Wear-resistant ultraviolet aging-resistant glass fiber silicon core composite board and preparation method thereof

Abstract

This invention relates to the field of composite panels and discloses a wear-resistant and UV-resistant fiberglass-silicon core composite panel and its preparation method. The composite panel comprises melamine-faced paper, fiberglass mat, and calcium silicate board impregnated with adhesive. The adhesive includes deionized water, melamine-formaldehyde resin, modified aluminum hydroxide, organosilicon flexibility agent, and coupling agent. The modified aluminum hydroxide is prepared by reacting a functional modifier, N,N'-bis-(2,2,6,6-tetramethyl-4-piperidinyl)-1,6-hexanediamine with benzophenone derivatives and pyridylthiazole derivatives, with 3-chloropropyltriethoxysilane and grafted onto aluminum hydroxide. The organosilicon flexibility agent is prepared by modifying phenyl hydrogen-containing silicone oil with allyl polyoxyethylene ether and glycidyl methacrylate. This invention achieves an integrated structure of the panel, maintaining a surface free of blistering and cracking under complex environmental conditions, with the overall material intact and without delamination, and possessing good antibacterial, fire-resistant, and UV-resistant properties.

Description

Technical Field

[0001] This invention belongs to the field of composite board technology, specifically relating to a wear-resistant and UV-resistant glass fiber silicon core composite board and its preparation method. Background Technology

[0002] There are two main methods for manufacturing fiberglass-silicon core composite panels: ① Low-pressure bonding method: Fiberglass mat and calcium silicate board are bonded together using adhesive. The disadvantage is insufficient composite strength, easy delamination, and cracking and delamination under large temperature differences; ② High-temperature and high-pressure integrated molding composite method: Fiberglass mat and calcium silicate board are bonded together using high temperature and high pressure. However, it is prone to cracking and delamination under large temperature differences and dry air, making it unsuitable for use in northern China, especially the northwest. Under current material and technological conditions, the commonly used high-temperature and high-pressure integrated molding composite method can only achieve surface bonding and cannot achieve material integration. Furthermore, the panels on the market will crack and delaminate under large temperature differences, dry air, and water aging. In addition, existing fiberglass-silicon core composite panels are insufficient in terms of antibacterial properties, fire resistance, and outdoor UV aging resistance, and cannot adequately meet user needs. Summary of the Invention

[0003] To address the shortcomings mentioned in the background art, the present invention aims to provide a wear-resistant and UV-resistant fiberglass-silicon core composite board and its preparation method, which achieves an integrated structure of the board. Under complex environmental conditions (such as large temperature difference, dry air, and water boiling aging), the surface remains free from blistering and cracking, and the overall material is intact without delamination. At the same time, it has good antibacterial properties, fire resistance, and UV aging resistance.

[0004] The objective of this invention can be achieved through the following technical solutions:

[0005] A wear-resistant and UV-resistant fiberglass-silicon core composite board comprises, in sequence, melamine face paper, fiberglass mat, calcium silicate board, fiberglass mat, and melamine face paper. The melamine face paper, fiberglass mat, and calcium silicate board are all prepared by impregnation with an adhesive followed by drying. The adhesive comprises the following components by weight: 15-22 parts deionized water, 30-42 parts melamine-formaldehyde resin, 10-25 parts modified aluminum hydroxide, 1.5-3 parts organosilicon flexibility agent, and 0.3-0.5 parts coupling agent.

[0006] The modified aluminum hydroxide is prepared by grafting a functional silane coupling agent, which is prepared by a nucleophilic substitution reaction between a functional modifier and 3-chloropropyltriethoxysilane, onto the surface of aluminum hydroxide; the functional modifier is prepared by simultaneously reacting N,N'-bis-(2,2,6,6-tetramethyl-4-piperidinyl)-1,6-hexanediamine with benzophenone derivatives and pyridylthiazole derivatives via a Michael addition reaction.

[0007] The benzophenone derivative was prepared by a nucleophilic substitution reaction between 2,4-dihydroxybenzophenone and acryloyl chloride; the pyridylthiazole derivative was prepared by a nucleophilic substitution reaction between 2-mercapto-4-(4-pyridyl)thiazole and methacryloyl chloride.

