A waterproof and wear-resistant panel material and a manufacturing method thereof

Abstract

The application discloses a waterproof and wear-resistant panel material and a manufacturing method thereof, and relates to the technical field of decorative materials.The waterproof and wear-resistant panel material is prepared from the following components in parts by mass: 20-35 parts of epoxy resin, 2-6 parts of a modifier, 10-20 parts of polyurethane, 5-10 parts of a compatilizer, 5-15 parts of modified filler, 2-4 parts of curing agent A, 4-6 parts of curing agent B, 1-2 parts of a defoaming agent and 40 parts of acetone.Under the synergistic effect of the modifier, the polyurethane, the compatilizer and the modified filler, the epoxy resin is comprehensively modified, the original waterproof and wear-resistant properties of the epoxy resin are enhanced, and the defects of the epoxy resin are improved, so that a panel material with excellent comprehensive properties is finally obtained.

Description

Technical Field

[0001] This invention relates to the field of decorative materials technology, specifically a waterproof and wear-resistant panel material and its manufacturing method. Background Technology

[0002] With the increasing demands for material performance in fields such as building decoration, transportation, and electronic equipment, panel materials that combine high strength, water resistance, and wear resistance have become a technological direction that the industry urgently needs to break through. Although traditional epoxy resin-based materials have excellent mechanical strength and chemical resistance, they are brittle, lack aging resistance, and are prone to surface powdering and cracking under long-term friction or humid oxidation environments.

[0003] Based on this, in order to better adapt to daily practical needs, the present invention will comprehensively prepare a new type of panel material by modifying epoxy resin and compounding resin, etc., while improving its waterproof and wear-resistant properties, and also improving its weather resistance and toughness, so that it has a wider range of applications and has important practical significance. Summary of the Invention

[0004] The purpose of this invention is to provide a waterproof and wear-resistant panel material and its manufacturing method to solve the problems mentioned in the background art.

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

[0006] A waterproof and wear-resistant panel material, the raw materials of which include the following components: by weight, 20-35 parts epoxy resin, 2-6 parts modifier, 10-20 parts polyurethane, 5-10 parts compatibilizer, 5-15 parts modified filler, 2-4 parts curing agent A, 4-6 parts curing agent B, 1-2 parts defoamer, and 40 parts acetone.

[0007] Further, the preparation method of the modifier is as follows: (1) Under nitrogen protection, aminopropyl-terminated polydimethylsiloxane, ditert-butyl dicarbonate, triethylamine, and anhydrous ethanol are added to the reaction vessel. After stirring and adjusting the temperature to 0-20°C in a water bath, the mixture is refluxed for 6-24 hours. The reaction is then stopped. After the reaction system naturally returns to room temperature, the reaction solution is washed with 5-10 wt% hydrochloric acid aqueous solution, saturated sodium bicarbonate aqueous solution, and deionized water in sequence. The solution is then dried and rotary evaporated to obtain pretreated aminopropyl-terminated polydimethylsiloxane; (2) Lignin and 5-15 wt% sodium hydroxide aqueous solution are added to the reaction vessel. After stirring and heating to 60-90°C, the mixture is stirred at a constant temperature for 20-60 minutes. Then, the mixture is added to the reaction system. Add γ-aminopropyltriethoxysilane, continue to stir at constant temperature for 1-6 hours, stop the reaction, and after the reaction system naturally returns to room temperature, add 20wt% hydrochloric acid aqueous solution to adjust the pH to 2-3, centrifuge, precipitate, separate and purify to obtain amino lignin; (3) Under nitrogen protection, add pretreated aminopropyl-terminated polydimethylsiloxane, N,N'-dicarbonyldiimidazole and dichloromethane into the reaction vessel, stir and heat to 70-85℃, stir at constant temperature for 1-6 hours, add amino lignin to the reaction system, continue to stir at constant temperature for 2-12 hours, stop the reaction, and after the reaction system naturally returns to room temperature, add trifluoroacetic acid, stir at room temperature for 6-24 hours, rotary evaporate to obtain the modifier.

[0008] Further, the molar ratio of aminopropyl-terminated polydimethylsiloxane, ditert-butyl dicarbonate, and triethylamine is 1:(0.4~0.6):(1~1.5); wherein the molecular weight of aminopropyl-terminated polydimethylsiloxane is 400~1000.

[0009] Furthermore, the mass ratio of lignin to γ-aminopropyltriethoxysilane is 1:(0.05~0.1).

[0010] Furthermore, the raw materials required for the preparation of the modifier include the following components: by mass parts, 4-6 parts of pretreated aminopropyl-terminated polydimethylsiloxane, 0.8-1.2 parts of N,N'-dicarbonyl diimidazole, 1.2-2.5 parts of amino-modified lignin, 0.5-1 part of trifluoroacetic acid, and 25 parts of dichloromethane.

[0011] Further, the compatibilizer is prepared as follows: (1) Diisocyanate and stannous octoate are added to the reaction vessel, stirred and heated to 50~80℃, and then stirred and mixed at a constant temperature for 10~30 min; then 2,3-dihydroxypropyl acrylate and hydroquinone are added to the reaction system, and stirred and reacted at a constant temperature for 1~3 h; then polyester diol is added to the reaction system, and stirred and reacted at a constant temperature for 1~6 h, and then cooled for later use; (2) Acetone and unsaturated monomer are added to (1), stirred and mixed evenly, and then stirred and heated to 60~85℃, then dicumyl peroxide is added dropwise to the reaction system, and stirred and reacted at a constant temperature for 2~12 h, the reaction is ended, and after the reaction system naturally returns to room temperature, the compatibilizer is obtained.

