A reinforced polymethacrylimide foam composite material and its preparation method

Abstract

This invention relates to the field of foam composite materials technology, specifically to a reinforced polymethacrylamide foam composite material and its preparation method, comprising the following raw materials in parts by weight: 45-50 parts methacrylic acid, 40-45 parts methacrylonitrile, 8-12 parts of a reinforcing filler, 6-9 parts of a modifier / blender, 5-7 parts of a flame retardant, 5-7 parts of hollow glass microspheres, 0.3-0.5 parts of an initiator, 2-5 parts of a foaming agent, 1-3 parts of a crosslinking agent, and 1-2 parts of a nucleating agent. The reinforced polymethacrylamide foam composite material of this invention utilizes methacrylic acid and methacrylonitrile in combination with functional additives such as flame retardants, hollow glass microspheres, and initiators to enhance the product's flame retardancy and thermal insulation properties. Furthermore, through optimized blending and coordination of the raw materials, the product's mechanical properties, flame retardancy, and thermal insulation are improved, while also exhibiting significant weather resistance and corrosion resistance.

Description

Technical Field

[0001] This invention relates to the field of foam composite materials technology, specifically to an enhanced polymethacrylimide foam composite material and its preparation method. Background Technology

[0002] Polymethacrylimide (PMI) foam is a thermosetting rigid foam material with a 100% closed-cell structure. Its uniformly cross-linked pore wall structure gives it outstanding structural stability and excellent mechanical properties, making it an ideal core material for manufacturing lightweight, high-strength composite sandwich structures. It has been widely used in large passenger and transport aircraft, fighter jets, helicopters, high-speed trains, wind turbine blades, satellites, and launch vehicles.

[0003] Existing polymethacrylimide foam materials have poor mechanical properties. At the same time, it is difficult to balance and improve the flame retardancy and thermal insulation properties with mechanical properties. In addition, the products have poor weather resistance and corrosion resistance, which limits the efficiency of product use. Summary of the Invention

[0004] To address the shortcomings of existing technologies, the present invention aims to provide an enhanced polymethacrylamide foam composite material and its preparation method, thereby resolving the problems mentioned in the background section.

[0005] The present invention solves the technical problem by adopting the following technical solution:

[0006] This invention provides a reinforced polymethacrylimide foam composite material, comprising the following raw materials in parts by weight:

[0007] The ingredients are: 45-50 parts methacrylic acid, 40-45 parts methacrylonitrile, 8-12 parts filler based on reinforcing function, 6-9 parts modifier and blender, 5-7 parts flame retardant, 5-7 parts hollow glass microspheres, 0.3-0.5 parts initiator, 2-5 parts foaming agent, 1-3 parts crosslinking agent and 1-2 parts nucleating agent.

[0008] Preferably, the flame retardant is magnesium hydroxide; the initiator is tert-butyl perbenzoate; the foaming agent is N,N-dimethylurea; the crosslinking agent is allyl methacrylate; and the nucleating agent is N-methylformamide.

[0009] Preferably, the preparation method of the filler based on the enhanced function is as follows:

[0010] S11: Mix 3-5 parts by weight of mullite whiskers, 2-3 parts by weight of flake α-alumina and 5-8 parts by weight of dopamine solution evenly to obtain reinforced solution A;

[0011] The dopamine solution is prepared by uniformly mixing 5% (w / w) dopamine hydrochloride solution and 3% (w / w) sodium silicate solution in a weight ratio of 4:3.

[0012] S12: Mix 2-3 parts by weight of kaolin, 4-6 parts by weight of nanocellulose, 1-2 parts by weight of titanium isopropoxide and 5-7 parts by weight of chitosan solution with a mass fraction of 5% to obtain reinforcing agent B.

[0013] S13: Zirconium silicate, silicon micro powder and carbon nanotubes are mixed evenly in a weight ratio of (3-5):(1-2):5 to obtain a filler;

[0014] The filler and reinforcing solution A were mixed and ball-milled at a weight ratio of 7:5, then filtered and dried to obtain the filler based on A reinforcement.

[0015] S14: Based on filler A and reinforcer B, the mixture is ball-milled at a weight ratio of 5:3. After ball milling, it is filtered and dried to obtain filler with enhanced function.

[0016] The filler for enhancing functionality is made by blending zirconium silicate, silica powder, and carbon nanotubes. It is further improved by co-regulating and optimizing the reinforcement A solution and reinforcement B agent. The mullite whiskers and flake α-alumina in reinforcement A solution are blended and optimized with dopamine solution. Meanwhile, the reinforcement B agent is further improved by co-regulating and optimizing the raw materials of kaolin, nanocellulose, titanium isopropoxide, and chitosan solution. Through the co-regulation and optimization of the raw materials, the reinforcement A solution and reinforcement B agent work together to improve the performance of the product system, thereby further improving the coordination and stability of the product system's performance.