[0008] The organosilicon flexibility agent is prepared by modifying phenyl hydrogen-containing silicone oil through a hydrosilylation reaction using allyl polyoxyethylene ether and glycidyl methacrylate as raw materials; the coupling agent is prepared by a nucleophilic addition reaction between polyhexamethylene guanidine hydrochloride and propyltriethoxysilane isocyanate.

[0009] Preferably, the method for preparing the modified aluminum hydroxide includes the following steps:

[0010] A. Add functional modifier and N,N-dimethylformamide to the reactor, stir and mix, then add 3-chloropropyltriethoxysilane and triethylamine, and stir and react at 70~80℃ for 4~6h. After the reaction is completed, remove triethylamine hydrochloride by vacuum filtration and remove organic solvent by rotary evaporation to prepare functional silane coupling agent.

[0011] B. Disperse aluminum hydroxide in ethanol and deionized water using ultrasound, then add a functional silane coupling agent, and stir the mixture at 70-85°C for 4-6 hours. After the reaction is complete, filter, wash, and dry the mixture to obtain modified aluminum hydroxide.

[0012] Preferably, the preparation method of the functional modifier in step A includes the following steps:

[0013] A1. Acryloyl chloride and dichloromethane were added to the reactor. A dichloromethane solution containing 2,4-dihydroxybenzophenone and triethylamine was slowly added dropwise under ice-water bath conditions. After reacting at room temperature for 2-3 hours, the mixture was washed with water and separated. The organic phase was concentrated by rotary evaporation at 50°C. Then methanol was added and the organic phase was concentrated by rotary evaporation at 50°C again. After cooling and standing, crystals precipitated. After filtration and drying, benzophenone derivatives were prepared.

[0014] A2. Add 2-mercapto-4-(4-pyridyl)thiazole, triethylamine and tetrahydrofuran to the reactor, stir to dissolve, and then slowly add methacryloyl chloride under ice-water bath conditions. Stir the reaction for 3-4 hours. After the reaction is complete, extract with ethyl acetate, collect the organic phase, wash with water, dry, remove the organic solvent by rotary evaporation, and separate by column chromatography to prepare the pyridylthiazole derivative.

[0015] A3. Add benzophenone derivative, pyridylthiazole derivative and dichloromethane to the reactor. Under ice-water bath conditions, slowly add a dichloromethane solution containing N,N'-bis-(2,2,6,6-tetramethyl-4-piperidinyl)-1,6-hexanediamine while stirring continuously. After the addition is complete, raise the temperature to room temperature and react for 5-6 hours. After the reaction is complete, wash with water, separate the liquid, and remove the organic solvent by rotary evaporation to prepare the functional modifier.

[0016] Preferably, in step A1, the molar ratio of 2,4-dihydroxybenzophenone to acryloyl chloride is 1:1 to 1.2; and in step A2, the molar ratio of 2-mercapto-4-(4-pyridyl)thiazole to methacryloyl chloride is 1:1 to 1.2.

[0017] Preferably, in step A3, the molar ratio of benzophenone derivative, pyridylthiazole derivative and N,N'-bis-(2,2,6,6-tetramethyl-4-piperidinyl)-1,6-hexanediamine is 1~1.1:1~1.1:1.

[0018] Preferably, the method for preparing the organosilicon flexible agent includes the following steps:

[0019] Phenyl hydrosilicone oil and isopropanol were added to the reactor, and the temperature was slowly raised to 75-80°C. Chloroplatinic acid was added as a catalyst for activation. When the temperature reached 100-110°C, allyl polyoxyethylene ether and glycidyl methacrylate were added dropwise using a dropping funnel. The mixture was stirred and reacted for 5-6 hours. After the reaction was completed, the isopropanol solvent was removed by vacuum distillation at 60°C. The product was then dissolved in dichloromethane and poured into a separatory funnel. The pH was adjusted to 6-7 with sodium hydroxide solution. After standing and separating the layers, the lower layer was taken and removed by vacuum distillation at 60°C and 0.09 MPa to remove dichloromethane and unreacted raw materials, thus preparing the organosilicon flexible agent.

[0020] Preferably, the preparation method of the coupling agent includes the following steps: adding polyhexamethylene guanidine hydrochloride and toluene to a reactor, then slowly adding propyltriethoxysilane isocyanate dropwise, controlling the addition to be completed in 2-3 hours, then raising the temperature to 70-75°C and holding it at that temperature for 2-3 hours, and finally distilling under reduced pressure after the reaction is completed to obtain the coupling agent.

