Nanometer silicon-based heat-insulation fireproof glass film and preparation method thereof

Abstract

The invention relates to the technical field of fireproof glass, in particular to a nanometer silicon-based heat-insulation fireproof glass film and a preparation method thereof. The film comprises a film base layer as well as a sound insulation layer and a flame-retardant layer which are sequentially arranged on the film base layer, and the film base layer comprises the following components in parts by weight: 10-30 parts of nano silicon dioxide, 50-70 parts of matrix resin, 1-3 parts of a dispersing agent, 1-3 parts of a stabilizer, 1-3 parts of a cross-linking agent, 5-10 parts of a plasticizer and 10-32 parts of a solvent. The glass film has good heat insulation, fire resistance and high temperature resistance, can effectively isolate a fire source and prevent fire from spreading, has good tensile strength and mechanical strength, and avoids the problems of breakage and the like in the use process. And the film is colorless, transparent and high in light transmittance.

Description

Technical Field

[0001] The invention relates to the technical field of fireproof glass, and in particular to a nano silicon-based heat-insulating fireproof glass film and a preparation method thereof. Background Art

[0002] Laminated glass is a composite glass product made of two or more pieces of glass with one or more layers of organic polymer interlayer in between. After special high-temperature pre-pressing (or vacuuming) and high-temperature and high-pressure processing, the glass and the interlayer are permanently bonded together. Commonly used interlayer films for laminated glass include: PVB, SGP, EVA, PU, ​​etc.

[0003] The Chinese patent application number CN110605885B discloses a laminated composite glass with a multi-layer structure, including a first inner layer glass and a second inner layer glass, a vacuum layer is provided between the first inner layer glass and the second inner layer glass, a first inner layer film is provided on one side of the first inner layer glass, a transparent conductive film is provided on one side of the first inner layer film, indoor glass is provided on one side of the transparent conductive film, indoor glass is provided on one side of the transparent conductive film, a second inner layer film is provided on one side of the second inner layer glass, a photoelectric glass is provided on one side of the second inner layer film, outdoor glass is provided on one side of the photoelectric glass, and a hollow layer is provided between the outdoor glass and the photoelectric glass. The invention uses a multi-layer structural design, a transparent conductive film and a photoelectric glass structural design to enable the laminated composite glass to have self-generated electricity and defogging functions, and uses the design of the hollow layer and the vacuum layer to improve the heat insulation and sound insulation effects of the laminated composite glass. The Chinese patent document with application number CN202411695392.8 discloses an SGP film laminated glass and its production process. The laminated sheet is prepared by mixing a modified resin and an SGP laminated resin and extruding and casting them into a film. The laminated sheet is placed between two pieces of glass and pressed at high temperature. When the modified resin and the SGP laminated resin are melted, the double bonds on the modified resin can be grafted with the molecular chains on the SGP laminated resin. The main body of the modified resin molecular chain is a polyurethane structure containing an organic silicon chain segment, which can improve the thermal insulation effect of the SGP laminated resin. The modified filler contains a multi-void structure, which further improves the thermal insulation effect. The titanium-containing organic silicon resin segment in the modified resin, the tin dioxide on the surface of the modified filler, and the benzotriazole structure in the modified resin can increase the absorption of ultraviolet rays by the laminated sheet and reduce the exposure to ultraviolet rays.

[0004] Single resin as the film matrix, thermal insulation performance, mechanical properties, etc. cannot meet the requirements. Nano silicon oxide can improve the above properties. However, nano silicon particles are easy to agglomerate due to van der Waals force, resulting in poor solution fluidity and uneven coating thickness, which seriously affects the thermal insulation performance and transparency. In practical applications, this agglomeration phenomenon will lead to poor local thermal insulation effect of the film, and may even cause hot spots, affecting the overall performance of fireproof glass. In addition, agglomerated nano silicon particles will also affect the transparency of the film and reduce the lighting effect of the glass. During long-term storage or transportation, nano silicon particles are prone to sedimentation or gelation, resulting in poor product performance consistency. Sedimentation will cause uneven distribution of nano silicon particles in the film, affecting thermal insulation performance and mechanical strength. Gelation will make the film hard and brittle, reduce its flexibility and processing performance, and may even cause the film to crack during use. In light and humid environments, traditional products are prone to yellowing, bubbling, and fogging, affecting the appearance and performance. Yellowing will cause the transparency of the film to decrease, affecting the lighting effect of the glass. Bubbling and fogging will cause defects on the film surface, reduce its mechanical strength and thermal insulation properties, and may even cause the film to fall off during use.

[0005] At present, there is an urgent need for a new type of nano-silicone sheet and preparation method with high dispersibility, high stability, good equipment compatibility and low cost to solve the problems of yellowing, bubbling, fogging, poor fire stability and optical deformation caused by plastic flow when used with glass. Specifically, there is a need for a nano-silicone sheet that can be industrially produced on existing production equipment, which should have good dispersibility and stability, be able to maintain stable performance in light and humid environments, have a long fire resistance limit and low thermal conductivity, and avoid optical deformation caused by plastic flow when used with glass. Summary of the invention

[0006] In order to solve the above problems, the present invention provides a nano-silicon-based heat-insulating fireproof glass film and a preparation method thereof, the glass film has good heat insulation, fire resistance and high temperature resistance, can effectively isolate the fire source and prevent the spread of fire, and has good tensile resistance and mechanical strength, avoiding problems such as breakage during use. The film is colorless and transparent with high light transmittance.

[0007] The technical solution adopted by the present invention to achieve the above-mentioned purpose is:

[0008] A nano-silicon-based heat-insulating fireproof glass film comprises a film base layer, and a sound insulation layer and a flame retardant layer sequentially arranged on the film base layer. The film base layer comprises the following components by weight: 10-30 parts of nano-silicon dioxide, 50-70 parts of a matrix resin, 1-3 parts of a dispersant, 1-3 parts of a stabilizer, 1-3 parts of a cross-linking agent, 5-10 parts of a plasticizer, and 10-32 parts of a solvent. The matrix resin is modified polyvinyl alcohol or polyurethane. The preparation method of the modified polyvinyl alcohol is as follows:

[0009] Step S1, dissolving polyvinyl alcohol in water, adding polyethylene glycol diglycidyl ether as a cross-linking agent, reacting at 50-60° C. under alkaline conditions for 2-4 hours, and obtaining a cross-linked polyvinyl alcohol resin after purification by dialysis and drying;

[0010] Step S2, dispersing the cross-linked polyvinyl alcohol resin obtained in step S1 in a mixed solvent of N,N-dimethylformamide and water, adding maleic acid and a free radical initiator, reacting at 90-100° C. for 4-6 hours under nitrogen protection, then precipitating, centrifuging, and drying to obtain a graft-modified polyvinyl alcohol resin;

[0011] Step S3, compounding the nanocellulose and the grafted modified polyvinyl alcohol resin obtained in step S2 by mechanical blending.