[0017] Preferably, the size of the sheet-like α-alumina microplates is 2-3 μm and the thickness is 1.0-1.2 nm.

[0018] Preferably, in S13, the ball milling process involves a ball milling speed of 1500 r / min and a ball milling time of 1 h; in S14, the ball milling process involves a ball milling speed of 1000-1200 r / min and a ball milling time of 2 h.

[0019] Preferably, the modified blending agent is prepared by:

[0020] S21: Add 3-5 parts by weight of 2-methylimidazole, 1-2 parts by weight of titanium dioxide and 3-5 parts by weight of silane coupling agent KH560 to 5-8 parts by weight of acetone solvent to obtain the modified solution.

[0021] S22: Mix illite with a sufficient amount of potassium permanganate solution until homogeneous, then wash with water, filter and dry to obtain illite agent;

[0022] The illite agent and the modifying liquid were stirred evenly at a weight ratio of 3:5 to obtain the modified illite liquid;

[0023] S23: The modified illite liquid and the blending agent are mixed and ball-milled at a weight ratio of 7:5. The ball milling speed is 1000-1200 r / min and the ball milling time is 2h. After the ball milling is completed, the mixture is filtered and dried to obtain the modified blending agent.

[0024] Preferably, the potassium permanganate solution has a mass fraction of 8-12%.

[0025] Preferably, the preparation method of the blending agent is as follows:

[0026] Tetraethoxysilane was mixed with ethanol and deionized water, and then 10% citric acid solution was added to adjust the pH to 5.0. Finally, γ-aminopropyltriethoxysilane was added and reacted at 45°C for 2 hours to obtain a silane modifier.

[0027] Add 2-3 parts by weight of mesoporous silica and 1-2 parts by weight of polyethylene fiber to 5-8 parts by weight of silane modifier, then add 3-5 parts by weight of montmorillonite, stir and treat, filter and dry to obtain the blending agent.

[0028] The modified blending agent is made by activating illite with potassium permanganate solution, and then further improved by blending with the modifying liquid. The 2-methylimidazole, titanium dioxide and silane coupling agent KH560 in the modifying liquid are blended and optimized. At the same time, the blending agent is ball-milled to improve the co-formulation. The mesoporous silica, polyethylene fiber and silane modifier and montmorillonite in the blending agent are blended and optimized. The silane modifier is used as a medium to enhance the interfacial properties between raw materials, thereby better blending the blending agent into the system, thus optimizing the coordination effect of the modified blending agent in the system and improving the performance stability of the product.

[0029] Preferably, the mass ratio of the tetraethoxysilane, ethanol, deionized water and γ-aminopropyltriethoxysilane is (10-15):(40-45):(15-20):2;

[0030] The mesoporous silica has a particle size of 70-100 nm and a pore size of 15-20 nm; the stirring speed is 450-500 r / min, the stirring time is 2 h, and the stirring temperature is 50-55℃.

[0031] This invention also provides a method for preparing reinforced polymethacrylimide foam composite material, comprising the following steps:

[0032] Step 1: Weigh the raw materials of the reinforced polymethacrylimide foam composite material according to the weight parts, mix the raw materials evenly and inject them into two parallel glass pieces sealed with rubber strips, and polymerize at 55-60℃ for 48-52h to obtain the product.

[0033] Step 2: Preheat the product at 120-130℃ for 2 hours, then foam it at 210-230℃ for 48 minutes to obtain the foam.

[0034] Step 3: Heat treat the foam at 150-170℃ for 2 hours to obtain the foam composite material.

[0035] Compared with the prior art, the present invention has the following beneficial effects:

[0036] The reinforced polymethacrylamide foam composite material of the present invention uses methacrylic acid, methacrylonitrile, flame retardants, hollow glass microspheres, initiators and other functional additives to enhance the flame retardancy and heat insulation properties of the product. Through the optimization and improvement of the blending and combination of raw materials, the mechanical properties, flame retardancy and heat insulation of the product are enhanced, and the weather resistance and corrosion resistance of the product are significantly improved. Detailed Implementation

[0037] The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to specific examples. 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 skilled in the art without creative effort are within the scope of protection of the present invention.

[0038] This embodiment of a reinforced polymethacrylamide foam composite material comprises the following raw materials in parts by weight:

[0039] The ingredients are: 45-50 parts methacrylic acid, 40-45 parts methacrylonitrile, 8-12 parts filler based on reinforcing function, 6-9 parts modifier and blender, 5-7 parts flame retardant, 5-7 parts hollow glass microspheres, 0.3-0.5 parts initiator, 2-5 parts foaming agent, 1-3 parts crosslinking agent and 1-2 parts nucleating agent.

[0040] In this embodiment, the flame retardant is magnesium hydroxide; the initiator is tert-butyl perbenzoate; the foaming agent is N,N-dimethylurea; the crosslinking agent is allyl methacrylate; and the nucleating agent is N-methylformamide.

