Fireproof layer structure and preparation method thereof, fireproof layer material and outdoor thermochromic insulation fireproof glass

Abstract

The present invention relates to a fireproof layer structure, its preparation method, fireproof layer material, and outdoor thermochromic insulating fireproof glass. The fireproof layer material, in parts by weight, is composed of the following raw materials: 50-400 parts of core-shell silica particles, 55-250 parts of deionized water, 0.5-20 parts of an inorganic color-changing agent, 20-60 parts of a composite functional additive, and 15-200 parts of 85% pure potassium hydroxide. The fireproof layer material is prepared using an in-situ constant temperature reaction technique and has a "lamellar" corrugated structure. Its pre-reaction solution has a low viscosity, enabling the infusion of thinner and larger thermochromic insulating composite fireproof glass for outdoor use. The thermochromic response temperature range is controllably adjustable from 40°C to 90°C, while the low-temperature operating temperature can reach -65°C ± 1°C. It also offers UV irradiation resistance exceeding 3,000 hours.

Description

Technical Field

[0001] The present invention relates to the field of safety glass, and in particular to a fireproof layer structure having a "sheet"-like pleated structure, a preparation method thereof, a fireproof layer material, and thermochromic insulating fireproof glass for outdoor use. Background Art

[0002] With the accelerating pace of urbanization, building windows are becoming larger and larger. Elegant, beautiful, and functional glass components are gaining popularity among designers both domestically and internationally, leading to the rapid development of various safety and specialty glass types within the architectural glass industry. Architectural glass has evolved from a simple lighting and decorative material to encompass multiple functions, including light control, room temperature regulation, noise reduction, and improved living environments.

[0003] In addition to sharing some of the properties of ordinary glass, fireproof glass also has the ability to control the spread of fire, isolate smoke, and insulate heat. This provides valuable time for effective rescue in the event of a fire, minimizing the loss of life, property, and buildings. Fireproof glass protects escapees and rescuers from thermal radiation and minimizes the destructive power of fire. Due to the recent frequent fires in some well-known large buildings at home and abroad, people have begun to pay attention to the research, development, production, and use of composite fireproof glass. However, existing composite fireproof glass does not have intelligent color-changing functions. Therefore, the development of thermochromic fireproof materials has achieved the goal of autonomously adjusting the visible light transmittance of the window according to the ambient temperature without consuming external energy. It also has fireproof and heat-insulating properties, which have far-reaching significance for building safety and energy conservation and emission reduction.

[0004] Currently, thermochromic materials (liquid crystals, hydrogels, VO2) cannot respond cyclically in the strong alkaline environment of K2O·nSiO2 and require the use of spacer layers to ensure isolation from each other, which increases the load-bearing capacity of the frame and building and reduces the visible light transmittance of the window. Domestic work on special fire-resistant layer materials for composite fire-resistant glass is at the basic research stage. The existing composite fireproof glass has poor low-temperature performance and requires a large amount of anti-condensation agent. At the same time, most products will freeze and turn white under low temperature conditions, and cannot meet the long-term use requirements for outdoor windows and curtain walls in cold northern regions; the existing composite fireproof glass also has poor ultraviolet radiation resistance, and PVB film needs to be added to the outer glass to reduce the damage of ultraviolet radiation to the fireproof layer material; the main component of the fireproof layer material of the existing composite fireproof glass, water glass, is limited by its own viscosity, leveling and other factors, resulting in the formation of thickness differences in the fireproof layer material during the preparation process, resulting in an uneven surface of the fireproof layer; at the same time, the fireproof layer of the existing composite fireproof glass itself is prone to bubbles, which easily leads to a large number of microbubbles in the interlayer. The presence of microbubbles reduces the hardness and actual fireproof effect of the fireproof layer, and will cause the apparent quality of the composite fireproof glass, seriously affecting the use effect and service life of the composite fireproof glass. Summary of the Invention

[0005] The main purpose of the present invention is to provide a fireproof layer structure and its preparation method, a fireproof layer material and thermochromic insulating fireproof glass for outdoor use, which overcomes the disadvantages of the fireproof layer material in the prior art that it cannot be thermochromic and cannot be used outdoors, and avoids the shortcomings of the fireproof layer such as yellowing, glue flow, bubbling, and poor apparent quality.

[0006] The purpose of the present invention and the solution to the technical problem are achieved by adopting the following technical solutions.

[0007] The heat-insulating fireproof glass proposed in the present invention is formed by laminating at least two sheets of glass, with an interlayer provided between the two adjacent sheets of glass. At least one of the interlayers is a fireproof layer made of a thermochromic fireproof layer material. The fireproof layer is a fireproof layer structure having a "sheet"-like pleated structure, and the color change temperature response range of the fireproof layer structure is 50°C to 80°C. The fireproof layer structure is manufactured by the following steps:

[0008] Step 1) preparing a pre-reaction liquid of a fireproof layer material;

[0009] Step 2) The prepared fireproof layer material pre-reaction liquid with a solid content of SiO2 ≥ 55wt% and a viscosity of less than 200mPa·s is poured layer by layer into the composite fireproof glass cavity. After sealing the pouring port, the glass is placed horizontally at room temperature for 2 hours, and then placed in a 60°C oven for constant temperature reaction for 10 hours until the visible light transmittance of the glass no longer changes, thereby obtaining a fireproof layer structure with a "lamellar" pleated structure.

[0010] The purpose of the present invention and the solution to its technical problems can be further achieved by adopting the following technical measures.

[0011] Preferably, the raw materials of the aforementioned fireproof layer material are composed of the following substances, calculated by weight: 100 to 250 parts of core-shell structured silica particles, 150 to 200 parts of deionized water, 2 to 15 parts of inorganic induced color change agent, 25 to 40 parts of composite functional additives and 50 to 150 parts of potassium hydroxide with a purity of 85%.

[0012] Preferably, in the aforementioned fireproof layer material, the particle sizes of the core-shell structured silica particles are 200nm-250nm, 1250nm-1400nm, and 8000nm-8500nm, respectively.

[0013] Preferably, in the aforementioned fireproof layer material, the inorganic induced color change agent is at least one of ammonium bicarbonate, ammonium carbonate, ammonium nitrate, ammonium phosphate, ammonium sulfate, and ammonium bisulfate; and the composite functional additive is at least two of ethylene glycol, glycerol, and pentaerythritol.

[0014] The purpose of the present invention and the solution to the technical problem are also achieved by adopting the following technical solutions.

[0015] The present invention provides a K2O·nSiO2-based thermochromic fireproof layer material having a "lamellar" corrugated structure and a preparation method thereof, comprising:

[0016] The composite functional additive, core-shell structured silica aggregates with particle sizes of 150 nm to 300 nm, 1200 nm to 1500 nm, and 7500 nm to 9000 nm, and deionized water are mixed at a weight ratio of 5 to 10:40 to 320:8 to 64:2 to 16:55 to 250 at a high stirring speed of 500 to 3500 rpm and a high stirring dispersion time of 20 min to 40 min to obtain a first mixed solution;

[0017] Using ball milling dispersion technology, 5 to 10 parts by weight of the composite functional additive and 100 to 650 parts by weight of the first mixed solution are added to a ball mill jar in the proportions of 55%, 30%, and 15% by weight, respectively. The ball milling speed is 60 to 150 rpm, and the ball milling time is 10 to 20 minutes per time to obtain a graded silica solution.

