High-temperature-resistant waterproof glass wool and preparation method thereof

Abstract

The invention belongs to the technical field of glass wool, and particularly relates to high-temperature-resistant waterproof glass wool and a preparation method thereof. The high-temperature-resistant waterproof glass wool comprises the following raw materials in parts by weight: 65-80 parts of high-aluminum borosilicate glass fibers, 15-20 parts of mullite fibers, 8-10 parts of an additive A, 6-8 parts of an additive B and 2-5 parts of silicon carbide whiskers, according to the invention, high-aluminum borosilicate glass wool fibers are used as a matrix, the additive B is firstly used for preparing and realizing uniform dispersion of reinforcing filler in a ceramic precursor, and then the additive A is used for constructing a basic bonding hydrophobic network, in the preparation process, all the materials are efficiently and positively cooperated, and the additive and the glass wool fibers are used for reinforcing the bonding firmness through a multi-interface effect; the hydrophobic component and the ceramic phase realize functional complementation to guarantee lasting waterproofness and high-temperature stability, the reinforcing filler and the ceramic skeleton synergistically improve the mechanical property, and the high temperature resistance, lasting waterproofness, good mechanical property and environmental protection property of the final glass wool are realized.

Description

Technical Field

[0001] This invention belongs to the field of glass wool technology, specifically relating to a high-temperature resistant and waterproof glass wool and its preparation method. Background Technology

[0002] Glass wool is widely used in high-temperature applications such as industrial kiln insulation, high-temperature pipeline insulation, and aerospace thermal protection due to its lightweight and low thermal conductivity. Glass wool materials that combine high-temperature stability with durable waterproofing are crucial for adapting to complex, high-temperature, and humid service environments. Current technologies primarily employ two approaches to achieve high-temperature resistance and waterproofing in glass wool: one is to ceramicize the glass wool matrix or dope it with inorganic fillers to improve high-temperature stability; the other is to coat the glass wool surface with an organic or inorganic hydrophobic coating to achieve waterproofing. However, both of these existing solutions have insurmountable technical shortcomings, resulting in products whose overall performance cannot meet the demands of stringent operating conditions.

[0003] In the construction of surface waterproof coatings, while organic coating modification can achieve good hydrophobic effects at room temperature, organic materials themselves have poor high-temperature resistance and are prone to decomposition and carbonization in high-temperature environments above 300℃. Inorganic coating modification often suffers from high brittleness and weak bonding with glass wool fibers, making it prone to damage during transportation, installation, or long-term vibration, thus failing to guarantee durable waterproof performance. Some solutions use toxic and harmful adhesives such as formaldehyde-containing phenolic resins to improve bonding strength and waterproof effect, which can easily release harmful substances during production and use, endangering the environment and human health. Therefore, developing a preparation technology that integrates high-temperature stability, durable waterproof performance, and excellent mechanical properties has become the core research direction and technological breakthrough point in this field. Summary of the Invention

[0004] To address the shortcomings of existing technologies, this invention provides a high-temperature resistant waterproof glass wool and its preparation method. This application first uses additive B to achieve uniform dispersion of reinforcing filler in a ceramic precursor, then constructs a basic bonding hydrophobic network through a composite system of additive A. After fiber mixing and molding, gradient heat treatment, and surface superhydrophobic post-treatment, a high-performance high-temperature resistant waterproof glass wool is finally formed. This achieves integrated high-temperature stability, durable waterproofing, excellent mechanical properties, and environmental friendliness, effectively solving the core shortcomings of existing technologies, improving the overall service performance of the product, expanding its application range in high-temperature and complex working conditions, and possessing significant industrial application value.

[0005] To achieve the above-mentioned technical objectives, the technical solution adopted by the present invention is as follows: This invention provides a high-temperature resistant and waterproof glass wool, wherein the high-temperature resistant and waterproof glass wool comprises the following raw materials in parts by weight: 65-80 parts of high-alumina borosilicate glass fiber, 15-20 parts of mullite fiber, 8-10 parts of additive A, 6-8 parts of additive B, 2-5 parts of silicon carbide whiskers, and 1-2 parts of TiO2. Additive A comprises raw materials in the following mass ratio: TiB2:polyferrocene-based carbosilane = 1:5; The preparation method of additive A includes the following steps: (1) Weigh TiB2 and add it to anhydrous ethanol. The mass ratio of anhydrous ethanol to TiB2 is 8-12:1. Disperse the mixture by ultrasonication for 30-40 minutes to form a suspension. (2) Weigh out polyferrocene-based carbon silane and a tetrahydrofuran (THF) solution of 0.5 mol / L 9-BBN (9-boronbicyclo[3.3.1]nonane). The ratio of polyferrocene-based carbon silane to THF solution is 1 g: 2-5 mL. Mix them under an argon atmosphere, heat the reaction mixture to 30 °C and stir for 24 hours. Finally, remove the solvent under vacuum to obtain a viscous oily precursor. (3) Transfer all the suspension to the ball mill jar, add the oily precursor, then add the zirconia grinding balls, control the grinding balls, install the ball mill jar on the planetary ball mill, and perform ball milling. After the ball milling is completed, let the ball mill jar stand at room temperature, collect the slurry, and form additive A.

