CN113248158B - High-heat-resistance explosion-proof glass and production process thereof - Google Patents
High-heat-resistance explosion-proof glass and production process thereof Download PDFInfo
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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
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G14/00—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00
- C08G14/02—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes
- C08G14/04—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols
- C08G14/06—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols and monomers containing hydrogen attached to nitrogen
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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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
- C03C2218/00—Methods for coating glass
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- C03C2218/13—Deposition methods from melts
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- C08J2361/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
- C08J2361/34—Condensation polymers of aldehydes or ketones with monomers covered by at least two of the groups C08J2361/04, C08J2361/18, and C08J2361/20
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Abstract
The invention discloses high-heat-resistance explosion-proof glass and a production process thereof, and relates to the field of glass materials, wherein high-temperature-resistance resin is melted, and the melted high-temperature-resistance resin is uniformly spread on the upper surface and the lower surface of toughened glass to form a layer of thin film so as to form a heat-resistance explosion-proof film, so that the high-heat-resistance explosion-proof glass is obtained; this heat-resisting rupture membrane has fire behavior, and is compound can effectively separate heat transfer behind the toughened glass surface to given the good heat resistance of toughened glass, simultaneously, the existence of heat-resisting rupture membrane has improved toughened glass's mechanical properties, makes it be difficult to break, and the piece is by two-layer heat-resisting rupture membrane adhesion after breaking simultaneously, can significantly reduce the injury to personnel and valuables when meeting with the violence and assault, and the security is high.
Description
Technical Field
The invention relates to the field of glass materials, in particular to high-heat-resistance explosion-proof glass and a production process thereof.
Background
At present, with the continuous development of technology and the gradual change of aesthetic concepts of people, glass materials are more and more widely applied in life due to the transparency, the aesthetic property, the easy cleaning property and the multifunctionality of glass, so the glass materials are also more and more widely applied in the building industry, and especially have unique application in the partition rooms and the curtain walls of houses, however, the glass used at present often has the phenomenon of bursting when exposed fire occurs, so the glass cannot play a role of fire prevention and can cause injury to personnel, and due to the good heat conduction effect of the glass, a user can be scalded by scorching glass during escape;
therefore, how to improve the problems that the existing glass material is easy to crack and difficult to prevent fire and resist heat is a problem to be solved by the invention.
Disclosure of Invention
In order to overcome the technical problems, the invention aims to provide high-heat-resistance explosion-proof glass and a production process thereof.
The purpose of the invention can be realized by the following technical scheme:
the high-heat-resistance explosion-proof glass comprises tempered glass and heat-resistant explosion-proof films positioned on the upper and lower surfaces of the tempered glass, wherein the heat-resistant explosion-proof films are made of high-temperature-resistant resin;
the high-temperature resistant resin is prepared by the following steps:
s1: adding 3, 5-difluoroaniline into a three-neck flask provided with a constant-pressure dropping funnel and a stirrer, adding glacial acetic acid, stirring at the temperature of 30-35 ℃ and the stirring speed of 100-200r/min until the 3, 5-difluoroaniline is completely dissolved, then adding deionized water, continuously stirring for 10-20min, then dropwise adding concentrated sulfuric acid, controlling the dropwise adding speed to be 1 drop/s, maintaining the temperature of the reaction system to be not higher than 45 ℃ in the dropwise adding process, continuously stirring and reacting for 10-20min after the dropwise adding is finished, then cooling the reaction system to 0 ℃, stirring and dropwise adding a sodium nitrite solution under the stirring speed of 500-800r/min, controlling the dropwise adding speed to be 0.8-1mL/min, continuously stirring and reacting for 30-50min after the dropwise adding is finished, adding diethyl ether, continuously stirring for 30-40min, until the solid is completely separated out, carrying out vacuum filtration on the reaction product, placing the filter cake in a vacuum drying oven, and drying the filter cake to constant weight at the temperature of 40-70 ℃ to obtain an intermediate 1;
