CN113942278B - Antifogging glass and preparation method and application thereof - Google Patents
Antifogging glass and preparation method and application thereof Download PDFInfo
- Publication number
- CN113942278B CN113942278B CN202111411777.3A CN202111411777A CN113942278B CN 113942278 B CN113942278 B CN 113942278B CN 202111411777 A CN202111411777 A CN 202111411777A CN 113942278 B CN113942278 B CN 113942278B
- Authority
- CN
- China
- Prior art keywords
- reaction
- cellulose
- glass
- antifogging
- sodium hydroxide
- 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
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
- B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
- B32B17/08—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of cellulosic plastic substance or gelatin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B23/00—Layered products comprising a layer of cellulosic plastic substances, i.e. substances obtained by chemical modification of cellulose, e.g. cellulose ethers, cellulose esters, viscose
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/10—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/12—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B38/00—Ancillary operations in connection with laminating processes
- B32B38/16—Drying; Softening; Cleaning
- B32B38/164—Drying
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
-
- 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
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B1/00—Preparatory treatment of cellulose for making derivatives thereof, e.g. pre-treatment, pre-soaking, activation
- C08B1/08—Alkali cellulose
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B9/00—Cellulose xanthate; Viscose
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B38/00—Ancillary operations in connection with laminating processes
- B32B38/16—Drying; Softening; Cleaning
- B32B38/164—Drying
- B32B2038/168—Removing solvent
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/582—Tearability
- B32B2307/5825—Tear resistant
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/714—Inert, i.e. inert to chemical degradation, corrosion
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/726—Permeability to liquids, absorption
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2605/00—Vehicles
- B32B2605/18—Aircraft
Landscapes
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Polymers & Plastics (AREA)
- Biochemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Geochemistry & Mineralogy (AREA)
- General Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Fluid Mechanics (AREA)
- Laminated Bodies (AREA)
Abstract
The invention relates to the field of functional glass, in particular to antifogging glass and a preparation method and application thereof. The preparation method of the antifogging glass provided by the invention comprises the following steps: soaking wood pulp or cotton pulp in a sodium hydroxide solution for alkalization treatment to obtain alkali cellulose; mixing alkali cellulose and carbon disulfide, heating for reaction, and adding a sodium hydroxide solution into a reaction solution after the reaction is finished to obtain cellulose viscose; forming a thin film by cellulose viscose in a curing solution to obtain an antifogging glass film; coating the gelatin solution on the surface of the glass substrate, and then covering an antifogging glass film on the gelatin solution to obtain the antifogging glass. The antifogging glass obtained by the method provided by the invention can effectively improve the hydrophilic property of the glass, can absorb the moisture on the surface of the film layer, so that the glass has antifogging capability, and meanwhile, the prepared antifogging glass film has excellent tear resistance, so that the service life of the glass is greatly prolonged.
Description
Technical Field
The invention relates to the field of functional glass, in particular to antifogging glass and a preparation method and application thereof.
Background
An aircraft may undergo a rise and fall process in a short time while performing a high altitude mission, while the outside temperature may be different at different altitudes. Under the condition that the temperature difference is large and the air humidity reaches a certain degree, the fog phenomenon of different degrees can occur on the protective glass outside the instrument panel of the airplane, so that the accurate observation of the instrument panel of a pilot is influenced.
The prior art generally adopts an electric heating method to heat instrument glass so as to achieve the defogging effect, but the technology has some defects: electric heating need set up the circuit alone, if meet the trouble, can lead to defogging functional failure, electric heating programming rate can not be too fast simultaneously, otherwise can cause glass to break, and progressively heaies up and can lead to the defogging untimely, influences pilot's observation. In order to solve the above problems, the prior art generally adopts a method of covering a layer of organic protective film on the glass surface to improve the hydrophilicity of the glass surface, but the effect is limited, and the formed glass film has poor tear resistance, thereby affecting the service life of the glass.
Disclosure of Invention
Therefore, the invention aims to overcome the defects that the anti-fog effect and the service life of glass are influenced by poor hydrophilicity and limited tear resistance of an organic protective film covered on the surface of anti-fog glass in the prior art, and further provides the anti-fog glass and a preparation method and application thereof.
A preparation method of antifogging glass comprises the following steps:
1) soaking wood pulp or cotton pulp in sodium hydroxide solution for alkalization, filtering and crushing to obtain alkali cellulose;
2) mixing alkali cellulose and carbon disulfide, heating for reaction, and adding a sodium hydroxide solution into a reaction solution after the reaction is finished to obtain cellulose viscose;
3) extruding the cellulose viscose through a film drawing machine, and then forming a thin film in a curing solution to obtain an antifogging glass film;
4) coating the gelatin solution on the surface of a glass substrate, then covering an antifogging glass film on the gelatin solution, rolling, standing and drying to obtain the antifogging glass.