[0006] Additive B comprises the following raw materials in the following mass ratio: microcrystalline cellulose: NaIO4: magnesium acrylate: perfluorooctane = 5:8-9.5:1:0.05; The preparation method of additive B includes the following steps: (a) Weigh microcrystalline cellulose and NaIO4, add them to deionized water, and stir for 72 hours at room temperature in the dark. At the end of the reaction, add ethylene glycol to the mixture to quench the reaction. The ratio of microcrystalline cellulose, deionized water and ethylene glycol is 1g:20-30mL:10mL. Then dialyze the mixture to obtain a purified DAC (dialdehyde cellulose) suspension. Subsequently, stir the DAC suspension at 100°C for 1 hour to dissolve it, then centrifuge for 30 minutes and collect the supernatant to obtain the DAC solution. (b) Add perfluorooctane to the DAC solution, stir and mix evenly to stabilize the pH at 4.5, stir the reaction in a constant temperature water bath for 5 hours, centrifuge for 10 minutes, wash and dry to obtain the modified powder; (c) Weigh magnesium acrylate, dissolve it in a mixed solvent to prepare a magnesium acrylate solution, add the modified powder to the magnesium acrylate solution, start high-speed stirring, stir for 30 minutes, and then ultrasonically disperse for 20 minutes to ensure that the modified powder is evenly dispersed to obtain additive B.

[0007] This invention also provides a method for preparing high-temperature resistant and waterproof glass wool, specifically including the following steps: S1. In a container with a stirrer, add deionized water and dispersant in sequence, stir at low speed until uniform, keep stirring, slowly add TiO2 and silicon carbide whiskers, and disperse at high speed for 30 minutes to ensure that the filler is uniformly dispersed without agglomeration. Adjust the stirring speed to medium speed, and slowly add additive B and additive A in sequence, and continue stirring at medium speed for 2 hours to form a composite impregnation solution. S2, put the high-alumina borosilicate glass wool fiber into the opening machine, fully open it, remove the clumps, put the opened high-alumina borosilicate glass wool fiber into the paddle mixer, start the stirring, and spray the composite impregnation liquid evenly into the tumbling fiber through the spray device, continue mixing for 15-20 minutes until all the fibers are evenly coated with the impregnation liquid and form moist granules. S3. Spread the moist granules evenly into the mold, filter them, and apply light pressure of 0.1-0.2 MPa to form a wet felt blank of a specified density. Transfer the wet felt blank into a forced-air drying oven and perform programmed temperature rise curing: raise the temperature from room temperature to 80℃ at a rate of 2-3℃ / min and hold for 4 hours, then raise the temperature to 120℃ at a rate of 2℃ / min and hold for 2 hours, and then raise the temperature from 120℃ to 180℃ at a rate of 1-2℃ / min and hold for 3 hours to form a pre-cured blank. S4. The pre-cured preform is placed in an inert atmosphere tube furnace and subjected to programmed heat treatment under an inert atmosphere. The temperature is increased to 350°C at a rate of 2°C / min and held for 1 hour. Then, the temperature is increased to 600°C at a rate of 3°C / min and held for 1 hour to allow the organic components in the composite agent A to decompose and carbonize slowly, avoiding rapid decomposition and gas generation that could cause the preform to crack. The temperature is increased to 900°C at a rate of 5°C / min and held for 1 hour. Then, the temperature is increased to 1100°C at a rate of 5°C / min and held for 2 hours. After the program is completed, the heating device is turned off and the preform is cooled to below 80°C in the furnace to obtain the skeleton substrate. S5. Place the skeleton substrate into a vacuum drying oven and perform gas phase modification simultaneously: close the vacuum drying oven door, evacuate to a pressure ≤ -0.09MPa, heat to 150℃, maintain for 2 hours, and cool to room temperature to obtain high-temperature resistant waterproof glass wool.

[0008] Furthermore, the dispersant is selected from one of polyethylene glycol, sodium lignosulfonate, KH-550, and KH560.

[0009] Compared with the prior art, the beneficial effects achieved by the present invention are as follows: 1. Additive B forms stable hydrogen bonds with the hydroxyl groups on the surface of high-alumina borosilicate glass wool fibers, and the carboxyl groups of magnesium acrylate form coordination with metal ions on the fiber surface. The multiple interfacial interactions not only improve the bonding strength between the composite coating and the fiber, preventing the coating from falling off under high-temperature conditions, but also alleviate the difference in thermal expansion coefficients between the fiber and the coating, reducing structural damage caused by thermal stress.

[0010] 2. Inert perfluorooctane hydrophobic chains are covalently grafted onto a dialdehyde cellulose backbone rich in active aldehyde groups. This not only acts as a hydrophobic agent, but its aldehyde groups themselves are also powerful chemical bonding centers, capable of bonding with the glass fiber surface and other components within the system, achieving a fundamental unity of waterproofing and bonding functions. The perfluoroalkyl groups introduced by the perfluorooctane and the perfluoro segments formed by gas-phase modification superimpose to construct a double hydrophobic barrier; simultaneously, the silicon carbide and other ceramic phases formed during the ceramization process provide a stable supporting framework for the hydrophobic components, preventing the hydrophobic groups from being lost or decomposed at high temperatures, thus solving the problem of high-temperature failure in traditional organic hydrophobic materials.