[0041] The preparation method of the filler based on enhanced function in this embodiment is as follows:

[0042] S11: Mix 3-5 parts by weight of mullite whiskers, 2-3 parts by weight of flake α-alumina and 5-8 parts by weight of dopamine solution evenly to obtain reinforced solution A;

[0043] The dopamine solution is prepared by uniformly mixing 5% (w / w) dopamine hydrochloride solution and 3% (w / w) sodium silicate solution in a weight ratio of 4:3.

[0044] S12: Mix 2-3 parts by weight of kaolin, 4-6 parts by weight of nanocellulose, 1-2 parts by weight of titanium isopropoxide and 5-7 parts by weight of chitosan solution with a mass fraction of 5% to obtain reinforcing agent B.

[0045] S13: Zirconium silicate, silicon micro powder and carbon nanotubes are mixed evenly in a weight ratio of (3-5):(1-2):5 to obtain a filler;

[0046] The filler and reinforcing solution A were mixed and ball-milled at a weight ratio of 7:5, then filtered and dried to obtain the filler based on A reinforcement.

[0047] S14: Based on filler A and reinforcer B, the mixture is ball-milled at a weight ratio of 5:3. After ball milling, it is filtered and dried to obtain filler with enhanced function.

[0048] The sheet-like α-alumina microplates in this embodiment are 2-3 μm in size and 1.0-1.2 nm thick.

[0049] In this embodiment, the ball milling speed for the S13 co-mixed ball milling treatment is 1500 r / min, and the ball milling time is 1 h; the ball milling speed for the S14 co-mixed ball milling treatment is 1000-1200 r / min, and the ball milling time is 2 h.

[0050] The preparation method of the modified blending agent in this embodiment is as follows:

[0051] S21: Add 3-5 parts by weight of 2-methylimidazole, 1-2 parts by weight of titanium dioxide and 3-5 parts by weight of silane coupling agent KH560 to 5-8 parts by weight of acetone solvent to obtain the modified solution.

[0052] S22: Mix illite with a sufficient amount of potassium permanganate solution until homogeneous, then wash with water, filter and dry to obtain illite agent;

[0053] The illite agent and the modifying liquid were stirred evenly at a weight ratio of 3:5 to obtain the modified illite liquid;

[0054] S23: The modified illite liquid and the blending agent are mixed and ball-milled at a weight ratio of 7:5. The ball milling speed is 1000-1200 r / min and the ball milling time is 2h. After the ball milling is completed, the mixture is filtered and dried to obtain the modified blending agent.

[0055] The mass fraction of the potassium permanganate solution in this embodiment is 8-12%.

[0056] The preparation method of the blending agent in this embodiment is as follows:

[0057] Tetraethoxysilane was mixed with ethanol and deionized water, and then 10% citric acid solution was added to adjust the pH to 5.0. Finally, γ-aminopropyltriethoxysilane was added and reacted at 45°C for 2 hours to obtain a silane modifier.

[0058] Add 2-3 parts by weight of mesoporous silica and 1-2 parts by weight of polyethylene fiber to 5-8 parts by weight of silane modifier, then add 3-5 parts by weight of montmorillonite, stir and treat, filter and dry to obtain the blending agent.

[0059] In this embodiment, the mass ratio of tetraethoxysilane, ethanol, deionized water and γ-aminopropyltriethoxysilane is (10-15):(40-45):(15-20):2.

[0060] The mesoporous silica has a particle size of 70-100 nm and a pore size of 15-20 nm; the stirring speed is 450-500 r / min, the stirring time is 2 h, and the stirring temperature is 50-55℃.

[0061] The preparation method of the reinforced polymethacrylimide foam composite material of this embodiment includes the following steps:

[0062] Step 1: Weigh the raw materials of the reinforced polymethacrylimide foam composite material according to the weight parts, mix the raw materials evenly and inject them into two parallel glass pieces sealed with rubber strips, and polymerize at 55-60℃ for 48-52h to obtain the product.

[0063] Step 2: Preheat the product at 120-130℃ for 2 hours, then foam it at 210-230℃ for 48 minutes to obtain the foam.

[0064] Step 3: Heat treat the foam at 150-170℃ for 2 hours to obtain the foam composite material.

[0065] Example 1: A reinforced polymethacrylimide foam composite material, comprising the following raw materials in parts by weight:

[0066] The mixture contains 45 parts methacrylic acid, 40 parts methacrylonitrile, 8 parts of filler based on reinforcing function, 6 parts modifier, 5 parts flame retardant, 5 parts hollow glass microspheres, 0.3 parts initiator, 2 parts foaming agent, 1 part crosslinking agent, and 1 part nucleating agent.