the reaction principle is as follows:
s2: adding concentrated sulfuric acid and deionized water into a three-neck flask provided with a stirrer and a reflux condenser, heating to 140-150 ℃, dividing the intermediate 1 into equal parts, sequentially adding the intermediate 1 into the three-neck flask for 4-6 times under the condition that the stirring speed is 50-100r/min, stirring until the intermediate 1 is completely dissolved, adding ether for extraction, layering, distilling an extract, recovering ether, and cooling and crystallizing a distillation product to obtain an intermediate 2;
the reaction principle is as follows:
s3: adding the intermediate 2 and chloroform into a four-neck flask provided with a stirrer, a reflux condenser tube and a constant-pressure dropping funnel, stirring at the stirring speed of 100-200r/min until the intermediate 2 is completely dissolved, cooling to below 2 ℃, then dropwise adding a bromine solution, controlling the dropwise adding speed to be 1-5mL/min, continuing stirring for 1-2h after the dropwise adding is finished, then adding a saturated sodium bisulfite solution at normal temperature, then standing and layering the reaction product, distilling the organic phase to remove the solvent, and cooling and crystallizing to obtain an intermediate 3;
the reaction principle is as follows:
s4: adding the intermediate 3, sodium carbonate, 5% palladium carbon, N-2-methylacetamide into a three-neck flask provided with a magnetic stirrer and a gas guide tube, introducing nitrogen for protection, heating to 140 ℃ and 150 ℃ under the condition of 100 ℃ and 200r/min while stirring, controlling the heating rate to be 5 ℃/min, then adding potassium ferrocyanide, continuously stirring for reaction for 1-2h, cooling to room temperature after the reaction is completed, adding ethyl acetate, carrying out vacuum filtration, washing the filtrate with distilled water, then taking an organic phase to dry with anhydrous sodium sulfate, carrying out reduced pressure distillation to recover ethyl acetate, and recrystallizing the distillation product with an ethanol solution to obtain an intermediate 4;
the reaction principle is as follows:
s5: adding the intermediate 4, trifluoromethanesulfonic acid and anhydrous dichloromethane into a three-neck flask provided with a stirrer and a reflux condenser, stirring for 20-30min under the condition of 300r/min at 250-;
the reaction principle is as follows:
s6: adding dioxane, triethylamine, paraformaldehyde and aniline into a flask, stirring for 20-30min under the condition of 300r/min of 250-one, then adding an intermediate 5, continuously stirring and reacting for 2-3h under the condition of heating to 90-95 ℃, controlling the heating rate to be 2-5 ℃/min, carrying out reduced pressure distillation on a reaction product to form a sticky substance, adding dichloromethane to completely dissolve the sticky substance, then washing for 3-5 times by using a sodium carbonate aqueous solution and distilled water respectively, then carrying out reduced pressure distillation and recrystallizing by using absolute ethyl alcohol to obtain an intermediate 6;
the reaction principle is as follows:
s7: and placing the intermediate 6 in a constant-temperature drying oven, curing for 2h at 140 ℃, curing for 2h at 160 ℃, curing for 2h at 180 ℃ to obtain an intermediate 7, curing for 2h at 200 ℃, curing for 2h at 220 ℃ to obtain the intermediate 7, and rearranging the intermediate 7 to obtain the high-temperature-resistant resin. The reaction principle is as follows:
as a further scheme of the invention: the use amount ratio of the 3, 5-difluoroaniline, the glacial acetic acid, the deionized water, the concentrated sulfuric acid, the sodium nitrite solution and the diethyl ether in the step S1 is 24.7 g: 130 g: 80 g: 60 g: 73 g: 150mL, the mass fraction of the concentrated sulfuric acid is 95-98%, and the sodium nitrite solution is sodium nitrite according to the weight ratio of 17: 56 in deionized water.
As a further scheme of the invention: the dosage ratio of the concentrated sulfuric acid, the deionized water, the intermediate 1 and the diethyl ether in the step S2 is 100 mL: 50mL of: 20 g: 150mL, and the mass fraction of the concentrated sulfuric acid is 95-98%.
As a further scheme of the invention: the dosage ratio of the intermediate 2, chloroform, bromine solution and saturated sodium bisulfite solution under the normal temperature condition in the step S3 is 130 g: 100mL of: 240 g: 20mL, wherein the bromine solution is bromine according to the weight ratio of 33: 15 in chloroform.
As a further scheme of the invention: the intermediate 3, sodium carbonate, 5% palladium on carbon, N-2-methylacetamide, potassium ferrocyanide, ethyl acetate and distilled water in the step S4 are used in an amount ratio of 0.1 mol: 0.1 mol: 8.9 g: 100mL of: 0.02 mol: 100mL of: 250mL, and the volume fraction of the ethanol solution is 90%.
