Borosilicate 4.0 fireproof glass and preparation method thereof

Abstract

The application discloses borosilicate 4.0 fireproof glass and a preparation method thereof, and belongs to the field of high-borosilicate fireproof glass. The borosilicate 4.0 fireproof glass comprises a first glass layer and a second glass layer; a modified silica composite fireproof liquid is filled between the first glass layer and the second glass layer; the first glass layer and the second glass layer are borosilicate 4.0 glass; and the modified silica composite fireproof liquid comprises the following components in parts by weight: modified silica 10-20 parts, silica 5-8 parts, modified zinc borate 5-10 parts, water glass 3-5 parts, potassium silicate 8-12 parts, modified zirconium phosphate 1-3 parts and other additives 1-2 parts. The borosilicate 4.0 fireproof glass has high fire resistance, good weather resistance and good material stability of the fireproof liquid.

Description

Technical Field

[0001] This invention relates to the field of high borosilicate fireproof glass, and particularly to a borosilicate 4.0 fireproof glass and its preparation method. Background Technology

[0002] Fire-resistant glass is a core functional material in the field of building fire protection. It is mainly used in key parts such as building curtain walls, fire-resistant partitions, and fire-resistant doors and windows. In the event of a fire, it can block the spread of high-temperature flames and isolate toxic fumes, while maintaining structural integrity and light transmission, thus buying time for personnel evacuation and fire rescue. According to national standards, fire-resistant glass can be divided into three categories based on its fire resistance performance. Among them, Class A borosilicate fire-resistant glass meets both fire resistance integrity and heat insulation requirements, and can control the temperature of the unexposed surface. It is the first choice for key parts such as fire-resistant partitions and curtain walls of evacuation routes.

[0003] Class A borosilicate fire-resistant glass mainly comes in monolithic and composite types. Monolithic glass relies on the glass's own high-temperature resistance but suffers from insufficient thermal insulation and high cost. Composite glass consists of a glass layer and an intermediate fire-resistant layer. Currently, the technological bottlenecks of Class A borosilicate composite fire-resistant glass lie in the stability of the fire-retardant liquid, the interfacial compatibility between the glass and the fire-retardant liquid, and long-term weather resistance. Domestic mainstream processes often use low-modulus potassium silicate water glass as the fire-retardant liquid, but its poor chemical stability leads to decreased light transmittance during use, and the reaction of potassium ions with air to form salts causes glass fogging. It also easily traps air, forming bubbles, and after curing, heat and vibration can cause resin leakage, affecting appearance and fire-retardant performance. The porous high-temperature foaming layer also results in insufficient flame-retardant durability. Furthermore, borosilicate glass and fire-retardant liquid have compatibility issues; acidic catalysts or impurities can corrode the glass surface, and the two are only physically bonded, making them prone to peeling under temperature changes and vibrations.

[0004] Therefore, there is an urgent need to develop a borosilicate fireproof glass that has strong chemical stability, good heat resistance stability when exposed to high temperatures for a long time, a high fire resistance rating, and good compatibility with fire retardant liquids. Summary of the Invention

[0005] The purpose of this invention is to provide a borosilicate 4.0 fireproof glass to solve the problems of corrosion of glass materials by inorganic fire retardant liquid, poor weather resistance, poor material stability, and defects such as bubbles and glue flow that occur in the use of existing composite borosilicate fireproof glass.

[0006] The present invention also aims to provide a method for preparing borosilicate 4.0 fireproof glass.

[0007] In a first aspect, the present invention provides a borosilicate 4.0 fireproof glass, comprising a first glass layer and a second glass layer;

[0008] A modified silica composite fire retardant liquid is filled between the first glass layer and the second glass layer;

[0009] The first and second glass layers are borosilicate 4.0 glass;

[0010] The modified silica composite fire retardant liquid comprises the following components in parts by weight:

[0011] 10-20 parts modified silica, 5-8 parts silica, 5-10 parts modified zinc borate, 3-5 parts water glass, 8-12 parts potassium silicate, 1-3 parts modified zirconium phosphate, and 1-2 parts other additives.

[0012] By employing the above technical solution and filling the space between two layers of borosilicate 4.0 glass with modified silica composite fire retardant liquid, not only can the fire resistance of borosilicate 4.0 glass be improved, but the problems of poor material stability of fire retardant liquid, bubbles, glue flow and weak weather resistance during use can also be solved.

