A high sound insulation ultrafine glass fiber material and its preparation process

Abstract

This invention relates to the field of glass fiber materials technology, specifically disclosing a high sound insulation ultrafine glass fiber material and its preparation process. First, ultrafine glass fibers are prepared by flame blowing. Then, the glass fibers are blended with basalt fibers, dispersed evenly, and sprayed with borosilicate-modified phenolic resin impregnating agent and self-healing thioacrylate-epoxy resin binder. After heating and curing, basalt-reinforced glass fibers are obtained. Finally, the fibers are soaked in polyvinyl alcohol-silica gel solution and dried to fix them in polyvinyl alcohol-silica aerogel, further enhancing their mechanical properties, sound insulation properties, and flame-retardant and heat-insulating properties, enabling the glass fiber material to meet the requirements of use under harsh working conditions.

Description

Technical Field

[0001] This invention relates to the field of glass fiber materials technology, specifically to a high sound insulation ultrafine glass fiber material and its preparation process. Background Technology

[0002] The application of fiber materials in the field of sound insulation can be traced back to the mid-20th century. With the development of industry, industrial machines and equipment inevitably bring noise problems during operation. People began to look for lightweight and efficient sound insulation materials. Initially, people found that natural fibers such as wool and cotton have a loose and porous structure. When sound waves enter the fiber layer, the elastic structure in the fiber can absorb the vibration of the sound waves and reduce the reflection of the sound waves. When sound propagates in the fiber, the vibrating air molecules rub against the fiber surface, and the sound energy is converted into heat energy and dissipated, which has a certain sound insulation effect. However, natural fibers have poor weather resistance and a short service life in harsh working environments. Therefore, people have developed a series of artificial fibers (such as glass fiber, basalt fiber, etc.) to replace natural fibers to meet the needs of production.

[0003] Fiberglass is a nonwoven material created by imitating the loose, porous structure of natural fibers. It is made by randomly or orientedly arranging micrometer-diameter glass fibers using an adhesive and then heating and curing them. It possesses advantages such as flame retardancy, high-temperature resistance, corrosion resistance, and chemical stability. Its applications range from conventional sound and thermal insulation fields like building exterior wall insulation and cold chain transportation to high-end sound and thermal insulation fields like aircraft and shipbuilding. However, fiberglass still faces some challenges, such as poor bonding between fibers and adhesives, and poor tensile strength leading to susceptibility to breakage, resulting in suboptimal sound and thermal insulation performance. Summary of the Invention

[0004] The purpose of this invention is to provide a high sound insulation ultrafine glass fiber material and its preparation process, thereby solving the problem of poor sound insulation and heat preservation performance of glass fiber materials due to poor bonding between fibers and adhesives and poor tensile properties that make them prone to breakage.

[0005] To solve the above-mentioned technical problems, the present invention provides the following technical solution:

[0006] A preparation process for a high sound insulation ultrafine glass fiber material is as follows:

[0007] Step 1: Mix quartz sand, alumina, calcium oxide, magnesium oxide and reinforcement, and ball mill for 20-30 minutes to obtain mixed powder. Then, process the mixed powder through melt shaping, cooling and annealing to obtain high-strength glass blocks.

[0008] Step 2: Using flame blowing technology, the high-strength glass block is melted a second time and then blown into extremely fine glass fibers;

[0009] Step 3: Mix the ultra-fine glass fiber with basalt fiber, disperse it evenly, and then spray it with a wetting agent and binder to obtain basalt-reinforced glass fiber;

[0010] Step 4: Immerse basalt-reinforced glass fiber in polyvinyl alcohol-silica solution, age at room temperature for 20-24 hours, and then dry at 55-60℃ and 10-12MPa for 3-5 hours using supercritical carbon dioxide drying technology to obtain high sound insulation ultrafine glass fiber material.

[0011] As a limitation of the present invention, in step 1, the mass ratio of quartz sand, alumina, calcium oxide and magnesium oxide is (55-60):(15-20):(8-10):(6-8); the reinforcing body is a mixture of zinc oxide, lithium oxide, bismuth oxide, titanium oxide and cerium oxide, wherein the amount of zinc oxide is 1%-3% of the total mass of the raw materials, the amount of bismuth oxide is 1%-2% of the total mass of the raw materials, and the amounts of lithium oxide, titanium oxide and cerium oxide are 0.5%-1.5% of the total mass of the raw materials, respectively.

[0012] As a limitation of this invention, in step 1, the method for preparing the high-strength glass block is as follows:

[0013] The mixed powder is heated to 1550-1600℃ to melt, and held at 1550-1600℃ for 6-10 hours. After holding, the molten liquid is transferred into a mold to solidify, cooled to room temperature and then demolded. Finally, it is annealed at 750-800℃ for 2 hours and cooled to room temperature to obtain a high-strength glass block.

[0014] As a limitation of this invention, in step 2, during the flame blowing treatment, the secondary melting temperature is 1250-1300℃, the initial fiber diameter is 30-50μm, and the combustion gas used in the blowing process is coking gas with a flow rate of 80-90m³. 3 / h, the crater jet velocity is 480-500m / s, the crater jet temperature is 1350-1400℃, the outlet temperature is 180-200℃, and the outlet velocity is 10-15m / s.

[0015] As a limitation of the present invention, in step 3, the mass ratio of ultrafine glass fiber to basalt fiber is (6-8):(2-4); the amount of sizing agent is 2%-5% of the total fiber mass; and the amount of binder is 8%-12% of the total fiber mass.

[0016] As a limitation of this invention, the wetting agent is a borosilicate modified phenolic resin wetting agent, and the preparation method is as follows:

[0017] Phenol and ammonia were added to a methanol solution and reacted at 70-75℃ for 1.5-2 hours. Boric acid was then added, and the temperature was raised to 95-100℃ to continue the reaction for 1-1.5 hours. After the reaction was completed, the solution was distilled under reduced pressure to remove water. Methyltrimethoxysilane was added and the reaction was continued for 1-1.5 hours. After the reaction was completed, the solution was cooled to obtain a borosilicate-modified phenolic resin impregnating agent.

[0018] As a limitation of the present invention, the concentration of methanol in the methanol solution is 0.35-0.37 g / mL; the mass ratio of phenol, boric acid and methyltrimethoxysilane is (92-96):(9-11):(11-13).

[0019] As a limitation of this invention, the adhesive is a self-healing thioacrylate-epoxy resin adhesive, and its preparation method is as follows:

[0020] E51 epoxy resin, acrylic acid and dithiodipropionic acid were mixed and stirred evenly. Hydroquinone, an inhibitor of polymerization, was added. Then, under nitrogen protection, tetrabutylammonium bromide, a catalyst, was added. The mixture was reacted in an oil bath at 85-90℃ for 1-1.5h, and then the temperature was raised to 105-110℃ and the reaction was continued for 2-3h. After the reaction was completed, the mixture was cooled to room temperature to obtain thioacrylic acid-epoxy resin oligomer.