As a further scheme of the invention: the dosage ratio of the intermediate 4, the trifluoromethanesulfonic acid and the anhydrous dichloromethane in the step S5 is 0.03 mol: 1.8 g: 40mL, the sodium bicarbonate aqueous solution and the sodium chloride aqueous solution are saturated solutions at 25 ℃.
As a further scheme of the invention: the dosage ratio of dioxane, triethylamine, paraformaldehyde, aniline and intermediate 5 in the step S6 is 50 mL: 1mL of: 1.8 g: 0.03 mol: 0.01mol, wherein the sodium carbonate aqueous solution is a saturated solution at the temperature of 25 ℃.
As a further scheme of the invention: a production process of high-heat-resistance explosion-proof glass comprises the steps of melting high-temperature-resistant resin, carrying out flow-equalizing extension on the upper surface and the lower surface of toughened glass by the melted high-temperature-resistant resin to form a layer of thin film, forming a heat-resistant explosion-proof film, and obtaining the high-heat-resistance explosion-proof glass.
The invention has the beneficial effects that:
the invention relates to high heat-resistant explosion-proof glass and a production process thereof.A high-temperature-resistant resin is melted, and the melted high-temperature-resistant resin is uniformly spread on the upper surface and the lower surface of toughened glass to form a layer of film so as to form a heat-resistant explosion-proof film, thus obtaining the high heat-resistant explosion-proof glass; the heat-resistant explosion-proof film has fireproof performance, and can effectively block heat transfer after being compounded on the surface of toughened glass, so that the toughened glass is endowed with good heat-resistant performance, meanwhile, the existence of the heat-resistant explosion-proof film improves the mechanical performance of the toughened glass, the toughened glass is difficult to break, fragments after being broken are adhered by the two layers of heat-resistant explosion-proof films, the damage to personnel and valuables when the fragments are subjected to violent impact can be greatly reduced, and the safety is high;
preparing a high-temperature resistant resin in the process of preparing the high-heat-resistance explosion-proof glass, namely generating a diazonium salt intermediate 1 by 3, 5-difluoroaniline under the conditions of diazotization agent sodium nitrite and acid environment, then carrying out nitrogen release reaction on the intermediate 1 under the acid condition to generate an intermediate 2, replacing a hydrogen atom on a hydroxyl para position of the intermediate 2 by a bromine atom to generate an intermediate 3, then carrying out cyanation reaction on the intermediate 3 and potassium ferrocyanide to generate an intermediate 4, then forming a triazine ring by a cyano group in the intermediate 4 to generate an intermediate 5, then reacting the intermediate 5, paraformaldehyde and aniline to generate an intermediate 6, carrying out ring-opening polymerization on the intermediate 6 to form an intermediate 7, and then carrying out rearrangement reaction on the intermediate 7 under the condition of 200-220 ℃ to obtain the stable high-polymer high-temperature resistant resin which has a large number of benzene rings and C-F bonds, the high-temperature-resistant resin has good stability, is difficult to damage, has heat resistance, and simultaneously has triazine ring which is a structure rich in tertiary nitrogen, and the compound containing the tertiary nitrogen structure has excellent carbonization effect, forms a tight carbon deposition layer to cover the surface, and blocks oxygen to prevent combustion from spreading, so that the high-temperature-resistant resin has good fire resistance under the synergistic action of a large number of benzene rings, C-F bonds and the tertiary nitrogen structure, thereby endowing the explosion-proof glass with good heat resistance.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1:
this example is a high temperature resistant resin, which is prepared by the following steps:
s1: adding 3, 5-difluoroaniline into a three-neck flask provided with a constant-pressure dropping funnel and a stirrer, adding glacial acetic acid, stirring at the temperature of 30 ℃ and the stirring speed of 100r/min until the 3, 5-difluoroaniline is completely dissolved, then adding deionized water, continuously stirring for 10min, then dropwise adding concentrated sulfuric acid, controlling the dropwise adding speed to be 1 drop/s, maintaining the temperature of a reaction system to be not higher than 45 ℃ in the dropwise adding process, continuously stirring and reacting for 10min after the dropwise adding is finished, then cooling the reaction system to 0 ℃, stirring and dropwise adding a sodium nitrite solution under the stirring speed of 500r/min, controlling the dropwise adding speed to be 0.8mL/min, continuously stirring and reacting for 30min after the dropwise adding is finished, adding diethyl ether, continuously stirring for 30min until solids are completely separated out, carrying out vacuum filtration on a reaction product, placing a filter cake into a vacuum drying box, drying the mixture to constant weight at the temperature of 40 ℃ to obtain an intermediate 1; controlling the dosage ratio of 3, 5-difluoroaniline, glacial acetic acid, deionized water, concentrated sulfuric acid, sodium nitrite solution and ether to be 24.7 g: 130 g: 80 g: 60 g: 73 g: 150mL, the mass fraction of concentrated sulfuric acid is 98%, and the sodium nitrite solution is sodium nitrite according to the weight ratio of 17: 56 in deionized water;