[0021] Preferably, the preparation method of the impregnation adhesive includes the following steps: weighing each raw material according to the weight parts, adding deionized water, melamine-formaldehyde resin, modified aluminum hydroxide, organosilicon flexible agent and coupling agent into a reaction vessel, heating to 90~95℃ and stirring for 0.5~1h, cooling and discharging to prepare the impregnation adhesive.

[0022] Preferably, the melamine paper impregnation adhesive contains additional abrasion-resistant powder, which is aluminum oxide, and the amount of abrasion-resistant powder added accounts for 5% of the weight of the impregnation adhesive.

[0023] The preparation method of the wear-resistant and UV-resistant glass fiber-silicon core composite board as described above includes the following steps:

[0024] S1. Sand the calcium silicate board with a 120-mesh sander belt, fix the thickness, level it, and remove dust before use.

[0025] S2. Soak the melamine face paper, fiberglass mat, and calcium silicate board in the impregnation glue and then dry them for later use.

[0026] S3. Following the order of melamine face paper, fiberglass mat, calcium silicate board, fiberglass mat, and melamine face paper, the materials soaked in the adhesive and dried are placed into a high-temperature and high-pressure equipment. When the temperature rises to 135~140℃, it is kept at a constant temperature for 25~40 minutes. Then, the temperature is lowered to below 50℃, the pressure is released, and the board is removed to prepare a wear-resistant and UV-resistant fiberglass silicon core composite board.

[0027] The beneficial effects of this invention are:

[0028] This invention utilizes a nucleophilic substitution reaction between 2,4-dihydroxybenzophenone and acryloyl chloride to prepare benzophenone derivatives. Simultaneously, it utilizes a nucleophilic substitution reaction between 2-mercapto-4-(4-pyridyl)thiazole and methacryloyl chloride to prepare pyridylthiazole derivatives. Then, the -NH groups at both ends of the -HN-(CH2)6-NH- group in N,N'-bis-(2,2,6,6-tetramethyl-4-piperidinyl)-1,6-hexanediamine undergo Michael addition reactions with the double bond groups introduced in the benzophenone and pyridylthiazole derivatives, respectively, to prepare functional modifiers. These functional modifiers construct benzophenone and hindered amine groups... Within the same molecule, the synergistic effect between the two components results in better photostability. Simultaneously, the introduction of a pyridylthiazole derivative with antibacterial activity imparts excellent antibacterial properties to the material. Furthermore, a functional silane coupling agent is prepared by nucleophilic substitution of the remaining ungrafted hydroxyl groups in the functional modifier with 3-chloropropyltriethoxysilane. This functional silane coupling agent is then grafted onto the surface of the inorganic flame retardant aluminum hydroxide using a dehydration condensation reaction. This improves the compatibility of aluminum hydroxide with the matrix material, allowing the flame retardant properties of the inorganic flame retardant to be fully utilized. Moreover, the strong chemical bonding enhances the material's long-term UV aging resistance and antibacterial properties.

[0029] This invention utilizes allyl polyoxyethylene ether and glycidyl methacrylate as raw materials to prepare an organosilicon flexibility agent by co-modifying phenyl hydrogen-containing silicone oil through a hydrosilylation reaction. The organosilicon flexibility agent introduces hydrophilic and flexible long polyether side chains into its molecular chain, greatly improving the material's flexibility and low-temperature performance, and imparting wetting and spreading capabilities. Simultaneously, the introduced epoxy groups provide the ability to chemically bond with substrates (such as hydroxyl groups in melamine paper, fiberglass mat, and calcium silicate board), significantly improving adhesion and durability, and solving the problem of… To address the issues of easy migration and poor washability of organosilicon, this invention utilizes a nucleophilic addition reaction between polyhexamethylene guanidine hydrochloride and propyltriethoxysilane isocyanate to prepare a coupling agent. Polyhexamethylene guanidine hydrochloride possesses excellent antibacterial and environmentally friendly properties. Furthermore, this coupling agent is applied to reinforce the connection between melamine paper, fiberglass mat, and calcium silicate board. The polyhexamethylene guanidine segments linked by stable urea bonds can persistently act on the material interface and surface, thereby improving the long-lasting antibacterial and antifungal properties of the matrix material. Detailed Implementation

[0030] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0031] Example 1: A method for preparing modified aluminum hydroxide includes the following steps:

[0032] A. Add 9.2g of functional modifier and 100mL of N,N-dimethylformamide to the reactor, stir and mix, then add 2.5g of 3-chloropropyltriethoxysilane and 1.1g of triethylamine, and stir and react at 75℃ for 5h. After the reaction is completed, remove the triethylamine hydrochloride by vacuum filtration and remove the organic solvent by rotary evaporation to prepare the functional silane coupling agent.

