Explosion-proof ultra-thin glass containing silicone resin coating and method of manufacturing the same

Abstract

The present application relates to the technical field of explosion-proof glass preparation, and particularly discloses an explosion-proof ultrathin glass containing a silicone resin coating and a preparation method thereof, wherein the explosion-proof ultrathin glass containing the silicone resin coating is prepared by taking acrylic modified silicone resin as a main film-forming matrix, giving the coating excellent weather resistance and chemical stability, introducing modified polyurethane to significantly enhance the toughness and wear resistance of the coating, taking vinyl silicone oil to enhance the flexibility and improve the leveling property and surface finish of the coating, and also to reduce the surface tension of the coating, so that the coating is more uniformly distributed on the glass surface; and taking benzoyl peroxide as an initiator to promote the cross-linking and curing of the resin under low temperature conditions, improve the cross-linking density, effectively block the transmission of external force impact, and improve the impact resistance of the coating.

Description

Technical Field

[0001] This invention relates to the field of explosion-proof glass manufacturing technology, specifically to an explosion-proof ultrathin glass containing an organosilicon resin coating and its manufacturing method. Background Technology

[0002] Ultrathin glass, typically referring to special glass with a thickness of less than 1.1 mm, especially in the range of 0.1 mm to 0.7 mm, has become an indispensable key material for modern cutting-edge technology products due to its extremely thin thickness, excellent flexibility, high optical transmittance, good surface flatness, and chemical stability. It demonstrates enormous potential and value in applications such as consumer electronics (e.g., foldable screen phones, tablet cover glass, wearable device displays), new display technologies (e.g., flexible OLED substrates), high-efficiency thin-film solar cells, advanced semiconductor packaging, and micro-sensors and optical components. The application of ultrathin glass has greatly promoted the development of devices towards thinner, more flexible, higher-resolution, and more integrated designs, meeting consumers' demands for portability, novel form factors, and advanced performance.

[0003] While ultra-thin glass offers numerous advantages, its inherent physical properties also present significant challenges to its mechanical performance, particularly in terms of impact resistance. Due to its extremely thin thickness, the glass's volume and supporting structure are drastically reduced, leading to stress concentration when subjected to external impacts (whether point, line, or surface impacts). Furthermore, there is a lack of sufficient material to effectively absorb and disperse impact energy, significantly weakening its resistance to breakage. Common everyday occurrences such as drops, impacts from hard objects, or even excessive localized pressure on the screen can easily cause cracks or even complete shattering on the surface or edges of ultra-thin glass. This inherent brittleness and low impact resistance not only reduce product reliability and durability, increasing user costs and risks, but also limit the widespread adoption of ultra-thin glass in harsher environments or applications with higher reliability requirements.

[0004] Therefore, developing new strengthening technologies or composite material structures to significantly improve the impact resistance and toughness of ultrathin glass while maintaining its core advantages has become a key technical challenge that urgently needs to be overcome in the field of materials science and engineering applications. Summary of the Invention

[0005] To address the shortcomings of existing technologies, the present invention aims to provide an explosion-proof ultrathin glass containing an organosilicon resin coating and a method for preparing the same.

[0006] To achieve the above objectives, the present invention adopts the following technical solution: An explosion-proof ultrathin glass containing an organosilicon resin coating, the explosion-proof ultrathin glass comprising an ultrathin glass substrate and coatings applied to the upper and lower surfaces of the ultrathin glass substrate.

[0007] In the technical solution disclosed in this invention, the coating comprises the following raw materials by weight: 60-80 parts of acrylic modified silicone resin, 15-25 parts of modified polyurethane, 5-10 parts of vinyl silicone oil, 4-8 parts of sodium dodecylbenzenesulfonate, 2-4 parts of sodium lauryl sulfate, and 0.5-1 parts of benzoyl peroxide.

[0008] In the technical solution disclosed in this invention, acrylic modified silicone resin is used as the main film-forming substance of the coating, providing excellent weather resistance, heat resistance and chemical corrosion resistance. The amount of acrylic modified silicone resin can be selected as 60 parts, 62 parts, 65 parts, 68 parts, 70 parts, 72 parts, 75 parts, 76 parts, 78 parts and 80 parts, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0009] In the technical solution disclosed in this invention, the preparation method of modified polyurethane is as follows: S1. The composite modified montmorillonite, polyol and diisocyanate are reacted under the action of a catalyst to obtain polyurethane prepolymer; S2. Add a chain extender to the polyurethane prepolymer and continue the reaction. Then adjust the viscosity of the system with acetone to obtain the polyurethane prepolymer. S3. Add triethylamine, a neutralizing agent, to the polyurethane prepolymer and stir to react, thus obtaining the modified polyurethane.