[0013] Specifically, by modifying silica, not only can the aggregation caused by its surface hydroxyl groups be broken, ensuring uniform dispersion in the fire retardant liquid, but it can also form a cross-linking density with potassium silicate and water glass in the fire retardant liquid. In addition, it can form BOB bonds with BO4 on the surface of borosilicate 4.0 glass, improving the interfacial bonding force. Furthermore, unmodified silica is added to the composite fire retardant liquid, which can form a dense gel with a high expansion ratio with water glass, avoiding the looseness of the high-temperature foaming layer.

[0014] Zinc borate, as a highly efficient flame retardant, releases water of crystallization at high temperatures and forms a covering glassy protective layer. By modifying zinc borate, for example by encapsulating it with low-melting-point glass powder, a "core-shell structure" can be constructed. This structure delays the decomposition of zinc borate, allowing it to function more effectively in the critical temperature zones during the early stages of a fire, and better synchronizes with the system's melting process, thereby optimizing the foaming process and the insulation layer structure.

[0015] Zirconium phosphate possesses a unique layered structure that effectively absorbs ultraviolet light, enhancing the system's weather resistance. Through intercalation modification, using long-chain silane coupling agents to widen its interlayer spacing, not only can its compatibility and dispersibility in the inorganic matrix be greatly improved, preventing a decrease in light transmittance due to agglomeration, but the active functional groups at the intercalation agent's ends, such as amino or epoxy groups, can also participate in the overall cross-linking network of the fire retardant, transforming zirconium phosphate from a physical filler into a chemical cross-linking point, further enhancing the structural integrity and aging resistance of the cured colloid.

[0016] The addition of other additives can synergistically optimize the process performance and final properties of the fire retardant liquid. Curing agents can accelerate the formation of the silica network; leveling agents can improve the spreadability of the liquid and ensure uniform interlayer thickness; defoamers can effectively suppress air bubbles introduced during mixing and filling, better ensuring the light transmittance and appearance quality of the fire-retardant glass.

[0017] Preferably, the method for preparing modified silica includes the following steps:

[0018] Silica is dispersed in an aqueous ethanol solution to prepare a silica suspension; an epoxy silane coupling agent is added, and the mixture is stirred for 1-3 hours. Boric acid is then added, and the mixture is stirred for 1-2 hours. The solution is then filtered and dried to obtain the final product.

[0019] Preferably, the mass ratio of silica, aqueous ethanol solution, epoxy silane coupling agent and boric acid is 1: (1-3): (0.01-0.08): (0.05-0.5).

[0020] Preferably, the epoxy silane coupling agents include KH550 and KH560.

[0021] By employing the above technical solution, silica is first treated with an epoxy-based silane coupling agent to graft active epoxy groups onto its surface, improving the dispersibility of silica particles and providing sites for subsequent reactions. Then, boric acid is added. The B-OH groups of boric acid undergo a ring-opening reaction with the epoxy groups. On one hand, the boric acid molecules form a weak pre-crosslinked network between multiple silica particles, enhancing the stability of the fire retardant under normal conditions. On the other hand, boron is firmly introduced into the silica surface through chemical bonding, enabling it to more efficiently catalyze ceramic formation and lower the melting temperature during a fire. Silica modified in this way can improve its normal performance by forming an interface between the boron groups and the glassy structure of borosilicate 4.0, and it can also improve the compressive strength of the fire retardant after curing by crosslinking the epoxy groups with potassium silicate.

[0022] Preferably, the method for preparing modified zirconium phosphate includes the following steps:

[0023] Zirconium phosphate is dispersed in a deionized aqueous solution, a long-chain silane coupling agent is added, and the mixture is ultrasonically treated for 1-2 hours. After centrifugation, washing, and drying, the product is obtained.

[0024] Preferably, the mass ratio of zirconium phosphate to long-chain aminosilane is 1:(0.3-1.5); the long-chain aminosilane includes N-β-aminoethyl-γ-aminopropyltrimethoxysilane and γ-(2,3-epoxypropoxy)propyltrimethoxysilane.