[0067] In this embodiment, the flame retardant is magnesium hydroxide; the initiator is tert-butyl perbenzoate; the foaming agent is N,N-dimethylurea; the crosslinking agent is allyl methacrylate; and the nucleating agent is N-methylformamide.

[0068] The preparation method of the filler based on enhanced function in this embodiment is as follows:

[0069] S11: Mix 3 parts by weight of mullite whiskers, 2 parts by weight of flake α-alumina and 5 parts by weight of dopamine solution evenly to obtain reinforced solution A;

[0070] The dopamine solution is prepared by uniformly mixing 5% (w / w) dopamine hydrochloride solution and 3% (w / w) sodium silicate solution in a weight ratio of 4:3.

[0071] S12: Mix 2 parts by weight of kaolin, 4 parts by weight of nanocellulose, 1 part by weight of titanium isopropoxide and 5 parts by weight of chitosan solution with a mass fraction of 5% to obtain reinforcing agent B.

[0072] S13: Zirconium silicate, silicon micro powder and carbon nanotubes are mixed evenly in a weight ratio of 3:1:5 to obtain a filler;

[0073] The filler and reinforcing solution A were mixed and ball-milled at a weight ratio of 7:5, then filtered and dried to obtain the filler based on A reinforcement.

[0074] S14: Based on filler A and reinforcer B, the mixture is ball-milled at a weight ratio of 5:3. After ball milling, it is filtered and dried to obtain filler with enhanced function.

[0075] The sheet-like α-alumina microplates in this embodiment are 2 μm in size and 1.0 nm thick.

[0076] In this embodiment, the ball milling speed for the S13 co-mixed ball milling treatment is 1500 r / min, and the ball milling time is 1 h; the ball milling speed for the S14 co-mixed ball milling treatment is 1000 r / min, and the ball milling time is 2 h.

[0077] The preparation method of the modified blending agent in this embodiment is as follows:

[0078] S21: Add 3 parts by weight of 2-methylimidazole, 1 part by weight of titanium dioxide and 3 parts by weight of silane coupling agent KH560 to 5 parts by weight of acetone solvent to obtain the modified solution.

[0079] S22: Mix illite with a sufficient amount of potassium permanganate solution until homogeneous, then wash with water, filter and dry to obtain illite agent;

[0080] The illite agent and the modifying liquid were stirred evenly at a weight ratio of 3:5 to obtain the modified illite liquid;

[0081] S23: The modified illite liquid and the blending agent were mixed and ball-milled at a weight ratio of 7:5. The ball milling speed was 1000 r / min and the ball milling time was 2 h. After the ball milling was completed, the mixture was filtered and dried to obtain the modified blending agent.

[0082] The potassium permanganate solution in this embodiment has a mass fraction of 8%.

[0083] The preparation method of the blending agent in this embodiment is as follows:

[0084] Tetraethoxysilane was mixed with ethanol and deionized water, and then 10% citric acid solution was added to adjust the pH to 5.0. Finally, γ-aminopropyltriethoxysilane was added and reacted at 45°C for 2 hours to obtain a silane modifier.

[0085] Two parts by weight of mesoporous silica and one part by weight of polyethylene fiber were added to five parts by weight of silane modifier, followed by three parts by weight of montmorillonite. The mixture was stirred and then filtered and dried to obtain the blending agent.

[0086] In this embodiment, the mass ratio of tetraethoxysilane, ethanol, deionized water, and γ-aminopropyltriethoxysilane is 10:40:15:2.

[0087] The mesoporous silica has a particle size of 70 nm and a pore size of 15 nm; the stirring speed is 450 r / min, the stirring time is 2 h, and the stirring temperature is 50 °C.

[0088] The preparation method of the reinforced polymethacrylimide foam composite material of this embodiment includes the following steps:

[0089] Step 1: Weigh the raw materials of the reinforced polymethacrylimide foam composite material according to the weight parts, mix the raw materials evenly and inject them into two parallel glass pieces sealed with rubber strips, and polymerize at 55℃ for 48 hours to obtain the product.

[0090] Step 2: Preheat the product at 120℃ for 2 hours, then foam it at 210℃ for 48 minutes to obtain the foam body;

[0091] Step 3: Heat treat the foam at 150℃ for 2 hours to obtain the foam composite material.

[0092] Example 2: A reinforced polymethacrylimide foam composite material, comprising the following raw materials in parts by weight:

[0093] The mixture contains 50 parts methacrylic acid, 45 parts methacrylonitrile, 12 parts of filler based on reinforcing function, 9 parts modifier, 7 parts flame retardant, 7 parts hollow glass microspheres, 0.5 parts initiator, 5 parts foaming agent, 3 parts crosslinking agent and 2 parts nucleating agent.

[0094] In this embodiment, the flame retardant is magnesium hydroxide; the initiator is tert-butyl perbenzoate; the foaming agent is N,N-dimethylurea; the crosslinking agent is allyl methacrylate; and the nucleating agent is N-methylformamide.