[0012] Furthermore, the raw materials required for preparing the compatibilizer include the following components by mass: 5 parts diisocyanate, 0.5-1.5 parts propyl 2,3-dihydroxyacrylate, 1.5-2.5 parts polyester diol, 0.05-0.1 parts stannous octoate, 0.05-0.1 parts hydroquinone, 4-8 parts unsaturated monomer, 0.05-0.1 parts dicumyl peroxide, and 20 parts acetone.

[0013] Furthermore, the diisocyanate includes, but is not limited to, one or more combinations of toluene diisocyanate, isophorone diisocyanate, 4,4'-diphenylmethane diisocyanate, and hexamethylene diisocyanate.

[0014] Furthermore, the polyester diol includes, but is not limited to, at least one of polyethylene adipate, diethylene glycol oxophosphate, and neopentyl glycol oxophosphate, with a molecular weight of 1000-2000.

[0015] Furthermore, the unsaturated monomers include, but are not limited to, one or more combinations of acrylic acid, glycidyl acrylate, glycidyl methacrylate, acrylamide, and butyl acrylate.

[0016] Further, the preparation method of the modified filler is as follows: (1) γ-aminopropyltriethoxysilane, deionized water and anhydrous ethanol are added to the reaction vessel, stirred and mixed evenly, and acetic acid is added to adjust the pH to 4.5~6. Stirring and mixing is continued for 10~20 min to obtain silane hydrolysate; the filler is dispersed in anhydrous ethanol to obtain filler dispersion; (2) the filler dispersion is heated to 50~60℃, and silane hydrolysate is slowly added dropwise. After the addition is completed, stirring is continued for 6~12 h. After filtration, washing and drying, the modified filler is obtained.

[0017] Furthermore, the mass ratio of the filler and γ-aminopropyltriethoxysilane is 1:(0.05~0.1).

[0018] Furthermore, the mass ratio of the γ-aminopropyltriethoxysilane, deionized water, and anhydrous ethanol is 1:1:10.

[0019] Furthermore, the filler is a mixed filler composed of nanoparticles and nanofibers.

[0020] Furthermore, in this embodiment of the invention, the filler is preferably a mixed filler composed of nano-silica and carbon fiber in a mass ratio of 1:1.

[0021] Furthermore, the curing agent A is an imidazole curing agent, including any one of 2-methylimidazole and 2-ethyl-4-methylimidazole.

[0022] Furthermore, the curing agent B is an isocyanate curing agent, including any one of toluene diisocyanate, isophorone diisocyanate, 4,4'-diphenylmethane diisocyanate, and hexamethylene diisocyanate.

[0023] Furthermore, the manufacturing method of the waterproof and wear-resistant panel material is as follows: (1) First, epoxy resin, acetone and modifier are added to the mixer and stirred for 1-6 hours; then polyurethane and compatibilizer are added to the mixer and stirred for 1-3 hours; then modified filler is added to the mixer and stirred for 30-60 minutes; then curing agent A, curing agent B and defoamer are added to the mixer and stirred for 1-3 hours to finally obtain the mixture; (2) The mixture is injected into the mold and dried and cured at 90-110°C for 1-3 hours to obtain the panel material.

[0024] Furthermore, the panel material may also contain fiber cloth. The method of setting the fiber cloth is as follows: after fixing the fiber cloth of the corresponding size horizontally in the middle of the mold, the mixture is injected into the mold, dried, and cured to obtain the panel material containing the fiber cloth.

[0025] Because epoxy resin possesses excellent waterproof and wear-resistant properties, this invention designs it as the main raw material for panel materials, and uses it in conjunction with other raw materials to prepare a high-performance waterproof and wear-resistant panel. However, the inventors also considered that epoxy resin has poor toughness and oxidation resistance; if it is directly used as a raw material to process the panel, the resulting panel is prone to breakage and has poor weather resistance, resulting in a short service life. Therefore, this invention first considers modifying the epoxy resin to enhance its toughness and oxidation resistance, thereby increasing the panel's service life. This invention prepares a modifier by first subjecting aminopropyl-terminated polydimethylsiloxane to BOC protection pretreatment, protecting one amino group at the chain end. Then, using N,N'-dicarbonyldiimidazole as a bridge, the pretreated aminopropyl-terminated polydimethylsiloxane and aminated lignin are linked together. After BOC deprotection, the panel is prepared. The modifier contains polydimethylsiloxane chain ends and lignin structure. The polydimethylsiloxane chain ends can improve the toughness and water resistance of epoxy resin, while the lignin can impart certain antioxidant properties to epoxy resin, giving it a certain degree of weather resistance. In addition, due to BOC protection, the modifier also contains amino groups, which can combine with epoxy resin during subsequent mixing to achieve effective modification of epoxy resin.

