Fire resistant roof panel of foamed aluminum-glass fiber reinforced composite

Abstract

This invention discloses a fireproof roofing panel made of aluminum foam-glass fiber reinforced composite material, belonging to the field of building materials technology, and includes the following steps: S1. Preparing grafted glass fiber mat; S2. Preparing FRP panels; S3. Coating the bonding surface of the FRP panels with a high-temperature epoxy adhesive, and precisely stacking them in the order of upper FRP panel, adhesive, aluminum foam core layer, adhesive, and lower FRP panel to obtain a composite blank, placing the composite blank into a pressing device for pressing, and curing the pressed composite blank at high temperature to obtain a rough blank; S4. Spraying a coating onto the surface of the rough blank, and curing the sprayed rough blank to obtain the fireproof roofing panel made of aluminum foam-glass fiber reinforced composite material. In this invention, the coating sprayed onto the surface of the rough blank can firmly adhere to the outer surface of the panel, effectively preventing rainwater, dust, ultraviolet rays, and various corrosive substances from penetrating into the interior of the panel, and relying on its own hard texture to resist daily scratches from hard objects and minor external impacts.

Description

Technical Field

[0001] This invention relates to the field of building materials technology, and in particular to fireproof roof panels made of aluminum foam-glass fiber reinforced composite materials. Background Technology

[0002] Fire-resistant roof panels are covering materials used in building roofing systems that have specified fire resistance properties. Their core function is to effectively block flames and high temperatures in the event of a fire, delaying the spread of fire to the interior of the building or other areas, and buying valuable time for personnel evacuation and fire rescue.

[0003] Traditional roof panels generally suffer from limited functionality, poor fire resistance and thermal insulation, insufficient wind resistance, and susceptibility to corrosion and aging due to external environmental factors. The bonding between layers is often weak, leading to delamination and leaks over time. Their weight also increases the structural load on buildings, requiring additional support structures for large spans, thus raising construction costs. Furthermore, their overall lifespan is relatively short, requiring frequent maintenance and resulting in higher overall operating costs. Therefore, this invention provides a fire-resistant roof panel made of aluminum foam-glass fiber reinforced composite material. Summary of the Invention

[0004] The main objective of this invention is to provide a fireproof roofing panel made of aluminum foam-glass fiber reinforced composite material with high oxygen index and high interlaminar shear strength, which can be used in fireproof roofing panels made of aluminum foam-glass fiber reinforced composite material.

[0005] To achieve the above objectives, the technical solution adopted by the present invention is as follows: This invention provides a fire-resistant roof panel made of aluminum foam-glass fiber reinforced composite material, the preparation of which includes the following steps: S1. Preparation of grafted glass fiber mat.

[0006] S2. Preparation of FRP panels.

[0007] S3. Apply a high-temperature epoxy adhesive to the bonding surface of the FRP panel, setting the coating amount to 0.8-1.2 kg / m². 2 The FRP panel, high-temperature epoxy adhesive, aluminum foam core layer, high-temperature epoxy adhesive, and lower FRP panel are precisely stacked in the following order to obtain a composite blank. The composite blank is placed in a pressing equipment for pressing, with a static pressure of 0.3-0.5 MPa and a pressing time of 10 minutes. The pressed composite blank is then cured at a high temperature, with a heating rate of 2-3℃ / min to 120-150℃ and a pressure of 0.4-0.6 MPa. It is then cured at a constant temperature for 90-120 minutes, cooled to 100℃ at a cooling rate of 2-3℃ / min, and then cooled to 60℃ at a cooling rate of 1-2℃ / min to obtain a rough blank.

[0008] S4. Spray the coating onto the surface of the rough blank, with a coating amount of 0.2-0.3 kg / m². 2 The sprayed blank is cured at a set temperature of 80℃ for 30 minutes to obtain a fireproof roof panel made of aluminum foam-glass fiber reinforced composite material.

[0009] The fireproof roof panel made of aluminum foam-glass fiber reinforced composite material achieves both fireproof and heat insulation functions through the internal aluminum foam core material. Combined with the modified glass fiber composite panel, it strengthens the overall structural strength and effectively improves wind resistance. Furthermore, the outer protective coating resists various external corrosion attacks, integrating fireproof, heat insulation, lightweight, wind uplift resistance and corrosion resistance into one, successfully solving the shortcomings of traditional roof panels with single functions.

[0010] During the production process, the glass fiber is first modified at the interface, and then modified resin is used to complete the overall laying and bonding. Combined with high-temperature curing composite processing, the bonding tightness between the structural layers of the board is greatly improved, effectively avoiding problems such as delamination and water seepage in the later stage. The long-term stability is greatly improved, and the overall durability is significantly improved compared with traditional roofing panels.

[0011] The porosity of the aluminum foam core layer is 70%-85%, the closed-cell rate is ≥90%, it is Class A non-combustible, and the thickness is 60-120mm.

[0012] The adhesive has a room temperature viscosity of 8000-15000 mPa·s, a curing temperature of 120-150℃, and a shear bond strength ≥3.5 MPa.

[0013] The heat resistance temperature of the silicone-based release agent is ≥180℃.

[0014] Furthermore, the preparation of the grafted glass fiber mat includes the following steps: A1. Heat the sodium hydroxide solution to 45°C, add the glass fiber mat to soak for 10 minutes, wash the soaked glass fiber mat with deionized water until neutral, dry the washed glass fiber mat at 60°C for 15 minutes to obtain activated glass fiber mat.

[0015] A2. Immerse the activated glass fiber mat in the treatment solution for 15 minutes, remove the activated glass fiber mat, squeeze out the excess treatment solution with a roller, and dry the glass fiber mat after the roller is removed. Set the temperature to 80℃ and dry for 30 minutes to obtain the grafted glass fiber mat.