[0095] The preparation method of the filler based on enhanced function in this embodiment is as follows:

[0096] S11: Mix 5 parts by weight of mullite whiskers, 3 parts by weight of flake α-alumina and 8 parts by weight of dopamine solution evenly to obtain reinforced solution A;

[0097] The dopamine solution is prepared by uniformly mixing 5% (w / w) dopamine hydrochloride solution and 3% (w / w) sodium silicate solution in a weight ratio of 4:3.

[0098] S12: Mix 3 parts by weight of kaolin, 6 parts by weight of nanocellulose, 2 parts by weight of titanium isopropoxide and 7 parts by weight of chitosan solution with a mass fraction of 5% to obtain reinforcing agent B.

[0099] S13: Zirconium silicate, silicon micro powder and carbon nanotubes are mixed evenly in a weight ratio of 5:2:5 to obtain a filler;

[0100] The filler and reinforcing solution A were mixed and ball-milled at a weight ratio of 7:5, then filtered and dried to obtain the filler based on A reinforcement.

[0101] S14: Based on filler A and reinforcer B, the mixture is ball-milled at a weight ratio of 5:3. After ball milling, it is filtered and dried to obtain filler with enhanced function.

[0102] The sheet-like α-alumina microplates in this embodiment are 3 μm in size and 1.2 nm thick.

[0103] In this embodiment, the ball milling speed for the S13 co-mixed ball milling treatment is 1500 r / min, and the ball milling time is 1 h; the ball milling speed for the S14 co-mixed ball milling treatment is 1200 r / min, and the ball milling time is 2 h.

[0104] The preparation method of the modified blending agent in this embodiment is as follows:

[0105] S21: Add 5 parts by weight of 2-methylimidazole, 2 parts by weight of titanium dioxide and 5 parts by weight of silane coupling agent KH560 to 8 parts by weight of acetone solvent to obtain the modified solution.

[0106] S22: Mix illite with a sufficient amount of potassium permanganate solution until homogeneous, then wash with water, filter and dry to obtain illite agent;

[0107] The illite agent and the modifying liquid were stirred evenly at a weight ratio of 3:5 to obtain the modified illite liquid;

[0108] S23: The modified illite liquid and the blending agent were mixed and ball-milled at a weight ratio of 7:5. The ball milling speed was 1200 r / min and the milling time was 2 h. After the ball milling was completed, the mixture was filtered and dried to obtain the modified blending agent.

[0109] The potassium permanganate solution in this embodiment has a mass fraction of 12%.

[0110] The preparation method of the blending agent in this embodiment is as follows:

[0111] Tetraethoxysilane was mixed with ethanol and deionized water, and then 10% citric acid solution was added to adjust the pH to 5.0. Finally, γ-aminopropyltriethoxysilane was added and reacted at 45°C for 2 hours to obtain a silane modifier.

[0112] Three parts by weight of mesoporous silica and two parts by weight of polyethylene fiber were added to eight parts by weight of silane modifier, followed by five parts by weight of montmorillonite. The mixture was stirred and then filtered and dried to obtain the blending agent.

[0113] In this embodiment, the mass ratio of tetraethoxysilane, ethanol, deionized water and γ-aminopropyltriethoxysilane is 15:45:20:2.

[0114] The mesoporous silica has a particle size of 100 nm and a pore size of 20 nm; the stirring speed is 500 r / min, the stirring time is 2 h, and the stirring temperature is 55 °C.

[0115] The preparation method of the reinforced polymethacrylimide foam composite material of this embodiment includes the following steps:

[0116] Step 1: Weigh the raw materials of the reinforced polymethacrylimide foam composite material according to the weight parts, mix the raw materials evenly and inject them into two parallel glass pieces sealed with rubber strips, and polymerize at 60℃ for 52 hours to obtain the product.

[0117] Step 2: Preheat the product at 130℃ for 2 hours, then foam it at 230℃ for 48 minutes to obtain the foam body;

[0118] Step 3: Heat treat the foam at 170℃ for 2 hours to obtain the foam composite material.

[0119] Example 3: A reinforced polymethacrylimide foam composite material, comprising the following parts by weight of raw materials:

[0120] The composition includes 47.5 parts methacrylic acid, 42.5 parts methacrylonitrile, 10 parts filler based on reinforcing function, 7.5 parts modifier, 6 parts flame retardant, 6 parts hollow glass microspheres, 0.4 parts initiator, 3.5 parts foaming agent, 2 parts crosslinking agent and 1.5 parts nucleating agent.

[0121] In this embodiment, the flame retardant is magnesium hydroxide; the initiator is tert-butyl perbenzoate; the foaming agent is N,N-dimethylurea; the crosslinking agent is allyl methacrylate; and the nucleating agent is N-methylformamide.