[0011] 3. Additive A undergoes gradual decomposition and carbonization during gradient heat treatment, providing a carbon source for the ceramization reaction and avoiding structural defects caused by rapid decomposition and gas generation. The decomposition products are tightly combined with the ceramic phase formed by the transformation of the ceramic precursor, achieving a smooth transition from the organic phase to the inorganic phase. This ensures that the material maintains its complete structure after high-temperature ceramization, while retaining some of the hydrophobic properties brought about by organic modification, thus achieving a balance between high-temperature stability and water resistance. Attached Figure Description

[0012] Figure 1 Thermogravimetric curve of the high-temperature resistant waterproof glass wool prepared according to the present invention; Figure 2 SEM image of the high-temperature resistant and waterproof glass wool prepared according to the present invention; Figure 3 The hydrophobic angle diagram is shown for the high-temperature resistant and waterproof glass wool prepared according to the present invention. Detailed Implementation

[0013] To enable those skilled in the art to better understand the technical solutions of the present invention and to make the above-mentioned features, objectives, and advantages of the present invention clearer and easier to understand, the present invention will be further described below with reference to embodiments. These embodiments are for illustrative purposes only and are not intended to limit the scope of the present invention.

[0014] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those familiar to those skilled in the art. Furthermore, any methods and materials similar to or equivalent to those described herein may be applied to this invention. The preferred embodiments and materials described herein are for illustrative purposes only and do not limit the scope of this application.

[0015] Unless otherwise specified, all methods described in the following embodiments are conventional. Unless otherwise specified, all materials used in the following embodiments are new materials purchased from the market.

[0016] Example 1: This example provides a high-temperature resistant waterproof glass wool, which includes the following raw materials in parts by weight: 65 parts high-alumina borosilicate glass fiber, 15 parts mullite fiber, 8 parts additive A, 6 parts additive B, 2 parts silicon carbide whiskers, and 1 part TiO2. Additive A comprises raw materials in the following mass ratio: TiB2:polyferrocene-based carbosilane = 1:5; The preparation method of additive A includes the following steps: (1) Weigh TiB2 and add it to a beaker containing anhydrous ethanol. The mass ratio of anhydrous ethanol to TiB2 is 8:1. Place the beaker in an ultrasonic cleaner and ultrasonically disperse for 30 minutes. During the ultrasonic process, an ice water bath should be used to cool the outside of the beaker to prevent excessive ethanol evaporation and the formation of a preliminary dispersed suspension. (2) Weigh out polyferrocene-based carbosilane and THF solution with a concentration of 0.5 mol / L 9-BBN. The ratio of polyferrocene-based carbosilane to THF solution is 1 g: 2 mL. Add them to a Schlenk flask equipped with a magnetic stirrer and a reflux condenser. Mix them under an argon atmosphere. Heat the reaction mixture to 30 °C and stir for 24 hours. Finally, remove the solvent under vacuum to obtain a viscous oily precursor. (3) Transfer all the suspension to the ball mill jar, add the oily precursor, then add the zirconia grinding balls, control the grinding balls, install the ball mill jar on the planetary ball mill, set the spindle revolution speed to 280 rpm, run for 6 hours, after the ball milling is completed, let the ball mill jar stand at room temperature, open the ball mill jar, use a scraper to scrape off the slurry attached to the jar wall and grinding balls, collect them together to form additive A.

[0017] Additive B comprises the following raw materials in the following mass ratio: microcrystalline cellulose: NaIO4: magnesium acrylate: perfluorooctane = 5:8:1:0.05; The preparation method of additive B includes the following steps: (a) Weigh microcrystalline cellulose and NaIO4, add them to deionized water, and stir for 72 hours at room temperature in the dark. At the end of the reaction, add ethylene glycol to the mixture to quench the reaction. The ratio of microcrystalline cellulose, deionized water and ethylene glycol is 1 g: 20 mL: 10 mL. Dialyze the completed suspension in deionized water using a dialysis bag at 3500 Da for 7 days to obtain a purified DAC suspension. Then, dissolve the DAC suspension by stirring at 100 °C for 1 hour, and then centrifuge at 14000 rpm for 30 minutes to remove a small amount of insoluble matter. Collect the supernatant to obtain the DAC solution. (b) Take the DAC solution and place it in a three-necked flask. Add perfluorooctane and stir to mix evenly. Add acetate buffer solution with pH 4.5 to stabilize the pH of the reaction system at 4.5. Place the three-necked flask in a 60°C constant temperature water bath, turn on the stirrer, and react for 5 hours to allow the amino group of perfluorooctane and the aldehyde group of DAC to fully undergo the Schiff base reaction. After the reaction is complete, slowly pour the mixture into excess anhydrous ethanol to precipitate a yellow precipitate. Centrifuge at 8000 rpm for 10 minutes to collect the precipitate. Wash the precipitate 3 times with anhydrous ethanol. Place the precipitate in a 60°C oven to dry for 2 hours to obtain the modified powder. (c) Weigh magnesium acrylate and dissolve it in a mixed solvent, which is a mixture of ethanol and deionized water in a volume ratio of 1:1 to prepare a magnesium acrylate solution with a mass concentration of 20%. Add the modified powder to the magnesium acrylate solution, start high-speed stirring at 1500 rpm, stir for 30 minutes, and then ultrasonically disperse for 20 minutes to ensure that the modified powder is evenly dispersed to obtain additive B.