[0018] By means of semi-continuous blending technology, 0.5 to 20 parts by weight of an inorganic induced color change agent and 5 to 30 parts by weight of a composite functional additive are sequentially added to a silica graded solution at room temperature (20°C to 25°C) for 20 to 60 minutes to obtain a base solution of a fireproof layer material;

[0019] To 100-700 parts by weight of the fireproof layer material base solution, 5-10 parts by weight of a composite functional additive and 15-200 parts by weight of 85% pure potassium hydroxide were added in sequence, vacuumed at low temperature for 30 minutes, and stirred evenly to obtain a fireproof layer material pre-reaction liquid:

[0020] With the help of a peristaltic pump, a K2O·nSiO2-based thermochromic pre-reaction liquid with high solid content (SiO2≥55wt%,%) and low viscosity (less than 200mPa·s) was poured layer by layer into the cavity of the composite fire-proof glass. After sealing the pouring port, the glass was placed horizontally at room temperature for 2 hours, and then placed in a 60°C oven for constant temperature reaction for 10 hours until the visible light transmittance of the glass no longer changed, thereby obtaining a K2O·nSiO2-based thermochromic fire-proof layer material with a "lamellar" pleated structure.

[0021] The purpose of the present invention and the solution to its technical problems can be further achieved by adopting the following technical measures.

[0022] Preferably, in the aforementioned outdoor insulating thermochromic fireproof glass, the thickness of the fireproof layer is 1.5-5.0 mm.

[0023] By means of the above technical solution, the thermochromic fireproof layer material, preparation method thereof, and fireproof glass provided by the present invention have at least the following advantages:

[0024] 1. Doping K2O·nSiO2-based fireproof materials with inorganic induced color-changing agents can give K2O·nSiO2 reversible thermochromic properties. With the help of high-stir dispersion technology, the grading effect of nano-silica agglomerates is further optimized, and the viscosity of the system is greatly reduced: the silica solution after high-stir dispersion has a lower viscosity than silica solutions prepared by other technologies under the premise of the same solid content. At the same time, the specific wide-distributed silica agglomerates make the pre-reaction solution of the fireproof layer material have shear-thinning properties, which can be poured into thinner glass cavities faster.

[0025] 2. The fireproof layer material of the present invention adopts core-shell structured silica particles as the main raw material. The core-shell structured silica particles are narrowly distributed particles of different particle sizes. The core layer material is a size-controllable silica particle agglomerate, and the shell layer material is a copolymer of poly(butyl acrylate-styrene). The shell layer thickness is less than 10nm. After the pre-reaction liquid of the fireproof layer material containing the raw materials comes into contact with the glass, it will corrode the glass surface to form a diffusion layer of a certain thickness, thereby improving the adhesion between the fireproof adhesive layer and the glass; when the glass is heated and cracks are generated, the cracks will not expand, thereby not causing the entire piece of glass to shatter, greatly improving the strength of the fireproof glass.

[0026] 3. By introducing special processes such as in-situ constant temperature reaction during the preparation of thermochromic fireproof layer materials, a synergistic effect is generated between the various components of the fireproof layer materials, eliminating bubbles in the composite fireproof glass interlayer, and preparing high-performance, microbubble-free thermochromic composite fireproof glass with a transmittance of 75-88%, a fireproof time of up to about 300 minutes, an ultraviolet radiation resistance time of more than 3000 hours, a thermochromic response temperature between 40°C and 90°C, and the ability to be used in low temperature environments (-65°C) and suitable for outdoor environments.

[0027] 4. The fireproof layer material of the present invention has the characteristics of thermochromism, low temperature resistance and ultraviolet radiation resistance because the inorganic induced color change agent hydrolyzes to generate NH4 +It can combine with the silanol groups in K2O·nSiO2-based fireproof materials to form a reversible reaction, thereby achieving thermochromic behavior; the specially designed ball milling process of core-shell structured silica particles optimizes the grading effect of the system, reduces the viscosity of the reaction system, and ensures that the solid content of silica is further increased (can exceed 55%). Correspondingly, the free water in the fireproof layer material is reduced; the "lamellar" pleated structure increases the strength of the fireproof layer material and its ability to resist ultraviolet radiation; the free water in the fireproof layer material is firmly locked by the alcohol substances in the composite functional additives, preventing the free water from forming large-sized, continuous ice crystal phases in low-temperature environments, ensuring the transparency of the composite fireproof glass under extremely cold conditions, thereby improving the low-temperature resistance of the fireproof layer material.

[0028] The above description is only an overview of the technical solution of the present invention. In order to more clearly understand the technical means of the present invention and implement it according to the contents of the specification, the following is a detailed description of the preferred embodiments of the present invention with reference to the accompanying drawings. BRIEF DESCRIPTION OF THE DRAWINGS

[0029] Figure 1 This is a schematic structural diagram of an outdoor heat-insulating thermochromic fire-resistant glass according to an embodiment;

[0030] Figure 2 This is a schematic structural diagram of outdoor heat-insulating thermochromic fire-resistant glass according to another embodiment;

[0031] Figure 3 The thermochromic response of the K2O·nSiO2-based thermochromic composite fire-resistant glass in different seasons according to an embodiment;

[0032] Figure 4 is a graph showing the relationship between the viscosity of the dispersion of silica particles and the shear rate;

[0033] Figure 5 is a particle size distribution diagram of a dispersion of silicon dioxide particles;

[0034] Figure 6 The thermochromic process of the K2O·nSiO2-based thermochromic fireproofing layer material and the electron microscope photograph of the K2O·nSiO2-based thermochromic fireproofing layer material with a "lamellar" wrinkled structure;

[0035] Figure 7 FTIR spectra of K2O·nSiO2 thermochromic fireproof material (K4) and control sample (K3). DETAILED DESCRIPTION

[0036] The outdoor insulating thermochromic fireproof glass of the present invention is formed by laminating at least two sheets of glass, with an interlayer between the adjacent sheets of glass. At least one of the interlayers is a fireproof layer made of a thermochromic fireproof layer material. The thermochromic fireproof layer material is composed, by parts by weight, of the following materials:

[0037] 50 to 400 parts of core-shell structured silica particles, 55 to 250 parts of deionized water, 0.5 to 20 parts of an inorganic induced color-changing agent, 20 to 60 parts of a composite functional additive, and 15 to 200 parts of potassium hydroxide with a purity of 85%. The thermochromic fireproof layer material is prepared using in-situ constant temperature reaction technology, and the modulus of the fireproof material is between 3.8 and 5.2.

[0038] As a preferred embodiment, the fireproof layer material is composed of the following raw materials, calculated in parts by weight: 100 to 250 parts of core-shell structured silica particles, 150 to 200 parts of deionized water, 2 to 15 parts of an inorganic induced color-changing agent, 25 to 40 parts of a composite functional additive, and 50 to 150 parts of potassium hydroxide with a purity of 85%.

[0039] As a preferred embodiment, the particle sizes of the core-shell structured silica particles are 200nm-250nm, 1250nm-1400nm, and 8000nm-8500nm, respectively.

