Waterproof and wear-resistant panel material and manufacturing method thereof

Abstract

The invention 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 comprises the following raw material 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 a modified filler, 2-4 parts of a curing agent A, 4-6 parts of a 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, comprehensive modification of the epoxy resin is realized, the original waterproof and wear-resisting properties of the epoxy resin are enhanced, the defects of the epoxy resin are improved, and finally the panel material with excellent comprehensive performance is processed and manufactured by using the epoxy resin.

Description

Technical Field

[0001] The invention relates to the technical field of decorative materials, in particular to a waterproof and wear-resistant panel material and a manufacturing method thereof. Background Art

[0002] With the increasing requirements for material performance in the fields of architectural decoration, transportation, and electronic equipment, panel materials with high strength, waterproofness, and wear resistance have become a technical direction that the industry urgently needs to break through. Although traditional epoxy resin-based materials have excellent mechanical strength and chemical resistance, they are highly brittle, have insufficient anti-aging properties, and are prone to surface powdering and cracking in 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 through methods such as epoxy resin modification and resin compounding. While improving its waterproof and wear-resistant properties, its weather resistance and toughness are also improved to a certain extent, so that it has a better application space and has important practical significance. Summary of the invention

[0004] The object of the present invention is to provide a waterproof and wear-resistant panel material and a manufacturing method thereof, so as to solve the problems raised in the above background technology.

[0005] In order to solve the above technical problems, the present invention provides the following technical solutions: A waterproof and wear-resistant panel material, whose raw materials include the following components: by mass, 20-35 parts of epoxy resin, 2-6 parts of modifier, 10-20 parts of polyurethane, 5-10 parts of compatibilizer, 5-15 parts of modified filler, 2-4 parts of curing agent A, 4-6 parts of curing agent B, 1-2 parts of defoaming agent, and 40 parts of acetone.

[0006] Further, the preparation method of the modifier is as follows: (1) Under nitrogen protection, aminopropyl-terminated polydimethylsiloxane, di-tert-butyl dicarbonate, triethylamine, and absolute ethanol are added into a reaction vessel. After stirring and adjusting the temperature of the water bath to 0-20°C, reflux reaction is carried out for 6-24 h to end the reaction. After the reaction system naturally returns to room temperature, the reaction solution is washed successively with 5-10 wt% hydrochloric acid aqueous solution, saturated sodium bicarbonate aqueous solution, and deionized water, dried, and rotary evaporated to obtain pretreated aminopropyl-terminated polydimethylsiloxane; (2) Lignin and 5-15 wt% sodium hydroxide aqueous solution are added into a reaction vessel. After stirring and heating to 60-90°C, constant-temperature stirring reaction is carried out for 20-60 min. Then, γ-aminopropyltriethoxysilane is added into the reaction system, and constant-temperature stirring reaction is continued for 1-6 h to end the reaction. After the reaction system naturally returns to room temperature, 20 wt% hydrochloric acid aqueous solution is added thereto to adjust the pH to 2-3, centrifuged to precipitate, separated and purified to obtain amino-functionalized lignin; (3) Under nitrogen protection, pretreated aminopropyl-terminated polydimethylsiloxane, N,N'-carbonyldiimidazole, and dichloromethane are added into a reaction vessel. After stirring and heating to 70-85°C, constant-temperature stirring reaction is carried out for 1-6 h. Then, amino-functionalized lignin is added into the reaction system, and constant-temperature stirring reaction is continued for 2-12 h to end the reaction. After the reaction system naturally returns to room temperature, trifluoroacetic acid is added, and stirring reaction is carried out at room temperature for 6-24 h, and rotary evaporation is carried out to obtain the modifier.

[0007] Further, the molar ratio of aminopropyl-terminated polydimethylsiloxane, di-tert-butyl dicarbonate, and triethylamine is 1:(0.4-0.6):(1-1.5); wherein, the molecular weight of aminopropyl-terminated polydimethylsiloxane is 400-1000.

[0008] Further, the mass ratio of lignin to γ-aminopropyltriethoxysilane is 1:(0.05-0.1).

[0009] Further, the raw materials required for the preparation of the modifier include the following components: by mass, 4-6 parts of pretreated aminopropyl-terminated polydimethylsiloxane, 0.8-1.2 parts of N,N'-carbonyldiimidazole, 1.2-2.5 parts of amino-functionalized lignin, 0.5-1 part of trifluoroacetic acid, and 25 parts of dichloromethane.

[0010] Further, the preparation method of the compatibilizer is as follows: (1) Add diisocyanate and stannous octoate into a reaction vessel, stir and heat to 50-80°C, then keep stirring and mixing at a constant temperature for 10-30 minutes; then add 2,3-dihydroxypropyl acrylate and hydroquinone into the reaction system, and keep stirring and reacting at a constant temperature for 1-3 hours; then add polyester diol into the reaction system, and keep stirring and reacting at a constant temperature for 1-6 hours, and then cool down for standby; (2) Add acetone and unsaturated monomer into (1), stir and mix evenly, then stir and heat up to 60-85°C, and then dropwise add dicumyl peroxide into the reaction system, keep stirring and reacting at a constant temperature for 2-12 hours to end the reaction. After the reaction system naturally returns to room temperature, the compatibilizer is obtained.

