 h, and continuously carrying out ultrasonic treatment at 40 ℃ for 20 h, and then carrying out ultrasonic treatment to prepare the anti-fog glass.
Comparative example 3
(1) Under the conditions of 55 ℃ and argon protection, the mass fraction of the concentrated nitric acid is 68% and the mass fraction of the concentrated sulfuric acid is 98% according to the mass ratio of 1:1, mixing, stirring for 20min at 400r/min, then dripping 3,4,9, 10-tetracyanopylene with the mass of 1.3 times of concentrated nitric acid at 50 r/min, stirring for 2h at 700r/min, continuously dripping sodium hydroxide solution with the mass fraction of 25% to adjust the pH value to 7, adding palladium-carbon catalyst with the mass fraction of 0.07 times of concentrated nitric acid, introducing hydrogen with the mass of 2.5 times of concentrated nitric acid at 2.5 m/min at 2MPa and 80 ℃, stirring for 2h at 700r/min, then adding sodium hydroxide solution with the mass fraction of 25% with the mass fraction of 2.5 times of concentrated nitric acid, heating to 100 ℃ at 10 ℃/min, and continuously stirring for 7h to prepare the amino tetracyanopylene; adding amino-tetracyano perylene into hydrochloric acid solution with the mass fraction of 42% which is 6 times of that of the amino-tetracyano perylene at the temperature of 2 ℃ under the protection of argon, stirring for 20min at 400r/min, then adding the amino-tetracyano perylene into sodium nitrite with the mass of 0.3 times of that of the amino-tetracyano perylene, and continuously stirring for 2h to prepare tetracyano perylene hydrazine hydrochloride; under the protection of argon at the temperature, the mass ratio of the chloroacrylonitrile to the tetracyano-perylene hydrazine hydrochloride is 1:0.2, mixing, stirring for 25min at 400r/min, then adding aluminum trichloride with the mass of 0.04 times that of the acrylonitrile, cooling to 2 ℃ at 5 ℃/min, and stirring for 8h at 600r/min to prepare acrylonitrile-based perylene tetracarboxylic acid hydrazine hydrochloride;
(2) Under the protection of argon at the temperature, chlorovinyl alcohol and 4, 4'' -triamino triphenylamine are mixed according to the mass ratio of 1:0.4, mixing, stirring for 25min at 400r/min, then adding aluminum trichloride with the mass of 0.03 times of that of the formaldehyde chloride, cooling to 2 ℃ at 5 ℃/min, and stirring for 8h at 600r/min to prepare the trivinyl alcohol-based triamino triphenylamine; dropwise adding 0.4 times of acrylonitrile-perylene tetracarboxylic acid hydrazine hydrochloride into trivinyl alcohol-based triaminobenzidine at 70 ℃ under the protection of 4MPa and argon at 50 drops/min, stirring for 25min at 400r/min, then dropwise adding 0.2 times of dibenzoyl peroxide into the trivinyl alcohol-based triaminobenzidine at 50 drops/min, stirring for 3h at 600r/min, naturally cooling to room temperature, adding 80% sulfuric acid solution with the mass fraction of 4 times of the trivinyl alcohol-based triaminobenzidine, continuously stirring and refluxing for 3h at 110 ℃, steaming for 2h at 1500r/min and 110 ℃, then adding 4 times of N, N-dimethylformamide into the trivinyl alcohol-based triaminobenzidine, stirring for 35min at 400r/min, heating to 153 ℃ at 5 r/min, stirring and refluxing for 5h at 900r/min, continuously heating to 350 ℃ and preserving heat for 2h to prepare anti-fog film liquid;