[0012] Furthermore, in step S1, the amount of polyethylene glycol diglycidyl ether added is 5-15% of the mass of polyvinyl alcohol; and the weight volume ratio of polyvinyl alcohol to water is 8-12 g:100 ml.

[0013] Furthermore, in step S1, the alkaline condition has a pH of 10-11, which is adjusted by sodium hydroxide; and the dialysis purification uses a dialysis bag with a molecular weight cutoff of 8000-14000, which lasts for 48-72 hours.

[0014] Furthermore, in step S2, the amount of maleic acid added is 8-20% of the mass of the cross-linked polyvinyl alcohol in step S1; the free radical initiator is potassium persulfate, and the amount added is 2-3% of the mass of the maleic acid; the weight volume ratio of the cross-linked polyvinyl alcohol obtained in step 1 to the mixed solvent is: 5-10g:100ml, and the weight ratio of N,N-dimethylformamide to water in the mixed solvent is 4:0.8-1.2.

[0015] Furthermore, in step S3, the amount of nanocellulose added is 5-15% of the mass of the graft-modified polyvinyl alcohol resin in step S2.

[0016] In the above modification of polyvinyl alcohol, polyethylene glycol diglycidyl ether (PEGDE) is used as a flexible crosslinking agent to react with PVA hydroxyl groups under alkaline conditions to form a three-dimensional crosslinked network. The high degree of crosslinking gives excellent thermal stability and mechanical strength. The appropriate amount of polyethylene glycol diglycidyl ether can not only ensure the density of the network, but also avoid the brittleness caused by excessive crosslinking. The crosslinked polyvinyl alcohol resin has a higher thermal decomposition temperature and can remain stable under high temperature conditions. The crosslinked structure can effectively prevent the hydrolysis and degradation of polyvinyl alcohol in a chemical environment and improve its chemical stability. Step S2 introduces polar carboxyl functional groups on the polyvinyl alcohol molecular chain through maleic acid. These functional groups can form hydrogen bonds and other interactions with the polyvinyl alcohol molecular chains, thereby enhancing the bonding force between the molecular chains, thereby improving the tensile strength, modulus and other mechanical properties of the material. The grafting of maleic acid can improve the thermal stability of polyvinyl alcohol, increase its decomposition temperature at high temperatures, reduce the generation of thermal decomposition products, and thus extend the service life of the material. Polyvinyl alcohol modified by maleic acid grafting has better polarity and better compatibility with a variety of other materials (such as inorganic fillers, other polymers, etc.), which is conducive to the preparation of composite materials with excellent performance. The bonding performance of the grafted polyvinyl alcohol resin to the glass surface is significantly improved. This is because the carboxyl functional groups introduced by maleic acid grafting can chemically bond or hydrogen bond with the hydroxyl groups on the glass surface, thereby enhancing the bonding strength between the film and the glass. The water resistance of the modified polyvinyl alcohol resin is improved, and its bonding performance with the glass can remain stable even in a humid environment, and it is not easy to reduce the bonding strength due to the penetration of water molecules.

[0017] The stability of the polyvinyl alcohol resin modified with maleic acid is enhanced under environmental factors such as ultraviolet radiation and temperature changes, and the weather resistance of the glass film is improved, which can better adapt to different environmental conditions.

[0018] Nanocellulose has high strength and high modulus. It is evenly dispersed in the resin matrix and can effectively enhance the tensile strength and impact resistance of the composite material. Nanocellulose itself has good thermal stability, and its composite with polyvinyl alcohol further improves the heat resistance of the composite material. Cross-linked polyvinyl alcohol itself has certain flame retardant properties. The composite structure of cross-linked polyvinyl alcohol and nanocellulose can form a stable carbonization layer at high temperature, effectively preventing the transfer of heat and oxygen, thereby extending the fireproof time of the material and further improving the fireproof performance of the composite material. At the same time, the dense filling of nanocellulose reduces the gas permeation path, reduces the oxygen permeability, and synergistically enhances the thermal insulation and fireproof properties. The addition of nanocellulose not only enhances the strength of the material, but also improves the flexibility of the composite material through its unique nanostructure. The mechanical blending and compounding of nanocellulose and modified polyvinyl alcohol enables the two to be evenly dispersed to form a good composite structure. At the same time, the composite structure of nanocellulose and nano-silica can effectively block heat transfer and improve the thermal insulation performance of the material. The addition of nanocellulose further enhances the sound insulation effect of the composite material, and the composite structure of nanocellulose and nano-silica can improve the optical properties of the material, such as transparency and light scattering properties.

[0019] The modified polyvinyl alcohol and the surface hydroxyl groups of nano-SiO2 are bonded through hydrogen bonding or esterification reaction to form a strong "resin-filler" interface layer, which reduces stress concentration and improves mechanical properties. The multi-scale pores of the nano-SiO2 structure and nano-cellulose synergistically inhibit heat conduction, reduce thermal conductivity, and improve thermal insulation performance. The modified polyvinyl alcohol cross-linked network carbonizes at high temperature to form a dense carbon layer. Nano-SiO2 and nano-cellulose act as inorganic barriers to inhibit the diffusion of combustible gases, and their synergistic effect further improves flame retardancy.

[0020] Furthermore, in step S3, the nanocellulose is pretreated with a silane coupling agent KH-550.

[0021] Furthermore, the nanocellulose pretreatment step is as follows: disperse the nanocellulose in deionized water, treat with an ultrasonic disperser for 25-35 minutes to obtain solution 1; dissolve the silane coupling agent in ethanol, stir evenly, then add the solution 1, stir and react at 60-80°C for 1.5-2.5 hours, after the reaction is completed, separate by centrifugation, wash with ethanol and deionized water for 3 times, dry the precipitate, and obtain pretreated nanocellulose; wherein the weight-to-volume ratio of nanocellulose to deionized water is 10g:90-110ml, the weight-to-volume ratio of silane coupling agent to ethanol is 2g:180-220ml, and the dosage ratio of nanocellulose to silane coupling agent is 10:0.15-0.25.

[0022] Silane coupling agent KH-550 pre-treats nanocellulose and introduces active groups such as amino groups, which significantly improves the surface activity of nanocellulose. The pre-treated nanocellulose can be more evenly dispersed in the polyvinyl alcohol matrix to avoid agglomeration, thereby improving the overall performance of the composite material. The pre-treated nanocellulose can form a stronger interface bond with the polyvinyl alcohol matrix, and further enhance the bonding force between the two through hydrogen bonding or esterification reaction. The strong interface layer can effectively disperse stress and reduce stress concentration, thereby improving the mechanical properties of the composite material. The pre-treated nanocellulose can better combine with the polyvinyl alcohol or polyurethane matrix at high temperature, thereby improving the thermal stability of the composite material. The pre-treated nanocellulose can be more densely filled in the resin matrix, reducing the gas permeation path and further improving the barrier properties of the composite material. The pre-treated nanocellulose can better combine with the resin matrix during the mechanical blending process, thereby improving the processing performance of the composite material. The uniformly dispersed nanocellulose can improve the molding quality of the composite material and reduce defects and non-uniformity.