[0021] Sodium hydroxide, silicon dioxide, and deionized water were mixed and ultrasonically dispersed until uniform. The mixture was then reacted at room temperature for 3-4 hours. Sodium chloride, tetrahydrofuran, and hydrochloric acid were then added, and the reaction was continued for 30-50 minutes. After the reaction was completed, the mixture was allowed to stand and separate into layers. The upper liquid was dehydrated with anhydrous magnesium sulfate, filtered, and distilled to obtain a silicon polymer. Graphene oxide was dispersed in tetrahydrofuran to obtain a graphene oxide dispersion. The silicon polymer was slowly added to the graphene oxide dispersion, and the temperature was raised to 60-70℃ and reacted for 3-5 hours. After the reaction was completed, the mixture was cooled to room temperature to obtain a silicon polymer-modified graphene dispersion.

[0022] Thioacrylate-epoxy resin oligomers were added to N,N-dimethylformamide and stirred until homogeneous. Then, silicon polymer-modified graphene dispersion was added and ultrasonically dispersed for 20-30 minutes to ensure uniform mixing, thus obtaining a self-healing thioacrylate-epoxy resin adhesive.

[0023] As a limitation of this invention, the mass ratio of E51 epoxy resin, acrylic acid, and dithiodipropionic acid is (35-40):(2-4):(6-7); the mass ratio of sodium hydroxide, silicon dioxide, sodium chloride, and tetrahydrofuran is 1:(2.5-3.5):(35-38):(150-170); in the graphene oxide dispersion, the concentration of graphene oxide is 0.1-0.3 mg / mL, and the concentration of added silicon polymer is 1-3 mg / mL; the mass ratio of thioacrylic acid-epoxy resin oligomer, N,N-dimethylformamide, and silicon polymer-modified graphene dispersion is (20-25):(55-60):(15-20).

[0024] As a limitation of the present invention, the preparation method of the polyvinyl alcohol-silica gel solution is as follows:

[0025] Polyvinyl alcohol is added to deionized water, heated to 80-90℃ and stirred continuously to fully dissolve it, thus obtaining a polyvinyl alcohol aqueous solution. Then, vinyltriethoxysilane is added at 70-80℃, and stirred for 10-15 minutes under nitrogen protection. Then, a 3-5% potassium persulfate aqueous solution is added to initiate the reaction. The reaction is stirred at 70-80℃ for 3-5 hours to obtain a silane-modified polyvinyl alcohol aqueous solution.

[0026] Ethyl orthosilicate, ethanol, and deionized water are mixed and stirred until homogeneous. The pH is then adjusted to 2-3 with hydrochloric acid. After stirring for 0.5-1 h, the mixture is allowed to stand for 8-12 h to obtain a precursor solution. A silane-modified polyvinyl alcohol solution is added to the precursor solution and ultrasonically dispersed for 10-15 min. Ammonia water is then added to adjust the pH to 7-8, and the mixture is stirred for 5-10 min to obtain a polyvinyl alcohol-silica solution.

[0027] As a limitation of the present invention, the mass ratio of polyvinyl alcohol to vinyltriethoxysilane is 1:(0.1-0.2); the mass ratio of tetraethyl orthosilicate, ethanol and deionized water is (8-12):(8-10):(6-8); and the volume ratio of the precursor solution to the silane-modified polyvinyl alcohol solution is 1:(0.5-1).

[0028] Compared with the prior art, the beneficial effects of the present invention are:

[0029] This invention first optimizes the glass formulation by introducing zinc oxide, lithium oxide, bismuth oxide, titanium oxide, and cerium oxide into the silica-magnesium-aluminum-calcium glass system. Among these, zinc oxide and lithium oxide help lower the melting temperature. The zinc-oxygen-silicon bond network formed by zinc oxide can reduce deformation caused by temperature changes and improve the mechanical properties and acid and alkali resistance of the glass. Lithium oxide has a small ionic radius, which can form a denser network structure, reduce the coefficient of thermal expansion of the glass, and improve the acid and alkali resistance of the glass. The addition of bismuth oxide and titanium oxide increases the number of bridging oxygen bonds in the glass, further enhancing the structural stability. The addition of cerium oxide helps to densify the glass network, reduce the coefficient of thermal expansion of the glass, and improve the strength of the glass fibers.

[0030] This invention synthesizes a borosilicate modified phenolic resin impregnating agent using boric acid, methyltrimethoxysilane, and phenol as raw materials. The addition of boron promotes the graphitization transformation of phenolic resin during high-temperature pyrolysis, thereby improving the heat resistance of the material. Methyltrimethoxysilane improves the compatibility between the resin and the fiber, which helps the resin form a tight polymer film on the fiber surface.

[0031] This invention synthesizes a self-healing adhesive using epoxy resin, acrylic acid, and dithiodipropionic acid. The addition of dithiodipropionic acid introduces dynamic disulfide bonds as crosslinking points into the epoxy-acrylic resin network. Under temperature stimulation, the disulfide bonds undergo dynamic breakage and recombination, causing the molecular chains at the fracture points to reconnect, thus giving the adhesive self-healing properties and enhancing its bonding ability. The mechanical properties and weather resistance of the material are also strengthened. Furthermore, a well-dispersible silicon polymer—graphene oxide—is added to the adhesive. The high specific surface area and layered structure of graphene oxide enhance the scattering and reflection of sound waves, absorb impact energy, and slow down heat conduction, thereby enhancing the sound insulation performance of the material while also improving its thermal stability and mechanical properties.

[0032] This invention employs flame blowing technology to blow glass blocks into extremely fine glass fibers. Further, the glass fibers are blended with basalt fibers, which have similar chemical compositions. Basalt fibers possess high strength, good heat resistance, and good weather resistance. After blending with the glass fibers, an impregnating agent and binder are sprayed onto the fibers to form a fiber material with excellent overall performance. Finally, the fiber material is incorporated as a skeleton into polyvinyl alcohol-silica aerogel, further enhancing the sound insulation and heat insulation properties of the fiber material. Detailed Implementation

[0033] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of the present invention, not all embodiments, and all are small-scale laboratory tests, which can be scaled up proportionally in actual production processes. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0034] Quartz sand (purity: 99%), E51 epoxy resin (epoxy value: 0.48-0.54eq / 100g, viscosity: 6-26Pa·s), graphene oxide (sheet diameter: 80-200nm, thickness: 10-20nm), basalt fiber (diameter: 3-5μm), polyvinyl alcohol (PVA1788, degree of hydrolysis: 78-79%).