(3) Placing a glass substrate into a reaction kettle with the pressure of 12.5MPa at room temperature, introducing ammonia gas with the mass of 3 times of that of the glass substrate at the speed of 4m 3/min, heating to 158.5 ℃ at the speed of 10 ℃/min, preserving heat for 40min, taking out, then scraping a 70nm thick anti-fog layer film liquid on the surface of the glass substrate at the temperature of 230 ℃, naturally cooling to the room temperature, and then placing into an oven with the temperature of 80 ℃ for baking for 3 hours to prepare the anti-fog glass; then under the protection of argon, immersing the anti-fog glass in 98% concentrated sulfuric acid with the mass fraction of 0.3 times of that of the anti-fog glass, carrying out ultrasonic treatment for 15min at 35kHz, standing for 2.5h, then carrying out ultrasonic treatment for 50min at 2 ℃ in an aluminum trichloride solution with the mass fraction of 6% of that of the anti-fog glass of 0.4 times of that of the anti-fog glass under the microwave condition of 2400MHz and 800W, taking out, then placing into a 40 ℃ oven for baking for 3h, then dropwise adding 40% concentrated hydrochloric acid with the mass fraction of 0.4 times of that of the anti-fog glass at 50 drops/min, placing into a 12.5MPa reaction kettle, introducing 3 times of ammonia gas with the mass of the anti-fog glass at 4m 3/min, carrying out ultrasonic treatment for 50min at 10 ℃/min, then carrying out ultrasonic treatment for 50min at 10 ℃/min to 185 ℃, then carrying out ultrasonic treatment for 45min at 110 ℃, then carrying out ultrasonic treatment for 220min at the temperature rising for 220 ℃ under the microwave condition of 800 MHz and cooling for 40 h, and finally placing into a base layer for preparing ultraviolet-proof glass.
Comparative example 4
Comparative example 4 differs from example 2 only in the difference of step (4), the modification of step (4) to: at room temperature, scraping and coating an anti-fog layer film liquid with the thickness of 70nm on the surface of a glass base layer by using a scraper, naturally cooling to room temperature, and then placing into an oven with the temperature of 80 ℃ for baking for 3 hours to prepare the anti-fog glass; then under the protection of argon, immersing the anti-fog glass in acrylic acid-based chloropropyl phenylboronic acid with the mass of 1.4 times of the anti-fog glass, taking out the anti-fog glass, standing for 2.5h, baking at 35 ℃ for 0.75h, carrying out ultrasonic treatment at 35kHz for 15min, then treating for 30min under the microwave condition of 2400MHz and 800W, dropwise adding concentrated sulfuric acid with the mass of 0.3 times of the anti-fog glass with the mass of 98%, continuing ultrasonic treatment for 35min, immersing the anti-fog glass in aluminum trichloride solution with the mass of 0.4 times of the mass of 6% at 2 ℃ for 50min, taking out the anti-fog glass, then placing the anti-fog glass into a baking oven at 40 ℃ for 3h, then dropwise adding concentrated hydrochloric acid with the mass of 0.4 times of the anti-fog glass with the mass of 40% at 50 ℃, continuing ultrasonic treatment for 50min, then heating to 185 ℃ at 10 ℃/min, cooling to 50 ℃ at 10 ℃/min, continuing ultrasonic treatment at 110 ℃ for 45min, then treating at 2400MHz and 800W, carrying out ultrasonic treatment at 220 ℃ for 220 ℃ and cooling to room temperature, and placing the anti-fog glass into a basic layer for 3h, thus obtaining the anti-ultraviolet glass. The remaining preparation steps were the same as in example 2.
Effect example
The following table 1 shows the analysis results of the anti-fog property, self-cleaning property, impact resistance and light stability of the super-hydrophilic self-cleaning anti-fog glasses prepared by using the examples 1 to 3 and the comparative examples 1 to 4 of the present invention.