[0023] The film prepared by using the modified polyvinyl alcohol or polyurethane as the resin matrix and composited with nano-silicon has significant advantages in mechanical properties, barrier properties, interface bonding, thermal insulation properties and flame retardancy. Pre-treatment of nanocellulose can further enhance its surface activity, interface bonding and dispersibility, thereby further improving the overall performance of the composite material. These improvements make the composite material have good application prospects in high-performance application fields.

[0024] Furthermore, the dispersant is polyacrylamide, the stabilizer is sodium carboxymethyl cellulose, the cross-linking agent is a silane coupling agent, the plasticizer is dibutyl phthalate, and the solvent is anhydrous ethanol.

[0025] Furthermore, the sound insulation layer is mainly made of thermoplastic polyurethane elastomer rubber and hollow glass microbeads, and the flame retardant layer is mainly made of water-based acrylic resin and ammonium polyphosphate.

[0026] The preparation method of the above-mentioned nano-silicon-based heat-insulating and fire-proof glass film, wherein the preparation method of the film base layer includes the following steps: nano-silicon dioxide pretreatment → ultrasonic dispersion → resin dissolution → mixing → filtration and degassing → hot pressing molding, gradient cooling → cross-linking curing, and polishing.

[0027] Specifically, the steps of preparing the film base layer are as follows:

[0028] Step 1, vacuum drying the nano-silicon dioxide at 95-105° C. for 1.8-2.2 hours to remove surface adsorbed water and avoid the influence of moisture on the dispersion effect and product performance; vacuum drying can effectively remove the adsorbed water on the surface of the nano-silicon dioxide and prevent it from reacting with the solvent during the dispersion process, thereby affecting the dispersion effect and product performance;

[0029] Step 2, mixing nano silicon dioxide with anhydrous ethanol at a ratio of 1:5-10 (weight to volume ratio), then adding polyacrylamide PAM, and magnetically stirring at a speed of 450-550rpm for 8-12 minutes to preliminarily disperse the nano silicon dioxide in the ethanol; then, ultrasonic treatment is performed for 30-60 minutes at a frequency of 30-40kHz and a power of 180-220W, and the solution temperature is controlled at 25-30°C; the preliminary dispersion can reduce the agglomeration phenomenon and create good conditions for subsequent ultrasonic dispersion; the high-frequency vibration of the ultrasonic wave further breaks the agglomerates of the nano silicon particles to make them evenly dispersed, and at the same time, the temperature is controlled to prevent the performance of the dispersant and the nano silicon dioxide from being affected by excessive temperature, thereby improving the performance and stability of the film;

[0030] Step 3, filtering with a 0.2 μm filter membrane at a pressure of 0.2 MPa to remove large particles that are not dispersed in the solution after ultrasonic dispersion in step 2, to ensure the uniformity and stability of the solution and to prevent large particles from affecting the performance and appearance quality of the film;

[0031] Step 4, adding modified polyvinyl alcohol PVA or polyurethane PU to the solution filtered in step 3, stirring at 60-80°C until completely dissolved. The appropriate temperature helps the resin to dissolve quickly, and controlling the viscosity facilitates the mixing of subsequent additives;

[0032] Step 5, in the solution obtained in step 4, stabilizer sodium carboxymethyl cellulose (CMC), cross-linking agent KH-550, plasticizer (dibutyl phthalate DBP) and the remaining solvent are added in sequence, and high-speed shear stirring is performed at a speed of 1400-1600 rpm for 15-25 minutes to uniformly disperse the additives in the solution, give full play to their respective functions, and improve the performance and stability of the film; then, the 0.2 μm filter membrane is used again to remove the residual impurities in the reaction solution; the secondary filtration can remove the residual impurities in the solution, further improve the purity of the product, and ensure the performance and appearance quality of the film; after filtration, degassing is performed at a vacuum degree of -0.1 MPa for 12-18 minutes to ensure that the residual amount of bubbles is ≤0.1%, so as to avoid defects of the film due to the presence of bubbles during the molding process; vacuum degassing can effectively remove bubbles in the solution, avoid defects of the film due to the presence of bubbles during the molding process, and improve the strength and thermal insulation performance of the film;

[0033] Step 6, hot pressing and molding at 160-180°C and 8-10MPa using a flat vulcanizer, with a holding time of 4-6 minutes, to initially form the film; then, cooling is performed using a gradient cooling method of 80°C → 50°C → room temperature; the hot pressing process can allow the components in the solution to fully fuse and react to form a uniform film, thereby improving the performance and strength of the film; the gradient cooling can prevent the internal stress from causing the film to warp and deform, thereby ensuring its dimensional stability and appearance quality;

[0034] Step 7, placing the cooled film in an oven at 80-100°C for curing for 2.5-3.5 hours, and then polishing it with a chemical polishing liquid with a pH value of 8-9 until the surface roughness Ra ≤ 0.1 μm. The cross-linking curing can enhance the chemical bond connection inside the film, fully cross-link the chemical bonds inside the film, improve the mechanical properties, heat resistance and chemical stability of the film, and enhance the overall performance of the film. Surface polishing can effectively remove tiny defects on the surface of the film, improve its surface smoothness and optical properties, and enhance the aesthetics and use effect of the film.

[0035] Furthermore, the preparation method of the sound insulation layer is as follows: thermoplastic polyurethane elastomer rubber and hollow glass microspheres are mixed in a weight ratio of 100:10-15, and then calendered into a film by an extruder, and then hot-pressed with a film base layer, the hot-pressing temperature is 120-130°C, the pressure is 0.8MPa, and the time is 30-60 seconds;

[0036] Furthermore, the preparation method of the flame retardant layer is: after uniformly mixing water-based acrylic resin ammonium polyphosphate, aluminum hydroxide, acrylic emulsion, and substrate wetting agent TEGO Twin 4100, coating it on the sound insulation layer, and then drying it at 75-85°C, wherein the weight ratio of water-based acrylic resin ammonium polyphosphate, aluminum hydroxide, acrylic emulsion and substrate wetting agent TEGO Twin 4100 is 50-65:15-25:10-20:5-10:1-3.