[0016] The glass fiber mat has an alkali metal oxide content of ≤0.8% and a fiber diameter of 10-13 μm.

[0017] Further, the preparation of the treatment solution includes the following steps: propylene glycol methyl ether acetate and deionized water are mixed and stirred at 300 rpm for 10 minutes; citric acid monohydrate is added and stirred for 3 minutes; vinyltris(β-methoxyethoxy)silane and N-phosphorylpropyltriethoxysilane are added sequentially and stirred at 500 rpm for 20 minutes; nano-hollow titanium dioxide is added and stirred at 800 rpm for 15 minutes; stirring is stopped, and the mixture is allowed to stand for 5 minutes to obtain the treatment solution.

[0018] The nano-hollow titanium dioxide is silane-modified nano-hollow titanium dioxide with a particle size of 20-30 nm and surface activated by silane.

[0019] Furthermore, the pH is adjusted to 4-4.5 by adding citric acid monohydrate; The mass ratio of propylene glycol methyl ether acetate, deionized water, vinyltris(β-methoxyethoxy)silane, N-phosphorylpropyltriethoxysilane, and nano-hollow titanium dioxide is 60:40:5:3:2.

[0020] Furthermore, the preparation of the FRP panel includes the following steps: applying a silicone-based release agent to the surface of the mold, placing the pretreated glass fiber mat into the mold and applying modified vinyl ester resin for curing, setting the temperature to 25-30℃, curing for 2 hours, demolding, and obtaining the FRP panel.

[0021] Further, the preparation of the modified vinyl ester resin includes the following steps: nitrogen gas is introduced into a reaction vessel, bisphenol A type epoxy vinyl ester resin and a portion of styrene are added and stirred at a speed of 400 rpm. The reaction vessel is heated to 85°C at a heating rate of 2-3°C / min. Hydroxyl-terminated polyurethane prepolymer and a portion of hydroquinone are added and stirred at a speed of 400 rpm for 60 minutes. The remaining styrene and DOPO-based methacrylate monomer are added and stirred for 20 minutes. A portion of di-tert-butyl peroxide is added and stirred for 70 minutes. The reaction vessel is cooled at a rate of 1-2°C / min. The mixture was cooled to 75°C, and γ-methacryloyloxypropyltrimethoxysilane was added and stirred at 400 rpm for 40 minutes. Nano-silica and MBS core-shell elastomer toughening particles were added and stirred at 1500 rpm for 30 minutes. Stirring was stopped, and the mixture was allowed to stand for degassing for 15 minutes. The reactor was then cooled to 40°C at a rate of 1-2°C / min. The remaining di-tert-butyl peroxide was added and stirred at 300 rpm for 20 minutes to obtain a mixture. The mixture was sealed and allowed to stand for 24 hours to mature, resulting in modified vinyl ester resin.

[0022] Further, the mass ratio of the bisphenol A type epoxy vinyl ester resin, a portion of styrene, hydroxyl-terminated polyurethane prepolymer, a portion of hydroquinone, the remaining styrene, DOPO-based methacrylate monomer, a portion of di-tert-butyl peroxide, γ-methacryloyloxypropyltrimethoxysilane, nano-silica, MBS core-shell elastomer toughening particles, and the remaining di-tert-butyl peroxide is 100:7.5:13.5:0.02:2.5:9:0.25:4.5:4:4:0.85.

[0023] The modified glass fiber mat exhibits a good synergistic effect with the modified vinyl ester resin after being immersed in the treatment solution. The treatment solution optimizes the surface state of the glass fiber, forming an active structure that can be mated and a rough contact surface. The modified resin fully adheres to the fiber due to its excellent wettability and adhesion. The combination of the two greatly improves the interlayer bonding strength and allows the flame retardant components in the resin to be evenly attached and distributed, simultaneously enhancing the mechanical strength and overall fire resistance of the board.

[0024] After being immersed in the treatment solution, the glass fiber mat has a synergistic effect with the self-made coating. The composite board modified by the treatment solution has a stable and compact internal interface, and the surface texture of the substrate is more uniform and dense. This reduces the surface micropores and defects, provides a high-quality adhesion base for the outer self-made coating, effectively improves the coating bonding effect and long-lasting adhesion, and at the same time reduces the damage of environmental erosion to the coating substrate by means of the stable internal structure.

[0025] The bisphenol A type epoxy vinyl ester resin has a solid content of ≥98%, a viscosity of 4000-8000 mPa·s at 25℃, and a heat distortion temperature of ≥110℃.

[0026] The number average molecular weight of the hydroxyl-terminated polyurethane prepolymer is about 800, and the hydroxyl content meets the standard.

[0027] The DOPO-based methacrylate monomer has a compliant phosphorus content, contains active double bonds, can participate in free radical copolymerization, and its flame-retardant groups are not easily migrated.

[0028] The nano-silica is silane-modified nano-silica with a particle size of 20-30nm. The surface modification is complete, there is no agglomeration, and it has excellent heat resistance and reinforcing effect.

[0029] The MBS core-shell elastomer toughening particles have a rubber phase content of 60%-70% and a particle size of 100-300nm.

[0030] Further, the preparation of the coating includes the following steps: hydroxyl FEVE fluorocarbon resin and γ-aminopropyltriethoxysilane are mixed and stirred at a speed of 500 rpm for 10 minutes; MBS core-shell elastomer, hollow ceramic microspheres, polyacrylate dispersant and organosilicon defoamer are added and stirred at a speed of 1500 rpm for 30 minutes; the speed is then adjusted to 300 rpm; polyether-modified siloxane leveling agent, stabilizer and blocked isocyanate curing agent are added and stirred for 15 minutes to obtain material A; material A is then degassed under vacuum at a vacuum degree of -0.095 MPa for 10 minutes to obtain the coating.

