High boron-silicon composite fireproof glass and preparation method thereof

Abstract

The application relates to the technical field of fireproof glass, and discloses high borosilicate composite fireproof glass and a preparation method thereof. The high borosilicate composite fireproof glass comprises, from top to bottom, an upper layer of high borosilicate glass, a composite fireproof liquid and a lower layer of high borosilicate glass. The composite fireproof liquid comprises the following raw materials in mass percentage: modified silicon dioxide 45-60%, carbonation agent 1-5%, carbonation aid 0.8-2.4%, boride 1-4%, curing agent 3-5%, alkali adjusting agent 0.3-0.8%, leveling agent 0.8-1.2% and defoaming agent 0.4-1.2%, and the rest is water. The modified silicon dioxide comprises basic magnesium carbonate coated silicon dioxide. The basic magnesium carbonate coated silicon dioxide is added into the composite fireproof liquid to improve the fire resistance of the high borosilicate composite fireproof glass, and the problem of insufficient fire resistance of the existing high borosilicate composite fireproof glass is solved.

Description

Technical Field

[0001] This invention relates to the field of fire-resistant glass technology, specifically to a high borosilicate composite fire-resistant glass and its preparation method. Background Technology

[0002] Currently, safety standards for building fire protection, rail transit, industrial equipment, and high-end public venues are constantly improving, leading to a growing market demand for fire-resistant glass that is resistant to high temperatures, thermal shock, and has high light transmittance. High borosilicate glass, with its low coefficient of thermal expansion, high softening point, and excellent shatter resistance, is the core substrate for composite fire-resistant glass. This type of glass can be used in various fire-resistant applications such as fire-resistant partitions, fire-resistant doors and windows, and protective viewing windows for equipment. It is a crucial light-transmitting fire-resistant material for ensuring the integrity of spaces and protecting personnel safety in fire environments.

[0003] Most mainstream high borosilicate composite fireproof glass on the market currently uses a double-layer or multi-layer high borosilicate glass substrate structure. It is formed by injecting composite fireproof adhesive between the layers and then curing it. High borosilicate substrates have good physical stability and will not crack like ordinary glass when subjected to rapid cooling. They can meet the basic requirements of short-term fire insulation and smoke and fire protection for ordinary civil buildings. Furthermore, the overall production process is mature, making it the most widely used fireproof glass structure on the market.

[0004] However, current composite fireproof glass has significant drawbacks, primarily concerning the interlayer fire retardant. Conventional fire retardants carbonize rapidly at high temperatures, exhibit unstable thermal insulation performance, have short fire resistance duration, and suffer from poor overall fire resistance limit and resistance to high-temperature attenuation. This fails to meet high fire protection standards and cannot achieve long-term fire-resistant and thermal insulation protection, thus limiting the promotion and application of high borosilicate composite fireproof glass in high-end applications. Summary of the Invention

[0005] To address the above technical problems, this invention provides a high borosilicate composite fireproof glass and its preparation method. The addition of basic magnesium carbonate-coated silica to the composite fireproof liquid provided by this invention improves the fire resistance of the high borosilicate composite fireproof glass, solving the problem of insufficient fire resistance of existing high borosilicate composite fireproof glass.

[0006] The specific technical solution of the present invention is as follows: According to one aspect of the present invention, the present invention provides a high borosilicate composite fireproof glass, comprising an upper layer of high borosilicate glass, a composite fireproof liquid, and a lower layer of high borosilicate glass disposed from top to bottom; The composite fire retardant liquid comprises the following raw materials in the following mass percentages: 45%~60% modified silica, 1%~5% charring agent, 0.8%~2.4% charring aid, 1%~4% boride, 3%~5% curing agent, 0.3%~0.8% alkali regulator, 0.8%~1.2% leveling agent, 0.4%~1.2% defoamer, and the balance being water; The modified silica includes basic magnesium carbonate coated silica.

[0007] In the above technical solution, the preparation method of basic magnesium carbonate coated with silica includes the following steps: S1. Add water to silica and mix well. Adjust the pH to 9-10 to obtain a suspension. S2. Add magnesium chloride solution to the suspension and stir to obtain the first solution; S3. Add urea to the first solution, mix until completely dissolved, react, cool to room temperature, let stand and age, filter, wash, and dry to obtain the basic magnesium carbonate coated silica.

[0008] In the above technical solution, the mass ratio of silicon dioxide to water is 1:8~12.

[0009] In the above technical solution, the volume ratio of the suspension to the magnesium chloride solution is 4~6:1.

[0010] In the above technical solution, the concentration of the magnesium chloride solution is 0.8~1.2 mol / L.

[0011] In the above technical solution, the molar ratio of magnesium ions in the first solution to urea is 1:3~4.

[0012] In the above technical solution, the reaction temperature is 75~80℃ and the time is 4~8h.

[0013] In the above technical solution, the modified silica further includes boron oxide-coated silica.

[0014] In the above technical solution, the modified silica includes basic magnesium carbonate coated silica and boron oxide coated silica in a mass ratio of 7~8:3~2.

[0015] In the above technical solution, the method for preparing boron oxide-coated silicon dioxide includes the following steps: A1. Add water to silica and mix well to obtain a suspension; A2. Add boric acid to the suspension, stir, and dehydrate to obtain boron oxide-coated silica.