s2: adding concentrated sulfuric acid and deionized water into a three-neck flask provided with a stirrer and a reflux condenser, heating to 140 ℃, dividing the intermediate 1 into equal parts, sequentially adding the intermediate 1 into the three-neck flask for 4 times under the condition that the stirring speed is 50r/min, stirring until the intermediate 1 is completely dissolved, adding ether for extraction, layering, distilling extract liquor, recovering ether, and cooling and crystallizing a distillation product to obtain an intermediate 2; controlling the dosage ratio of the concentrated sulfuric acid, the deionized water, the intermediate 1 and the diethyl ether to be 100 mL: 50mL of: 20 g: 150mL, the mass fraction of concentrated sulfuric acid is 98%;
s3: adding the intermediate 2 and chloroform into a four-neck flask provided with a stirrer, a reflux condenser tube and a constant-pressure dropping funnel, stirring at a stirring speed of 100r/min until the intermediate 2 is completely dissolved, cooling to below 2 ℃, then dropwise adding a bromine solution, controlling the dropwise adding speed to be 1mL/min, continuing stirring for 1h after the dropwise adding is finished, then adding a saturated sodium bisulfite solution at normal temperature, then standing and layering reaction products, distilling an organic phase to remove a solvent, and cooling and crystallizing to obtain an intermediate 3; controlling the dosage ratio of the intermediate 2, chloroform, bromine solution and saturated sodium bisulfite solution under normal temperature to be 130 g: 100mL of: 240 g: 20mL, bromine solution as bromine according to 33: 15 in chloroform;
s4: adding the intermediate 3, sodium carbonate, 5% palladium carbon, N-2-methylacetamide into a three-neck flask provided with a magnetic stirrer and a gas guide tube, introducing nitrogen for protection, heating to 140 ℃ while stirring under the condition of 100r/min, controlling the heating rate to be 5 ℃/min, then adding potassium ferrocyanide, continuously stirring for reaction for 1h, cooling to room temperature after the reaction is completed, adding ethyl acetate, carrying out vacuum filtration, washing filtrate with distilled water, then taking an organic phase, drying with anhydrous sodium sulfate, carrying out reduced pressure distillation to recover ethyl acetate, and recrystallizing a distillation product with an ethanol solution to obtain an intermediate 4; controlling the dosage ratio of the intermediate 3, sodium carbonate, 5% palladium carbon, N-2-methylacetamide, potassium ferrocyanide, ethyl acetate and distilled water to be 0.1 mol: 0.1 mol: 8.9 g: 100mL of: 0.02 mol: 100mL of: 250mL, the volume fraction of the ethanol solution is 90%;
s5: adding the intermediate 4, trifluoromethanesulfonic acid and anhydrous dichloromethane into a three-neck flask provided with a stirrer and a reflux condenser, stirring for 20min under the condition of 250r/min, heating a reaction system to boiling, carrying out reflux reaction for 15h, adding a sodium bicarbonate aqueous solution to adjust the reaction system to be neutral, carrying out vacuum filtration, washing a filter cake for 3 times respectively with a sodium chloride aqueous solution and distilled water, placing the filter cake in a vacuum drying box, drying the filter cake to constant weight under the condition of 60 ℃, and recrystallizing a dried product with anhydrous ethanol to obtain an intermediate 5; controlling the dosage ratio of the intermediate 4, the trifluoromethanesulfonic acid and the anhydrous dichloromethane to be 0.03 mol: 1.8 g: 40mL, wherein the sodium bicarbonate aqueous solution and the sodium chloride aqueous solution are saturated solutions at the temperature of 25 ℃;
s6: adding dioxane, triethylamine, paraformaldehyde and aniline into a flask, stirring for 20min under the condition of 250r/min, adding an intermediate 5, heating to 90 ℃, continuing stirring for reaction for 2h, controlling the heating rate to be 2 ℃/min, carrying out reduced pressure distillation on a reaction product to form a sticky substance, adding dichloromethane to completely dissolve the sticky substance, washing for 3 times by using a sodium carbonate aqueous solution and distilled water respectively, carrying out reduced pressure distillation, and recrystallizing by using absolute ethyl alcohol to obtain an intermediate 6; controlling the dosage ratio of dioxane, triethylamine, paraformaldehyde, aniline and intermediate 5 to be 50 mL: 1mL of: 1.8 g: 0.03 mol: 0.01mol, and the sodium carbonate aqueous solution is a saturated solution at the temperature of 25 ℃;
s7: and placing the intermediate 6 in a constant-temperature drying oven, curing for 2h at 140 ℃, curing for 2h at 160 ℃, curing for 2h at 180 ℃ to obtain an intermediate 7, curing for 2h at 200 ℃, curing for 2h at 220 ℃ to obtain the intermediate 7, and rearranging the intermediate 7 to obtain the high-temperature-resistant resin.
