High-hardness impact-resistant alloy modified transparent acrylic material as well as preparation method and application thereof

Abstract

The invention discloses a high-hardness impact-resistant alloy modified transparent acrylic material as well as a preparation method and application thereof, belongs to the technical field of acrylic material processing, and aims at solving the technical problem that the transparency, impact resistance and damp-heat aging resistance of an acrylic material in the prior art need to be further improved. The glass fiber reinforced plastic specifically comprises the following components in parts by weight: 75-85 parts of mixed dry powder, 15-20 parts of polysiloxane coated glass fiber and 1 part of additive. According to the invention, the glass fiber is subjected to coating treatment, and the prepared polysiloxane coated glass fiber is matched with PC-OH and PMMA-OH, so that high transparency, high hardness and high impact toughness of a glass fiber reinforcing system are enhanced, and meanwhile, the performance retention rate of the material under damp-heat aging conditions is increased; and therefore, the decorative film shows good decorative and visual effects in products such as kitchen ware and knife handles.

Description

Technical Field

[0001] This invention relates to the field of acrylic material processing technology, specifically to high-hardness, impact-resistant alloy-modified transparent acrylic materials, their preparation methods, and applications. Background Technology

[0002] Polymethyl methacrylate (PMMA), commonly known as acrylic material, is one of the most transparent general-purpose plastics. It has advantages such as high light transmittance, beautiful appearance, and easy processing and molding. It is widely used in optical devices, architectural decoration, transparent automotive parts, and high-end daily consumer goods. Especially in products such as kitchenware and knife handles, transparent acrylic can meet personalized design needs due to its good decorative and visual effects. It is also easy to clean and has a bright texture, so its application prospects are broad.

[0003] Currently, acrylic materials have a relatively rigid molecular chain structure, but lack toughness, making them brittle and prone to cracking. They also have low impact strength and are prone to stress cracking under external impact or stress concentration conditions. In addition, acrylic materials have limited heat resistance and resistance to humid heat aging. In high temperature and high humidity environments, they are prone to problems such as mechanical property decay, decreased light transmittance, and microcrack propagation, which also limits their promotion in high-strength and long-life application scenarios. To improve the overall performance of acrylic materials, an alloy system can be formed by introducing engineering plastics such as polycarbonate (PC), which can improve the toughness of the material to a certain extent. By adding high-modulus reinforcing phases such as glass fiber, the hardness and rigidity of the material can be significantly improved. However, the interfacial compatibility between glass fiber and transparent polymer matrix is ​​poor, which easily leads to interfacial pores or debonding defects. This not only reduces the reinforcing effect but also generates light scattering centers, thereby significantly reducing the light transmittance of the material. At the same time, under impact load, failure modes such as interfacial debonding and fiber pull-out are common, making it difficult for the material to simultaneously achieve high transparency and high impact resistance.

[0004] To address this technical deficiency, a solution is proposed. Summary of the Invention

[0005] The purpose of this invention is to provide a high-hardness, impact-resistant alloy-modified transparent acrylic material, its preparation method, and its application, in order to solve the technical problem that the transparency, impact resistance, and resistance to damp heat aging of acrylic materials in the prior art need to be further improved.

[0006] The objective of this invention can be achieved through the following technical solution: a high-hardness, impact-resistant alloy-modified transparent acrylic material, comprising the following components by weight: 75-85 parts of mixed dry powder, 15-20 parts of polysiloxane-coated glass fiber, and 1 part of additives; The method for preparing the mixed dry powder is as follows: PC-OH and PMMA-OH are mixed in a weight ratio of 2-3:7-8 and then pulverized. The mixture is passed through a 50-mesh sieve to obtain mixed powder. The mixed powder is then transferred to a drying oven at a temperature of 110-120℃ and vacuum dried for 10-12 hours to obtain mixed dry powder.

[0007] Furthermore, the preparation method of PC-OH is as follows: PC, 1,6-hexanediol and catalyst are mixed and added to a twin-screw extruder. After melting and mixing for 2-3 minutes, the mixture is extruded, cooled and solidified, and then pelletized to obtain PC-OH.

[0008] Furthermore, the weight ratio of PC, 1,6-hexanediol, and catalyst is 100:0.2-0.3:0.01, the catalyst is stannous octoate, the temperature of the twin-screw extruder is 230℃ in zone I, 240℃ in zone II, 240℃ in zone III, 240℃ in zone IV, 240℃ in zone V, and 245℃ in zone VI, the spindle speed of the twin-screw extruder is 18-22 rpm, and the vacuum degree is -0.08~-0.095 MPa.

[0009] Furthermore, the preparation method of PMMA-OH is as follows: methyl methacrylate, hydroxyethyl methacrylate, 4-allyl-2,6-di-tert-butylphenol, toluene and initiator are mixed and stirred, the reaction system is heated to 70-80℃, and the reaction is maintained at this temperature for 6-8 hours. After post-treatment, PMMA-OH is obtained.

[0010] The synthesis reaction formula for PMMA-OH is as follows: Furthermore, the ratio of methyl methacrylate, hydroxyethyl methacrylate, 4-allyl-2,6-di-tert-butylphenol, toluene, and initiator is 10g:1g:1.5g:50mL:0.03g. The initiator is composed of azobisisobutyronitrile and dodecyl mercaptan in a weight ratio of 2:1. The post-treatment includes: after the reaction is complete, the reaction system is subjected to negative pressure, and low-boiling substances are removed by vacuum evaporation to obtain PMMA-OH.

[0011] Furthermore, the polysiloxane-coated glass fiber is obtained by the following steps: A1. Crosslinked polysiloxane, 1,2-epoxy-5-hexene, chloroplatinic acid and toluene are mixed and stirred. The reaction system is heated to 75-85℃ and kept at the temperature for 6-8 hours. After post-treatment, activated polysiloxane is obtained. The synthesis reaction formula for activated polysiloxanes is as follows: A2. Mix and stir activated glass fiber, activated polysiloxane and epoxy cyclohexyl-cage polysilsesquioxane, heat the reaction system to 70-80℃, and keep the reaction at this temperature for 90-120 minutes to obtain polysiloxane-coated glass fiber.

