A thermochromic fireproof layer structure, a preparation method thereof, a fireproof layer material, and a heat-insulating fireproof glass for outdoor use

Abstract

The present invention relates to a thermochromic fireproof layer structure, a preparation method thereof, a fireproof layer material and an outdoor heat-insulating fireproof glass. The fireproof layer material, by weight, consists of the following raw materials: 50-400 parts of gas-phase nano-silica particles, 0.01-5 parts of tetraethyl orthosilicate, 0.001-0.05 parts of ammonia water, 55-250 parts of deionized water, 1-40 parts of an organic induced color-changing agent, 10-30 parts of a composite functional additive, and 15-200 parts of potassium hydroxide with a purity of 85%. The fireproof layer material of the present invention is prepared by an in-situ gradient temperature control reaction technology and has a "fiber"-shaped laminated structure. Its pre-reaction solution has the characteristic of low viscosity, and can be used to pour thinner and larger-sized outdoor thermochromic heat-insulating composite fireproof glass. The thermochromic response temperature range can be controllably adjusted from 60°C to 80°C. At the same time, the low-temperature service temperature can reach -55°C ± 1°C, and the ultraviolet radiation resistance time exceeds 2000 hours.

Description

Technical Field

[0001] The present invention relates to the field of safety glass, and particularly to a K2O·nSiO2-based thermochromic fireproof layer structure with a "fiber" - like laminated structure, a preparation method thereof, a fireproof layer material, and an outdoor heat - insulating fireproof glass. Background Art

[0002] With the accelerating pace of urbanization, the building windows of houses are becoming larger and larger. Elegant, beautiful, functional and safe glass components are gradually favored by designers at home and abroad, which directly leads to the rapid development of various safety glasses and special glasses in the architectural glass industry. Architectural glass has gradually developed from a simple lighting and decorative material to a direction of multi - functional combination with functions such as light control, room temperature adjustment, noise reduction, and improvement of living environment.

[0003] In addition to certain properties of ordinary glass, fireproof glass also has properties such as controlling the spread of fire, smoke isolation, and heat insulation, providing valuable rescue time for effective rescue in case of a fire, and minimizing the losses of personnel, property, and buildings. Fireproof glass can protect escape and rescue personnel from thermal radiation damage and reduce the destructive power of fire to the minimum. Due to frequent fires in some well - known large - scale buildings at home and abroad recently, people have gradually paid attention to the research, production, and use effects of composite fireproof glass. However, the existing composite fireproof glass does not have an intelligent color - changing function. Therefore, the research and development of thermochromic fireproof materials, which can achieve autonomous adjustment of the visible light transmittance of windows only based on the ambient temperature without consuming external energy and also have fireproof and heat - insulating characteristics, is of great significance for building safety and energy conservation and emission reduction.

[0004] At present, thermochromic materials (liquid crystals, hydrogels, VO2) cannot cycle and respond in the strong alkaline environment of K2O·nSiO2. It is necessary to use a spacer layer to ensure isolation from each other, which increases the frame and building load-bearing capacity and reduces the visible light transmittance of the window. The domestic work on the special fireproof layer materials for composite fireproof glass is in the basic research stage. The existing composite fireproof glass has poor low-temperature performance, requires a large amount of anti-condensation agent, and most products will freeze and turn white under low-temperature conditions, unable to meet the long-term use requirements for outdoor windows and curtain walls in cold northern regions. The existing composite fireproof glass also has very poor ultraviolet radiation resistance, and it is necessary to cooperate with PVB film in the outer layer of glass to reduce the damage of ultraviolet radiation to the fireproof layer materials. The main component of the fireproof layer material of the existing composite fireproof glass, water glass, is restricted by factors such as its own viscosity and leveling property, resulting in an easy formation of thickness differences during the preparation of the fireproof layer material, thus causing the surface of the fireproof layer to be uneven. At the same time, the fireproof layer of the existing composite fireproof glass is prone to generating bubbles, which easily leads to a large number of micro-bubbles in the interlayer. The existence of micro-bubbles reduces the hardness and actual fireproof effect of the fireproof layer, and will also affect the appearance 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 K2O·nSiO2-based thermochromic fireproof layer structure body with a "fiber" - like laminated structure, its preparation method, fireproof layer material, and outdoor heat-insulating fireproof glass, which overcomes the drawbacks in the prior art that the fireproof layer material cannot be thermochromic and cannot be used outdoors, and avoids the disadvantages such as yellowing, glue flow, bubbling, and poor appearance quality of the fireproof layer.

[0006] The object of the present invention and the solution to its technical problems are achieved by adopting the following technical solutions.

[0007] An outdoor heat-insulating fireproof glass according to the present invention is formed by laminating at least two glass layers. An anti-reflection layer is provided on the outer surface of at least one outer glass layer. There is an interlayer between two adjacent glasses, and at least one of the interlayers is a thermochromic fireproof layer. The fireproof layer material used in the thermochromic fireproof layer is composed of the following substances in parts by weight:

[0008] 50 - 400 parts of gas-phase nano-silica particles, 0.01 - 5 parts of tetraethyl orthosilicate, 0.001 - 0.05 parts of ammonia water, 55 - 250 parts of deionized water, 1 - 40 parts of organic induced color-changing agent, 10 - 30 parts of composite functional additives, and 15 - 200 parts of potassium hydroxide with a purity of 85%. Among them, the thermochromic fireproof layer material is prepared by using the in-situ gradient temperature control reaction technology, and the modulus of this fireproof material is between 4.0 and 5.0.

[0009] The object of the present invention and the technical problems solved thereby can be further achieved by the following technical measures.

[0010] Preferably, for the aforementioned fireproof layer material, by weight, its raw materials are composed of the following substances: 100-250 parts of gas-phase nano-silica particles, 1-2.5 parts of tetraethyl orthosilicate, 0.01-0.02 parts of ammonia water, 150-200 parts of deionized water, 4-30 parts of organic induced color-changing agent, 15-20 parts of composite functional additive, and 50-150 parts of potassium hydroxide with a purity of 85%.

[0011] Preferably, for the aforementioned fireproof layer material, the particle size of the gas-phase nano-silica particles is 60nm-80nm, and the specific surface area is 40-60m 2 / g.

[0012] Preferably, for the aforementioned fireproof layer material, the organic induced color-changing agent is at least one of primary amines, secondary amines, and tertiary amines such as methylamine, ethylenediamine, ethanolamine, dimethylethanolamine, and tetrabutylammonium bromide; the composite functional additive is at least two of ethylene glycol, glycerol, and pentaerythritol.

[0013] The object of the present invention and the technical problems solved thereby are also achieved by the following technical solutions.

