Glass fiber composite material for 3D printing and preparation method thereof

Abstract

The invention relates to the field of high-performance compounding, in particular to a glass fiber composite material for 3D printing and a preparation method of the glass fiber composite material. The glass fiber composite material for 3D printing is characterized by comprising the following raw materials in parts by weight: 10-30 parts of a modified glass fiber blend, 30-80 parts of PEI, 10-50 parts of PPSU, 3-5 parts of a plasticizer, 5-8 parts of a compatilizer and 1-5 parts of a processing aid, the modified glass fiber blending material is prepared by sequentially treating glass fibers with a wetting activator and an interface enhancer and then blending the treated glass fibers with TPSiV; the effective component of the wetting activator is a reactive polyether functional polymer. The modified glass fiber blending material, the PEI and the PPSU have synergistic interaction, and the glass fiber and resin matrix interface bonding strength is excellent, so that the composite material has high strength, high rigidity and good toughness, and can resist complex external force impact and vibration.

Description

Technical Field

[0001] The present application relates to the field of high-performance composites, and more specifically, to a glass fiber composite material for 3D printing and a preparation method thereof. Background Art

[0002] In recent years, drone technology has experienced rapid development, demonstrating immense application value in numerous fields, including aerial photography, surveying and mapping, logistics and distribution, and agricultural plant protection. As drone applications continue to expand, performance requirements for drone components are also increasing. Drones must operate in complex environments, subject to various external forces, shocks, vibrations, and varying climatic conditions. Therefore, their components must possess high strength, high rigidity, excellent heat resistance, and dimensional stability. 3D printing, as an advanced manufacturing technology, offers advantages such as rapid prototyping, the ability to design complex structures, and personalized customization, providing a new approach to the manufacturing of drone components. 3D printing enables the rapid production of drone components that meet specific design requirements, shortening R&D cycles and reducing production costs. However, traditional 3D printing materials often lack the strength and rigidity required for drone components. Therefore, developing high-performance materials for 3D printing is of great practical significance. Glass fiber composites, with their excellent mechanical properties, such as high strength and high modulus, are an ideal choice for 3D printing of drone components.

[0003] In the field of 3D printing, research on glass fiber composites has made some progress. A common preparation method is to compound glass fiber with a thermoplastic resin matrix and prepare it into filaments or particles suitable for 3D printing through a specific process. Commonly used thermoplastic resin matrices include acrylonitrile-butadiene-styrene copolymer (ABS) and polyamide (PA). During the preparation process, the glass fiber and the resin matrix are usually mixed evenly at high temperature by melt blending, and then extruded into filaments or particles. Some studies have also treated the surface of the glass fiber to improve its interfacial bonding with the resin matrix, thereby enhancing the overall performance of the composite material. In addition, in order to improve the fluidity and print quality during the 3D printing process, some additives such as lubricants and plasticizers are also added.

[0004] While existing technologies have achieved some success in glass fiber composites for 3D printing, some significant drawbacks remain. Despite surface treatment, the interfacial bonding between the glass fiber and the resin matrix remains suboptimal. During the use of drone components, when subjected to external forces, debonding between the glass fiber and the resin matrix can occur, resulting in a decrease in the material's mechanical properties and impacting the reliability and service life of the components. Summary of the Invention

[0005] The purpose of this application is to overcome the above technical problems and provide a glass fiber composite material for 3D printing and a preparation method.

[0006] In the first aspect, a glass fiber composite material for 3D printing comprises the following raw materials in parts by weight: 10-30 parts of modified glass fiber blend PEI: 30-80 parts PPSU: 10-50 parts Plasticizer: 3-5 parts Compatibilizer: 5-8 parts Processing aids: 1-5 parts; The modified glass fiber blend is prepared by sequentially treating glass fiber with a wetting activator and an interfacial strengthening agent, and then blending with TPSiV; the active ingredient of the wetting activator is a reactive polyether functional polymer; the active ingredient of the interfacial strengthening agent is a mixture of 1,3-bis(3-methacryloxypropyl)tetrakis(trimethylsiloxy)disiloxane, side-chain acrylate-modified silicone oil, and organic polyborosilazane.