[0040] The present invention uses core-shell silica particles as the primary raw material for the fireproofing layer. The shell material of the core-shell silica particles is poly(butyl acrylate-styrene) copolymer, and the shell thickness is less than 10 nm. The core-shell silica particles are nanoparticles with a narrow distribution of different particle sizes. The present invention has low viscosity and a low reaction rate at room temperature (20°C), enabling the infusion of thinner and larger outdoor thermally insulating composite fireproof glass. Furthermore, the low-temperature operating temperature can reach -65°C ± 1°C and the UV radiation resistance lasts for over 3,000 hours.

[0041] The reason why the K2O·nSiO2-based heat-insulating composite fire-resistant glass has the properties of thermochromism, low temperature resistance and ultraviolet radiation resistance is:

[0042] 1. NH4 generated by hydrolysis of inorganic induced color change agent + It can combine with the silanol groups in K2O·nSiO2-based fireproof materials to form a reversible reaction, thereby achieving thermochromic behavior, such as Figure 3 As shown;

[0043] 2. The solid content of the solution system of silica agglomerates is high (can exceed 55%), and accordingly, the free water in the fireproof layer material is reduced;

[0044] 3. "Layered" fold structure, such as Figure 6 As shown, the strength of the fireproof layer material and the ability to resist ultraviolet radiation are increased;

[0045] 4. The free water in the fireproof layer material is firmly locked by the alcohol substances in the composite functional additives, preventing the free water from forming large-sized, continuous ice crystal phases in low-temperature environments, ensuring the transparency of the composite fireproof glass under extremely cold conditions, thereby improving the low-temperature resistance of the fireproof layer material.

[0046] The core-shell structured silicon dioxide particles of the invention exist in the form of a dispersion liquid, and the mass concentration of the dispersion liquid is 50%-60%.

[0047] As a preferred embodiment, the inorganic color-changing agent is at least one of ammonium bicarbonate, ammonium carbonate, ammonium nitrate, ammonium phosphate, ammonium sulfate, and ammonium bisulfate.

[0048] As a preferred embodiment, the composite functional additive is at least two of ethylene glycol, glycerol, and pentaerythritol.

[0049] The functions of the raw materials used in the thermochromic fireproof layer material of the present invention are as follows:

[0050] Inorganic induced color change agent: Inorganic ammonium salts are selected as inorganic induced color change agents. They hydrolyze to generate NH3, which can react with the silanol (Si-OH) in the K2O·nSiO2-based fireproof material to generate Si-O-NH4. When the temperature rises, NH4 + The bound water in the K2O·nSiO2-based fireproof material can be taken away to generate NH4OH, and at the same time, Si-O-NH4 can be converted into silanol (Si-OH), causing the system to turn white; because the system is closed, when the temperature drops, NH4OH reacts with silanol (Si-OH) again to generate bound water and Si-O-NH4, making the system transparent again and realizing a thermoreversible cycle. The inorganic induced color-changing agent used in the embodiment of the present invention is selected from at least one of ammonium bicarbonate, ammonium carbonate, ammonium nitrate, ammonium phosphate, ammonium sulfate, and ammonium bisulfate. These inorganic induced color-changing agents can be hydrolyzed in the K2O·nSiO2-based fireproof material to generate NH3. Under the action of temperature, they can be desorbed and generated from the bound water, thereby realizing a thermoreversible cycle. The inorganic induced color-changing agent can couple with the Si-O-Si network, which can increase the transmittance of the material by 4% to 5%, the fireproof performance by more than 50%, and the ultraviolet resistance by more than 30%.

[0051] Composite functional agent: Low molecular weight polyol is selected as the composite functional agent, which has the function of a surfactant to a certain extent, and has a certain defoaming effect. The hydroxyl group it contains can also convert the free water in the system into bound water, which has an antifreeze effect. At high temperatures, the fireproof adhesive layer foams and produces pores. The composite functional additive is carbonized to form long-chain carbonized products, which are deposited in the pores. The long-chain carbonized products can absorb a large amount of heat, thereby enhancing the fireproof performance of the glass. The composite functional additive used in the embodiment of the present invention is selected from at least two of ethylene glycol, propylene glycol, and pentaerythritol. These composite functional additives can all form long-chain carbonized products at high temperatures. The long-chain carbonized products can absorb a large amount of heat, thereby enhancing the fireproof performance of the glass. In addition, these composite functional agents can also be carbonized at high temperatures to form long-chain carbonized products, which absorb a large amount of heat and enhance the fireproof performance of the glass.

[0052] Core-shell structured silica particles: Core-shell structured silica particles use grading design to form a high-solid content silica particle solution. The fireproof layer material pre-reaction liquid prepared using this solution will corrode the glass surface to form a diffusion layer of a certain thickness when it comes into contact with glass, thereby improving the adhesion between the fireproof adhesive layer and the glass; when the glass is heated and cracks are generated, the cracks will not expand, thereby preventing the entire piece of glass from shattering, greatly improving the strength of the fireproof glass; at the same time, the fireproof layer material pre-reaction solution has the characteristics of shear thinning.

[0053] The nano-core-shell silica particles used in the embodiments of the present invention have a core-shell structure, wherein the core material is a narrow distribution of silica aggregate particles with different particle sizes, and the shell material is a poly(butyl acrylate-styrene) copolymer. During low-temperature storage, the shell material of the core-shell silica particles in the fire-retardant liquid encapsulates the core silica particles and isolates the silica particles from the potassium hydroxide solution in the fire-retardant material, preventing a reaction. When the temperature is high, that is, higher than the glass transition temperature of the shell polymer, the shell polymer changes from a glassy state to a rubbery state, and the potassium hydroxide solution penetrates into the shell and reacts with the silica particles to form a potassium silicate solution, i.e., potassium water glass (whose structural formula is K2O·nSiO2, where n is the modulus). The silica network skeleton formed after the potassium water glass hardens has a very small drop in hardness at high temperatures, has good flame retardancy, is resistant to high temperatures and fire, and has a high hardness, which enhances the hardness and heat resistance of the composite fire-resistant glass.

[0054] The core-shell silica particles used in the embodiments of the present invention have narrowly distributed particle sizes of 150 nm to 300 nm, 1200 nm to 1500 nm, and 7500 nm to 9000 nm, respectively. Research has found that, utilizing the principles of particle grading design, the resulting high-solids, low-viscosity SiO2 dispersion also exhibits shear-thinning properties. By optimizing the addition of other additives, the addition of these additives does not affect the shear-thinning properties of the system. Consequently, the resulting pre-reaction solution for the fireproofing layer material also exhibits shear-thinning properties.