[0033] B. Take 5g of aluminum hydroxide and ultrasonically disperse it in 90mL of ethanol and 20mL of deionized water. Then add 3.7g of functional silane coupling agent and stir the mixture at 80℃ for 5h. After the reaction is completed, filter, wash and dry to prepare modified aluminum hydroxide.

[0034] The preparation method of the functional modifier in step A includes the following steps:

[0035] A1. Add 9.9g of acryloyl chloride and 100mL of dichloromethane to a reactor. Under ice-water bath conditions, slowly add 50mL of dichloromethane solution containing 21.4g of 2,4-dihydroxybenzophenone and 11.1g of triethylamine. After reacting at room temperature for 2 hours, wash with water and separate the liquids. The organic phase is concentrated to 50mL by rotary evaporation at 50℃. Then, add 50mL of methanol and concentrate the organic phase to 50mL by rotary evaporation at 50℃ again. After cooling and standing, crystals precipitate. After filtration and drying, benzophenone derivative is prepared.

[0036] A2. 7.8 g of 2-mercapto-4-(4-pyridyl)thiazole, 4.8 g of triethylamine and 50 mL of tetrahydrofuran were added to the reactor. After stirring and dissolving, 5 g of methacryloyl chloride was slowly added dropwise under ice-water bath conditions. The reaction was stirred for 3 h. After the reaction was completed, the mixture was extracted with ethyl acetate. The organic phase was collected, washed with water, dried, and the organic solvent was removed by rotary evaporation. The mixture was then separated by column chromatography using petroleum ether / ethyl acetate (volume ratio 12:1) as the eluent to prepare the pyridylthiazole derivative.

[0037] A3. Add 2.7g of benzophenone derivative, 2.6g of pyridylthiazole derivative and 50mL of dichloromethane to the reactor. Under ice-water bath conditions, slowly add 20mL of dichloromethane solution containing 3.9g of N,N'-bis-(2,2,6,6-tetramethyl-4-piperidinyl)-1,6-hexanediamine while stirring continuously. After the addition is complete, raise the temperature to room temperature and react for 6 hours. After the reaction is complete, wash with water, separate the contents, and remove the organic solvent by rotary evaporation to prepare the functional modifier.

[0038] Example 2: A method for preparing an organosilicon flexible agent includes the following steps:

[0039] Add 29.7 g of phenyl hydrogen-containing silicone oil (0.5% hydrogen content, 20% benzene content) and 50 mL of isopropanol to the reactor, slowly raise the temperature to 80 °C, and add 1 mL of chloroplatinic acid catalyst (0.0046 mol·L⁻¹). -1 Activation was performed by adding 32.6 g of allyl polyoxyethylene ether-400 and 11.2 g of glycidyl methacrylate dropwise using a dropping funnel when the temperature reached 110°C. The mixture was stirred for 5.5 h. After the reaction was completed, the isopropanol solvent was removed by vacuum distillation at 60°C. The product was then dissolved in dichloromethane and poured into a separatory funnel. The pH was adjusted to 7 with sodium hydroxide solution. After standing and separating the layers, the lower layer was collected and removed by vacuum distillation at 60°C and 0.09 MPa to remove dichloromethane and unreacted raw materials, thus preparing the organosilicon flexible agent.

[0040] Example 3 A method for preparing a coupling agent includes the following steps:

[0041] 10g of polyhexamethylene guanidine hydrochloride (Mn=1000) and 50mL of toluene were added to the reactor, and then 5g of propyltriethoxysilane isocyanate was slowly added dropwise over 2.5h. The temperature was then raised to 75℃ and held for 3h. After the reaction was completed, the coupling agent was obtained by vacuum distillation.