[0037] The hollow glass beads in the sound insulation layer have low density and high porosity, which can effectively reflect and absorb sound waves and reduce the penetration of sound. This structure enables the sound insulation layer to have good sound insulation effect in a wider frequency range. Thermoplastic polyurethane elastomer rubber has good elasticity and flexibility, which can further absorb and disperse sound wave energy and enhance the sound insulation effect. The addition of thermoplastic polyurethane elastomer rubber makes the sound insulation layer have good flexibility and impact resistance, and can withstand certain external forces without being easily broken. Thermoplastic polyurethane elastomer rubber has good durability and can maintain stable sound insulation performance during long-term use. The low density of hollow glass beads enables the sound insulation layer to achieve lightweight design while maintaining high-efficiency sound insulation performance, which is suitable for application scenarios with strict weight requirements.

[0038] In the flame retardant layer, ammonium polyphosphate is a highly efficient intumescent flame retardant that can decompose to generate phosphoric acid at high temperatures, promote the formation of a carbonized layer on the surface of the substrate, and prevent the transfer of heat and oxygen. Aluminum hydroxide decomposes and absorbs a large amount of heat, reduces the surface temperature of the material, and delays combustion. At the same time, the generated water vapor can dilute the concentration of combustible gases and inhibit the spread of flames. The residual Al2O3 forms a dense insulation layer on the surface of the material to block the transfer of oxygen and heat. Acrylic emulsion can form a uniform coating and improve the adhesion and durability of the flame retardant layer. The substrate wetting agent TEGO Twin 4100 can improve the adhesion between the flame retardant layer and the sound insulation layer, ensure uniform distribution of the coating, and improve the stability and durability of the flame retardant layer.

[0039] The combination of the sound insulation layer and the flame retardant layer makes the composite material not only have excellent sound insulation performance, but also have efficient fire resistance. This multifunctional integrated design enables the material to meet multiple performance requirements in a variety of building scenarios at the same time. The flexibility of the sound insulation layer and the adhesion of the flame retardant layer work together to further improve the overall mechanical properties of the composite material. For example, the elasticity of the thermoplastic polyurethane elastomer rubber can enhance the impact resistance of the flame retardant layer, while the uniform coating of the flame retardant layer can improve the durability of the sound insulation layer. The porous structure of the sound insulation layer can further reduce heat conduction and improve the thermal insulation performance of the material, while the carbonized layer formed by the flame retardant layer at high temperature can further enhance the thermal insulation effect. In emergency situations such as fire, the addition of the sound insulation layer and the flame retardant layer can further enhance the mechanical properties of the film base layer. The carbonized layer formed by the flame retardant layer at high temperature can protect the film base layer and prevent it from rapid decomposition at high temperature. This protective effect not only improves the fire resistance of the material, but also extends the service life of the material. The synergistic effect of the sound insulation layer and the flame retardant layer can optimize the acoustic and thermal properties of the material. The addition of the sound insulation layer and the flame retardant layer makes the film base not only have excellent heat insulation and fireproof performance, but also have good sound insulation effect. This versatility makes the material have a wider application prospect in various application scenarios.

[0040] The present invention has the following beneficial effects:

[0041] The nano silicon-based heat-insulating fireproof glass film provided by the present invention has good heat insulation, fire resistance and high temperature resistance, can effectively isolate the fire source and prevent the spread of fire, and can meet different fire resistance time requirements. Among them, the addition of ingredients such as nano silicon dioxide can effectively reduce heat radiation and heat transfer, so that the glass film can still maintain good heat insulation performance under high temperature environment. By using modified polyvinyl alcohol and other matrix resins, and the reinforcing effect of nano cellulose, the tensile strength and mechanical strength of the film are improved, avoiding problems such as breakage during use. And the film is colorless and transparent with high light transmittance.

[0042] Among them, nano-silicon dioxide has the characteristics of low thermal conductivity, and there is a void structure inside it, which is filled with air, effectively blocking heat transfer. Nano-silicon dioxide has a selective characteristic for the solar spectrum and can effectively shield infrared thermal radiation, thereby reducing heat absorption. The addition of nano-silicon dioxide forms a dense thermal barrier that can reflect or scatter infrared radiation. Combined with the resin matrix, it effectively blocks heat conduction and is suitable for building energy-saving glass. Nano-silicon dioxide strengthens the resin matrix and combines with the cross-linking agent to form a three-dimensional network structure, which improves the tensile strength and impact resistance. The stabilizer prevents material aging and extends the service life. The dispersant makes the nano-material dispersed evenly, reduces light scattering, and maintains high light transmittance. The plasticizer adjusts the flexibility. The components work synergistically to obtain a high-strength, aging-resistant, and light-transmitting fireproof glass film.

[0043] Furthermore, the addition of the sound insulation layer and the flame retardant layer significantly improves the performance of the composite material, not only improving the sound insulation and fire resistance of the material, but also enhancing the mechanical properties and thermal stability of the material. This multifunctional integrated design makes the material have good application prospects in high-performance application fields.

[0044] This film preparation method achieves high performance and process stability control of nano-composite materials through multi-step precise control, solving the defects of uneven dispersion and unstable performance in traditional composite materials. It is particularly suitable for application scenarios with strict requirements on optical, mechanical and thermal insulation properties. DETAILED DESCRIPTION

[0045] The following will be combined with the embodiments of the present application to clearly and completely describe the technical solutions in the embodiments of the present application. Obviously, the described embodiments are only part of the embodiments of the present application, not all of the embodiments. Based on the embodiments in the present application, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of this application.

[0046] The raw materials used in the following examples are all common commercially available products. Nano-silicon dioxide, 15-50nm, Luoyang Tongrun Nanotechnology Co., Ltd.; polyvinyl alcohol, active ingredient content 99%, Inner Mongolia Meiguan Environmental Protection Products Co., Ltd.; polyacrylamide, white granules, Renqiu Hengyu Chemical Co., Ltd.; sodium carboxymethyl cellulose, white or slightly yellow powder, Zibo Daoqin New Materials Co., Ltd.; polyethylene glycol diglycidyl ether, active ingredient content 99%, Wuhan Shuer Biotechnology Co., Ltd.; nanocellulose, active ingredient content 99%, Zibo Daoqin New Materials Co., Ltd.; TEGO Twin 4100, Shanghai Zhenlishi Network Technology Co., Ltd.

[0047] Example 1

[0048] A nano silicon-based heat-insulating fireproof glass film comprises a film base layer, and a sound insulation layer and a flame retardant layer sequentially arranged on the film base layer. The film base layer comprises the following components in parts by weight: 20 parts of nano silicon dioxide, 60 parts of base resin, 2 parts of dispersant, 2 parts of stabilizer, 2 parts of cross-linking agent, 7 parts of plasticizer, and 22 parts of solvent. The base resin is modified polyvinyl alcohol, the dispersant is polyacrylamide, the stabilizer is sodium carboxymethyl cellulose, the cross-linking agent is silane coupling agent KH-550, the plasticizer is dibutyl phthalate, and the solvent is anhydrous ethanol.