[0014] A K2O·nSiO2-based thermochromic fireproof layer material with a "fiber"-like laminated structure and its preparation method according to the present invention include:

[0015] Mix the composite functional additive, tetraethyl orthosilicate, ammonia water, and deionized water according to a weight ratio of 1-5:0.01-5:0.001-0.05:50-200, stand for aging for 24-96h, and wait for tetraethyl orthosilicate to be alcoholized to generate a silica seed solution with a particle size of 30nm-120nm of silica particles to obtain a first mixed solution;

[0016] By means of gradient pre-dispersion technology, gradually disperse 1-5 parts by weight of the composite functional additive and 50-400 parts by weight of gas-phase nano-silica particles into the first mixed solution in sequence according to 3%, 12%, and 85% by weight, with a high-speed stirring speed of 500-3500rpm and a pre-dispersion time of 2min, 10min, and 45min each time to obtain a silica grading solution;

[0017] By means of semi-continuous blending technology, at room temperature (20°C-25°C), add 1-40 parts by weight of the organic induced color-changing agent, 4-15 parts by weight of the composite functional additive, and 5-50 parts by weight of deionized water into the silica grading solution in sequence, with a blending time of 20-60min to obtain a fireproof layer material basic solution;

[0018] Add 5 - 10 parts by weight of the composite functional auxiliary agent and 15 - 200 parts by weight of potassium hydroxide with a purity of 85% to 100 - 700 parts by weight of the basic solution of the fireproof layer material in sequence, evacuate under low temperature for 30 minutes, and stir evenly to obtain the pre-reaction solution of the fireproof layer material;

[0019] With the aid of a peristaltic pump, layer by layer perfusion of the K2O·nSiO2-based thermochromic pre-reaction solution with a high solid content (SiO2≥55wt,%) and low viscosity (less than 200mPa·s) into the cavity of the composite fireproof glass. After sealing the perfusion port, place the glass horizontally in a room temperature environment for 2 hours, then place it in an oven at 35°C for constant temperature reaction for 5 hours, raise the temperature of the oven to 40°C for constant temperature reaction for 5 hours, raise the temperature of the oven to 45°C for constant temperature reaction for 5 hours, raise the temperature of the oven to 50°C for constant temperature reaction for 5 hours until the visible light transmittance of the glass no longer changes, and obtain the K2O·nSiO2-based thermochromic fireproof layer material with a "fiber" - shaped laminated structure.

[0020] The object of the present invention and the solution to its technical problems can also be further realized by the following technical measures.

[0021] Preferably, for the aforementioned fireproof glass, the material of the anti-reflection layer is SiO2, TiO2, SiO2 / TiO2, TiO2 / SiO2 or SiO2 / TiO2 / SiO2.

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

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

[0024] 1. Doping an organic induced color-changing agent in the K2O·nSiO2-based fireproof material can endow K2O·nSiO2 with reversible thermochromic characteristics; by gradually dispersing with the aid of gradient pre-dispersion technology, the grading effect of nano-silica aggregates is further optimized, and the viscosity of the system is greatly reduced: the silica solution after pre-dispersion has a lower viscosity than the silica solution prepared by other technologies under the premise of the same solid content. At the same time, the specific wide-distribution silica aggregates enable the pre-reaction solution of the fireproof layer material to have the characteristic of shear thinning, and can be poured into a thinner glass cavity faster.

[0025] 2. The fireproof layer material of the present invention uses nano-silica particles as the main raw material. After the fireproof layer material containing this raw material contacts the glass, it will corrode the glass surface to form a diffusion layer with a certain thickness, improving the adhesion between the fireproof adhesive layer and the glass; when the glass generates cracks due to heat, the cracks will not expand, thus preventing the fragmentation of the whole glass, and greatly improving the strength of the fireproof glass.

[0026] 3. By introducing special processes such as in-situ gradient temperature control reaction during the preparation of the thermochromic fireproof layer material, a synergistic effect is generated among the components of the fireproof layer material, eliminating the bubbles in the interlayer of the composite fireproof glass, and preparing a high-performance microbubble-free thermochromic composite fireproof glass suitable for outdoor environments with a transmittance of 75 - 88%, a fire resistance time of up to about 300 min, an ultraviolet radiation resistance time of more than 2000 h, a thermochromic response temperature ranging from 50°C to 80°C, and can be used under low-temperature environment (-55°C) conditions.

[0027] 4. The reasons why the fireproof layer material of the present invention has thermochromism, low-temperature resistance, and ultraviolet radiation resistance are as follows: NH4 generated by the hydrolysis of the organic-induced color-changing agent + can combine with the silanol groups in the K2O·nSiO2-based fireproof material to form a reversible reaction, thereby realizing the thermochromic behavior; the specially designed pre-dispersion process optimizes the grading effect of the nano-core-shell structure organic / inorganic hybrid particles, reduces the viscosity of the reaction system, and ensures that the solid content of silica is further increased (it can exceed 55%). Correspondingly, the free water in the fireproof layer material is reduced; the "fiber"-shaped laminated structure increases the strength of the fireproof layer material and the ability to resist ultraviolet radiation; the free water in the fireproof layer material is firmly locked by the polyhydric alcohol generated by the hydrolysis of the organic-induced color-changing agent, preventing the formation of large-sized and continuous ice crystal phases by free water under low-temperature environments, ensuring the transparency of the composite fireproof glass under extremely cold conditions, and thus 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 better understand the technical means of the present invention and be able to implement it according to the content of the specification, the following describes in detail with the preferred embodiments of the present invention and in conjunction with the accompanying drawings. Brief Description of the Drawings

[0029] Figure 1 It is a schematic structural diagram of the outdoor heat-insulating thermochromic fireproof glass according to an embodiment of the present invention;

[0030] Figure 2 It is a schematic structural diagram of the outdoor heat-insulating thermochromic fireproof glass according to another embodiment of the present invention;

[0031] Figure 3 It is a schematic structural diagram of the outdoor heat-insulating thermochromic fireproof glass according to still another embodiment of the present invention;

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

[0033] Figure 5 It is a particle size distribution diagram of the dispersion liquid of the silica particles of the present invention.

[0034] Figure 6 The thermochromic process of the K2O·nSiO2-based thermochromic fireproof coating material and the electron microscope photograph of the K2O·nSiO2-based thermochromic fireproof coating material with a "fiber"-shaped laminated structure. Detailed implementation manners

[0035] The outdoor heat-insulating thermochromic fireproof glass in the present invention is formed by laminating at least two glass sheets. There is an interlayer between two adjacent glass sheets. At least one of the interlayers is a fireproof layer made of a thermochromic fireproof coating material. An antireflection layer is provided on the outer surface of at least one outer glass sheet of the fireproof glass.

[0036] Among them, the thermochromic fireproof coating material, by weight, is composed of the following raw materials:

[0037] 50 - 400 parts of gas-phase nano-silica particles, 0.01 - 5 parts of tetraethyl orthosilicate, 0.001 - 0.05 parts of ammonia water, 55 - 250 parts of deionized water, 1 - 40 parts of an organic induced color-changing agent, 10 - 30 parts of a composite functional additive, and 15 - 200 parts of potassium hydroxide with a purity of 85%. Among them, the thermochromic fireproof coating material is prepared by using an in-situ gradient temperature control reaction technology, and the modulus of this fireproof material is between 4.0 and 5.0.

[0038] As a preferred embodiment, the fireproof coating material, by weight, is composed of the following raw materials: 100 - 250 parts of gas-phase nano-silica particles, 1 - 2.5 parts of tetraethyl orthosilicate, 0.01 - 0.02 parts of ammonia water, 150 - 200 parts of deionized water, 4 - 30 parts of an organic induced color-changing agent, 15 - 20 parts of a composite functional additive, and 50 - 150 parts of potassium hydroxide with a purity of 85%.

[0039] As a preferred embodiment, the particle size of the gas-phase nano-silica particles is 60nm - 80nm, and the specific surface area is between 40 and 60m 2 / g.