[0016] In the above technical solution, in step A1, the mass ratio of silicon dioxide to water is 1:3~4.

[0017] In the above technical solution, the mass ratio of silicon dioxide to boric acid is 1:0.2~0.26.

[0018] In the above technical solution, the dehydration includes a first stage of dehydration, a second stage of dehydration, and a third stage of dehydration.

[0019] In the above technical solution, the temperature of the first stage of dehydration is 100~110℃ and the time is 2h; the temperature of the second stage of dehydration is 140~160℃ and the time is 2h; and the temperature of the third stage of dehydration is 260~290℃ and the time is 2h.

[0020] In the above technical solution, the char-forming agent includes one or more of glucose, sucrose, and pentaerythritol.

[0021] In the above technical solution, the char-forming aid includes one of potassium dihydrogen phosphate and dipotassium hydrogen phosphate.

[0022] In the above technical solution, the boride includes borax.

[0023] In the above technical solution, the curing agent includes one of sodium fluorosilicate and potassium fluorosilicate.

[0024] In the above technical solution, the alkali regulator includes potassium hydroxide.

[0025] In the above technical solution, the leveling agent includes polyether-modified organosilicon BYK-345.

[0026] In the above technical solution, the defoamer includes an organosilicone defoamer.

[0027] According to another aspect of the present invention, the present invention also provides a method for preparing the above-mentioned high borosilicate composite fireproof glass, comprising the following steps: The raw materials of the composite fire retardant liquid are stirred evenly to obtain the composite fire retardant liquid; a butyl rubber strip is wrapped around the edge of the upper layer of high borosilicate glass, leaving a grouting port; the lower layer of high borosilicate glass is aligned with the upper layer of high borosilicate glass, and then glued and hot-pressed to form a cavity; silicone sealant is filled on the outside of the butyl rubber strip, and the mixture is left to stand; the composite fire retardant liquid is poured into the cavity through the grouting port; the grouting port is sealed with the butyl rubber strip, and the gaps in the grouting port are sealed with silicone sealant; the mixture is then cured to obtain high borosilicate composite fire retardant glass.

[0028] Compared with existing technologies, this invention provides a high borosilicate composite fireproof glass. Basic magnesium carbonate-coated silica is added to the composite fireproof liquid, improving the fire resistance of the high borosilicate composite fireproof glass. After basic magnesium carbonate coating, the silica is more evenly dispersed in the fireproof liquid. Simultaneously, at high temperatures, the surface basic magnesium carbonate preferentially undergoes thermal decomposition, absorbing a large amount of combustion heat, reducing the overall temperature rise rate of the glass. Furthermore, the magnesium oxide generated from the decomposition can combine with silica and the system's carbon layer to form a composite dense inorganic barrier layer, effectively blocking flames, high-temperature gases, and heat radiation conduction. This synergistic effect with the carbon-forming components in the system enhances the fireproof and heat-insulating effect, improves the fire resistance limit of the high borosilicate composite fireproof glass, and effectively extends the fire resistance integrity time. Detailed Implementation

[0029] To make the objectives, technical solutions, and advantages of this invention more apparent, the invention is described in detail below. It should be understood that the invention is not limited to the description herein.

[0030] Modified silica This invention utilizes a modified silica composition of 7-8:3-2, consisting of basic magnesium carbonate-coated silica and boron oxide-coated silica, which further enhances the fire resistance of high-borosilicate composite fireproof glass. The basic magnesium carbonate-coated silica, when exposed to high-temperature fires, gradually decomposes and absorbs heat, slowing the heating rate of the fireproof liquid layer and thus further reducing the temperature rise of the glass surface. Simultaneously, the generated magnesium oxide, silica, and the carbon layer form a supporting framework, effectively mitigating the shrinkage and cracking of the carbon layer at high temperatures. The boron oxide in the boron oxide-coated silica melts at high temperatures, effectively filling the small pores and micro-cracks on the magnesium oxide framework and carbon layer surface. The combined effect of these two components—framework support and molten sealing—effectively blocks heat conduction, heat radiation, and flame penetration, extending the fire resistance integrity maintenance time of the fireproof glass. When the ratio is lower than this, the proportion of basic magnesium carbonate-coated silica is insufficient, resulting in inadequate framework integrity; when the ratio is higher, the molten sealing effect is weakened, leading to a decrease in fire resistance.

[0031] charring agent The charring agent used in this invention is a known charring agent in the art that can be used in composite fire retardant liquids, and this invention is not limited to glucose, sucrose, and pentaerythritol listed below. As an example, the charring agent can be one or more of glucose, sucrose, pentaerythritol, mannitol, sorbitol, and starch. In the composite fire retardant liquid of this invention, the role of the charring agent is to rapidly dehydrate and carbonize at high temperatures to form a dense char layer, thereby blocking heat and flame transfer.

[0032] charcoal forming aid The char-forming aid used in this invention is a known char-forming aid in the art that can be used in composite fire retardant liquids, and this invention is not limited to potassium dihydrogen phosphate and dipotassium hydrogen phosphate listed below. As an example, the char-forming aid can be one or more of potassium dihydrogen phosphate, dipotassium hydrogen phosphate, phosphoric acid, and ammonium polyphosphate. In the composite fire retardant liquid of this invention, the role of the char-forming aid is to catalyze the carbonization of the char-forming agent, thereby improving the density and stability of the char layer.