[0042] Example 4. An impregnation adhesive comprises the following components by weight: 16 parts deionized water, 33 parts melamine-formaldehyde resin, 11 parts modified aluminum hydroxide prepared in Example 1, 1.6 parts organosilicon flexible agent prepared in Example 2, and 0.3 parts coupling agent prepared in Example 3.

[0043] The preparation method of the above-mentioned impregnation adhesive includes the following steps: weigh each raw material according to the weight parts, add deionized water, melamine formaldehyde resin, modified aluminum hydroxide, organosilicon flexible agent and coupling agent into the reaction vessel, heat to 95℃ and stir for 0.5h, cool down and discharge the material to prepare the impregnation adhesive.

[0044] A method for preparing a wear-resistant and UV-resistant glass fiber-silicon core composite board includes the following steps:

[0045] S1. Sand the calcium silicate board with a 120-mesh sander belt, fix the thickness, level it, and remove dust before use.

[0046] S2. Melamine face paper, fiberglass mat, and calcium silicate board are soaked in impregnation glue and then dried for later use. The melamine face paper impregnation glue contains an additional 5% abrasion-resistant aluminum oxide powder by weight of the impregnation glue.

[0047] S3. Following the order of melamine face paper, fiberglass mat, calcium silicate board, fiberglass mat, and melamine face paper, the materials soaked in the adhesive and dried are placed in a high-temperature and high-pressure equipment. When the temperature rises to 138°C, it is kept at a constant temperature for 30 minutes. Then, the temperature is lowered to below 50°C, the pressure is released, and the board is removed to prepare a wear-resistant and UV-resistant fiberglass silicon core composite board.

[0048] Example 5 An impregnation adhesive comprises the following components by weight: 17 parts deionized water, 38 parts melamine-formaldehyde resin, 17 parts modified aluminum hydroxide prepared in Example 1, 2.2 parts organosilicon flexible agent prepared in Example 2, and 0.4 parts coupling agent prepared in Example 3.

[0049] The preparation method of the above-mentioned impregnating adhesive is the same as that in Example 4.

[0050] The preparation method of a wear-resistant and UV-resistant glass fiber silicon core composite board is the same as in Example 4.

[0051] Example 6 An impregnation adhesive comprises the following components by weight: 20 parts deionized water, 40 parts melamine-formaldehyde resin, 22 parts modified aluminum hydroxide prepared in Example 1, 2.8 parts organosilicon flexible agent prepared in Example 2, and 0.5 parts coupling agent prepared in Example 3.

[0052] The preparation method of the above-mentioned impregnating adhesive is the same as that in Example 4.

[0053] The preparation method of a wear-resistant and UV-resistant glass fiber silicon core composite board is the same as in Example 4.

[0054] Comparative Example 1: An impregnation adhesive comprises the following components in parts by weight: 20 parts deionized water, 40 parts melamine-formaldehyde resin, 22 parts aluminum hydroxide, 2.8 parts of the organosilicon flexible agent prepared in Example 2, and 0.5 parts of the coupling agent prepared in Example 3.

[0055] The preparation method of the above-mentioned impregnating adhesive is the same as that in Example 4.

[0056] The preparation method of a wear-resistant and UV-resistant glass fiber silicon core composite board is the same as in Example 4.

[0057] Comparative Example 2: An impregnation adhesive comprises the following components in parts by weight: 20 parts deionized water, 40 parts melamine-formaldehyde resin, 22 parts modified aluminum hydroxide prepared in Example 1, 2.8 parts phenyl hydrogen-containing silicone oil (0.5% hydrogen content, 20% benzene content), and 0.5 parts coupling agent prepared in Example 3.

[0058] The preparation method of the above-mentioned impregnating adhesive is the same as that in Example 4.

[0059] The preparation method of a wear-resistant and UV-resistant glass fiber silicon core composite board is the same as in Example 4.

[0060] Comparative Example 3: An impregnation adhesive comprises the following components in parts by weight: 20 parts deionized water, 40 parts melamine-formaldehyde resin, 22 parts modified aluminum hydroxide prepared in Example 1, 2.8 parts organosilicon flexible agent prepared in Example 2, and 0.5 parts polyhexamethylene guanidine hydrochloride.

[0061] The preparation method of the above-mentioned impregnating adhesive is the same as that in Example 4.

[0062] The preparation method of a wear-resistant and UV-resistant glass fiber silicon core composite board is the same as in Example 4.