[0026] Polyurethane also possesses excellent waterproof and abrasion-resistant properties, with its abrasion resistance even surpassing that of epoxy resin. Furthermore, polyurethane exhibits superior toughness. When compounded with modified epoxy resin, it can undoubtedly produce panels with even superior performance. Therefore, the inventors further considered introducing polyurethane to synergistically enhance the epoxy resin with a modifier. However, considering the differences in compatibility between the two, a compatibilizer was further prepared in this invention to better prepare a panel material with superior overall performance in terms of waterproofness, abrasion resistance, and toughness. Similarly, to further enhance and improve the relevant properties of the panel material, modified fillers were also added in this invention.

[0027] Compared with the prior art, the beneficial effects achieved by the present invention are:

[0028] (1) In this invention, aminopropyl-terminated polydimethylsiloxane and amino-modified lignin are linked together by N,N'-dicarbonyldiimidazole. This modifier can effectively improve epoxy resin, reducing its water absorption and improving its antioxidant properties.

[0029] (2) The compatibilizer in this invention contains a structure similar to that of polyurethane and polypropylene chain ends, which can greatly promote the compatibility of polyurethane and epoxy resin.

[0030] (3) The modified filler in this invention is composed of a mixture of nanoparticles and nanofibers. The nanoparticles mainly play the role of enhancing the wear resistance of the panel material, while the nanofibers mainly play the role of enhancing the toughness of the panel material. Both can also improve the weather resistance of the panel material to a certain extent.

[0031] In summary, this invention utilizes the synergistic effect of modifiers, polyurethane, compatibilizers, and modified fillers to comprehensively prepare a panel material with excellent overall properties, including waterproofing, wear resistance, weather resistance, and toughness. Detailed Implementation

[0032] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of the present invention, 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.

[0033] It should be noted that the following quantities are by weight, and there are no special restrictions on the suppliers of all raw materials involved in this invention. Exemplary examples include:

[0034] In the following examples, the epoxy resin, type E51, was purchased from Guangzhou Zhongye Chemical Co., Ltd.

[0035] Polyurethane, 99% purity, item number: WB11060, purchased from Guangdong Wengjiang Chemical Reagent Co., Ltd.

[0036] The following products were purchased from Shanghai Mairui Biochemical Technology Co., Ltd.: aminopropyl-terminated polydimethylsiloxane with a purity of 98% (product number: GEL-SSP-085, molecular weight approximately 1000), di-tert-butyl dicarbonate with a purity of 99%, and triethylamine with a purity of 99%.

[0037] The following materials were purchased from Hubei Yongkuo Technology Co., Ltd.: lignin with a purity of 99% (item number: 9005-53-2), γ-aminopropyltrimethoxysilane with a purity of 99%, N,N'-dicarbonyldiimidazole with a purity of 99%, silicon dioxide with a purity of 99% and a particle size of 10~30nm, dichloromethane with a purity of 99%, 2-methylimidazole with a purity of 99%, and carbon fiber with a purity of 99%, a diameter of 5~8μm, and an aspect ratio of 5~20.

[0038] 2,3-Dihydroxypropyl acrylate, with a purity of 98%, was purchased from Shanghai Boyi Biomedical Technology Co., Ltd.

[0039] Isophorone diisocyanate, purity 99%, polyethylene adipate, purity 96%, molecular weight approximately 1000, acrylic acid, purity 99%, glycidyl acrylate, purity 99%, glycidyl methacrylate, purity 99%, acrylamide, purity 99%, and butyl acrylate, purity 99%, were all purchased from Shanghai Dingmiao Chemical Technology Co., Ltd.

[0040] The defoamer, model BYK-A 530, was purchased from Shanghai Buding Chemical Co., Ltd.; each part by weight in the example was 100g.

[0041] Example 1: A method for manufacturing a waterproof and wear-resistant panel material:

[0042] 1. Preparation of modifier: (1) Under nitrogen protection, 10 parts of aminopropyl-terminated polydimethylsiloxane, 1.08 parts of ditert-butyl dicarbonate, 1.3 parts of triethylamine, and 30 parts of anhydrous ethanol were added to the reaction vessel. After stirring and adjusting the temperature to 0°C in a water bath, the mixture was refluxed for 24 hours. The reaction was then stopped. After the reaction system naturally returned to room temperature, the reaction solution was washed with 8wt% hydrochloric acid aqueous solution, saturated sodium bicarbonate aqueous solution, and deionized water in sequence. The solution was dried and rotary evaporated to obtain pretreated aminopropyl-terminated polydimethylsiloxane; (2) 3 parts of lignin and 10 parts of 15wt% sodium hydroxide aqueous solution were added to the reaction vessel. After stirring and heating to 80°C, the mixture was stirred at a constant temperature for 60 minutes. Then, 0.3 parts of γ- (2) Ammoniated triethoxysilane was stirred at a constant temperature for 6 hours. The reaction was stopped. After the reaction system naturally returned to room temperature, 20 wt% hydrochloric acid aqueous solution was added to adjust the pH to 2.5. The mixture was centrifuged, the precipitate was separated and purified to obtain amino lignin. (3) Under nitrogen protection, 6 parts of pretreated aminopropyl-terminated polydimethylsiloxane, 1.2 parts of N,N'-dicarbonyl diimidazole and 25 parts of dichloromethane were added to the reaction vessel. The mixture was stirred and heated to 80°C and stirred at a constant temperature for 6 hours. Then 2.5 parts of amino lignin were added to the reaction system and stirred at a constant temperature for 12 hours. The reaction was stopped. After the reaction system naturally returned to room temperature, 1 part of trifluoroacetic acid was added and stirred at room temperature for 24 hours. The mixture was then rotary evaporated to obtain the modifier.