[0018] This embodiment also provides a method for preparing high-temperature resistant and waterproof glass wool, which specifically includes the following steps: S1. In a container with a stirrer, add deionized water and polyethylene glycol in sequence, stir at low speed until homogeneous, and continue stirring. Slowly add TiO2 and silicon carbide whiskers, start a high-speed shear disperser at 3000 rpm, and disperse for 30 minutes to ensure uniform dispersion of the filler without agglomeration. Adjust the stirring speed to medium speed at 1000 rpm, and slowly add additive B and additive A in sequence. Continue stirring at medium speed for 2 hours to form a composite impregnation solution. By adding anhydrous ethanol, the solid content is controlled at 18%. S2, put the high-alumina borosilicate glass wool fiber into the opening machine, fully open it, remove clumps, and ensure that the fiber is fluffy and uniform. Then, put the opened high-alumina borosilicate glass wool fiber into the paddle mixer, start the stirring, and spray the composite impregnation liquid evenly into the tumbling fiber through the spray device. Continue mixing for 15 minutes until all the fibers are evenly coated with the impregnation liquid and form moist granules. S3. The moist granules are evenly spread into a mold of predetermined size, placed on a vacuum filtration device for filtration, and simultaneously subjected to a light pressure of 0.1 MPa to form a product with a density of 80 kg / m³. 3 The wet felt blank is transferred into a forced-air drying oven and subjected to programmed temperature rise and curing: the temperature is raised from room temperature to 80°C at a rate of 2°C / min and held for 4 hours, then raised to 120°C at a rate of 2°C / min and held for 2 hours, and then raised from 120°C to 180°C at a rate of 1°C / min and held for 3 hours to form a pre-cured blank. S4. Place the pre-cured preform into an atmosphere tube furnace, introduce high-purity argon gas, and replace the air in the furnace three times to ensure inert atmosphere protection throughout the process. Perform programmed heat treatment: heat from room temperature to 350°C at a rate of 2°C / min and hold for 1 hour, then heat to 600°C at a rate of 3°C / min and hold for 1 hour to allow the organic components in composite agent A to decompose and carbonize slowly, avoiding rapid decomposition and gas generation that could cause the preform to crack. Then heat to 900°C at a rate of 5°C / min and hold for 1 hour, then heat to 1100°C at a rate of 5°C / min and hold for 2 hours. After the program is completed, turn off the heating device and cool with the furnace to below 80°C before removing it from the furnace to obtain the skeleton substrate. S5. Place the skeleton substrate into a vacuum drying oven, and at the same time place an open container filled with POTS liquid inside the oven for gas phase modification: close the vacuum drying oven door, evacuate to a pressure of -0.09MPa, raise the temperature to 150℃, maintain for 2 hours, and after the treatment is completed, cool to room temperature with the oven to obtain high temperature resistant waterproof glass wool.

[0019] Example 2: This example provides a high-temperature resistant waterproof glass wool, which includes the following raw materials in parts by weight: 70 parts high-alumina borosilicate glass fiber, 18 parts mullite fiber, 9 parts additive A, 7 parts additive B, 3 parts silicon carbide whiskers, and 1.5 parts TiO2. Additive A comprises raw materials in the following mass ratio: TiB2:polyferrocene-based carbosilane = 1:5; The preparation method of additive A includes the following steps: (1) Weigh TiB2 and add it to a beaker containing anhydrous ethanol. The mass ratio of anhydrous ethanol to TiB2 is 10:1. Place the beaker in an ultrasonic cleaner and ultrasonically disperse for 35 minutes. During the ultrasonic process, an ice water bath should be used to cool the outside of the beaker to prevent excessive ethanol evaporation and the formation of a preliminary dispersed suspension. (2) Weigh out polyferrocene-based carbosilane and THF solution with a concentration of 0.5 mol / L 9-BBN. The ratio of polyferrocene-based carbosilane to THF solution is 1 g: 3 mL. Add them to a Schlenk flask equipped with a magnetic stirrer and a reflux condenser. Mix them under an argon atmosphere. Heat the reaction mixture to 30 °C and stir for 24 hours. Finally, remove the solvent under vacuum to obtain a viscous oily precursor. (3) Transfer all the suspension to the ball mill jar, add the oily precursor, then add the zirconia grinding balls, control the grinding balls, install the ball mill jar on the planetary ball mill, set the spindle revolution speed to 300 rpm, run for 7 hours, after the ball milling is completed, let the ball mill jar stand at room temperature, open the ball mill jar, use a scraper to scrape off the slurry attached to the jar wall and grinding balls, collect them together to form additive A.