[0122] The preparation method of the filler based on enhanced function in this embodiment is as follows:

[0123] S11: Mix 4 parts by weight of mullite whiskers, 2.5 parts by weight of flake α-alumina and 6.5 parts by weight of dopamine solution evenly to obtain reinforced solution A;

[0124] The dopamine solution is prepared by uniformly mixing 5% (w / w) dopamine hydrochloride solution and 3% (w / w) sodium silicate solution in a weight ratio of 4:3.

[0125] S12: 2.5 parts by weight of kaolin, 5 parts by weight of nanocellulose, 1.5 parts by weight of titanium isopropoxide and 6 parts by weight of chitosan solution with a mass fraction of 5% are mixed evenly to obtain reinforcing agent B.

[0126] S13: Zirconium silicate, silicon micro powder and carbon nanotubes are mixed evenly in a weight ratio of 4:1.5:5 to obtain a filler;

[0127] The filler and reinforcing solution A were mixed and ball-milled at a weight ratio of 7:5, then filtered and dried to obtain the filler based on A reinforcement.

[0128] S14: Based on filler A and reinforcer B, the mixture is ball-milled at a weight ratio of 5:3. After ball milling, it is filtered and dried to obtain filler with enhanced function.

[0129] The sheet-like α-alumina microplates in this embodiment are 2.5 μm in size and 1.1 nm thick.

[0130] In this embodiment, the ball milling speed for the S13 co-mixed ball milling treatment is 1500 r / min, and the ball milling time is 1 h; the ball milling speed for the S14 co-mixed ball milling treatment is 1100 r / min, and the ball milling time is 2 h.

[0131] The preparation method of the modified blending agent in this embodiment is as follows:

[0132] S21: Add 4 parts by weight of 2-methylimidazole, 1.5 parts by weight of titanium dioxide and 4 parts by weight of silane coupling agent KH560 to 6.5 parts by weight of acetone solvent to obtain the modified solution;

[0133] S22: Mix illite with a sufficient amount of potassium permanganate solution until homogeneous, then wash with water, filter and dry to obtain illite agent;

[0134] The illite agent and the modifying liquid were stirred evenly at a weight ratio of 3:5 to obtain the modified illite liquid;

[0135] S23: The modified illite liquid and the blending agent were mixed and ball-milled at a weight ratio of 7:5. The ball milling speed was 1100 r / min and the milling time was 2 h. After the ball milling was completed, the mixture was filtered and dried to obtain the modified blending agent.

[0136] The potassium permanganate solution in this embodiment has a mass fraction of 10%.

[0137] The preparation method of the blending agent in this embodiment is as follows:

[0138] Tetraethoxysilane was mixed with ethanol and deionized water, and then 10% citric acid solution was added to adjust the pH to 5.0. Finally, γ-aminopropyltriethoxysilane was added and reacted at 45°C for 2 hours to obtain a silane modifier.

[0139] 2.5 parts by weight of mesoporous silica and 1.5 parts by weight of polyethylene fiber were added to 6.5 parts by weight of silane modifier, followed by 4 parts by weight of montmorillonite. The mixture was stirred and then filtered and dried to obtain the blending agent.

[0140] In this embodiment, the mass ratio of tetraethoxysilane, ethanol, deionized water, and γ-aminopropyltriethoxysilane is 12.5:42.5:17.5:2.

[0141] The mesoporous silica has a particle size of 90 nm and a pore size of 17.5 nm; the stirring speed is 470 r / min, the stirring time is 2 h, and the stirring temperature is 52.5 °C.

[0142] The preparation method of the reinforced polymethacrylimide foam composite material of this embodiment includes the following steps:

[0143] Step 1: Weigh the raw materials of the reinforced polymethacrylimide foam composite material according to the weight parts, mix the raw materials evenly and inject them into two parallel glass pieces sealed with rubber strips, and polymerize at 57.5℃ for 50h to obtain the product body;

[0144] Step 2: Preheat the product at 125℃ for 2 hours, then foam it at 220℃ for 48 minutes to obtain the foam.

[0145] Step 3: Heat treat the foam at 160℃ for 2 hours to obtain the foam composite material.

[0146] Comparative Example 1:

[0147] Unlike Example 3, no filler based on enhancement function was added.

[0148] Comparative Example 2:

[0149] Unlike Example 3, no reinforcement A solution was added during the preparation of the filler based on the enhanced function.

[0150] Comparative Example 3:

[0151] Unlike Example 3, no mullite whiskers or flake-shaped α-alumina were added to the enhanced solution A.

[0152] Comparative Example 4:

[0153] Unlike Example 3, no reinforcing agent B was added in the preparation of the filler based on the enhanced function.

[0154] Comparative Example 5:

[0155] Unlike Example 3, kaolin and nanocellulose were not added in the preparation of Enhancer B.

[0156] Comparative Example 6:

[0157] Unlike Example 3, no filler was added in the preparation of the filler based on the enhanced function.