[0012] The synthesis reaction formula for polysiloxane-coated glass fiber is as follows: Further, in step A1, the ratio of the crosslinked polysiloxane, 1,2-epoxy-5-hexene, chloroplatinic acid, and toluene is 10g:2-3g:0.05g:50mL. The post-treatment includes: after the reaction is complete, cooling the reaction system to room temperature, adding purified water to the reaction system, stirring and dispersing for 5-8 minutes, allowing it to stand and separate the liquids, washing the organic phase three times with purified water, and then transferring it to a rotary evaporator with a water bath temperature of 80-90℃ to remove low-boiling substances under reduced pressure to obtain activated polysiloxane.

[0013] Furthermore, in step A2, the weight ratio of the activated glass fiber, activated polysiloxane, and epoxy cyclohexyl-cage polysilsesquioxane is 5:6-7:3, and the activated glass fiber is KH-550 modified glass fiber.

[0014] Furthermore, the cross-linked polysiloxane is obtained by the following steps: B1. Mix and stir octamethylcyclotetrasiloxane, tetramethyltetraphenylcyclotetrasiloxane, 1,3,5,7-tetramethylcyclotetrasiloxane, and sulfuric acid. Heat the reaction system to 80-90℃ and maintain the temperature for 40-50 min. Add 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane to the reaction system and maintain the temperature for 80-90 min. After post-treatment, amino-terminated polysiloxane is obtained. The synthesis reaction formula for amino-terminated polysiloxanes is as follows: B2. Mix and stir amino-terminated polysiloxane, 1,3,5-triazine-2,4,6-tricarboxaldehyde and toluene. Heat the reaction system to 80-90℃ and keep it at that temperature for 90-120 min. After post-treatment, cross-linked polysiloxane is obtained.

[0015] The synthesis reaction formula for crosslinked polysiloxanes is as follows: Further, in step B1, the ratio of octamethylcyclotetrasiloxane, tetramethyltetraphenylcyclotetrasiloxane, 1,3,5,7-tetramethylcyclotetrasiloxane, sulfuric acid, and 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane is 8-10g:7-8g:3-4g:2-3mL:2.1-2.5g, and the concentration of sulfuric acid is 10-12mol / L. The post-treatment includes: after the reaction is complete, cooling the reaction system to room temperature, adding purified water and toluene to the reaction system, stirring and dispersing for 20-30 minutes, allowing it to stand and separate the liquids, washing the organic phase three times with purified water, and then transferring it to a rotary evaporator with a water bath temperature of 80-90℃ to remove low-boiling substances under reduced pressure to obtain amino-terminated polysiloxane.

[0016] Further, in step B2, the ratio of amino-terminated polysiloxane, 1,3,5-triazine-2,4,6-tricarboxaldehyde, and toluene is 10g:1.6-1.8g:50mL. The post-treatment includes: after the reaction is complete, the reaction system is subjected to negative pressure to remove low-boiling substances by vacuum evaporation, the reaction system is cooled to room temperature, acetone is added to the reaction system, the mixture is stirred and dispersed for 30-50 minutes, the mixture is allowed to stand and separate, and the oily substance is transferred to a rotary evaporator with a water bath temperature of 80-90℃ to remove low-boiling substances by vacuum evaporation to obtain cross-linked polysiloxane.

[0017] Furthermore, the activated glass fiber is obtained by the following steps: C1. Mix and stir glass fiber and alkaline solution, heat the reaction system to 70-80℃, keep it at the temperature and stir for 60-90 min, and then perform post-treatment to obtain pretreated glass fiber. C2. Mix and stir the pretreated glass fiber, KH-550 and anhydrous ethanol. Heat the reaction system to 50-60℃, add sodium hydroxide solution to the reaction system, keep the reaction at this temperature for 40-50 minutes, and then perform post-treatment to obtain activated glass fiber.

[0018] Further, in step C1, the solid-liquid ratio of the glass fiber and the alkaline solution is 1:7-8, and the alkaline solution is composed of potassium hydroxide, anhydrous ethanol, deionized water and sodium dodecyl sulfate in a ratio of 3g:4-5mL:5-6mL:0.1g. The post-treatment includes: after the reaction is completed, the reaction system is cooled to room temperature, filtered, the filter cake is washed with purified water until neutral and then dried, the filter cake is transferred to a drying oven at a temperature of 70-80℃ and vacuum dried to constant weight to obtain pretreated glass fiber.

[0019] Further, in step C2, the ratio of the pretreated glass fiber, KH-550, anhydrous ethanol, and sodium hydroxide solution is 10g:1.2-1.3g:70mL:7mL, and the concentration of the sodium hydroxide solution is 2-3mol / L. The post-treatment includes: after the reaction is complete, the reaction system is cooled to room temperature, filtered, the filter cake is washed with purified water until neutral, dried under vacuum, and the filter cake is transferred to a drying oven at a temperature of 60-70℃ and vacuum dried to constant weight to obtain activated glass fiber.

[0020] The present invention also proposes a method for preparing a high-hardness, impact-resistant alloy-modified transparent acrylic material. The method involves adding mixed dry powder, polysiloxane-coated glass fiber, and additives into a twin-screw extruder, melting and mixing for 2-3 minutes, then injecting the mixture into a molding die, holding the pressure until the die cools to room temperature, and finally discharging the material to obtain the transparent acrylic material.

[0021] Furthermore, the temperature of the twin-screw extruder is 235℃ in zone I, 245℃ in zone II, 245℃ in zone III, 245℃ in zone IV, 245℃ in zone V, and 250℃ in zone VI. The spindle speed of the twin-screw extruder is 20-25 rpm, and the extrusion pressure is 7-9 MPa.

[0022] This invention also proposes the application of a high-hardness, impact-resistant alloy-modified transparent acrylic material, which is used to prepare impact-resistant, transparent functional knife handle materials.