[0020] Additive B comprises the following raw materials in the following mass ratio: microcrystalline cellulose: NaIO4: magnesium acrylate: perfluorooctane = 5:8.5:1:0.05; The preparation method of additive B includes the following steps: (a) Weigh microcrystalline cellulose and NaIO4, add them to deionized water, and stir for 72 hours at room temperature in the dark. At the end of the reaction, add ethylene glycol to the mixture to quench the reaction. The ratio of microcrystalline cellulose, deionized water and ethylene glycol is 1 g: 25 mL: 10 mL. Dialyze the completed suspension in deionized water using a dialysis bag at 3500 Da for 7 days to obtain a purified DAC suspension. Then, dissolve the DAC suspension by stirring at 100 °C for 1 hour, and then centrifuge at 14000 rpm for 30 minutes to remove a small amount of insoluble matter. Collect the supernatant to obtain the DAC solution. (b) Take the DAC solution and place it in a three-necked flask. Add perfluorooctane and stir to mix evenly. Add acetate buffer solution with pH 4.5 to stabilize the pH of the reaction system at 4.5. Place the three-necked flask in a 60°C constant temperature water bath, turn on the stirrer, and react for 5 hours to allow the amino group of perfluorooctane and the aldehyde group of DAC to fully undergo the Schiff base reaction. After the reaction is complete, slowly pour the mixture into excess anhydrous ethanol to precipitate a yellow precipitate. Centrifuge at 8000 rpm for 10 minutes to collect the precipitate. Wash the precipitate 3 times with anhydrous ethanol. Place the precipitate in a 60°C oven to dry for 2 hours to obtain the modified powder. (c) Weigh magnesium acrylate and dissolve it in a mixed solvent, which is a mixture of ethanol and deionized water in a volume ratio of 1:1 to prepare a magnesium acrylate solution with a mass concentration of 20%. Add the modified powder to the magnesium acrylate solution, start high-speed stirring at 1500 rpm, stir for 30 minutes, and then ultrasonically disperse for 20 minutes to ensure that the modified powder is evenly dispersed to obtain additive B.

[0021] This embodiment also provides a method for preparing high-temperature resistant and waterproof glass wool, which specifically includes the following steps: S1. In a container with a stirrer, add deionized water and sodium lignosulfonate in sequence, stir at low speed until homogeneous, and while maintaining the stirring state, slowly add TiO2 and silicon carbide whiskers. Start a high-speed shear disperser at 3000 rpm and disperse for 30 minutes to ensure uniform dispersion of the filler without agglomeration. Adjust the stirring speed to medium speed at 1000 rpm, and slowly add additive B and additive A in sequence, continuing to stir at medium speed for 2 hours to form a composite impregnation solution. By adding anhydrous ethanol, the solid content is controlled at 20%. S2, put the high-alumina borosilicate glass wool fiber into the opening machine, fully open it, remove clumps, and ensure that the fiber is fluffy and uniform. Then, put the opened high-alumina borosilicate glass wool fiber into the paddle mixer, start the stirring, and spray the composite impregnation liquid evenly into the tumbling fiber through the spray device. Continue mixing for 18 minutes until all the fibers are evenly coated with the impregnation liquid and form moist granules. S3. The moist granules are evenly spread into a mold of predetermined size, placed on a vacuum filtration device for filtration, and simultaneously subjected to a light pressure of 0.2 MPa to form a product with a density of 100 kg / m³. 3 The wet felt blank is transferred into a forced-air drying oven and subjected to programmed temperature rise and curing: the temperature is raised from room temperature to 80°C at a rate of 2.5°C / min and held for 4 hours, then raised to 120°C at a rate of 2°C / min and held for 2 hours, and then raised from 120°C to 180°C at a rate of 1.5°C / min and held for 3 hours to form a pre-cured blank; S4. Place the pre-cured preform into an atmosphere tube furnace, introduce high-purity argon gas, and replace the air in the furnace three times to ensure inert atmosphere protection throughout the process. Perform programmed heat treatment: heat from room temperature to 350°C at a rate of 2°C / min and hold for 1 hour, then heat to 600°C at a rate of 3°C / min and hold for 1 hour to allow the organic components in composite agent A to decompose and carbonize slowly, avoiding rapid decomposition and gas generation that could cause the preform to crack. Then heat to 900°C at a rate of 5°C / min and hold for 1 hour, then heat to 1100°C at a rate of 5°C / min and hold for 2 hours. After the program is completed, turn off the heating device and cool with the furnace to below 80°C before removing it from the furnace to obtain the skeleton substrate. S5. Place the skeleton substrate into a vacuum drying oven, and at the same time place an open container filled with POTS liquid inside the oven for gas phase modification: close the vacuum drying oven door, evacuate to a pressure of -0.1MPa, raise the temperature to 150℃, maintain for 2 hours, and after the treatment is completed, cool to room temperature with the oven to obtain high temperature resistant waterproof glass wool.