[0033] Borides The boride used in this invention is a boride known in the art for use in composite fire retardant liquids, and this invention is not limited to borax listed below. As an example, the boride may be one or more of borax, boric acid, zinc borate, and sodium tetraborate. In the composite fire retardant liquid of this invention, the boride serves to assist in flame retardancy and improve the overall heat resistance integrity of the glass.

[0034] curing agent The curing agent used in this invention is a known curing agent in the art that can be used in composite fire retardant liquids, and this invention is not limited to sodium fluorosilicate and potassium fluorosilicate listed below. As an example, the curing agent can be one or more of sodium fluorosilicate, potassium fluorosilicate, and lithium silicate. In the composite fire retardant liquid of this invention, the function of the curing agent is to promote the cross-linking and curing of the fire retardant liquid, forming a stable adhesive layer that adheres to the glass substrate without detaching.

[0035] Alkali regulator The alkali regulator used in this invention is a known alkali regulator in the art that can be used in composite fire retardant liquids, and this invention is not limited to potassium hydroxide listed below. As an example, the alkali regulator can be one or more of potassium hydroxide, sodium hydroxide, ammonia, and triethanolamine. In the composite fire retardant liquid of this invention, the role of the alkali regulator is to control the overall pH value, ensure stable reaction of raw materials, and maintain the storage stability of the fire retardant liquid.

[0036] Leveling agent The leveling agent used in this invention is a known leveling agent in the art that can be used in composite fire retardant liquids. In the composite fire retardant liquid of this invention, the leveling agent functions to reduce the surface tension of the fire retardant liquid.

[0037] Defoamer The defoamer used in this invention is a known defoamer in the art that can be used in composite fire retardant liquids. In the composite fire retardant liquid of this invention, the role of the defoamer is to eliminate air bubbles generated during the stirring and coating of the fire retardant liquid, ensuring a dense adhesive layer and avoiding affecting fire resistance and light transmittance.

[0038] High borosilicate composite fireproof glass This invention provides a high borosilicate composite fireproof glass, comprising an upper layer of high borosilicate glass, a composite fireproof liquid, and a lower layer of high borosilicate glass arranged from top to bottom; The composite fire retardant liquid comprises the following raw materials by mass percentage: 45%~60% modified silica, 1%~5% charring agent, 0.8%~2.4% charring aid, 1%~4% boride, 3%~5% curing agent, 0.3%~0.8% alkali regulator, 0.8%~1.2% leveling agent, 0.4%~1.2% defoamer, and the balance being water; the modified silica includes basic magnesium carbonate coated silica.

[0039] In the composite fire retardant liquid, the mass percentage of modified silica is 45% to 60%, preferably 48% to 58%, and more preferably 52% to 54%.

[0040] In the composite fire retardant liquid, the mass percentage of the charring agent is 1% to 5%, preferably 2% to 4%.

[0041] In the composite fire retardant liquid, the mass percentage of char-forming aid is 0.8% to 2.4%, preferably 1.2% to 2%, and more preferably 1.6% to 1.8%.

[0042] In the composite fire retardant liquid, the mass percentage of boride is 1% to 4%, preferably 2% to 3%.

[0043] In the composite fire retardant liquid, the mass percentage of the curing agent is 3% to 5%, preferably 3.5% to 4.5%.

[0044] In the composite fire retardant liquid, the mass percentage of the alkali modifier is 0.3% to 0.8%, preferably 0.5% to 0.6%.

[0045] In the composite fire retardant liquid, the mass percentage of leveling agent is 0.8% to 1.2%, preferably 0.9% to 1.1%.

[0046] In the composite fire retardant liquid, the mass percentage of defoamer is 0.4% to 1.2%, preferably 0.6% to 1%.

[0047] Preparation method of basic magnesium carbonate coated silica The present invention also provides a method for preparing basic magnesium carbonate coated with silica as described above, comprising the following steps: S1. Add water to silica and mix well. Adjust the pH to 9-10 to obtain a suspension. S2. Add magnesium chloride solution to the suspension and stir to obtain the first solution; S3. Add urea to the first solution, mix until completely dissolved, react, cool to room temperature, let stand and age, filter, wash, and dry to obtain basic magnesium carbonate coated silica.

[0048] In the preparation of basic magnesium carbonate coated silica, the mass ratio of silica to water is 1:8~12; the volume ratio of suspension to magnesium chloride solution is 4~6:1; in step S2, the stirring speed is 300~500 rpm and the time is 40~60 min; the concentration of magnesium chloride solution is 0.8~1.2 mol / L; the molar ratio of magnesium ions to urea in the first solution is 1:3~4; the reaction temperature is 75~80℃ and the time is 4~8 h.

[0049] Preparation method of boron oxide coated silica The present invention also provides a method for preparing boron oxide-coated silica as described above, comprising the following steps: A1. Add water to silica and mix well to obtain a suspension; A2. Add boric acid to the suspension, stir, and dehydrate to obtain boron oxide-coated silica.

[0050] In the preparation of boron oxide-coated silica, the mass ratio of silica to water is 1:3~4; the mass ratio of silica to boric acid is 1:0.2~0.26; in step A2, the stirring is carried out at 400~600 rpm for 1.5~2.5 h; the dehydration includes a first stage of dehydration, a second stage of dehydration and a third stage of dehydration; the temperature of the first stage of dehydration is 100~110℃ for 2 h; the temperature of the second stage of dehydration is 140~160℃ for 2 h; the temperature of the third stage of dehydration is 260~290℃ for 2 h.