[0043] 2. Preparation of compatibilizer: (1) Add 5 parts of isophorone diisocyanate and 0.08 parts of stannous octoate to the reaction vessel, stir and heat to 70°C, and then stir and mix at a constant temperature for 20 min; then add 1.5 parts of propyl 2,3-dihydroxyacrylate and 0.1 parts of hydroquinone to the reaction system, and stir and react at a constant temperature for 2 h; then add 2 parts of polyethylene adipate to the reaction system, stir and react at a constant temperature for 6 h, and then cool down for later use; (2) Add 20 parts of acetone and 8 parts of unsaturated monomer (acrylic acid, glycidyl acrylate, glycidyl methacrylate, acrylamide and butyl acrylate mixed in a mass ratio of 1:1:1:1:1) to (1), stir and mix evenly, stir and heat to 75°C, then add 0.1 parts of dicumyl peroxide to the reaction system, stir and react at a constant temperature for 12 h, end the reaction, and after the reaction system naturally returns to room temperature, the compatibilizer is obtained.

[0044] 3. Preparation of modified filler: (1) Add 1.5 parts of γ-aminopropyltriethoxysilane, 1.5 parts of deionized water and 15 parts of anhydrous ethanol to the reaction vessel, stir and mix evenly, add acetic acid to adjust the pH to 5, and continue stirring and mixing for 20 min to obtain silane hydrolysate; disperse 15 parts of filler (a mixed filler composed of nano silica and carbon fiber in a mass ratio of 1:1) into 30 parts of anhydrous ethanol to obtain filler dispersion; (2) Heat the filler dispersion to 55℃, and slowly add silane hydrolysate to it. After the addition is complete, continue stirring for 12 h, filter, wash and dry to obtain modified filler.

[0045] 4. Preparation of panel material: (1) First, add 35 parts of E51 type epoxy resin, 40 parts of acetone and 6 parts of modifier into the mixer and stir for 6 hours; then add 20 parts of polyurethane and 10 parts of compatibilizer into the mixer and stir for 3 hours; then add 15 parts of modified filler into the mixer and stir for 60 minutes; then add 4 parts of 2-methylimidazole, 6 parts of isophorone diisocyanate and 2 parts of BYK-A 530 type defoamer into the mixer and stir for 3 hours to finally obtain the mixture; (2) Inject the mixture into the mold and dry and cure at 100°C for 2 hours to obtain a 5mm thick panel material.

[0046] Example 2: A method for manufacturing a waterproof and wear-resistant panel material:

[0047] 1. Preparation of modifier: (1) Under nitrogen protection, 10 parts of aminopropyl-terminated polydimethylsiloxane, 1.08 parts of ditert-butyl dicarbonate, 1.3 parts of triethylamine, and 30 parts of anhydrous ethanol were added to the reaction vessel. After stirring and adjusting the temperature to 0°C in a water bath, the mixture was refluxed for 24 hours. The reaction was then stopped. After the reaction system naturally returned to room temperature, the reaction solution was washed with 8wt% hydrochloric acid aqueous solution, saturated sodium bicarbonate aqueous solution, and deionized water in sequence. The solution was dried and rotary evaporated to obtain pretreated aminopropyl-terminated polydimethylsiloxane. (2) 3 parts of lignin and 10 parts of 10wt% sodium hydroxide aqueous solution were added to the reaction vessel. After stirring and heating to 80°C, the mixture was stirred at a constant temperature for 60 minutes. Then, 0.225 parts of γ-hydroxyl group were added to the reaction system. -Aminopropyltriethoxysilane, continue to stir at constant temperature for 6h, end the reaction, wait for the reaction system to naturally return to room temperature, add 20wt% hydrochloric acid aqueous solution to adjust pH to 2.5, centrifuge, precipitate, separate and purify to obtain amino lignin; (3) Under nitrogen protection, add 6 parts of pretreated aminopropyl-terminated polydimethylsiloxane, 1.2 parts of N,N'-dicarbonyldiimidazole and 25 parts of dichloromethane into the reaction vessel, stir and heat to 80℃, stir at constant temperature for 6h, then add 1.8 parts of amino lignin to the reaction system, continue to stir at constant temperature for 12h, end the reaction, wait for the reaction system to naturally return to room temperature, add 1 part of trifluoroacetic acid, stir at room temperature for 24h, rotary evaporate to obtain the modifier.

[0048] 2. Preparation of compatibilizer: (1) Add 5 parts of isophorone diisocyanate and 0.08 parts of stannous octoate to the reaction vessel, stir and heat to 70°C, and stir and mix at a constant temperature for 20 min; then add 1 part of propyl 2,3-dihydroxyacrylate and 0.075 parts of hydroquinone to the reaction system, and stir and react at a constant temperature for 2 h; then add 2 parts of polyethylene adipate to the reaction system, stir and react at a constant temperature for 6 h, and cool down for later use; (2) Add 20 parts of acetone and 6 parts of unsaturated monomer (acrylic acid, glycidyl acrylate, glycidyl methacrylate, acrylamide, and butyl acrylate mixed in a mass ratio of 1:1:1:1:1) to (1), stir and mix evenly, stir and heat to 75°C, then add 0.75 parts of dicumyl peroxide to the reaction system, stir and react at a constant temperature for 12 h, end the reaction, and after the reaction system naturally returns to room temperature, the compatibilizer is obtained.