[0158] Comparative Example 7:

[0159] Unlike Example 3, no silicon micropowder and carbon nanotubes were added to the filler.

[0160] Comparative Example 8:

[0161] Unlike Example 3, no modifier was added.

[0162] Comparative Example 9:

[0163] Unlike Example 3, no modified illite liquid was added to the modified blending agent.

[0164] Comparative Example 10:

[0165] Unlike Example 3, no modified liquid was added in the preparation of the modified illite liquid.

[0166] Comparative Example 11:

[0167] Unlike Example 3, 2-methylimidazole and titanium dioxide were not added to the modified solution.

[0168] Comparative Example 12:

[0169] Unlike Example 3, no modifier was added during the preparation of the modified modifier.

[0170] Under standard testing conditions and stability testing conditions, the mechanical properties, flame retardancy, and thermal insulation properties of the products from Examples 1-3 and Comparative Examples 1-12 were tested respectively; the stability testing condition was to place the products at 500 W / m 2Irradiated under ultraviolet light for 24 hours, and then placed under 5% hydrochloric acid mist for 24 hours; the test results are shown in Table 1.

[0171] Table 1. Product performance test results of Examples 1-3 and Comparative Examples 1-12:

[0172]

[0173] As can be seen from Comparative Examples 1-12 and Examples 1-3, the product of Example 3 has excellent mechanical properties, flame retardancy and heat insulation properties. The performance of the product can be improved in a coordinated manner. At the same time, the product has excellent performance stability under weathering and corrosion resistance conditions.

[0174] As can be seen from Comparative Examples 1-12 and Example 3, the performance of the product deteriorated significantly when neither the filler based on the reinforcing function nor the modifier was added. Furthermore, the performance of the product deteriorated to varying degrees when the preparation of the filler based on the reinforcing function did not include the reinforcing agent A, the reinforcing agent B, the reinforcing agent B, or the filler itself did not contain silica powder or carbon nanotubes. The filler based on the reinforcing function prepared using the specific method of this invention, which combines the reinforcing agent A and reinforcing agent B with the filler, exhibited the most significant performance improvement. Other methods used as substitutes were not as effective as those of this invention.

[0175] In the modified blending agent, no modified illite liquid was added; in the preparation of the modified illite liquid, no modified liquid was added; in the modified liquid, no 2-methylimidazole or titanium dioxide was added; and in the preparation of the modified blending agent, no blending agent was added, the performance of the products all showed a trend of deterioration to varying degrees. The modified blending agent obtained by the specific method of this invention has the most significant performance effect on the product. At the same time, the inventors of this invention also found that the blending agent has a significant effect on improving the performance of the product.

[0176] Based on the above tests, the blending agent has a significant impact on the performance of the product. Therefore, further research is conducted on this invention.

[0177] Experimental Example 1:

[0178] Same as Example 3, except that mesoporous silica was not added to the blending agent.

[0179] Experimental Example 2:

[0180] Same as Example 3, except that montmorillonite was not added to the blending agent.

[0181] Experimental Example 3:

[0182] Same as Example 3, except that polyethylene fibers were not added to the blending agent.

[0183] Experiment Example 4:

[0184] Same as Example 3, except that tetraethoxysilane and γ-aminopropyltriethoxysilane were not added in the preparation of the silane modifier.

[0185] The products in Experiment Examples 1-4 were subjected to performance tests under the same conditions, and the test results are shown in Table 2.

[0186] Table 2. Product performance test results for Experiment Examples 1-4:

[0187]

[0188] As can be seen from Experiments 1-4, the absence of montmorillonite in the blending agent resulted in the most significant deterioration in product performance among the factors affecting the preparation of the blending agent. This was followed by the absence of polyethylene fiber in the blending agent. Additionally, the absence of mesoporous silica in the blending agent, and the absence of tetraethoxysilane and γ-aminopropyltriethoxysilane in the preparation of the silane modifier all showed a trend of deterioration in product performance. Only the blending agent prepared using the method of this invention exhibited the most significant performance improvement. In the preparation of the blending agent, all raw materials are indispensable; only by using the specific raw material ratio of this invention can the effect be significantly improved compared to other raw material ratios.

[0189] 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.

[0190] Furthermore, it should be understood that although this specification describes embodiments, not every embodiment contains only one independent technical solution. This narrative style is merely for clarity. Those skilled in the art should consider the specification as a whole, and the technical solutions in each embodiment can also be appropriately combined to form other embodiments that can be understood by those skilled in the art.