Preferably, in the step 1), the dipping temperature is 45-55 ℃, the dipping time is 50-80min, the mass ratio of the wood pulp or cotton pulp to the sodium hydroxide solution is 1 (8-11), and the mass fraction of the sodium hydroxide solution is 17-20%;
heating to react at 30-38 ℃ in the step 2), wherein the reaction time is 30-40min, the mass ratio of the alkali cellulose to the carbon disulfide is 1 (1-1.2), the mass fraction of the sodium hydroxide solution is 7-9%, and the addition amount of the sodium hydroxide solution is 28-35% of the mass of the alkali cellulose;
the concentration of the sulfuric acid in the curing liquid in the step 3) is 85-95g/L, and the concentration of the sodium sulfate is 220-240 g/L;
in the step 4), the mass fraction of the gelatin solution is 18-22%, the standing temperature is room temperature, the standing time is 5-8h, the drying temperature is 78-85 ℃, and the drying time is 25-35 min.
Preferably, the cellulose viscose in step 3) further comprises the steps of curing, filtering and defoaming before being extruded by a film drawing machine.
Preferably, the wood pulp or cotton pulp in the step 1) is modified wood pulp or cotton pulp, and the preparation method of the modified wood pulp or modified cotton pulp comprises the following steps:
a) mixing zinc oxide, 3-aminopropyltriethoxysilane and carbon tetrachloride, heating for reaction, cooling to room temperature after the reaction is finished, filtering, and drying to obtain aminated zinc oxide;
b) mixing aminated zinc oxide, 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride, N- (4-aminobenzoyl) -L-glutamic acid, 4-dimethylaminopyridine and dichloromethane, and heating for amidation reaction to obtain modified zinc oxide;
c) mixing wood pulp or cotton pulp, sodium periodate and water, reacting at room temperature in a dark place, filtering reaction liquid after the reaction is finished, washing with water, and drying to obtain aldehyde cellulose;
d) mixing the aldehyde cellulose, methanol, sodium hydroxide and water, stirring, adding the modified zinc oxide obtained in the step b) for reaction, and filtering, washing and drying a reaction solution after the reaction is finished to obtain the modified zinc oxide grafted cellulose.
Preferably, the preparation method of the antifogging glass comprises the following steps:
a) mixing zinc oxide, 3-aminopropyltriethoxysilane and carbon tetrachloride, heating for reaction, cooling to room temperature after the reaction is finished, filtering, and drying to obtain aminated zinc oxide;
b) mixing aminated zinc oxide, 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride, N- (4-aminobenzoyl) -L-glutamic acid, 4-dimethylaminopyridine and dichloromethane, and heating for amidation reaction to obtain modified zinc oxide;
c) mixing wood pulp or cotton pulp, sodium periodate and water, reacting at room temperature in a dark place, filtering reaction liquid after the reaction is finished, washing with water, and drying to obtain aldehyde cellulose;
d) mixing and stirring aldehyde cellulose, methanol, sodium hydroxide and water, then adding the modified zinc oxide obtained in the step b) to react, and filtering, washing and drying a reaction solution after the reaction is finished to obtain modified zinc oxide grafted cellulose;
e) soaking the modified zinc oxide grafted cellulose in a sodium hydroxide solution for alkalization, and then filtering and crushing to obtain alkali cellulose;
f) mixing alkali cellulose and carbon disulfide, heating for reaction, and adding a sodium hydroxide solution into a reaction solution after the reaction is finished to obtain cellulose viscose;
g) extruding the cellulose viscose through a film drawing machine, and then forming a thin film in a curing solution to obtain an antifogging glass film;
k) coating the gelatin solution on the surface of a glass substrate, then covering an antifogging glass film on the gelatin solution, rolling, standing and drying to obtain the antifogging glass.
Preferably, the mass ratio of the zinc oxide, the 3-aminopropyltriethoxysilane and the carbon tetrachloride in the step a) is 1 (0.6-0.8) to (9-11), the heating reaction temperature is 80-88 ℃, and the reaction time is 10-14 h;
in the step b), the mass ratio of the aminated zinc oxide, the 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride, the N- (4-aminobenzoyl) -L-glutamic acid, the 4-dimethylaminopyridine and the dichloromethane is 1 (0.2-0.4) to (2-4) to (0.2-0.4) to (4-6), the amidation reaction temperature is 45-55 ℃, and the reaction time is 18-22 h.
Preferably, the reaction time in the step c) is kept away from light for 40-60min, and the mass ratio of wood pulp, sodium periodate and water is 1 (1.9-2.2) to (3-5);
in the step d), the stirring temperature is room temperature, the stirring time is 20-40min, the reaction temperature is 38-45 ℃, the reaction time is 4-6h, and the mass ratio of the aldehyde cellulose, the methanol, the sodium hydroxide, the water and the modified zinc oxide is 1: (4-6):(0.18-2.2):(0.4-0.6):(0.08-0.2).