[0049] 3. Preparation of modified filler: (1) Add 1.125 parts of γ-aminopropyltriethoxysilane, 1.125 parts of deionized water and 11.25 parts of anhydrous ethanol to the reaction vessel, stir and mix evenly, add acetic acid to adjust the pH to 5, continue stirring and mixing for 20 min to obtain silane hydrolysate; disperse 15 parts of filler (a mixed filler composed of nano silica and carbon fiber in a mass ratio of 1:1) into 30 parts of anhydrous ethanol to obtain filler dispersion; (2) Heat the filler dispersion to 55℃, slowly add silane hydrolysate to it, after the addition is complete, continue stirring for 12 h, filter, wash and dry to obtain modified filler.

[0050] 4. Preparation of panel material: (1) First, add 35 parts of E51 type epoxy resin, 40 parts of acetone and 6 parts of modifier into the mixer and stir for 6 hours; then add 20 parts of polyurethane and 10 parts of compatibilizer into the mixer and stir for 3 hours; then add 15 parts of modified filler into the mixer and stir for 60 minutes; then add 4 parts of 2-methylimidazole, 6 parts of isophorone diisocyanate and 2 parts of BYK-A 530 type defoamer into the mixer and stir for 3 hours to finally obtain the mixture; (2) Inject the mixture into the mold and dry and cure at 100°C for 2 hours to obtain a 5mm thick panel material.

[0051] Example 3: A method for manufacturing a waterproof and wear-resistant panel material:

[0052] 1. Preparation of modifier: (1) Under nitrogen protection, 10 parts of aminopropyl-terminated polydimethylsiloxane, 1.08 parts of ditert-butyl dicarbonate, 1.3 parts of triethylamine, and 30 parts of anhydrous ethanol were added to the reaction vessel. After stirring and adjusting the temperature to 0°C in a water bath, the mixture was refluxed for 24 hours. The reaction was then stopped. After the reaction system naturally returned to room temperature, the reaction solution was washed with 8wt% hydrochloric acid aqueous solution, saturated sodium bicarbonate aqueous solution, and deionized water in sequence. The solution was dried and rotary evaporated to obtain pretreated aminopropyl-terminated polydimethylsiloxane; (2) 3 parts of lignin and 10 parts of 5wt% sodium hydroxide aqueous solution were added to the reaction vessel. After stirring and heating to 80°C, the mixture was stirred at a constant temperature for 60 minutes. Then, 0.15 parts of γ- (2) Ammoniated triethoxysilane was stirred at a constant temperature for 6 hours. The reaction was stopped. After the reaction system naturally returned to room temperature, 20 wt% hydrochloric acid aqueous solution was added to adjust the pH to 2.5. The mixture was centrifuged, the precipitate was separated and purified to obtain amino lignin. (3) Under nitrogen protection, 6 parts of pretreated aminopropyl-terminated polydimethylsiloxane, 1.2 parts of N,N'-dicarbonyl diimidazole and 25 parts of dichloromethane were added to the reaction vessel. The mixture was stirred and heated to 80°C. The reaction was stirred at a constant temperature for 6 hours. Then 1.2 parts of amino lignin were added to the reaction system. The reaction was stirred at a constant temperature for 12 hours. The reaction was stopped. After the reaction system naturally returned to room temperature, 1 part of trifluoroacetic acid was added. The reaction was stirred at room temperature for 24 hours. The mixture was then rotary evaporated to obtain the modifier.

[0053] 2. Preparation of compatibilizer: (1) Add 5 parts of isophorone diisocyanate and 0.08 parts of stannous octoate to the reaction vessel, stir and heat to 70°C, and then stir and mix at a constant temperature for 20 min; then add 0.5 parts of propyl 2,3-dihydroxyacrylate and 0.05 parts of hydroquinone to the reaction system, and stir and react at a constant temperature for 2 h; then add 2 parts of polyethylene adipate to the reaction system, stir and react at a constant temperature for 6 h, and then cool down for later use; (2) Add 20 parts of acetone and 4 parts of unsaturated monomer (acrylic acid, glycidyl acrylate, glycidyl methacrylate, acrylamide, and butyl acrylate mixed in a mass ratio of 1:1:1:1:1) to (1), stir and mix evenly, stir and heat to 75°C, then add 0.05 parts of dicumyl peroxide to the reaction system, stir and react at a constant temperature for 12 h, end the reaction, and after the reaction system naturally returns to room temperature, the compatibilizer is obtained.

[0054] 3. Preparation of modified filler: (1) Add 0.75 parts of γ-aminopropyltriethoxysilane, 0.75 parts of deionized water and 7.5 parts of anhydrous ethanol to the reaction vessel, stir and mix evenly, add acetic acid to adjust the pH to 5, and continue stirring and mixing for 20 min to obtain silane hydrolysate; disperse 15 parts of filler (a mixed filler composed of nano silica and carbon fiber in a mass ratio of 1:1) into 30 parts of anhydrous ethanol to obtain filler dispersion; (2) heat the filler dispersion to 55℃, and slowly add silane hydrolysate to it. After the addition is complete, continue stirring for 12 h, filter, wash and dry to obtain modified filler.