[0010] In the technical solution disclosed in this invention, by weight, the composite modified montmorillonite comprises 5-10 parts, the polyol comprises 25-40 parts, the diisocyanate comprises 15-20 parts, the catalyst comprises 0.5-1 parts, the chain extender comprises 4-8 parts, and the triethylamine comprises 1-3 parts.

[0011] In the technical solution disclosed in this invention, the preparation method of the composite modified montmorillonite in step S1 is as follows: (1) Disperse montmorillonite in deionized water using ultrasonication, then add soluble zirconium salt, stir until homogeneous, adjust the pH of the solution to 10-12, heat to react, and after the reaction is complete, filter, wash, dry and calcine to obtain montmorillonite composite material. (2) The montmorillonite composite material was dispersed in an aqueous ethanol solution, and then vinyltriethoxysilane was added to it. The mixture was stirred and then filtered, washed and dried to obtain the vinyl-grafted montmorillonite composite material. (3) The vinyl-grafted montmorillonite composite material is dispersed in an organic solvent, and then 2-butene-1,4-diol and benzoyl peroxide are added to it. The mixture is heated to react. After the reaction is completed, it is filtered, washed and dried to obtain the composite modified montmorillonite.

[0012] Specifically, in step (1), the mass ratio of montmorillonite to soluble zirconium salt is 4-8:5-10. For example, 4:5, 4:8, 4:10, 6:5, 6:8, 4:10, 8:5, 8:6, and 8:8 can be selected, but are not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0013] Specifically, the soluble zirconium salt is selected from zirconium oxychloride, zirconium nitrate, or zirconium sulfate.

[0014] Specifically, in step (1), the temperature of the heating reaction is 60-80℃, for example, 60℃, 65℃, 70℃, 75℃, 80℃ can be selected; the heating reaction time is 3-5h, for example, 3h, 3.5h, 4h, 4.5h, 5h can be selected, but not limited to the listed values, other unlisted values ​​within the range are also applicable.

[0015] Specifically, in step (2), the mass ratio of montmorillonite composite material to vinyltriethoxysilane is 5-10:1-3. For example, 5:1, 5:2, 5:3, 8:1, 8:2, 8:3, 10:1, 10:2, and 10:3 can be selected, but not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0016] Specifically, in step (3), the mass ratio of vinyl-grafted montmorillonite composite material, 2-butene-1,4-diol and benzoyl peroxide is 5-10:3-6:0.05-0.1.

[0017] Specifically, in step (3), the temperature of the heating reaction is 60-80℃, for example, 60℃, 65℃, 70℃, 75℃, 80℃ can be selected; the heating reaction time is 2-4h, for example, 2h, 2.5h, 3h, 3.5h, 4h can be selected, but not limited to the listed values, other unlisted values ​​within the range are also applicable.

[0018] In the technical solution disclosed in this invention, montmorillonite is a layered silicate material with a large specific surface area and ion exchange capacity. Soluble zirconium salts hydrolyze under alkaline conditions to generate zirconium hydroxide, which is then calcined to form zirconium oxide particles that adhere to the surface and interlayer of montmorillonite, improving its hardness and wear resistance. Subsequently, carbon-carbon double bonds are introduced onto the surface of the montmorillonite composite material to facilitate subsequent reactions. Then, through an addition reaction between the double bonds, 2-butene-1,4-diol is polymerized and grafted onto the surface of the montmorillonite composite material. The hydroxyl groups in 2-butene-1,4-diol can react with diisocyanate to embed the montmorillonite composite material into the polyurethane backbone. The montmorillonite composite material can hinder polymer chain slippage, while the flexible alkyl long-chain structure in 2-butene-1,4-diol can reduce the rigidity of the molecular chain, thereby improving the impact resistance of the polyurethane material.

[0019] In the technical solution disclosed in this invention, in step S1, the polyol is selected from polyether glycol or polyester glycol; the diisocyanate is selected from isophorone diisocyanate or hexamethylene diisocyanate; the catalyst is selected from organotin catalysts, such as stannous octoate, dibutyltin dilaurate or dibutyltin oxide.