[0049] The preparation method of the modified polyvinyl alcohol is as follows:

[0050] Step S1, dissolving polyvinyl alcohol in water, adding polyethylene glycol diglycidyl ether (PEGDE) as a cross-linking agent, reacting at 55°C for 3 hours under a pH of 10-11, dialysis purification, and drying to obtain a cross-linked polyvinyl alcohol resin; the molecular weight of the polyethylene glycol diglycidyl ether (PEGDE) is 400-1000, and the amount added is 10% of the mass of the polyvinyl alcohol; the weight volume ratio of the polyvinyl alcohol to water is 10g:100ml; the alkaline condition is adjusted by adding a sodium hydroxide solution with a concentration of 30%; the dialysis purification uses a dialysis bag with a molecular weight cutoff of 8000-14000 for 60 hours; then, vacuum drying is performed at 55°C for 36 hours;

[0051] Step S2, dispersing the cross-linked polyvinyl alcohol resin obtained in step S1 in a mixed solvent of N, N-dimethylformamide and water, adding maleic acid and a free radical initiator, reacting at 95° C. for 5 hours under nitrogen protection, cooling to room temperature in an ice bath, then dropping the reaction solution into anhydrous ethanol 4 times the volume of the reaction solution for precipitation, stirring to avoid agglomeration during the precipitation process, then centrifuging at 9000 rpm for 12 minutes, washing once with a mixed solution of ethanol and water in a volume ratio of 3:1, washing twice with anhydrous ethanol, and finally drying at 45° C. in a vacuum drying chamber to obtain a grafted modified polyvinyl alcohol resin; the amount of maleic acid added is 14% of the mass of the cross-linked polyvinyl alcohol in step S1; the free radical initiator is potassium persulfate, and the amount added is 2.5% of the mass of maleic acid; the weight volume ratio of the cross-linked polyvinyl alcohol obtained in step 1 to the mixed solvent is: 7g:100ml, and the weight ratio of N, N-dimethylformamide to water in the mixed solvent is 4:1;

[0052] Step S3, nanocellulose composite reinforcement: the nanocellulose and the grafted modified polyvinyl alcohol resin obtained in step S2 are mechanically blended and compounded to obtain the obtained product; the mechanical blending is carried out by a high-speed shear emulsifier at a speed of 10,000 rpm for 30 minutes; the amount of the nanocellulose added is 10% of the mass of the grafted modified polyvinyl alcohol resin in step S2;

[0053] The nanocellulose is first pretreated with a silane coupling agent KH-550, and the specific steps are as follows: disperse the nanocellulose in deionized water, and use an ultrasonic disperser to treat for 30 minutes to obtain a solution 1, wherein the weight volume ratio of the nanocellulose to the deionized water is 10g:100ml; dissolve the silane coupling agent in ethanol, stir evenly, and then add it to the solution 1, and stir and react at 70°C for 2 hours, wherein the weight volume ratio of the silane coupling agent to ethanol is 2g:200ml, and the dosage ratio of the nanocellulose to the silane coupling agent is 10:0.25; after the reaction is completed, centrifuge, wash with ethanol and deionized water for 3 times, and dry the precipitate to constant weight to obtain the pretreated nanocellulose.

[0054] The preparation method of the nano silicon-based heat-insulating fire-proof glass film comprises the following steps:

[0055] Step 1, vacuum drying the nano-silicon dioxide at 100° C. for 2 hours to remove surface adsorbed water and avoid the influence of moisture on the dispersion effect and product performance;

[0056] Step 2, mixing nano-silica with anhydrous ethanol at a ratio of 1:7 (weight to volume ratio), then adding polyacrylamide PAM, and magnetically stirring at a speed of 500 rpm for 10 minutes to preliminarily disperse the nano-silica in the ethanol; then, ultrasonically treating at a frequency of 35 kHz and a power of 200 W for 45 minutes, and controlling the solution temperature at 27°C;

[0057] Step 3, filtering with a 0.2 μm filter membrane at a pressure of 0.2 MPa to remove large particles that are not dispersed in the solution after ultrasonic dispersion in step 2, to ensure the uniformity and stability of the solution and to prevent large particles from affecting the performance and appearance quality of the film;

[0058] Step 4, adding modified polyvinyl alcohol PVA to the solution filtered in step 3, stirring at 70°C until completely dissolved. The appropriate temperature helps the resin to dissolve quickly, and controlling the viscosity facilitates the mixing of subsequent additives;

[0059] Step 5, in the solution obtained in step 4, stabilizer CMC, crosslinker KH-550, plasticizer (dibutyl phthalate DBP) and the remaining solvent are added in sequence, and high-speed shear stirring is performed at a speed of 1500 rpm for 20 minutes; then, the residual impurities in the reaction solution are removed by using a 0.2 μm filter membrane again; after filtering, degassing is performed at a vacuum degree of -0.1 MPa for 15 minutes to ensure that the residual bubble amount is ≤0.1%;

[0060] Step 6, hot pressing and molding at 170°C and 9MPa using a flat vulcanizer for 5 minutes, the film is initially formed, and then cooled by a gradient cooling method of 80°C → 50°C → room temperature;

[0061] Step 7, placing the cooled film in a 90° C. oven for curing for 3 hours; then polishing it with a chemical polishing solution of pH=8-9 until the surface roughness Ra≤0.1 μm, to obtain a film base layer;

[0062] Step 8, mixing thermoplastic polyurethane elastomer rubber and hollow glass microspheres in a weight ratio of 100:12, calendering into a film through an extruder, and then hot-pressing and compounding with the film base layer at a hot-pressing temperature of 125° C., a pressure of 0.8 MPa, and a time of 45 seconds;

[0063] Step 9, after uniformly mixing the water-based acrylic resin ammonium polyphosphate, aluminum hydroxide, acrylic emulsion, and substrate wetting agent TEGOTwin 4100, apply it on the sound insulation layer, and then dry it at 80°C. The weight ratio of the water-based acrylic resin ammonium polyphosphate, aluminum hydroxide, acrylic emulsion, and substrate wetting agent TEGO Twin 4100 is 58:20:10-20:5:2.

[0064] Example 2

[0065] A nano silicon-based heat-insulating fireproof glass film comprises a film base layer, and a sound insulation layer and a flame retardant layer sequentially arranged on the film base layer. The film base layer comprises the following components in parts by weight: 10 parts of nano silicon dioxide, 70 parts of base resin, 3 parts of dispersant, 1 part of stabilizer, 3 parts of cross-linking agent, 10 parts of plasticizer, and 32 parts of solvent. The base resin is modified polyvinyl alcohol, the dispersant is polyacrylamide, the stabilizer is sodium carboxymethyl cellulose, the cross-linking agent is silane coupling agent KH-550, the plasticizer is dibutyl phthalate, and the solvent is anhydrous ethanol.