[0025] By adopting the above technical solutions, zirconium phosphate possesses the ability to absorb ultraviolet light, which can alleviate the hydrolytic aging of potassium silicate in fire retardant liquids. Through intercalation modification, long-chain silane molecules, such as diaminosilanes or epoxysilanes, are inserted into the interlayer space. This expands the interlayer spacing and effectively prevents the recombination of zirconium phosphate nanosheets using the steric hindrance effect of long-chain alkyl groups, achieving long-term stable dispersion in the fire retardant liquid and avoiding decreased transparency and uneven performance caused by agglomeration. Furthermore, the active functional groups (amino or epoxy) at the ends of the intercalating agent can chemically react with the inorganic silicon-oxygen network or other components during the curing process of the fire retardant liquid, anchoring the zirconium phosphate particles within the three-dimensional network. This significantly enhances interfacial bonding and inhibits interfacial delamination caused by thermal cycling, thereby comprehensively improving the durability of the composite glass.

[0026] Preferably, the preparation method of the modified silica composite fire retardant liquid includes the following steps:

[0027] S1. Disperse low-melting-point glass powder and zinc borate in toluene, add Tween 80 to form an emulsion, and remove the toluene to obtain modified zinc borate;

[0028] S2. Add modified silica to the solvent, then add modified zinc borate, water glass, potassium silicate, modified zirconium phosphate and other additives, mix, let stand, and filter to obtain the final product.

[0029] Preferably, in step S1, the mass ratio of zinc borate, low melting point glass powder and Tween 80 is 1:(1-2):(1-3).

[0030] Preferably, other additives include curing agents, leveling agents, and defoamers; the mass ratio of curing agent, leveling agent, and defoamer is 1:(0.05-0.3):(0.01-0.1); the curing agent includes sodium fluorosilicate and potassium fluorosilicate; the leveling agent includes polyether-modified polysiloxane and fluorocarbon compounds; and the defoamer is BYK-024.

[0031] Secondly, the present invention also provides a method for preparing borosilicate 4.0 fire-resistant glass, comprising the following steps:

[0032] Modified silica composite fire retardant liquid is injected into the interlayer between the first and second glass layers. After the composite fire retardant liquid is pre-cured and fully cured into a glue, the filling port is sealed with glass strips and transparent flame retardant glue to obtain a borosilicate 4.0 fire retardant glass.

[0033] Preferably, the pre-curing conditions are 50-60℃ for 1-2 hours; the complete curing conditions are 75-85℃ for 1-1.5 hours.

[0034] The beneficial effects of this invention are:

[0035] 1. This invention improves the fire resistance of borosilicate 4.0 glass by filling modified silica composite fire retardant liquid between two layers of borosilicate 4.0 glass. Furthermore, the modified silica composite fire retardant liquid of this invention not only enhances the stability of the fire retardant liquid but also solves the problems of reduced light transmittance, bubbles, and resin flow caused by low chemical stability in existing fire retardant liquids.

[0036] 2. The modified zirconium phosphate in the composite fire retardant of this invention can effectively absorb ultraviolet light, preventing the glass surface from yellowing or degrading due to long-term ultraviolet radiation, thereby enhancing long-term weather resistance. Furthermore, by intercalating and modifying the zirconium phosphate, the interfacial compatibility between the borosilicate 4.0 glass and the fire retardant is further optimized. The intercalated zirconium phosphate, through its combination with a long-chain silane coupling agent, improves the chemical bonding force between the fire retardant and the glass substrate, reduces delamination caused by temperature fluctuations and vibrations, and enhances the overall stability of the glass structure.

[0037] 3. This invention further optimizes the expansion, curing properties, and material stability of the composite fire retardant liquid through precise control of modified silica, zinc borate, and other additives. Adding low-melting-point glass powder to encapsulate zinc borate improves the stability of the composite fire retardant liquid at high temperatures and avoids common problems such as flow and foaming of low-modulus potassium silicate water glass at high temperatures.

[0038] 4. The composite fire retardant liquid of this invention has good compatibility among its components, stable dispersion, and is not prone to sedimentation or bubble formation. Combined with highly efficient defoamers and leveling agents, it results in fewer bubbles in the interlayer after filling, uniform thickness, high light transmittance, and a clean and aesthetically pleasing appearance. Detailed Implementation

[0039] To make the above-mentioned objects, features and advantages of the present invention more apparent and understandable, specific embodiments of the present invention will be described in detail below.