[0020] In the technical solution disclosed in this invention, in step S1, the reaction temperature is 80-90℃, for example, 80℃, 81℃, 82℃, 83℃, 84℃, 85℃, 86℃, 87℃, 88℃, 89℃, or 90℃ can be selected; the reaction time is 2-4h, for example, 2h, 2.5h, 3h, 3.5h, or 4h can be selected, but it is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0021] In the technical solution disclosed in this invention, in step S2, the chain extender is selected from at least one of dimethylolpropionic acid and dimethylolbutyric acid.

[0022] In the technical solution disclosed in this invention, in step S2, the temperature for continuing the reaction is 80-90℃, for example, 80℃, 81℃, 82℃, 83℃, 84℃, 85℃, 86℃, 87℃, 88℃, 89℃, or 90℃ can be selected; the reaction time is 1-3h, for example, 1h, 1.5h, 2h, 2.5h, or 3h can be selected, but it is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0023] In the technical solution disclosed in this invention, in step S2, acetone is added to dilute the system to a solid content of 40-60%. For example, 40%, 45%, 50%, 55%, and 60% can be selected, but the values ​​are not limited to those listed. Other unlisted values ​​within the range are also applicable.

[0024] In the technical solution disclosed in this invention, in step S3, the stirring reaction time is 30-60 min, for example, 30 min, 35 min, 40 min, 45 min, 50 min, 55 min, 60 min can be selected, but it is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0025] In the technical solution disclosed in this invention, by adding modified polyurethane, the toughness of the coating can be improved, thereby improving the impact resistance of the glass; at the same time, the modified polyurethane can also improve the wear resistance and durability of the coating. The amount of modified polyurethane can be selected as 15 parts, 16 parts, 17 parts, 18 parts, 19 parts, 20 parts, 21 parts, 22 parts, 23 parts, 24 parts, or 25 parts, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0026] In the technical solution disclosed in this invention, vinyl silicone oil plays a role in enhancing flexibility and improving the leveling and surface smoothness of the coating. At the same time, it can also reduce the surface tension of the coating, so that the coating is more evenly distributed on the glass surface. The number of parts of vinyl silicone oil can be 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, or 10 parts, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0027] In the technical solution disclosed in this invention, sodium dodecylbenzenesulfonate is used as a surfactant to reduce the surface tension of the coating system and improve the wettability and leveling properties of the coating. The amount of sodium dodecylbenzenesulfonate can be 4 parts, 5 parts, 6 parts, 7 parts, or 8 parts, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0028] In the technical solution disclosed in this invention, sodium lauryl sulfate is used as an emulsifier and dispersant to help the components in the coating to be evenly dispersed. The amount of sodium lauryl sulfate can be 2 parts, 2.5 parts, 3 parts, 3.5 parts, or 4 parts, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0029] In the technical solution disclosed in this invention, benzoyl peroxide, as a free radical initiator, initiates a cross-linking reaction of the double bonds in the coating during the curing process, thereby forming a robust three-dimensional network structure and improving the hardness of the coating. The amount of benzoyl peroxide can be selected from 0.5 parts, 0.6 parts, 0.7 parts, 0.8 parts, 0.9 parts, and 1 part, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0030] The present invention also provides a method for preparing the above-mentioned explosion-proof ultra-thin glass, comprising the following steps: after cleaning and drying the ultra-thin glass substrate, coating is applied to the upper and lower surfaces of the ultra-thin glass substrate, and the coating is heated and cured to obtain explosion-proof ultra-thin glass containing an organosilicon resin coating.

[0031] Compared with the prior art, the present invention has the following beneficial effects: (1) The explosion-proof ultrathin glass containing an organosilicon resin coating provided by the present invention uses acrylic modified organosilicon resin as the main film-forming matrix, which gives the coating excellent weather resistance and chemical stability. The introduction of modified polyurethane significantly enhances the toughness and wear resistance of the coating. Vinyl silicone oil plays a role in enhancing flexibility and improving the leveling and surface smoothness of the coating. At the same time, it can also reduce the surface tension of the coating, making the coating more evenly distributed on the glass surface. Benzoyl peroxide, as an initiator, promotes the cross-linking and curing of the resin under low temperature conditions, increases the cross-linking density, effectively blocks the transmission of external force impact, and improves the impact resistance of the coating. The explosion-proof ultrathin glass provided by the present invention has excellent impact resistance and wear resistance.