[0035] Example 1: A preparation process for a high sound insulation ultrafine glass fiber material, specifically as follows:

[0036] Step 1: Mix 59g of quartz sand, 18g of alumina, 9g of calcium oxide, 7.5g of magnesium oxide, 2g of zinc oxide, 1g of lithium oxide, 1.5g of bismuth oxide, 1g of titanium oxide, and 1g of cerium oxide, and ball mill for 30 minutes to obtain a mixed powder. Then heat the mixed powder to 1550℃ to melt it and keep it at 1550℃ for 8 hours. After the holding time is completed, transfer the molten liquid into a mold to solidify it. After cooling to room temperature, demold it and finally anneal it at 750℃ for 2 hours. After cooling to room temperature, obtain a high-strength glass block.

[0037] Step 2: Using a flame blowing method, the glass block is melted and then blown into extremely fine glass fibers. The secondary melting temperature is controlled at 1250℃, and the initial fiber diameter is 30μm. The combustion gas used in the blowing process is coking gas. The flow rate is 90m³ / h. 3 / h, crater jet velocity is 500m / s, crater jet temperature is 1350℃, outlet temperature is 180℃, and outlet velocity is 13m / s.

[0038] Step 3: Add 94g of phenol and 12g of ammonia to 130mL of methanol solution with a concentration of 0.37g / mL. After reacting at 70℃ for 1.5h, add 10g of boric acid, raise the temperature to 100℃ and continue the reaction for 1h. After the reaction is completed, distill under reduced pressure to remove water, add 12g of methyltrimethoxysilane and continue the reaction for 1h. After the reaction is completed, cool to obtain borosilicate modified phenolic resin impregnating agent.

[0039] Step 4: Mix 370g of E51 epoxy resin, 30g of acrylic acid and 65g of dithiodipropionic acid, stir evenly, add 0.06g of polymerization inhibitor hydroquinone, and then add 0.3g of catalyst tetrabutylammonium bromide under nitrogen protection. After reacting in an oil bath at 90℃ for 1h, raise the temperature to 110℃ and continue the reaction for 2h. After the reaction is completed, cool to room temperature to obtain thioacrylic acid-epoxy resin oligomer.

[0040] Step 5: Mix 1.0g sodium hydroxide, 3.0g silicon dioxide and 60mL deionized water, disperse evenly by ultrasonication, and react at room temperature for 3h. Then add 36g sodium chloride, 160g tetrahydrofuran and 60mL hydrochloric acid and continue the reaction for 30min. After the reaction is complete, let it stand and separate into layers. Dehydrate the upper liquid with anhydrous magnesium sulfate, filter, and distill to obtain silicon polymer. Disperse graphene oxide in tetrahydrofuran to obtain a graphene oxide dispersion of 0.2mg / mL. Slowly add silicon polymer to the graphene oxide dispersion until the concentration of silicon polymer in the dispersion is 2mg / mL. Heat to 60℃ and react for 4h. After the reaction is complete, cool to room temperature to obtain a silicon polymer modified graphene dispersion.

[0041] Step 6: Add 24g of thioacrylic acid-epoxy resin oligomer to 56g of N,N-dimethylformamide, stir evenly, then add 20g of silicon polymer modified graphene dispersion, and ultrasonically disperse for 20min to mix evenly to obtain self-healing thioacrylic acid-epoxy resin adhesive.

[0042] Step 7: Mix ultrafine glass fiber and basalt fiber at a mass ratio of 8:2, disperse evenly, spray with 2% of the total fiber mass of borosilicate modified phenolic resin impregnating agent, cure at 80℃ for 2 hours, then spray with 8% of the total fiber mass of self-healing thioacrylate-epoxy resin binder, cure at 100℃ for 2 hours to obtain basalt reinforced glass fiber.

[0043] Step 8: Add 100g of polyvinyl alcohol to 400g of deionized water, heat to 90℃ and stir continuously to fully dissolve it, to obtain a polyvinyl alcohol aqueous solution. Then add 15g of vinyltriethoxysilane at 80℃, stir for 15min under nitrogen protection, add 10mL of 3% potassium persulfate aqueous solution to initiate the reaction, stir at 80℃ for 3h to obtain silane-modified polyvinyl alcohol aqueous solution.

[0044] Step 9: Mix 10g of tetraethyl orthosilicate, 9g of ethanol and 7g of deionized water, stir well and adjust the pH to 2.5 with hydrochloric acid. Continue stirring for 1 hour and let stand for 12 hours to obtain the precursor solution. Add 50g of silane-modified polyvinyl alcohol solution to 50g of the precursor solution, sonicate for 15 minutes and add ammonia water to adjust the pH to 7.5. Continue stirring for 5 minutes to obtain polyvinyl alcohol-silica solution.

[0045] Step 10: Place the basalt-reinforced glass fiber into the mold, then add polyvinyl alcohol-silica gel solution to completely immerse the basalt-reinforced glass fiber. Seal the mold and age it at room temperature for 24 hours. After aging, open the mold and use supercritical carbon dioxide drying technology to dry it at 60℃ and 12MPa for 4 hours to obtain a high sound insulation ultrafine glass fiber material.

[0046] Example 2: A preparation process for a high sound insulation ultrafine glass fiber material, specifically as follows:

[0047] Step 1: Mix 59g of quartz sand, 18g of alumina, 9g of calcium oxide, 7.5g of magnesium oxide, 2g of zinc oxide, 1g of lithium oxide, 1.5g of bismuth oxide, 1g of titanium oxide, and 1g of cerium oxide, and ball mill for 30 minutes to obtain a mixed powder. Then heat the mixed powder to 1550℃ to melt it and keep it at 1550℃ for 8 hours. After the holding time is completed, transfer the molten liquid into a mold to solidify it. After cooling to room temperature, demold it and finally anneal it at 750℃ for 2 hours. After cooling to room temperature, obtain a high-strength glass block.

[0048] Step 2: Using a flame blowing method, the glass block is melted and then blown into extremely fine glass fibers. The secondary melting temperature is controlled at 1250℃, and the initial fiber diameter is 30μm. The combustion gas used in the blowing process is coking gas. The flow rate is 90m³ / h. 3 / h, crater jet velocity is 500m / s, crater jet temperature is 1350℃, outlet temperature is 180℃, and outlet velocity is 13m / s.

[0049] Step 3: Add 94g of phenol and 12g of ammonia to 130mL of methanol solution with a concentration of 0.37g / mL. After reacting at 70℃ for 1.5h, add 10g of boric acid, raise the temperature to 100℃ and continue the reaction for 1h. After the reaction is completed, distill under reduced pressure to remove water, add 12g of methyltrimethoxysilane and continue the reaction for 1h. After the reaction is completed, cool to obtain borosilicate modified phenolic resin impregnating agent.