[0040] A borosilicate 4.0 fire-resistant glass, comprising a first glass layer and a second glass layer;

[0041] A modified silica composite fire retardant liquid is filled between the first glass layer and the second glass layer;

[0042] The first and second glass layers are borosilicate 4.0 glass;

[0043] The modified silica composite fire retardant liquid comprises the following components in parts by weight:

[0044] 10-20 parts modified silica, 5-8 parts silica, 5-10 parts modified zinc borate, 3-5 parts water glass, 8-12 parts potassium silicate, 1-3 parts modified zirconium phosphate, and 1-2 parts other additives.

[0045] By filling the space between two layers of borosilicate 4.0 glass with modified silica composite fire retardant, not only can the fire resistance of borosilicate 4.0 glass be improved, but the problems of poor material stability, bubbles, glue flow and weak weather resistance of fire retardant can also be solved.

[0046] Specifically, by modifying silica, not only can the aggregation caused by its surface hydroxyl groups be broken, ensuring uniform dispersion in the fire retardant liquid, but it can also form a cross-linking density with potassium silicate and water glass in the fire retardant liquid. In addition, it can form BOB bonds with BO4 on the surface of borosilicate 4.0 glass, improving the interfacial bonding force. Furthermore, unmodified silica is added to the composite fire retardant liquid, which can form a dense gel with a high expansion ratio with water glass, avoiding the looseness of the high-temperature foaming layer.

[0047] Zinc borate, as a highly efficient flame retardant, releases water of crystallization at high temperatures and forms a covering glassy protective layer. By modifying zinc borate, for example by encapsulating it with low-melting-point glass powder, a "core-shell structure" can be constructed. This structure delays the decomposition of zinc borate, allowing it to function more effectively in the critical temperature zones during the early stages of a fire, and better synchronizes with the system's melting process, thereby optimizing the foaming process and the insulation layer structure.

[0048] Zirconium phosphate possesses a unique layered structure that effectively absorbs ultraviolet light, enhancing the system's weather resistance. Through intercalation modification, using long-chain silane coupling agents to widen its interlayer spacing, not only can its compatibility and dispersibility in the inorganic matrix be greatly improved, preventing a decrease in light transmittance due to agglomeration, but the active functional groups at the intercalation agent's ends, such as amino or epoxy groups, can also participate in the overall cross-linking network of the fire retardant, transforming zirconium phosphate from a physical filler into a chemical cross-linking point, further enhancing the structural integrity and aging resistance of the cured colloid.

[0049] The addition of other additives can synergistically optimize the process performance and final properties of the fire retardant liquid. Curing agents can accelerate the formation of the silica network; leveling agents can improve the spreadability of the liquid and ensure uniform interlayer thickness; defoamers can effectively suppress air bubbles introduced during mixing and filling, better ensuring the light transmittance and appearance quality of the fire-retardant glass.

[0050] In some embodiments, the method for preparing modified silica includes the following steps:

[0051] Silica is dispersed in an aqueous ethanol solution to prepare a silica suspension; an epoxy silane coupling agent is added, and the mixture is stirred for 1-3 hours. Boric acid is then added, and the mixture is stirred for 1-2 hours. The solution is then filtered and dried to obtain the final product.

[0052] In some embodiments, the epoxy silane coupling agent includes KH550 and KH560.

[0053] First, silica is treated with an epoxy-based silane coupling agent to graft active epoxy groups onto its surface, improving the dispersibility of silica particles and providing sites for subsequent reactions. By adding boric acid, the B-OH groups of boric acid undergo a ring-opening reaction with the epoxy groups. This allows boric acid molecules to form a weak pre-crosslinked network between multiple silica particles, improving the stability of the fire retardant under normal conditions. Furthermore, boron is chemically bonded to the silica surface, enabling it to more efficiently catalyze ceramic formation and lower melting temperature during fire. Silica modified in this way not only improves its normal performance through interfacial bonding between boron oxide groups and the glassy structure of borosilicate 4.0, but also enhances the compressive strength of the cured fire retardant through crosslinking of epoxy groups with potassium silicate.

[0054] In some embodiments, the mass ratio of silica, aqueous ethanol solution, epoxy silane coupling agent and boric acid is 1:(1-3):(0.01-0.08):(0.05-0.5). Using this mass ratio range ensures that the silica particles are fully and uniformly modified, while avoiding side reactions or system instability caused by excessive coupling agent or boric acid.