[0055] 4. Preparation of panel material: (1) First, add 35 parts of E51 type epoxy resin, 40 parts of acetone and 6 parts of modifier into the mixer and stir for 6 hours; then add 20 parts of polyurethane and 10 parts of compatibilizer into the mixer and stir for 3 hours; then add 15 parts of modified filler into the mixer and stir for 60 minutes; then add 4 parts of 2-methylimidazole, 6 parts of isophorone diisocyanate and 2 parts of BYK-A 530 type defoamer into the mixer and stir for 3 hours to finally obtain the mixture; (2) Inject the mixture into the mold and dry and cure at 100°C for 2 hours to obtain a 5mm thick panel material.

[0056] The following are examples 4-6 based on Example 1, as detailed below:

[0057] Example 4: Example 4 is based on Example 1, with the following adjustment: aramid fiber cloth is also added to the panel material, while other processes remain unchanged. Specifically:

[0058] 4. Preparation of panel material: (1) First, add 35 parts of E51 type epoxy resin, 40 parts of acetone and 6 parts of modifier into the mixer and stir for 6 hours; then add 20 parts of polyurethane and 10 parts of compatibilizer into the mixer and stir for 3 hours; then add 15 parts of modified filler into the mixer and stir for 60 minutes; then add 4 parts of 2-methylimidazole, 6 parts of isophorone diisocyanate and 2 parts of BYK-A 530 type defoamer into the mixer and stir for 3 hours to finally obtain the mixture; (2) After fixing the aramid fiber cloth horizontally in the middle of the mold, inject the mixture into the mold and dry and cure at 100°C for 2 hours to obtain a 5mm thick panel material.

[0059] Example 5: Example 5 is based on Example 1, with the following adjustment: the raw material composition of the panel material remains unchanged, specifically:

[0060] 4. Preparation of panel material: (1) First, add 35 parts of E51 epoxy resin, 40 parts of acetone and 4 parts of modifier to the mixer and stir for 6 hours; then add 15 parts of polyurethane and 7.5 parts of compatibilizer to the mixer and stir for 3 hours; then add 10 parts of modified filler to the mixer and stir for 60 minutes; then add 4 parts of 2-methylimidazole, 6 parts of isophorone diisocyanate and 2 parts of BYK-A 530 defoamer to the mixer and stir for 3 hours to finally obtain the mixture; (2) Inject the mixture into the mold and dry and cure at 100°C for 2 hours to obtain a 5mm thick panel material.

[0061] Example 6: Example 6 is based on Example 1, but with the following adjustment: the raw material composition of the panel material remains unchanged, while other processes remain the same. Specifically:

[0062] 4. Preparation of panel material: (1) First, add 35 parts of E51 type epoxy resin, 40 parts of acetone and 2 parts of modifier into the mixer and stir for 6 hours; then add 10 parts of polyurethane and 5 parts of compatibilizer into the mixer and stir for 3 hours; then add 5 parts of modified filler into the mixer and stir for 60 minutes; then add 4 parts of 2-methylimidazole, 6 parts of isophorone diisocyanate and 2 parts of BYK-A 530 type defoamer into the mixer and stir for 3 hours to finally obtain the mixture; (2) Inject the mixture into the mold and dry and cure at 100°C for 2 hours to obtain a 5mm thick panel material.

[0063] The following is a control experiment based on Example 1, with comparative examples 1 to 4, as detailed below:

[0064] Comparative Example 1: Comparative Example 1 is based on Example 1, with the following adjustment: no modifier was added, while other processes remained unchanged. Specifically:

[0065] 4. Preparation of panel material: (1) First, add 35 parts of E51 epoxy resin and 40 parts of acetone to the mixer and stir for 6 hours; then add 20 parts of polyurethane and 10 parts of compatibilizer to the mixer and stir for 3 hours; then add 15 parts of modified filler to the mixer and stir for 60 minutes; then add 4 parts of 2-methylimidazole, 6 parts of isophorone diisocyanate and 2 parts of BYK-A 530 defoamer to the mixer and stir for 3 hours to finally obtain the mixture; (2) Inject the mixture into the mold and dry and cure at 100°C for 2 hours to obtain a 5mm thick panel material.

[0066] Comparative Example 2: Comparative Example 2 is based on Example 1, with the following adjustment: no compatibilizer is added, while other processes remain unchanged. Specifically:

[0067] 4. Preparation of panel material: (1) First, add 35 parts of E51 type epoxy resin, 40 parts of acetone and 6 parts of modifier into the mixer and stir for 6 hours; then add 20 parts of polyurethane into the mixer and stir for 3 hours; then add 15 parts of modified filler into the mixer and stir for 60 minutes; then add 4 parts of 2-methylimidazole, 6 parts of isophorone diisocyanate and 2 parts of BYK-A 530 type defoamer into the mixer and stir for 3 hours to finally obtain the mixture; (2) Inject the mixture into the mold and dry and cure at 100°C for 2 hours to obtain a 5mm thick panel material.