[0050] Step 4: Mix 370g of E51 epoxy resin, 30g of acrylic acid and 65g of dithiodipropionic acid, stir evenly, add 0.06g of polymerization inhibitor hydroquinone, and then add 0.3g of catalyst tetrabutylammonium bromide under nitrogen protection. After reacting in an oil bath at 90℃ for 1h, raise the temperature to 110℃ and continue the reaction for 2h. After the reaction is completed, cool to room temperature to obtain thioacrylic acid-epoxy resin oligomer.

[0051] Step 5: Mix 1.0g sodium hydroxide, 3.0g silicon dioxide and 60mL deionized water, disperse evenly by ultrasonication, and react at room temperature for 3h. Then add 36g sodium chloride, 160g tetrahydrofuran and 60mL hydrochloric acid and continue the reaction for 30min. After the reaction is complete, let it stand and separate into layers. Dehydrate the upper liquid with anhydrous magnesium sulfate, filter, and distill to obtain silicon polymer. Disperse graphene oxide in tetrahydrofuran to obtain a graphene oxide dispersion of 0.2mg / mL. Slowly add silicon polymer to the graphene oxide dispersion until the concentration of silicon polymer in the dispersion is 2mg / mL. Heat to 60℃ and react for 4h. After the reaction is complete, cool to room temperature to obtain a silicon polymer modified graphene dispersion.

[0052] Step 6: Add 24g of thioacrylic acid-epoxy resin oligomer to 56g of N,N-dimethylformamide, stir evenly, then add 20g of silicon polymer modified graphene dispersion, and ultrasonically disperse for 20min to mix evenly to obtain self-healing thioacrylic acid-epoxy resin adhesive.

[0053] Step 7: Mix ultrafine glass fiber and basalt fiber at a mass ratio of 7.5:2.5, disperse evenly, spray with 3% of the total fiber mass of borosilicate modified phenolic resin impregnating agent, cure at 80℃ for 2 hours, then spray with 9% of the total fiber mass of self-healing thioacrylate-epoxy resin binder, cure at 100℃ for 2 hours to obtain basalt reinforced glass fiber;

[0054] Step 8: Add 100g of polyvinyl alcohol to 400g of deionized water, heat to 90℃ and stir continuously to fully dissolve it, to obtain a polyvinyl alcohol aqueous solution. Then add 15g of vinyltriethoxysilane at 80℃, stir for 15min under nitrogen protection, add 10mL of 3% potassium persulfate aqueous solution to initiate the reaction, stir at 80℃ for 3h to obtain silane-modified polyvinyl alcohol aqueous solution.

[0055] Step 9: Mix 10g of tetraethyl orthosilicate, 9g of ethanol and 7g of deionized water, stir well and adjust the pH to 2.5 with hydrochloric acid. Continue stirring for 1 hour and let stand for 12 hours to obtain the precursor solution. Add 50g of silane-modified polyvinyl alcohol solution to 50g of the precursor solution, sonicate for 15 minutes and add ammonia water to adjust the pH to 7.5. Continue stirring for 5 minutes to obtain polyvinyl alcohol-silica solution.

[0056] Step 10: Place the basalt-reinforced glass fiber into the mold, then add polyvinyl alcohol-silica gel solution to completely immerse the basalt-reinforced glass fiber. Seal the mold and age it at room temperature for 24 hours. After aging, open the mold and use supercritical carbon dioxide drying technology to dry it at 60℃ and 12MPa for 4 hours to obtain a high sound insulation ultrafine glass fiber material.

[0057] Example 3: A preparation process for a high sound insulation ultrafine glass fiber material, specifically as follows:

[0058] Step 1: Mix 59g of quartz sand, 18g of alumina, 9g of calcium oxide, 7.5g of magnesium oxide, 2g of zinc oxide, 1g of lithium oxide, 1.5g of bismuth oxide, 1g of titanium oxide, and 1g of cerium oxide, and ball mill for 30 minutes to obtain a mixed powder. Then heat the mixed powder to 1550℃ to melt it and keep it at 1550℃ for 8 hours. After the holding time is completed, transfer the molten liquid into a mold to solidify it. After cooling to room temperature, demold it and finally anneal it at 750℃ for 2 hours. After cooling to room temperature, obtain a high-strength glass block.

[0059] Step 2: Using a flame blowing method, the glass block is melted and then blown into extremely fine glass fibers. The secondary melting temperature is controlled at 1250℃, and the initial fiber diameter is 30μm. The combustion gas used in the blowing process is coking gas. The flow rate is 90m³ / h. 3 / h, crater jet velocity is 500m / s, crater jet temperature is 1350℃, outlet temperature is 180℃, and outlet velocity is 13m / s.

[0060] Step 3: Add 94g of phenol and 12g of ammonia to 130mL of methanol solution with a concentration of 0.37g / mL. After reacting at 70℃ for 1.5h, add 10g of boric acid, raise the temperature to 100℃ and continue the reaction for 1h. After the reaction is completed, distill under reduced pressure to remove water, add 12g of methyltrimethoxysilane and continue the reaction for 1h. After the reaction is completed, cool to obtain borosilicate modified phenolic resin impregnating agent.

[0061] Step 4: Mix 370g of E51 epoxy resin, 30g of acrylic acid and 65g of dithiodipropionic acid, stir evenly, add 0.06g of polymerization inhibitor hydroquinone, and then add 0.3g of catalyst tetrabutylammonium bromide under nitrogen protection. After reacting in an oil bath at 90℃ for 1h, raise the temperature to 110℃ and continue the reaction for 2h. After the reaction is completed, cool to room temperature to obtain thioacrylic acid-epoxy resin oligomer.

[0062] Step 5: Mix 1.0g sodium hydroxide, 3.0g silicon dioxide and 60mL deionized water, disperse evenly by ultrasonication, and react at room temperature for 3h. Then add 36g sodium chloride, 160g tetrahydrofuran and 60mL hydrochloric acid and continue the reaction for 30min. After the reaction is complete, let it stand and separate into layers. Dehydrate the upper liquid with anhydrous magnesium sulfate, filter, and distill to obtain silicon polymer. Disperse graphene oxide in tetrahydrofuran to obtain a graphene oxide dispersion of 0.2mg / mL. Slowly add silicon polymer to the graphene oxide dispersion until the concentration of silicon polymer in the dispersion is 2mg / mL. Heat to 60℃ and react for 4h. After the reaction is complete, cool to room temperature to obtain a silicon polymer modified graphene dispersion.