[0023] The present invention has the following beneficial effects: 1. This invention uses glass fiber as a high-modulus reinforcing phase, which can effectively participate in load bearing under strong interfacial conditions. The phenylsiloxane units and cage-like polysilsesquioxane in the coating layer improve the interfacial layer modulus and structural rigidity, preventing the interfacial layer from becoming a weak slip zone under high temperature or humid heat conditions, thus ensuring the effective manifestation of hardness. The allyl hindered phenol structural units introduced in PMMA-OH are fixed on the polymer chain in a reactive manner, inhibiting the migration and precipitation of antioxidant components, reducing the risk of thermo-oxidative degradation and micro-defect formation. The triazine crosslinking of the glass fiber and the phenylsiloxane structure together improve the thermal stability and antioxidant capacity of the coating layer. Combined with the inhibitory effect of the reactive hindered phenol stabilizing units in the matrix on molecular chain degradation and migration and precipitation, it effectively slows down interfacial damage, chain breakage and performance degradation under humid heat conditions. This allows the material to maintain high hardness while having excellent heat and wet aging resistance. Furthermore, the improved interfacial stability and the matrix molecular stabilization design effectively slow down interfacial relaxation, molecular chain breakage and performance degradation caused by humid heat aging, allowing the material to maintain high hardness while having excellent heat and wet aging resistance.

[0024] 2. This invention further involves alkaline etching, silane coupling, and subsequent epoxy reaction of the glass fiber to form a dense polysiloxane coating layer chemically bonded to the matrix on the glass fiber surface. This significantly reduces air porosity and abrupt changes in refractive index at the glass fiber-matrix interface. Furthermore, the introduction of phenyl-containing polysiloxane structures into the coating layer increases its refractive index, making the refractive index gradient between the glass fiber, coating layer, and polymer matrix smoother. This reduces interface reflection and scattering from an optical mechanism perspective. Simultaneously, the PC-OH / PMMA-OH hydroxylated alloy matrix effectively suppresses phase region coarsening by enhancing compatibility, avoiding the formation of visible light-scale phase separation structures. Thus, even with the introduction of glass fiber reinforcement, high light transmittance is maintained.

[0025] 3. This invention also utilizes the epoxy-amine ring-opening reaction between the amino groups on the glass fiber surface and the activated polysiloxane and cage-like polysilsesquioxane to form a covalently linked interfacial transition layer, which significantly improves the interfacial shear strength and suppresses fiber pull-out and interfacial debonding voids commonly encountered during impact. At the same time, the polysiloxane segments themselves have high flexibility and can undergo significant deformation and dissipate energy under impact loads. The introduced cage-like polysilsesquioxane acts as a nanoscale rigid node, confining the silicon oxide segments and enabling the interfacial layer to maintain load-bearing stability while dissipating energy. Through the synergistic effect of interfacial covalentization, flexible energy dissipation, and rigid confinement, the difficulty of crack initiation and propagation is significantly increased, improving the notched impact strength of the material and maintaining minimal performance degradation even after damp heat aging. Detailed Implementation

[0026] The technical solution of the present invention will be clearly and completely described below with reference to the embodiments. 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.

[0027] In this application, PC refers to polycarbonate, the brand is Mitsubishi, and the grade is S-1000R. In this application, the glass fiber has a diameter of 11 μm, a length of 3-4 mm, and a density of 0.23 kg / m³. 3 ; In this application, KH-550 is γ-aminopropyltriethoxysilane, CAS number 919-30-2.

[0028] Example 1 This embodiment provides a method for preparing polysiloxane-coated glass fibers, including the following steps: Step 1: Preparation of activated glass fibers Potassium hydroxide, anhydrous ethanol, deionized water, and sodium dodecyl sulfate were mixed evenly in a ratio of 3g:4mL:5mL:0.1g to obtain an alkaline solution. Glass fiber and alkaline solution were added to a reaction flask at a solid-liquid ratio of 1:7 and stirred. The reaction flask was heated to 70°C and stirred for 60 minutes. The reaction flask was then cooled to room temperature and filtered. The filter cake was washed with purified water until neutral and then dried under vacuum. The filter cake was transferred to a drying oven at 70°C and dried under vacuum until constant weight to obtain pretreated glass fiber. Weigh out 100g of pretreated glass fiber, 12g of KH-550 and 700mL of anhydrous ethanol and add them to the reaction flask. Stir the mixture and heat the reaction flask to 50℃. Add 70mL of 2mol / L sodium hydroxide solution to the reaction flask and keep it at this temperature for 40min. Cool the reaction flask to room temperature and filter it. Wash the filter cake with purified water until it is neutral and then dry it under vacuum. Transfer the filter cake to a drying oven at 60℃ and dry it under vacuum until it reaches constant weight to obtain activated glass fiber.

[0029] During the processing, the silicon-oxygen network on the surface of the glass fiber undergoes partial hydrolysis under alkaline conditions, causing the Si-O-Si bonds to break and generating a large number of surface silanol groups. Subsequently, the introduced KH-550 hydrolyzes in the alkaline environment to generate silanol, which then undergoes a condensation reaction with the Si-OH on the surface of the glass fiber to form stable Si-O-Si covalent bonds, thereby firmly anchoring the aminopropyl functional groups on the surface of the glass fiber and preparing activated glass fiber.

[0030] The glass fiber surface undergoes slight corrosion and hydrolysis in alkaline solution, which removes the original sizing / contaminants and generates more surface Si-OH, making the surface cleaner and more reactive, which is conducive to the formation of a continuous coating layer. KH-550 silane coupling activation promotes the chemical bonding between the subsequent coating layer and the fiber surface, forming a denser interface, thereby reducing residual air micropores at the interface, reducing the refractive index difference between air and resin, reducing scattering sources, improving the light transmittance of the material, and activating the epoxy groups modified on the glass fiber to provide reaction sites for the subsequent epoxy-amine reaction, improving the impact strength of the material.