[0031] Furthermore, the mass ratio of the hydroxyl FEVE fluorocarbon resin, γ-aminopropyltriethoxysilane, MBS core-shell elastomer, hollow ceramic microspheres, polyacrylate dispersant, silicone defoamer, polyether-modified siloxane leveling agent, stabilizer, and blocked isocyanate curing agent is 60:3:8:12:1.5:1:1:2.5:11.

[0032] The modified vinyl ester resin and the coating work synergistically inside and out. The modified resin forms a high-strength, highly flame-retardant, and temperature-stable internal matrix for the board, laying the foundation for core performance. The coating forms a dense protective layer on the outer layer, blocking ultraviolet rays, rainwater, and corrosive substances from penetrating the interior. The internal and external workings work together to not only firmly retain the original structure and fire resistance of the board, but also comprehensively improve the overall weather resistance, impact resistance, and anti-aging capabilities.

[0033] Furthermore, the stabilizer is composed of 2-hydroxy-4-n-octyloxybenzophenone and polytetramethylpiperidinol polysuccinate in a mass ratio of 1:1.

[0034] The hydroxyl FEVE fluorocarbon resin has a hydroxyl content of 3%-5%, a solid content of 50%-60%, excellent weather resistance, and salt spray resistance ≥2000h.

[0035] The MBS core-shell elastomer is a weather-resistant toughened modified material that does not crack at low temperatures, thus improving the coating's impact resistance.

[0036] The hollow ceramic microspheres have a particle size of 30-50 μm and a compressive strength of ≥100 MPa.

[0037] The polyacrylate dispersant used is BYK-110.

[0038] The polyether-modified siloxane leveling agent used is BYK-333.

[0039] The closed-type isocyanate curing agent used is Bayhydur 3100.

[0040] The silicone defoamer used is BYK-024.

[0041] The present invention has the following beneficial effects: 1. In this invention, the glass fiber mat is soaked in a treatment solution to complete the surface activation and modification of the glass fiber. Active reactive groups and flame retardant groups are grafted onto the fiber surface, and nanofillers are attached to form a micro-anchoring structure. This effectively eliminates the inert interface on the fiber surface, greatly improves the wetting and fusion ability of the glass fiber and the self-made modified vinyl ester resin, and forms a stable chemical bond after curing. This not only strengthens the interlayer adhesion effect and avoids delamination in the later stage, but also gives the fiber surface flame retardant basic properties and optimizes the internal structure density of the overall board.

[0042] 2. In this invention, modified vinyl ester resin is added, wherein bisphenol A type epoxy vinyl ester resin constitutes the main molding skeleton of the resin, styrene adjusts the resin viscosity to facilitate complete impregnation of glass fibers, hydroxyl-terminated polyurethane prepolymer improves the overall toughness and high-temperature resistance of the resin, hydroquinone prevents premature solidification and failure of the resin during processing, DOPO-based methacrylate monomer imparts stable and durable flame retardant properties to the resin, di-tert-butyl peroxide regulates the resin curing reaction rate in stages, methacryloxysilane enhances the interfacial adhesion between the resin and various substrates, silane-modified nano-silica improves the resin's heat resistance and dimensional stability, and MBS core-shell... Elastomer toughening particles improve the resin's brittleness and cracking defects. All raw materials are used in combination to give the resin excellent molding effect, bonding strength, fire resistance and comprehensive mechanical properties. As the core matrix bonding material inside the fireproof roof panel, the resin can completely impregnate the pretreated glass fiber material, tightly wrap the fiber to form a stable reinforced skeleton structure. It carries flame retardant groups and interface bonding groups, which can firmly bond the glass fiber reinforcement layer and the aluminum foam core layer into a whole, build a stable and reliable overall structure of the board, and at the same time improve the heat resistance, corrosion resistance and bending deformation resistance of the board from the matrix level, and firmly guarantee the fire resistance performance and overall structural mechanical strength of the board.

[0043] 3. In this invention, a coating is sprayed onto the surface of the rough blank. Hydroxyfluorocarbon resin serves as the main film-forming substance in the coating, establishing a complete and stable protective film framework. Aminopropyltriethoxysilane enhances the adhesion between the coating and the board surface. MBS core-shell elastomer improves the coating's flexibility, preventing cracking under hot and cold environments. Hollow ceramic microspheres enhance the coating's impact resistance and heat insulation / wear resistance. Polyacrylate dispersants ensure uniform dispersion of various powder materials, preventing agglomeration and sedimentation. Polyether-modified siloxane leveling agents improve the spraying effect, resulting in a smooth and flat board surface. Ultraviolet absorbers are combined with polytetramethylpiperidinol succinate... It resists UV damage and slows down coating aging. The closed isocyanate curing agent allows the coating to cure quickly under low temperature baking, and the silicone defoamer eliminates air bubbles generated during the mixing and construction process, ensuring that the coating is dense, flat and flawless after curing. It can firmly adhere to the outer surface of the board, effectively blocking rainwater, dust, ultraviolet rays and various corrosive substances from penetrating into the board. Relying on its own hard texture, it can resist daily scratches from hard objects and minor external impacts, fill the tiny gaps on the board surface, further enhance the overall waterproof and seepage-proof ability of the board, slow down the aging and damage of the internal substrate, and comprehensively improve the outdoor protection effect of the board. Detailed Implementation

[0044] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0045] It should be noted that all raw materials used in the following experiments are commercially available.