[0063] Step 6: Add 24g of thioacrylic acid-epoxy resin oligomer to 56g of N,N-dimethylformamide, stir evenly, then add 20g of silicon polymer modified graphene dispersion, and ultrasonically disperse for 20min to mix evenly to obtain self-healing thioacrylic acid-epoxy resin adhesive.

[0064] Step 7: Mix ultrafine glass fiber and basalt fiber at a mass ratio of 7:3, disperse evenly, spray with 4% of the total fiber mass of borosilicate modified phenolic resin impregnating agent, cure at 80℃ for 2 hours, then spray with 10% of the total fiber mass of self-healing thioacrylate-epoxy resin binder, and cure at 100℃ for 2 hours to obtain basalt reinforced glass fiber.

[0065] Step 8: Add 100g of polyvinyl alcohol to 400g of deionized water, heat to 90℃ and stir continuously to fully dissolve it, to obtain a polyvinyl alcohol aqueous solution. Then add 15g of vinyltriethoxysilane at 80℃, stir for 15min under nitrogen protection, add 10mL of 3% potassium persulfate aqueous solution to initiate the reaction, stir at 80℃ for 3h to obtain silane-modified polyvinyl alcohol aqueous solution.

[0066] Step 9: Mix 10g of tetraethyl orthosilicate, 9g of ethanol and 7g of deionized water, stir well and adjust the pH to 2.5 with hydrochloric acid. Continue stirring for 1 hour and let stand for 12 hours to obtain the precursor solution. Add 50g of silane-modified polyvinyl alcohol solution to 50g of the precursor solution, sonicate for 15 minutes and add ammonia water to adjust the pH to 7.5. Continue stirring for 5 minutes to obtain polyvinyl alcohol-silica solution.

[0067] Step 10: Place the basalt-reinforced glass fiber into the mold, then add polyvinyl alcohol-silica gel solution to completely immerse the basalt-reinforced glass fiber. Seal the mold and age it at room temperature for 24 hours. After aging, open the mold and use supercritical carbon dioxide drying technology to dry it at 60℃ and 12MPa for 4 hours to obtain a high sound insulation ultrafine glass fiber material.

[0068] Based on Example 1, the following comparative experiments were conducted, specifically Comparative Example 1, Comparative Example 2, and Comparative Example 3, as described below:

[0069] Comparative Example 1: This comparative example relates to a method for deep treatment of wastewater based on adsorbents. The difference from Example 1 is that basalt fiber was not added. Specifically:

[0070] Step 1: Mix 59g of quartz sand, 18g of alumina, 9g of calcium oxide, 7.5g of magnesium oxide, 7.5g of magnesium oxide, 2g of zinc oxide, 1g of lithium oxide, 1.5g of bismuth oxide, 1g of titanium oxide, and 1g of cerium oxide, and ball mill for 30 minutes to obtain a mixed powder. Then heat the mixed powder to 1550℃ to melt it and keep it at 1550℃ for 8 hours. After the holding time is completed, transfer the molten liquid into a mold to solidify it. After cooling to room temperature, demold it and finally anneal it at 750℃ for 2 hours. After cooling to room temperature, obtain a high-strength glass block.

[0071] Step 2: Using a flame blowing method, the glass block is melted and then blown into extremely fine glass fibers. The secondary melting temperature is controlled at 1250℃, and the initial fiber diameter is 30μm. The combustion gas used in the blowing process is coking gas. The flow rate is 90m³ / h. 3 / h, crater jet velocity is 500m / s, crater jet temperature is 1350℃, outlet temperature is 180℃, and outlet velocity is 13m / s.

[0072] Step 3: Add 94g of phenol and 12g of ammonia to 130mL of methanol solution with a concentration of 0.37g / mL. After reacting at 70℃ for 1.5h, add 10g of boric acid, raise the temperature to 100℃ and continue the reaction for 1h. After the reaction is completed, distill under reduced pressure to remove water, add 12g of methyltrimethoxysilane and continue the reaction for 1h. After the reaction is completed, cool to obtain borosilicate modified phenolic resin impregnating agent.

[0073] Step 4: Mix 370g of E51 epoxy resin, 30g of acrylic acid and 65g of dithiodipropionic acid, stir evenly, add 0.06g of polymerization inhibitor hydroquinone, and then add 0.3g of catalyst tetrabutylammonium bromide under nitrogen protection. After reacting in an oil bath at 90℃ for 1h, raise the temperature to 110℃ and continue the reaction for 2h. After the reaction is completed, cool to room temperature to obtain thioacrylic acid-epoxy resin oligomer.

[0074] Step 5: Mix 1.0g sodium hydroxide, 3.0g silicon dioxide and 60mL deionized water, disperse evenly by ultrasonication, and react at room temperature for 3h. Then add 36g sodium chloride, 160g tetrahydrofuran and 60mL hydrochloric acid and continue the reaction for 30min. After the reaction is complete, let it stand and separate into layers. Dehydrate the upper liquid with anhydrous magnesium sulfate, filter, and distill to obtain silicon polymer. Disperse graphene oxide in tetrahydrofuran to obtain a graphene oxide dispersion of 0.2mg / mL. Slowly add silicon polymer to the graphene oxide dispersion until the concentration of silicon polymer in the dispersion is 2mg / mL. Heat to 60℃ and react for 4h. After the reaction is complete, cool to room temperature to obtain a silicon polymer modified graphene dispersion.

[0075] Step 6: Add 24g of thioacrylic acid-epoxy resin oligomer to 56g of N,N-dimethylformamide, stir evenly, then add 20g of silicon polymer modified graphene dispersion, and ultrasonically disperse for 20min to mix evenly to obtain self-healing thioacrylic acid-epoxy resin adhesive.

[0076] Step 7: Spray 2% of the total fiber mass of borosilicate modified phenolic resin impregnating agent onto the ultra-fine glass fiber, cure at 80°C for 2 hours, then spray 8% of the total fiber mass of self-healing thioacrylate-epoxy resin adhesive, and cure at 100°C for 2 hours to obtain reinforced glass fiber.

[0077] Step 8: Add 100g of polyvinyl alcohol to 400g of deionized water, heat to 90℃ and stir continuously to fully dissolve it, to obtain a polyvinyl alcohol aqueous solution. Then add 15g of vinyltriethoxysilane at 80℃, stir for 15min under nitrogen protection, add 10mL of 3% potassium persulfate aqueous solution to initiate the reaction, stir at 80℃ for 3h to obtain silane-modified polyvinyl alcohol aqueous solution.