[0031] Step 2: Preparation of cross-linked polysiloxane Weigh out 80g of octamethylcyclotetrasiloxane, 70g of tetramethyltetraphenylcyclotetrasiloxane, 30g of 1,3,5,7-tetramethylcyclotetrasiloxane, and 20mL of 10mol / L sulfuric acid and add them to a reaction flask. Stir the mixture and heat the reaction flask to 80℃. Keep the temperature for 40min. Add 21g of 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane to the reaction flask and keep the temperature for 80min. Cool the reaction flask to room temperature and add 500mL of purified water and 700mL of toluene. Stir and disperse for 20min. Let the mixture stand and separate the liquids. Wash the organic phase three times with purified water and transfer it to a rotary evaporator at 80℃ to remove low-boiling substances under reduced pressure to obtain amino-terminated polysiloxane. Weigh out 200g of amino-terminated polysiloxane, 32g of 1,3,5-triazine-2,4,6-tricarboxaldehyde, and 1000mL of toluene and add them to a reaction flask. Stir the mixture and heat it to 80℃. Keep the mixture at this temperature for 90min. Apply negative pressure to the reaction flask and remove low-boiling substances by vacuum evaporation. Cool the reaction flask to room temperature and add 1000mL of acetone. Stir and disperse the mixture for 30min. Allow it to stand and separate the liquids. Transfer the oily substance to a rotary evaporator with a water bath temperature of 80-90℃ and remove low-boiling substances by vacuum evaporation to obtain crosslinked polysiloxane.

[0032] In the reaction, octamethylcyclotetrasiloxane, phenyl-containing cyclosiloxane, and Si-H-containing cyclosiloxane undergo ring-opening polymerization under acid catalysis to generate linear polysiloxanes with a Si-O-Si main chain. An amino-containing disiloxane is added as a capping agent. After hydrolysis, amino groups are formed on the Si-O-Si linear polysiloxane main chain to obtain amino-capped polysiloxanes. The amino groups in the amino-capped polysiloxanes undergo Schiff base condensation with triazine tricarboxaldehyde to form C=N bonds and construct a triazine-type crosslinked structure, forming a three-dimensional crosslinked network to prepare crosslinked polysiloxanes.

[0033] The three-dimensional cross-linked polysiloxane network improves the modulus and structural stability of the coating layer. The phenylsiloxane structure increases the refractive index, making the refractive index of the coating layer closer to that of the glass fiber and the matrix, which is beneficial for optical matching. The cross-linking structure inhibits the migration or flow of polysiloxane in high temperature and high humidity environments, and the triazine and hindered phenol work synergistically to improve the aging resistance of the material.

[0034] Step 3: Preparation of activated polysiloxane Weigh out 200g of crosslinked polysiloxane, 40g of 1,2-epoxy-5-hexene, 1g of chloroplatinic acid, and 1000mL of toluene and add them to a reaction flask. Stir the mixture and heat the reaction flask to 75℃. Keep the mixture at this temperature for 6 hours. Cool the reaction flask to room temperature and add 800mL of purified water to the reaction flask. Stir and disperse the mixture for 5 minutes. Allow the mixture to stand and separate the liquids. Wash the organic phase three times with purified water and then transfer it to a rotary evaporator at a water bath temperature of 80℃ to remove low-boiling substances under reduced pressure to obtain activated polysiloxane.

[0035] In the reaction, in the presence of a platinum catalyst, the Si-H-containing structure undergoes a hydrosilylation reaction with 1,2-epoxy-5-hexene, introducing a large number of epoxy groups onto the side chain of the polysiloxane. The introduction of epoxy groups endows the polysiloxane with the ability to undergo ring-opening reactions with amine groups, providing reaction sites for subsequent reactions with amino groups on the glass fiber surface and epoxycyclohexyl-cage polysilsesquioxane, thus constructing a chemically bondable interfacial transition layer.

[0036] Step 4: Preparation of polysiloxane-coated glass fibers Weigh out 500g of activated glass fiber, 600g of activated polysiloxane, and 300g of epoxy cyclohexyl-cage polysilsesquioxane and add them to a reaction flask. Stir the mixture and heat the reaction flask to 70°C. Keep the temperature for 90 minutes to obtain polysiloxane-coated glass fiber.

[0037] In the reaction, the amino groups on the surface of the glass fiber undergo ring-opening condensation with the epoxy groups in the activated polysiloxane and the epoxy groups in the epoxycyclohexyl-cage polysilsesquioxane to generate a β-hydroxyamine structure, which constructs a multi-level covalent network coating layer on the outside of the glass fiber, thus preparing polysiloxane-coated glass fiber.

[0038] Chemical bonding enhances interfacial shear strength. The polysiloxane segments are flexible, suppressing fiber pull-out and interfacial debonding during impact. They deform and dissipate energy under impact. The epoxy cyclohexyl-cage-shaped polysilsesquioxane cage structure serves as a nano-rigid node, increasing the interfacial layer modulus. The combination of rigidity and flexibility improves both hardness and impact toughness.

[0039] Example 2 This embodiment provides a method for preparing polysiloxane-coated glass fibers, including the following steps: Step 1: Preparation of activated glass fibers Potassium hydroxide, anhydrous ethanol, deionized water, and sodium dodecyl sulfate were mixed evenly in a ratio of 3g:4.5mL:5.5mL:0.1g to obtain an alkaline solution. Glass fiber and alkaline solution were added to a reaction flask at a solid-liquid ratio of 1:7.5 and stirred. The reaction flask was heated to 75°C and stirred for 75 minutes. The reaction flask was then cooled to room temperature and filtered. The filter cake was washed with purified water until neutral and then dried. The filter cake was transferred to a drying oven at 75°C and dried under vacuum until constant weight to obtain pretreated glass fiber. Weigh out 100g of pretreated glass fiber, 12.5g of KH-550 and 700mL of anhydrous ethanol and add them to a reaction flask. Stir the mixture and heat the reaction flask to 55℃. Add 70mL of 2.5mol / L sodium hydroxide solution to the reaction flask and keep it at this temperature for 45min. Cool the reaction flask to room temperature and filter it. Wash the filter cake with purified water until it is neutral and then dry it under vacuum. Transfer the filter cake to a drying oven at 65℃ and dry it under vacuum until it reaches constant weight to obtain activated glass fiber.