[0032] (2) This invention improves the hardness and wear resistance of montmorillonite by attaching zirconium oxide particles to the surface and interlayer of montmorillonite. Then, 2-butene-1,4-diol is polymerized and grafted onto the surface of the montmorillonite composite material. The hydroxyl groups in 2-butene-1,4-diol can react with diisocyanate to embed the montmorillonite composite material into the polyurethane backbone. The montmorillonite composite material can hinder the slippage of the polymer chain. At the same time, the flexible alkyl long chain structure in 2-butene-1,4-diol can reduce the rigidity of the molecular chain. Together with the montmorillonite composite material, it improves the impact resistance of the polyurethane material. Detailed Implementation

[0033] The present invention will be further described in detail below through specific preferred embodiments, but the present invention is not limited to the following embodiments.

[0034] It should be noted that, unless otherwise specified, all chemical reagents involved in this invention were purchased through commercial channels.

[0035] The acrylic modified silicone resin used in this embodiment of the invention is grade JP-R03, sourced from Shanghai Kaiyin Chemical Co., Ltd.; the montmorillonite is calcium-based montmorillonite with a mesh size of 325 mesh; the vinyl silicone oil has CAS number 26710-23-6, sourced from Jinan Shanhai Chemical Technology Co., Ltd.; and the polytetrahydrofuran diol has CAS number 25190-06-1.

[0036] Example 1

[0037] A method for preparing explosion-proof ultrathin glass includes the following steps: After cleaning and drying an ultra-thin glass substrate with a thickness of 0.3 mm, a coating is applied to the upper and lower surfaces of the ultra-thin glass substrate. The substrate is then heated and cured at 150°C for 3 hours. After curing, the coating thickness is 50 μm. The substrate is then cooled to room temperature to obtain an explosion-proof ultra-thin glass containing an organosilicon resin coating.

[0038] The coating comprises, by weight, the following raw materials: 80 parts acrylic modified silicone resin, 20 parts modified polyurethane, 8 parts vinyl silicone oil, 6 parts sodium dodecylbenzene sulfonate, 3 parts sodium lauryl sulfate, and 1 part benzoyl peroxide.

[0039] The modified polyurethane is prepared as follows: (1) Disperse 6g of montmorillonite in 100mL of deionized water using ultrasonication, then add 8g of zirconium oxychloride octahydrate, stir until uniform, adjust the pH of the solution to 10, heat the reaction at 80℃ for 3h, and after the reaction is complete, filter, wash, dry, and calcine at 500℃ for 3h to obtain montmorillonite composite material. (2) Disperse 8g of montmorillonite composite material in 100mL of ethanol aqueous solution (volume ratio of ethanol to water is 4:1), then add 2g of vinyltriethoxysilane, stir at room temperature for 2h, and then filter, wash and dry to obtain vinyl-grafted montmorillonite composite material. (3) Disperse 8g of vinyl-grafted montmorillonite composite material in 100mL of organic solvent DMF, then add 4g of 2-butene-1,4-diol and 0.05g of benzoyl peroxide, heat at 80℃ for 2h, and after the reaction is completed, filter, wash and dry to obtain composite modified montmorillonite.

[0040] (4) First, mix 5 parts of composite modified montmorillonite and 25 parts of polytetrahydrofuran diol evenly to obtain a mixture. Then, add the mixture, 15 parts of isophorone diisocyanate and 0.5 parts of catalyst stannous octoate into the reactor and react at 90°C for 2 hours to obtain polyurethane prepolymer. (5) Add 4 parts of chain extender dimethylolpropionic acid to the polyurethane prepolymer, continue the reaction at 90°C for 1 hour, cool and add acetone to dilute to the solid content of the system to 50% to obtain polyurethane prepolymer. (6) Add 2 parts of neutralizing agent triethylamine to the polyurethane prepolymer and stir the reaction at room temperature for 45 min to obtain modified polyurethane.

[0041] Example 2

[0042] A method for preparing explosion-proof ultrathin glass includes the following steps: After cleaning and drying an ultra-thin glass substrate with a thickness of 0.3 mm, a coating is applied to the upper and lower surfaces of the ultra-thin glass substrate. The substrate is then heated and cured at 150°C for 3 hours. After curing, the coating thickness is 50 μm. The substrate is then cooled to room temperature to obtain an explosion-proof ultra-thin glass containing an organosilicon resin coating.

[0043] The coating comprises, by weight, the following raw materials: 60 parts acrylic modified silicone resin, 15 parts modified polyurethane, 5 parts vinyl silicone oil, 4 parts sodium dodecylbenzene sulfonate, 2 parts sodium lauryl sulfate, and 0.5 parts benzoyl peroxide.