Preferably, in the step e), the dipping temperature is 45-55 ℃, the dipping time is 50-80min, the mass ratio of the use amount of the modified zinc oxide grafted cellulose to the sodium hydroxide solution is 1 (8-11), and the mass fraction of the sodium hydroxide solution is 17-20%;
step f), heating to react at 30-38 ℃ for 30-40min, wherein the mass ratio of the alkali cellulose to the carbon disulfide is 1 (1-1.2), the mass fraction of the sodium hydroxide solution is 7-9%, and the addition amount of the sodium hydroxide solution is 28-35% of the mass of the alkali cellulose;
the concentration of the sulfuric acid in the curing liquid in the step g) is 85-95g/L, and the concentration of the sodium sulfate is 220-240 g/L;
the step g) also comprises the steps of washing, desulfurizing, bleaching and drying the film. In the present invention, after bleaching, desalting and plasticizing (glycerin and ethylene glycol) steps may be performed on the bleached film according to actual needs. In the invention, the desulfurization, the bleaching and the drying are conventional means in the field, and optionally, the concentration of sodium sulfate in desulfurization solution adopted by the desulfurization is 7-9g/L, the concentration of sodium carbonate is 3-5g/L, hydrogen peroxide of 0.4-0.6g/L is adopted for the bleaching, the drying temperature is 75-85 ℃, and the drying time is 0.8-1.5 h.
The mass fraction of the gelatin solution in the step k) is 18-22%, the standing temperature is room temperature, the standing time is 5-8h, the drying temperature is 78-85 ℃, and the drying time is 25-35 min.
Preferably, the cellulose viscose in the step g) further comprises the steps of curing, filtering and defoaming before being extruded by a film drawing machine. Preferably, the curing treatment temperature is 23-28 ℃, and the treatment time is 1-3 h.
Preferably, the wood pulp or cotton pulp has an alpha-cellulose content of not less than 85wt% and a cellulose polymerization degree of 500-1000.
The invention also provides antifogging glass prepared by the method.
Preferably, the antifogging glass comprises a glass substrate, and an adhesive layer and an antifogging glass film which are sequentially arranged on the glass substrate. The thickness of the adhesive layer and the thickness of the antifogging glass film are not specifically limited, and optionally, the thickness of the adhesive layer is 1-10 mu m, and the thickness of the antifogging glass film is 0.5-1.5 mu m.
The invention also provides application of the antifogging glass in a fighter instrument.
The technical scheme of the invention has the following advantages:
1. according to the preparation method of the antifogging glass, wood pulp or cotton pulp is subjected to alkalization treatment and then reacts with carbon disulfide, and after the reaction is finished, a sodium hydroxide solution is added into a reaction solution to obtain orange cellulose viscose; extruding the cellulose viscose through a film drawing machine, forming a film in the curing liquid to obtain an anti-fog glass film, and adhering the anti-fog glass film to the surface of glass through a gelatin to obtain the anti-fog glass. The antifogging glass obtained by the method provided by the invention can effectively improve the hydrophilic property of the glass, can absorb the moisture on the surface of the film layer, so that the glass has antifogging capability, and meanwhile, the prepared antifogging glass film has excellent tear resistance, so that the service life of the glass is greatly prolonged. Meanwhile, the antifogging glass provided by the invention has good optical property, is nontoxic and tasteless, can effectively resist the corrosion of various organic solvents, does not need to be provided with a circuit, does not have the problem of failure, greatly improves the reliability, and can effectively deal with various complex working environments.
2. The preparation method of the antifogging glass provided by the invention further comprises the steps of adopting modified wood pulp or cotton pulp to bond specific N- (4-aminobenzoyl) -L-glutamic acid to aminated zinc oxide through amidation reaction so as to obtain modified zinc oxide, and grafting the modified zinc oxide to cellulose so as to obtain the modified zinc oxide grafted cellulose. According to the invention, N- (4-aminobenzoyl) -L-glutamic acid and zinc oxide are grafted to the cellulose, so that wood pulp is modified, and the N- (4-aminobenzoyl) -L-glutamic acid and the zinc oxide are cooperatively matched to act with the cellulose in the wood pulp, so that the hydrophilic property of the glass is improved, and the tear resistance of the antifogging glass film is improved.
Detailed Description
The following examples are provided to further understand the present invention, not to limit the scope of the present invention, but to provide the best mode, not to limit the content and the protection scope of the present invention, and any product similar or similar to the present invention, which is obtained by combining the present invention with other prior art features, falls within the protection scope of the present invention.
The examples do not show the specific experimental steps or conditions, and can be performed according to the conventional experimental steps described in the literature in the field. The reagents or instruments used are not indicated by manufacturers, and are all conventional reagent products which can be obtained commercially.