[0040] Step 2: Preparation of cross-linked polysiloxane Weigh out 90g of octamethylcyclotetrasiloxane, 75g of tetramethyltetraphenylcyclotetrasiloxane, 35g of 1,3,5,7-tetramethylcyclotetrasiloxane, and 25mL of 11mol / L sulfuric acid and add them to a reaction flask. Stir the mixture and heat the reaction flask to 85℃. Keep the temperature for 45min. Add 23g of 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane to the reaction flask and keep the temperature for 85min. Cool the reaction flask to room temperature and add 500mL of purified water and 700mL of toluene. Stir and disperse for 25min. Let the mixture stand and separate the liquids. Wash the organic phase three times with purified water and transfer it to a rotary evaporator at 85℃ to remove low-boiling substances under reduced pressure to obtain amino-terminated polysiloxane. Weigh out 200g of amino-terminated polysiloxane, 34g of 1,3,5-triazine-2,4,6-tricarboxaldehyde, and 1000mL of toluene and add them to a reaction flask. Stir the mixture and heat it to 85℃. Keep the mixture at this temperature for 105min. Apply negative pressure to the reaction flask and remove low-boiling substances by vacuum evaporation. Cool the reaction flask to room temperature and add 1000mL of acetone. Stir and disperse the mixture for 40min. Allow it to stand and separate the liquids. Transfer the oily substance to a rotary evaporator at 85℃ and remove low-boiling substances by vacuum evaporation to obtain crosslinked polysiloxane.

[0041] Step 3: Preparation of activated polysiloxane Weigh out 200g of crosslinked polysiloxane, 50g of 1,2-epoxy-5-hexene, 1g of chloroplatinic acid, and 1000mL of toluene and add them to a reaction flask. Stir the mixture and heat the reaction flask to 80℃. Keep the mixture at this temperature for 7 hours. Cool the reaction flask to room temperature and add 800mL of purified water. Stir and disperse the mixture for 6.5 minutes. Allow the mixture to stand and separate the liquids. Wash the organic phase three times with purified water and then transfer it to a rotary evaporator at a water bath temperature of 85℃ to remove low-boiling substances under reduced pressure to obtain activated polysiloxane.

[0042] Step 4: Preparation of polysiloxane-coated glass fibers Weigh out 500g of activated glass fiber, 650g of activated polysiloxane, and 300g of epoxy cyclohexyl-cage polysilsesquioxane and add them to a reaction flask. Stir the mixture and heat the reaction flask to 75°C. Keep the temperature for 105 minutes to obtain polysiloxane-coated glass fiber.

[0043] Example 3 This embodiment provides a method for preparing polysiloxane-coated glass fibers, including the following steps: Step 1: Preparation of activated glass fibers Potassium hydroxide, anhydrous ethanol, deionized water and sodium dodecyl sulfate were mixed evenly in a ratio of 3g:5mL:6mL:0.1g to obtain an alkaline solution. Glass fiber and alkaline solution were added to a reaction flask at a solid-liquid ratio of 1:8 and stirred. The reaction flask was heated to 80°C and stirred for 90 minutes. The reaction flask was then cooled to room temperature and filtered. The filter cake was washed with purified water until neutral and then dried. The filter cake was transferred to a drying oven at 80°C and dried under vacuum until constant weight to obtain pretreated glass fiber. Weigh out 100g of pretreated glass fiber, 13g of KH-550 and 700mL of anhydrous ethanol and add them to a reaction flask. Stir the mixture and heat the reaction flask to 60℃. Add 70mL of 3mol / L sodium hydroxide solution to the reaction flask and keep it at this temperature for 50min. Cool the reaction flask to room temperature and filter it. Wash the filter cake with purified water until it is neutral and then dry it under vacuum. Transfer the filter cake to a drying oven at 70℃ and dry it under vacuum until it reaches constant weight to obtain activated glass fiber.

[0044] Step 2: Preparation of cross-linked polysiloxane Weigh out 100g of octamethylcyclotetrasiloxane, 80g of tetramethyltetraphenylcyclotetrasiloxane, 40g of 1,3,5,7-tetramethylcyclotetrasiloxane, and 30mL of 12mol / L sulfuric acid and add them to a reaction flask. Stir the mixture and heat it to 90℃. Keep the temperature for 50min. Add 25g of 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane to the reaction flask and keep the temperature for 90min. Cool the reaction flask to room temperature and add 500mL of purified water and 700mL of toluene. Stir and disperse for 30min. Let the mixture stand and separate the liquids. Wash the organic phase three times with purified water and transfer it to a rotary evaporator at a water bath temperature of 90℃ to remove low-boiling substances under reduced pressure to obtain amino-terminated polysiloxane. Weigh out 200g of amino-terminated polysiloxane, 36g of 1,3,5-triazine-2,4,6-tricarboxaldehyde, and 1000mL of toluene and add them to a reaction flask. Stir the mixture and heat it to 90℃. Keep the mixture at this temperature for 120min. Apply negative pressure to the reaction flask and remove low-boiling substances by vacuum evaporation. Cool the reaction flask to room temperature and add 1000mL of acetone. Stir and disperse the mixture for 50min. Allow it to stand and separate the liquids. Transfer the oily substance to a rotary evaporator at a water bath temperature of 90℃ and remove low-boiling substances by vacuum evaporation to obtain crosslinked polysiloxane.

[0045] Step 3: Preparation of activated polysiloxane Weigh out 200g of crosslinked polysiloxane, 60g of 1,2-epoxy-5-hexene, 1g of chloroplatinic acid, and 1000mL of toluene and add them to a reaction flask. Stir the mixture and heat the reaction flask to 85℃. Keep the mixture at this temperature for 8 hours. Cool the reaction flask to room temperature and add 800mL of purified water to the reaction flask. Stir and disperse the mixture for 8 minutes. Allow the mixture to stand and separate the liquids. Wash the organic phase three times with purified water and then transfer it to a rotary evaporator at a water bath temperature of 90℃ to remove low-boiling substances under reduced pressure to obtain activated polysiloxane.

[0046] Step 4: Preparation of polysiloxane-coated glass fibers Weigh out 500g of activated glass fiber, 700g of activated polysiloxane, and 300g of epoxy cyclohexyl-cage polysilsesquioxane and add them to a reaction flask. Stir the mixture and heat the reaction flask to 80℃. Keep the temperature for 120 minutes to obtain polysiloxane-coated glass fiber.