[0066] The preparation method of the modified polyvinyl alcohol is as follows:

[0067] Step S1, dissolving polyvinyl alcohol in water, adding polyethylene glycol diglycidyl ether (PEGDE) as a cross-linking agent, reacting at 50°C for 4 hours at a pH of 10-11, dialysis purification, and drying to obtain a cross-linked polyvinyl alcohol resin; the molecular weight of the polyethylene glycol diglycidyl ether (PEGDE) is 400-1000, and the amount added is 5% of the mass of the polyvinyl alcohol; the weight volume ratio of the polyvinyl alcohol to water is 8g:100ml; the alkaline condition is adjusted by adding a sodium hydroxide solution with a concentration of 30%; the dialysis purification uses a dialysis bag with a molecular weight cutoff of 8000-14000 for 72 hours; then, vacuum drying is performed at 60°C for 24 hours;

[0068] Step S2, dispersing the cross-linked polyvinyl alcohol resin obtained in step S1 in a mixed solvent of N,N-dimethylformamide and water, adding maleic acid and a free radical initiator, reacting at 90° C. for 6 hours under nitrogen protection, cooling to room temperature in an ice bath, then dropping the reaction solution into anhydrous ethanol 5 times the volume of the reaction solution for precipitation, stirring to avoid agglomeration during the precipitation process, then centrifuging at 8000 rpm for 15 minutes, washing once with a mixed solution with a volume ratio of ethanol to water of 3:1, washing twice with anhydrous ethanol, and then drying at 40° C. in a vacuum drying chamber to obtain a grafted modified polyvinyl alcohol resin; the amount of maleic acid added is 8% of the mass of the cross-linked polyvinyl alcohol in step S1; the free radical initiator is potassium persulfate, and the amount added is 2% of the mass of maleic acid; the weight volume ratio of the cross-linked polyvinyl alcohol obtained in step 1 to the mixed solvent is: 5g:100ml, and the weight ratio of N,N-dimethylformamide to water in the mixed solvent is 4:0.8;

[0069] Step S3, nanocellulose composite reinforcement: the nanocellulose and the grafted modified polyvinyl alcohol resin obtained in step S2 are mechanically blended and compounded to obtain the obtained product; the mechanical blending is carried out using a high-speed shear emulsifier at a speed of 8000 rpm for 40 minutes; the amount of the nanocellulose added is 15% of the mass of the grafted modified polyvinyl alcohol resin in step S2.

[0070] The nanocellulose is first pretreated with a silane coupling agent KH-550, and the specific steps are as follows: disperse the nanocellulose in deionized water, use an ultrasonic disperser to treat for 25 minutes, and obtain solution 1, wherein the weight volume ratio of nanocellulose to deionized water is 10g:90ml; dissolve the silane coupling agent in ethanol, stir evenly, and then add it to solution 1, and stir and react at 60°C for 2.5 hours, wherein the weight volume ratio of the silane coupling agent to ethanol is 2g:220ml, and the dosage ratio of nanocellulose to the silane coupling agent is 10:0.2; after the reaction is completed, centrifuge, wash with ethanol and deionized water for 3 times, and dry the precipitate to constant weight to obtain pretreated nanocellulose.

[0071] The preparation method of the nano silicon-based heat-insulating fire-proof glass film comprises the following steps:

[0072] Step 1, vacuum drying the nano-silicon dioxide at 95° C. for 2.2 hours to remove surface adsorbed water and avoid the influence of moisture on the dispersion effect and product performance;

[0073] Step 2, mixing nano-silica with anhydrous ethanol at a ratio of 1:10 (weight to volume ratio), then adding polyacrylamide PAM, and magnetically stirring at a speed of 450 rpm for 12 minutes to preliminarily disperse the nano-silica in the ethanol; then, ultrasonically treating at a frequency of 30 kHz and a power of 180 W for 60 minutes, and controlling the solution temperature at 30°C;

[0074] Step 3, filtering with a 0.2 μm filter membrane at a pressure of 0.2 MPa to remove large particles that are not dispersed in the solution after ultrasonic dispersion in step 2, to ensure the uniformity and stability of the solution and to prevent large particles from affecting the performance and appearance quality of the film;

[0075] Step 4, adding polyurethane PU to the solution filtered in step 3, stirring at 60°C until completely dissolved. The appropriate temperature helps the resin to dissolve quickly, and controlling the viscosity facilitates the mixing of subsequent additives;

[0076] Step 5, in the solution obtained in step 4, stabilizer CMC, crosslinker KH-550, plasticizer (dibutyl phthalate DBP) and the remaining solvent are added in sequence, and high-speed shear stirring is performed at a speed of 1400 rpm for 25 minutes; then, the residual impurities in the reaction solution are removed again using a 0.2 μm filter membrane; after filtering, degassing is performed at a vacuum degree of -0.1 MPa for 12 minutes to ensure that the residual bubble amount is ≤0.1%;

[0077] Step 6, hot pressing and molding at 180°C and 10MPa using a flat vulcanizer for 4 minutes, the film is initially formed, and then cooled by a gradient cooling method of 80°C → 50°C → room temperature;

[0078] Step 7, placing the cooled film in an oven at 80° C. for curing for 3.5 hours; then polishing it with a chemical polishing liquid with a pH value of 8-9 until the surface roughness Ra ≤ 0.1 μm, to obtain a film base layer;

[0079] Step 8, mixing thermoplastic polyurethane elastomer rubber and hollow glass microspheres in a weight ratio of 100:15, calendering into a film through an extruder, and then hot-pressing and compounding with the film base layer at a hot-pressing temperature of 120° C., a pressure of 0.8 MPa, and a time of 60 seconds;

[0080] Step 9, after uniformly mixing the water-based acrylic resin ammonium polyphosphate, aluminum hydroxide, acrylic emulsion, and substrate wetting agent TEGOTwin 4100, apply it on the sound insulation layer, and then dry it at 75°C. The weight ratio of the water-based acrylic resin ammonium polyphosphate, aluminum hydroxide, acrylic emulsion, and substrate wetting agent TEGO Twin 4100 is 65:15:20:10:3.

[0081] Example 3

[0082] A nano silicon-based heat-insulating fireproof glass film comprises a film base layer, and a sound insulation layer and a flame retardant layer sequentially arranged on the film base layer. The film base layer comprises the following components in parts by weight: 30 parts of nano silicon dioxide, 50 parts of base resin, 1 part of dispersant, 3 parts of stabilizer, 1 part of cross-linking agent, 5 parts of plasticizer, and 10 parts of solvent. The base resin is modified polyvinyl alcohol, the dispersant is polyacrylamide, the stabilizer is sodium carboxymethyl cellulose, the cross-linking agent is silane coupling agent KH-550, the plasticizer is dibutyl phthalate, and the solvent is anhydrous ethanol.