[0022] Example 3: This example provides a high-temperature resistant waterproof glass wool, which includes the following raw materials in parts by weight: 80 parts high-alumina borosilicate glass fiber, 20 parts mullite fiber, 10 parts additive A, 8 parts additive B, 5 parts silicon carbide whiskers, and 2 parts TiO2. Additive A comprises raw materials in the following mass ratio: TiB2:polyferrocene-based carbosilane = 1:5; The preparation method of additive A includes the following steps: (1) Weigh TiB2 and add it to a beaker containing anhydrous ethanol. The mass ratio of anhydrous ethanol to TiB2 is 12:1. Place the beaker in an ultrasonic cleaner and ultrasonically disperse for 40 minutes. During the ultrasonic process, an ice water bath should be used to cool the outside of the beaker to prevent excessive ethanol evaporation and the formation of a preliminary dispersed suspension. (2) Weigh out polyferrocene-based carbosilane and THF solution with a concentration of 0.5 mol / L 9-BBN. The ratio of polyferrocene-based carbosilane to THF solution is 1 g: 5 mL. Add them to a Schlenk flask equipped with a magnetic stirrer and a reflux condenser. Mix them under an argon atmosphere. Heat the reaction mixture to 30 °C and stir for 24 hours. Finally, remove the solvent under vacuum to obtain a viscous oily precursor. (3) Transfer all the suspension to the ball mill jar, add the oily precursor, then add the zirconia grinding balls, control the grinding balls, install the ball mill jar on the planetary ball mill, set the spindle revolution speed to 300 rpm, run for 8 hours, after the ball milling is completed, let the ball mill jar stand at room temperature, open the ball mill jar, use a scraper to scrape off the slurry attached to the jar wall and grinding balls, collect them together to form additive A.

[0023] Additive B comprises the following raw materials in the following mass ratio: microcrystalline cellulose: NaIO4: magnesium acrylate: perfluorooctane = 5:9.5:1:0.05; The preparation method of additive B includes the following steps: (a) Weigh microcrystalline cellulose and NaIO4, add them to deionized water, and stir for 72 hours at room temperature in the dark. At the end of the reaction, add ethylene glycol to the mixture to quench the reaction. The ratio of microcrystalline cellulose, deionized water and ethylene glycol is 1 g: 30 mL: 10 mL. Dialyze the completed suspension in deionized water using a dialysis bag at 3500 Da for 7 days to obtain a purified DAC suspension. Then, dissolve the DAC suspension by stirring at 100 °C for 1 hour, and then centrifuge at 14000 rpm for 30 minutes to remove a small amount of insoluble matter. Collect the supernatant to obtain the DAC solution. (b) Take the DAC solution and place it in a three-necked flask. Add perfluorooctane and stir to mix evenly. Add acetate buffer solution with pH 4.5 to stabilize the pH of the reaction system at 4.5. Place the three-necked flask in a 60°C constant temperature water bath, turn on the stirrer, and react for 5 hours to allow the amino group of perfluorooctane and the aldehyde group of DAC to fully undergo the Schiff base reaction. After the reaction is complete, slowly pour the mixture into excess anhydrous ethanol to precipitate a yellow precipitate. Centrifuge at 8000 rpm for 10 minutes to collect the precipitate. Wash the precipitate 3 times with anhydrous ethanol. Place the precipitate in a 60°C oven to dry for 2 hours to obtain the modified powder. (c) Weigh magnesium acrylate and dissolve it in a mixed solvent, which is a mixture of ethanol and deionized water in a volume ratio of 1:1 to prepare a magnesium acrylate solution with a mass concentration of 20%. Add the modified powder to the magnesium acrylate solution, start high-speed stirring at 1500 rpm, stir for 30 minutes, and then ultrasonically disperse for 20 minutes to ensure that the modified powder is evenly dispersed to obtain additive B.

[0024] This embodiment also provides a method for preparing high-temperature resistant and waterproof glass wool, which specifically includes the following steps: S1. In a container with a stirrer, add deionized water and KH-550 in sequence, stir at low speed until homogeneous, and while maintaining the stirring state, slowly add TiO2 and silicon carbide whiskers. Start a high-speed shear disperser at 3000 rpm and disperse for 30 minutes to ensure that the filler is evenly dispersed without agglomeration. Adjust the stirring speed to medium speed at 1000 rpm, and slowly add additive B and additive A in sequence, continuing to stir at medium speed for 2 hours to form a composite impregnation solution. By adding anhydrous ethanol, the solid content is controlled at 22%. S2. Place the high-alumina borosilicate glass wool fibers into the opening machine, open them fully, remove clumps, and ensure that the fibers are fluffy and uniform. Then, put the opened high-alumina borosilicate glass wool fibers into the paddle mixer, start the stirring, and spray the composite impregnation liquid evenly into the tumbling fibers through the spray device. Continue mixing for 20 minutes until all the fibers are evenly coated with the impregnation liquid and form moist granules. S3. The moist granules are evenly spread into a mold of predetermined size, placed on a vacuum filtration device for filtration, and simultaneously subjected to a light pressure of 0.2 MPa to form a product with a density of 120 kg / m³. 3 The wet felt blank is transferred into a forced-air drying oven and subjected to programmed temperature rise and curing: the temperature is raised from room temperature to 80°C at a rate of 3°C / min and held for 4 hours, then raised to 120°C at a rate of 2°C / min and held for 2 hours, and then raised from 120°C to 180°C at a rate of 2°C / min and held for 3 hours to form a pre-cured blank. S4. Place the pre-cured preform into an atmosphere tube furnace, introduce high-purity argon gas, and replace the air in the furnace three times to ensure inert atmosphere protection throughout the process. Perform programmed heat treatment: heat from room temperature to 350°C at a rate of 2°C / min and hold for 1 hour, then heat to 600°C at a rate of 3°C / min and hold for 1 hour to allow the organic components in composite agent A to decompose and carbonize slowly, avoiding rapid decomposition and gas generation that could cause the preform to crack. Then heat to 900°C at a rate of 5°C / min and hold for 1 hour, then heat to 1100°C at a rate of 5°C / min and hold for 2 hours. After the program is completed, turn off the heating device and cool with the furnace to below 80°C before removing it from the furnace to obtain the skeleton substrate. S5. Place the skeleton substrate into a vacuum drying oven, and at the same time place an open container filled with POTS liquid inside the oven for gas phase modification: close the vacuum drying oven door, evacuate to a pressure of -0.1MPa, raise the temperature to 150℃, maintain for 2 hours, and after the treatment is completed, cool to room temperature with the oven to obtain high temperature resistant waterproof glass wool.