[0078] Step 9: Mix 10g of tetraethyl orthosilicate, 9g of ethanol and 7g of deionized water, stir well and adjust the pH to 2.5 with hydrochloric acid. Continue stirring for 1 hour and let stand for 12 hours to obtain the precursor solution. Add 50g of silane-modified polyvinyl alcohol solution to 50g of the precursor solution, sonicate for 15 minutes and add ammonia water to adjust the pH to 7.5. Continue stirring for 5 minutes to obtain polyvinyl alcohol-silica solution.

[0079] Step 10: Place the reinforcing glass fiber into the mold, then add polyvinyl alcohol-silica gel solution to completely immerse the reinforcing glass fiber. Seal the mold and age it at room temperature for 24 hours. After aging, open the mold and use supercritical carbon dioxide drying technology to dry it at 60℃ and 12MPa for 4 hours to obtain a high sound insulation ultrafine glass fiber material.

[0080] Comparative Example 2: This comparative example relates to a method for deep treatment of wastewater based on adsorbents. The difference from Example 1 is that no wetting agent was used to treat the glass fibers. Specifically:

[0081] Step 1: Mix 59g of quartz sand, 18g of alumina, 9g of calcium oxide, 7.5g of magnesium oxide, 2g of zinc oxide, 1g of lithium oxide, 1.5g of bismuth oxide, 1g of titanium oxide, and 1g of cerium oxide, and ball mill for 30 minutes to obtain a mixed powder. Then heat the mixed powder to 1550℃ to melt it and keep it at 1550℃ for 8 hours. After the holding time is completed, transfer the molten liquid into a mold to solidify it. After cooling to room temperature, demold it and finally anneal it at 750℃ for 2 hours. After cooling to room temperature, obtain a high-strength glass block.

[0082] Step 2: Using a flame blowing method, the glass block is melted and then blown into extremely fine glass fibers. The secondary melting temperature is controlled at 1250℃, and the initial fiber diameter is 30μm. The combustion gas used in the blowing process is coking gas. The flow rate is 90m³ / h. 3 / h, crater jet velocity is 500m / s, crater jet temperature is 1350℃, outlet temperature is 180℃, and outlet velocity is 13m / s.

[0083] Step 3: Mix 370g of E51 epoxy resin, 30g of acrylic acid and 65g of dithiodipropionic acid, stir evenly, add 0.06g of hydroquinone as a polymerization inhibitor, and then add 0.3g of tetrabutylammonium bromide as a catalyst under nitrogen protection. After reacting in an oil bath at 90°C for 1 hour, raise the temperature to 110°C and continue the reaction for 2 hours. After the reaction is completed, cool to room temperature to obtain the thioacrylic acid-epoxy resin oligomer.

[0084] Step 4: Mix 1.0g sodium hydroxide, 3.0g silicon dioxide and 60mL deionized water, and after ultrasonic dispersion, react at room temperature for 3h. Then add 36g sodium chloride, 160g tetrahydrofuran and 60mL hydrochloric acid and continue the reaction for 30min. After the reaction is complete, let it stand and separate into layers. Dehydrate the upper liquid with anhydrous magnesium sulfate, filter, and distill to obtain silicon polymer. Disperse graphene oxide in tetrahydrofuran to obtain a graphene oxide dispersion of 0.2mg / mL. Slowly add silicon polymer to the graphene oxide dispersion until the concentration of silicon polymer in the dispersion is 2mg / mL. Heat to 60℃ and react for 4h. After the reaction is complete, cool to room temperature to obtain a silicon polymer modified graphene dispersion.

[0085] Step 5: Add 24g of thioacrylic acid-epoxy resin oligomer to 56g of N,N-dimethylformamide, stir evenly, then add 20g of silicon polymer modified graphene dispersion, and ultrasonically disperse for 20min to mix evenly to obtain self-healing thioacrylic acid-epoxy resin adhesive.

[0086] Step 6: Mix ultrafine glass fiber and basalt fiber at a mass ratio of 8:2, disperse evenly, and then spray with 8% of the total fiber mass of self-healing thioacrylate-epoxy resin adhesive. Cure at 100℃ for 2 hours to obtain basalt-reinforced glass fiber.

[0087] Step 7: Add 100g of polyvinyl alcohol to 400g of deionized water, heat to 90℃ and stir continuously to dissolve it completely to obtain a polyvinyl alcohol aqueous solution. Then add 15g of vinyltriethoxysilane at 80℃, stir for 15min under nitrogen protection, add 10mL of 3% potassium persulfate aqueous solution to initiate the reaction, and stir the reaction at 80℃ for 3h to obtain a silane-modified polyvinyl alcohol aqueous solution.

[0088] Step 8: Mix 10g of tetraethyl orthosilicate, 9g of ethanol and 7g of deionized water, stir well and adjust the pH to 2.5 with hydrochloric acid. Continue stirring for 1 hour and let stand for 12 hours to obtain the precursor solution. Add 50g of silane-modified polyvinyl alcohol solution to 50g of the precursor solution, sonicate for 15 minutes and add ammonia water to adjust the pH to 7.5. Continue stirring for 5 minutes to obtain polyvinyl alcohol-silica solution.

[0089] Step 9: Place the basalt-reinforced glass fiber into the mold, then add polyvinyl alcohol-silica gel solution to completely immerse the basalt-reinforced glass fiber. Seal the mold and age it at room temperature for 24 hours. After aging, open the mold and use supercritical carbon dioxide drying technology to dry it at 60℃ and 12MPa for 4 hours to obtain a high sound insulation ultrafine glass fiber material.

[0090] Comparative Example 3: This comparative example relates to a method for deep treatment of wastewater based on adsorbents. The difference from Example 1 is that silane-modified polyvinyl alcohol was not added to the silica gel solution. Specifically:

[0091] Step 1: Mix 59g of quartz sand, 18g of alumina, 9g of calcium oxide, 7.5g of magnesium oxide, 2g of zinc oxide, 1g of lithium oxide, 1.5g of bismuth oxide, 1g of titanium oxide, and 1g of cerium oxide, and ball mill for 30 minutes to obtain a mixed powder. Then heat the mixed powder to 1550℃ to melt it and keep it at 1550℃ for 8 hours. After the holding time is completed, transfer the molten liquid into a mold to solidify it. After cooling to room temperature, demold it and finally anneal it at 750℃ for 2 hours. After cooling to room temperature, obtain a high-strength glass block.

[0092] Step 2: Using a flame blowing method, the glass block is melted and then blown into extremely fine glass fibers. The secondary melting temperature is controlled at 1250℃, and the initial fiber diameter is 30μm. The combustion gas used in the blowing process is coking gas. The flow rate is 90m³ / h. 3 / h, crater jet velocity is 500m / s, crater jet temperature is 1350℃, outlet temperature is 180℃, and outlet velocity is 13m / s.