[0044] The modified polyurethane is prepared as follows: (1) Disperse 4g of montmorillonite in 100mL of deionized water using ultrasonication, then add 5g of zirconium oxychloride octahydrate, stir until uniform, adjust the pH of the solution to 10, heat the reaction at 80℃ for 3h, and after the reaction is complete, filter, wash, dry, and calcine at 500℃ for 3h to obtain montmorillonite composite material. (2) Disperse 5g of montmorillonite composite material in 100mL of ethanol aqueous solution (volume ratio of ethanol to water is 4:1), then add 1g of vinyltriethoxysilane, stir at room temperature for 2h, and then filter, wash and dry to obtain vinyl-grafted montmorillonite composite material. (3) Disperse 5g of vinyl-grafted montmorillonite composite material in 100mL of organic solvent DMF, then add 3g of 2-butene-1,4-diol and 0.05g of benzoyl peroxide, heat at 80℃ for 2h, and after the reaction is completed, filter, wash and dry to obtain composite modified montmorillonite.

[0045] (4) First, mix 10 parts of composite modified montmorillonite and 40 parts of polytetrahydrofuran diol evenly to obtain a mixture. Then, add the mixture, 20 parts of isophorone diisocyanate and 1 part of catalyst stannous octoate into the reactor and react at 90°C for 2 hours to obtain polyurethane prepolymer. (5) Add 8 parts of chain extender dimethylolpropionic acid to the polyurethane prepolymer, continue the reaction at 90°C for 1 hour, cool and add acetone to dilute to the solid content of the system to 50% to obtain the polyurethane prepolymer. (6) Add 3 parts of neutralizing agent triethylamine to the polyurethane prepolymer and stir the reaction at room temperature for 45 min to obtain modified polyurethane.

[0046] Example 3

[0047] A method for preparing explosion-proof ultrathin glass includes the following steps: After cleaning and drying an ultra-thin glass substrate with a thickness of 0.3 mm, a coating is applied to the upper and lower surfaces of the ultra-thin glass substrate. The substrate is then heated and cured at 150°C for 3 hours. After curing, the coating thickness is 50 μm. The substrate is then cooled to room temperature to obtain an explosion-proof ultra-thin glass containing an organosilicon resin coating.

[0048] The coating comprises, by weight, the following raw materials: 65 parts acrylic modified silicone resin, 20 parts modified polyurethane, 8 parts vinyl silicone oil, 6 parts sodium dodecylbenzene sulfonate, 3 parts sodium lauryl sulfate, and 0.5 parts benzoyl peroxide.

[0049] The modified polyurethane is prepared as follows: (1) Disperse 6g of montmorillonite in 100mL of deionized water using ultrasonication, then add 10g of zirconium oxychloride octahydrate, stir until uniform, adjust the pH of the solution to 10, heat the reaction at 80℃ for 3h, and after the reaction is complete, filter, wash, dry, and calcine at 500℃ for 3h to obtain montmorillonite composite material. (2) 10g of montmorillonite composite material was dispersed in 100mL of ethanol aqueous solution (the volume ratio of ethanol to water was 4:1), and then 3g of vinyltriethoxysilane was added to it. The mixture was stirred at room temperature for 2h, and then filtered, washed and dried to obtain vinyl-grafted montmorillonite composite material. (3) Disperse 8g of vinyl-grafted montmorillonite composite material in 100mL of organic solvent DMF, then add 6g of 2-butene-1,4-diol and 0.1g of benzoyl peroxide to it, heat at 80℃ for 2h, and after the reaction is completed, filter, wash and dry to obtain composite modified montmorillonite.

[0050] (4) First, mix 8 parts of composite modified montmorillonite and 30 parts of polytetrahydrofuran diol evenly to obtain a mixture. Then, add the mixture, 18 parts of isophorone diisocyanate and 1 part of catalyst stannous octoate into the reactor and react at 90°C for 2 hours to obtain polyurethane prepolymer. (5) Add 6 parts of chain extender dimethylolpropionic acid to the polyurethane prepolymer, continue the reaction at 90°C for 1 hour, cool and add acetone to dilute to the solid content of the system to 50% to obtain the polyurethane prepolymer. (6) Add 2 parts of neutralizing agent triethylamine to the polyurethane prepolymer and stir the reaction at room temperature for 45 min to obtain modified polyurethane.