[0051] Preparation method of high borosilicate composite fireproof glass This invention also provides a method for preparing the high borosilicate composite fireproof glass as described above, comprising the following steps: The raw materials of the composite fire retardant liquid are stirred evenly to obtain the composite fire retardant liquid; a butyl rubber strip is wrapped around the edge of the upper layer of high borosilicate glass, leaving a grouting port; the lower layer of high borosilicate glass is aligned with the upper layer of high borosilicate glass, and then glued and hot-pressed to form a cavity; silicone sealant is filled on the outside of the butyl rubber strip and left to stand; the composite fire retardant liquid is poured into the cavity through the grouting port, the grouting port is sealed with the butyl rubber strip, and the gap of the grouting port is sealed with silicone sealant; after curing, high borosilicate composite fire retardant glass is obtained.

[0052] To further illustrate the present invention, the following embodiments will provide a detailed description. The raw materials used in the following embodiments and comparative examples of the present invention are all commercially available products. Specifically, the thickness of the upper borosilicate glass layer is 6 mm; the thickness of the lower borosilicate glass layer is 6 mm; the average particle size of the silica is 200 nm; and the silicone defoamer is model BYK-024.

[0053] The percentages of each substance in the following examples and comparative examples are by mass percentages.

[0054] Example 1 A method for preparing high borosilicate composite fireproof glass includes the following steps: 45% basic magnesium carbonate coated silica, 1% glucose, and 1% borax were added to 47.7% water in sequence and mixed evenly. Then, 0.8% polyether modified organosilicon BYK-345, 0.4% organosilicon defoamer, 0.3% potassium hydroxide, 0.8% potassium dihydrogen phosphate, and 3% sodium fluorosilicate were added in sequence and mixed evenly to obtain a composite fire retardant liquid. A 6mm butyl rubber strip is wrapped around the edge of the upper borosilicate glass, leaving a grouting port. The lower borosilicate glass is aligned with the upper borosilicate glass, then glued and hot-pressed to form a 2.5mm cavity. Silicone sealant is filled on the outside of the butyl rubber strip, and the mixture is left to stand at room temperature for 10 hours. Composite fireproof liquid is then injected into the cavity through the grouting port. After filling, the grouting port is sealed with butyl rubber strip and silicone sealant, and then cured to obtain high borosilicate composite fireproof glass. The preparation method of basic magnesium carbonate coated silica includes the following steps: Add water to silica and mix well (mass ratio of silica to water is 1:8). Add 1 mol / L NaOH solution to adjust the pH to 10 to obtain a suspension. Then add 1.2 mol / L magnesium chloride solution to the suspension (volume ratio of suspension to magnesium chloride solution is 4:1). Stir at 300 rpm for 60 min to obtain the first solution. Urea was then added to the first solution (the molar ratio of magnesium ions to urea in the first solution was 1:3). After mixing until completely dissolved, the mixture was reacted at 80°C for 4 hours. After the reaction was completed, the mixture was cooled to room temperature and allowed to stand for 6 hours. The mixture was then filtered, washed, and dried to obtain basic magnesium carbonate coated silica.

[0055] Example 2 A method for preparing high borosilicate composite fireproof glass includes the following steps: 60% basic magnesium carbonate coated silica, 5% sucrose, and 4% borax were added to 21% water in sequence and mixed evenly. Then, 1.2% polyether modified organosilicon BYK-345, 0.6% organosilicon defoamer, 0.8% potassium hydroxide, 2.4% dipotassium hydrogen phosphate, and 5% potassium fluorosilicate were added in sequence and mixed evenly to obtain a composite fire retardant liquid. A 6mm butyl rubber strip is wrapped around the edge of the upper borosilicate glass, leaving a grouting port. The lower borosilicate glass is aligned with the upper borosilicate glass, then glued and hot-pressed to form a 2.5mm cavity. Silicone sealant is filled on the outside of the butyl rubber strip, and the mixture is left to stand at room temperature for 10 hours. Composite fireproof liquid is then injected into the cavity through the grouting port. After filling, the grouting port is sealed with butyl rubber strip and silicone sealant, and then cured to obtain high borosilicate composite fireproof glass. The preparation method of basic magnesium carbonate coated silica includes the following steps: Add water to silica and mix well (mass ratio of silica to water is 1:10). Add 1 mol / L NaOH solution to adjust the pH to 9 to obtain a suspension. Then add 0.8 mol / L magnesium chloride solution to the suspension (volume ratio of suspension to magnesium chloride solution is 6:1). Stir at 500 rpm for 40 min to obtain the first solution. Urea was then added to the first solution (the molar ratio of magnesium ions to urea in the first solution was 1:4). After mixing until completely dissolved, the mixture was reacted at 75°C for 8 hours. After the reaction was completed, the mixture was cooled to room temperature and allowed to stand for 6 hours. The mixture was then filtered, washed, and dried to obtain basic magnesium carbonate coated silica.