Example 2:
this example is a high temperature resistant resin, which is prepared by the following steps:
s1: adding 3, 5-difluoroaniline into a three-neck flask provided with a constant-pressure dropping funnel and a stirrer, adding glacial acetic acid, stirring at the temperature of 35 ℃ and the stirring speed of 200r/min until the 3, 5-difluoroaniline is completely dissolved, then adding deionized water, continuously stirring for 20min, then dropwise adding concentrated sulfuric acid, controlling the dropwise adding speed to be 1 drop/s, maintaining the temperature of a reaction system to be not higher than 45 ℃ in the dropwise adding process, continuously stirring and reacting for 20min after the dropwise adding is finished, then cooling the reaction system to 0 ℃, stirring and dropwise adding a sodium nitrite solution under the stirring speed of 800r/min, controlling the dropwise adding speed to be 1mL/min, continuously stirring and reacting for 50min after the dropwise adding is finished, adding diethyl ether, continuously stirring for 40min until the solid is completely separated out, carrying out vacuum filtration on the reaction product, placing a filter cake into a vacuum drying box, drying the mixture to constant weight at the temperature of 70 ℃ to obtain an intermediate 1; controlling the dosage ratio of 3, 5-difluoroaniline, glacial acetic acid, deionized water, concentrated sulfuric acid, sodium nitrite solution and ether to be 24.7 g: 130 g: 80 g: 60 g: 73 g: 150mL, the mass fraction of concentrated sulfuric acid is 98%, and the sodium nitrite solution is sodium nitrite according to the weight ratio of 17: 56 in deionized water;
s2: adding concentrated sulfuric acid and deionized water into a three-neck flask provided with a stirrer and a reflux condenser, heating to 150 ℃, dividing the intermediate 1 into equal parts, sequentially adding the intermediate 1 into the three-neck flask in 6 times at a stirring speed of 100r/min, stirring until the intermediate 1 is completely dissolved, adding ether for extraction, layering, distilling extract liquor, recovering ether, and cooling and crystallizing a distillation product to obtain an intermediate 2; controlling the dosage ratio of the concentrated sulfuric acid, the deionized water, the intermediate 1 and the diethyl ether to be 100 mL: 50mL of: 20 g: 150mL, the mass fraction of concentrated sulfuric acid is 98%;
s3: adding the intermediate 2 and chloroform into a four-neck flask provided with a stirrer, a reflux condenser tube and a constant-pressure dropping funnel, stirring at a stirring speed of 200r/min until the intermediate 2 is completely dissolved, cooling to below 2 ℃, then dropwise adding a bromine solution, controlling the dropwise adding speed to be 5mL/min, continuing stirring for 2 hours after the dropwise adding is finished, then adding a saturated sodium bisulfite solution at normal temperature, then standing and layering reaction products, distilling an organic phase to remove a solvent, and cooling and crystallizing to obtain an intermediate 3; controlling the dosage ratio of the intermediate 2, chloroform, bromine solution and saturated sodium bisulfite solution under normal temperature to be 130 g: 100mL of: 240 g: 20mL, bromine solution as bromine according to 33: 15 in chloroform;
s4: adding the intermediate 3, sodium carbonate, 5% palladium carbon, N-2-methylacetamide into a three-neck flask provided with a magnetic stirrer and an air guide tube, introducing nitrogen for protection, heating to 150 ℃ while stirring under the condition of 200r/min, controlling the heating rate to be 5 ℃/min, then adding potassium ferrocyanide, continuously stirring for reaction for 2 hours, cooling to room temperature after the reaction is completed, adding ethyl acetate, carrying out vacuum filtration, washing filtrate with distilled water, then taking an organic phase, drying with anhydrous sodium sulfate, carrying out reduced pressure distillation to recover ethyl acetate, and recrystallizing a distillation product with an ethanol solution to obtain an intermediate 4; controlling the dosage ratio of the intermediate 3, sodium carbonate, 5% palladium carbon, N-2-methylacetamide, potassium ferrocyanide, ethyl acetate and distilled water to be 0.1 mol: 0.1 mol: 8.9 g: 100mL of: 0.02 mol: 100mL of: 250mL, the volume fraction of the ethanol solution is 90%;