Claims

1. An enhanced polymethacrylimide foam composite, characterized by, The following raw materials are included by weight parts: 45~50 parts of methacrylic acid, 40~45 parts of methacrylonitrile, 8~12 parts of a filling agent based on enhancement function, 6~9 parts of a modified blending agent, 5~7 parts of a flame retardant, 5~7 parts of hollow glass microbeads, 0.3~0.5 parts of an initiator, 2~5 parts of a foaming agent, 1~3 parts of a crosslinking agent, and 1~2 parts of a nucleating agent; The preparation method of the filling agent based on the enhancement function is: S11: 3~5 parts by weight of mullite whiskers, 2~3 parts by weight of flaky alpha-aluminum oxide, and 5~8 parts by weight of dopamine solution are uniformly blended to obtain an enhancement A liquid; The dopamine solution is uniformly blended from a 5% by mass hydrochloric acid dopamine solution, a 3% by mass sodium silicate solution, and a weight ratio of 4:3; S12: 2~3 parts by weight of kaolin, 4~6 parts by weight of nanocellulose, 1~2 parts by weight of titanium isopropoxide, and 5~7 parts by weight of a 5% by mass chitosan solution are uniformly blended to obtain an enhancement B agent; S13: zirconium silicate, silicon powder, and carbon nanotubes are uniformly blended in a weight ratio of (3-5):(1-2):5 to obtain a filling agent; The filling agent and the enhancement A liquid are ball milled in a weight ratio of 7:5, filtered, and dried to obtain a filling agent based on A enhancement; S14: The filling agent based on A enhancement and the enhancement B agent are ball milled in a weight ratio of 5:3, filtered, and dried to obtain a filling agent based on enhancement function; The preparation method of the modified blending agent is: S21: 3-5 parts by weight of 2-methylimidazole, 1-2 parts by weight of titanium dioxide, and 3-5 parts by weight of silane coupling agent KH560 are added to 5-8 parts by weight of acetone solvent to obtain a modified liquid; S22: Illite is uniformly blended in an adequate amount of potassium permanganate solution, then washed with water, filtered, and dried to obtain an illite agent; The illite agent and the modified liquid are uniformly stirred in a weight ratio of 3:5 to obtain a modified illite liquid; S23: The modified illite liquid and the blending agent are ball milled in a weight ratio of 7:5, the ball milling speed is 1000-1200 r / min, the ball milling time is 2 h, then filtered and dried to obtain a modified blending agent; The preparation method of the blending agent is: The tetraethoxysilane, ethanol, and deionized water are uniformly mixed, then a 10% by mass citric acid solution is added to adjust the pH value to 5.0, finally, γ-aminopropyl triethoxysilane is added, and the reaction is carried out at 45°C for 2 h to obtain a silane modifier; 2-3 parts by weight of mesoporous silica, 1-2 parts by weight of polyethylene fiber, 3-5 parts by weight of montmorillonite are added to 5-8 parts by weight of the silane modifier, and then stirred to obtain a blending agent.

2. The reinforced polymethacrylimide foam composite according to claim 1, characterized in that The flame retardant is magnesium hydroxide; the initiator is tert-butyl perbenzoate; the foaming agent is N,N-dimethylurea; the crosslinking agent is allyl methacrylate; and the nucleating agent is N-methyl formamide.

3. The reinforced polymethacrylimide foam composite of claim 1, wherein, The flaky alpha-aluminum oxide has a flake size of 2-3 μm and a thickness of 1.0-1.2 nm.

4. The reinforced polymethacrylimide foam composite of claim 1, wherein, The ball milling speed of the ball milling treatment in S13 is 1500 r / min, and the ball milling time is 1 h; the ball milling speed of the ball milling treatment in S14 is 1000-1200 r / min, and the ball milling time is 2 h.

5. The reinforced polymethacrylimide foam composite of claim 1, wherein, The mass fraction of the potassium permanganate solution is 8-12%.

6. The reinforced polymethacrylimide foam composite of claim 1, wherein, The mass ratio of the tetraethoxysilane, ethanol, deionized water and gamma-aminopropyl triethoxysilane is (10-15):(40-45):(15-20):

2.

7. The reinforced polymethacrylimide foam composite of claim 1, wherein, The particle size of the mesoporous silica is 70-100 nm, and the pore size is 15-20 nm; the stirring speed of the stirring treatment is 450-500 r / min, the stirring time is 2 h, and the stirring temperature is 50-55 DEG C.

8. A process for the preparation of a reinforced polymethacrylimide foam composite for the preparation of a reinforced polymethacrylimide foam composite according to any one of claims 1 to 7, characterized in that The method comprises the following steps: Step one: the raw materials of the reinforced poly-methacrylimide foam composite material are weighed according to the weight parts, the raw materials are mixed uniformly, and then poured into two parallel glasses sealed by rubber strips, polymerized at 55-60 DEG C for 48-52 h, and the product body is obtained; Step two: the product body is preheated at 120-130 DEG C for 2 h, and then foamed at 210-230 DEG C for 48 min, and the foam body is obtained; Step three: the foam body is heat treated at 150-170 DEG C for 2 h, and the foam composite material is obtained.

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