TABLE 1
From table 1, it can be found that the super hydrophilic self-cleaning anti-fog glass prepared in examples 1,2 and 3 has stronger anti-fog property, self-cleaning property, impact resistance and light stability; from comparison of experimental data of examples 1,2 and 3 and comparative example 1, it can be found that the anti-fog layer is prepared by using acrylonitrile-based perylene tetracarboxylic acid hydrazine hydrochloride, quaternary ammonium salt and perylene imide can be formed, and the prepared super-hydrophilic self-cleaning anti-fog glass has stronger anti-fog property and self-cleaning property; from the experimental data of examples 1,2, 3 and comparative example 2, it can be found that the preparation of the anti-fog layer by using the tri-vinyl alcohol-based tri-amino triphenylamine can form quaternary ammonium salt, carboxyl and perylene imide, the subsequent preparation of the super-hydrophilic self-cleaning anti-fog glass can form hindered amine, and the prepared super-hydrophilic self-cleaning anti-fog glass has stronger anti-fog property, self-cleaning property and light stability; from the experimental data of examples 1,2, 3 and comparative example 3, it can be found that the super-hydrophilic self-cleaning anti-fog glass prepared by using acrylic acid-based chloropropyl phenylboronic acid can form hindered amine and form a three-dimensional network structure between the glass base layer and the anti-fog layer, and the prepared super-hydrophilic self-cleaning anti-fog glass has stronger impact resistance and light stability; from experimental data of examples 1,2, 3 and comparative example 4, it can be found that the super-hydrophilic self-cleaning anti-fog glass prepared by the supercritical ammonia-assisted knife coating process can form hindered amine and form a three-dimensional network structure between the glass base layer and the anti-fog layer, and the prepared super-hydrophilic self-cleaning anti-fog glass has strong impact resistance and light stability.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. The present embodiments are, therefore, to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Any reference sign in a claim should not be construed as limiting the claim concerned.

Claims (1)

1. A preparation method of super-hydrophilic self-cleaning anti-fog glass is characterized by comprising the following steps: the preparation method comprises the following preparation steps:
(1) Under the conditions of 55 ℃ and argon protection, the mass fraction of the concentrated nitric acid is 68% and the mass fraction of the concentrated sulfuric acid is 98% according to the mass ratio of 1:1, mixing, stirring for 20min at 400r/min, then dripping 3,4,9, 10-tetracyanopylene with the mass of 1.3 times of concentrated nitric acid at 50 r/min, stirring for 2h at 700r/min, continuously dripping sodium hydroxide solution with the mass fraction of 25% to adjust the pH value to 7, adding palladium-carbon catalyst with the mass fraction of 0.07 times of concentrated nitric acid, introducing hydrogen with the mass of 2.5 times of concentrated nitric acid at 2.5 m/min at 2MPa and 80 ℃, stirring for 2h at 700r/min, then adding sodium hydroxide solution with the mass fraction of 25% with the mass fraction of 2.5 times of concentrated nitric acid, heating to 100 ℃ at 10 ℃/min, and continuously stirring for 7h to prepare the amino tetracyanopylene; adding amino-tetracyano perylene into hydrochloric acid solution with the mass fraction of 42% which is 6 times of that of the amino-tetracyano perylene at the temperature of 2 ℃ under the protection of argon, stirring for 20min at 400r/min, then adding the amino-tetracyano perylene into sodium nitrite with the mass of 0.3 times of that of the amino-tetracyano perylene, and continuously stirring for 2h to prepare tetracyano perylene hydrazine hydrochloride; under the protection of argon at the temperature, the mass ratio of the chloroacrylonitrile to the tetracyano-perylene hydrazine hydrochloride is 1:0.2, mixing, stirring for 25min at 400r/min, then adding aluminum trichloride with the mass of 0.04 times that of the acrylonitrile, cooling to 2 ℃ at 5 ℃/min, and stirring for 8h at 600r/min to prepare acrylonitrile-based perylene tetracarboxylic acid hydrazine hydrochloride;