[0055] Because the core-shell structured silica particle solution has the characteristics of low viscosity and low reaction rate at room temperature (20°C), it can be used to pour thinner and larger outdoor insulation thermochromic composite fire-resistant glass. Its thermochromic response temperature is between 40°C and 90°C, and the low-temperature operating temperature can reach -65°C ± 1°C. It can withstand ultraviolet radiation for more than 3000 hours. Its results and mechanism of action are different from those of non-core-shell structured SiO2 dispersions, such as Figure 5 The figure below shows the relationship between viscosity and shear rate for a 55wt% nano-SiO2 particle dispersion of the present invention. While the core-shell structured dispersion has a much higher SiO2 solids content than the non-core-shell structured SiO2 dispersion, the two key factors influencing the initial viscosity of the system—the silanol content on the particle surface and the void area within the particles—are significantly different. For a SiO2 dispersion with a nearly spherical core-shell structure, the surface silanol groups and the internal voids are fully or partially encapsulated by the shell polymer, significantly reducing the impact of these two factors on the system's viscosity and thus lowering the initial viscosity. At the same time, as the shear rate increases, the small-sized particles of about 150nm to 300nm, which are composed of dozens of SiO2 particles agglomerated together, are equivalent to the lubricant in the gears; and the particles of about 1200nm to 1500nm, which are composed of hundreds of SiO2 particles agglomerated together, are equivalent to the beads in the gears, filling between the large-sized particles of about 7500nm to 9000nm, which are composed of thousands of SiO2 particles agglomerated together, play a role of lubrication, and the greater the shear rate, the lower the viscosity. Figure 4 The relationship between the viscosity μ of the fitting system and the rotation speed V can satisfy the following formula:

[0056] μ=79.78+7.01e (-V / 16.83)

[0057] The core-shell structured silica particles can rely on the steric hindrance effect of the shell polymer to make the core-shell particles reach a stable state. The embodiment of the present invention uses poly (butyl acrylate-styrene) copolymer as the shell material, which can play the above role. This is because the shell polymer contains a hydrophobic group -CH3, so some monomers can approximately play an isolating role, and the glass transition temperature of polystyrene is relatively high (over 100 degrees). Its copolymer is calculated according to the Fox formula to be in a glassy state at room temperature, with a certain rigidity, avoiding the generation of viscous adsorption between particles, which is beneficial to the protection of silica particles and preventing the agglomeration between core-shell particles. It can be evenly dispersed in the fireproof liquid and can fully react with potassium hydroxide solution. It should be emphasized that in the fireproof layer material of the present invention, the high-solid core-shell structured silica dispersion itself has the properties of resistance to low temperature and ultraviolet radiation, and the composite functional additive enhances the low temperature resistance while providing a steric hindrance effect.

[0058] The reasons why the fireproof layer material has the properties of thermochromism, low temperature resistance and ultraviolet radiation resistance are:

[0059] 1. NH4 generated by hydrolysis of inorganic induced color change agent + It can combine with the silanol groups in K2O·nSiO2-based fireproof materials to form a reversible reaction, thereby achieving thermochromic behavior;

[0060] 2. The solid content of the solution system of silica agglomerates is high (can exceed 55%), and accordingly, the free water in the fireproof layer material is reduced;

[0061] 3. "Layered" fold structure, such as Figure 6 As shown, the strength of the fireproof layer material and the ability to resist ultraviolet radiation are increased;

[0062] 4. The free water in the fireproof layer material is firmly locked by the alcohol substances in the composite functional additives, preventing the free water from forming large-sized, continuous ice crystal phases in low-temperature environments, ensuring the transparency of the composite fireproof glass under extremely cold conditions, thereby improving the low-temperature resistance of the fireproof layer material.

[0063] Among them, the causes of thermochromism are: Figure 7 As shown in the figure, it can be seen from the FTI R spectra of K2O·nSiO2 thermochromic fireproof material (K4) and the control sample (K3) that: in the fingerprint area (1330-667cm -1 ), 775-780cm -1 and 1036-1047cm -1 The frequency bands are designated as symmetric Si-O-Si stretching and asymmetric Si-O-Si stretching, in the characteristic frequency region (4000-1330cm -1 ), 1665cm -1and 3400-3500cm -1 The frequency bands at 1390-1485 cm are attributed to the vibration of SiO2 network and the stretching vibration of absorbed water, which are not the response region of thermochromism. -1 area, 1410cm -1 The band centered on + The vibration of the thermochromic refractory material and the control sample showed a clear difference. The presence of SiO2 network and bound water was observed in both materials. This is due to the addition of NH4 + It is the key to making K2O·nSiO2 material have thermochromic properties at a specific temperature.

[0064] The K2O·nSiO2-based thermochromic fireproof layer material having a "lamellar" corrugated structure in the present invention is prepared by the following steps:

[0065] (1) mixing a composite functional additive, core-shell structured silica aggregates having particle sizes of 150 nm to 300 nm, 1200 nm to 1500 nm, and 7500 nm to 9000 nm, and deionized water in a weight ratio of 5 to 10:40 to 320:8 to 64:2 to 16:55 to 250 at a high stirring speed of 500 to 3500 rpm and a high stirring dispersion time of 20 min to 40 min to obtain a first mixed solution;

[0066] (2) Using ball milling dispersion technology, 5 to 10 parts by weight of the composite functional additive and 100 to 650 parts by weight of the first mixed solution are added to a ball mill jar in the proportions of 55%, 30%, and 15% by weight, respectively, at a ball milling speed of 60 to 150 rpm and a ball milling time of 10 to 20 minutes each time to obtain a graded silica solution;

[0067] (3) Using semi-continuous blending technology, 0.5 to 20 parts by weight of an inorganic induced color change agent and 5 to 30 parts by weight of a composite functional additive are sequentially added to the silica graded solution at room temperature (20°C to 25°C) for a blending time of 20 to 60 minutes to obtain a base solution of a fireproof layer material;

[0068] (4) Add 5 to 10 parts by weight of a composite functional additive and 15 to 200 parts by weight of 85% pure potassium hydroxide to 100 to 700 parts by weight of the fireproof layer material base solution, evacuate at low temperature for 30 minutes, and stir evenly to obtain a pre-reaction liquid of the fireproof layer material:

[0069] (5) A K2O·nSiO2-based thermochromic pre-reaction liquid with high solid content (SiO2≥55wt%) and low viscosity (less than 200mPa.s) was poured layer by layer into the composite fireproof glass cavity by means of a peristaltic pump. After the pouring port was sealed, the glass was placed horizontally at room temperature for 2 hours, and then placed in a 60°C oven for constant temperature reaction for 10 hours until the visible light transmittance of the glass no longer changed, thereby obtaining a K2O·nSiO2-based thermochromic fireproof layer material with a "lamellar" pleated structure, and a temperature response range of 40°C to 90°C.

[0070] The particle sizes of the core-shell structured silica particles are 200 nm to 250 nm, 1250 nm to 1400 nm, and 8000 nm to 8500 nm, respectively. Furthermore, in the above step 3), the stirring time is 20 to 60 min, preferably 30 min.

[0071] When preparing the fireproof adhesive for fireproof glass in the embodiment of the present invention, the composite functional additive and core-shell structured silica particles are first added to deionized water and dispersed at high stirring to obtain a first mixed solution; the composite functional additive and the first mixed solution are added to a ball mill according to a proportion by means of a ball milling dispersion technology to obtain a silica graded solution; the inorganic induced color change agent and the composite functional additive are added to the silica graded solution by means of a semi-continuous blending technology to obtain a basic solution of a fireproof layer material; the composite functional additive and potassium hydroxide with a purity of 85% are added to the basic solution of the fireproof layer material, and the mixture is vacuumed. The mixture was slowly stirred under negative pressure to eliminate microbubbles in the system, thereby obtaining a pre-reaction liquid of the fireproof layer material; the K2O·nSiO2-based fireproof layer material pre-reaction liquid was poured layer by layer into the composite fireproof glass cavity with the help of a peristaltic pump. After the pouring port was sealed, the glass was placed horizontally at room temperature for 2 hours, and then placed in a 60°C oven for constant temperature reaction for 10 hours, until the visible light transmittance of the glass no longer changed, thereby obtaining a K2O·nSiO2-based thermochromic fireproof layer material with a "lamellar" pleated structure and a temperature response range of 40°C to 90°C.