[0063] Performance testing

[0064] The performance of the fiberglass-silicon core composite boards prepared in Examples 4-6 and Comparative Examples 1-3 was tested:

[0065] (1) Test of cold and heat resistance: The fiberglass silicon core composite board was placed in a freezer at -30~-35℃ for 10 hours, then taken out and placed at room temperature for 2 hours, then placed in an oven at 80~85℃ for 10 hours, then taken out and placed at room temperature for 2 hours. This is one cycle. After 10 cold and heat cycles, the board was observed to see if there was any blistering, cracking or delamination on the surface. The data results are shown in Table 1.

[0066] (2) Dry heat resistance test: The fiberglass silicon core composite board was placed in an oven at 80~85℃ for 120h. The results were observed to see whether the board exhibited surface blistering, cracking, or delamination. The data results are shown in Table 1.

[0067] (3) Water resistance test: The fiberglass silicon core composite board was boiled in boiling water at 100℃ for 6 hours. The results were observed to see if the board surface blistering or delamination occurred. The data results are shown in Table 1.

[0068] Table 1. Results of environmental change resistance tests on samples

[0069]

[0070] As can be seen from the results in Table 1, the plates prepared in Examples 4-6 of this invention achieve an integrated structure, maintaining a surface free of blistering and cracking under complex environmental conditions (such as large temperature differences, dry air, and boiling aging), and the overall material remains intact without delamination. In Comparative Example 2, the organosilicon flexible agent was replaced with an equal amount of phenyl hydrogen silicone oil. The plate exhibited blistering, delamination, and cracking after testing for cold and heat cycling, dry heat, and boiling performance, indicating that the addition of organosilicon flexible agent is beneficial to improving the plate's resistance to cold and heat cycling, dry heat, and boiling.

[0071] (4) Antibacterial performance test: Gram-negative bacteria (Escherichia coli) and Gram-positive bacteria (Staphylococcus aureus) were selected as test objects according to GB / T 31402-2023. The antibacterial performance of the samples was evaluated by the inhibition rate. The data results are shown in Table 2.

[0072] (5) Anti-ultraviolet aging performance test: The sample was placed under an ultraviolet lamp with a distance of 0.8~1.0m, a power of 30W and a wavelength of 253nm for 7 days and the antibacterial rate was tested according to GB / T 31402-2023. The data results are shown in Table 2.

[0073] Table 2. Test results of antibacterial properties and UV aging resistance of the samples.

[0074]

[0075] As can be seen from the data in Table 2, the plates prepared in Examples 4-6 of this invention possess excellent antibacterial and UV-resistant properties. In Comparative Example 1, no modification treatment was performed on the aluminum hydroxide. The measured inhibition rates of *E. coli* and *Staphylococcus aureus* under normal conditions and after UV aging were lower than those in Examples 4-6. This is because the bonding of pyridylthiazole derivatives with antibacterial activity to the surface of aluminum hydroxide imparts good antibacterial properties to the material. Simultaneously, the introduction of benzophenone and hindered amine groups imparts good UV-resistant properties. In Comparative Example 3, the coupling agent was replaced with an equal amount of polyhexamethylene guanidine hydrochloride. The measured inhibition rates of *E. coli* and *Staphylococcus aureus* after UV aging were lower than those in Examples 4-6. This is because the coupling agent prepared by grafting propyltriethoxysilane isocyanate with polyhexamethylene guanidine hydrochloride can persistently act on the material interface and surface, exerting a long-lasting antibacterial effect.

[0076] (6) Fire resistance performance test: The test was conducted in accordance with GB / T 14402-2007, GB / T 20284-2006 and GB / T 20285-2006 standards. The sample size was 2440mm×1220mm×8.0mm. The data results are shown in Table 3.

[0077] Table 2. Test results of fire resistance of samples

[0078]

[0079]

[0080] As can be seen from the data results in Table 3, the boards prepared in Examples 4-6 and Comparative Examples 2-3 of the present invention meet the requirements of the A2-s1, d0, t0 fire performance level. According to GB 8624-2012, the fire performance of the product reaches the non-combustible A (A2-s1, d0, t0) level. According to GB 20286-2006, the fire performance of the product meets the requirements of flame-retardant building products for public places. Among them, the fire resistance of Comparative Example 1 was slightly worse than that of Examples 4-6. The possible reason is that aluminum hydroxide has poor compatibility with the matrix, which leads to a decrease in fire resistance.