[0040] The present invention uses nano-silica particles as the main raw material of the fireproof coating material. The particle size of the gas-phase nano-silica particles is 30nm - 120nm, and the specific surface area is between 30 and 80m 2 / g. The particle size of the silica particle aggregates is 200nm - 12000nm, and the particle size distribution is a multi-peak wide distribution. The present invention has the characteristics of small viscosity and low reaction rate at room temperature (20°C), can be used to pour thinner and larger-sized outdoor heat-insulating thermochromic composite fireproof glass. The thermochromic response temperature is in the range of 50°C - 80°C, and at the same time, the low-temperature use temperature can reach -55°C ± 1°C, and the ultraviolet radiation resistance time exceeds 2000 hours.

[0041] The reasons for the thermochromic, low-temperature resistance, and ultraviolet radiation resistance properties of the K2O·nSiO2-based heat-insulating composite fireproof glass are as follows:

[0042] 1. NH4 generated by the hydrolysis of the organic-induced color-changing agent + can combine with the silanol groups in the K2O·nSiO2-based fireproof material to form a reversible reaction, thereby realizing the thermochromic behavior;

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

[0044] 3. The "fiber"-shaped laminated structure, as Figure 6 shown, increases the strength of the fireproof layer material and the ability to resist ultraviolet radiation;

[0045] 4. The free water in the fireproof layer material is firmly locked by the polyols generated by the hydrolysis of the organic-induced color-changing agent, preventing the formation of large-sized and continuous ice crystal phases by free water under low-temperature environments, ensuring the transparency of the composite fireproof glass under extremely cold conditions, and thus improving the low-temperature resistance of the fireproof layer material.

[0046] The invented silica particles and their aggregates 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 organic-induced color-changing agent is at least one of primary amines, secondary amines, and tertiary amines such as methylamine, ethylenediamine, ethanolamine, dimethylethanolamine, and tetrabutylammonium bromide.

[0048] As a preferred embodiment, the composite functional auxiliary agent 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] Organic-induced color-changing agent: Selecting organic amines as the organic-induced color-changing agent, they hydrolyze to generate NH3, which can react with the silanol groups (Si-OH) in the K2O·nSiO2-based fireproof material to form Si-O-NH4. When the temperature rises, NH4 +It can take away the bound water in the K2O·nSiO2-based fireproof material to generate NH4OH, and at the same time convert Si-O-NH4 into silanol (Si-OH), resulting in the whitening of the system; due to the closed system, when the temperature decreases, NH4OH reacts with silanol (Si-OH) again to generate bound water and Si-O-NH4, making the system recover transparency and realizing a thermally induced reversible cycle. The organic induced color-changing agent used in the embodiments of the present invention is selected from at least one of primary amines, secondary amines, and tertiary amines such as methylamine, ethylenediamine, ethanolamine, dimethylethanolamine, and tetrabutylammonium bromide. These organic induced color-changing agents can all hydrolyze in the K2O·nSiO2-based fireproof material to generate alcohol substances and NH3, and under the action of temperature, realize the desorption and generation of bound water, thereby realizing a thermally induced reversible cycle.

[0051] Composite functional agent: Select low-molecular-weight polyols as the composite functional agent, which has the function of a surfactant to a certain extent, and itself has a certain defoaming effect. The hydroxyl groups it contains can also convert the free water in the system into bound water, playing an antifreeze effect. At high temperatures, the fireproof glue layer foams to generate pores, and the composite functional auxiliary agent carbonizes to form long-chain carbonized substances, which are deposited in the pores. The long-chain carbonized substances can absorb a large amount of heat, thereby enhancing the fireproof performance of the glass. The composite functional auxiliary agents used in the embodiments of the present invention are selected from at least two of ethylene glycol, glycerol, and pentaerythritol. These composite functional auxiliary agents can all form long-chain carbonized substances at high temperatures, and the long-chain carbonized substances can absorb a large amount of heat, thereby enhancing the fireproof performance of the glass. In addition, the alcohol substances generated by the hydrolysis of the organic induced color-changing agent used in the embodiments of the present invention also have an antifreeze effect, and can also carbonize at high temperatures to form long-chain carbonized substances, absorbing a large amount of heat and enhancing the fireproof performance of the glass.

[0052] Silica particles and their aggregates: The silica particles and their aggregates are mixed with deionized water to form a solution of silica particles and their aggregates. After the fireproof layer material containing this solution contacts the glass, it will corrode the glass surface to form a diffusion layer with a certain thickness, improving the adhesion between the fireproof glue layer and the glass; when the glass is heated and cracks occur, the cracks will not expand, thus not causing the fragmentation of the whole glass, greatly improving the strength of the fireproof glass; at the same time, the pre-reaction solution of the fireproof layer material has the characteristic of shear thinning.

[0053] The silica particles and their aggregates used in the embodiments of the present invention are multi-peak wide-distribution particles, and their particle size is 200nm to 12000nm. Research has found that: relying on the principle of particle size grading design, the prepared SiO2 dispersion liquid with wide distribution, high solid content, and low viscosity also has the characteristic of shear thinning. Through the optimization of other additives, the addition of other additives does not affect the shear thinning characteristic of the system. Therefore, the pre-reaction solution of the prepared fireproof layer material also has the characteristic of shear thinning.

[0054] Since the silica particles and their aggregates are wide-distribution nanoparticles with the characteristics of low viscosity and low reaction rate at room temperature (20 °C), they can be used to pour thinner and larger-sized outdoor heat-insulating thermochromic composite fireproof glass. Its thermochromic response temperature ranges from 50 °C to 80 °C, the low-temperature service temperature can reach -55 °C ± 1 °C, and the ultraviolet radiation resistance time exceeds 2000 hours. Its results and action mechanism are different from those of the core-shell structure SiO2 dispersion liquid. For example, Figure 4 As shown, it is the relationship diagram of the viscosity and shear rate of the nano-SiO2 particle dispersion liquid (55wt%) of the present invention. Compared with the core-shell structure SiO2 dispersion liquid, by screening the specific surface area, hydroxyl content, and particle size of the silica particles, the influence on the system viscosity is close to that of the core-shell structure SiO2 dispersion liquid, making the process production simpler and more convenient. At the same time, as the shear rate increases, those small-sized particles about 200 nm to 400 nm, which are aggregated by dozens of SiO2 particles, are equivalent to the lubricant in the gear; while those particles about 1500 nm to 2000 nm, which are aggregated by hundreds of SiO2 particles, are equivalent to the sliding beads in the gear and are filled between the large-sized particles about 10 to 12 microns, which are aggregated by thousands of SiO2 particles. Although the shear thinning effect is not as good as that of the core-shell structure particles, the initial viscosity is much smaller than the latter. By Figure 4 Fitting the relationship between the system viscosity μ and the rotational speed V can satisfy the following formula:

[0055] μ = 89.86 + 1.17e (-V / 37.82)

[0056] The above-mentioned silica particle aggregates can reach a stable state by relying on the steric hindrance effect of the composite functional additives adsorbed on the surface of the aggregates, the electrostatic repulsion force on the surface of the aggregates caused by high-speed stirring, and the capillary force between the particles inside the aggregates. It should be emphasized that in the fireproof layer material of the present invention, the high-solid-content silica dispersion liquid itself has the properties of low-temperature resistance and ultraviolet radiation resistance, and the composite functional additives strengthen the low-temperature resistance while providing the steric hindrance effect.