[0072] Because the base solution of the fireproofing material reacts with potassium hydroxide when mixed, they must be stored separately before use. The base solution can be stored for a long time and has a shelf life of at least 180 days when sealed and protected from light. Potassium hydroxide can be stored normally. When in use, mixing the base solution with potassium hydroxide on site can better ensure the performance of the fireproofing material.

[0073] The fireproof glass provided by the embodiments of the present invention has a fireproof layer that rapidly foams and expands to form a heat-insulating, fire-resistant foam layer when exposed to fire, absorbing a large amount of heat generated by the fire and having excellent fireproofing properties. The fireproof layer of the fireproof glass formed using the fireproof layer material prepared above has the advantages of being free of microbubbles, having a high transmittance, and having a long fireproofing time. Preferably, the fireproof interlayers are at least two, one of which is a hollow layer and the other is a layer.

[0074] More preferably, the interlayer between two adjacent pieces of glass is a fireproof layer.

[0075] As a preferred embodiment, Figure 1 As shown, a fireproof glass comprises a first glass layer 11, a first fireproof layer 21, a second glass layer 12, a second fireproof layer 22 and a third glass layer 13 in sequence, wherein the first fireproof layer 21 and the second fireproof layer 22 are made of the above-mentioned fireproof layer material.

[0076] As another preferred embodiment, Figure 2 As shown, a fireproof glass includes a first glass layer 11, a first fireproof layer 21, a second glass layer 12, a second fireproof layer 22, a third glass layer 13, a vacuum layer 41, a fourth glass layer 14, a third fireproof layer 23 and a fifth glass layer 15 in sequence, wherein the first fireproof layer 21, the second fireproof layer 22 and the third fireproof layer 23 are made of the above-mentioned fireproof layer material, and the hollow layer is formed by sealing the two pieces of glass on all sides and sealing the gap therebetween.

[0077] As a preferred embodiment, the thickness of the fireproof layer is 1.5 to 5 mm.

[0078] The present invention can control the thickness of the fireproof layer to 1.5 to 5 mm. Under the premise of ensuring the fireproof performance of the fireproof glass, the thickness of the manufactured fireproof glass is relatively thin, the production cost of the glass is reduced, and the application range of the glass is expanded. The fireproof layer in the fireproof glass of the embodiment of the present invention will expand to form a porous heat-insulating layer after encountering fire. The thickness of the expansion layer is about 10 to 15 times the thickness of the original fireproof layer. After encountering fire, the fire-facing glass will first burst, and then the fireproof adhesive layer attached thereto will gradually form a heat-insulating layer of about 10 mm to 30 mm; if the thickness of the fireproof adhesive layer is less than 1.5 mm, the fireproof adhesive layer is too thin, and the formed heat-insulating layer cannot isolate the heat transfer within a certain period of time, resulting in the overall fireproof time being lower than the design value; if the thickness of the fireproof adhesive layer is greater than 5 mm, the fireproof adhesive layer is too thick, which will increase the overall weight of the fireproof glass and increase the cost. At the same time, since the fireproof adhesive layer expands layer by layer, an overly thick expansion layer will cause the glass to fall off as a whole, which will reduce the fireproof performance.

[0079] The present invention is further described below with reference to specific examples, but is not intended to limit the present invention.

[0080] The reagents used in the embodiments of the present invention are all commercially available products.

[0081] Example 1

[0082] The thermochromic fireproof layer material in this embodiment is prepared by the following steps:

[0083] (1) Weigh the raw materials of the thermochromic fireproof layer material according to the following weights:

[0084] 200 kg of core-shell silica particles with a particle size of 200 nm, 40 kg of core-shell silica particles with a particle size of 1250 nm, 10 kg of core-shell silica particles with a particle size of 8000 nm, 169.78 kg of deionized water, 4.5 kg of an inorganic induced color change agent (ammonium bicarbonate), 30 kg of a composite functional additive (glycerol / ethylene glycol = 1:1) and 119.49 kg of potassium hydroxide with a purity of 85%; since the particle size of the core-shell silica particles is distributed by a graded design, particles of various particle sizes can exist in the present invention. As shown in the figure, which is a distribution diagram of different particle sizes of the SiO2 dispersion of the present invention, the single peak of each particle size presents a narrow distribution state. Similarly, the particle size of the core-shell silica particles in the following examples is also narrowly distributed;

[0085] (2) Prepare the fireproof layer material by the following steps:

[0086] 5 kg of composite functional additive (glycerol / ethylene glycol = 1:1), 40 kg of core-shell structured silica particles with a particle size of 200 nm, 8 kg of core-shell structured silica particles with a particle size of 1250 nm, 2 kg of core-shell structured silica particles with a particle size of 8000 nm, and 169.78 kg of deionized water were mixed at high speed, with a high stirring speed of 2000 rpm, and the mixture was dispersed at high stirring for 30 minutes to prepare a first mixed solution;

[0087] By means of ball milling dispersion technology, 5 kg of composite functional additive (glycerol / ethylene glycol = 1:1) and the first mixed solution were added to a ball mill jar in the proportions of 55%, 30%, and 15% by weight, respectively. The ball milling speeds were 80 rpm, 100 rpm, and 120 rpm, and the ball milling times were 10 min, 15 min, and 20 min, respectively, to obtain a graded silica solution.

[0088] By means of semi-continuous blending technology, 4.5 kg of ammonium bicarbonate and 20 kg of composite functional additive (propylene glycol / ethylene glycol = 1:1) were added to the silica graded solution at room temperature (20°C to 25°C) for 30 minutes to obtain a basic solution of the fireproof layer material.