[0056] Example 3 A method for preparing high borosilicate composite fireproof glass includes the following steps: 50% basic magnesium carbonate coated silica, 2.5% pentaerythritol, and 2% borax were added sequentially to 37.4% water and mixed evenly. Then, 1% polyether modified organosilicon BYK-345, 1.2% organosilicon defoamer, 0.5% potassium hydroxide, 1.4% potassium dihydrogen phosphate, and 4% potassium fluorosilicate were added sequentially and mixed evenly to obtain a composite fire retardant liquid. A 6mm butyl rubber strip is wrapped around the edge of the upper borosilicate glass, leaving a grouting port. The lower borosilicate glass is aligned with the upper borosilicate glass, then glued and hot-pressed to form a 2.5mm cavity. Silicone sealant is filled on the outside of the butyl rubber strip, and the mixture is left to stand at room temperature for 10 hours. Composite fireproof liquid is then injected into the cavity through the grouting port. After filling, the grouting port is sealed with butyl rubber strip and silicone sealant, and then cured to obtain high borosilicate composite fireproof glass. The preparation method of basic magnesium carbonate coated silica includes the following steps: Add water to silica and mix well (mass ratio of silica to water is 1:12). Add 1 mol / L NaOH solution to adjust the pH to 10 to obtain a suspension. Then add 1 mol / L magnesium chloride solution to the suspension (volume ratio of suspension to magnesium chloride solution is 5:1). Stir at 400 rpm for 60 min to obtain the first solution. Urea was then added to the first solution (the molar ratio of magnesium ions to urea in the first solution was 1:3). After mixing until completely dissolved, the mixture was reacted at 75°C for 6 hours. After the reaction was completed, the mixture was cooled to room temperature and allowed to stand for 6 hours. The mixture was then filtered, washed, and dried to obtain basic magnesium carbonate coated silica.

[0057] Example 4 A method for preparing high borosilicate composite fireproof glass includes the following steps: 30% basic magnesium carbonate coated silica, 20% boron oxide coated silica, 2.5% pentaerythritol, and 2% borax were added sequentially to 37.4% water and mixed evenly. Then, 1% polyether modified organosilicon BYK-345, 1.2% organosilicon defoamer, 0.5% potassium hydroxide, 1.4% potassium dihydrogen phosphate, and 4% potassium fluorosilicate were added sequentially and mixed evenly to obtain a composite fire retardant liquid. A 6mm butyl rubber strip is wrapped around the edge of the upper borosilicate glass, leaving a grouting port. The lower borosilicate glass is aligned with the upper borosilicate glass, then glued and hot-pressed to form a 2.5mm cavity. Silicone sealant is filled on the outside of the butyl rubber strip, and the mixture is left to stand at room temperature for 10 hours. Composite fireproof liquid is then injected into the cavity through the grouting port. After filling, the grouting port is sealed with butyl rubber strip and silicone sealant, and then cured to obtain high borosilicate composite fireproof glass. The preparation method of basic magnesium carbonate coated silica includes the following steps: Add water to silica and mix well (mass ratio of silica to water is 1:12). Add 1 mol / L NaOH solution to adjust the pH to 10 to obtain a suspension. Then add 1 mol / L magnesium chloride solution to the suspension (volume ratio of suspension to magnesium chloride solution is 5:1). Stir at 400 rpm for 60 min to obtain the first solution. Urea was added to the first solution (the molar ratio of magnesium ions to urea in the first solution was 1:3). After mixing until completely dissolved, the mixture was reacted at 75°C for 6 hours. After the reaction was completed, the mixture was cooled to room temperature and allowed to stand for 6 hours. The mixture was then filtered, washed, and dried to obtain basic magnesium carbonate coated silica. A method for preparing boron oxide-coated silica includes the following steps: Water was added to silica and mixed evenly (the mass ratio of silica to water was 1:3) to obtain a suspension. Boric acid was added to the suspension (the mass ratio of silica to boric acid was 1:0.26), and the mixture was stirred at 400 rpm for 2.5 h. After stirring, dehydration was carried out, first at 110℃ for 2 h, then at 160℃ for 2 h, and finally at 290℃ for 2 h to obtain boron oxide-coated silica.

[0058] Example 5 A method for preparing high borosilicate composite fireproof glass includes the following steps: 30% basic magnesium carbonate coated silica, 20% boron oxide coated silica, 2.5% pentaerythritol, and 2% borax were added sequentially to 37.4% water and mixed evenly. Then, 1% polyether modified organosilicon BYK-345, 1.2% organosilicon defoamer, 0.5% potassium hydroxide, 1.4% potassium dihydrogen phosphate, and 4% potassium fluorosilicate were added sequentially and mixed evenly to obtain a composite fire retardant liquid. A 6mm butyl rubber strip is wrapped around the edge of the upper borosilicate glass, leaving a grouting port. The lower borosilicate glass is aligned with the upper borosilicate glass, then glued and hot-pressed to form a 2.5mm cavity. Silicone sealant is filled on the outside of the butyl rubber strip, and the mixture is left to stand at room temperature for 10 hours. Composite fireproof liquid is then injected into the cavity through the grouting port. After filling, the grouting port is sealed with butyl rubber strip and silicone sealant, and then cured to obtain high borosilicate composite fireproof glass. The preparation method of basic magnesium carbonate coated silica includes the following steps: Add water to silica and mix well (mass ratio of silica to water is 1:12). Add 1 mol / L NaOH solution to adjust the pH to 10 to obtain a suspension. Then add 1 mol / L magnesium chloride solution to the suspension (volume ratio of suspension to magnesium chloride solution is 5:1). Stir at 400 rpm for 60 min to obtain the first solution. Urea was added to the first solution (the molar ratio of magnesium ions to urea in the first solution was 1:3). After mixing until completely dissolved, the mixture was reacted at 75°C for 6 hours. After the reaction was completed, the mixture was cooled to room temperature and allowed to stand for 6 hours. The mixture was then filtered, washed, and dried to obtain basic magnesium carbonate coated silica. A method for preparing boron oxide-coated silica includes the following steps: Water was added to silica and mixed evenly (the mass ratio of silica to water was 1:4) to obtain a suspension. Boric acid was added to the suspension (the mass ratio of silica to boric acid was 1:0.2), and the mixture was stirred at 600 rpm for 1.5 h. After stirring, dehydration was carried out, first at 100℃ for 2 h, then at 140℃ for 2 h, and finally at 260℃ for 2 h to obtain boron oxide-coated silica.