[0011] Further, the raw materials required for the preparation of the compatibilizer include the following components: by mass, 5 parts of diisocyanate, 0.5-1.5 parts of 2,3-dihydroxypropyl acrylate, 1.5-2.5 parts of polyester diol, 0.05-0.1 part of stannous octoate, 0.05-0.1 part of hydroquinone, 4-8 parts of unsaturated monomer, 0.05-0.1 part of dicumyl peroxide, and 20 parts of acetone.

[0012] Further, the diisocyanate includes but is not limited to one or a combination of more of toluene diisocyanate, isophorone diisocyanate, 4,4'-diphenylmethane diisocyanate, and hexamethylene diisocyanate.

[0013] Further, the polyester diol includes but is not limited to at least one of polyethylene adipate, polyethylene glycol diglycol adipate, and neopentyl glycol adipate, and its molecular weight is 1000-2000.

[0014] Further, the unsaturated monomer includes but is not limited to one or a combination of more of acrylic acid, glycidyl acrylate, glycidyl methacrylate, acrylamide, and butyl acrylate.

[0015] Further, the preparation method of the modified filler is as follows: (1) Add γ-aminopropyltriethoxysilane, deionized water, and absolute ethanol into a reaction vessel, stir and mix evenly, and add acetic acid to adjust the pH to 4.5-6, and continue to stir and mix for 10-20 minutes to obtain a silane hydrolysis solution; disperse the filler in absolute ethanol to obtain a filler dispersion; (2) Heat the filler dispersion to 50-60°C, and then slowly dropwise add the silane hydrolysis solution thereto. After the addition is completed, continue to stir for 6-12 hours, and after filtration, washing, and drying, the modified filler is obtained.

[0016] Further, the mass ratio of the filler to γ-aminopropyltriethoxysilane is 1:(0.05-0.1).

[0017] Further, the mass ratio of the γ-aminopropyltriethoxysilane, deionized water, and absolute ethanol is 1:1:10.

[0018] Further, the filler is a mixed filler composed of nanoparticles and nanofibers.

[0019] Further, in the embodiment of the present invention, the filler is preferably a mixed filler composed of nano-silica and carbon fiber in a mass ratio of 1:1.

[0020] Further, the curing agent A is an imidazole-based curing agent, including any one of 2-methylimidazole and 2-ethyl-4-methylimidazole.

[0021] Further, the curing agent B is an isocyanate-based curing agent, including any one of toluene diisocyanate, isophorone diisocyanate, 4,4'-diphenylmethane diisocyanate, and hexamethylene diisocyanate.

[0022] Further, the manufacturing method of the waterproof and wear-resistant panel material specifically includes the following steps: (1) First, add epoxy resin, acetone, and modifier into a mixer and stir and mix for 1 to 6 hours; then add polyurethane and compatibilizer into the mixer and stir and mix for 1 to 3 hours; then add the modified filler into the mixer and stir and mix for 30 to 60 minutes; then add curing agent A, curing agent B, and defoaming agent into the mixer and stir and mix for 1 to 3 hours to finally obtain a mixture; (2) Inject the mixture into a mold and dry and cure at 90 to 110 °C for 1 to 3 hours to obtain the panel material.

[0023] Further, a fiber cloth can be provided in the panel material. The setting method is as follows: After horizontally fixing a fiber cloth with a corresponding size in the middle of the mold, inject the mixture into the mold, dry, and cure and form to obtain the panel material provided with the fiber cloth.

[0024] Due to the excellent waterproof and wear-resistant properties of epoxy resin, in the present invention, it is designed to be used as the main raw material of the panel material, and together with other raw materials, a waterproof and wear-resistant panel with excellent performance is prepared. At the same time, the inventor also considered that the toughness and oxidation resistance of epoxy resin are poor. If it is directly used as a raw material to process into a panel, the obtained panel is extremely prone to fracture, and its weather resistance is poor, resulting in a relatively low service life of the prepared panel. Based on this, the present invention first considers modifying epoxy resin to enhance its toughness and oxidation resistance in order to increase the service life of the panel. In the present invention, a modifier is prepared. First, boc protection pretreatment is carried out on aminopropyl-terminated polydimethylsiloxane to protect one amino group on its chain end. Through the use of N,N'-dicarbonyl diimidazole as a bridge, the pretreated aminopropyl-terminated polydimethylsiloxane and amino-functionalized lignin are then connected together, and after boc deprotection, it is prepared. The modifier contains a polydimethylsiloxane chain end and a lignin structure. Among them, the polydimethylsiloxane chain end can improve the toughness of epoxy resin and enhance the waterproof property of epoxy resin, while lignin can endow epoxy resin with certain antioxidant properties, making it have certain weather resistance; in addition, due to boc protection, the modifier also contains an amino group, which can combine with epoxy resin during the subsequent mixing process with epoxy resin to achieve effective modification of epoxy resin.