[0007] By employing this technical solution, the glass fiber composite material achieves comprehensive improvements in mechanical properties, heat resistance, and 3D printing performance through a unique modification process and ingredient combination. It is particularly suitable for the manufacture of drone components and has broad application prospects. The specific preparation process for the modified glass fiber blend involves sequentially treating the glass fiber with a wetting activator and an interfacial strengthening agent before blending with TPSiV. This step-by-step process ensures that each step is fully effective.

[0008] The wetting activator treatment imparts excellent wettability to the glass fiber surface, providing an ideal foundation for the adsorption and reaction of the interfacial strengthener. The interfacial strengthener treatment constructs a multi-layered, high-strength interfacial structure on the glass fiber surface, significantly enhancing the interfacial bonding between the glass fiber and the resin matrix. After blending with TPSiV, its unique sea-island structure imparts excellent flexibility and processing properties to the blend, while its excellent heat resistance, chemical resistance, environmental protection properties, good adhesion, and recyclability further enhance the overall performance of the composite material.

[0009] The reactive polyether functionalized wetting activator works together with the interfacial strengthener to form a transition layer with good wettability and reactivity on the surface of the glass fiber, thereby enhancing the interfacial bonding between the glass fiber and the resin matrix. This significantly improves the mechanical properties, heat resistance and 3D printing performance of the composite material, meeting the use requirements of UAV components in complex environments and enhancing the flight performance, safety and overall reliability of the UAV.

[0010] Preferably, the weight ratio of the 1,3-bis(3-methacryloxypropyl)tetrakis(trimethylsiloxy)disiloxane, the side chain acrylate modified silicone oil, and the organic polyborosilazane is 3:(0.5-1):(0.1-0.5).

[0011] By adopting the above technical solution, 1,3-bis(3-methacryloyloxypropyl)tetrakis(trimethylsiloxy)disiloxane, side chain acrylate modified silicone oil, and organic polyborosilazane are used in a weight ratio of 3:(0.5-1):(0.1-0.5) to prepare a modified glass fiber blend. The three can form a "point-surface-bond" synergistic system through structural complementarity and functional division of labor in the surface modification of glass fibers, significantly improving the interfacial bonding strength, weather resistance and compatibility between the glass fiber and the resin matrix, and are particularly suitable for the pretreatment of glass fibers for high-performance composite materials. The combination of modified glass fiber blends with PEI, PPSU and other ingredients gives the composite material excellent mechanical properties, which can effectively resist complex external force impact and vibration, ensuring the integrity and reliability of the component structure; it has excellent heat resistance and remains stable in high temperature environments without softening or deformation, meeting the use needs of drones in extreme environments; it has excellent 3D printing performance, avoiding blockage and wire breakage problems, ensuring continuous and efficient printing, high product surface quality, and low shrinkage, meeting the assembly precision requirements of drone parts.

[0012] Preferably, the reactive polyether functional polymer is a combination of trimethylol hexyl lactone cross-linked polymer, branched polyether modified polysiloxane, and polyethylene glycol diglycidyl ether.

[0013] By adopting the above technical solution, trimethylol hexyl lactone cross-linked polymer, branched polyether modified polysiloxane, and polyethylene glycol diglycidyl ether work together to enhance the compatibility and interfacial bonding between the glass fiber and the resin matrix; the modified glass fiber blend forms strong chemical bonds and physical anchors with PEI and PPSU, significantly improving the overall strength, rigidity and toughness of the composite material and optimizing the material's impact resistance; the composite material has excellent stability in high temperature environments and maintains dimensional accuracy; the composite material exhibits excellent fluidity during the 3D printing process, avoiding problems such as clogging and wire breakage, ensuring the continuity and efficiency of printing, and the printed products have high surface quality and extremely low shrinkage, meeting the requirements of drones for component assembly accuracy.