[0046] Example 1: Fire-resistant roofing panel made of aluminum foam-glass fiber reinforced composite material. The preparation of the fire-resistant roofing panel made of aluminum foam-glass fiber reinforced composite material includes the following steps: S1. To prepare grafted glass fiber mat, heat sodium hydroxide solution to 45°C, add glass fiber mat for soaking, soak for 10 minutes, wash the soaked glass fiber mat with deionized water until neutral, dry the washed glass fiber mat at 60°C for 15 minutes to obtain activated glass fiber mat; immerse the activated glass fiber mat in treatment solution for 15 minutes, remove the activated glass fiber mat, squeeze off excess treatment solution with rollers, dry the glass fiber mat after rollers at 80°C for 30 minutes to obtain grafted glass fiber mat.

[0047] S2. Preparation of FRP panel: Apply silicone-based release agent to the mold surface, place pretreated glass fiber mat into the mold and apply modified vinyl ester resin for curing. Set the temperature to 25℃ and cure for 2 hours. Remove the mold to obtain FRP panel.

[0048] S3. Apply a high-temperature epoxy adhesive to the bonding surface of the FRP panel, setting the coating amount to 0.8 kg / m². 2 The FRP panel, adhesive, aluminum foam core layer, adhesive, and lower FRP panel are precisely stacked in the following order to obtain a composite blank. The composite blank is placed in a pressing equipment for pressing, with a static pressure of 0.3 MPa and a pressing time of 10 minutes. The pressed composite blank is then cured at high temperature, with a heating rate of 2℃ / min to 120℃ and a pressure of 0.4 MPa. It is then cured at a constant temperature for 90 minutes, cooled to 100℃ at a cooling rate of 2℃ / min, and then cooled to 60℃ at a cooling rate of 1℃ / min to obtain a rough blank.

[0049] S4. Spray the coating onto the surface of the rough blank, with a coating amount of 0.2 kg / m². 2 The sprayed blank is cured at a set temperature of 80℃ for 30 minutes to obtain a fireproof roof panel made of aluminum foam-glass fiber reinforced composite material.

[0050] The preparation of the treatment solution includes the following steps: propylene glycol methyl ether acetate and deionized water are mixed and stirred at 300 rpm for 10 minutes; citric acid monohydrate is added and stirred for 3 minutes; vinyltris(β-methoxyethoxy)silane and N-phosphorylpropyltriethoxysilane are added sequentially and stirred at 500 rpm for 20 minutes; nano-hollow titanium dioxide is added and stirred at 800 rpm for 15 minutes; stirring is stopped and the mixture is allowed to stand for 5 minutes to obtain the treatment solution.

[0051] Add citric acid monohydrate to adjust the pH to 4.

[0052] The mass ratio of propylene glycol methyl ether acetate, deionized water, vinyltris(β-methoxyethoxy)silane, N-phosphorylpropyltriethoxysilane, and nano-hollow titanium dioxide is 60:40:5:3:2.

[0053] The preparation of modified vinyl ester resin includes the following steps: Nitrogen gas is introduced into a reaction vessel, bisphenol A type epoxy vinyl ester resin and a portion of styrene are added and stirred at a speed of 400 rpm. The reaction vessel is heated to 85°C at a heating rate of 2°C / min. Hydroxyl-terminated polyurethane prepolymer and a portion of hydroquinone are added and stirred at a speed of 400 rpm for 60 minutes. The remaining styrene and DOPO-based methacrylate monomer are added and stirred for 20 minutes. A portion of di-tert-butyl peroxide is added and stirred for 70 minutes. The reaction vessel is then cooled to a temperature of 1°C / min. At 75℃, γ-methacryloxypropyltrimethoxysilane was added and stirred at 400 rpm for 40 minutes. Nano-silica and MBS core-shell elastomer toughening particles were added and stirred at 1500 rpm for 30 minutes. Stirring was stopped, and the mixture was allowed to stand for degassing for 15 minutes. The reactor was then cooled to 40℃ at a rate of 1℃ / min. The remaining di-tert-butyl peroxide was added and stirred at 300 rpm for 20 minutes to obtain a mixture. The mixture was sealed and allowed to stand for 24 hours to mature, resulting in modified vinyl ester resin.

[0054] The mass ratio of bisphenol A type epoxy vinyl ester resin, a portion of styrene, hydroxyl-terminated polyurethane prepolymer, a portion of hydroquinone, the remainder of styrene, DOPO-based methacrylate monomer, a portion of di-tert-butyl peroxide, γ-methacryloyloxypropyltrimethoxysilane, nano-silica, MBS core-shell elastomer toughening particles, and the remainder of di-tert-butyl peroxide is 100:7.5:13.5:0.02:2.5:9:0.25:4.5:4:4:0.85.

[0055] The coating preparation includes the following steps: hydroxyl FEVE fluorocarbon resin and γ-aminopropyltriethoxysilane are mixed and stirred at 500 rpm for 10 minutes. MBS core-shell elastomer, hollow ceramic microspheres, polyacrylate dispersant and organosilicon defoamer are added and stirred at 1500 rpm for 30 minutes. The speed is then adjusted to 300 rpm. Polyether-modified siloxane leveling agent, stabilizer and blocked isocyanate curing agent are added and stirred for 15 minutes to obtain material A. Material A is then degassed under vacuum at a vacuum degree of -0.095 MPa for 10 minutes to obtain the coating.

[0056] The mass ratio of hydroxyl FEVE fluorocarbon resin, γ-aminopropyltriethoxysilane, MBS core-shell elastomer, hollow ceramic microspheres, polyacrylate dispersant, silicone defoamer, polyether-modified siloxane leveling agent, stabilizer and blocked isocyanate curing agent is 60:3:8:12:1.5:1:1:2.5:11.