Example 1
The embodiment provides antifogging glass, which consists of a glass substrate, and an adhesive layer (with the thickness of 3 microns) and an antifogging glass film (with the thickness of 1 micron) which are sequentially arranged on the glass substrate;
the preparation method of the antifogging glass comprises the following steps:
1) wood pulp (the content of alpha-cellulose in the wood pulp is 85wt%, the polymerization degree of cellulose is 900) is soaked in a sodium hydroxide solution for alkalization treatment, the mass fraction of the sodium hydroxide solution is 18%, the mass ratio of the wood pulp to the sodium hydroxide solution is 1:10, the soaking temperature is 50 ℃, the soaking time is 60min, then squeezing and filtering are carried out, and a filter cake is crushed to obtain alkali cellulose;
2) mixing alkali cellulose and carbon disulfide, heating for reaction at 35 ℃ for 40min, wherein the mass ratio of the alkali cellulose to the carbon disulfide is 1:1, and adding a sodium hydroxide solution (the mass fraction of the sodium hydroxide solution is 8%, and the addition amount of the sodium hydroxide solution is 30% of the mass of the alkali cellulose) into a reaction solution after the reaction is finished to obtain cellulose viscose;
3) curing cellulose viscose at 25 ℃ for 2 hours, filtering and defoaming, extruding the obtained viscose in a film drawing machine, flowing into a solidification bath (the solidification bath contains solidification liquid, the concentration of sulfuric acid in the solidification liquid is 90g/L, and the concentration of sodium sulfate is 230g/L) to form a film, washing the obtained film with water, desulfurizing (the concentration of sodium sulfate in the desulfurization liquid is 8g/L, the concentration of sodium carbonate is 4g/L), bleaching (the concentration of bleaching liquid is 0.5g/L of hydrogen peroxide), drying (the drying temperature is 80 ℃, and the drying time is 1h) to obtain an antifogging glass film;
4) mixing gelatin powder with water to prepare a gelatin solution (the mass fraction of the gelatin solution is 20%), uniformly coating the gelatin solution on the surface of clean glass, flatly covering an antifogging glass film on the gelatin, uniformly rolling the glass film by using a glass rod, naturally standing for 6 hours at room temperature, putting the glass film into an oven, and drying for 30 minutes at 80 ℃ to obtain the antifogging glass.
Example 2
The embodiment provides antifogging glass, which consists of a glass substrate, and an adhesive layer (with the thickness of 3 microns) and an antifogging glass film (with the thickness of 1 micron) which are sequentially arranged on the glass substrate;
the preparation method of the antifogging glass comprises the following steps:
1) wood pulp (the content of alpha-cellulose in the wood pulp is 86 wt%, the polymerization degree of cellulose is 800) is soaked in a sodium hydroxide solution for alkalization treatment, the mass fraction of the sodium hydroxide solution is 18%, the mass ratio of the wood pulp to the sodium hydroxide solution is 1:8, the soaking temperature is 48 ℃, the soaking time is 70min, then squeezing and filtering are carried out, and a filter cake is crushed to obtain alkali cellulose;
2) mixing alkali cellulose and carbon disulfide, heating for reaction at 32 ℃, reacting for 35min at the mass ratio of 1:1.1, and adding a sodium hydroxide solution (the mass fraction of the sodium hydroxide solution is 8%, and the addition amount of the sodium hydroxide solution is 32% of the mass of the alkali cellulose) into a reaction solution after the reaction is finished to obtain the cellulose viscose;
3) curing cellulose viscose at 26 ℃ for 2.5 hours, filtering and defoaming, extruding the obtained viscose in a film drawing machine, flowing into a solidification bath (the solidification bath contains solidification liquid, the concentration of sulfuric acid in the solidification liquid is 92g/L, and the concentration of sodium sulfate is 220g/L) to form a film, washing the film with water, desulfurizing (the concentration of sodium sulfate in the desulfurization liquid is 8g/L, the concentration of sodium carbonate is 4g/L), bleaching (the concentration of bleaching liquid is 0.5g/L of hydrogen peroxide), drying (the drying temperature is 80 ℃, and the drying time is 1 hour), and obtaining the antifogging glass film;
4) mixing gelatin powder with water to prepare a gelatin solution (the mass fraction of the gelatin solution is 21%), uniformly coating the gelatin solution on the surface of clean glass, flatly covering an antifogging glass film on the gelatin, uniformly rolling the glass film by using a glass rod, naturally standing for 7 hours at room temperature, putting the glass film into an oven, and drying for 28 minutes at 82 ℃ to obtain the antifogging glass.