[0089] 5 kg of composite functional additive (glycerol / ethylene glycol = 1:1) and 119.49 kg of potassium hydroxide with a purity of 85% were added to the above-mentioned fireproof layer material base solution in sequence, and vacuumed for 30 minutes at low temperature and stirred evenly to obtain a thermochromic fireproof layer material pre-reaction liquid;

[0090] The outdoor heat-insulating thermochromic fire-proof glass in this embodiment is an outdoor heat-insulating thermochromic fire-proof glass made by using the above-mentioned fireproof layer material through the following steps:

[0091] (1) Prepare five sheets of 3mm thick glass, two of which are physically tempered glass; in order to ensure that the composite fireproof glass has high strength, the glass in the middle is preferably slightly thicker than the other layers of glass;

[0092] (2) Using a thickness-setting adhesive strip, the above-mentioned physical tempered glass is used as the outermost layer of glass and a piece of non-physical tempered glass to form a cavity with a thickness of 5 mm. Then, using a thickness-setting adhesive strip, the remaining two pieces of non-physical tempered glass are stacked in sequence, with a 5 mm thick cavity between each piece of glass. Finally, using a thickness-setting adhesive strip, another piece of physical tempered glass is laminated with the above-mentioned multi-layer cavity glass, and a layer of 5 mm thick cavity is added to ensure that the outer surface of the multi-layer cavity glass is all physically tempered glass;

[0093] (3) Using a peristaltic pump, a pre-reaction liquid of a K2O·nSiO2-based fireproof layer material with a high solid content (SiO2 ≥ 55 wt%) and a low viscosity (less than 200 mPa·s) is poured layer by layer into the composite fireproof glass cavity (5 glasses and 4 cavities). The liquid is allowed to stand for defoaming, and after the pouring port is sealed, the glass is placed horizontally at room temperature for 2 hours, and then placed in a 60°C oven for constant temperature reaction for 10 hours, until the visible light transmittance of the glass no longer changes, thereby obtaining a K2O·nSiO2-based low-temperature thermochromic composite fireproof glass with a "lamellar" pleated structure.

[0094] Example 2

[0095] The thermochromic fireproof layer material in this embodiment is prepared by the following steps:

[0096] (1) Weigh the raw materials of the thermochromic fireproof layer material according to the following weights:

[0097] 200 kg of core-shell silica particles with a particle size of 200 nm, 40 kg of core-shell silica particles with a particle size of 1250 nm, 10 kg of core-shell silica particles with a particle size of 8000 nm, 169.78 kg of deionized water, 4.5 kg of an inorganic color-changing agent (ammonium hydrogen phosphate), 30 kg of a composite functional additive (glycerol / ethylene glycol = 1:1), and 119.49 kg of potassium hydroxide with a purity of 85%;

[0098] (2) The above raw materials were used to prepare a thermochromic fireproof layer material according to the same preparation method as in Example 1.

[0099] The preparation method of the outdoor heat-insulating thermochromic fire-proof glass in this embodiment is the same as the preparation method of the outdoor heat-insulating thermochromic fire-proof glass in Example 1, the difference being that the composition of the thermochromic fire-proof layer material is different.

[0100] Example 3

[0101] The fireproof layer material in this embodiment is prepared by the following steps:

[0102] The thermochromic fireproof layer material in this embodiment is prepared by the following steps:

[0103] (1) Weigh the raw materials of the thermochromic fireproof layer material according to the following weights:

[0104] 200 kg of core-shell silica particles with a particle size of 200 nm, 40 kg of core-shell silica particles with a particle size of 1250 nm, 10 kg of core-shell silica particles with a particle size of 8000 nm, 197.94 kg of deionized water, 4.5 kg of an inorganic color-changing agent (ammonium bicarbonate), 30 kg of a composite functional additive (glycerol / ethylene glycol = 1:1), and 119.49 kg of potassium hydroxide with a purity of 85%;

[0105] (2) The above raw materials were used to prepare a thermochromic fireproof layer material according to the same preparation method as in Example 1.

[0106] The preparation method of the outdoor heat-insulating thermochromic fire-proof glass in this embodiment is the same as the preparation method of the outdoor heat-insulating thermochromic fire-proof glass in Example 1, the difference being that the composition of the thermochromic fire-proof layer material is different.

[0107] Example 4

[0108] The fireproof layer material in this embodiment is prepared by the following steps:

[0109] The thermochromic fireproof layer material in this embodiment is prepared by the following steps:

[0110] (1) Weigh the raw materials of the thermochromic fireproof layer material according to the following weights:

[0111] 200 kg of core-shell silica particles with a particle size of 200 nm, 40 kg of core-shell silica particles with a particle size of 1250 nm, 10 kg of core-shell silica particles with a particle size of 8000 nm, 216.54 kg of deionized water, 4.5 kg of an inorganic color-changing agent (ammonium bicarbonate), 30 kg of a composite functional additive (glycerol / ethylene glycol = 1:1), and 119.49 kg of potassium hydroxide with a purity of 85%;

[0112] (2) The above raw materials were used to prepare a thermochromic fireproof layer material according to the same preparation method as in Example 1.

[0113] The preparation method of the outdoor heat-insulating thermochromic fire-proof glass in this embodiment is the same as the preparation method of the outdoor heat-insulating thermochromic fire-proof glass in Example 1, the difference being that the composition of the thermochromic fire-proof layer material is different.

[0114] Example 5

[0115] The thermochromic fireproof layer material in this embodiment is prepared by the following steps:

[0116] (1) Weigh the raw materials of the thermochromic fireproof layer material according to the following weights:

[0117] 200 kg of core-shell silica particles with a particle size of 200 nm, 40 kg of core-shell silica particles with a particle size of 1250 nm, 10 kg of core-shell silica particles with a particle size of 8000 nm, 169.78 kg of deionized water, 3.75 kg of an inorganic color-changing agent (ammonium bicarbonate), 30 kg of a composite functional additive (glycerol / ethylene glycol = 1:1), and 119.49 kg of potassium hydroxide with a purity of 85%;

[0118] (2) The above raw materials were used to prepare a thermochromic fireproof layer material according to the same preparation method as in Example 1.

[0119] The preparation method of the outdoor heat-insulating thermochromic fire-proof glass in this embodiment is the same as the preparation method of the outdoor heat-insulating thermochromic fire-proof glass in Example 1, the difference being that the composition of the thermochromic fire-proof layer material is different.

[0120] Example 6

[0121] The thermochromic fireproof layer material in this embodiment is prepared by the following steps:

[0122] (1) Weigh the raw materials of the thermochromic fireproof layer material according to the following weights:

[0123] 200 kg of core-shell silica particles with a particle size of 200 nm, 40 kg of core-shell silica particles with a particle size of 1250 nm, 10 kg of core-shell silica particles with a particle size of 8000 nm, 169.78 kg of deionized water, 5.25 kg of an inorganic color-changing agent (ammonium bicarbonate), 30 kg of a composite functional additive (glycerol / ethylene glycol = 1:1), and 119.49 kg of potassium hydroxide with a purity of 85%;

[0124] (2) The above raw materials were used to prepare a thermochromic fireproof layer material according to the same preparation method as in Example 1.

[0125] The preparation method of the outdoor heat-insulating thermochromic fire-proof glass in this embodiment is the same as the preparation method of the outdoor heat-insulating thermochromic fire-proof glass in Example 1, the difference being that the composition of the thermochromic fire-proof layer material is different.

[0126] Example 7

[0127] The fireproof layer material in this embodiment is prepared by the following steps:

[0128] (1) Weigh the same raw materials of the fireproof layer material as in Example 1:

[0129] (2) The above raw materials are used to prepare a fireproof layer material according to the same preparation method as in Example 1.