(2) Under the protection of argon at the temperature, chlorovinyl alcohol and 4, 4'' -triamino triphenylamine are mixed according to the mass ratio of 1:0.4, mixing, stirring for 25min at 400r/min, then adding aluminum trichloride with the mass of 0.03 times of that of the formaldehyde chloride, cooling to 2 ℃ at 5 ℃/min, and stirring for 8h at 600r/min to prepare the trivinyl alcohol-based triamino triphenylamine; dropwise adding 0.4 times of acrylonitrile-perylene tetracarboxylic acid hydrazine hydrochloride into trivinyl alcohol-based triaminobenzidine at 70 ℃ under the protection of 4MPa and argon at 50 drops/min, stirring for 25min at 400r/min, then dropwise adding 0.2 times of dibenzoyl peroxide into the trivinyl alcohol-based triaminobenzidine at 50 drops/min, stirring for 3h at 600r/min, naturally cooling to room temperature, adding 80% sulfuric acid solution with the mass fraction of 4 times of the trivinyl alcohol-based triaminobenzidine, continuously stirring and refluxing for 3h at 110 ℃, steaming for 2h at 1500r/min and 110 ℃, then adding 4 times of N, N-dimethylformamide into the trivinyl alcohol-based triaminobenzidine, stirring for 35min at 400r/min, heating to 153 ℃ at 5 r/min, stirring and refluxing for 5h at 900r/min, continuously heating to 350 ℃ and preserving heat for 2h to prepare anti-fog film liquid;
(3) Under the protection of argon at the temperature, dichloropropane and (2E) -3- [4- (boric acid group) phenyl ] acrylic acid are mixed according to the mass ratio of 1:0.3 mixing, stirring for 25min at 400r/min, then adding aluminum trichloride with the mass of 0.04 times of that of the chlorformaldehyde, cooling to 2 ℃ at 5 ℃/min, stirring for 8h at 600r/min, naturally heating to room temperature, adding formamide with the mass of 0.9 times of that of the dichloropropane, continuously stirring for 25min, then adding nano titanium dioxide with the mass of 0.08 times of that of the dichloropropane, heating to 90 ℃ at 9.5 ℃/min, and continuously stirring for 3h to obtain acrylic acid chloropropyl phenylboronic acid;
(4) Placing a glass substrate into a reaction kettle with the pressure of 12.5MPa at room temperature, introducing ammonia gas with the mass of 3 times of that of the glass substrate at the speed of 4m 3/min, heating to 158.5 ℃ at the speed of 10 ℃/min, preserving heat for 40min, taking out, then scraping a 70nm thick anti-fog layer film liquid on the surface of the glass substrate at the temperature of 230 ℃, naturally cooling to the room temperature, and then placing into an oven with the temperature of 80 ℃ for baking for 3 hours to prepare the anti-fog glass; then under the protection of argon, immersing the anti-fog glass in acrylic acid-based chloropropyl phenylboric acid with the mass of 1.4 times of the anti-fog glass, taking out the anti-fog glass, standing for 2.5h, baking at 35 ℃ for 0.75h, processing at 2400MHz and 800W microwave conditions for 30min after ultrasonic treatment at 35kHz for 15min, dropwise adding concentrated sulfuric acid with the mass fraction of 0.3 times of the anti-fog glass at 50 ℃/min for 98%, continuing to ultrasonically process for 35min, immersing the anti-fog glass in aluminum trichloride solution with the mass fraction of 0.4 times of the anti-fog glass for 6% at 2 ℃ for 50min, taking out the anti-fog glass, then placing the anti-fog glass into a baking oven for 3h at 40 ℃, dropwise adding concentrated hydrochloric acid with the mass fraction of 0.4 times of the anti-fog glass into a reaction kettle of 12.5MPa, introducing ammonia gas with the mass of 3 times of 4m 3 MPa, heating to 158.5 ℃ at 10 ℃/min, continuing to ultrasonically heat for 50min, then continuously heating to 185 ℃ at 10 ℃/min, continuously heating to 50 ℃ for 50min, ultrasonic treatment at 50 ℃ for 50min, continuously cooling to 50 ℃ for 40 MHz, continuously heating to 40 MHz, and cooling the anti-fog glass at 40 ℃ for 40 MHz, continuously cooling at 40 ℃ for 20 h, and continuously carrying out ultrasonic treatment at 40 ℃ for 20 h, and then carrying out ultrasonic treatment to prepare the anti-fog glass.
CN202410431383.1A 2022-05-18 2022-05-18 Preparation method of super-hydrophilic self-cleaning anti-fog glass Pending CN118495827A (en)

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US3488215A (en) * 1968-06-21 1970-01-06 Nat Patent Dev Corp Nonfogging transparent material
ATE403707T1 (en) * 1998-04-10 2008-08-15 Matsushita Electric Works Ltd METHOD FOR PRODUCING A HYDROPHILIC INORGANIC COATING FILM AND A COMPOSITION FOR INORGANIC COATINGS
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