Example 3
The embodiment provides antifogging glass, which consists of a glass substrate, and an adhesive layer (with the thickness of 3 microns) and an antifogging glass film (with the thickness of 1 micron) which are sequentially arranged on the glass substrate;
the preparation method of the antifogging glass comprises the following steps:
1) mixing zinc oxide, 3-aminopropyltriethoxysilane and carbon tetrachloride (the mass ratio of the zinc oxide to the 3-aminopropyltriethoxysilane to the carbon tetrachloride is 1:0.7:10), heating the mixed solution to 85 ℃ for reaction for 12 hours, cooling to room temperature after the reaction is finished, filtering, and drying a filter cake to obtain aminated zinc oxide;
2) mixing aminated zinc oxide, 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride (EDC & HCl), N- (4-aminobenzoyl) -L-glutamic acid, 4-dimethylaminopyridine and dichloromethane (the mass ratio of the aminated zinc oxide to the 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride to the N- (4-aminobenzoyl) -L-glutamic acid to the 4-dimethylaminopyridine to the dichloromethane is 1:0.3:3:0.3:5), heating to perform amidation reaction, wherein the amidation reaction temperature is 50 ℃, the reaction time is 20 hours, cooling to room temperature after the reaction is finished, then putting the reaction liquid into deionized water for dialysis, and performing vacuum drying to obtain modified zinc oxide;
3) mixing wood pulp (the content of alpha-cellulose in the wood pulp is 85wt%, the polymerization degree of the cellulose is 900), sodium periodate and water (the mass ratio of the wood pulp to the sodium periodate to the water is 1:2:4), reacting for 50min at room temperature in a dark place, adding ethylene glycol to terminate the reaction, filtering the reaction solution, washing the filter cake with water, and drying to obtain aldehyde cellulose;
4) mixing the aldehyde cellulose, methanol, sodium hydroxide and water, stirring at room temperature for 30min, and adding the modified zinc oxide obtained in the step 2) (the mass ratio of the aldehyde cellulose, the methanol, the sodium hydroxide, the water and the modified zinc oxide is 1: 5:0.2:0.5:0.1), reacting for 5 hours at 40 ℃, filtering, washing and drying reaction liquid after the reaction is finished to obtain modified zinc oxide grafted cellulose;
5) soaking the modified zinc oxide grafted cellulose in a sodium hydroxide solution (the mass fraction of the sodium hydroxide solution is 18%) for alkalization treatment, wherein the mass ratio of the modified zinc oxide grafted cellulose to the sodium hydroxide solution is 1:10, the soaking temperature is 50 ℃, the soaking time is 60min, then squeezing and filtering, and crushing a filter cake to obtain alkali cellulose;
6) mixing alkali cellulose and carbon disulfide, heating for reaction at 35 ℃ for 40min, wherein the mass ratio of the alkali cellulose to the carbon disulfide is 1:1, and adding a sodium hydroxide solution (the mass fraction of the sodium hydroxide solution is 8%, and the addition amount of the sodium hydroxide solution is 30% of the mass of the alkali cellulose) into a reaction solution after the reaction is finished to obtain cellulose viscose;
7) curing cellulose viscose at 25 ℃ for 2 hours, filtering and defoaming, extruding the obtained viscose in a film drawing machine, flowing into a solidification bath (the solidification bath contains solidification liquid, the concentration of sulfuric acid in the solidification liquid is 90g/L, and the concentration of sodium sulfate is 230g/L) to form a film, washing the obtained film with water, desulfurizing (the concentration of sodium sulfate in the desulfurization liquid is 8g/L, the concentration of sodium carbonate is 4g/L), bleaching (the concentration of bleaching liquid is 0.5g/L of hydrogen peroxide), drying (the drying temperature is 80 ℃, and the drying time is 1h) to obtain an antifogging glass film;
8) mixing gelatin powder and water to prepare a gelatin solution (the mass fraction of the gelatin solution is 20%), uniformly coating the gelatin solution on the clean glass surface, flatly covering an antifogging glass film on the gelatin, uniformly rolling the antifogging glass film on the glass film by using a glass rod, naturally standing for 6 hours at room temperature, putting the antifogging glass film into an oven, and drying the antifogging glass film for 30 minutes at 80 ℃ to obtain the antifogging glass.
Example 4
The embodiment provides antifogging glass, which consists of a glass substrate, and an adhesive layer (with the thickness of 3 microns) and an antifogging glass film (with the thickness of 1 micron) which are sequentially arranged on the glass substrate;
the preparation method of the antifogging glass comprises the following steps:
1) mixing zinc oxide, 3-aminopropyltriethoxysilane and carbon tetrachloride (the mass ratio of the zinc oxide to the 3-aminopropyltriethoxysilane to the carbon tetrachloride is 1:0.7:10), heating the mixed solution to 85 ℃ for reaction for 12 hours, cooling to room temperature after the reaction is finished, filtering, and drying a filter cake to obtain aminated zinc oxide;
2) mixing wood pulp (the content of alpha-cellulose in the wood pulp is 85wt%, the polymerization degree of the cellulose is 900), sodium periodate and water (the mass ratio of the wood pulp to the sodium periodate to the water is 1:2:4), reacting for 50min at room temperature in a dark place, adding ethylene glycol to terminate the reaction, filtering the reaction solution, washing the filter cake with water, and drying to obtain aldehyde cellulose;
3) mixing aldehyde cellulose, methanol, sodium hydroxide and water, stirring for 30min at room temperature, and adding the aminated zinc oxide obtained in the step 1) (the mass ratio of aldehyde cellulose, methanol, sodium hydroxide, water to aminated zinc oxide is 1: 5:0.2:0.5:0.1), reacting for 5 hours at 40 ℃, filtering, washing and drying reaction liquid after the reaction is finished to obtain modified zinc oxide grafted cellulose;
4) soaking the modified zinc oxide grafted cellulose in a sodium hydroxide solution (the mass fraction of the sodium hydroxide solution is 18%) for alkalization treatment, wherein the mass ratio of the modified zinc oxide grafted cellulose to the sodium hydroxide solution is 1:10, the soaking temperature is 50 ℃, the soaking time is 60min, then squeezing and filtering, and crushing a filter cake to obtain alkali cellulose;
5) mixing alkali cellulose and carbon disulfide, heating for reaction at 35 ℃ for 40min, wherein the mass ratio of the alkali cellulose to the carbon disulfide is 1:1, and adding a sodium hydroxide solution (the mass fraction of the sodium hydroxide solution is 8%, and the addition amount of the sodium hydroxide solution is 30% of the mass of the alkali cellulose) into a reaction solution after the reaction is finished to obtain cellulose viscose;
6) curing cellulose viscose at 25 ℃ for 2 hours, filtering and defoaming, extruding the obtained viscose in a film drawing machine, flowing into a solidification bath (the solidification bath contains solidification liquid, the concentration of sulfuric acid in the solidification liquid is 90g/L, and the concentration of sodium sulfate is 230g/L) to form a film, washing the obtained film with water, desulfurizing (the concentration of sodium sulfate in the desulfurization liquid is 8g/L, the concentration of sodium carbonate is 4g/L), bleaching (the concentration of bleaching liquid is 0.5g/L of hydrogen peroxide), drying (the drying temperature is 80 ℃, and the drying time is 1h) to obtain an antifogging glass film;
7) mixing gelatin powder with water to prepare a gelatin solution (the mass fraction of the gelatin solution is 20%), uniformly coating the gelatin solution on the surface of clean glass, flatly covering an antifogging glass film on the gelatin, uniformly rolling the glass film by using a glass rod, naturally standing for 6 hours at room temperature, putting the glass film into an oven, and drying for 30 minutes at 80 ℃ to obtain the antifogging glass.