[0093] Step 3: Add 94g of phenol and 12g of ammonia to 130mL of methanol solution with a concentration of 0.37g / mL. After reacting at 70℃ for 1.5h, add 10g of boric acid, raise the temperature to 100℃ and continue the reaction for 1h. After the reaction is completed, distill under reduced pressure to remove water, add 12g of methyltrimethoxysilane and continue the reaction for 1h. After the reaction is completed, cool to obtain borosilicate modified phenolic resin impregnating agent.

[0094] Step 4: Mix 370g of E51 epoxy resin, 30g of acrylic acid and 65g of dithiodipropionic acid, stir evenly, add 0.06g of polymerization inhibitor hydroquinone, and then add 0.3g of catalyst tetrabutylammonium bromide under nitrogen protection. After reacting in an oil bath at 90℃ for 1h, raise the temperature to 110℃ and continue the reaction for 2h. After the reaction is completed, cool to room temperature to obtain thioacrylic acid-epoxy resin oligomer.

[0095] Step 5: Mix 1.0g sodium hydroxide, 3.0g silicon dioxide and 60mL deionized water, disperse evenly by ultrasonication, and react at room temperature for 3h. Then add 36g sodium chloride, 160g tetrahydrofuran and 60mL hydrochloric acid and continue the reaction for 30min. After the reaction is complete, let it stand and separate into layers. Dehydrate the upper liquid with anhydrous magnesium sulfate, filter, and distill to obtain silicon polymer. Disperse graphene oxide in tetrahydrofuran to obtain a graphene oxide dispersion of 0.2mg / mL. Slowly add silicon polymer to the graphene oxide dispersion until the concentration of silicon polymer in the dispersion is 2mg / mL. Heat to 60℃ and react for 4h. After the reaction is complete, cool to room temperature to obtain a silicon polymer modified graphene dispersion.

[0096] Step 6: Add 24g of thioacrylic acid-epoxy resin oligomer to 56g of N,N-dimethylformamide, stir evenly, then add 20g of silicon polymer modified graphene dispersion, and ultrasonically disperse for 20min to mix evenly to obtain self-healing thioacrylic acid-epoxy resin adhesive.

[0097] Step 7: Mix ultrafine glass fiber and basalt fiber at a mass ratio of 8:2, disperse evenly, spray with 2% of the total fiber mass of borosilicate modified phenolic resin impregnating agent, cure at 80℃ for 2 hours, then spray with 8% of the total fiber mass of self-healing thioacrylate-epoxy resin binder, cure at 100℃ for 2 hours to obtain basalt reinforced glass fiber.

[0098] Step 8: Mix 10g of tetraethyl orthosilicate, 9g of ethanol and 7g of deionized water, stir well and adjust the pH to 2.5 with hydrochloric acid, continue stirring for 1 hour and let stand for 12 hours. After aging, add ammonia water, adjust the pH to 7.5 and continue stirring for 5 minutes to obtain silica gel solution.

[0099] Step 9: Place the basalt-reinforced glass fiber into the mold, then add silica gel solution to completely immerse the basalt-reinforced glass fiber. Seal the mold and age it at room temperature for 24 hours. After aging, open the mold and use supercritical carbon dioxide drying technology to dry it at 60℃ and 12MPa for 4 hours to obtain a high sound insulation ultrafine glass fiber material.

[0100] Testing experiment:

[0101] High sound insulation ultrafine glass fiber material samples were processed according to the processing technology in each embodiment and comparative example, and tensile performance, thermal insulation performance and sound insulation performance were tested.

[0102] Tensile property test: The tensile properties of fiber materials are tested using a universal testing machine. The test sample size is 25mm × 75mm and the test sample thickness is 2mm. The sample is fixed on the fixture of the universal testing machine. A rubber pad of the same size as the fixture surface is placed between the fixture and the test sample. The universal testing machine is started and the tensile rate is set to 300mm / min until the sample is broken. The tensile strength of the test sample is then calculated.

[0103] Thermal insulation performance test: The thermal insulation performance of fiber materials was tested using a DECCA-Ⅲ thermal conductivity tester (DECCA Precision Instruments). The test sample diameter was 50 mm and the thickness was 2 mm. The test environment temperature was 25℃. The instrument hot end temperature was set to 50℃ and the cold end temperature to 20℃. The test sample was installed on the fixture, the instrument was started and the test was started, and the thermal conductivity of the test sample was calculated.

[0104] Sound insulation performance test: The sound insulation performance test of fiber materials is conducted in accordance with "Measurement of sound absorption coefficient and acoustic impedance in acoustic impedance tubes - Part 2: Transfer function method" (GB / T 18696.2-2002). The test uses SW4601 impedance tubes (Beijing Shengwang). The test sample has a diameter of 30mm and a thickness of 3mm. The test sample is mounted on a fixture, and a small amount of Vaseline is applied to the edge of the sample to prevent sound leakage. Then, the microphone is inserted into the reserved hole on the side wall of the impedance tube. After connecting the power amplifier and data acquisition system, the test is carried out. The sound insulation (dB) of each test sample at different frequencies is measured to determine the sound insulation performance of the sample.

[0105]

[0106] Conclusion: The test data shows that the high sound insulation ultrafine glass fiber material provided by this invention has good sound insulation performance, and the sound insulation also increases with the increase of sound frequency. In addition, the glass fiber material has high tensile strength and low thermal conductivity, and has good tensile strength and thermal insulation properties, which can meet the needs of use under harsh working conditions.

[0107] It will be apparent to those skilled in the art that the present invention is not limited to the details of the exemplary embodiments described above, and that the invention can be implemented in other specific forms without departing from the spirit or essential characteristics of the invention. Therefore, the embodiments should be considered in all respects as exemplary and non-limiting, and the scope of the invention is defined by the appended claims rather than the foregoing description. Thus, it is intended that all variations falling within the meaning and scope of equivalents of the claims be included within the present invention.