[0055] In some embodiments, the method for preparing modified zirconium phosphate includes the following steps:

[0056] Zirconium phosphate is dispersed in a deionized aqueous solution, a long-chain silane coupling agent is added, and the mixture is ultrasonically treated for 1-2 hours. After centrifugation, washing, and drying, the product is obtained.

[0057] In some embodiments, the mass ratio of zirconium phosphate to long-chain aminosilane is 1:(0.3-1.5); the long-chain aminosilane includes N-β-aminoethyl-γ-aminopropyltrimethoxysilane and γ-(2,3-epoxypropoxy)propyltrimethoxysilane; using this mass ratio of zirconium phosphate and long-chain aminosilane can achieve optimal intercalation effect and surface modification without destroying the crystal structure of zirconium phosphate itself, ensuring that it can be stably dispersed in fire retardant liquid and effectively participate in crosslinking reaction.

[0058] By intercalating zirconium phosphate with long-chain silane molecules, such as N-β-aminoethyl-γ-aminopropyltrimethoxysilane, the interlayer spacing can be expanded. The steric hindrance effect of the long-chain alkyl group can effectively prevent the recombination of zirconium phosphate nanosheets, achieving long-term stable dispersion in fire retardant liquid and avoiding the decrease in transparency and uneven performance caused by agglomeration. On the other hand, the active functional group amino at the end of the intercalator can chemically react with the inorganic silicon-oxygen network or other components during the curing process of the fire retardant liquid, anchoring the zirconium phosphate particles in the three-dimensional network, significantly enhancing the interfacial bonding force, inhibiting interfacial delamination caused by thermal cycling, and thus comprehensively improving the durability of the composite glass.

[0059] In some embodiments, the preparation method of the modified silica composite fire retardant liquid includes the following steps:

[0060] S1. Disperse low-melting-point glass powder and zinc borate in toluene, add Tween 80 to form an emulsion, and remove the toluene to obtain modified zinc borate;

[0061] S2. Add modified silica to the solvent, then add modified zinc borate, water glass, potassium silicate, modified zirconium phosphate and other additives, mix, let stand, and filter to obtain the final product.

[0062] In step S1, low-melting-point glass powder is coated onto the surface of zinc borate using an emulsion method, forming a core-shell structure with heat delay function. In step S2, the components are added and mixed in sequence to ensure that the modified functional filler can be uniformly dispersed and fully wetted in the continuous phase composed of potassium silicate and water glass. Finally, by settling and filtering, any possible agglomerates and bubbles are removed to obtain a homogeneous and stable composite fire retardant liquid.

[0063] In some embodiments, in step S1, the mass ratio of zinc borate, low-melting-point glass powder, and Tween 80 is 1:(1-2):(1-3). Using this mass ratio, a complete and appropriately thick coating layer can be formed, effectively controlling the decomposition temperature of zinc borate, while ensuring the stability of the emulsification process and avoiding phase separation.

[0064] In some embodiments, other additives include curing agents, leveling agents, and defoamers; the mass ratio of curing agent, leveling agent, and defoamer is 1:(0.05-0.3):(0.01-0.1); the curing agent includes sodium fluorosilicate and potassium fluorosilicate; the leveling agent includes polyether-modified polysiloxane and fluorocarbon compounds; and the defoamer is BYK-024.

[0065] The curing agent can accelerate the gelation and curing process of the entire system by promoting the hydrolysis and condensation reaction of potassium silicate and water glass, forming a stable three-dimensional network structure; the leveling agent can reduce the surface tension of the fire retardant, allowing it to spread better in the glass interlayer and form a uniform, defect-free adhesive layer; the defoamer can quickly eliminate introduced air during mixing and filling, preventing air bubbles from appearing in the finished product and affecting light transmittance and aesthetics. When the mass ratio of the three is 1:(0.05~0.3):(0.01~0.1), it can ensure sufficient curing while taking into account both excellent leveling effect and efficient defoaming ability, avoiding the influence of excessive leveling agent or defoamer on the curing reaction or causing surface defects.

[0066] A method for preparing borosilicate 4.0 fire-resistant glass includes the following steps:

[0067] Modified silica composite fire retardant liquid is injected into the interlayer between the first and second glass layers. After the composite fire retardant liquid is pre-cured and fully cured into a glue, the filling port is sealed with glass strips and transparent flame retardant glue to obtain a borosilicate 4.0 fire retardant glass.