[0025] Polyurethane also has excellent waterproof and wear-resistant properties, and its wear-resistant property is even better than that of epoxy resin. In addition, polyurethane also has excellent toughness. If it is compounded with modified epoxy resin, undoubtedly a panel with more excellent performance can be prepared. Therefore, the inventor further considers introducing polyurethane to cooperate with the modifier to enhance and modify epoxy resin. However, considering the difference in compatibility between the two, in order to better prepare a panel material with more excellent comprehensive properties such as waterproof, wear-resistant, and tough, a compatibilizer is further prepared in the present invention. Also, in order to further improve the relevant properties of the panel material, modified fillers are further added in the present invention.

[0026] Compared with the prior art, the beneficial effects achieved by the present invention are: (1) In the present invention, N,N'-dicarbonyl diimidazole is used to connect aminopropyl-terminated polydimethylsiloxane and amino-functionalized lignin together. This modifier can effectively improve epoxy resin, which can not only reduce its water absorption, but also improve the oxidation resistance of epoxy resin; (2) The compatibilizer in the present invention contains a structure similar to polyurethane and a polyacrylate chain end, which can greatly promote the compatibility between polyurethane and epoxy resin; (3) The modified filler in the present invention is composed of a mixture of nanoparticles and nanofibers. Among them, the nanoparticles mainly play a role in enhancing the wear resistance of the panel material, the nanofibers mainly play a role in enhancing the toughness of the panel material, and both can also improve the weather resistance of the panel material to a certain extent.

[0027] In summary, through the synergistic effect of the modifier, polyurethane, compatibilizer, and modified filler, the present invention comprehensively prepares a panel material with excellent comprehensive properties such as waterproofness, wear resistance, weather resistance, and toughness. Detailed implementation manners

[0028] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts shall fall within the protection scope of the present invention.

[0029] It should be noted that the following parts are by weight. There are no special restrictions on the purchase manufacturers of all raw materials involved in the present invention. Exemplarily, they include: In the following embodiments, epoxy resin, model E51, was purchased from Guangzhou Zhongye Chemical Co., Ltd.; Polyurethane, with a purity of 99%, product number: WB11060, was purchased from Guangdong Wengjiang Chemical Reagent Co., Ltd.; Aminopropyl-terminated polydimethylsiloxane, with a purity of 98%, product number: GEL-SSP-085, molecular weight of about 1000, di-tert-butyl dicarbonate, with a purity of 99%, and triethylamine, with a purity of 99%, were all purchased from Shanghai Merck Chemical Technology Co., Ltd.; Lignin with a purity of 99%, product number: 9005-53-2, γ-aminopropyltrimethoxysilane, with a purity of 99%, N,N'-dicarbonyl diimidazole, with a purity of 99%, silicon dioxide, with a purity of 99%, particle size of 10 - 30nm, dichloromethane, with a purity of 99%, 2-methylimidazole, with a purity of 99%, carbon fiber, with a purity of 99%, diameter of 5 - 8μm, aspect ratio of 5 - 20, were all purchased from Hubei Yongkuo Technology Co., Ltd.; 2,3-Dihydroxypropyl acrylate, with a purity of 98%, was purchased from Shanghai Boyi Biomedical Technology Co., Ltd.; Isophorone diisocyanate, with a purity of 99%, polyethylene glycol adipate, with a purity of 96%, molecular weight of about 1000, acrylic acid, with a purity of 99%, glycidyl acrylate, with a purity of 99%, glycidyl methacrylate, with a purity of 99%, acrylamide, with a purity of 99%, butyl acrylate, with a purity of 99%, were all purchased from Shanghai Dingmiao Chemical Technology Co., Ltd.; Defoamer, model BYK-A 530, purchased from Shanghai Buding Chemical Co., Ltd.; each part by mass in the examples is 100 g.

[0030] Example 1: A manufacturing method of a waterproof and wear-resistant panel material: 1. Preparation of modifier: (1) Under nitrogen protection, 10 parts of aminopropyl-terminated polydimethylsiloxane, 1.08 parts of di-tert-butyl dicarbonate, 1.3 parts of triethylamine, and 30 parts of absolute ethanol were added to a reaction vessel. After stirring and adjusting the temperature of the water bath to 0 °C, reflux reaction was carried out for 24 h to end the reaction. After the reaction system naturally returned to room temperature, the reaction solution was washed successively with 8 wt% hydrochloric acid aqueous solution, saturated sodium bicarbonate aqueous solution, and deionized water, dried, and rotary evaporated to obtain pretreated aminopropyl-terminated polydimethylsiloxane; (2) 3 parts of lignin and 10 parts of 15 wt% sodium hydroxide aqueous solution were added to a reaction vessel. After stirring and heating to 80 °C, constant temperature stirring reaction was carried out for 60 min. Then 0.3 part of γ-aminopropyltriethoxysilane was added to the reaction system, and constant temperature stirring reaction was continued for 6 h to end the reaction. After the reaction system naturally returned to room temperature, 20 wt% hydrochloric acid aqueous solution was added thereto to adjust the pH to 2.5, centrifuged, the precipitate was separated out, and purified to obtain amino-functionalized 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 a reaction vessel. After stirring and heating to 80 °C, constant temperature stirring reaction was carried out for 6 h. Then 2.5 parts of amino-functionalized lignin was added to the reaction system, and constant temperature stirring reaction was continued for 12 h to end the reaction. After the reaction system naturally returned to room temperature, 1 part of trifluoroacetic acid was added, and stirring reaction was carried out at room temperature for 24 h, and rotary evaporation was carried out to obtain the modifier.