[0081] The foregoing has shown and described the basic principles, main features, and advantages of the present invention. Those skilled in the art should understand that the present invention is not limited to the above embodiments. The embodiments and descriptions in the specification are merely illustrative of the principles of the invention. Various changes and modifications can be made to the invention without departing from its spirit and scope, and all such changes and modifications fall within the scope of the claimed invention.

Claims

1. A wear-resistant, ultraviolet-aging-resistant glass fiber-silicon core composite board, characterized in that, The melamine face paper, the glass fiber felt and the calcium silicate board are all prepared by soaking and drying after being soaked by the impregnation glue, and the impregnation glue comprises the following components in parts by weight: deionized water 15-22 parts, melamine formaldehyde resin 30-42 parts, modified aluminum hydroxide 10-25 parts, organic silicon flexible agent 1.5-3 parts, and coupling agent 0.3-0.5 parts. The modified aluminum hydroxide is prepared by grafting a functional silane coupling agent on the surface of aluminum hydroxide through nucleophilic substitution reaction of a functional modifier and 3-chloropropyl triethoxysilane; the functional modifier is prepared by Michael addition reaction of N,N'-bis-(2,2,6,6-tetramethyl-4-piperidyl)-1,6-hexanediamine with benzophenone derivative and pyridyl thiazole derivative at the same time; The benzophenone derivative is prepared by nucleophilic substitution reaction of 2,4-dihydroxybenzophenone and acryloyl chloride; and the pyridyl thiazole derivative is prepared by nucleophilic substitution reaction of 2-mercapto-4-(4-pyridyl)thiazole and methacryloyl chloride; The organic silicon flexible agent is prepared by modifying phenyl hydrogen-containing silicone oil through silicon hydrogen addition reaction with allyl polyoxyethylene ether and glycidyl methacrylate as raw materials; and the coupling agent is prepared by nucleophilic addition reaction of polyhexamethylene guanidine hydrochloride and isocyanic acid propyl triethoxysilane.

2. The wear resistant, ultraviolet aging resistant fiberglass-silica core composite board of claim 1, wherein, The preparation method of the modified aluminum hydroxide comprises the following steps: A, functional modifier and N,N-dimethylformamide are added to a reactor, stirred and mixed, then 3-chloropropyl triethoxysilane and triethylamine are added, stirred and reacted at 70-80 DEG C for 4-6 h, then triethylamine hydrochloride is removed by reduced pressure filtration and the organic solvent is removed by rotary evaporation to prepare a functional silane coupling agent; B, the aluminum hydroxide is ultrasonically dispersed in ethanol and deionized water, then the functional silane coupling agent is added, stirred and reacted at 70-85 DEG C for 4-6 h, then the reaction is completed by filtration, washing and drying to prepare modified aluminum hydroxide.

3. The wear resistant, ultraviolet aging resistant fiberglass-silica core composite board of claim 2, wherein, The preparation method of the functional modifier in step A comprises the following steps: A1, acryloyl chloride and dichloromethane are added to a reactor, then a dichloromethane solution containing 2,4-dihydroxybenzophenone and triethylamine is slowly added dropwise under ice water bath condition, reacted at room temperature for 2-3 h, then water washed, separated, the organic phase is concentrated by rotary evaporation at 50 DEG C, then methanol is added and the organic phase is concentrated by rotary evaporation at 50 DEG C again, then crystals are precipitated after cooling and standing, filtered and dried to prepare a benzophenone derivative; A2, 2-mercapto-4-(4-pyridyl)thiazole, triethylamine and tetrahydrofuran are added to a reactor, stirred and dissolved, then methyl acryloyl chloride is slowly added dropwise under ice water bath condition, stirred and reacted for 3-4 h, then extracted with ethyl acetate, water washed, dried, the organic solvent is removed by rotary evaporation, and column chromatography separation is performed to prepare a pyridyl thiazole derivative; A3, the benzophenone derivative, the pyridyl thiazole derivative and dichloromethane are added into the reactor, the dichloromethane solution containing N,N'-bis-(2,2,6,6-tetramethyl-4-piperidyl)-1,6-hexanediamine is slowly added dropwise under ice water bath condition, and stirring is continuously carried out, after the dropwise addition is completed, the reaction is carried out at room temperature for 5-6 h, after the reaction is completed, water washing, liquid separation, and removal of the organic solvent by rotary evaporation are carried out, and the functional modifier is prepared.