[0057] The reasons for the thermochromic, low-temperature resistant, and ultraviolet radiation resistant properties of the fireproof layer material are as follows:

[0058] 1. NH4 generated by the hydrolysis of the organic-induced colorant can combine with the silanol groups in the K2O·nSiO2-based fireproof material to form a reversible reaction, thus realizing the thermochromic behavior; + can combine with the silanol groups in the K2O·nSiO2-based fireproof material to form a reversible reaction, thus realizing the thermochromic behavior;

[0059] 2. The solid content of the solution system of the silica aggregates is relatively high (can exceed 55%), and correspondingly, the free water in the fireproof layer material is reduced;

[0060] 3. The "fiber" - shaped laminated structure, as Figure 6 shown, increases the strength of the fire - resistant layer material and its ability to resist ultraviolet radiation;

[0061] 4. The free water in the fire - resistant layer material is firmly locked by the polyol generated after hydrolysis by the organic induced color - changing agent, preventing the formation of large - sized and continuous ice crystal phases by free water in a low - temperature environment, ensuring the transparency of the composite fire - resistant glass under extremely cold conditions, and thus improving the low - temperature resistance of the fire - resistant layer material.

[0062] Among them, when the ambient temperature is lower than 150 °C, the bound water in the K2O·nSiO2 material will not flow out of the Si - O - Si network, resulting in the matrix being in an irreversible state. However, a small amount of NH 4+ makes this thermochromic material have reversible thermochromic properties at a specific temperature (such as 60 °C), which is higher than the initial change temperature (TC). It can be inferred that NH 4+ reduces the energy barrier for the dissociation of bound water from the silicon - based network to form NH4OH. At the same time, when the temperature decreases, the dissociated NH4OH in the closed space is captured by Si - OH in the network and becomes new bound water, so that the K2O·nSiO2 thermochromic fire - resistant glass returns to the transparent state again. Moreover, the organic induced color - changing agent couples with the Si - O - Si network, which can increase the transmittance of the material by 3% - 4%, improve the fire - resistance performance by more than 50%, and enhance the ultraviolet - resistance performance by more than 30%.

[0063] The organic induced color - changing agent will hydrolyze into alcohol and NH 4+ , while endowing the material with thermochromism, the alcohol substances can also improve the low - temperature service performance, so the dosage of the multifunctional additive can be reduced, but the dosage of the organic induced color - changing agent is increased.

[0064] The K2O·nSiO2 - based thermochromic fire - resistant layer material with a "fiber" - shaped laminated structure in the invention is prepared by the following steps:

[0065] (1) Mix the composite functional additive, tetraethyl orthosilicate, ammonia water, and deionized water according to a weight ratio of 1 - 5:0.01 - 5:0.001 - 0.05:50 - 200, stand for aging for 24 - 96 h. After the tetraethyl orthosilicate is alcoholized to form a silicon dioxide seed solution, the particle size of the silicon dioxide particles is 10 nm - 60 nm, and a first mixed solution is prepared;

[0066] (2) Gradually disperse with the aid of gradient predispersion technology. Add 1 - 5 parts by weight of the composite functional additive and 50 - 400 parts by weight of gas-phase nano-silica particles to the first mixed solution in sequence according to 3%, 12%, and 85% of the parts by weight, with a high stirring speed of 500 - 3500 rpm. The predispersion time is 2 min, 10 min, and 45 min respectively each time to obtain a silica graded solution;

[0067] (3) With the aid of semi-continuous blending technology, add 1 - 40 parts by weight of the organic induced color-changing agent, 4 - 15 parts by weight of the composite functional additive, and 5 - 50 parts by weight of deionized water to the silica graded solution in sequence at room temperature (20°C - 25°C). The blending time is 20 - 60 min to obtain a basic solution of the fireproof layer material;

[0068] (4) Add 5 - 10 parts by weight of the composite functional additive and 15 - 200 parts by weight of potassium hydroxide with a purity of 85% to 100 - 700 parts by weight of the basic solution of the fireproof layer material in sequence. Vacuumize at low temperature for 30 minutes and stir evenly to obtain a pre-reaction solution of the fireproof layer material;

[0069] (5) With the aid of a peristaltic pump, layer by layer pour the K2O·nSiO2-based thermochromic pre-reaction solution with a high solid content (SiO2≥55 wt,%) and low viscosity (less than 200 mPa·s) into the cavity of the composite fireproof glass. After sealing the pouring port, horizontally place the glass in a room temperature environment for 2 hours, then place it in an oven at 35°C for constant temperature reaction for 5 hours, raise the temperature of the oven to 40°C for constant temperature reaction for 5 hours, raise the temperature of the oven to 45°C for constant temperature reaction for 5 hours, raise the temperature of the oven to 50°C for constant temperature reaction for 5 hours until the visible light transmittance of the glass no longer changes, to obtain a K2O·nSiO2-based thermochromic fireproof layer material with a "fiber"-shaped laminated structure, and the temperature response range is 50°C - 80°C.

[0070] The particle size of the gas-phase nano-silica particles is 30 nm - 120 nm, and the specific surface area is 30 - 80 m 2 / g. Its aggregates are multi-peak wide-distribution particles, and their particle size is 200 nm - 12000 nm. Further, in the above step (3), the stirring time is 20 - 60 min, preferably 30 min.

[0071] When preparing the fireproof glue for fireproof glass in the embodiments of the present invention, first add the composite functional auxiliary agent, tetraethyl orthosilicate, and ammonia water to deionized water, and let it stand for aging to obtain a first mixed solution; gradually disperse it with the gradient predispersion technology, and add the composite functional auxiliary agent and gas-phase nano-silica particles to the first mixed solution to obtain a silica grading solution; with the semi-continuous blending technology, add the organic induced color-changing agent, composite functional auxiliary agent, and deionized water to the silica grading solution to obtain a basic solution of the fireproof layer material; add the composite functional auxiliary agent and potassium hydroxide with a purity of 85% to the basic solution of the fireproof layer material, and slowly stir under the condition of vacuum pumping. The purpose is to use negative pressure to remove the microbubbles in the system, so as to obtain a pre-reaction solution of the fireproof layer material; use a peristaltic pump to pour the pre-reaction solution of the K2O·nSiO2-based fireproof layer material into the cavity of the composite fireproof glass layer by layer. After sealing the pouring port, place the glass horizontally in a room temperature environment for 2 hours, then place it in an oven at 35°C for constant temperature reaction for 5 hours, raise the temperature of the oven to 40°C for constant temperature reaction for 5 hours, raise the temperature of the oven to 45°C for constant temperature reaction for 5 hours, raise the temperature of the oven to 50°C for constant temperature reaction for 5 hours, until the visible light transmittance of the glass no longer changes, and obtain a K2O·nSiO2-based thermochromic fireproof layer material with a "fiber" - shaped laminated structure, and the temperature response range is 50°C to 80°C.

[0072] Since the basic solution of the fireproof layer material will react when mixed with potassium hydroxide, therefore, before use, the basic solution of the fireproof layer material and potassium hydroxide need to be stored separately. The basic solution of the fireproof layer material can be stored for a long time for use, and the shelf life under sealed and light-proof storage is not less than 180 days; potassium hydroxide can be stored conventionally. When in use, mixing the basic solution of the fireproof layer material and potassium hydroxide on-site can better ensure the performance of the fireproof layer material.

[0073] The fireproof glass provided by the embodiments of the present invention, when encountering a fire, the fireproof layer in the fireproof glass quickly foams and expands to form an adiabatic refractory and heat-insulating foam layer, which absorbs a large amount of heat generated by the fire and has good fireproof performance; using the above-prepared fireproof layer material to form the fireproof layer in the above fireproof glass makes the fireproof glass have the advantages of no microbubbles, high transmittance, and long fireproof time. Preferably, there are at least two fireproof interlayers, one of the interlayers is a hollow layer, and the rest of the interlayers are layers.