[0068] The above preparation method can ensure that the fire retardant liquid fully reacts and solidifies within the interlayer, forming a uniform, transparent fire retardant adhesive layer that is firmly bonded to the glass. Ultimately, the sealing process ensures the long-term airtightness and durability of the product.

[0069] In some embodiments, the pre-curing conditions are 50–60°C for 1–2 hours; the complete curing conditions are 75–85°C for 1–1.5 hours. This two-stage curing process allows for gradient curing of the fire retardant, avoiding defects caused by excessively rapid surface crusting or the inability of internal solvents or bubbles to escape due to direct high-temperature curing. The pre-curing stage allows the fire retardant to initially gel and solidify, forming a basic framework; the complete curing stage promotes full cross-linking of silicon-oxygen bonds at a higher temperature, enabling the fire retardant layer to achieve its final strength, hardness, and stability.

[0070] The specific embodiments of the present invention will be described in detail below, but it should be understood that the scope of protection of the present invention is not limited to the specific embodiments.

[0071] Preparation Example

[0072] Preparation Example 1: A modified silica composite fire retardant liquid was prepared according to the following method:

[0073] S1. Disperse 1g of silica in 3g of 90% ethanol aqueous solution to prepare silica suspension; add 0.02g of KH550, stir for 2h, add 0.1g of boric acid, stir for 1-2h, filter and dry to obtain modified silica.

[0074] S2. Disperse 1g of zirconium phosphate in 100mL of deionized water, add 1g of N-β-aminoethyl-γ-aminopropyltrimethoxysilane, sonicate for 1h, centrifuge, wash and dry to obtain modified zirconium phosphate.

[0075] S3. Disperse 10g of zinc borate and 15g of low melting point glass powder (initial melting temperature 350℃) in 100g of toluene, add 20g of Tween 80 to form an emulsion, and remove the toluene to obtain modified zinc borate.

[0076] S2. Add 15 parts of modified silica and 5 parts of silica to 30g of 1M potassium hydroxide solution, then add 5 parts of modified zinc borate, 3 parts of water glass, 8 parts of potassium silicate, 1 part of modified zirconium phosphate and 1 part of other additives (sodium fluorosilicate, polyether-modified polysiloxane, BYK-024), mix, let stand, and filter to obtain a modified silica composite fire retardant liquid.

[0077] The mass ratio of curing agent, leveling agent and defoamer is 1:0.05:0.01.

[0078] Preparation Examples 2 to 7 describe a modified silica composite fire retardant liquid, which differs from Preparation Example 1 only in that the proportions of its raw materials were adjusted, as shown in Table 1.

[0079] Table 1. Formulation of Modified Silica Composite Fire Retardant Liquid

[0080]

[0081] Example

[0082] Example 1: A borosilicate 4.0 fire-resistant glass was prepared by the following method:

[0083] The modified silica composite fire retardant liquid prepared in Preparation Example 1 was injected into the interlayer between the first glass layer and the second glass layer. After the composite fire retardant liquid was pre-cured and fully cured into a gel, the filling port was sealed with a glass strip and transparent flame retardant adhesive to obtain a borosilicate 4.0 fire retardant glass. The pre-curing condition was to keep it at 50°C for 1 hour; the fully cured condition was to keep it at 80°C for 1 hour.

[0084] Example 2, a borosilicate 4.0 fireproof glass, differs from Example 1 only in that the modified silica composite fireproof liquid prepared in Example 1 is replaced with the same amount of the modified silica composite fireproof liquid prepared in Example 2.

[0085] Example 3, a borosilicate 4.0 fireproof glass, differs from Example 1 only in that the modified silica composite fireproof liquid prepared in Example 1 is replaced with the same amount of the modified silica composite fireproof liquid prepared in Example 3.

[0086] Comparative Example

[0087] Comparative Example 1 is a borosilicate 4.0 fireproof glass, which differs from Example 1 only in that the modified silica composite fireproof liquid prepared in Example 1 is replaced with the same amount of the modified silica composite fireproof liquid prepared in Example 4.

[0088] Comparative Example 2, a borosilicate 4.0 fireproof glass, differs from Example 1 only in that the modified silica composite fireproof liquid prepared in Example 1 is replaced with the same amount of the modified silica composite fireproof liquid prepared in Example 5.