[0031] 2. Preparation of compatibilizer: (1) 5 parts of isophorone diisocyanate and 0.08 part of stannous octoate were added to a reaction vessel. After stirring and heating to 70 °C, constant temperature stirring and mixing were carried out for 20 min; then 1.5 parts of 2,3-dihydroxypropyl acrylate and 0.1 part of hydroquinone were added to the reaction system, and constant temperature stirring reaction was carried out for 2 h; then 2 parts of polyethylene glycol adipate were added to the reaction system, and constant temperature stirring reaction was carried out for 6 h, and the temperature was lowered for standby; (2) 20 parts of acetone and 8 parts of unsaturated monomers (a mixture of acrylic acid, glycidyl acrylate, glycidyl methacrylate, acrylamide, and butyl acrylate in a mass ratio of 1:1:1:1:1) were added to (1). After stirring and mixing evenly, the temperature was raised to 75 °C by stirring. Then 0.1 part of diisopropylbenzene peroxide was added dropwise to the reaction system, and constant temperature stirring reaction was carried out for 12 h to end the reaction. After the reaction system naturally returned to room temperature, the compatibilizer was obtained.

[0032] 3. Preparation of modified filler: (1) Add 1.5 parts of γ-aminopropyltriethoxysilane, 1.5 parts of deionized water, and 15 parts of absolute ethanol into a reaction vessel, stir and mix evenly, add acetic acid to adjust the pH to 5, and continue to stir and mix for 20 min to obtain a silane hydrolysis solution; 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 absolute ethanol to obtain a filler dispersion; (2) After heating the filler dispersion to 55 °C, slowly dropwise add the silane hydrolysis solution thereto. After the addition is completed, continue to stir for 12 h, filter, wash, and dry to obtain the modified filler.

[0033] 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 a blender, stir and mix for 6 h; Then add 20 parts of polyurethane and 10 parts of compatibilizer into the blender, stir and mix for 3 h; Then add 15 parts of modified filler into the blender, stir and mix for 60 min; Then add 4 parts of 2-methylimidazole, 6 parts of isophorone diisocyanate, and 2 parts of BYK-A 530 defoaming agent into the blender, stir and mix for 3 h to finally obtain a mixture; (2) Inject the mixture into a mold and dry and cure at 100 °C for 2 h to obtain a 5-mm-thick panel material.

[0034] Example 2: A manufacturing method of a waterproof and wear-resistant panel material: 1. Preparation of modifier: (1) Under nitrogen protection, add 10 parts of aminopropyl-terminated polydimethylsiloxane, 1.08 parts of di-tert-butyl dicarbonate, 1.3 parts of triethylamine, and 30 parts of absolute ethanol into a reaction vessel, stir and adjust the temperature to 0 °C in a water bath, reflux and react for 24 h to end the reaction. After the reaction system naturally returns to room temperature, wash the reaction solution successively with 8 wt% hydrochloric acid aqueous solution, saturated sodium bicarbonate aqueous solution, and deionized water, dry, and rotary evaporate to obtain pretreated aminopropyl-terminated polydimethylsiloxane; (2) Add 3 parts of lignin and 10 parts of 10 wt% sodium hydroxide aqueous solution into a reaction vessel, stir and heat to 80 °C, then stir and react at a constant temperature for 60 min. Then add 0.225 parts of γ-aminopropyltriethoxysilane into the reaction system, continue to stir and react at a constant temperature for 6 h to end the reaction. After the reaction system naturally returns to room temperature, add 20 wt% hydrochloric acid aqueous solution thereto to adjust the pH to 2.5, centrifuge, precipitate, separate and purify to obtain amino-functionalized lignin; (3) Under nitrogen protection, add 6 parts of pretreated aminopropyl-terminated polydimethylsiloxane, 1.2 parts of N,N'-dicarbonyl diimidazole, and 25 parts of dichloromethane into a reaction vessel, stir and heat to 80 °C, then stir and react at a constant temperature for 6 h. Then add 1.8 parts of amino-functionalized lignin into the reaction system, continue to stir and react at a constant temperature for 12 h to end the reaction. After the reaction system naturally returns to room temperature, add 1 part of trifluoroacetic acid, stir and react at room temperature for 24 h, and rotary evaporate to obtain the modifier.

[0035] 2. Preparation of compatibilizer: (1) Add 5 parts of isophorone diisocyanate and 0.08 part of stannous octoate into a reaction vessel, stir and heat to 70 °C, then keep stirring and mixing for 20 min at a constant temperature; then add 1 part of 2,3-dihydroxypropyl acrylate and 0.075 part of hydroquinone into the reaction system, and react with constant stirring for 2 h; then add 2 parts of polyethylene glycol adipate into the reaction system, and react with constant stirring for 6 h, and then cool down for standby; (2) Add 20 parts of acetone and 6 parts of unsaturated monomers (a mixture of acrylic acid, glycidyl acrylate, glycidyl methacrylate, acrylamide, and butyl acrylate in a mass ratio of 1:1:1:1:1) into (1), stir and mix evenly, then stir and heat up to 75 °C, and then dropwise add 0.75 part of diisopropylbenzene peroxide into the reaction system, and react with constant stirring for 12 h to end the reaction. After the reaction system naturally returns to room temperature, the compatibilizer is obtained.