4. The wear resistant, ultraviolet aging resistant fiberglass-silica core composite board of claim 1, wherein, The molar ratio of the 2,4-dihydroxybenzophenone and the acryloyl chloride in the step A1 is 1:1-1.2; the molar ratio of the 2-mercapto-4-(4-pyridyl)thiazole and the methacryloyl chloride in the step A2 is 1:1-1.

2.

5. The wear resistant, ultraviolet aging resistant fiberglass-silica core composite board of claim 1, wherein, The molar ratio of the benzophenone derivative, the pyridyl thiazole derivative and N,N'-bis-(2,2,6,6-tetramethyl-4-piperidyl)-1,6-hexanediamine in the step A3 is 1-1.1:1-1.1:

1.

6. The wear resistant ultraviolet aging resistant glass fiber silicon core composite board according to claim 1, characterized in that, The preparation method of the silicone flexible agent comprises the following steps: The phenyl hydrogen-containing silicone oil and isopropyl alcohol are added into the reactor, the temperature is slowly increased to 75-80 DEG C, the catalyst chloroplatinic acid is added for activation, when the temperature is increased to 100-110 DEG C, the allyl polyoxyethylene ether and the glycidyl methacrylate are added dropwise through a dropping funnel, the reaction is carried out under stirring for 5-6 h, after the reaction is completed, the isopropyl alcohol solvent is removed by distillation under reduced pressure at 60 DEG C, then the product is dissolved in dichloromethane, the pH is adjusted to 6-7 by using a sodium hydroxide solution, after the materials are separated by standing, the lower layer liquid is taken out, the dichloromethane and the unreacted raw material are removed by distillation under reduced pressure at 60 DEG C and 0.09 MPa, and the silicone flexible agent is prepared.

7. The wear resistant ultraviolet aging resistant glass fiber silicon core composite board according to claim 1, characterized in that, The preparation method of the coupling assistant comprises the following steps: the polyhexamethylene guanidine hydrochloride and toluene are added into the reactor, then the propyl triethoxysilane isocyanate is slowly added dropwise, the dropwise addition is controlled to be completed in 2-3 h, then the temperature is increased to 70-75 DEG C and kept for 2-3 h, after the reaction is completed, the coupling assistant is obtained by distillation under reduced pressure.

8. The wear resistant, ultraviolet aging resistant fiberglass-silica core composite board of claim 1, wherein, The preparation method of the impregnation adhesive comprises the following steps: the raw materials are weighed according to the weight parts, the deionized water, the melamine formaldehyde resin, the modified aluminum hydroxide, the silicone flexible agent and the coupling assistant are put into the reactor, the temperature is increased to 90-95 DEG C, and stirring is carried out for 0.5-1 h, then the temperature is decreased, and the impregnation adhesive is prepared.

9. The wear resistant ultraviolet aging resistant glass fiber silicon core composite board according to claim 1, characterized in that, The melamine facing paper impregnation adhesive additionally contains wear-resistant powder, the wear-resistant powder is aluminum oxide, and the addition amount of the wear-resistant powder accounts for 5% of the weight of the impregnation adhesive.

10. A method for preparing the wear-resistant anti-ultraviolet-aging glass fiber silicon core composite board according to any one of claims 1-9, characterized in that, The preparation method comprises the following steps: S1, the calcium silicate board is sanded, thicknessed, leveled and dusted by using a 120-mesh abrasive belt, and is reserved; S2, the melamine facing paper, the glass fiber mat and the calcium silicate board are respectively soaked in the impregnation adhesive and dried, and are reserved; S3, the materials soaked in the impregnation adhesive and dried are arranged in the order of melamine facing paper, glass fiber mat, calcium silicate board, glass fiber mat and melamine facing paper, and are put into a high-temperature and high-pressure equipment, the temperature is increased to 135-140 DEG C, and is kept constant for 25-40 min, then the temperature is decreased to below 50 DEG C, the pressure is released, and the wear-resistant and ultraviolet aging-resistant glass fiber and silicon core composite board is prepared.

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