[0089] Comparative Example 3 is a borosilicate 4.0 fireproof glass, which differs from Example 1 only in that the modified silica composite fireproof liquid prepared in Example 1 is replaced with the same amount of the modified silica composite fireproof liquid prepared in Example 6.

[0090] Comparative Example 4, a borosilicate 4.0 fireproof glass, differs from Example 1 only in that the modified silica composite fireproof liquid prepared in Example 1 is replaced with the same amount of the modified silica composite fireproof liquid prepared in Example 7.

[0091] Performance testing

[0092] The following performance tests were performed on the borosilicate 4.0 fire-resistant glass prepared in Examples 1-3 and Comparative Examples 1-4:

[0093] 1. Fire resistance test: The fire resistance of borosilicate 4.0 fireproof glass was tested according to GB / T 12513-2006. The heating rate was 5℃ / min, and the fire resistance time was the time when the temperature of a single point on the back of the borosilicate fireproof glass sample reached 180℃ or the average temperature reached 140℃.

[0094] 2. Light transmittance test: The transmittance is tested in accordance with GB / T 2680-2021 "Determination of visible light transmittance, direct solar transmittance, total solar transmittance, ultraviolet transmittance and related window glass parameters of architectural glass".

[0095] 3. Surface stress value test: Place the glass to be tested on the measuring stage of the glass surface stress meter with the tin-plated side facing upwards. Determine the measurement point according to section 6.4.1 of the national standard GB17841-1999 "Tempered and Semi-Tempered Glass for Curtain Walls". Wipe the glass surface to be measured with alcohol. After 1 minute, drop a drop of refractive oil on the measurement point. Then place the bottom surface of the prism of the glass surface stress meter on the refractive oil. Adjust the eyepiece of the glass surface stress meter and read the values ​​of the horizontal axis of the micrometer eyepiece coordinate line along the upper and lower ends of the step in the field of view. Calculate the difference (which is the measured step height D). The measured step height D × 3 is the surface stress value of the glass being tested.

[0096] 4. Weather resistance test: The weather resistance test was conducted using the irradiation chamber required by GB15763.2-2009. The test conditions were 45℃ and irradiation with a 750W ultraviolet lamp for 100 hours. The transmittance before and after irradiation was tested.

[0097] The performance test results are shown in Table 2:

[0098] Table 2 Performance test results

[0099]

[0100] According to Table 2, and in conjunction with Example 1 and Comparative Example 1, it can be seen that the fire resistance time, transmittance after ultraviolet irradiation, and surface stress of Comparative Example 1 are lower than those of Example 1. This is because Comparative Example 1 did not add modified silica compared to Example 1. Therefore, the fire retardant liquid lacks the uniform dispersion, increased crosslinking density with potassium silicate and water glass, and enhanced interfacial bonding force with the BO4 bond formed on the borosilicate 4.0 glass surface provided by modified silica. This results in a loose structure after the fire retardant liquid solidifies, and the fire retardant layer formed at high temperatures is not dense enough, leading to reduced fire resistance. Simultaneously, the weakened interfacial bonding force reduces surface stress, and uneven dispersion may affect the stability of light transmittance.

[0101] Combining Example 1 and Example 2, it can be seen that the fire resistance time and surface stress of Comparative Example 2 are lower than those of Example 1. The reason is that Comparative Example 2 did not add modified zinc borate compared to Example 1. Therefore, the fire retardant liquid lacks the core-shell structure of modified zinc borate, which cannot delay the decomposition of zinc borate and shorten the fire resistance time. In addition, it lacks the reaction between zinc borate and potassium silicate to form a hard, glassy borosilicate ceramic skeleton.

[0102] Combining Examples 1 and 3, it can be seen that the fire resistance time, transmittance after ultraviolet irradiation, and surface stress of Comparative Example 3 are lower than those of Example 1. This is because Comparative Example 3 did not contain modified zirconium phosphate, thus lacking the ultraviolet absorption capacity and chemical crosslinking function of modified zirconium phosphate. This results in poor weather resistance and a significant decrease in transmittance after ultraviolet irradiation. Simultaneously, the crosslinking network is incomplete, the structural integrity of the cured colloid is weakened, and the interfacial bonding force is reduced, thereby affecting surface stress and fire resistance performance.