[0130] The outdoor heat-insulating thermochromic fire-proof glass in this embodiment is an outdoor heat-insulating thermochromic fire-proof glass made by using the above-mentioned fireproof layer material through the following steps:

[0131] (1) Prepare four sheets of 3mm thick glass, two of which are physically tempered glass; in order to ensure that the composite fireproof glass has high strength, the glass in the middle is preferably slightly thicker than the other layers of glass;

[0132] (2) Using a thickness-setting adhesive strip, the above-mentioned piece of physical tempered glass is used as the outermost layer of glass and a piece of non-physical tempered glass to form a cavity with a thickness of 5 mm. Then, using a thickness-setting adhesive strip, the remaining pieces of non-physical tempered glass are stacked in sequence, with a cavity with a thickness of 5 mm between each piece of glass. Finally, using a thickness-setting adhesive strip, another piece of physical tempered glass is laminated with the above-mentioned multi-layer cavity glass, and a layer of 5 mm thick cavity is added to ensure that the outer surface of the multi-layer cavity glass is all physically tempered glass;

[0133] (3) Using a peristaltic pump, the pre-reaction liquid of the K2O·nSiO2-based thermochromic fireproof layer material with high solid content (≥55wt%, %) and low viscosity (less than 200mPa·s) was poured layer by layer into the composite fireproof glass cavity (4 glasses and 3 cavities). After standing to defoam, the pouring port was sealed and the glass was placed horizontally at room temperature for 2 hours. It was then placed in a 60°C oven for constant temperature reaction for 10 hours until the visible light transmittance of the glass no longer changed, thereby obtaining a K2O·nSiO2-based thermochromic composite fireproof glass with a "lamellar" pleated structure.

[0134] Example 8

[0135] The fireproof layer material in this embodiment is prepared by the following steps:

[0136] (1) Weigh the same raw materials of the fireproof layer material as in Example 1:

[0137] (2) The above raw materials are used to prepare a fireproof layer material according to the same preparation method as in Example 1.

[0138] The outdoor heat-insulating thermochromic fire-proof glass in this embodiment is an outdoor heat-insulating thermochromic fire-proof glass made by using the above-mentioned fireproof layer material through the following steps:

[0139] (1) Prepare three sheets of 3mm thick glass, two of which are physically tempered glass; in order to ensure that the composite fireproof glass has high strength, the glass in the middle is preferably slightly thicker than the other layers of glass;

[0140] (2) Using a thickness-setting adhesive strip, the aforementioned piece of physically tempered glass as the outermost layer of glass and a piece of non-physically tempered glass are combined to form a cavity having a thickness of 5 mm. Then, using a thickness-setting adhesive strip, another piece of physically tempered glass is laminated with the aforementioned multi-layer cavity glass to add a layer of 5 mm thick cavity, ensuring that the outer surface of the multi-layer cavity glass is all physically tempered glass;

[0141] (3) Using a peristaltic pump, the pre-reaction liquid of the K2O·nSiO2-based thermochromic fireproof layer material with high solid content (≥55wt%, %) and low viscosity (less than 200mPa·s) was poured layer by layer into the composite fireproof glass cavity (3 glasses and 2 cavities). After standing to defoam, the pouring port was sealed. After that, the glass was placed horizontally at room temperature for 2 hours, and then placed in a 60℃ oven for constant temperature reaction for 10 hours until the visible light transmittance of the glass no longer changed, thereby obtaining a K2O·nSiO2-based thermochromic composite fireproof glass with a "lamellar" pleated structure.

[0142] Comparative Example 1

[0143] This comparative example provides a fireproof layer material, the raw material of which is pure potassium water glass with a modulus of 3.4.

[0144] The preparation method of the fireproof glass in this comparative example is the same as the preparation method of the outdoor heat-insulating fireproof glass in Example 1, except that the composition of the fireproof layer material is different.

[0145] Comparative Example 2

[0146] The fireproof layer material in this comparative example is prepared by the following steps:

[0147] (1) Weigh the raw materials of the thermochromic fireproof layer material according to the following weights:

[0148] 200 kg of core-shell silica particles with a particle size of 200 nm, 40 kg of core-shell silica particles with a particle size of 1250 nm, 10 kg of core-shell silica particles with a particle size of 8000 nm, 169.78 kg of deionized water, 30 kg of a composite functional additive (glycerol / ethylene glycol = 1:1), and 119.49 kg of potassium hydroxide with a purity of 85%;

[0149] (2) The above raw materials were used to prepare a thermochromic fireproof layer material according to the same preparation method as in Example 1.

[0150] The preparation method of the outdoor heat-insulating thermochromic fire-proof glass in this embodiment is the same as the preparation method of the outdoor heat-insulating thermochromic fire-proof glass in Example 1, the difference being that the composition of the thermochromic fire-proof layer material is different.

[0151] Fire resistance tests were conducted on fire-resistant glass prepared using the fireproof layer materials provided in Examples 1-8 and Comparative Examples 1-2 according to the fire resistance test method for glazed components specified in GB / T12513-2006. The fire resistance duration of the fire-resistant glass was determined. Four parallel samples were collected, and the average of the data was taken as the experimental result. The transmittance of each fire-resistant glass was determined by glass transmittance testing, and the apparent quality of each fire-resistant glass was determined by visual observation. The performance parameters of the fire-resistant glass prepared in the Examples and Comparative Examples are shown in Table 1.

[0152] Table 1 Performance parameters of fire-resistant glass

[0153]

[0154] *ΔT=(T t0 -T tn ) / T t0

[0155] T tn is the transmittance after 3000h of ultraviolet irradiation, T t0 is the initial transmittance.

[0156] As shown in Table 1, the outdoor heat-insulating thermochromic fire-resistant glass of the present invention contains no microbubbles, while the fire-resistant glass prepared in the comparative example contains a large number of microbubbles. The fire-resistant time of the outdoor heat-insulating thermochromic fire-resistant glass of the present invention without microbubbles is 1.5-2.5 times that of the fire-resistant glass of Comparative Example 1, and its transmittance and ultraviolet radiation resistance are also significantly higher than those of the fire-resistant glass of Comparative Example 1. The fire-resistant time of the outdoor heat-insulating thermochromic fire-resistant glass of the present invention without microbubbles is 20% longer than that of the fire-resistant glass of Comparative Example 2 (without the addition of an inorganic color-changing agent), and its transmittance and ultraviolet radiation resistance are also significantly higher than those of the fire-resistant glass of Comparative Example 2. The above shows that the use of potassium water glass as the fireproof layer of fire-resistant glass easily causes the generation of a large number of microbubbles in the glass. The presence of a large number of microbubbles reduces the hardness and fireproof and heat-resistant properties of the fire-resistant glass, and seriously affects the light transmittance and apparent quality of the fire-resistant glass. By improving the formulation of the fireproof layer, the present invention creates a synergistic effect between the various components of the fireproof layer, eliminating bubbles in the fireproof glass interlayer and providing the composite fireproof glass with improved fire and heat resistance. Furthermore, the K2O·nSiO2-based thermochromic fireproof layer material with a "lamellar" pleated structure improves the low-temperature resistance of the fireproof glass, allowing it to be used in low-temperature (-65°C) and outdoor environments. The fireproof glass prepared according to the embodiments of the present invention has the advantages of being free of microbubbles, having good adhesion, high transmittance, long-term fire protection, and resistance to low temperatures and UV radiation.

[0157] It can be seen from the data recorded in Table 1 that there are no microbubbles in the outdoor insulating fireproof glass of the present invention. The reason is that the viscosity of the pre-reaction solution of the fireproof layer material in the present invention is relatively low, which is conducive to the escape of bubbles, thereby facilitating the discharge of the gas in the fireproof layer during the preparation of the fireproof layer, saving work time.