[0083] The preparation method of the modified polyvinyl alcohol is as follows:

[0084] Step S1, dissolving polyvinyl alcohol in water, adding polyethylene glycol diglycidyl ether (PEGDE) as a cross-linking agent, reacting at 60°C for 2 hours at a pH of 10-11, dialysis purification, and drying to obtain a cross-linked polyvinyl alcohol resin; the molecular weight of the polyethylene glycol diglycidyl ether (PEGDE) is 400-1000, and the amount added is 15% of the mass of the polyvinyl alcohol; the weight volume ratio of the polyvinyl alcohol to water is 12g:100ml; the alkaline condition is adjusted by adding a sodium hydroxide solution with a concentration of 30%; the dialysis purification uses a dialysis bag with a molecular weight cutoff of 8000-14000 for 48 hours; then, vacuum drying is performed at 50°C for 48 hours;

[0085] Step S2, dispersing the cross-linked polyvinyl alcohol resin obtained in step S1 in a mixed solvent of N,N-dimethylformamide and water, adding maleic acid and a free radical initiator, reacting at 100°C for 4 hours under nitrogen protection, cooling to room temperature in an ice bath, then dropping the reaction solution into anhydrous ethanol 3 times the volume of the reaction solution for precipitation, stirring to avoid agglomeration during the precipitation process, then centrifuging at 10000rpm for 10 minutes, washing once with a mixed solution with a volume ratio of ethanol to water of 3:1, washing twice with anhydrous ethanol, and then drying at 45°C in a vacuum drying chamber to obtain a grafted modified polyvinyl alcohol resin; the amount of maleic acid added is 20% of the mass of the cross-linked polyvinyl alcohol in step S1; the free radical initiator is potassium persulfate, and the amount added is 3% of the mass of maleic acid; the weight volume ratio of the cross-linked polyvinyl alcohol obtained in step 1 to the mixed solvent is: 10g:100ml, and the weight ratio of N,N-dimethylformamide to water in the mixed solvent is 4:1.2;

[0086] Step S3, nanocellulose composite reinforcement: the nanocellulose and the grafted modified polyvinyl alcohol resin obtained in step S2 are mechanically blended and compounded to obtain the obtained product; the mechanical blending is carried out using a high-speed shear emulsifier at a speed of 12000 rpm for 20 minutes; the amount of the nanocellulose added is 5% of the mass of the grafted modified polyvinyl alcohol resin in step S2.

[0087] The nanocellulose is first pretreated with a silane coupling agent KH-550, and the specific steps are as follows: disperse the nanocellulose in deionized water, use an ultrasonic disperser to treat for 35 minutes, and obtain solution 1, wherein the weight volume ratio of nanocellulose to deionized water is 10g:110ml; dissolve the silane coupling agent in ethanol, stir evenly, and then add it to solution 1, and stir and react at 80°C for 1.5 hours, wherein the weight volume ratio of the silane coupling agent to ethanol is 2g:180ml, and the dosage ratio of nanocellulose to the silane coupling agent is 10:0.15; after the reaction is completed, centrifuge, wash with ethanol and deionized water for 3 times, and dry the precipitate to constant weight to obtain pretreated nanocellulose.

[0088] The preparation method of the nano silicon-based heat-insulating fire-proof glass film comprises the following steps:

[0089] Step 1, vacuum drying the nano-silicon dioxide at 105° C. for 1.8 hours to remove surface adsorbed water and avoid the influence of moisture on the dispersion effect and product performance;

[0090] Step 2, mixing nano-silica with anhydrous ethanol at a ratio of 1:5 (weight to volume ratio), then adding polyacrylamide PAM, and magnetically stirring at a speed of 550 rpm for 8 minutes to preliminarily disperse the nano-silica in the ethanol; then, ultrasonically treating at a frequency of 40 kHz and a power of 220 W for 30 minutes, and controlling the solution temperature at 25°C;

[0091] Step 3, filtering with a 0.2 μm filter membrane at a pressure of 0.2 MPa to remove large particles that are not dispersed in the solution after ultrasonic dispersion in step 2, to ensure the uniformity and stability of the solution and to prevent large particles from affecting the performance and appearance quality of the film;

[0092] Step 4, adding modified polyvinyl alcohol PVA to the solution filtered in step 3, stirring at 80°C until completely dissolved. The appropriate temperature helps the resin to dissolve quickly, and controlling the viscosity facilitates the mixing of subsequent additives;

[0093] Step 5, in the solution obtained in step 4, stabilizer CMC, crosslinker KH-550, plasticizer (dibutyl phthalate DBP) and the remaining solvent are added in sequence, and high-speed shear stirring is performed at a speed of 1600 rpm for 15 minutes; then, the residual impurities in the reaction solution are removed by using a 0.2 μm filter membrane again; after filtering, degassing is performed at a vacuum degree of -0.1 MPa for 18 minutes to ensure that the residual bubble amount is ≤0.1%;

[0094] Step 6, hot pressing and molding at 160°C and 8MPa using a flat vulcanizer for 6 minutes, the film is initially formed, and then cooled by a gradient cooling method of 80°C → 50°C → room temperature;

[0095] Step 7, placing the cooled film in an oven at 100° C. for curing for 2.5 hours; then polishing with a chemical polishing solution of pH=8-9 until the surface roughness Ra≤0.1 μm, to obtain a film base layer;

[0096] Step 8, mixing thermoplastic polyurethane elastomer rubber and hollow glass microspheres in a weight ratio of 100:10, calendering into a film through an extruder, and then hot-pressing and compounding with the film base layer at a hot-pressing temperature of 130° C., a pressure of 0.8 MPa, and a time of 30 seconds;

[0097] Step 9, after evenly mixing the water-based acrylic resin ammonium polyphosphate, aluminum hydroxide, acrylic emulsion, and substrate wetting agent TEGOTwin 4100, apply it on the sound insulation layer, and then dry it at 85° C., wherein the weight ratio of the water-based acrylic resin ammonium polyphosphate, aluminum hydroxide, acrylic emulsion, and substrate wetting agent TEGO Twin 4100 is 50:25:10:8:1.

[0098] Example 4

[0099] A nano-silicon-based heat-insulating fireproof glass film, wherein the base resin is polyurethane, and the rest is the same as in Example 1.

[0100] Comparative Example 1

[0101] A nano-silicon-based heat-insulating fireproof glass film, wherein the base resin is unmodified polyvinyl alcohol, and the rest is the same as in Example 1.

[0102] Performance testing and results

[0103] The films obtained in the above-mentioned Examples 1-4 and the comparative example were compounded with two glass substrates to form a fireproof glass having a structure of two glass sheets with a film sandwiched between them, and then the performance of the obtained fireproof glass was tested.