Example 5
The embodiment provides antifogging glass, which consists of a glass substrate, and an adhesive layer (with the thickness of 3 microns) and an antifogging glass film (with the thickness of 1 micron) which are sequentially arranged on the glass substrate;
the preparation method of the antifogging glass comprises the following steps:
1) mixing wood pulp (the content of alpha-cellulose in the wood pulp is 85wt%, the polymerization degree of the cellulose is 900), sodium periodate and water (the mass ratio of the wood pulp to the sodium periodate to the water is 1:2:4), reacting for 50min at room temperature in a dark place, adding ethylene glycol to terminate the reaction, filtering the reaction solution, washing the filter cake with water, and drying to obtain aldehyde cellulose;
2) mixing the aldehyde cellulose, methanol, sodium hydroxide and water, stirring at room temperature for 30min, and adding N- (4-aminobenzoyl) -L-glutamic acid (the mass ratio of the aldehyde cellulose, the methanol, the sodium hydroxide, the water and the N- (4-aminobenzoyl) -L-glutamic acid is 1: 5:0.2:0.5:0.1), reacting at 40 ℃ for 5h, filtering, washing and drying the reaction solution after the reaction is finished to obtain the N- (4-aminobenzoyl) -L-glutamic acid grafted cellulose;
3) soaking the N- (4-aminobenzoyl) -L-glutamic acid grafted cellulose in a sodium hydroxide solution (the mass fraction of the sodium hydroxide solution is 18%) for alkalization, wherein the mass ratio of the N- (4-aminobenzoyl) -L-glutamic acid grafted cellulose to the sodium hydroxide solution is 1:10, the soaking temperature is 50 ℃, the soaking time is 60min, then squeezing and filtering, and crushing a filter cake to obtain alkali cellulose;
4) mixing alkali cellulose and carbon disulfide, heating for reaction at 35 ℃ for 40min, wherein the mass ratio of the alkali cellulose to the carbon disulfide is 1:1, and adding a sodium hydroxide solution (the mass fraction of the sodium hydroxide solution is 8%, and the addition amount of the sodium hydroxide solution is 30% of the mass of the alkali cellulose) into a reaction solution after the reaction is finished to obtain cellulose viscose;
5) curing cellulose viscose at 25 ℃ for 2 hours, filtering and defoaming, extruding the obtained viscose in a film drawing machine, flowing into a solidification bath (the solidification bath contains solidification liquid, the concentration of sulfuric acid in the solidification liquid is 90g/L, and the concentration of sodium sulfate is 230g/L) to form a film, washing the obtained film with water, desulfurizing (the concentration of sodium sulfate in the desulfurization liquid is 8g/L, the concentration of sodium carbonate is 4g/L), bleaching (the concentration of bleaching liquid is 0.5g/L of hydrogen peroxide), drying (the drying temperature is 80 ℃, and the drying time is 1h) to obtain an antifogging glass film;
6) mixing gelatin powder with water to prepare a gelatin solution (the mass fraction of the gelatin solution is 20%), uniformly coating the gelatin solution on the surface of clean glass, flatly covering an antifogging glass film on the gelatin, uniformly rolling the glass film by using a glass rod, naturally standing for 6 hours at room temperature, putting the glass film into an oven, and drying for 30 minutes at 80 ℃ to obtain the antifogging glass.
Example 6
This example provides an antifogging glass, which differs from example 3 in that N- (4-aminobenzoyl) -L-glutamic acid is replaced with L-glutamic acid in step 2).
Test example
The anti-tear properties of the anti-fog glass films obtained in the above examples were respectively tested, and then the water contact angles of the anti-fog glasses obtained in the above examples were respectively tested, wherein the anti-tear strength was measured according to the national standard GB/T16578.2-2009 "measurement of tear resistance of plastic films and sheets", and the test results are shown in table 1.