[0057] The stabilizer is a mixture of 2-hydroxy-4-n-octyloxybenzophenone and polytetramethylpiperidinol succinate in a mass ratio of 1:1.

[0058] Example 2: Fire-resistant roofing panel made of aluminum foam-glass fiber reinforced composite material. The preparation of the fire-resistant roofing panel made of aluminum foam-glass fiber reinforced composite material includes the following steps: S1. To prepare grafted glass fiber mat, heat sodium hydroxide solution to 45°C, add glass fiber mat for soaking, soak for 10 minutes, wash the soaked glass fiber mat with deionized water until neutral, dry the washed glass fiber mat at 60°C for 15 minutes to obtain activated glass fiber mat; immerse the activated glass fiber mat in treatment solution for 15 minutes, remove the activated glass fiber mat, squeeze off excess treatment solution with rollers, dry the glass fiber mat after rollers at 80°C for 30 minutes to obtain grafted glass fiber mat.

[0059] S2. Preparation of FRP panel: Apply silicone-based release agent to the mold surface, place pretreated glass fiber mat into the mold and apply modified vinyl ester resin for curing. Set the temperature to 28℃ and cure for 2 hours. Remove the mold to obtain FRP panel.

[0060] S3. Apply a high-temperature epoxy adhesive to the bonding surface of the FRP panel, setting the coating amount to 1 kg / m². 2 The FRP panel, adhesive, aluminum foam core layer, adhesive, and lower FRP panel are precisely stacked in the following order to obtain a composite blank. The composite blank is placed in a pressing equipment for pressing, with a static pressure of 0.4 MPa and a pressing time of 10 minutes. The pressed composite blank is then cured at a high temperature, with a heating rate of 2.5℃ / min to 135℃ and a pressure of 0.5 MPa. It is then cured at a constant temperature for 105 minutes, cooled to 100℃ at a cooling rate of 2.5℃ / min, and then cooled to 60℃ at a cooling rate of 1.5℃ / min to obtain a rough blank.

[0061] S4. Spray the coating onto the surface of the rough blank, with a coating amount of 0.25 kg / m². 2 The sprayed blank is cured at a set temperature of 80℃ for 30 minutes to obtain a fireproof roof panel made of aluminum foam-glass fiber reinforced composite material.

[0062] The preparation of the treatment solution includes the following steps: propylene glycol methyl ether acetate and deionized water are mixed and stirred at 300 rpm for 10 minutes; citric acid monohydrate is added and stirred for 3 minutes; vinyltris(β-methoxyethoxy)silane and N-phosphorylpropyltriethoxysilane are added sequentially and stirred at 500 rpm for 20 minutes; nano-hollow titanium dioxide is added and stirred at 800 rpm for 15 minutes; stirring is stopped and the mixture is allowed to stand for 5 minutes to obtain the treatment solution.

[0063] Add citric acid monohydrate to adjust the pH to 4.3.

[0064] The mass ratio of propylene glycol methyl ether acetate, deionized water, vinyltris(β-methoxyethoxy)silane, N-phosphorylpropyltriethoxysilane, and nano-hollow titanium dioxide is 60:40:5:3:2.

[0065] The preparation of modified vinyl ester resin includes the following steps: Nitrogen gas is introduced into a reaction vessel, bisphenol A type epoxy vinyl ester resin and a portion of styrene are added and stirred at a speed of 400 rpm. The reaction vessel is heated to 85°C at a heating rate of 2.5°C / min. Hydroxyl-terminated polyurethane prepolymer and a portion of hydroquinone are added and stirred at a speed of 400 rpm for 60 minutes. The remaining styrene and DOPO-based methacrylate monomer are added and stirred for 20 minutes. A portion of di-tert-butyl peroxide is added and stirred for 70 minutes. The reaction vessel is then cooled at a cooling rate of 1.5°C / min. At 75°C, γ-methacryloxypropyltrimethoxysilane was added and stirred at 400 rpm for 40 minutes. Nano-silica and MBS core-shell elastomer toughening particles were added and stirred at 1500 rpm for 30 minutes. Stirring was stopped, and the mixture was allowed to stand for degassing for 15 minutes. The reactor was then cooled to 40°C at a rate of 1.5°C / min. The remaining di-tert-butyl peroxide was added and stirred at 300 rpm for 20 minutes to obtain a mixture. The mixture was sealed and allowed to stand for 24 hours to mature, resulting in modified vinyl ester resin.

[0066] The mass ratio of bisphenol A type epoxy vinyl ester resin, a portion of styrene, hydroxyl-terminated polyurethane prepolymer, a portion of hydroquinone, the remainder of styrene, DOPO-based methacrylate monomer, a portion of di-tert-butyl peroxide, γ-methacryloyloxypropyltrimethoxysilane, nano-silica, MBS core-shell elastomer toughening particles, and the remainder of di-tert-butyl peroxide is 100:7.5:13.5:0.02:2.5:9:0.25:4.5:4:4:0.85.

[0067] The coating preparation includes the following steps: hydroxyl FEVE fluorocarbon resin and γ-aminopropyltriethoxysilane are mixed and stirred at 500 rpm for 10 minutes. MBS core-shell elastomer, hollow ceramic microspheres, polyacrylate dispersant and organosilicon defoamer are added and stirred at 1500 rpm for 30 minutes. The speed is then adjusted to 300 rpm. Polyether-modified siloxane leveling agent, stabilizer and blocked isocyanate curing agent are added and stirred for 15 minutes to obtain material A. Material A is then degassed under vacuum at a vacuum degree of -0.095 MPa for 10 minutes to obtain the coating.