[0036] 3. Preparation of modified filler: (1) Add 1.125 parts of γ-aminopropyltriethoxysilane, 1.125 parts of deionized water, and 11.25 parts of absolute ethanol into a reaction vessel, stir and mix evenly, add acetic acid to adjust the pH to 5, and continue to stir and mix for 20 min to obtain a silane hydrolysis solution; 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 absolute ethanol to obtain a filler dispersion; (2) Heat the filler dispersion to 55 °C, and then slowly dropwise add the silane hydrolysis solution. After the addition is completed, continue to stir for 12 h, and then obtain the modified filler through filtration, washing, and drying.

[0037] 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 a mixer, and stir and mix for 6 h; then add 20 parts of polyurethane and 10 parts of compatibilizer into the mixer, and stir and mix for 3 h; then add 15 parts of modified filler into the mixer, and stir and mix for 60 min; then add 4 parts of 2-methylimidazole, 6 parts of isophorone diisocyanate, and 2 parts of BYK-A 530 defoamer into the mixer, and stir and mix for 3 h to finally obtain a mixture; (2) Inject the mixture into a mold and dry and cure it at 100 °C for 2 h to obtain a 5-mm-thick panel material.

[0038] Example 3: A manufacturing method of a waterproof and wear-resistant panel material: 1. Preparation of modifier: (1) Under nitrogen protection, 10 parts of aminopropyl-terminated polydimethylsiloxane, 1.08 parts of di-tert-butyl dicarbonate, 1.3 parts of triethylamine, and 30 parts of absolute ethanol were added to a reaction vessel. After stirring and adjusting the temperature of the water bath to 0 °C, reflux reaction was carried out for 24 h to end the reaction. After the reaction system naturally returned to room temperature, the reaction solution was washed successively with 8 wt% hydrochloric acid aqueous solution, saturated sodium bicarbonate aqueous solution, and deionized water, dried, and rotary evaporated to obtain pretreated aminopropyl-terminated polydimethylsiloxane; (2) 3 parts of lignin and 10 parts of 5 wt% sodium hydroxide aqueous solution were added to a reaction vessel. After stirring and heating to 80 °C, constant temperature stirring reaction was carried out for 60 min. Then, 0.15 part of γ-aminopropyltriethoxysilane was added to the reaction system, and constant temperature stirring reaction was continued for 6 h to end the reaction. After the reaction system naturally returned to room temperature, 20 wt% hydrochloric acid aqueous solution was added to adjust the pH to 2.5, centrifuged to precipitate, separated and purified to obtain amino-functionalized lignin; (3) Under nitrogen protection, 6 parts of pretreated aminopropyl-terminated polydimethylsiloxane, 1.2 parts of N,N'-carbonyldiimidazole, and 25 parts of dichloromethane were added to a reaction vessel. After stirring and heating to 80 °C, constant temperature stirring reaction was carried out for 6 h. Then, 1.2 parts of amino-functionalized lignin was added to the reaction system, and constant temperature stirring reaction was continued for 12 h to end the reaction. After the reaction system naturally returned to room temperature, 1 part of trifluoroacetic acid was added, and stirring reaction was carried out at room temperature for 24 h, and then rotary evaporated to obtain the modifier.

[0039] 2. Preparation of compatibilizer: (1) 5 parts of isophorone diisocyanate and 0.08 part of stannous octoate were added to a reaction vessel. After stirring and heating to 70 °C, constant temperature stirring and mixing were carried out for 20 min; then, 0.5 part of 2,3-dihydroxypropyl acrylate and 0.05 part of hydroquinone were added to the reaction system, and constant temperature stirring reaction was carried out for 2 h; then, 2 parts of polyethylene glycol adipate were added to the reaction system, and constant temperature stirring reaction was carried out for 6 h, and then cooled for standby; (2) 20 parts of acetone and 4 parts of unsaturated monomers (a mixture of acrylic acid, glycidyl acrylate, glycidyl methacrylate, acrylamide, and butyl acrylate in a mass ratio of 1:1:1:1:1) were added to (1). After stirring and mixing evenly, the temperature was raised to 75 °C by stirring. Then, 0.05 part of diisopropylbenzene peroxide was added dropwise to the reaction system, and constant temperature stirring reaction was carried out for 12 h to end the reaction. After the reaction system naturally returned to room temperature, the compatibilizer was obtained.

[0040] 3. Preparation of modified filler: (1) Add 0.75 part of γ-aminopropyltriethoxysilane, 0.75 part of deionized water, and 7.5 parts of absolute ethanol into a reaction vessel, stir and mix evenly, add acetic acid to adjust the pH to 5, and continue to stir and mix for 20 min to obtain a silane hydrolysis solution; 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 absolute ethanol to obtain a filler dispersion; (2) After heating the filler dispersion to 55 °C, slowly dropwise add the silane hydrolysis solution thereto. After the addition is complete, continue to stir for 12 h, filter, wash, and dry to obtain the modified filler.