[0068] Comparative Example 3: Comparative Example 3 is based on Example 1, with the following adjustment: no modified filler was added, while other processes remained unchanged. Specifically:

[0069] 4. Preparation of panel material: (1) First, add 35 parts of E51 type epoxy resin, 40 parts of acetone and 6 parts of modifier into the mixer and stir for 6 hours; then add 20 parts of polyurethane and 10 parts of compatibilizer into the mixer and stir for 3 hours; then add 4 parts of 2-methylimidazole, 6 parts of isophorone diisocyanate and 2 parts of BYK-A 530 type defoamer into the mixer and stir for 3 hours to finally obtain the mixture; (2) Inject the mixture into the mold and dry and cure at 100°C for 2 hours to obtain a 5mm thick panel material.

[0070] Comparative Example 4: Comparative Example 4 is based on Example 1, with the following adjustment: no treatment of aminopropyl-terminated polydimethylsiloxane is performed, while other processes remain unchanged. Specifically:

[0071] 1. Preparation of modifier: (1) Add 3 parts of lignin and 10 parts of 15wt% sodium hydroxide aqueous solution to the reaction vessel, stir and heat to 80℃, and stir at constant temperature for 60 min. Then add 0.3 parts of γ-aminopropyltriethoxysilane to the reaction system, and continue to stir at constant temperature for 6 h. After the reaction system naturally returns to room temperature, add 20wt% hydrochloric acid aqueous solution to adjust the pH to 2.5, centrifuge, precipitate, separate and purify to obtain aminated lignin; (3) Under nitrogen protection, add 6 parts of aminopropyl-terminated polydimethylsiloxane, 1.2 parts of N,N'-dicarbonyldiimidazole and 25 parts of dichloromethane to the reaction vessel, stir and heat to 80℃, and stir at constant temperature for 6 h. Then add 2.5 parts of aminated lignin to the reaction system, and continue to stir at constant temperature for 12 h. After the reaction system naturally returns to room temperature, evaporate by rotary evaporation to obtain modifier.

[0072] Performance testing: The panel materials prepared in Examples 1-6 and Comparative Examples 1-4 were cut into samples of 20cm (length) × 10cm (width), and then relevant performance tests were conducted. The specific test contents are as follows:

[0073] (1) Waterproof performance: The panel material samples corresponding to each example were placed in a drying oven and dried at 60℃ to a constant weight m1. After cooling to room temperature, they were immersed in water at the same temperature as room temperature for 24 hours. After soaking, they were taken out, the water on the sample surface was wiped off, and their weight m2 was weighed. The water absorption rate was calculated based on this. Water absorption rate (%) = (m2-m1) / m1×100%;

[0074] (2) Wear resistance: The wear resistance was tested using a Taber wear tester; under a load of 500g, the CS-10 grinding wheel was rotated 1000 times for friction; the mass m3 before friction and the mass m4 after friction were weighed and the wear rate was calculated based on them; Wear rate (%) = (m3-m4) / m3×100%;

[0075] (3) Antioxidant performance: According to the test method of GB / T 16422.3-2022, a UVA-340 lamp was used with a power of 0.76W / (m²) 2 The sample was irradiated with ·nm for 168 hours and then subjected to an artificial accelerated climate aging test. After the aging test, its bending strength was tested.

[0076] The test data results are shown in Table 1 below:

[0077] Table 1

[0078]

[0079] Results Analysis: As shown in Table 1 above, the comparative examples and Comparative Examples 1-4 demonstrate that the modifier, polyurethane, compatibilizer, and modified filler all exhibit significant practical effects in the panel material, and none of them can be omitted. This invention achieves a panel material with excellent comprehensive properties such as waterproofing, wear resistance, weather resistance, and toughness through the synergistic effect of these four components. Furthermore, the strength of the panel material can be enhanced by incorporating fiber cloth, thus expanding its application scope.