Claims

1. A preparation process for a high sound insulation ultrafine glass fiber material, characterized in that: Specifically: Step 1: Mix quartz sand, alumina, calcium oxide, magnesium oxide and reinforcement, and ball mill for 20-30 minutes to obtain mixed powder. Then, process the mixed powder through melt shaping, cooling and annealing to obtain high-strength glass blocks. Step 2: Using flame blowing technology, the high-strength glass block is melted a second time and then blown into extremely fine glass fibers; Step 3: Mix the ultra-fine glass fiber with the basalt fiber, disperse it evenly, and then spray it with a wetting agent and a binder to obtain basalt-reinforced glass fiber; Step 4: Immerse basalt-reinforced glass fiber in polyvinyl alcohol-silica solution, age at room temperature for 20-24 hours, and then dry at 55-60℃ and 10-12MPa for 3-5 hours using supercritical carbon dioxide drying technology to obtain high sound insulation ultrafine glass fiber material. The adhesive is a self-healing thioacrylate-epoxy resin adhesive, and its preparation method is as follows: E51 epoxy resin, acrylic acid and dithiodipropionic acid were mixed and stirred evenly. Hydroquinone, an inhibitor of polymerization, was added. Then, under nitrogen protection, tetrabutylammonium bromide, a catalyst, was added. The mixture was reacted in an oil bath at 85-90℃ for 1-1.5h, and then the temperature was raised to 105-110℃ and the reaction was continued for 2-3h. After the reaction was completed, the mixture was cooled to room temperature to obtain thioacrylic acid-epoxy resin oligomer. Sodium hydroxide, silicon dioxide, and deionized water were mixed and ultrasonically dispersed until uniform. The mixture was then reacted at room temperature for 3-4 hours. Sodium chloride, tetrahydrofuran, and hydrochloric acid were then added, and the reaction was continued for 30-50 minutes. After the reaction was completed, the mixture was allowed to stand and separate into layers. The upper liquid was dehydrated with anhydrous magnesium sulfate, filtered, and distilled to obtain a silicon polymer. Graphene oxide was dispersed in tetrahydrofuran to obtain a graphene oxide dispersion. The silicon polymer was slowly added to the graphene oxide dispersion, and the temperature was raised to 60-70℃ and reacted for 3-5 hours. After the reaction was completed, the mixture was cooled to room temperature to obtain a silicon polymer-modified graphene dispersion. Thioacrylate-epoxy resin oligomers were added to N,N-dimethylformamide and stirred until homogeneous. Then, silicon polymer-modified graphene dispersion was added and ultrasonically dispersed for 20-30 minutes to ensure uniform mixing, thus obtaining a self-healing thioacrylate-epoxy resin adhesive.

2. The preparation process of a high sound insulation ultrafine glass fiber material according to claim 1, characterized in that: In step 1, the mass ratio of quartz sand, alumina, calcium oxide, and magnesium oxide is (55-60):(15-20):(8-10):(6-8); the reinforcing agent is a mixture of zinc oxide, lithium oxide, bismuth oxide, titanium oxide, and cerium oxide, with zinc oxide accounting for 1%-3% of the total mass of the raw materials, bismuth oxide accounting for 1%-2% of the total mass of the raw materials, and lithium oxide, titanium oxide, and cerium oxide accounting for 0.5%-1.5% of the total mass of the raw materials, respectively.

3. The preparation process of a high sound insulation ultrafine glass fiber material according to claim 1, characterized in that: In step 1, the method for preparing the high-strength glass block is as follows: The mixed powder is heated to 1550-1600℃ to melt, and held at 1550-1600℃ for 6-10 hours. After holding, the molten liquid is transferred into a mold to solidify, cooled to room temperature and then demolded. Finally, it is annealed at 750-800℃ for 2 hours and cooled to room temperature to obtain a high-strength glass block.

4. The preparation process of a high sound insulation ultrafine glass fiber material according to claim 1, characterized in that: In step 2, during flame blowing treatment, the secondary melting temperature is 1250-1300℃, the initial fiber diameter is 30-50μm, and the combustion gas used in the blowing process is coking gas with a flow rate of 80-90m³. 3 / h, the crater jet velocity is 480-500m / s, the crater jet temperature is 1350-1400℃, the outlet temperature is 180-200℃, and the outlet velocity is 10-15m / s.

5. The preparation process of a high sound insulation ultrafine glass fiber material according to claim 1, characterized in that: In step 3, the mass ratio of ultrafine glass fiber to basalt fiber is (6-8):(2-4); the amount of sizing agent is 2%-5% of the total fiber mass; and the amount of binder is 8%-12% of the total fiber mass.

6. The preparation process of a high sound insulation ultrafine glass fiber material according to claim 1, characterized in that: The impregnating agent is a borosilicate modified phenolic resin impregnating agent, and the preparation method is as follows: Phenol and ammonia were added to a methanol solution and reacted at 70-75℃ for 1.5-2 hours. Boric acid was then added, and the temperature was raised to 95-100℃ to continue the reaction for 1-1.5 hours. After the reaction was completed, the solution was distilled under reduced pressure to remove water. Methyltrimethoxysilane was added and the reaction was continued for 1-1.5 hours. After the reaction was completed, the solution was cooled to obtain a borosilicate-modified phenolic resin impregnating agent.

7. The preparation process of a high sound insulation ultrafine glass fiber material according to claim 6, characterized in that: The concentration of methanol in the methanol solution is 0.35-0.37 g / mL; the mass ratio of phenol, boric acid, and methyltrimethoxysilane is (92-96):(9-11):(11-13).

8. The preparation process of a high sound insulation ultrafine glass fiber material according to claim 1, characterized in that: The mass ratio of E51 epoxy resin, acrylic acid, and dithiodipropionic acid is (35-40):(2-4):(6-7); the mass ratio of sodium hydroxide, silicon dioxide, sodium chloride, and tetrahydrofuran is 1:(2.5-3.5):(35-38):(150-170); in the graphene oxide dispersion, the concentration of graphene oxide is 0.1-0.3 mg / mL, and the concentration of added silicon polymer is 1-3 mg / mL; the mass ratio of thioacrylic acid-epoxy resin oligomer, N,N-dimethylformamide, and silicon polymer-modified graphene dispersion is (20-25):(55-60):(15-20).

9. The preparation process of a high sound insulation ultrafine glass fiber material according to claim 1, characterized in that: The preparation method of polyvinyl alcohol-silica gel solution is as follows: Polyvinyl alcohol is added to deionized water, heated to 80-90℃ and stirred continuously to fully dissolve it, thus obtaining a polyvinyl alcohol aqueous solution. Then, vinyltriethoxysilane is added at 70-80℃, and stirred for 10-15 minutes under nitrogen protection. Then, a 3-5% potassium persulfate aqueous solution is added to initiate the reaction. The reaction is stirred at 70-80℃ for 3-5 hours to obtain a silane-modified polyvinyl alcohol aqueous solution. Ethyl orthosilicate, ethanol, and deionized water are mixed and stirred until homogeneous. The pH is then adjusted to 2-3 with hydrochloric acid. After stirring for 0.5-1 h, the mixture is allowed to stand for 8-12 h to obtain a precursor solution. A silane-modified polyvinyl alcohol solution is added to the precursor solution and ultrasonically dispersed for 10-15 min. Ammonia water is then added to adjust the pH to 7-8, and the mixture is stirred for 5-10 min to obtain a polyvinyl alcohol-silica solution.

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