[0041] 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 a mixer, stir and mix for 6 h; Then add 20 parts of polyurethane and 10 parts of compatibilizer into the mixer, stir and mix for 3 h; Next, add 15 parts of modified filler into the mixer, stir and mix for 60 min; Then add 4 parts of 2-methylimidazole, 6 parts of isophorone diisocyanate, and 2 parts of BYK-A 530 defoaming agent into the mixer, stir and mix for 3 h to finally obtain a mixture; (2) Inject the mixture into a mold and dry and cure at 100 °C for 2 h to obtain a 5-mm-thick panel material.

[0042] The following are based on Example 1 to set Examples 4 to 6, specifically as follows: Example 4: Example 4 is based on Example 1 and is adjusted as follows: An aramid fiber cloth is also provided in the panel material, and other processes remain unchanged. Specifically: 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 a mixer, stir and mix for 6 h; Then add 20 parts of polyurethane and 10 parts of compatibilizer into the mixer, stir and mix for 3 h; Next, add 15 parts of modified filler into the mixer, stir and mix for 60 min; Then add 4 parts of 2-methylimidazole, 6 parts of isophorone diisocyanate, and 2 parts of BYK-A 530 defoaming agent into the mixer, stir and mix for 3 h to finally obtain a mixture; (2) After horizontally fixing the aramid fiber cloth in the middle of the mold, inject the mixture into the mold and dry and cure at 100 °C for 2 h to obtain a 5-mm-thick panel material.

[0043] Example 5: Example 5 is based on Example 1 and is adjusted as follows: The raw material components of the panel material are adjusted, and other processes remain unchanged. Specifically: 4. Preparation of panel material: (1) First, add 35 parts of E51 type epoxy resin, 40 parts of acetone, and 4 parts of modifier into a blender and stir and mix for 6 h; then add 15 parts of polyurethane and 7.5 parts of compatibilizer into the blender and stir and mix for 3 h; then add 10 parts of modified filler into the blender and stir and mix for 60 min; then add 4 parts of 2-methylimidazole, 6 parts of isophorone diisocyanate, and 2 parts of BYK-A 530 defoamer into the blender and stir and mix for 3 h to finally obtain a mixture; (2) Inject the mixture into a mold and dry and cure it at 100 °C for 2 h to obtain a 5-mm-thick panel material.

[0044] Example 6: Example 6 is based on Example 1 and adjusted: the raw material components of the panel material, and other processes remain unchanged. Specifically: 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 a blender and stir and mix for 6 h; then add 10 parts of polyurethane and 5 parts of compatibilizer into the blender and stir and mix for 3 h; then add 5 parts of modified filler into the blender and stir and mix for 60 min; then add 4 parts of 2-methylimidazole, 6 parts of isophorone diisocyanate, and 2 parts of BYK-A 530 defoamer into the blender and stir and mix for 3 h to finally obtain a mixture; (2) Inject the mixture into a mold and dry and cure it at 100 °C for 2 h to obtain a 5-mm-thick panel material.

[0045] The following is based on Example 1 for a control experiment, and Comparative Examples 1 to 4 are set up, specifically as follows: Comparative Example 1: Comparative Example 1 is based on Example 1 and adjusted: without adding modifier, and other processes remain unchanged. Specifically: 4. Preparation of panel material: (1) First, add 35 parts of E51 type epoxy resin and 40 parts of acetone into a blender and stir and mix for 6 h; then add 20 parts of polyurethane and 10 parts of compatibilizer into the blender and stir and mix for 3 h; then add 15 parts of modified filler into the blender and stir and mix for 60 min; then add 4 parts of 2-methylimidazole, 6 parts of isophorone diisocyanate, and 2 parts of BYK-A 530 defoamer into the blender and stir and mix for 3 h to finally obtain a mixture; (2) Inject the mixture into a mold and dry and cure it at 100 °C for 2 h to obtain a 5-mm-thick panel material.

[0046] Comparative Example 2: Comparative Example 2 is based on Example 1 and adjusted: without adding compatibilizer, and other processes remain unchanged. Specifically: 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 a blender and stir and mix for 6 h; then add 20 parts of polyurethane into the blender and stir and mix for 3 h; then add 15 parts of modified filler into the blender and stir and mix for 60 min; then add 4 parts of 2-methylimidazole, 6 parts of isophorone diisocyanate, and 2 parts of BYK-A 530 defoamer into the blender and stir and mix for 3 h to finally obtain a mixture; (2) Inject the mixture into a mold and dry and cure at 100 °C for 2 h to obtain a 5-mm-thick panel material.