[0014] Preferably, the weight ratio of the trimethylol hexyl lactone crosslinked polymer, the branched polyether modified polysiloxane, and the polyethylene glycol diglycidyl ether is 1:(1-2):(3-5).

[0015] By adopting the above technical solution, the trimethylol hexyl lactone cross-linked polymer, branched polyether modified polysiloxane, and polyethylene glycol diglycidyl ether in the reactive polyether functionalized polymer are combined in a weight ratio of 1: (1-2): (3-5), which can further exert the synergistic effect of the three, enhance the compatibility and interfacial bonding between the glass fiber and the resin matrix; combine the synergistic effect of the modified glass fiber blend with PEI and PPSU, and improve the strength, rigidity and toughness of the composite material, effectively resist complex external force impact and vibration, ensure the structural integrity and reliability of the UAV components, and improve flight performance and safety. The combination of high-performance thermoplastic resin matrix, unique interface reinforcement structure of modified glass fiber blend and excellent heat resistance of TPSiV makes the composite material stable in high temperature environment, maintains dimensional accuracy, and expands the application range and service life of UAVs. With the good processing performance of TPSiV, good compatibility between raw materials, and treatment of glass fiber surface by wetting activator and interface reinforcement agent, the composite material has good printing fluidity, avoids clogging and wire breakage problems, improves production efficiency, reduces costs, and prints products with high surface quality and low shrinkage, meeting the assembly precision requirements of UAV parts and improving overall performance and reliability.

[0016] Preferably, the diameter of the glass fiber is 1-100 microns.

[0017] By adopting the above technical solution, this glass fiber diameter range can better cooperate with other raw materials. When preparing glass fiber composites for 3D printing, it helps to fully mix the modified glass fiber blend with raw materials such as PEI and PPSU, further improving the mechanical properties, heat resistance and 3D printing performance of the composite material. For example, it enhances the strength and rigidity of the composite material, improves the dimensional stability in high temperature environments, avoids problems such as blockage and wire breakage during 3D printing, and ensures the surface quality and dimensional accuracy of the printed products.

[0018] Preferably, the modified glass fiber blend is prepared by the following method: wetting and activating the glass fiber filaments with a wetting activator, and then treating them with an interfacial strengthening agent after surface drying. The glass fibers are sheared to obtain glass fibers, which are then uniformly mixed with molten TPSiV to obtain the modified glass fiber blend.

[0019] By adopting the above technical solution, the step-by-step treatment method ensures that each treatment step can precisely perform its role. The wetting activator treatment improves the wettability of the glass fiber surface, creating ideal conditions for the subsequent adsorption and reaction of the interfacial strengthener, allowing the interfacial strengthener to be more evenly coated on the glass fiber surface. The interfacial strengthener treatment constructs a multi-layered, high-strength interface structure on the glass fiber surface, greatly enhancing the interfacial bonding between the glass fiber and the resin matrix, and effectively preventing the glass fiber from pulling out and slipping when the composite is subjected to stress. TPSiV is uniformly mixed with the molten state. The unique sea-island structure of TPSiV imparts excellent flexibility and processing properties to the blend. At the same time, its excellent heat resistance, chemical resistance, environmental protection, good adhesion, and recyclability further enhance the overall performance of the composite material, resulting in excellent mechanical properties, heat resistance, and 3D printing performance. Specifically, the composite material has high strength, high rigidity, good toughness, good stability in high temperature environments, high dimensional accuracy, good flowability during 3D printing, can avoid plugging and wire breakage, high surface quality of the finished product, and low shrinkage.

[0020] Preferably, the plasticizer is triphenyl phosphate and / or polypropylene adipate.

[0021] By adopting the above technical solution, a modified glass fiber blend is combined with PEI, PPSU, a plasticizer, a compatibilizer, and a processing aid. The modified glass fiber blend is prepared by treating the glass fiber with a wetting activator and an interfacial strengthening agent before blending it with TPSiV. This improves the overall mechanical and heat resistance of the material, enhances the interfacial bonding strength between the glass fiber and the resin matrix, and improves the material's 3D printing performance. The use of triphenyl phosphate and / or polypropylene adipate as plasticizers further optimizes the material's plasticity and flexibility, making it easier to form during processing and improving production efficiency and product quality.