TABLE 1 test results
| Water contact angle | Tear Strength/N/mm | |
| Example 1 | 21° | 55 |
| Example 2 | 20° | 53 |
| Example 3 | 8° | 67 |
| Example 4 | 22° | 59 |
| Example 5 | 14° | 57 |
| Example 6 | 10° | 64 |
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.
Claims (10)
1. The preparation method of the antifogging glass is characterized by comprising the following steps of:
1) soaking wood pulp or cotton pulp in sodium hydroxide solution for alkalization, filtering and crushing to obtain alkali cellulose;
2) mixing alkali cellulose and carbon disulfide, heating for reaction, and adding a sodium hydroxide solution into a reaction solution after the reaction is finished to obtain cellulose viscose;
3) extruding the cellulose viscose through a film drawing machine, and then forming a thin film in a curing solution to obtain an antifogging glass film;
4) coating the gelatin solution on the surface of a glass substrate, then covering an antifogging glass film on the gelatin solution, rolling, standing and drying to obtain the antifogging glass.
2. The preparation method of the antifogging glass according to claim 1, characterized in that in the step 1), the dipping temperature is 45-55 ℃, the dipping time is 50-80min, the mass ratio of the wood pulp or cotton pulp to the sodium hydroxide solution is 1 (8-11), and the mass fraction of the sodium hydroxide solution is 17-20%;
heating to react at 30-38 ℃ in the step 2), wherein the reaction time is 30-40min, the mass ratio of the alkali cellulose to the carbon disulfide is 1 (1-1.2), the mass fraction of the sodium hydroxide solution is 7-9%, and the addition amount of the sodium hydroxide solution is 28-35% of the mass of the alkali cellulose;
the concentration of the sulfuric acid in the curing liquid in the step 3) is 85-95g/L, and the concentration of the sodium sulfate is 220-240 g/L;
the mass fraction of the gelatin solution in the step 4) is 18-22%, the standing temperature is room temperature, the standing time is 5-8h, the drying temperature is 78-85 ℃, and the drying time is 25-35 min.
3. The method for preparing the antifogging glass according to claim 1 or 2, wherein the cellulose viscose in the step 3) further comprises the steps of curing, filtering and defoaming before being extruded by a film drawing machine.
4. The preparation method of the antifogging glass according to claim 1, characterized in that the wood pulp or cotton pulp in step 1) is modified wood pulp or cotton pulp, and the preparation method of the modified wood pulp or modified cotton pulp comprises the following steps:
a) mixing zinc oxide, 3-aminopropyltriethoxysilane and carbon tetrachloride, heating for reaction, cooling to room temperature after the reaction is finished, filtering, and drying to obtain aminated zinc oxide;
b) mixing aminated zinc oxide, 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride, N- (4-aminobenzoyl) -L-glutamic acid, 4-dimethylaminopyridine and dichloromethane, and heating for amidation reaction to obtain modified zinc oxide;
c) mixing wood pulp or cotton pulp, sodium periodate and water, reacting at room temperature in a dark place, filtering reaction liquid after the reaction is finished, washing and drying to obtain aldehyde cellulose;
d) mixing the aldehyde cellulose, methanol, sodium hydroxide and water, stirring, then adding the modified zinc oxide obtained in the step b) to react, and after the reaction is finished, filtering, washing and drying the reaction solution to obtain the modified zinc oxide grafted cellulose.
5. The method for preparing the antifogging glass according to claim 4, characterized in that the mass ratio of the zinc oxide, the 3-aminopropyltriethoxysilane and the carbon tetrachloride in the step a) is 1 (0.6-0.8) to (9-11), the heating reaction temperature is 80-88 ℃, and the reaction time is 10-14 h;
in the step b), the mass ratio of the aminated zinc oxide, the 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride, the N- (4-aminobenzoyl) -L-glutamic acid, the 4-dimethylaminopyridine and the dichloromethane is 1 (0.2-0.4) to (2-4) to (0.2-0.4) to (4-6), the amidation reaction temperature is 45-55 ℃, and the reaction time is 18-22 h.
6. The preparation method of the antifogging glass according to claim 4, characterized in that the reaction time in the dark place in the step c) is 40-60min, and the mass ratio of wood pulp, sodium periodate and water is 1 (1.9-2.2) to (3-5);
in the step d), the stirring temperature is room temperature, the stirring time is 20-40min, the reaction temperature is 38-45 ℃, the reaction time is 4-6h, and the mass ratio of the aldehyde cellulose, the methanol, the sodium hydroxide, the water and the modified zinc oxide is 1: (4-6):(0.18-2.2):(0.4-0.6):(0.08-0.2).
7. The method for preparing anti-fog glass according to claim 1, wherein the content of alpha-cellulose in the wood pulp or cotton pulp is not less than 85wt%, and the degree of polymerization of cellulose is 500-1000.
8. An antifogging glass, characterized by being produced by the method of any one of claims 1 to 7.
9. The antifogging glass according to claim 8, wherein the antifogging glass comprises a glass substrate, and an adhesive layer and an antifogging glass film sequentially disposed on the glass substrate.