s5: adding the intermediate 4, trifluoromethanesulfonic acid and anhydrous dichloromethane into a three-neck flask provided with a stirrer and a reflux condenser, stirring for 30min under the condition of 300r/min, heating a reaction system to boiling, carrying out reflux reaction for 20h, adding a sodium bicarbonate aqueous solution to adjust the reaction system to be neutral, carrying out vacuum filtration, washing a filter cake for 5 times respectively with a sodium chloride aqueous solution and distilled water, placing the filter cake in a vacuum drying box, drying the filter cake to constant weight under the condition of 90 ℃, and recrystallizing a dried product with anhydrous ethanol to obtain an intermediate 5; controlling the dosage ratio of the intermediate 4, the trifluoromethanesulfonic acid and the anhydrous dichloromethane to be 0.03 mol: 1.8 g: 40mL, wherein the sodium bicarbonate aqueous solution and the sodium chloride aqueous solution are saturated solutions at the temperature of 25 ℃;
s6: adding dioxane, triethylamine, paraformaldehyde and aniline into a flask, stirring for 30min under the condition of 300r/min, then adding an intermediate 5, heating to 95 ℃, continuing stirring for reaction for 3h, controlling the heating rate to be 5 ℃/min, carrying out reduced pressure distillation on a reaction product to form a sticky substance, adding dichloromethane to completely dissolve the sticky substance, then washing for 5 times by using a sodium carbonate aqueous solution and distilled water respectively, then carrying out reduced pressure distillation, and recrystallizing by using absolute ethyl alcohol to obtain an intermediate 6; controlling the dosage ratio of dioxane, triethylamine, paraformaldehyde, aniline and intermediate 5 to be 50 mL: 1mL of: 1.8 g: 0.03 mol: 0.01mol, and the sodium carbonate aqueous solution is a saturated solution at the temperature of 25 ℃;
s7: and placing the intermediate 6 in a constant-temperature drying oven, curing for 2h at 140 ℃, curing for 2h at 160 ℃, curing for 2h at 180 ℃ to obtain an intermediate 7, curing for 2h at 200 ℃, curing for 2h at 220 ℃ to obtain the intermediate 7, and rearranging the intermediate 7 to obtain the high-temperature-resistant resin.
Example 3:
this example is a production process of high heat-resistant explosion-proof glass, in which the high heat-resistant resin from example 1 is melted, and the melted high-temperature-resistant resin is uniformly spread on the upper and lower surfaces of toughened glass to form a thin film, so as to form a heat-resistant explosion-proof film, thereby obtaining the high heat-resistant explosion-proof glass.
Example 4:
this example is a production process of high heat-resistant explosion-proof glass, in which the high heat-resistant resin from example 2 is melted, and the melted high-temperature-resistant resin is uniformly spread on the upper and lower surfaces of toughened glass to form a thin film, so as to form a heat-resistant explosion-proof film, thereby obtaining the high heat-resistant explosion-proof glass.
Comparative example 1:
the comparative example 1 is different from the example 4 in that the high temperature resistant resin is not added, and is the tempered glass in the example.
Comparative example 2:
comparative example 2 is a fire-resistant glass as provided in application No. cn201810555701. x.