[0059] Example 6 A method for preparing high borosilicate composite fireproof glass includes the following steps: 35% basic magnesium carbonate coated silica, 15% boron oxide coated silica, 2.5% pentaerythritol, and 2% borax were added sequentially to 37.4% water and mixed evenly. Then, 1% polyether modified organosilicon BYK-345, 1.2% organosilicon defoamer, 0.5% potassium hydroxide, 1.4% potassium dihydrogen phosphate, and 4% potassium fluorosilicate were added sequentially and mixed evenly to obtain a composite fire retardant liquid. A 6mm butyl rubber strip is wrapped around the edge of the upper borosilicate glass, leaving a grouting port. The lower borosilicate glass is aligned with the upper borosilicate glass, then glued and hot-pressed to form a 2.5mm cavity. Silicone sealant is filled on the outside of the butyl rubber strip, and the mixture is left to stand at room temperature for 10 hours. Composite fireproof liquid is then injected into the cavity through the grouting port. After filling, the grouting port is sealed with butyl rubber strip and silicone sealant, and then cured to obtain high borosilicate composite fireproof glass. The preparation method of basic magnesium carbonate coated silica includes the following steps: Add water to silica and mix well (mass ratio of silica to water is 1:12). Add 1 mol / L NaOH solution to adjust the pH to 10 to obtain a suspension. Then add 1 mol / L magnesium chloride solution to the suspension (volume ratio of suspension to magnesium chloride solution is 5:1). Stir at 400 rpm for 60 min to obtain the first solution. Urea was added to the first solution (the molar ratio of magnesium ions to urea in the first solution was 1:3). After mixing until completely dissolved, the mixture was reacted at 75°C for 6 hours. After the reaction was completed, the mixture was cooled to room temperature and allowed to stand for 6 hours. The mixture was then filtered, washed, and dried to obtain basic magnesium carbonate coated silica. A method for preparing boron oxide-coated silica includes the following steps: Water was added to silica and mixed evenly (the mass ratio of silica to water was 1:3) to obtain a suspension. Boric acid was added to the suspension (the mass ratio of silica to boric acid was 1:0.26), and the mixture was stirred at 400 rpm for 2.5 h. After stirring, dehydration was carried out, first at 110℃ for 2 h, then at 160℃ for 2 h, and finally at 290℃ for 2 h to obtain boron oxide-coated silica.

[0060] Example 7 A method for preparing high borosilicate composite fireproof glass includes the following steps: 40% basic magnesium carbonate coated silica, 10% boron oxide coated silica, 2.5% pentaerythritol, and 2% borax were added sequentially to 37.4% water and mixed evenly. Then, 1% polyether modified organosilicon BYK-345, 1.2% organosilicon defoamer, 0.5% potassium hydroxide, 1.4% potassium dihydrogen phosphate, and 4% potassium fluorosilicate were added sequentially and mixed evenly to obtain a composite fire retardant liquid. A 6mm butyl rubber strip is wrapped around the edge of the upper borosilicate glass, leaving a grouting port. The lower borosilicate glass is aligned with the upper borosilicate glass, then glued and hot-pressed to form a 2.5mm cavity. Silicone sealant is filled on the outside of the butyl rubber strip, and the mixture is left to stand at room temperature for 10 hours. Composite fireproof liquid is then injected into the cavity through the grouting port. After filling, the grouting port is sealed with butyl rubber strip and silicone sealant, and then cured to obtain high borosilicate composite fireproof glass. The preparation method of basic magnesium carbonate coated silica includes the following steps: Add water to silica and mix well (mass ratio of silica to water is 1:12). Add 1 mol / L NaOH solution to adjust the pH to 10 to obtain a suspension. Then add 1 mol / L magnesium chloride solution to the suspension (volume ratio of suspension to magnesium chloride solution is 5:1). Stir at 400 rpm for 60 min to obtain the first solution. Urea was added to the first solution (the molar ratio of magnesium ions to urea in the first solution was 1:3). After mixing until completely dissolved, the mixture was reacted at 75°C for 6 hours. After the reaction was completed, the mixture was cooled to room temperature and allowed to stand for 6 hours. The mixture was then filtered, washed, and dried to obtain basic magnesium carbonate coated silica. A method for preparing boron oxide-coated silica includes the following steps: Water was added to silica and mixed evenly (the mass ratio of silica to water was 1:3) to obtain a suspension. Boric acid was added to the suspension (the mass ratio of silica to boric acid was 1:0.26), and the mixture was stirred at 400 rpm for 2.5 h. After stirring, dehydration was carried out, first at 110℃ for 2 h, then at 160℃ for 2 h, and finally at 290℃ for 2 h to obtain boron oxide-coated silica.