[0022] Preferably, the compatibilizer is SEBS-g-MAH and / or PTW.

[0023] By adopting the above technical solution, SEBS-g-MAH and / or PTW are used as compatibilizers in glass fiber composite materials for 3D printing containing modified glass fiber blends, PEI, PPSU, plasticizers and processing aids. This can improve the compatibility between the raw materials, further enhance the overall performance of the composite material, make the composite material more fluid during the 3D printing process, avoid problems such as clogging and wire breakage, ensure the continuity and efficiency of printing, and at the same time, the printed products have higher surface quality, smaller shrinkage rate, and higher dimensional accuracy, meeting the requirements of drones for component assembly accuracy and improving the overall performance and reliability of drones.

[0024] Preferably, the processing aid is a mixture of one or more of a release agent, a lubricant, an antioxidant, an anti-UV agent, a heat stabilizer and an antibacterial agent.

[0025] By adopting the above technical solution, in a glass fiber composite material for 3D printing composed of a modified glass fiber blend, PEI, PPSU, a plasticizer, a compatibilizer, and a processing aid, one or more of a release agent, a lubricant, an antioxidant, an anti-UV agent, a heat stabilizer, and an antibacterial agent are used as processing aids. The release agent can enable the composite material to be smoothly removed from the mold after molding, thereby improving production efficiency and product quality; the lubricant can improve the fluidity of the material during processing, reduce friction, and make extrusion and other processing processes smoother; the antioxidant can prevent the material from being oxidized during processing and use, thereby extending the service life of the material; and the heat stabilizer works together to avoid thermal decomposition of some raw materials during high-temperature extrusion or 3D printing, thereby improving the stability of production quality and maintaining good quality even when used under long-term high temperatures; the anti-UV agent can enhance the material's resistance to ultraviolet rays and reduce the impact of ultraviolet rays on the material's properties; the antibacterial agent can inhibit bacterial growth, making the composite material suitable for application scenarios with requirements for sanitary conditions, thereby comprehensively improving the processing performance and use performance of the composite material.

[0026] In a second aspect, a method for preparing a glass fiber composite material for 3D printing comprises the following steps: weighing a modified glass fiber blend, PEI, PPSU, a plasticizer, a compatibilizer, and a processing aid in parts by weight, mixing them evenly, melt-extruding, and cooling to obtain a glass fiber composite material for 3D printing.

[0027] By adopting the above technical solution, the modified glass fiber blend, PEI, PPSU, plasticizer, compatibilizer, and processing aid are uniformly mixed by weight, melt-extruded, cooled, and granulated to produce a glass fiber composite material for 3D printing. This composite material has excellent mechanical properties, effectively resisting external impact and vibration, ensuring the structural integrity and reliability of drone components, and improving the flight performance and safety of drones. It also has excellent heat resistance and good stability in high-temperature environments, and can maintain dimensional accuracy for long periods of time, meeting the needs of drones in extreme environments. It also has excellent 3D printing performance, good fluidity during printing, avoiding blockages and broken wires, ensuring printing continuity and efficiency, and the product has high surface quality and low shrinkage, which can meet the strict requirements of drone component assembly precision.