The glass products in examples 3 to 4 and comparative examples 1 to 2 were prepared into 1100mm × 600mm samples according to GB/T12513-2006 "method for testing fire resistance of glazed elements", and then vertically mounted on a fire-resistant furnace, respectively, according to GB/T9978.1-2008 "method for testing fire resistance of building elements part 1: the temperature rise curve in the method of general requirements is subjected to temperature rise heating, and the glass breakage time is observed in the heating process.
| Sample (I) | Example 3 | Example 4 | Comparative example 1 | Comparative example 2 |
| Time to fire/min | 206 | 213 | 26 | 144 |
| Impact strength/MPa | 912 | 924 | 208 | 653 |
Referring to the data in the table, according to the comparison between the example and the comparative example 2, it is known that the high heat-resistant explosion-proof glass in the present invention has higher heat-resistant and fire-proof performance than the fire-proof glass in the prior art, and according to the comparison between the example and the comparative example, it is known that the heat-resistant and fire-proof performance of the general toughened glass is obviously improved, and meanwhile, the mechanical properties of the film formed by casting the high temperature-resistant resin can also be obviously improved.
In the description herein, references to the description of "one embodiment," "an example," "a specific example" or the like are intended to mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The foregoing is illustrative and explanatory only and is not intended to be exhaustive or to limit the invention to the precise embodiments described, and various modifications, additions, and substitutions may be made by those skilled in the art without departing from the scope of the invention or exceeding the scope of the claims.
Claims (8)
1. The high-heat-resistance explosion-proof glass is characterized by comprising tempered glass and heat-resistant explosion-proof films positioned on the upper surface and the lower surface of the tempered glass, wherein the heat-resistant explosion-proof films are made of high-temperature-resistant resin;
the high-temperature resistant resin is prepared by the following steps:
s1: adding 3, 5-difluoroaniline into a three-neck flask provided with a constant-pressure dropping funnel and a stirrer, adding glacial acetic acid, stirring at the temperature of 30-35 ℃ and the stirring speed of 100-200r/min until the 3, 5-difluoroaniline is completely dissolved, then adding deionized water, continuously stirring for 10-20min, then dropwise adding concentrated sulfuric acid, controlling the dropwise adding speed to be 1 drop/s, maintaining the temperature of the reaction system to be not higher than 45 ℃ in the dropwise adding process, continuously stirring and reacting for 10-20min after the dropwise adding is finished, then cooling the reaction system to 0 ℃, stirring and dropwise adding a sodium nitrite solution under the stirring speed of 500-800r/min, controlling the dropwise adding speed to be 0.8-1mL/min, continuously stirring and reacting for 30-50min after the dropwise adding is finished, adding diethyl ether, continuously stirring for 30-40min, until the solid is completely separated out, carrying out vacuum filtration on the reaction product, placing the filter cake in a vacuum drying oven, and drying the filter cake to constant weight at the temperature of 40-70 ℃ to obtain an intermediate 1;
s2: adding concentrated sulfuric acid and deionized water into a three-neck flask provided with a stirrer and a reflux condenser, heating to 140-150 ℃, dividing the intermediate 1 into equal parts, sequentially adding the intermediate 1 into the three-neck flask for 4-6 times under the condition that the stirring speed is 50-100r/min, stirring until the intermediate 1 is completely dissolved, adding ether for extraction, layering, distilling extract liquor, and cooling and crystallizing a distillation product to obtain an intermediate 2;
s3: adding the intermediate 2 and chloroform into a four-neck flask provided with a stirrer, a reflux condenser tube and a constant-pressure dropping funnel, stirring at the stirring speed of 100-200r/min until the intermediate 2 is completely dissolved, cooling to below 2 ℃, then dropwise adding a bromine solution, controlling the dropwise adding speed to be 1-5mL/min, continuing stirring for 1-2h after the dropwise adding is finished, then adding a saturated sodium bisulfite solution at normal temperature, then standing and layering the reaction product, distilling the organic phase, cooling and crystallizing to obtain an intermediate 3;