[0025] The difference between Comparative Example 1 and Example 1 is that additive A is not added; the rest is exactly the same as Example 2.

[0026] The difference between Comparative Example 1 and Example 1 is that additive B is not added; the rest is exactly the same as Example 2.

[0027] The difference between Comparative Example 3 and Example 1 is that no heat treatment process is performed; the rest is exactly the same as Example 2.

[0028] Experimental Example 1: Tear Strength / Elongation at Break: High-temperature resistant waterproof glass wool prepared in Examples 1-3 and Comparative Examples 1-3 of this invention was used as test specimens, and the tear strength was tested using an electronic single-yarn tensile strength tester. During the test, the test specimen must break away from the test fixture to ensure accurate results. If slippage occurs during the test or the specimen breaks at the fixture, the test must be repeated. The tear strength was calculated using the formula: F s =F max / d; where F s Tear strength, N / m; F max d represents the maximum tensile force for tearing cotton felt, in N; d is the thickness of the cotton felt, in mm. Elongation at break is calculated using the formula: In the formula, Elongation at break, % The value of l1 is the elongation within the gauge length when the specimen breaks, measured in mm; l0 is the original gauge length, measured in mm. The test results are recorded in Table 1.

[0029] Experimental Example 2: Thermal Conductivity: The room-temperature thermal conductivity of glass wool was tested using a Netzsch HFM 436 heat flow method thermal conductivity analyzer (Germany). High-temperature resistant waterproof glass wool prepared in Examples 1-3 and Comparative Examples 1-3 of this invention was used as test samples. The glass wool was cut into 300mm × 300mm pieces and placed horizontally on a cold plate. The hot plate was adjusted downwards to compress the wool to a certain thickness. The temperature gradient between the cold and hot plates was input (cold plate: 10℃, hot plate: 38℃). A calibrated heat flow sensor was used to measure the heat flow from the hot plate through the glass wool to the cold plate, and the thermal conductivity of the glass wool was calculated according to the following formula: In the formula, Q is the heat flow generated through the glass wool, and λ is the thermal conductivity. The thickness of the glass wool; For temperature gradient.

[0030] The high-temperature thermal conductivity of glass wool was tested using a Swedish HotDisk TPS 2500 thermal conductivity meter. Glass wool samples were cut into 100mm × 100mm pieces, and the temperature gradient between the hot and cold plates (-100-700℃) was input as required. The high-temperature thermal conductivity of the glass wool was calculated using the measured heat flow, glass wool thickness, and temperature gradient. The results of the room-temperature thermal conductivity and the high-temperature thermal conductivity at 600℃ are recorded in Table 1.

[0031] Table 1: Test Results of Basic Performance of the High-Temperature Resistant Waterproof Glass Wool of the Invention

[0032] As shown in Table 1, compared with Comparative Examples 1-3, Examples 1-3 exhibited superior mechanical properties and thermal conductivity. The results of Comparative Example 1 indicate that without additive A, the material lost its key high-temperature performance, with its high-temperature thermal conductivity decreasing by approximately 50% compared to the examples, demonstrating that additive A plays a crucial role in constructing a high-temperature resistant, low-thermal-conductivity ceramic network. The results of Comparative Example 2 indicate that without the initial chemical bonding and network provided by additive B, the fibers cannot be effectively bonded, demonstrating the fundamental role of additive B as a structural adhesive and waterproofing source. The results of Comparative Example 3 indicate that gradient heat treatment is indispensable for preparing high-performance high-temperature resistant fireproof glass wool.

[0033] Figure 1 and 3 The blank group consisted of high-alumina borosilicate glass wool fibers and mullite fibers, prepared using the same wet molding and gradient heat treatment process as in the examples. Figure 1 The results show that in Example 2 of the present invention, the mass residue rate was 90.5% at 790 °C, while that of the blank group was only 60%, indicating that the high-temperature resistant waterproof glass wool prepared by the present invention has excellent high-temperature resistance and can be applied in high-temperature fields. Figure 2The high-temperature resistant glass fibers prepared by this invention exhibit a continuous fiber morphology, with fibers bonded together and slight bulging at the overlaps. They intertwine and overlap to form a complex network structure, thereby improving the strength of the prepared high-temperature resistant waterproof glass wool. Figure 3 The results show that the high-temperature resistant, waterproof, glass wool-free material prepared by this invention is hydrophobic with a contact angle of 153.2°, while the blank group is hydrophilic.