[0104] 1. Visible light transmittance, thermal conductivity

[0105] The visible light transmittance was tested at a wavelength of 550 nm using a spectrophotometer, and the thermal conductivity was tested using LFA 467 NanoFlash.

[0106] 2. According to GB15763.1-2009 "Safety Glass for Buildings Part 1: Fireproof Glass", the fire resistance and impact resistance of the fireproof glasses prepared in Examples 1-4 and Comparative Example 1 were tested. The test results are shown in Table 1.

[0107] Table 1. Performance test results

[0108]

[0109] As can be seen from Table 1, the light transmittance, fire resistance, thermal insulation and impact resistance of the laminated glass obtained in Examples 1-4 of the present invention are all better than those of Comparative Example 1. Its high visible light transmittance can improve the lighting effect of the glass and meet the lighting needs of the building. The fire resistance time is ≥1.2 hours, which far exceeds the requirement of ≥1 hour for Class A fireproof glass of the national standard, and significantly improves the fire safety. The long fire resistance limit can enable the fireproof glass to provide longer protection in a fire, effectively protecting the safety of people and property. The low thermal conductivity is ≤0.1W / m·K, which effectively enhances the thermal insulation performance and reduces energy consumption. Low thermal conductivity can enable the fireproof glass to provide better thermal insulation effect while ensuring the fireproof performance, thereby reducing the energy consumption of the building. It has good impact resistance, no splashing when broken, and improved safety performance.

[0110] It should be noted that, in this article, relational terms such as first and second, etc. are only used to distinguish one entity or operation from another entity or operation, and do not necessarily require or imply any such actual relationship or order between these entities or operations. Moreover, the terms "include", "comprise" or any other variants thereof are intended to cover non-exclusive inclusion, so that a process, method, article or device including a series of elements includes not only those elements, but also other elements not explicitly listed, or also includes elements inherent to such process, method, article or device.

[0111] Although the embodiments of the present application have been shown and described, it will be appreciated by those skilled in the art that various changes, modifications, substitutions and variations may be made to the embodiments without departing from the principles and spirit of the present application, and that the scope of the present application is defined by the appended claims and their equivalents.

Claims

1. A nano-silicon-based heat-insulating fire-proof glass film, characterized in that: The invention comprises a film base layer, and a sound insulation layer and a flame retardant layer sequentially arranged on the film base layer. The film base layer comprises the following components by weight: 10-30 parts of nano silicon dioxide, 50-70 parts of base resin, 1-3 parts of dispersant, 1-3 parts of stabilizer, 1-3 parts of cross-linking agent, 5-10 parts of plasticizer, and 10-32 parts of solvent. The base resin is modified polyvinyl alcohol or polyurethane. The preparation method of the modified polyvinyl alcohol is as follows: Step S1, dissolving polyvinyl alcohol in water, adding polyethylene glycol diglycidyl ether as a cross-linking agent, reacting at 50-60° C. under alkaline conditions for 2-4 hours, and obtaining a cross-linked polyvinyl alcohol resin after purification by dialysis and drying; Step S2, dispersing the cross-linked polyvinyl alcohol resin obtained in step S1 in a mixed solvent of N,N-dimethylformamide and water, adding maleic acid and a free radical initiator, reacting at 90-100° C. for 4-6 hours under nitrogen protection, then precipitating, centrifuging, and drying to obtain a graft-modified polyvinyl alcohol resin; Step S3, compounding the nanocellulose and the grafted modified polyvinyl alcohol resin obtained in step S2 by mechanical blending.

2. The nano silicon-based heat-insulating fire-proof glass film according to claim 1, characterized in that: In step S1, the amount of polyethylene glycol diglycidyl ether added is 5-15% of the mass of polyvinyl alcohol; the weight volume ratio of polyvinyl alcohol to water is 8-12g:100ml.

3. The nano silicon-based heat-insulating fire-proof glass film according to claim 1, characterized in that: In step S1, the alkaline condition has a pH of 10-11, which is adjusted by sodium hydroxide; the dialysis purification uses a dialysis bag with a molecular weight cutoff of 8000-14000 and lasts for 48-72 hours.

4. The nano silicon-based heat-insulating fire-proof glass film according to claim 1, characterized in that: In step S2, the amount of maleic acid added is 8-20% of the mass of the cross-linked polyvinyl alcohol in step S1; the free radical initiator is potassium persulfate, and the amount added is 2-3% of the mass of the maleic acid; the weight volume ratio of the cross-linked polyvinyl alcohol obtained in step 1 to the mixed solvent is: 5-10g:100ml, and the weight ratio of N,N-dimethylformamide to water in the mixed solvent is 4:0.8-1.

2.

5. The nano silicon-based heat-insulating fire-proof glass film according to claim 1, characterized in that: In step S3, the amount of nanocellulose added is 5-15% of the mass of the graft-modified polyvinyl alcohol resin in step S2.

6. The nano silicon-based heat-insulating fire-proof glass film according to claim 1, characterized in that: In the step S3, the nanocellulose is first pretreated with a silane coupling agent KH-550.

7. The nano silicon-based heat-insulating fire-proof glass film according to claim 1, characterized in that: The specific steps of pretreating the nanocellulose with a silane coupling agent are as follows: dispersing the nanocellulose in deionized water, treating with an ultrasonic disperser for 25-35 minutes to obtain a solution 1; dissolving the silane coupling agent in ethanol, stirring evenly, then adding the solution to the solution 1, stirring and reacting at 60-80° C. for 1.5-2.5 hours, and after the reaction is completed, centrifuging, washing with ethanol and deionized water for 3 times, and drying the precipitate to obtain the pretreated nanocellulose; wherein the weight-to-volume ratio of the nanocellulose to the deionized water is 10 g:90-110 ml, the weight-to-volume ratio of the silane coupling agent to the ethanol is 2 g:180-220 ml, and the dosage ratio of the nanocellulose to the silane coupling agent is 10:0.15-0.

25.

8. The nano-silicon-based heat-insulating fire-proof glass film according to claim 1, characterized in that: The dispersant is polyacrylamide, the stabilizer is sodium carboxymethyl cellulose, the cross-linking agent is a silane coupling agent, the plasticizer is dibutyl phthalate, and the solvent is anhydrous ethanol.

9. The nano silicon-based heat-insulating fire-proof glass film according to claim 1, characterized in that: The sound insulation layer is mainly made of thermoplastic polyurethane elastomer rubber and hollow glass microbeads, and the flame retardant layer is mainly made of water-based acrylic resin and ammonium polyphosphate.

10. The method for preparing the nano-silicon-based heat-insulating fire-proof glass film according to any one of claims 1 to 8, characterized in that: The preparation method of the film base layer comprises the following steps: nano silicon dioxide pretreatment→ultrasonic dispersion→resin dissolution→mixing→filtration and degassing→hot pressing and molding, gradient cooling→crosslinking and curing, and polishing.

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