[0080] Finally, it should be noted that the above descriptions are merely preferred embodiments of the present invention and are not intended to limit the present invention. Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art can still modify the technical solutions described in the foregoing embodiments or make equivalent substitutions for some of the technical features. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A waterproof and wear-resistant panel material, characterized in that: The raw materials include the following components by mass: 20-35 parts epoxy resin, 2-6 parts modifier, 10-20 parts polyurethane, 5-10 parts compatibilizer, 5-15 parts modified filler, 2-4 parts curing agent A, 4-6 parts curing agent B, 1-2 parts defoamer, and 40 parts acetone. The method for preparing the modifier is as follows: (1) Under nitrogen protection, aminopropyl-terminated polydimethylsiloxane, ditert-butyl dicarbonate, triethylamine and anhydrous ethanol were added to the reaction vessel. After stirring and adjusting the temperature to 0~20℃ in a water bath, the reaction was refluxed for 6~24h. After the reaction was stopped, the reaction system was allowed to return to room temperature naturally. The reaction solution was washed with 5~10wt% hydrochloric acid aqueous solution, saturated sodium bicarbonate aqueous solution and deionized water in sequence, dried and rotary evaporated to obtain pretreated aminopropyl-terminated polydimethylsiloxane. (2) Add lignin and 5-15wt% sodium hydroxide aqueous solution to the reaction vessel, stir and heat to 60-90℃, and stir at a constant temperature for 20-60 min. Then add γ-aminopropyltriethoxysilane to the reaction system and continue stirring at a constant temperature for 1-6 h. After the reaction is stopped, wait for the reaction system to return to room temperature naturally, add 20wt% hydrochloric acid aqueous solution to adjust the pH to 2-3, centrifuge, precipitate, separate and purify to obtain amino lignin; (3) Under nitrogen protection, pretreated aminopropyl-terminated polydimethylsiloxane, N,N'-dicarbonyldiimidazole and dichloromethane were added to the reaction vessel, stirred and heated to 70~85℃, and stirred at constant temperature for 1~6h. Then, amino-modified lignin was added to the reaction system, and stirred at constant temperature for 2~12h. The reaction was then stopped. After the reaction system naturally returned to room temperature, trifluoroacetic acid was added, and stirred at room temperature for 6~24h. The mixture was then rotary evaporated to obtain the modifier. The molar ratio of aminopropyl-terminated polydimethylsiloxane, ditert-butyl dicarbonate, and triethylamine is 1:(0.4~0.6):(1~1.5); wherein the molecular weight of aminopropyl-terminated polydimethylsiloxane is 400~1000; and the mass ratio of lignin and γ-aminopropyltriethoxysilane is 1:(0.05~0.1). The raw materials required for the preparation of the modifier include the following components: by mass parts, 4-6 parts of pretreated aminopropyl-terminated polydimethylsiloxane, 0.8-1.2 parts of N,N'-dicarbonyl diimidazole, 1.2-2.5 parts of amino-modified lignin, 0.5-1 part of trifluoroacetic acid, and 25 parts of dichloromethane; The compatibilizer is prepared by: (1) Add diisocyanate and stannous octoate to the reaction vessel, stir and heat to 50~80℃, and then stir and mix at a constant temperature for 10~30 min; then add propyl 2,3-dihydroxyacrylate and hydroquinone to the reaction system, and stir and react at a constant temperature for 1~3 h; then add polyester diol to the reaction system, stir and react at a constant temperature for 1~6 h, and then cool down for later use. (2) Add acetone and unsaturated monomer to (1), stir and mix evenly, then stir and heat to 60~85℃, then add dicumyl peroxide dropwise to the reaction system, stir and react at constant temperature for 2~12h, end the reaction, and after the reaction system naturally returns to room temperature, the compatibilizer is obtained. The raw materials required for preparing the compatibilizer include the following components by mass: 5 parts diisocyanate, 0.5-1.5 parts propyl 2,3-dihydroxyacrylate, 1.5-2.5 parts polyester diol, 0.05-0.1 parts stannous octoate, 0.05-0.1 parts hydroquinone, 4-8 parts unsaturated monomer, 0.05-0.1 parts dicumyl peroxide, and 20 parts acetone; The modified filler is prepared by: (1) Add γ-aminopropyltriethoxysilane, deionized water and anhydrous ethanol into the reaction vessel, stir and mix evenly, add acetic acid to adjust the pH to 4.5~6, continue stirring and mixing for 10~20 min to obtain silane hydrolysate; disperse the filler in anhydrous ethanol to obtain filler dispersion; (2) After heating the filler dispersion to 50~60℃, slowly add silane hydrolysate dropwise. After the addition is complete, continue stirring for 6~12h. After filtration, washing and drying, the modified filler is obtained. The mass ratio of the filler and γ-aminopropyltriethoxysilane is 1:(0.05~0.1); the mass ratio of γ-aminopropyltriethoxysilane, deionized water, and anhydrous ethanol is 1:1:10; the filler is a mixed filler composed of nanoparticles and nanofibers. The curing agent A is an imidazole curing agent, including any one of 2-methylimidazole and 2-ethyl-4-methylimidazole; the curing agent B is an isocyanate curing agent, including any one of toluene diisocyanate, isophorone diisocyanate, 4,4'-diphenylmethane diisocyanate, and hexamethylene diisocyanate.

2. The waterproof and wear-resistant panel material according to claim 1, characterized in that: The diisocyanate includes one or more combinations of toluene diisocyanate, isophorone diisocyanate, 4,4'-diphenylmethane diisocyanate, and hexamethylene diisocyanate; the polyester diol includes one or more combinations of polyethylene adipate, polyethylene glycol dioxane, and neopentyl glycol polyethylene glycol, with a molecular weight of 1000-2000; the unsaturated monomer includes one or more combinations of acrylic acid, glycidyl acrylate, glycidyl methacrylate, acrylamide, and butyl acrylate.

3. A method for manufacturing a waterproof and wear-resistant panel material according to any one of claims 1 to 2, characterized in that: The specific process of the manufacturing method is as follows: (1) First, add epoxy resin, acetone and modifier to the mixer and mix for 1-6 hours; then add polyurethane and compatibilizer to the mixer and mix for 1-3 hours; then add modified filler to the mixer and mix for 30-60 minutes; then add curing agent A, curing agent B and defoamer to the mixer and mix for 1-3 hours to finally obtain the mixture. (2) Inject the mixture into the mold and dry and cure it at 90~110℃ for 1~3h to obtain the panel material.

4. The method for manufacturing a waterproof and wear-resistant panel material according to claim 3, characterized in that: The panel material may also contain fiber cloth; the method of setting is as follows: after fixing the fiber cloth of the corresponding size horizontally in the middle of the mold, the mixture is injected into the mold, dried, and cured to obtain the panel material containing fiber cloth.

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