s4: adding the intermediate 3, sodium carbonate, 5% palladium carbon, N-2-methylacetamide into a three-neck flask provided with a magnetic stirrer and a gas guide tube, introducing nitrogen for protection, heating to 140 ℃ and 150 ℃ under the condition of 100 ℃ and 200r/min while stirring, controlling the heating rate to be 5 ℃/min, then adding potassium ferrocyanide, continuously stirring for reaction for 1-2h, cooling to room temperature after the reaction is completed, adding ethyl acetate, carrying out vacuum filtration, washing the filtrate with distilled water, then taking an organic phase, drying with anhydrous sodium sulfate, carrying out reduced pressure distillation, and recrystallizing the distillation product with an ethanol solution to obtain an intermediate 4;
s5: adding the intermediate 4, trifluoromethanesulfonic acid and anhydrous dichloromethane into a three-neck flask provided with a stirrer and a reflux condenser, stirring for 20-30min under the condition of 300r/min at 250-;
s6: adding dioxane, triethylamine, paraformaldehyde and aniline into a flask, stirring for 20-30min under the condition of 300r/min of 250-one, then adding an intermediate 5, continuously stirring and reacting for 2-3h under the condition of heating to 90-95 ℃, controlling the heating rate to be 2-5 ℃/min, carrying out reduced pressure distillation on a reaction product to form a sticky substance, adding dichloromethane to completely dissolve the sticky substance, then washing for 3-5 times by using a sodium carbonate aqueous solution and distilled water respectively, then carrying out reduced pressure distillation and recrystallizing by using absolute ethyl alcohol to obtain an intermediate 6;
s7: and placing the intermediate 6 in a constant-temperature drying oven, curing for 2h at 140 ℃, curing for 2h at 160 ℃, curing for 2h at 180 ℃ to obtain an intermediate 7, curing for 2h at 200 ℃, curing for 2h at 220 ℃ to obtain the intermediate 7, and rearranging the intermediate 7 to obtain the high-temperature-resistant resin.
2. The explosion-proof glass with high heat resistance according to claim 1, wherein the amount ratio of the 3, 5-difluoroaniline, the glacial acetic acid, the deionized water, the concentrated sulfuric acid, the sodium nitrite solution and the ether in the step S1 is 24.7 g: 130 g: 80 g: 60 g: 73 g: 150mL, the mass fraction of the concentrated sulfuric acid is 95-98%, and the sodium nitrite solution is sodium nitrite according to the weight ratio of 17: 56 in deionized water.
3. The explosion-proof glass with high heat resistance according to claim 1, wherein the dosage ratio of concentrated sulfuric acid, deionized water, intermediate 1 and ether in step S2 is 100 mL: 50mL of: 20 g: 150mL, and the mass fraction of the concentrated sulfuric acid is 95-98%.
4. The explosion-proof glass with high heat resistance according to claim 1, wherein the intermediate 2, chloroform, bromine solution, and saturated sodium bisulfite solution under normal temperature conditions in step S3 are used in a ratio of 130 g: 100mL of: 240 g: 20mL, wherein the bromine solution is bromine according to the weight ratio of 33: 15 in chloroform.
5. The highly heat-resistant explosion-proof glass according to claim 1, wherein the intermediate 3, sodium carbonate, 5% palladium on carbon, N-2-methylacetamide, potassium ferrocyanide, ethyl acetate, and distilled water in step S4 are used in an amount ratio of 0.1 mol: 0.1 mol: 8.9 g: 100mL of: 0.02 mol: 100mL of: 250mL, and the volume fraction of the ethanol solution is 90%.
6. The explosion-proof glass with high heat resistance according to claim 1, wherein the intermediate 4, the trifluoromethanesulfonic acid and the anhydrous dichloromethane in the step S5 are used in an amount ratio of 0.03 mol: 1.8 g: 40mL, the sodium bicarbonate aqueous solution and the sodium chloride aqueous solution are saturated solutions at 25 ℃.
7. The explosion-proof glass with high heat resistance according to claim 1, wherein the dosage ratio of dioxane, triethylamine, paraformaldehyde, aniline and intermediate 5 in step S6 is 50 mL: 1mL of: 1.8 g: 0.03 mol: 0.01mol, wherein the sodium carbonate aqueous solution is a saturated solution at the temperature of 25 ℃.
8. The process for producing high heat-resistant explosion-proof glass according to claim 1, wherein the high heat-resistant explosion-proof glass is obtained by melting the high temperature-resistant resin, and uniformly casting the melted high temperature-resistant resin on the upper and lower surfaces of the tempered glass to form a thin film, thereby forming the heat-resistant explosion-proof film.
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