[0068] The mass ratio of hydroxyl FEVE fluorocarbon resin, γ-aminopropyltriethoxysilane, MBS core-shell elastomer, hollow ceramic microspheres, polyacrylate dispersant, silicone defoamer, polyether-modified siloxane leveling agent, stabilizer and blocked isocyanate curing agent is 60:3:8:12:1.5:1:1:2.5:11.

[0069] The stabilizer is a mixture of 2-hydroxy-4-n-octyloxybenzophenone and polytetramethylpiperidinol succinate in a mass ratio of 1:1.

[0070] Example 3: Fire-resistant roofing panel made of aluminum foam-glass fiber reinforced composite material. The preparation of the fire-resistant roofing panel made of aluminum foam-glass fiber reinforced composite material includes the following steps: S1. To prepare grafted glass fiber mat, heat sodium hydroxide solution to 45°C, add glass fiber mat for soaking, soak for 10 minutes, wash the soaked glass fiber mat with deionized water until neutral, dry the washed glass fiber mat at 60°C for 15 minutes to obtain activated glass fiber mat; immerse the activated glass fiber mat in treatment solution for 15 minutes, remove the activated glass fiber mat, squeeze off excess treatment solution with rollers, dry the glass fiber mat after rollers at 80°C for 30 minutes to obtain grafted glass fiber mat.

[0071] S2. Preparation of FRP panel: Apply silicone-based release agent to the mold surface, place pretreated glass fiber mat into the mold and apply modified vinyl ester resin for curing. Set the temperature to 30℃ and cure for 2 hours. Remove the mold to obtain FRP panel.

[0072] S3. Apply a high-temperature epoxy adhesive to the bonding surface of the FRP panel, setting the coating amount to 1.2 kg / m². 2 The FRP panel, adhesive, aluminum foam core layer, adhesive, and lower FRP panel are precisely stacked in the following order to obtain a composite blank. The composite blank is placed in a pressing equipment for pressing, with a static pressure of 0.5 MPa and a pressing time of 10 minutes. The pressed composite blank is then cured at high temperature, with a heating rate of 3℃ / min to 150℃ and a pressure of 0.6 MPa. It is then cured at a constant temperature for 120 minutes, cooled to 100℃ at a cooling rate of 3℃ / min, and then cooled to 60℃ at a cooling rate of 2℃ / min to obtain a rough blank.

[0073] S4. Spray the coating onto the surface of the rough blank, with a coating amount of 0.3 kg / m². 2 The sprayed blank is cured at a set temperature of 80℃ for 30 minutes to obtain a fireproof roof panel made of aluminum foam-glass fiber reinforced composite material.

[0074] The preparation of the treatment solution includes the following steps: propylene glycol methyl ether acetate and deionized water are mixed and stirred at 300 rpm for 10 minutes; citric acid monohydrate is added and stirred for 3 minutes; vinyltris(β-methoxyethoxy)silane and N-phosphorylpropyltriethoxysilane are added sequentially and stirred at 500 rpm for 20 minutes; nano-hollow titanium dioxide is added and stirred at 800 rpm for 15 minutes; stirring is stopped and the mixture is allowed to stand for 5 minutes to obtain the treatment solution.

[0075] Add citric acid monohydrate to adjust the pH to 4.5.

[0076] The mass ratio of propylene glycol methyl ether acetate, deionized water, vinyltris(β-methoxyethoxy)silane, N-phosphorylpropyltriethoxysilane, and nano-hollow titanium dioxide is 60:40:5:3:2.

[0077] The preparation of modified vinyl ester resin includes the following steps: Nitrogen gas is introduced into a reaction vessel, bisphenol A type epoxy vinyl ester resin and a portion of styrene are added and stirred at a speed of 400 rpm. The reaction vessel is heated to 85°C at a heating rate of 3°C / min. Hydroxyl-terminated polyurethane prepolymer and a portion of hydroquinone are added and stirred at a speed of 400 rpm for 60 minutes. The remaining styrene and DOPO-based methacrylate monomer are added and stirred for 20 minutes. A portion of di-tert-butyl peroxide is added and stirred for 70 minutes. The reaction vessel is then cooled to a temperature of 2°C / min. At 75℃, γ-methacryloxypropyltrimethoxysilane was added and stirred at 400 rpm for 40 minutes. Nano-silica and MBS core-shell elastomer toughening particles were added and stirred at 1500 rpm for 30 minutes. Stirring was stopped, and the mixture was allowed to stand for degassing for 15 minutes. The reactor was then cooled to 40℃ at a rate of 2℃ / min. The remaining di-tert-butyl peroxide was added and stirred at 300 rpm for 20 minutes to obtain a mixture. The mixture was sealed and allowed to stand for aging for 24 hours to obtain the modified vinyl ester resin.

[0078] The mass ratio of bisphenol A type epoxy vinyl ester resin, a portion of styrene, hydroxyl-terminated polyurethane prepolymer, a portion of hydroquinone, the remainder of styrene, DOPO-based methacrylate monomer, a portion of di-tert-butyl peroxide, γ-methacryloyloxypropyltrimethoxysilane, nano-silica, MBS core-shell elastomer toughening particles, and the remainder of di-tert-butyl peroxide is 100:7.5:13.5:0.02:2.5:9:0.25:4.5:4:4:0.85.

[0079] The coating preparation includes the following steps: hydroxyl FEVE fluorocarbon resin and γ-aminopropyltriethoxysilane are mixed and stirred at 500 rpm for 10 minutes. MBS core-shell elastomer, hollow ceramic microspheres, polyacrylate dispersant and organosilicon defoamer are added and stirred at 1500 rpm for 30 minutes. The speed is then adjusted to 300 rpm. Polyether-modified siloxane leveling agent, stabilizer and blocked isocyanate curing agent are added and stirred for 15 minutes to obtain material A. Material A is then degassed under vacuum at a vacuum degree of -0.095 MPa for 10 minutes to obtain the coating.