[0051] Comparative Example 1

[0052] A method for preparing explosion-proof ultrathin glass includes the following steps: After cleaning and drying an ultra-thin glass substrate with a thickness of 0.3 mm, a coating is applied to the upper and lower surfaces of the ultra-thin glass substrate. The substrate is then heated and cured at 150°C for 3 hours. After curing, the coating thickness is 50 μm. The substrate is then cooled to room temperature to obtain an explosion-proof ultra-thin glass containing an organosilicon resin coating.

[0053] The coating comprises, by weight, the following raw materials: 80 parts acrylic modified silicone resin, 20 parts modified polyurethane, 8 parts vinyl silicone oil, 6 parts sodium dodecylbenzene sulfonate, 3 parts sodium lauryl sulfate, and 1 part benzoyl peroxide.

[0054] The modified polyurethane is prepared as follows: (1) First, mix 5 parts of montmorillonite and 25 parts of polytetrahydrofuran diol evenly to obtain a mixture. Then, add the mixture, 15 parts of isophorone diisocyanate and 0.5 parts of catalyst stannous octoate into the reactor and react at 90°C for 2 hours to obtain polyurethane prepolymer. (2) Add 4 parts of chain extender dimethylolpropionic acid to the polyurethane prepolymer, continue the reaction at 90°C for 1 hour, cool and add acetone to dilute to the solid content of the system to 50% to obtain the polyurethane prepolymer. (3) Add 2 parts of neutralizing agent triethylamine to the polyurethane prepolymer and stir the reaction at room temperature for 45 min to obtain modified polyurethane.

[0055] Compared with Comparative Example 1 and Example 1, no modification treatment was performed on the montmorillonite.

[0056] Comparative Example 2

[0057] A method for preparing explosion-proof ultrathin glass includes the following steps: After cleaning and drying an ultra-thin glass substrate with a thickness of 0.3 mm, a coating is applied to the upper and lower surfaces of the ultra-thin glass substrate. The substrate is then heated and cured at 150°C for 3 hours. After curing, the coating thickness is 50 μm. The substrate is then cooled to room temperature to obtain an explosion-proof ultra-thin glass containing an organosilicon resin coating.

[0058] The coating comprises, by weight, the following raw materials: 80 parts acrylic modified silicone resin, 20 parts modified polyurethane, 8 parts vinyl silicone oil, 6 parts sodium dodecylbenzene sulfonate, 3 parts sodium lauryl sulfate, and 1 part benzoyl peroxide.

[0059] The modified polyurethane is prepared as follows: (1) Disperse 8g of montmorillonite in 100mL of ethanol aqueous solution (the volume ratio of ethanol to water is 4:1), then add 2g of vinyltriethoxysilane, stir at room temperature for 2h, and then filter, wash and dry to obtain vinyl-grafted montmorillonite. (2) Disperse 8g of vinyl-grafted montmorillonite in 100mL of organic solvent DMF, then add 4g of 2-butene-1,4-diol and 0.05g of benzoyl peroxide to it, heat at 80℃ for 2h, and after the reaction is completed, filter, wash and dry to obtain composite modified montmorillonite.

[0060] (3) First, mix 5 parts of composite modified montmorillonite and 25 parts of polytetrahydrofuran diol evenly to obtain a mixture. Then, add the mixture, 15 parts of isophorone diisocyanate and 0.5 parts of catalyst stannous octoate into the reactor and react at 90°C for 2 hours to obtain polyurethane prepolymer. (4) Add 4 parts of chain extender dimethylolpropionic acid to the polyurethane prepolymer, continue the reaction at 90°C for 1 hour, cool and add acetone to dilute to the solid content of the system to 50% to obtain the polyurethane prepolymer. (5) Add 2 parts of neutralizing agent triethylamine to the polyurethane prepolymer and stir the reaction at room temperature for 45 min to obtain modified polyurethane.

[0061] Compared to Example 1, Comparative Example 2 did not involve loading zirconium oxide onto montmorillonite.

[0062] Comparative Example 3

[0063] A method for preparing explosion-proof ultrathin glass includes the following steps: After cleaning and drying an ultra-thin glass substrate with a thickness of 0.3 mm, a coating is applied to the upper and lower surfaces of the ultra-thin glass substrate. The substrate is then heated and cured at 150°C for 3 hours. After curing, the coating thickness is 50 μm. The substrate is then cooled to room temperature to obtain an explosion-proof ultra-thin glass containing an organosilicon resin coating.