[0047] Comparative Example 3: Comparative Example 3 is based on Example 1 and is adjusted as follows: Do not add modified filler, and keep other processes unchanged. Specifically: 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 a blender and stir and mix for 6 h; then add 20 parts of polyurethane and 10 parts of compatibilizer into the blender and stir and mix for 3 h; then add 4 parts of 2-methylimidazole, 6 parts of isophorone diisocyanate, and 2 parts of BYK-A 530 defoamer into the blender and stir and mix for 3 h to finally obtain a mixture; (2) Inject the mixture into a mold and dry and cure at 100 °C for 2 h to obtain a 5-mm-thick panel material.

[0048] Comparative Example 4: Comparative Example 4 is based on Example 1 and is adjusted as follows: Do not treat the aminopropyl-terminated polydimethylsiloxane, and keep other processes unchanged. Specifically: 1. Preparation of modifier: (1) Add 3 parts of lignin and 10 parts of 15 wt% sodium hydroxide aqueous solution into a reaction vessel, stir and heat to 80 °C, then keep stirring and reacting for 60 min, then add 0.3 part of γ-aminopropyltriethoxysilane into the reaction system, continue to keep stirring and reacting for 6 h to end the reaction. After the reaction system naturally returns to room temperature, add 20 wt% hydrochloric acid aqueous solution to adjust the pH to 2.5, centrifuge to precipitate, separate and purify to obtain amino-functionalized lignin; (3) Under nitrogen protection, add 6 parts of aminopropyl-terminated polydimethylsiloxane, 1.2 parts of N,N'-dicarbonyl diimidazole, and 25 parts of dichloromethane into a reaction vessel, stir and heat to 80 °C, then keep stirring and reacting for 6 h, then add 2.5 parts of amino-functionalized lignin into the reaction system, continue to keep stirring and reacting for 12 h to end the reaction. After the reaction system naturally returns to room temperature, perform rotary evaporation to obtain the modifier.

[0049] Performance test: Cut the panel materials prepared in Examples 1 to 6 and Comparative Examples 1 to 4 into samples with a size of 20 cm (length) × 10 cm (width), and then conduct relevant performance tests. The specific test contents are as follows: (1)Waterproof performance: Place the panel material samples corresponding to each example in an oven and dry them at 60 °C until a constant weight m1 is reached. After cooling to room temperature, immerse them in water at the same temperature as room temperature. After soaking for 24 hours, take them out, wipe off the water on the surface of the samples, weigh them to obtain m2, and calculate the water absorption rate based on this; Water absorption rate (%) = (m2 - m1) / m1 × 100%; (2)Wear resistance: Use a Taber abrasion tester to conduct wear resistance tests; under a load of 500 g, use a CS-10 grinding wheel to rotate cyclically for 1000 times of friction; weigh the mass m3 before friction and the mass m4 after friction, and calculate the wear rate based on this; Wear rate (%) = (m3 - m4) / m3 × 100%; (3)Antioxidant performance: According to the experimental method of GB / T 16422.3-2022, use a UVA-340 lamp tube to irradiate for 168 h at 0.76 W / (m 2 ·nm) to conduct an artificial accelerated weathering test; after the aging test, test its flexural strength; The above test data results are shown in Table 1 below: Table 1 Result analysis: It can be seen from the data in Table 1 above that by comparing the examples and Comparative Examples 1-4, it can be seen that the modifier, polyurethane, compatibilizer, and modified filler all show obvious actual effects in the panel material and none of them can be missing; and the present invention precisely through the synergistic effect of the modifier, polyurethane, compatibilizer, and modified filler, a panel material with excellent comprehensive properties such as waterproof, wear-resistant, weather-resistant, and tough is prepared; in addition, the strength of the panel material can be enhanced by setting a fiber cloth in the panel material, so that it has a larger application space.

[0050] Finally, it should be noted that the above are only the preferred embodiments of the present invention and are not used to limit the present invention. Although the present invention has been described in detail with reference to the foregoing embodiments, for those skilled in the art, they can still modify the technical solutions recorded in the foregoing embodiments, or perform equivalent replacements for some of the technical features. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principle of the present invention shall be included within the protection scope of the present invention.

Claims

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

2. The waterproof and wear-resistant panel material according to claim 1, characterized in that: The preparation method of the modifier is: (1) Under nitrogen protection, aminopropyl-terminated polydimethylsiloxane, di-tert-butyl dicarbonate, triethylamine, and anhydrous ethanol are added to a reaction vessel, and after the temperature is adjusted to 0-20° C. in a stirring water bath, the reaction is refluxed for 6-24 hours to terminate the reaction. After the reaction system naturally returns to room temperature, the reaction solution is 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) adding lignin and 5-15 wt% sodium hydroxide aqueous solution into a reaction vessel, stirring and heating to 60-90°C, stirring and reacting at a constant temperature for 20-60 min, then adding γ-aminopropyltriethoxysilane into the reaction system, continuing to stir and react at a constant temperature for 1-6 h, terminating the reaction, and after the reaction system naturally returns to room temperature, adding 20 wt% hydrochloric acid aqueous solution thereto, adjusting the pH to 2-3, centrifuging, precipitating, separating and purifying, and obtaining amino lignin; (3) Under nitrogen protection, add pretreated aminopropyl-terminated polydimethylsiloxane, N,N'-dicarbonyldiimidazole and dichloromethane into a reaction vessel, stir and heat to 70-85°C, and stir and react at a constant temperature for 1-6 hours. Then add amino lignin to the reaction system, continue to stir and react at a constant temperature for 2-12 hours, terminate the reaction, and after the reaction system naturally returns to room temperature, add trifluoroacetic acid, stir and react at room temperature for 6-24 hours, and rotary evaporate to obtain a modifier.