[0103] Combining Examples 1 and 4, it can be seen that the fire resistance time, transmittance after ultraviolet irradiation, and surface stress of Comparative Example 4 are lower than those of Example 1. This is because Comparative Example 4 did not add water glass compared to Example 1, thus lacking the ability of water glass to form a dense gel with high expansion ratio with silica. This results in a loose foamed layer at high temperatures, reducing fire resistance; simultaneously, the colloid strength is insufficient after curing, leading to a decrease in surface stress.

[0104] The above-disclosed embodiments are merely a few specific examples of the present invention. However, the embodiments of the present invention are not limited thereto, and any variations that can be conceived by those skilled in the art should fall within the protection scope of the present invention.

Claims

1. A borosilicate 4.0 fire resistant glass characterized in that, Includes a first glass layer and a second glass layer; A modified silica composite fire retardant liquid is filled between the first glass layer and the second glass layer; The first and second glass layers are borosilicate 4.0 glass; The modified silica composite fire retardant liquid comprises the following components in parts by weight: 10-20 parts modified silica, 5-8 parts silica, 5-10 parts modified zinc borate, 3-5 parts water glass, 8-12 parts potassium silicate, 1-3 parts modified zirconium phosphate, and 1-2 parts other additives; The method for preparing the modified silica includes the following steps: Silica was dispersed in an aqueous ethanol solution to prepare a silica suspension; KH550 silane coupling agent was added, and the mixture was stirred for 1-3 hours. Boric acid was then added, and the mixture was stirred for 1-2 hours. The mixture was then filtered and dried to obtain the final product. The method for preparing the modified zirconium phosphate includes the following steps: Zirconium phosphate was dispersed in a deionized aqueous solution, a long-chain silane coupling agent was added, and the mixture was ultrasonically treated for 1-2 hours. After centrifugation, washing, and drying, the product was obtained. The preparation method of the modified silica composite fire retardant liquid includes the following steps: S1. Disperse low-melting-point glass powder and zinc borate in toluene, add Tween 80 to form an emulsion, and remove the toluene to obtain modified zinc borate; S2. Add modified silica to a solvent, then add modified zinc borate, water glass, potassium silicate, modified zirconium phosphate and other additives, mix, let stand, and filter to obtain the final product. The long-chain silane coupling agent includes one or both of N-β-aminoethyl-γ-aminopropyltrimethoxysilane and γ-(2,3-epoxypropoxy)propyltrimethoxysilane.

2. The borosilicate 4.0 fire resistant glass according to claim 1, wherein, The mass ratio of silica, aqueous ethanol solution, KH550 silane coupling agent and boric acid is 1: (1-3): (0.01-0.08): (0.05-0.5).

3. The borosilicate 4.0 fire resistant glass according to claim 1, wherein, The mass ratio of zirconium phosphate to long-chain silane coupling agent is 1:(0.3-1.5).

4. The borosilicate 4.0 fire resistant glass according to claim 1, wherein, In step S1, the mass ratio of zinc borate, low melting point glass powder and Tween 80 is 1:(1-2):(1-3).

5. The borosilicate 4.0 fire resistant glass according to claim 1, wherein, The other additives include a curing agent, a leveling agent, and a defoamer; the mass ratio of the curing agent, leveling agent, and defoamer is 1:(0.05-0.3):(0.01-0.1); the curing agent includes one or both of sodium fluorosilicate and potassium fluorosilicate; the leveling agent includes polyether-modified polysiloxane and / or fluorocarbon compounds; and the defoamer is BYK-024.

6. A method for preparing borosilicate 4.0 fire-resistant glass, used to prepare any one of the borosilicate 4.0 fire-resistant glass according to claims 1-5, characterized in that, Includes the following steps: Modified silica composite fire retardant liquid is injected into the interlayer between the first and second glass layers. After the composite fire retardant liquid is pre-cured and fully cured into a glue, the filling port is sealed with glass strips and transparent flame retardant glue to obtain a borosilicate 4.0 fire retardant glass.

7. The method for preparing borosilicate 4.0 fire-resistant glass according to claim 6, characterized in that, The pre-curing conditions are to keep the temperature at 50-60℃ for 1-2 hours; the complete curing conditions are to keep the temperature at 75-85℃ for 1-1.5 hours.

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