[0064] The coating comprises, by weight, the following raw materials: 80 parts acrylic modified silicone resin, 20 parts modified polyurethane, 8 parts vinyl silicone oil, 6 parts sodium dodecylbenzene sulfonate, 3 parts sodium lauryl sulfate, and 1 part benzoyl peroxide.

[0065] The modified polyurethane is prepared as follows: (1) Disperse 6g of montmorillonite in 100mL of deionized water using ultrasonication, then add 8g of zirconium oxychloride octahydrate, stir until uniform, adjust the pH of the solution to 10, heat the reaction at 80℃ for 3h, and after the reaction is complete, filter, wash, dry, and calcine at 500℃ for 3h to obtain montmorillonite composite material. (2) First, mix 5 parts of montmorillonite composite material and 25 parts of polytetrahydrofuran diol evenly to obtain a mixture. Then, add the mixture, 15 parts of isophorone diisocyanate and 0.5 parts of catalyst stannous octoate into the reactor and react at 90°C for 2 hours to obtain polyurethane prepolymer. (3) Add 4 parts of chain extender dimethylolpropionic acid to the polyurethane prepolymer, continue the reaction at 90°C for 1 hour, cool and add acetone to dilute to the solid content of the system to 50% to obtain polyurethane prepolymer. (4) Add 2 parts of neutralizing agent triethylamine to the polyurethane prepolymer and stir the reaction at room temperature for 45 min to obtain modified polyurethane.

[0066] Compared with Example 1, Comparative Example 3 did not graft 2-butene-1,4-diol onto the montmorillonite composite material.

[0067] Comparative Example 4

[0068] A method for preparing explosion-proof ultrathin glass includes the following steps: After cleaning and drying an ultra-thin glass substrate with a thickness of 0.3 mm, a coating is applied to the upper and lower surfaces of the ultra-thin glass substrate. The substrate is then heated and cured at 150°C for 3 hours. After curing, the coating thickness is 50 μm. The substrate is then cooled to room temperature to obtain an explosion-proof ultra-thin glass containing an organosilicon resin coating.

[0069] The coating comprises, by weight, the following raw materials: 80 parts of acrylic-modified silicone resin, 20 parts of modified polyurethane, 6 parts of sodium dodecylbenzenesulfonate, 3 parts of sodium lauryl sulfate, and 1 part of benzoyl peroxide.

[0070] The modified polyurethane is prepared as follows: (1) Disperse 6g of montmorillonite in 100mL of deionized water using ultrasonication, then add 8g of zirconium oxychloride octahydrate, stir until uniform, adjust the pH of the solution to 10, heat the reaction at 80℃ for 3h, and after the reaction is complete, filter, wash, dry, and calcine at 500℃ for 3h to obtain montmorillonite composite material. (2) Disperse 8g of montmorillonite composite material in 100mL of ethanol aqueous solution (volume ratio of ethanol to water is 4:1), then add 2g of vinyltriethoxysilane, stir at room temperature for 2h, and then filter, wash and dry to obtain vinyl-grafted montmorillonite composite material. (3) Disperse 8g of vinyl-grafted montmorillonite composite material in 100mL of organic solvent DMF, then add 4g of 2-butene-1,4-diol and 0.05g of benzoyl peroxide, heat at 80℃ for 2h, and after the reaction is completed, filter, wash and dry to obtain composite modified montmorillonite.

[0071] (4) First, mix 5 parts of composite modified montmorillonite and 25 parts of polytetrahydrofuran diol evenly to obtain a mixture. Then, add the mixture, 15 parts of isophorone diisocyanate and 0.5 parts of catalyst stannous octoate into the reactor and react at 90°C for 2 hours to obtain polyurethane prepolymer. (5) Add 4 parts of chain extender dimethylolpropionic acid to the polyurethane prepolymer, continue the reaction at 90°C for 1 hour, cool and add acetone to dilute to the solid content of the system to 50% to obtain polyurethane prepolymer. (6) Add 2 parts of neutralizing agent triethylamine to the polyurethane prepolymer and stir the reaction at room temperature for 45 min to obtain modified polyurethane.

[0072] Compared to Example 1, no vinyl silicone oil was added in Comparative Example 4.

[0073] The glass samples prepared in Examples 1-3 and Comparative Examples 1-4 were subjected to performance tests, as detailed below: Coating hardness test: The pencil hardness of the coating is tested using a pencil hardness tester; Abrasion resistance test: Using a Taber abrasion tester, the sample was abraded for 500 revolutions with a CS-10 grinding wheel under a pressure of 100 grams, and the weight loss of the sample was recorded. Impact resistance: Tested according to GB 15763.2-2005 standard; Weather resistance test: A xenon lamp aging test chamber was used at 0.55W / m 2 The samples were continuously exposed to irradiance for 200 hours, and the changes in their appearance were observed. The test results are shown in Table 1.