[0080] The mass ratio of hydroxyl FEVE fluorocarbon resin, γ-aminopropyltriethoxysilane, MBS core-shell elastomer, hollow ceramic microspheres, polyacrylate dispersant, silicone defoamer, polyether-modified siloxane leveling agent, stabilizer and blocked isocyanate curing agent is 60:3:8:12:1.5:1:1:2.5:11.

[0081] The stabilizer is a mixture of 2-hydroxy-4-n-octyloxybenzophenone and polytetramethylpiperidinol succinate in a mass ratio of 1:1.

[0082] Comparative Example 1: The difference between this comparative example and Example 1 is that: In this comparative example, the fiberglass mat was not immersed in the treatment solution.

[0083] Comparative Example 2: The difference between this comparative example and Example 1 is that: Unmodified vinyl ester resin was used in this comparative example.

[0084] Comparative Example 3 differs from Example 1 in that: This comparative example uses a commercially available coating (Miki FEVE-600).

[0085] Performance testing: Fireproof roofing panels made of aluminum foam-glass fiber reinforced composite materials prepared in Examples 1, 2, 3, 1, 2, and 3 were tested.

[0086] Performance testing: The relevant performance of the fireproof roof panels of aluminum foam-glass fiber reinforced composite materials provided in Examples 1-3 and Comparative Examples 1-3 were tested respectively, and the test data are recorded in Table 1 below: Table 1 - Performance Tests of Fire-Resistant Roofing Panels Made from Aluminum Foam-Glass Fiber Reinforced Composite Materials

[0087] Based on the above data, the following conclusions can be drawn: The interlaminar shear strength of the fireproof roof panels made of aluminum foam-glass fiber reinforced composite material prepared in Examples 1, 2, 3, 1, 2 and 3 was tested using the test method in GB / T1450.1.

[0088] The oxygen index of the fire-resistant roof panels of aluminum foam-glass fiber reinforced composite materials prepared in Examples 1, 2, 3, Comparative Examples 1, 2, and 3 was tested using the test method in GB / T2406.2.

[0089] The cross-cut coating adhesion of the fireproof roof panels made of aluminum foam-glass fiber reinforced composite material prepared in Examples 1, 2, 3, Comparative Examples 1, 2, and 3 was tested using the test method in GB / T9286.

[0090] The treatment solution removes impurities and excess additives from the surface of glass fibers, activates the fiber surface structure, and generates active binding groups on the fiber surface after hydrolysis. These groups can form chemical bonds with the matrix resin. Simultaneously, nanoparticles create a microscopic rough structure on the fiber surface, increasing the resin bonding contact area. The interface is strengthened through a combination of chemical bonding and physical interlocking, reducing interlaminar slippage under stress and effectively improving the interlaminar shear strength of the board. The modified vinyl ester resin introduces a phosphorus-nitrogen-containing flame-retardant component into the base resin. This component is uniformly distributed within the resin system and decomposes to capture combustion free radicals during combustion, blocking the combustion chain reaction. It also reduces the volatilization of combustible substances and increases the oxygen concentration required for the material to maintain its non-self-ignition, thereby improving the overall oxygen index and enhancing the flame-retardant and fire-resistant performance of the board. The addition of silane adhesive components to the self-made hydroxyl fluorocarbon coating can not only fuse with fluorocarbon resin, but also tightly bind to the active sites on the surface of the fireproof board substrate, forming a transitional adhesive layer between the coating and the board. This allows the coating to completely adhere to the board surface without gaps, resulting in a firm and tight bond after film formation. During cross-cut testing, the paint film is less prone to cracking and peeling, significantly improving the coating adhesion in cross-cut testing.

[0091] For both interlaminar shear strength and oxygen index, the higher the value, the better the performance. Higher shear strength indicates a more stable interlaminar bond and stronger resistance to delamination, while a higher oxygen index indicates a better flame retardant and fireproof effect. For cross-cut adhesion, the lower the grade value, the better the performance. A lower grade means that the coating adheres more tightly to the substrate and is less likely to peel off.

[0092] Based on the above demonstrations, the present invention is significantly superior to the comparative group in terms of interlayer shear strength, oxygen index, and cross-cut coating adhesion.

[0093] In the description of this specification, references to terms such as "an embodiment," "example," "specific example," etc., indicate that a specific feature, structure, material, or characteristic described in connection with that embodiment or example is included in at least one embodiment or example of the invention. In this specification, illustrative expressions of the above terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in one or more embodiments or examples.

[0094] The preferred embodiments of the present invention disclosed above are merely illustrative of the invention. These preferred embodiments do not exhaustively describe all details, nor do they limit the invention to the specific implementations described. Clearly, many modifications and variations can be made based on the content of this specification. This specification selects and specifically describes these embodiments to better explain the principles and practical applications of the invention, thereby enabling those skilled in the art to better understand and utilize the invention. The invention is limited only by the claims and their full scope and equivalents.