[0158] By comparing Examples 1 to 8 with Comparative Examples 1 to 2, it can be seen that when the same fireproof layer material is used and the number of glass layers is gradually reduced, the transmittance becomes better and better as the number of glass pieces decreases, the low temperature resistance remains unchanged, and the fireproof time gradually becomes shorter.

[0159] The hardness of the thermochromic, low-temperature, and ultraviolet radiation-resistant composite heat-insulating fire-resistant glass provided by the embodiments of the present invention can reach above 4H, and some even reach 6H.

[0160] In the above embodiments, the description of each embodiment has its own focus. For parts that are not described in detail in a certain embodiment, reference can be made to the relevant descriptions of other embodiments.

[0161] The above description is merely a preferred embodiment of the present invention and does not constitute any form of limitation to the present invention. Any simple modifications, equivalent changes and modifications made to the above embodiment based on the technical essence of the present invention still fall within the scope of the technical solution of the present invention.

Claims

1. A thermochromic insulating fireproof glass for outdoor use, wherein the insulating fireproof glass is formed by laminating at least two sheets of glass, with an interlayer provided between two adjacent sheets of glass, at least one of the interlayers being a fireproof layer made of a thermochromic fireproof layer material, characterized in that: The fireproof layer is a fireproof layer structure having a "sheet"-like pleated structure, and the color change temperature response range of the fireproof layer structure is 50°C to 80°C. The fireproof layer structure is manufactured by the following steps: Step 1) preparing a pre-reaction liquid of a fireproof layer material; the pre-reaction liquid of the fireproof layer material is a pre-reaction liquid of a K2O·nSiO2-based thermochromic hybrid material, wherein the K2O·nSiO2-based thermochromic hybrid material is prepared from core-shell silica aggregates of different particle sizes by gradation design, ball milling dispersion treatment, addition of an inorganic induced color-changing agent, and then utilizing an in-situ constant temperature reaction technology; the inorganic induced color-changing agent is at least one of ammonium bicarbonate, ammonium carbonate, ammonium nitrate, ammonium phosphate, ammonium sulfate, and ammonium bisulfate; and the composite functional additive is at least two of ethylene glycol, glycerol, and pentaerythritol; Step 2) The prepared fireproof layer material pre-reaction liquid having a solid content of SiO2 ≥ 55 wt% and a viscosity of less than 200 mPa·s is poured layer by layer into the composite fireproof glass cavity. After the pouring port is sealed, the glass is placed horizontally at room temperature for 2 hours, and then placed in a 60°C oven for constant temperature reaction for 10 hours until the visible light transmittance of the glass no longer changes, thereby obtaining a fireproof layer structure having a "lamellar" pleated structure.

2. The heat-insulating fireproof glass according to claim 1, characterized in that: The fireproof layer material pre-reaction liquid is prepared by the following steps: Step 1-1) The composite functional additive, core-shell silica aggregates having particle sizes of 150 nm to 300 nm, 1200 nm to 1500 nm, and 7500 nm to 9000 nm, and deionized water are stirred in a weight ratio of 5 to 10: 40 to 320: 8 to 64: 2 to 16: 55 to 250 at a stirring speed of 500 to 3500 rpm for a stirring and dispersion time of 20 to 40 minutes to obtain a first mixed solution; Step 1-2) Using ball milling dispersion technology, 5-10 parts by weight of the composite functional additive and 100-650 parts by weight of the first mixed solution are added to a ball mill jar in the proportions of 55%, 30%, and 15%, respectively, at a ball mill speed of 60-150 rpm for 10-20 minutes per ball milling to obtain a graded silica solution; Step 1-3) Using a semi-continuous blending technique, 0.5 to 20 parts by weight of an inorganic color-changing agent and 5 to 30 parts by weight of a composite functional additive are sequentially added to the silica graded solution at room temperature for 20 to 60 minutes to obtain a base solution of the fireproof layer material; Step 1-4) Add 5 to 10 parts by weight of a composite functional additive and 15 to 200 parts by weight of 85% pure potassium hydroxide to 100 to 700 parts by weight of the fireproof layer material base solution, evacuate at low temperature for 30 minutes, and stir evenly to obtain a pre-reaction solution of the fireproof layer material.

3. The heat-insulating fireproof glass according to claim 1, characterized in that: The modulus of the pre-reaction liquid of the fireproof layer material is 3.8 to 5.

2.

4. The heat-insulating fireproof glass according to any one of claims 1 to 3, characterized in that: The particle sizes of the core-shell structured silica agglomerates are 150nm-300nm, 1200nm-1500nm, and 7500nm-9000nm, respectively.

5. The heat-insulating fireproof glass according to any one of claims 1 to 3, characterized in that: The thickness of the fireproof layer is 1.5 to 5.0 mm.

6. Fireproof layer structure, characterized in that: The fireproof layer structure is the fireproof layer structure according to any one of claims 1 to 3.

7. Fireproof layer material, characterized in that: The fireproof layer material is a fireproof layer material made from the fireproof layer material pre-reaction liquid according to any one of claims 1 to 5.

8. The method for preparing a fireproof layer structure using the fireproof layer material according to claim 7, characterized in that: The steps include: Step 1) Prepare the pre-reaction liquid of the fireproof layer material, specifically the following steps: Step 1-1) The composite functional additive, core-shell silica aggregates having particle sizes of 150 nm to 300 nm, 1200 nm to 1500 nm, and 7500 nm to 9000 nm, and deionized water are stirred in a weight ratio of 5 to 10: 40 to 320: 8 to 64: 2 to 16: 55 to 250 at a stirring speed of 500 to 3500 rpm for a stirring and dispersion time of 20 to 40 minutes to obtain a first mixed solution; Step 1-2) Using ball milling dispersion technology, 5-10 parts by weight of the composite functional additive and 100-650 parts by weight of the first mixed solution are added to a ball mill jar in the proportions of 55%, 30%, and 15%, respectively, at a ball mill speed of 60-150 rpm for 10-20 minutes per ball milling to obtain a graded silica solution; Step 1-3) Using a semi-continuous blending technique, 0.5 to 20 parts by weight of an inorganic color-changing agent and 5 to 30 parts by weight of a composite functional additive are sequentially added to the silica graded solution at room temperature for 20 to 60 minutes to obtain a base solution of the fireproof layer material; Step 1-4) adding 5 to 10 parts by weight of a composite functional additive and 15 to 200 parts by weight of 85% pure potassium hydroxide to 100 to 700 parts by weight of the fireproof layer material base solution, vacuuming at low temperature for 30 minutes, and stirring evenly to obtain a fireproof layer material pre-reaction solution; Step 2) The prepared fireproof layer material pre-reaction liquid having a solid content of SiO2 ≥ 55 wt% and a viscosity of less than 200 mPa·s is poured layer by layer into the composite fireproof glass cavity. After the pouring port is sealed, the glass is placed horizontally at room temperature for 2 hours, and then placed in a 60°C oven for constant temperature reaction for 10 hours until the visible light transmittance of the glass no longer changes, thereby obtaining a fireproof layer structure having a "lamellar" pleated structure.

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