[0074] Table 1 Performance test results for different groups

[0075] As can be seen from the table, compared with comparative examples 1-4, the coating material prepared by embedding composite modified montmorillonite into the polyurethane main chain has excellent wear resistance and impact resistance, and also has relatively high hardness.

[0076] Finally, it should be noted that the above embodiments do not limit the present invention in any way. Those skilled in the art can make modifications and improvements based on the present invention. Therefore, any modifications or improvements made without departing from the spirit of the present invention are within the scope of protection claimed by the present invention.

Claims

1. An explosion-proof ultra-thin glass having a coating of silicone resin, characterized by, The explosion-proof ultra-thin glass includes an ultra-thin glass substrate and a coating applied to the upper and lower surfaces of the ultra-thin glass substrate. By weight, the coating comprises the following raw materials: 60-80 parts of acrylic modified silicone resin, 15-25 parts of modified polyurethane, 5-10 parts of vinyl silicone oil, 4-8 parts of sodium dodecylbenzenesulfonate, 2-4 parts of sodium lauryl sulfate, and 0.5-1 parts of benzoyl peroxide. The modified polyurethane is prepared as follows: S1. The composite modified montmorillonite, polyol and diisocyanate are reacted under the action of a catalyst to obtain polyurethane prepolymer; S2. Add a chain extender to the polyurethane prepolymer and continue the reaction. Then adjust the viscosity of the system with acetone to obtain the polyurethane prepolymer. S3. Add triethylamine, a neutralizing agent, to the polyurethane prepolymer and stir to react, thereby obtaining the modified polyurethane. In step S1, the preparation method of the composite modified montmorillonite is as follows: (1) Disperse montmorillonite in deionized water using ultrasonication, then add soluble zirconium salt, stir until homogeneous, adjust the pH of the solution to 10-12, heat to react, and after the reaction is complete, filter, wash, dry and calcine to obtain montmorillonite composite material. (2) The montmorillonite composite material was dispersed in an aqueous ethanol solution, and then vinyltriethoxysilane was added to it. The mixture was stirred and then filtered, washed and dried to obtain the vinyl-grafted montmorillonite composite material. (3) The vinyl-grafted montmorillonite composite material is dispersed in an organic solvent, and then 2-butene-1,4-diol and benzoyl peroxide are added to it. The mixture is heated to react. After the reaction is completed, it is filtered, washed and dried to obtain the composite modified montmorillonite.

2. The explosion-proof ultra-thin glass according to claim 1, characterized in that, By weight, the composite modified montmorillonite comprises 5-10 parts, the polyol comprises 25-40 parts, the diisocyanate comprises 15-20 parts, the catalyst comprises 0.5-1 parts, the chain extender comprises 4-8 parts, and the triethylamine comprises 1-3 parts.

3. The explosion-proof ultra-thin glass according to claim 1, characterized in that, In step (1), the mass ratio of montmorillonite to soluble zirconium salt is 4-8:5-10.

4. The explosion-proof ultra-thin glass according to claim 1, characterized in that, In step (2), the mass ratio of montmorillonite composite material to vinyltriethoxysilane is 5-10:1-3.

5. The explosion-proof ultra-thin glass according to claim 1, characterized in that, In step (3), the mass ratio of vinyl-grafted montmorillonite composite material, 2-butene-1,4-diol and benzoyl peroxide is 5-10:3-6:0.05-0.

1.

6. The explosion-proof ultra-thin glass according to claim 1, characterized in that, In step S1, the polyol is selected from polyether glycol or polyester glycol; the diisocyanate is selected from isophorone diisocyanate or hexamethylene diisocyanate; and the catalyst is selected from organotin catalysts.

7. The explosion-proof ultra-thin glass according to claim 1, characterized in that, In step S2, the chain extender is selected from at least one of dimethylolpropionic acid and dimethylolbutyric acid.

8. The method for preparing explosion-proof ultrathin glass according to any one of claims 1-7, characterized in that, The process includes the following steps: after cleaning and drying the ultra-thin glass substrate, a coating is applied to the upper and lower surfaces of the ultra-thin glass substrate, and then heated and cured to obtain explosion-proof ultra-thin glass containing an organosilicon resin coating.

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