[0074] More preferably, the interlayers between two adjacent glasses are both fireproof layers.

[0075] As a preferred embodiment, as Figure 1 shown, a fireproof glass sequentially includes 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. Among them, the first fireproof layer 21 and the second fireproof layer 22 are made of the above fireproof layer material.

[0076] As a preferred embodiment, an anti-reflection layer is provided on the outer surface of at least one outer layer glass of the fireproof glass.

[0077] It should be noted that the glass in the present invention can be glass with an anti-reflection layer. Since the fireproof layer material does not contain plasticizers, the possibility of chemical reaction between the plasticizer and the anti-reflection layer material is avoided. This is because mainly ether substances, and titanium dioxide in the anti-reflection layer has a photocatalytic effect, which will cause the ether substances to undergo a polycondensation reaction with silicon dioxide in the anti-reflection layer, forming corrosion spots that cannot be wiped off.

[0078] As a preferred embodiment, the anti-reflection layer is a SiO2 single-layer film, a TiO2 single-layer film, a SiO2 / TiO2 double-layer film, a TiO2 / SiO2 double-layer film or a SiO2 / TiO2 / SiO2 multi-layer composite film.

[0079] Furthermore, the thickness of the anti-reflection layer is 0.0001 mm - 0.1 mm.

[0080] As a preferred embodiment, as Figure 2 shown, a fireproof glass sequentially includes a first anti-reflection layer 31, 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 and a second anti-reflection layer 32. Among them, the first fireproof layer 21 and the second fireproof layer 22 are made of the above-mentioned fireproof layer material.

[0081] As another preferred embodiment, as Figure 3 shown, a fireproof glass sequentially includes a first anti-reflection layer 31, 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, a fifth glass layer 15 and a second anti-reflection layer 32. Among them, 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 hermetically sealing the four sides of two pieces of glass and sealing their gaps.

[0082] As a preferred embodiment, the thickness of the fireproof layer is 1.5 - 5 mm.

[0083] The present invention can control the thickness of the fireproof layer within the range of 1.5 to 5 mm. On the premise of ensuring the fireproof performance of the fireproof glass, the produced fireproof glass has a relatively thin thickness, reducing the production cost of the glass and expanding the application range of the glass. 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 its expansion layer is about 10 to 15 times that of the original fireproof layer. After encountering fire, the glass on the fire-facing surface will crack first, and then the fireproof glue layer attached thereto will gradually form a heat-insulating layer of about 10 mm to 30 mm; if the thickness of the fireproof glue layer < 1.5 mm, the fireproof glue 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 glue layer > 5 mm, the fireproof glue layer is too thick, which will cause an increase in the overall weight and cost of the fireproof glass. At the same time, since the fireproof glue layer expands layer by layer, the too thick expansion layer will cause the glass to fall off as a whole, instead reducing the fireproof performance.

[0084] The present invention will be further described below in conjunction with specific embodiments, but it is not limited to the present invention.

[0085] All the reagents used in the embodiments of the present invention are commercially available products.

[0086] Example 1

[0087] The thermochromic fireproof layer material in this embodiment is prepared through the following steps:

[0088] (1) Weigh the raw materials of the thermochromic fireproof layer material according to the following weights:

[0089] 250 kg of nano-silica particles with a particle size of 80 nm and a specific surface area of 40 ± 5 m 2 / g, 169.78 kg of deionized water, 20 kg of organic color-changing inducer (ethylenediamine), 15 kg of composite functional auxiliary agent (glycerol / ethylene glycol = 2:1), 1 kg of tetraethyl orthosilicate, 0.01 kg of ammonia water, and 119.49 kg of potassium hydroxide with a purity of 85%; since the particle size of the silica agglomerates is a wide distribution, various particle size sizes of microparticles can exist in the present invention, such as Figure 5 shown, which is the particle size distribution diagram of the SiO2 dispersion liquid of the present invention, presenting a multi-peak state. Similarly, the particle size of the silica agglomerates in the following examples is also a wide distribution;

[0090] (2) Prepare the fireproof layer material from the above raw materials according to the following steps:

[0091] Mix 2.5 kg of composite functional auxiliary agent (glycerol / ethylene glycol = 2:1), 1 kg of tetraethyl orthosilicate, 0.1 k ammonia water, and 150 kg of deionized water, and let it stand for aging for 48 h. After the tetraethyl orthosilicate is alcoholized to form a silica seed solution with a particle size of 30 nm to 120 nm, a first mixed solution is prepared;

[0092] Gradually disperse by means of gradient pre-dispersion technology. Add 250 kg of nano-silica particles with a particle size of 80 nm and a specific surface area of 40 ± 5 m 2 / g into the first mixed solution in sequence according to 3%, 12%, and 85% by weight. The high-stirring speed is 500 - 3500 rpm, and the pre-dispersion time for each time is 2 min, 10 min, and 45 min respectively to obtain a silica grading solution;

[0093] By means of semi-continuous blending technology, add 20 kg of ethylenediamine, 10 kg of composite functional additives (glycerol / ethylene glycol = 2:1), and 19.78 kg of deionized water into the silica grading solution at room temperature (20°C - 25°C), and blend for 30 min to obtain a basic solution for the fireproof layer material;

[0094] Add 2.5 kg of composite functional additives (glycerol / ethylene glycol = 2:1) and 119.49 kg of potassium hydroxide with a purity of 85% to the above-mentioned basic solution for the fireproof layer material in sequence, evacuate under low temperature for 30 minutes, and stir evenly to obtain a pre-reaction solution for the thermochromic fireproof layer material;

[0095] The outdoor heat-insulating thermochromic fireproof glass in this embodiment is the outdoor heat-insulating thermochromic fireproof glass prepared by using the above-mentioned fireproof layer material through the following steps:

[0096] (1) Prepare 5 pieces of glass with a thickness of 3 mm, and two of them are physically tempered glasses; in order to ensure that the fabricated composite fireproof glass has higher strength, it is preferred that the glass located in the middle position is slightly thicker than other layers of glass;

[0097] (2) Prepare the above 2 pieces of physically tempered glasses into glasses with a single-layer silica (SiO2) antireflection layer with a thickness of 100 nm - 0.1 mm, so that the refractive index of the composite fireproof glass in the range of 300 - 2500 nm is about 1.13 - 1.40. The antireflection layer can also be a single-layer titanium dioxide (TiO2) film, or a SiO2 / TiO2 or TiO2 / SiO2 double-layer film, or a SiO2 / TiO2 / SiO2 multi-layer composite film;

[0098] (3) Use a thickness-fixed rubber strip to combine one piece of the physically tempered glass with the antireflection layer as the outermost layer of glass and one piece of non-physically tempered glass to form a cavity with a thickness of 5 mm, and then use the thickness-fixed rubber strip to stack the remaining 2 pieces of non-physically tempered glasses in sequence, with a 5-mm-thick cavity between each piece of glass. Finally, use the thickness-fixed rubber strip to laminate another piece of the physically tempered glass with the antireflection layer and the above multi-layer cavity glass together, and add another 5-mm-thick cavity to ensure that the outer surfaces of the multi-layer cavity glass are all physically tempered glasses, and both antireflection layers face outward;

[0099] (4) With the help of a peristaltic pump, the pre-reaction liquid of the K2O·nSiO2-based fireproof layer material with a high solid content (SiO2≥55wt%) and a low viscosity (less than 200mPa·s) is poured layer by layer into the cavity of the composite fireproof glass (5 glasses and 4 cavities), left to stand for defoaming. After sealing the pouring port, the glass is placed horizontally in a room temperature environment for 2 hours, and then placed in an oven at 35°C for constant temperature reaction for 5 hours. The oven temperature is raised to 40°C for constant temperature reaction for 5 hours, then raised to 45°C for constant temperature reaction for 5 hours, and then raised to 50°C for constant temperature reaction for 5 hours until the visible light transmittance of the glass no longer changes, obtaining a low-temperature type thermochromic composite fireproof glass with a "fiber"-like laminated structure, based on K2O·nSiO2 and with an antireflection layer.