[0047] Example 4 This embodiment provides a method for preparing a high-hardness, impact-resistant alloy-modified transparent acrylic material, specifically including the following steps: Step S1: Preparation of PC-OH Weigh out 100 parts PC, 0.2 parts 1,6-hexanediol, and 0.01 parts stannous octoate catalyst by weight, mix them, and add them to a twin-screw extruder. Set the temperatures of the twin-screw extruder to 230℃ in zone I, 240℃ in zone II, 240℃ in zone III, 240℃ in zone IV, 240℃ in zone V, and 245℃ in zone VI. Set the spindle speed of the twin-screw extruder to 18 rpm and the vacuum degree to -0.08 MPa. After melting and mixing for 2 minutes, extrude the mixture, cool and solidify it, and then pelletize it to obtain PC-OH.

[0048] In the presence of a catalyst, PC undergoes transesterification with 1,6-hexanediol, during which some carbonate bonds are opened, introducing terminal hydroxyl structures to form terminally hydroxylated polycarbonate.

[0049] Introducing polar hydroxyl groups into the PC molecular chain improves its compatibility with PMMA-OH and polysiloxanes, reducing phase separation in the alloy system.

[0050] Step S2: Preparation of PMMA-OH Azobisisobutyronitrile and dodecyl mercaptan were mixed evenly at a weight ratio of 2:1 to obtain an initiator; Weigh out 5000g of methyl methacrylate, 500g of hydroxyethyl methacrylate, 750g of 4-allyl-2,6-di-tert-butylphenol, 25000mL of toluene, and 15g of initiator, add them to a reaction vessel and stir. Heat the reaction vessel to 70℃ and maintain the temperature for 6 hours. Then, apply negative pressure to the reaction system and remove low-boiling substances by vacuum distillation to obtain PMMA-OH.

[0051] During the free radical polymerization process, hydroxyethyl methacrylate copolymerizes into the PMMA backbone, introducing side chain hydroxyl groups into the PMMA molecular chain. 4-Allyl-2,6-di-tert-butylphenol participates in the free radical copolymerization and is chemically fixed into the PMMA chain segment to prepare PMMA-OH containing hindered phenolic side groups.

[0052] The hydroxyl groups improve the compatibility with PC-OH and polysiloxane coatings, while the hindered phenols exist in a covalent manner, avoiding migration and precipitation, thus improving the long-term thermo-oxidative stability and aging resistance of the material.

[0053] Step S3: Prepare mixed and dried powder PC-OH and PMMA-OH were mixed in a weight ratio of 2:7 and then pulverized. The mixture was passed through a 50-mesh sieve to obtain a mixed powder. The mixed powder was then transferred to a drying oven at 110°C and vacuum dried for 10 hours to obtain a mixed dried powder.

[0054] Numerous hydrogen bonds are formed between PC-OH and PMMA-OH. The hydrogen bond network reduces interfacial tension, inhibits macroscopic phase separation, and forms a fine-scale interpenetrating phase structure.

[0055] Step S4: Preparation of transparent acrylic material Stearate, antioxidant 1010, antistatic agent SN and PTFE anti-dripping agent are mixed evenly in a weight ratio of 4:1:7:2 to obtain the additives. Weigh out 75 parts by weight of the mixed dry powder, 15 parts by weight of the polysiloxane-coated glass fiber prepared in Example 1, and 1 part by weight of the additives, and add them to a twin-screw extruder. Set the temperature of zone I to 235°C, zone II to 245°C, zone III to 245°C, zone IV to 245°C, zone V to 245°C, and zone VI to 250°C. Set the spindle speed of the twin-screw extruder to 20 rpm. After melting and mixing for 2 minutes, inject the mixture into the molding die. Set the extrusion pressure to 7 MPa and hold the pressure until the die cools to room temperature. Discharge the material to obtain transparent acrylic material.

[0056] Example 5 This embodiment provides a method for preparing a high-hardness, impact-resistant alloy-modified transparent acrylic material, specifically including the following steps: Step S1: Preparation of PC-OH Weigh out 100 parts PC, 0.25 parts 1,6-hexanediol, and 0.01 parts stannous octoate catalyst by weight, mix them, and add them to a twin-screw extruder. Set the temperatures of the twin-screw extruder to 230℃ in zone I, 240℃ in zone II, 240℃ in zone III, 240℃ in zone IV, 240℃ in zone V, and 245℃ in zone VI. Set the spindle speed of the twin-screw extruder to 20 rpm and the vacuum degree to -0.09 MPa. After melting and mixing for 2.5 min, extrude the mixture, cool and solidify it, and then pelletize it to obtain PC-OH.

[0057] Step S2: Preparation of PMMA-OH Azobisisobutyronitrile and dodecyl mercaptan were mixed evenly at a weight ratio of 2:1 to obtain an initiator; Weigh out 5000g of methyl methacrylate, 500g of hydroxyethyl methacrylate, 750g of 4-allyl-2,6-di-tert-butylphenol, 25000mL of toluene, and 15g of initiator, add them to a reaction vessel and stir. Heat the reaction vessel to 75℃ and maintain the temperature for 7h. Then, apply negative pressure to the reaction system and remove low-boiling substances by vacuum distillation to obtain PMMA-OH.

[0058] Step S3: Prepare mixed and dried powder PC-OH and PMMA-OH were mixed at a weight ratio of 2.5:7.5 and then pulverized. The mixture was passed through a 50-mesh sieve to obtain a mixed powder. The mixed powder was then transferred to a drying oven at 115°C and vacuum dried for 11 hours to obtain a mixed dried powder.

[0059] Step S4: Preparation of transparent acrylic material Stearate, antioxidant 1010, antistatic agent SN and PTFE anti-dripping agent are mixed evenly in a weight ratio of 4:1:7:2 to obtain the additives. Weigh out the following by weight: 80 parts of mixed dry powder, 17.5 parts of polysiloxane-coated glass fiber prepared in Example 2, and 1 part of additives. Add them to a twin-screw extruder. Set the temperature of zone I to 235°C, zone II to 245°C, zone III to 245°C, zone IV to 245°C, zone V to 245°C, and zone VI to 250°C. Set the spindle speed of the twin-screw extruder to 23 rpm. After melting and mixing for 2.5 min, inject the mixture into the molding die. Set the extrusion pressure to 8 MPa. Hold the pressure until the die cools to room temperature, and then discharge the material to obtain transparent acrylic material.