3. The waterproof and wear-resistant panel material according to claim 2, characterized in that: The molar ratio of the aminopropyl-terminated polydimethylsiloxane, di-tert-butyl dicarbonate and triethylamine is 1:(0.4-0.6):(1-1.5); wherein the molecular weight of the aminopropyl-terminated polydimethylsiloxane is 400-1000; the mass ratio of the lignin and γ-aminopropyltriethoxysilane is 1:(0.05-0.1); The raw materials required for preparing the modifier include the following components: 4-6 parts of pretreated aminopropyl-terminated polydimethylsiloxane, 0.8-1.2 parts of N,N'-dicarbonyldiimidazole, 1.2-2.5 parts of amino lignin, 0.5-1 parts of trifluoroacetic acid, and 25 parts of dichloromethane, calculated by mass.

4. The waterproof and wear-resistant panel material according to claim 1, characterized in that: The preparation method of the compatibilizer is: (1) Add diisocyanate and stannous octoate into a reaction vessel, stir and heat to 50-80°C, and stir and mix at a constant temperature for 10-30 minutes; then add 2,3-dihydroxypropyl acrylate and hydroquinone into the reaction system, stir and react at a constant temperature for 1-3 hours; then add polyester diol into the reaction system, stir and react at a constant temperature for 1-6 hours, and cool down for use; (2) Add acetone and unsaturated monomer to (1), stir and mix evenly, then heat to 60-85°C, then drop diisopropylbenzene peroxide into the reaction system, stir and react at constant temperature for 2-12 hours, terminate the reaction, and wait until the reaction system naturally returns to room temperature to obtain a compatibilizer.

5. The waterproof and wear-resistant panel material according to claim 4, characterized in that: The raw materials required for preparing the compatibilizer include the following components: by weight, 5 parts of diisocyanate, 0.5-1.5 parts of 2,3-dihydroxypropyl acrylate, 1.5-2.5 parts of polyester diol, 0.05-0.1 parts of stannous octoate, 0.05-0.1 parts of hydroquinone, 4-8 parts of unsaturated monomers, 0.05-0.1 parts of dicumyl peroxide, and 20 parts of acetone; Among them, the diisocyanate includes a combination of one or more of toluene diisocyanate, isophorone diisocyanate, 4,4'-diphenylmethane diisocyanate, and hexamethylene diisocyanate; the polyester diol includes a combination of one or more of polyethylene adipate, polyethylene glycol oxalate, and polyethylene neopentyl glycol oxalate, and its molecular weight is 1000~2000; the unsaturated monomer includes a combination of one or more of acrylic acid, glycidyl acrylate, glycidyl methacrylate, acrylamide, and butyl acrylate.

6. The waterproof and wear-resistant panel material according to claim 1, characterized in that: The preparation method of the modified filler is: (1) Add γ-aminopropyltriethoxysilane, deionized water and anhydrous ethanol into a reaction container, stir and mix evenly, add acetic acid to adjust the pH to 4.5-6, and continue to stir and mix for 10-20 minutes to obtain a silane hydrolyzate; disperse the filler in anhydrous ethanol to obtain a filler dispersion; (2) After the filler dispersion is heated to 50-60°C, the silane hydrolyzate is slowly added thereto. After the addition is completed, stirring is continued for 6-12 hours. After filtering, washing and drying, a modified filler is obtained.

7. The waterproof and wear-resistant panel material according to claim 6, characterized in that: The mass ratio of the filler to γ-aminopropyltriethoxysilane is 1:(0.05-0.1); the mass ratio of the γ-aminopropyltriethoxysilane, deionized water and anhydrous ethanol is 1:1:10; and the filler is a mixed filler composed of nanoparticles and nanofibers.

8. The waterproof and wear-resistant panel material according to claim 1, characterized in that: 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.

9. The method for manufacturing a waterproof and wear-resistant panel material according to any one of claims 1 to 8, characterized in that: The specific process of the manufacturing method is as follows: (1) First, add epoxy resin, acetone and modifier into the mixer and stir and mix for 1 to 6 hours; then add polyurethane and compatibilizer into the mixer and stir and mix for 1 to 3 hours; then add modified filler into the mixer and stir and mix for 30 to 60 minutes; then add curing agent A, curing agent B and defoaming agent into the mixer and stir and mix for 1 to 3 hours to finally obtain a mixture; (2) The mixed material is injected into a mold and dried and cured at 90-110°C for 1-3 hours to obtain a panel material.

10. The method for manufacturing a waterproof and wear-resistant panel material according to claim 9, characterized in that: Fiber cloth can also be arranged in the panel material; the arrangement method is: after the fiber cloth of corresponding size is horizontally fixed in the middle of the mold, the mixture is injected into the mold, dried, cured and formed, and the panel material provided with the fiber cloth is obtained.

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