[0100] Example 2

[0101] The thermochromic fireproof layer material in this example is prepared through the following steps:

[0102] (1) Weigh the raw materials of the thermochromic fireproof layer material according to the following weights:

[0103] 250 kg of nano-silica particles with a particle size of 80 nm and a specific surface area of 40±5 m 2 / g, 169.78 kg of deionized water, 20 kg of organic color-changing inducer (ethanolamine), 15 kg of composite functional auxiliary (glycerol / ethylene glycol = 2:1), 1 kg of tetraethyl orthosilicate, 0.01 kg of ammonia water, and 119.49 kg of potassium hydroxide with a purity of 85%;

[0104] (2) Prepare the thermochromic fireproof layer material from the above raw materials according to the same preparation method as in Example 1.

[0105] The preparation method of the outdoor heat-insulating type thermochromic fireproof glass in this example is the same as that of the outdoor heat-insulating type thermochromic fireproof glass in Example 1, except for the different composition of the thermochromic fireproof layer material.

[0106] Example 3

[0107] The fireproof layer material in this example is prepared through the following steps:

[0108] The thermochromic fireproof layer material in this example is prepared through the following steps:

[0109] (1) Weigh the raw materials of the thermochromic fireproof layer material according to the following weights:

[0110] 250 kg of nano-silica particles with a particle size of 80 nm and a specific surface area of 40±5 m 2250 kg of nano-silica particles with a particle size of 80 nm and a specific surface area of 40 ± 5 m² / g, 197.94 kg of deionized water, 20 kg of organic color-changing agent (ethylenediamine), 15 kg of composite functional additive (glycerol / ethylene glycol = 2:1), 1 kg of tetraethyl orthosilicate, 0.01 kg of ammonia water, and 119.49 kg of potassium hydroxide with a purity of 85%;

[0111] (2) Prepare the thermochromic fireproof layer material from the above raw materials according to the same preparation method as in Example 1.

[0112] The preparation method of the outdoor heat-insulating thermochromic fireproof glass in this example is the same as that of the outdoor heat-insulating thermochromic fireproof glass in Example 1, except that the composition of the thermochromic fireproof layer material is different.

[0113] Example 4

[0114] The fireproof layer material in this example is prepared through the following steps:

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

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

[0117] 250 kg of nano-silica particles with a particle size of 80 nm and a specific surface area of 40 ± 5 m 2 / g, 216.54 kg of deionized water, 20 kg of organic color-changing agent (ethylenediamine), 15 kg of composite functional additive (glycerol / ethylene glycol = 2:1), 1 kg of tetraethyl orthosilicate, 0.01 kg of ammonia water, and 119.49 kg of potassium hydroxide with a purity of 85%;

[0118] (2) Prepare the thermochromic fireproof layer material from the above raw materials according to the same preparation method as in Example 1.

[0119] The preparation method of the outdoor heat-insulating thermochromic fireproof glass in this example is the same as that of the outdoor heat-insulating thermochromic fireproof glass in Example 1, except that the composition of the thermochromic fireproof layer material is different.

[0120] Example 5

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

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

[0123] 250 kg of nano-silica particles with a particle size of 80 nm and a specific surface area of 40 ± 5 m 2169.78 kg of deionized water, 17.5 kg of organic color-changing inducer (ethylenediamine), 15 kg of composite functional additive (glycerol / ethylene glycol = 2:1), 1 kg of tetraethyl orthosilicate, 0.01 kg of ammonia water, and 119.49 kg of potassium hydroxide with a purity of 85%;

[0124] (2) Prepare the thermochromic fireproof layer material from the above raw materials according to the same preparation method as in Example 1.

[0125] The preparation method of the outdoor heat-insulating thermochromic fireproof glass in this example is the same as that in Example 1, except for the different composition of the thermochromic fireproof layer material.

[0126] Example 6

[0127] The thermochromic fireproof layer material in this example is prepared through the following steps:

[0128] (1) Weigh the raw materials of the thermochromic fireproof layer material according to the following weights:

[0129] 250 kg of nano-silica particles with a particle size of 80 nm and a specific surface area of 40 ± 5 m 2 / g, 169.78 kg of deionized water, 22.5 kg of organic color-changing inducer (ethylenediamine), 15 kg of composite functional additive (glycerol / ethylene glycol = 2:1), 1 kg of tetraethyl orthosilicate, 0.01 kg of ammonia water, and 119.49 kg of potassium hydroxide with a purity of 85%;

[0130] (2) Prepare the thermochromic fireproof layer material from the above raw materials according to the same preparation method as in Example 1.

[0131] The preparation method of the outdoor heat-insulating thermochromic fireproof glass in this example is the same as that in Example 1, except for the different composition of the thermochromic fireproof layer material.

[0132] Example 7

[0133] The fireproof layer material in this example is prepared through the following steps:

[0134] (1) Weigh the same raw materials of the fireproof layer material as in Example 1:

[0135] (2) Prepare the fireproof layer material from the above raw materials according to the same preparation method as in Example 1.

[0136] The outdoor heat-insulating thermochromic fireproof glass in this example is the outdoor heat-insulating thermochromic fireproof glass prepared by the following steps using the above fireproof layer material:

[0137] (1) Prepare 4 pieces of glass with a thickness of 3 mm, two of which are physically tempered glass; in order to ensure that the fabricated composite fireproof glass has a relatively high strength, it is preferred that the glass located in the middle position is slightly thicker than the other layers of glass.

[0138] (2) Prepare the above-mentioned 2 pieces of physically tempered glass into glass with a single-layer silica (SiO2) antireflection layer with a thickness of 100 nm - 0.1 mm, so that the refractive index of the composite fireproof glass in the range of 300 - 2500 nm is about 1.13 - 1.40. The antireflection layer can also be a single-layer titanium dioxide (TiO2) film, or a SiO2 / TiO2 or TiO2 / SiO2 double-layer film, or a SiO2 / TiO2 / SiO2 multi-layer composite film.

[0139] (3) Use a thickness-fixed rubber strip to combine the above-mentioned 1 piece of physically tempered glass with an antireflection layer as the outermost layer of glass and 1 piece of non-physically tempered glass to form a cavity with a thickness of 5 mm. Then, use a thickness-fixed rubber strip to stack the remaining 1 piece of non-physically tempered glass in sequence. There is a cavity with a thickness of 5 mm between each piece of glass. Finally, use a thickness-fixed rubber strip to laminate another piece of physically tempered glass with an antireflection layer together with the above-mentioned multi-layer cavity glass, and add another cavity with a thickness of 5 mm to ensure that the outer surfaces of the multi-layer cavity glass are all physically tempered glass, and both antireflection layers face outwards.