Claims

1. A fireproof roofing panel made of aluminum foam-glass fiber reinforced composite material, characterized in that, The preparation of the fireproof roof panel of the aluminum foam-glass fiber reinforced composite material includes the following steps: S1. Preparation of grafted glass fiber mat; S2. Fabrication of FRP panels; S3. Apply a high-temperature epoxy adhesive to the bonding surface of the FRP panel, setting the coating amount to 0.8-1.2 kg / m². 2 The FRP panel, adhesive, aluminum foam core layer, adhesive, and lower FRP panel are precisely stacked in the following order to obtain a composite blank. The composite blank is placed in a pressing equipment for pressing, with a static pressure of 0.3-0.5MPa and a pressing time of 10 minutes. The pressed composite blank is then cured at high temperature, with a heating rate of 2-3℃ / min to 120-150℃ and a pressure of 0.4-0.6MPa. It is then cured at a constant temperature for 90-120 minutes, cooled to 100℃ at a cooling rate of 2-3℃ / min, and then cooled to 60℃ at a cooling rate of 1-2℃ / min to obtain a rough blank. S4. Spray the coating onto the surface of the rough blank, with a coating amount of 0.2-0.3 kg / m². 2 The sprayed blank is cured at a set temperature of 80℃ for 30 minutes to obtain a fireproof roof panel made of aluminum foam-glass fiber reinforced composite material.

2. The fireproof roofing panel of aluminum foam-glass fiber reinforced composite material according to claim 1, characterized in that, The preparation of the grafted glass fiber mat includes the following steps: A1. Heat the sodium hydroxide solution, add glass fiber mat to soak, wash the soaked glass fiber mat with deionized water until neutral, and dry the washed glass fiber mat to obtain activated glass fiber mat. A2. Immerse the activated glass fiber mat in the treatment solution, remove the activated glass fiber mat, squeeze out the excess treatment solution with a roller, and dry the glass fiber mat after the roller to obtain the grafted glass fiber mat.

3. The fireproof roofing panel of aluminum foam-glass fiber reinforced composite material according to claim 2, characterized in that, The preparation of the treatment solution includes the following steps: Propylene glycol methyl ether acetate and deionized water were mixed and stirred. Citric acid monohydrate was added and stirred. Vinyltris(β-methoxyethoxy)silane and N-phosphorylpropyltriethoxysilane were added and stirred in sequence. Nano-hollow titanium dioxide was added and stirred. Stirring was stopped and the mixture was allowed to stand to obtain the treatment solution.

4. The fireproof roofing panel of aluminum foam-glass fiber reinforced composite material according to claim 3, characterized in that, The pH is adjusted to 4-4.5 by adding citric acid monohydrate; The mass ratio of propylene glycol methyl ether acetate, deionized water, vinyltris(β-methoxyethoxy)silane, N-phosphorylpropyltriethoxysilane, and nano-hollow titanium dioxide is 60:40:5:3:

2.

5. The fireproof roofing panel of aluminum foam-glass fiber reinforced composite material according to claim 1, characterized in that, The preparation of the FRP panel includes the following steps: applying a silicone-based release agent to the surface of the mold, placing the pretreated glass fiber mat into the mold and applying modified vinyl ester resin for curing, setting the temperature to 25-30℃, curing for 2 hours, demolding, and obtaining the FRP panel.

6. The fireproof roofing panel of aluminum foam-glass fiber reinforced composite material according to claim 5, characterized in that, The preparation of the modified vinyl ester resin includes the following steps: nitrogen gas is introduced into a reaction vessel, bisphenol A type epoxy vinyl ester resin and a portion of styrene are added and stirred, hydroxyl-terminated polyurethane prepolymer and a portion of hydroquinone are added and stirred, the remaining styrene and DOPO-based methacrylate monomer are added and stirred, a portion of di-tert-butyl peroxide is added and stirred, γ-methacryloyloxypropyltrimethoxysilane is added and stirred, nano-silica and MBS core-shell elastomer toughening particles are added and stirred, stirring is stopped, the mixture is allowed to stand to degas, the remaining di-tert-butyl peroxide is added and stirred to obtain a mixture, the mixture is sealed and allowed to stand for aging to obtain the modified vinyl ester resin.

7. The fireproof roofing panel of aluminum foam-glass fiber reinforced composite material according to claim 5, characterized in that, The mass ratio of the bisphenol A type epoxy vinyl ester resin, a portion of styrene, hydroxyl-terminated polyurethane prepolymer, a portion of hydroquinone, the remaining styrene, DOPO-based methacrylate monomer, a portion of di-tert-butyl peroxide, γ-methacryloyloxypropyltrimethoxysilane, nano-silica, MBS core-shell elastomer toughening particles, and the remaining di-tert-butyl peroxide is 100:7.5:13.5:0.02:2.5:9:0.25:4.5:4:4:0.

85.

8. The fireproof roofing panel of aluminum foam-glass fiber reinforced composite material according to claim 1, characterized in that, The preparation of the coating includes the following steps: mixing and stirring hydroxyl FEVE fluorocarbon resin and γ-aminopropyltriethoxysilane, adding MBS core-shell elastomer, hollow ceramic microspheres, polyacrylate dispersant and organosilicon defoamer and stirring, adding polyether modified siloxane leveling agent, stabilizer and blocked isocyanate curing agent and stirring to obtain material A, and vacuum degassing material A to obtain the coating.

9. The fireproof roofing panel of aluminum foam-glass fiber reinforced composite material according to claim 8, characterized in that, The mass ratio of the hydroxyl FEVE fluorocarbon resin, γ-aminopropyltriethoxysilane, MBS core-shell elastomer, hollow ceramic microspheres, polyacrylate dispersant, silicone defoamer, polyether-modified siloxane leveling agent, stabilizer, and blocked isocyanate curing agent is 60:3:8:12:1.5:1:1:2.5:

11.

10. The fireproof roofing panel of the aluminum foam-glass fiber reinforced composite material according to claim 8, characterized in that, The stabilizer is composed of 2-hydroxy-4-n-octyloxybenzophenone and polytetramethylpiperidinol polysuccinate in a mass ratio of 1:1.

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