10. Use of the antifog glass of claim 8 or 9 in a fighter instrument.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111411777.3A CN113942278B (en) | 2021-11-25 | 2021-11-25 | Antifogging glass and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111411777.3A CN113942278B (en) | 2021-11-25 | 2021-11-25 | Antifogging glass and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113942278A CN113942278A (en) | 2022-01-18 |
| CN113942278B true CN113942278B (en) | 2022-06-21 |
Family
ID=79338624
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111411777.3A Active CN113942278B (en) | 2021-11-25 | 2021-11-25 | Antifogging glass and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113942278B (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1132448A2 (en) * | 2000-03-09 | 2001-09-12 | Central Glass Company, Limited | Article with antifogging film and process for producing same |
| JP2015004032A (en) * | 2013-06-24 | 2015-01-08 | 日本製紙株式会社 | Antifogging agent and antifogging film |
| CN108026305A (en) * | 2015-09-14 | 2018-05-11 | 富士胶片株式会社 | The manufacture method of antifog film |
| CN110467359A (en) * | 2019-08-27 | 2019-11-19 | 升为玻璃(上海)有限公司 | A kind of antifog glass and preparation method thereof |
| CN110885194A (en) * | 2019-12-13 | 2020-03-17 | 福州大学 | Preparation method of hydrophilic anti-fog film with wear resistance and freeze resistance |
| CN113018910A (en) * | 2021-03-05 | 2021-06-25 | 中海油节能环保服务有限公司 | Preparation method of novel super-hydrophilic oleophobic membrane |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TW202131061A (en) * | 2020-02-06 | 2021-08-16 | 建利光學股份有限公司 | Anti-fog lens and surface treatment method thereof |
-
2021
- 2021-11-25 CN CN202111411777.3A patent/CN113942278B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1132448A2 (en) * | 2000-03-09 | 2001-09-12 | Central Glass Company, Limited | Article with antifogging film and process for producing same |
| JP2015004032A (en) * | 2013-06-24 | 2015-01-08 | 日本製紙株式会社 | Antifogging agent and antifogging film |
| CN108026305A (en) * | 2015-09-14 | 2018-05-11 | 富士胶片株式会社 | The manufacture method of antifog film |
| CN110467359A (en) * | 2019-08-27 | 2019-11-19 | 升为玻璃(上海)有限公司 | A kind of antifog glass and preparation method thereof |
| CN110885194A (en) * | 2019-12-13 | 2020-03-17 | 福州大学 | Preparation method of hydrophilic anti-fog film with wear resistance and freeze resistance |
| CN113018910A (en) * | 2021-03-05 | 2021-06-25 | 中海油节能环保服务有限公司 | Preparation method of novel super-hydrophilic oleophobic membrane |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113942278A (en) | 2022-01-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102911342B (en) | Aqueous fluorinated polyurethane curing agent and preparation method thereof | |
| US20130192489A1 (en) | Process for producing cellulose film | |
| WO2008052646A1 (en) | Plasticizer for protective films | |
| US11820853B2 (en) | Impact-resistant and aging-resistant reflective plastic applied to automobiles | |
| CN111253869B (en) | Waterproof PVB film and preparation method thereof | |
| CN113942278B (en) | Antifogging glass and preparation method and application thereof | |
| CN102516426B (en) | High-elasticity polyvinyl butyral as well as synthetic method and application thereof | |
| CN110819000B (en) | Waterproof ventilated membrane of polypropylene | |
| CN111423772B (en) | Anti-fog and anti-fog coating and preparation method thereof | |
| CN111806030A (en) | Coating type high-barrier biaxially-oriented polyamide film and preparation method thereof | |
| CN109628048B (en) | High-strength polyether adhesive and preparation method thereof | |
| CN113105564A (en) | High-performance membrane material and preparation process thereof | |
| CN109504130A (en) | A kind of preparation of silane end capped polyurethane sealant nanometer calcium carbonate | |
| CN105440975A (en) | Styrene-butadiene latex adhesive and preparation method thereof | |
| CN116728928A (en) | Pearlescent film with extinction function and preparation method thereof | |
| CN108795362A (en) | A kind of Modified by Expandable Graphite flame-retardant polyurethane sealant and preparation method thereof | |
| CN110437624A (en) | A kind of novel transparent bifunctional epoxy resin-silicon rubber block network material | |
| CN116102702A (en) | Method for preparing castor oil-based polyurethane without solvent and catalyst and application thereof | |
| CN112523002B (en) | Degradable food packaging laminating paper and preparation method and application thereof | |
| CN114479142A (en) | Low-temperature acid and alkali resistant stained paper for glass and manufacturing process thereof | |
| CN111138657B (en) | Terpolymer resin | |
| CN113105835A (en) | Protective film production process | |
| US2459927A (en) | Process of manufacturing regenerated cellulose sheet material | |
| CN112455041A (en) | Multilayer composite fabric based on polysiloxane modification and preparation process thereof | |
| CN111944378A (en) | Polymer-based waterproof film, 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 |