[0140] (4) With the help of a peristaltic pump, gradually pour the pre-reaction liquid of the K2O·nSiO2-based thermochromic fireproof layer material with a high solid content (≥55 wt,%) and low viscosity (less than 200 mPa·s) into the cavity of the composite fireproof glass (4 glasses and 3 cavities). Let it stand to defoam. After sealing the pouring port, place the glass horizontally in a room temperature environment for 2 hours, and then place it in an oven at 35°C for constant temperature reaction for 5 hours. Raise the temperature of the oven to 40°C for constant temperature reaction for 5 hours, raise the temperature of the oven to 45°C for constant temperature reaction for 5 hours, and raise the temperature of the oven to 50°C for constant temperature reaction for 5 hours until the visible light transmittance of the glass no longer changes, obtaining a K2O·nSiO2-based thermochromic composite fireproof glass with a "fiber" - shaped laminated structure and an antireflection layer.

[0141] Example 8

[0142] The fireproof layer material in this example is prepared through the following steps:

[0143] (1) Weigh the same raw materials for the fireproof layer material as in Example 1:

[0144] (2) Prepare the fireproof layer material from the above-mentioned raw materials according to the same preparation method as in Example 1.

[0145] The outdoor heat-insulating thermochromic fireproof glass in this embodiment is an outdoor heat-insulating thermochromic fireproof glass prepared from the above fireproof layer material through the following steps:

[0146] (1) Prepare 3 pieces of 3-mm-thick glass, two of which are physically tempered glasses; to ensure that the manufactured composite fireproof glass has high strength, it is preferred that the glass located in the middle position is slightly thicker than the other layers of glass;

[0147] (2) Prepare the above 2 pieces of physically tempered glasses into glasses with a single-layer silicon dioxide (SiO2) antireflection layer with a thickness of 100 nm - 0.1 mm, so that the refractive index of the composite fireproof glass in the range of 300 - 2500 nm is about 1.13 - 1.40. The antireflection layer can also be a single-layer titanium dioxide (TiO2) film, or a SiO2 / TiO2 or TiO2 / SiO2 double-layer film, or a SiO2 / TiO2 / SiO2 multi-layer composite film;

[0148] (3) Use a thickness-fixed rubber strip to combine the above 1 piece of physically tempered glass with an antireflection layer as the outermost layer of glass and 1 piece of non-physically tempered glass to form a cavity with a thickness of 5 mm, and then use a thickness-fixed rubber strip to laminate another piece of physically tempered glass with an antireflection layer with the above multi-layer cavity glass, adding another 5-mm-thick cavity to ensure that the outer surfaces of the multi-layer cavity glass are all physically tempered glasses, and both antireflection layers face outward;

[0149] (4) With the aid of a peristaltic pump, gradually pour the pre-reaction liquid of the K2O·nSiO2-based thermochromic fireproof layer material with a high solid content (≥55 wt,%) and low viscosity (less than 200 mPa·s) into the cavity of the composite fireproof glass (3 glasses and 2 cavities), let it stand for defoaming, after sealing the pouring port, place the glass horizontally in a room-temperature environment for 2 hours, then place it in an oven at 35°C for constant-temperature reaction for 5 hours, raise the temperature of the oven to 40°C for constant-temperature reaction for 5 hours, raise the temperature of the oven to 45°C for constant-temperature reaction for 5 hours, raise the temperature of the oven to 50°C for constant-temperature reaction for 5 hours until the visible light transmittance of the glass no longer changes, obtaining a K2O·nSiO2-based, antireflection-layered thermochromic composite fireproof glass with a "fiber"-shaped laminated structure.

[0150] Comparative Example 1

[0151] This comparative example provides a fireproof layer material, the raw material of which is pure potassium water glass with a modulus of 3.4.

[0152] The preparation method of the fireproof glass in this comparative example is the same as that of the outdoor heat-insulating fireproof glass in Example 1, except for the different composition of the fireproof layer material.

[0153] Comparative Example 2

[0154] The fireproof layer material in this comparative example is prepared through the following steps:

[0155] (1) Weigh the raw materials of the thermochromic fireproof layer material according to the following weights:

[0156] 250 kg of nano-silica particles with a particle size of 80 nm and a specific surface area of 40 ± 5 m 2 / g, 169.78 kg of deionized water, 15 kg of a composite functional additive (glycerol / ethylene glycol = 2:1), 1 kg of tetraethyl orthosilicate, 0.01 kg of ammonia water, and 119.49 kg of potassium hydroxide with a purity of 85%;

[0157] (2) Prepare the thermochromic fireproof layer material from the above raw materials according to the same preparation method as in Example 1.

[0158] Fire resistance performance experiments were carried out on the fireproof glass prepared from the fireproof layer materials provided in Examples 1-8 and Comparative Examples 1-2 according to the fire resistance test method for glazed elements GB / T12513-2006 to obtain the fireproof time of the fireproof glass. 4 parallel specimens were taken for the experiment, and the average value of their data was taken as the experimental result; the transmittance of each fireproof glass was obtained through glass transmittance detection; and the apparent quality of each fireproof glass was obtained through visual observation. The performance parameters of the fireproof glass prepared in the examples and comparative examples of the present invention are shown in Table 1.

[0159] Table 1 Performance parameter table of fireproof glass

[0160]

[0161] *ΔT=(T t0 -T tn ) / T t0

[0162] T tn is the transmittance after 3000 h of ultraviolet irradiation, and T t0 is the initial transmittance.

[0163] As can be seen from Table 1, the outdoor heat-insulating thermochromic fireproof glass in the present invention has no microbubbles, while there are a large number of microbubbles inside the fireproof glass prepared in the comparative example; the fireproof time of the outdoor heat-insulating thermochromic fireproof glass without microbubbles in the present invention is 1.5-2.5 times that of the fireproof glass in Comparative Example 1, and the transmittance and the time of resistance to ultraviolet irradiation are also significantly higher than those of the fireproof glass in Comparative Example 1; the fireproof time of the outdoor heat-insulating thermochromic fireproof glass without microbubbles in the present invention is increased by 20% compared with that of the fireproof glass in Comparative Example 2 (without adding an organic color-changing inducer), and the transmittance and the time of resistance to ultraviolet irradiation are also significantly higher than those of the fireproof glass in Comparative Example 2. The above shows that using potassium silicate or pure potassium silicate as the fireproof layer of the fireproof glass is likely to cause a large number of microbubbles in the glass. The existence of a large number of microbubbles reduces the hardness and fireproof heat resistance of the fireproof glass, and seriously affects the light transmittance and the apparent quality of the fireproof glass. By improving the formula of the fireproof layer, a synergistic effect is generated among the components of the fireproof layer, eliminating the bubbles in the fireproof glass interlayer, so that the composite fireproof glass has better fireproof heat resistance. At the same time, the K2O·nSiO2-based thermochromic fireproof layer material with a "fiber" - like laminated structure improves the low-temperature resistance of the fireproof glass, and it can be used in a low-temperature (-55°C) outdoor environment. The fireproof glass prepared in the examples of the present invention has the advantages of no microbubbles, good adhesion, high transmittance, long fireproof time, low-temperature resistance and resistance to ultraviolet irradiation.

[0164] As can be seen from the data recorded in Table 1, there are no microbubbles in the outdoor heat-insulating fireproof glass in 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 beneficial to the escape of bubbles, so as to facilitate the discharge of the gas in the fireproof layer when preparing the fireproof layer, saving working hours.

[0165] By comparing Examples 1-8 with Comparative Examples 1-2, it can be seen that when using the same fireproof layer material and the number of glass layers gradually decreases, as the number of glass sheets decreases, the transmittance becomes better, the low-temperature resistance remains unchanged, and the fireproof time gradually becomes smaller.