[0060] Example 6 This embodiment provides a method for preparing a high-hardness, impact-resistant alloy-modified transparent acrylic material, specifically including the following steps: Step S1: Preparation of PC-OH Weigh out 100 parts PC, 0.3 parts 1,6-hexanediol, and 0.01 parts stannous octoate catalyst by weight, mix them, and add them to a twin-screw extruder. Set the temperatures of the twin-screw extruder to 230℃ in zone I, 240℃ in zone II, 240℃ in zone III, 240℃ in zone IV, 240℃ in zone V, and 245℃ in zone VI. Set the spindle speed of the twin-screw extruder to 22 rpm and the vacuum degree to -0.095 MPa. After melting and mixing for 3 minutes, extrude the mixture, cool and solidify it, and then pelletize it to obtain PC-OH.

[0061] Step S2: Preparation of PMMA-OH Azobisisobutyronitrile and dodecyl mercaptan were mixed evenly at a weight ratio of 2:1 to obtain an initiator; Weigh out 5000g of methyl methacrylate, 500g of hydroxyethyl methacrylate, 750g of 4-allyl-2,6-di-tert-butylphenol, 25000mL of toluene, and 15g of initiator, add them to a reaction vessel and stir. Heat the reaction vessel to 80℃ and maintain the temperature for 8 hours. Apply negative pressure to the reaction system and remove low-boiling substances by vacuum distillation to obtain PMMA-OH.

[0062] Step S3: Prepare mixed and dried powder PC-OH and PMMA-OH were mixed in a weight ratio of 3:8 and then pulverized. The mixture was passed through a 50-mesh sieve to obtain a mixed powder. The mixed powder was then transferred to a drying oven at 120°C and vacuum dried for 12 hours to obtain a mixed dried powder.

[0063] Step S4: Preparation of transparent acrylic material Stearate, antioxidant 1010, antistatic agent SN and PTFE anti-dripping agent are mixed evenly in a weight ratio of 4:1:7:2 to obtain the additives. Weigh out 85 parts by weight of the mixed dry powder, 20 parts by weight of the polysiloxane-coated glass fiber prepared in Example 3, and 1 part by weight of the additives, and add them to a twin-screw extruder. Set the temperature of zone I to 235°C, zone II to 245°C, zone III to 245°C, zone IV to 245°C, zone V to 245°C, and zone VI to 250°C. Set the spindle speed of the twin-screw extruder to 25 rpm. After melting and mixing for 3 minutes, inject the mixture into the molding die. Set the extrusion pressure to 9 MPa and hold the pressure until the die cools to room temperature. Discharge the material to obtain transparent acrylic material.

[0064] Comparative Example 1 The difference between this comparative example and Example 6 is that, in the preparation of the polysiloxane-coated glass fiber, the pretreated glass fiber in step 1 is used instead of the activated glass fiber in step 4.

[0065] Comparative Example 2 The difference between this comparative example and Example 6 is that, in the preparation of the polysiloxane-coated glass fiber, the amino-terminated polysiloxane in step 2 is used instead of the cross-linked polysiloxane in step 3.

[0066] Comparative Example 3 The difference between this comparative example and Example 6 is that, in the preparation of the polysiloxane-coated glass fiber, epoxy cyclohexyl-cage polysilsesquioxane was not added in step 4.

[0067] Comparative Example 4 The difference between this comparative example and Example 6 is that PC in step S1 is used instead of PC-OH in step S3.

[0068] Performance testing: The light transmittance of the transparent acrylic materials prepared in Examples 4-6 and Comparative Examples 1-4 was determined in accordance with the standard GB / T 2410-2008 "Determination of light transmittance and haze of transparent plastics". The notched impact strength of the transparent acrylic material type A notched specimens prepared in Examples 4-6 and Comparative Examples 1-4 was determined in accordance with the standard GB / T 1843-2008 "Determination of Impact Strength of Plastic Cantilever Beams". The Rockwell hardness of the transparent acrylic materials prepared in Examples 4-6 and Comparative Examples 1-4 was determined in accordance with the standard GB / T 3398.2-2008 "Determination of Hardness of Plastics - Part 2: Rockwell Hardness". In accordance with the standard GB / T 7141-2008 "Test Method for Thermal Aging of Plastics", the transparent acrylic materials prepared in Examples 4-6 and Comparative Examples 1-4 were placed in an environment with a temperature of 80°C and a humidity of 90% for 100 hours of thermal aging treatment. The light transmittance and unnotched impact strength of the samples were measured. The specific test data are shown in Table 1 below.

[0069] Table 1 - Performance Test Data of Samples Data Analysis: Comparative analysis of the data in Table 1 shows that the Rockwell hardness (HRA) of the transparent acrylic material prepared by this invention reaches 80-83, the light transmittance before damp heat aging reaches 91.5%-92.6%, and the notched impact strength reaches 15.8-16.0 kJ / m. 2 After damp heat aging, the light transmittance reaches 87.2%-89.4%, and the notched impact strength reaches 15.0-15.2 kJ / m. 2 The performance test data of the present invention are all superior to those of the comparative example, indicating that the present invention constructs a dense chemical coating layer on the surface of glass fiber by alkaline etching and silane coupling activation. This layer is mainly composed of triazine crosslinked and phenyl modified polysiloxane with cage-like polysilsesquioxane structure. This allows a stable covalent interface transition structure to be formed between the glass fiber and the hydroxylated PC / PMMA alloy matrix. At the same time, the compatibility design of PC-OH and PMMA-OH and the introduction of reactive hindered phenolic stabilizing units in the matrix inhibit phase separation and aging degradation. Under the premise of ensuring refractive index matching and phase stability, the invention enhances the high transparency, high hardness and high impact toughness of the glass fiber reinforced system, while improving the performance retention rate of the material under humid heat aging conditions.