[0061] Example 8 A method for preparing high borosilicate composite fireproof glass includes the following steps: 45% basic magnesium carbonate coated silica, 5% boron oxide coated silica, 2.5% pentaerythritol, and 2% borax were added sequentially to 37.4% water and mixed evenly. Then, 1% polyether modified organosilicon BYK-345, 1.2% organosilicon defoamer, 0.5% potassium hydroxide, 1.4% potassium dihydrogen phosphate, and 4% potassium fluorosilicate were added sequentially and mixed evenly to obtain a composite fire retardant liquid. A 6mm butyl rubber strip is wrapped around the edge of the upper borosilicate glass, leaving a grouting port. The lower borosilicate glass is aligned with the upper borosilicate glass, then glued and hot-pressed to form a 2.5mm cavity. Silicone sealant is filled on the outside of the butyl rubber strip, and the mixture is left to stand at room temperature for 10 hours. Composite fireproof liquid is then injected into the cavity through the grouting port. After filling, the grouting port is sealed with butyl rubber strip and silicone sealant, and then cured to obtain high borosilicate composite fireproof glass. The preparation method of basic magnesium carbonate coated silica includes the following steps: Add water to silica and mix well (mass ratio of silica to water is 1:12). Add 1 mol / L NaOH solution to adjust the pH to 10 to obtain a suspension. Then add 1 mol / L magnesium chloride solution to the suspension (volume ratio of suspension to magnesium chloride solution is 5:1). Stir at 400 rpm for 60 min to obtain the first solution. Urea was added to the first solution (the molar ratio of magnesium ions to urea in the first solution was 1:3). After mixing until completely dissolved, the mixture was reacted at 75°C for 6 hours. After the reaction was completed, the mixture was cooled to room temperature and allowed to stand for 6 hours. The mixture was then filtered, washed, and dried to obtain basic magnesium carbonate coated silica. A method for preparing boron oxide-coated silica includes the following steps: Water was added to silica and mixed evenly (the mass ratio of silica to water was 1:3) to obtain a suspension. Boric acid was added to the suspension (the mass ratio of silica to boric acid was 1:0.26), and the mixture was stirred at 400 rpm for 2.5 h. After stirring, dehydration was carried out, first at 110℃ for 2 h, then at 160℃ for 2 h, and finally at 290℃ for 2 h to obtain boron oxide-coated silica.

[0062] Comparative Example 1 A method for preparing high borosilicate composite fireproof glass includes the following steps: 50% silica, 2.5% pentaerythritol, and 2% borax were added to 37.4% water in sequence and mixed evenly. Then, 1% polyether-modified organosilicon BYK-345, 1.2% organosilicon defoamer, 0.5% potassium hydroxide, 1.4% potassium dihydrogen phosphate, and 4% potassium fluorosilicate were added in sequence and mixed evenly to obtain a composite fire retardant liquid. A 6mm butyl rubber strip is wrapped around the edge of the upper borosilicate glass, leaving a grouting port. The lower borosilicate glass is aligned with the upper borosilicate glass, then glued and hot-pressed to form a 2.5mm cavity. Silicone sealant is filled on the outside of the butyl rubber strip, and the mixture is left to stand at room temperature for 10 hours. Composite fireproof liquid is then injected into the cavity through the grouting port. After filling, the grouting port is sealed with butyl rubber strip and silicone sealant, and then cured to obtain high borosilicate composite fireproof glass.

[0063] Comparative Example 2 A method for preparing high borosilicate composite fireproof glass includes the following steps: 50% boron oxide-coated silica, 2.5% pentaerythritol, and 2% borax were added sequentially to 37.4% water and mixed evenly. Then, 1% polyether-modified organosilicon BYK-345, 1.2% organosilicon defoamer, 0.5% potassium hydroxide, 1.4% potassium dihydrogen phosphate, and 4% potassium fluorosilicate were added sequentially and mixed evenly to obtain a composite fire retardant liquid. A 6mm butyl rubber strip is wrapped around the edge of the upper borosilicate glass, leaving a grouting port. The lower borosilicate glass is aligned with the upper borosilicate glass, then glued and hot-pressed to form a 2.5mm cavity. Silicone sealant is filled on the outside of the butyl rubber strip, and the mixture is left to stand at room temperature for 10 hours. Composite fireproof liquid is then injected into the cavity through the grouting port. After filling, the grouting port is sealed with butyl rubber strip and silicone sealant, and then cured to obtain high borosilicate composite fireproof glass. A method for preparing boron oxide-coated silica includes the following steps: Water was added to silica and mixed evenly (the mass ratio of silica to water was 1:3) to obtain a suspension. Boric acid was added to the suspension (the mass ratio of silica to boric acid was 1:0.26), and the mixture was stirred at 400 rpm for 2.5 h. After stirring, dehydration was carried out, first at 110℃ for 2 h, then at 160℃ for 2 h, and finally at 290℃ for 2 h to obtain boron oxide-coated silica.