[0166] The hardness of the composite heat-insulating fireproof glass with thermochromism, low temperature resistance and resistance to ultraviolet irradiation provided by the examples of the present invention can reach above 4H, and some even reach 6H.

[0167] In the above examples, the descriptions of each example have their own emphases. For the parts not described in detail in a certain example, reference can be made to the relevant descriptions of other examples.

[0168] The above is only the preferred embodiments of the present invention, and does not impose any form of limitation on the present invention. Any simple modification, equivalent change and modification made to the above embodiments according to the technical essence of the present invention still fall within the scope of the technical solution of the present invention.

Claims

1. An outdoor heat-insulating and fireproof glass, wherein the heat-insulating and fireproof glass is formed by laminating at least two glass sheets, an interlayer is provided between two adjacent glass sheets, and at least one of the interlayers is a thermochromic fireproof layer made of a thermochromic fireproof layer material; an antireflection layer is provided on the outer surface of at least one outer glass sheet of the fireproof glass, and it is characterized in that, The thermochromic fireproof layer is a thermochromic fireproof layer structure with a "fiber"-shaped laminated structure, and the color change temperature response range of the thermochromic fireproof layer structure is 50°C to 80°C; the thermochromic fireproof layer structure is prepared through the following steps: Step 1) Prepare a pre-reaction solution of the fireproof layer material; the pre-reaction solution of the fireproof layer material is a K2O·nSiO2-based thermochromic hybrid material, and the K2O·nSiO2-based thermochromic hybrid material is prepared by using in-situ gradient temperature control reaction technology from gas-phase nano-silica particles and their aggregates and organic color-changing agents; Step 2) Pour the prepared pre-reaction solution of the fireproof layer material with a solid content of SiO2≥55wt% and a viscosity less than 200mPa·s layer by layer into the cavity of the composite fireproof glass. After sealing the pouring port, place the glass horizontally in a room temperature environment for 2 hours, then place it in an oven at 35°C for constant temperature reaction for 5 hours, raise the temperature of the oven to 40°C for constant temperature reaction for 5 hours, raise the temperature of the oven to 45°C for constant temperature reaction for 5 hours, raise the temperature of the oven to 50°C for constant temperature reaction for 5 hours until the visible light transmittance of the glass no longer changes, and obtain a thermochromic fireproof layer structure with a "fiber"-shaped laminated structure.

2. The heat-insulating fireproof glass according to claim 1, characterized in that, The pre-reaction solution of the fireproof layer material is prepared through the following steps: Step 1-1) Mix composite functional additives, tetraethyl orthosilicate, ammonia water, and deionized water according to a weight ratio of 1 to 5: 0.01 to 5: 0.001 to 0.05: 50 to 200, and let it stand and age for 24 to 96 hours. After tetraethyl orthosilicate is alcoholized to form a silica seed solution with a particle size of 10nm to 60nm of silica particles, a first mixed solution is obtained; among them, the composite functional additives are at least two of ethylene glycol, glycerol, and pentaerythritol; Step 1-2) With the help of gradient pre-dispersion technology, gradually disperse 1 to 5 parts by weight of composite functional additives and 50 to 400 parts by weight of gas-phase nano-silica particles into the first mixed solution in sequence according to 3%, 12%, and 85% by weight. The stirring speed is 500 to 3500rpm, and the pre-dispersion time each time is 2min, 10min, and 45min in sequence to obtain a silica grading solution; Step 1-3) With the help of semi-continuous blending technology, add 1 to 40 parts by weight of organic color-changing agent, 4 to 15 parts by weight of composite functional additives, and 5 to 50 parts by weight of deionized water to the silica grading solution in sequence at room temperature, and the blending time is 20 to 60min to obtain a basic solution of the fireproof layer material; Step 1-4) Add 5 to 10 parts by weight of composite functional additives and 15 to 200 parts by weight of potassium hydroxide with a purity of 85% to 100 to 700 parts by weight of the basic solution of the fireproof layer material in sequence, and perform low-temperature vacuum pumping 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 particle size of the gas-phase nano-silica particles is 30 nm to 120 nm, and the specific surface area is 30 to 80 m 2 / g.

4. The heat-insulating fireproof glass according to claim 1, wherein The organic color-changing agent is at least one of primary amine, secondary amine, and tertiary amine.

5. The heat-insulating fireproof glass according to claim 1, characterized in that, The modulus of the pre-reaction solution of the fireproof layer material is 4.0 to 5.

0.

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

7. A thermochromic fireproof layer structure, characterized in that, The thermochromic fireproof layer structure is the thermochromic fireproof layer structure described in any one of claims 1 to 6.

8. Fireproof layer material, characterized in that, The fireproof layer material is a fireproof layer material made from a pre-reaction solution of the fireproof layer material described in any one of claims 2 to 6.

9. A method for preparing a fireproof layer structure using the fireproof layer material according to claim 8, characterized in that, It includes the following steps: Step 1), preparing a pre-reaction solution of the fireproof layer material. The specific steps are as follows: Step 1-1), mixing a composite functional auxiliary agent, tetraethyl orthosilicate, ammonia water, and deionized water according to a weight ratio of 1 to 5: 0.01 to 5: 0.001 to 0.05: 50 to 200, standing for aging for 24 to 96 hours. After the tetraethyl orthosilicate is alcoholized to generate a silicon dioxide seed solution, the particle size of the silicon dioxide particles is 10 nm to 60 nm, and a first mixed solution is prepared; among them, the composite functional auxiliary agent is at least two of ethylene glycol, glycerol, and pentaerythritol. Step 1-2), gradually dispersing by means of gradient pre-dispersion technology. Add 1 to 5 parts by weight of the composite functional auxiliary agent and 50 to 400 parts by weight of gas-phase nano-silicon dioxide particles to the first mixed solution in sequence according to 3%, 12%, and 85% of the parts by weight respectively. The stirring speed is 500 to 3500 rpm, and the pre-dispersion time for each time is 2 minutes, 10 minutes, and 45 minutes respectively to obtain a silicon dioxide grading solution. Step 1-3), by means of semi-continuous blending technology, add 1 to 40 parts by weight of an organic induced color-changing agent, 4 to 15 parts by weight of the composite functional auxiliary agent, and 5 to 50 parts by weight of deionized water to the silicon dioxide grading solution in sequence at room temperature. The blending time is 20 to 60 minutes to obtain a basic solution of the fireproof layer material. Step 1-4), add 5 to 10 parts by weight of the composite functional auxiliary agent and 15 to 200 parts by weight of potassium hydroxide with a purity of 85% to 100 to 700 parts by weight of the basic solution of the fireproof layer material in sequence, evacuate at low temperature for 30 minutes, and stir evenly to obtain a pre-reaction solution of the fireproof layer material. Step 2), layer by layer pour the prepared pre-reaction solution of the fireproof layer material with a solid content of SiO2≥55wt% and a viscosity less than 200 mPa·s into the cavity of the composite fireproof glass. After sealing the pouring port, place the glass horizontally in a room temperature environment for 2 hours, then place it in an oven at 35°C for constant temperature reaction for 5 hours, raise the temperature of the oven to 40°C for constant temperature reaction for 5 hours, raise the temperature of the oven to 45°C for constant temperature reaction for 5 hours, raise the temperature of the oven to 50°C for constant temperature reaction for 5 hours until the visible light transmittance of the glass no longer changes, and obtain a thermochromic fireproof layer structure with a "fiber"-like laminated structure.

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