[0034] In summary, this application successfully achieved the efficient preparation of high-temperature resistant and waterproof glass wool through a multi-stage synergistic preparation process. This invention uses high-alumina borosilicate glass wool fiber as the matrix. First, additive B is used to prepare a uniform dispersion of reinforcing filler in a ceramic precursor. Then, a basic bonding hydrophobic network is constructed through a composite system using additive A. After fiber mixing and molding, gradient heat treatment, and superhydrophobic surface post-treatment, a high-performance finished product is finally formed. Throughout the preparation process, efficient positive synergy is formed among the various materials. The composite system and glass wool fiber strengthen the bonding through multiple interfacial interactions. The hydrophobic components and the ceramic phase achieve functional complementarity, ensuring long-lasting waterproofing and high-temperature stability. The reinforcing filler and the ceramic skeleton synergistically improve mechanical properties. The smooth transition between the organic and inorganic systems ensures structural integrity. This process not only avoids the core pain points of traditional technologies, such as the difficulty in simultaneously achieving waterproofing and high-temperature resistance, and weak interfacial bonding, but also improves environmental friendliness through the introduction of bio-based materials, constructing an innovative system integrating multiple properties. The prepared glass wool felt possesses excellent high-temperature resistance, long-lasting waterproofing, good mechanical properties, and environmental friendliness, demonstrating clear technological innovation and industrial application value.

[0035] The above description is only a preferred embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any equivalent substitutions or modifications made by those skilled in the art within the scope of the technology disclosed in the present invention, based on the technical solution and inventive concept of the present invention, should be covered within the scope of protection of the present invention.

Claims

1. A high-temperature resistant and waterproof glass wool, characterized in that, The raw materials include the following parts by weight: 65-80 parts high alumina borosilicate glass fiber, 15-20 parts mullite fiber, 8-10 parts additive A, 6-8 parts additive B, 2-5 parts silicon carbide whiskers, and 1-2 parts TiO2. Additive A comprises raw materials in the following mass ratio: TiB2:polyferrocene-based carbosilane = 1:5; The preparation method of additive A includes the following steps: (1) Weigh TiB2 and add it to anhydrous ethanol, then disperse it by ultrasonication to form a suspension; (2) Take polyferrocene-based carbosilane and THF solution, heat and stir under an inert atmosphere to obtain an oily precursor; (3) Add the oily precursor to the suspension, then add zirconium oxide grinding balls and ball mill to form additive A.

2. The high-temperature resistant and waterproof glass wool according to claim 1, characterized in that, In step (1), the mass ratio of anhydrous ethanol to TiB2 is 8-12:1; In step (2), the ratio of polyferrocene-based carbosilane to THF solution is 1g:2-5mL.

3. The high-temperature resistant and waterproof glass wool according to claim 1, characterized in that, Additive B comprises the following raw materials in the following mass ratio: microcrystalline cellulose: NaIO4: magnesium acrylate: perfluorooctane = 5:8-9.5:1:0.05; The preparation method of additive B includes the following steps: (a) Weigh microcrystalline cellulose and NaIO4, add them to deionized water, stir at room temperature in the dark to obtain a mixture, then add ethylene glycol to the mixture, dialyze, stir, centrifuge, collect the supernatant to obtain DAC solution; (b) Take the DAC solution, add perfluorooctane to it, stir and mix evenly, adjust the pH, stir in a constant temperature water bath, pour it into anhydrous ethanol, a yellow precipitate will precipitate, centrifuge, wash, dry, and obtain the modified powder. (c) Weigh magnesium acrylate and dissolve it in a mixed solvent to prepare a magnesium acrylate solution. Add the modified powder to the magnesium acrylate solution, stir at high speed, and then disperse by ultrasonication to obtain additive B.

4. The high-temperature resistant and waterproof glass wool according to claim 3, characterized in that, In step (a), the ratio of microcrystalline cellulose, deionized water and ethylene glycol is 1g:20-30mL:10mL.

5. A method for preparing high-temperature resistant and waterproof glass wool according to any one of claims 1-4, characterized in that, Specifically, the following steps are included: S1, mix the dispersant and deionized water, add TiO2 and silicon carbide whiskers in sequence under stirring, perform high-speed shearing, then reduce to medium speed, add additive B and additive A in sequence, and continue stirring at medium speed to form a composite impregnation solution; S2, the high-alumina borosilicate glass wool fibers are loosened and mixed with the composite impregnation liquid by spraying to form moist granules; S3, the moist granules are spread into the mold, lightly pressed to form a wet felt blank, dried, and then heated and cured according to the program to form a pre-cured blank; S4. The pre-cured preform is subjected to a programmed heat treatment in an inert atmosphere and cooled in the furnace to form a substrate skeleton. S5, the substrate skeleton is modified by vapor deposition and then cooled to obtain high-temperature resistant waterproof glass wool.

6. The method for preparing a high-temperature resistant and waterproof glass wool according to claim 5, characterized in that, In step S1, the dispersant is selected from one of polyethylene glycol, sodium lignosulfonate, KH-550, and KH560; In step S4, the heat treatment process is as follows: from room temperature, the temperature is increased to 350°C at a rate of 2°C / min and held for 1 hour; then the temperature is increased to 600°C at a rate of 3°C / min and held for 1 hour; then the temperature is increased to 900°C at a rate of 5°C / min and held for 1 hour; then the temperature is increased to 1100°C at a rate of 5°C / min and held for 2 hours.

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