[0064] Performance testing The test shall be conducted according to the method specified in GB 15763.1-2009 "Safety Glass for Building - Part 1: Fire-resistant Glass"; The performance of each embodiment and comparative example after testing is shown in Table 1.

[0065] Table 1 Performance test results of the high borosilicate composite fireproof glass prepared in Examples 1-8 and Comparative Examples 1-2

[0066] As shown in Table 1, the fire resistance integrity time of the high borosilicate composite fireproof glass prepared in Examples 1-7 is significantly higher than that of Comparative Example 1, indicating that adding basic magnesium carbonate-coated silica to the composite fireproof liquid can improve the fire resistance performance of the high borosilicate composite fireproof glass. The fire resistance integrity time of the high borosilicate composite fireproof glass prepared in Examples 4-8 is higher than that of Examples 3 and Comparative Example 2, indicating that the combination of basic magnesium carbonate-coated silica and boron oxide-coated silica can further improve the fire resistance performance of the high borosilicate composite fireproof glass. When the mass ratio of basic magnesium carbonate-coated silica to boron oxide-coated silica is limited to the range of 7-8:3-2, the fire resistance performance of the high borosilicate composite fireproof glass is further improved.

[0067] The above are merely preferred embodiments of the present invention and are not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A high borosilicate composite fireproof glass, characterized in that, It includes an upper layer of borosilicate glass, a composite fire retardant liquid, and a lower layer of borosilicate glass arranged from top to bottom; The composite fire retardant liquid comprises the following raw materials in the following mass percentages: 45%~60% modified silica, 1%~5% charring agent, 0.8%~2.4% charring aid, 1%~4% boride, 3%~5% curing agent, 0.3%~0.8% alkali regulator, 0.8%~1.2% leveling agent, 0.4%~1.2% defoamer, and the balance being water; The modified silica includes basic magnesium carbonate coated silica.

2. The high borosilicate composite fireproof glass according to claim 1, characterized in that, The preparation method of the basic magnesium carbonate coated silica includes the following steps: S1. Add water to silica and mix well. Adjust the pH to 9-10 to obtain a suspension. S2. Add magnesium chloride solution to the suspension and stir to obtain the first solution; S3. Add urea to the first solution, mix until completely dissolved, react, cool to room temperature, let stand and age, filter, wash, and dry to obtain the basic magnesium carbonate coated silica.

3. The high borosilicate composite fireproof glass according to claim 2, characterized in that, The mass ratio of silicon dioxide to water is 1:8~12; The volume ratio of the suspension to the magnesium chloride solution is 4~6:1; The concentration of the magnesium chloride solution is 0.8~1.2 mol / L; The molar ratio of magnesium ions to urea in the first solution is 1:3~4; The reaction is carried out at a temperature of 75-80°C for 4-8 hours.

4. The high borosilicate composite fireproof glass according to claim 1, characterized in that, The modified silica also includes boron oxide-coated silica.

5. The high borosilicate composite fireproof glass according to claim 4, characterized in that, The modified silica comprises basic magnesium carbonate coated silica and boron oxide coated silica in a mass ratio of 7~8:3~2.

6. The high borosilicate composite fireproof glass according to claim 4, characterized in that, The method for preparing boron oxide-coated silicon dioxide includes the following steps: A1. Add water to silica and mix well to obtain a suspension; A2. Add boric acid to the suspension, stir, and dehydrate to obtain boron oxide-coated silica.

7. The high borosilicate composite fireproof glass according to claim 6, characterized in that, The mass ratio of silicon dioxide to water is 1:3~4; The mass ratio of silicon dioxide to boric acid is 1:0.2~0.26; The dehydration includes a first stage of dehydration, a second stage of dehydration, and a third stage of dehydration; The first stage of dehydration is carried out at a temperature of 100~110℃ for 2 hours. The second stage of dehydration is carried out at a temperature of 140~160℃ for 2 hours. The third stage of dehydration is carried out at a temperature of 260~290℃ for 2 hours.

8. The high borosilicate composite fireproof glass according to claim 1, characterized in that, The char-forming agent includes one or more of glucose, sucrose, and pentaerythritol; The char-forming aid includes one of potassium dihydrogen phosphate and dipotassium hydrogen phosphate; The borides include borax.

9. The high borosilicate composite fireproof glass according to claim 1, characterized in that, The curing agent includes one of sodium fluorosilicate and potassium fluorosilicate; The alkali regulator includes potassium hydroxide; The leveling agent includes polyether-modified silicone BYK-345; The defoamer includes silicone defoamers.

10. A method for preparing high borosilicate composite fireproof glass, used to prepare the high borosilicate composite fireproof glass according to any one of claims 1 to 9, characterized in that, Includes the following steps: The raw materials of the composite fire retardant liquid are stirred evenly to obtain the composite fire retardant liquid; a butyl rubber strip is wrapped around the edge of the upper layer of high borosilicate glass, leaving a grouting port; the lower layer of high borosilicate glass is aligned with the upper layer of high borosilicate glass, and then glued and hot-pressed to form a cavity; silicone sealant is filled on the outside of the butyl rubber strip, and the mixture is left to stand; the composite fire retardant liquid is poured into the cavity through the grouting port; the grouting port is sealed with the butyl rubber strip, and the gaps in the grouting port are sealed with silicone sealant; the mixture is then cured to obtain high borosilicate composite fire retardant glass.

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