[0070] The preferred embodiments of the present invention disclosed above are merely illustrative of the invention. These preferred embodiments do not exhaustively describe all details, nor do they limit the invention to specific implementations. Clearly, many modifications and variations can be made based on the content of this specification. This specification selects and specifically describes these embodiments to better explain the principles and practical applications of the invention, thereby enabling those skilled in the art to better understand and utilize the invention. The invention is limited only by the claims and their full scope and equivalents.

Claims

1. A high-hardness, impact-resistant alloy-modified transparent acrylic material, characterized in that, It comprises the following components by weight: 75-85 parts of mixed dry powder, 15-20 parts of polysiloxane-coated glass fiber, and 1 part of additives; The method for preparing the mixed dry powder is as follows: PC-OH and PMMA-OH are mixed in a weight ratio of 2-3:7-8 and then pulverized. The mixture is passed through a 50-mesh sieve to obtain mixed powder. The mixed powder is then transferred to a drying oven at a temperature of 110-120℃ and vacuum dried for 10-12 hours to obtain mixed dry powder.

2. The high-hardness, impact-resistant alloy-modified transparent acrylic material according to claim 1, characterized in that, The preparation method of PC-OH is as follows: PC, 1,6-hexanediol and catalyst are mixed and added to a twin-screw extruder. After melting and mixing for 2-3 minutes, the mixture is extruded, cooled and solidified, and then pelletized to obtain PC-OH.

3. The high-hardness, impact-resistant alloy-modified transparent acrylic material according to claim 1, characterized in that, The preparation method of PMMA-OH is as follows: Methyl methacrylate, hydroxyethyl methacrylate, 4-allyl-2,6-di-tert-butylphenol, toluene and initiator are mixed and stirred, the reaction system is heated to 70-80℃, and the reaction is maintained for 6-8 hours. After post-treatment, PMMA-OH is obtained.

4. The high-hardness, impact-resistant alloy-modified transparent acrylic material according to claim 1, characterized in that, Polysiloxane-coated glass fibers are obtained through the following steps: A1. Crosslinked polysiloxane, 1,2-epoxy-5-hexene, chloroplatinic acid and toluene are mixed and stirred. The reaction system is heated to 75-85℃ and kept at the temperature for 6-8 hours. After post-treatment, activated polysiloxane is obtained. A2. Mix and stir activated glass fiber, activated polysiloxane and epoxy cyclohexyl-cage polysilsesquioxane, heat the reaction system to 70-80℃, and keep the reaction at this temperature for 90-120 minutes to obtain polysiloxane-coated glass fiber.

5. The high-hardness, impact-resistant alloy-modified transparent acrylic material according to claim 4, characterized in that, In step A1, the ratio of crosslinked polysiloxane, 1,2-epoxy-5-hexene, chloroplatinic acid, and toluene is 10g:2-3g:0.05g:50mL; in step A2, the weight ratio of activated glass fiber, activated polysiloxane, and epoxycyclohexyl-cage polysilsesquioxane is 5:6-7:3, and the activated glass fiber is KH-550 modified glass fiber.

6. The high-hardness, impact-resistant alloy-modified transparent acrylic material according to claim 4, characterized in that, Crosslinked polysiloxanes are obtained by the following steps: B1. Mix and stir octamethylcyclotetrasiloxane, tetramethyltetraphenylcyclotetrasiloxane, 1,3,5,7-tetramethylcyclotetrasiloxane, and sulfuric acid. Heat the reaction system to 80-90℃ and maintain the temperature for 40-50 min. Add 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane to the reaction system and maintain the temperature for 80-90 min. After post-treatment, amino-terminated polysiloxane is obtained. B2. Mix and stir amino-terminated polysiloxane, 1,3,5-triazine-2,4,6-tricarboxaldehyde and toluene. Heat the reaction system to 80-90℃ and keep it at that temperature for 90-120 min. After post-treatment, cross-linked polysiloxane is obtained.

7. The high-hardness, impact-resistant alloy-modified transparent acrylic material according to claim 6, characterized in that, In step B1, the ratio of octamethylcyclotetrasiloxane, tetramethyltetraphenylcyclotetrasiloxane, 1,3,5,7-tetramethylcyclotetrasiloxane, sulfuric acid, and 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane is 8-10g:7-8g:3-4g:2-3mL:2.1-2.5g, and the concentration of sulfuric acid is 10-12mol / L; in step B2, the ratio of amino-terminated polysiloxane, 1,3,5-triazine-2,4,6-tricarboxaldehyde, and toluene is 10g:1.6-1.8g:50mL.

8. The high-hardness, impact-resistant alloy-modified transparent acrylic material according to claim 4, characterized in that, Activated glass fibers are obtained through the following steps: C1. Mix and stir the glass fiber and alkaline solution, heat the reaction system to 70-80℃, keep it at the temperature and stir for 60-90 min, and then perform post-treatment to obtain pretreated glass fiber. The alkaline solution is composed of potassium hydroxide, anhydrous ethanol, deionized water and sodium dodecyl sulfate in the ratio of 3g:4-5mL:5-6mL:0.1g. C2. Mix and stir the pretreated glass fiber, KH-550 and anhydrous ethanol. Heat the reaction system to 50-60℃, add sodium hydroxide solution to the reaction system, keep the reaction at this temperature for 40-50 minutes, and then perform post-treatment to obtain activated glass fiber.

9. The method for preparing the high-hardness, impact-resistant alloy-modified transparent acrylic material according to any one of claims 1-8, characterized in that, The process includes the following steps: adding mixed dry powder, polysiloxane-coated glass fiber, and additives to a twin-screw extruder, melting and mixing for 2-3 minutes, then injecting the mixture into a molding die, holding the pressure until the die cools to room temperature, and finally discharging the material to obtain transparent acrylic material.

10. The application of a high-hardness, impact-resistant alloy-modified transparent acrylic material, characterized in that, The high-hardness, impact-resistant alloy-modified transparent acrylic material as described in any one of claims 1-8 is used to prepare impact-resistant, transparent functional knife handle materials.

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