[0028] In summary, this application includes at least one of the following beneficial technical effects: 1. The modified glass fiber blend works synergistically with PEI and PPSU, resulting in excellent interfacial bonding strength between the glass fiber and the resin matrix. This gives the composite material high strength, high rigidity, and good toughness, making it resistant to complex external forces, shocks, and vibrations. This ensures the structural integrity and reliability of UAV components, improving flight performance and safety. 2. Using PEI and PPSU as the resin matrix, combined with the unique interface reinforcement structure of the modified glass fiber blend and the excellent heat resistance of TPSiV, the composite material is stable at high temperatures, does not soften or deform, and can maintain dimensional accuracy for a long time, meeting the needs of UAV use in extreme environments; 3. Due to the good processing performance of TPSiV, good compatibility of various raw materials and effective surface treatment of glass fiber, composite materials have excellent fluidity during 3D printing, avoiding blockage and wire breakage, ensuring continuous and efficient printing, and improving production efficiency. The printed products have high surface quality, do not require complex subsequent processing, have low shrinkage rate, and high dimensional accuracy, meeting the assembly precision requirements of drone parts. DETAILED DESCRIPTION

[0029] The present application is further described in detail below with reference to the embodiments.

[0030] Source of raw materials: TPSiV: Kangdaoning nylon matrix TPSiV 1180; PEI (polyetherimide): molecular weight (Mn) 30,000-500,000; PPSU: Brand model: American Solvay PPSU R-5000; Organic polyborosilazane: It is a liquid precursor polymer composed of repeating Si-N units and Si-N-B units. It can be used as a thermosetting resin and is cross-linked and cured in air or an inert atmosphere at 120-180°C. The molecular weight (Mn) is 700-900; the viscosity at 25°C is 11,000-21,000 cp. Side chain acrylate modified silicone oil: Lana White, product number lnb-1013; Trimethylol hexyl lactone crosspolymer: Maidehao model MDH; Branched polyether modified polysiloxane: brand model IOTAIOTA13541; Polyethylene glycol diglycidyl ether: CAS No. 39443-66-8.

[0031] Preparation example of modified glass fiber blend Preparation Example 1 A modified glass fiber blend is prepared by the following method: The wetting activator is prepared by dissolving a reactive polyether functional polymer in an ethanol solution with a mass fraction of 70%, wherein the amount of the reactive polyether functional polymer is 30 g / L.

[0032] The interface strengthener is prepared by dispersing 50 g / L of active ingredient and 1 g / L of benzoyl peroxide in a diluent, wherein the diluent is a mixture of toluene and acetone in a weight ratio of 1:9. Glass fiber filaments with a diameter of 20 microns are conveyed to a tank containing a wetting activator at a rate of 1 m / min, so that the glass fiber filaments are fully in contact with the wetting activator for 5 minutes for wetting activation treatment, and then continued to be conveyed to a 60°C oven for 2 minutes to evaporate the solvent on the surface and dry the surface. Then, they are continued to be conveyed to a tank containing an interfacial strengthener and fully contacted with the interfacial strengthener for 5 minutes. Then, they are continued to be conveyed to a 120°C oven for 1 minute to evaporate the diluent on the surface, and then enter the shearing device for shearing to obtain glass fibers with a length of 50 microns. The glass fibers are then mixed evenly with TPSiV in a molten state at a temperature of 180°C, cooled to 25°C, crushed, and sieved through 50 mesh to obtain a modified glass fiber blend. The weight ratio of glass fibers with a length of 50 microns to TPSiV is 10:1.

[0033] The reactive polyether functional polymer is composed of trimethylol hexyl lactone cross-linked polymer and polyethylene glycol diglycidyl ether in a weight ratio of 1:3; the active ingredient of the interface strengthener is composed of 1,3-bis(3-methacryloyloxypropyl)tetrakis(trimethylsiloxy)disiloxane and organic polyborosilazane in a weight ratio of 3:1.

[0034] Preparation Example 2 Preparation Example 2 differs from Preparation Example 1 in that the reactive polyether functional polymer is composed of branched polyether-modified polysiloxane and polyethylene glycol diglycidyl ether in a weight ratio of 1:3.

[0035] Preparation Example 3 Preparation Example 3 is different from Preparation Example 1 in that the reactive polyether functional polymer is composed of trimethylol hexyl lactone crosslinked polymer, branched polyether modified polysiloxane, and polyethylene glycol diglycidyl ether in a weight ratio of 1:1:3.

[0036] Preparation Example 4 Preparation Example 4 differs from Preparation Example 3 in that the active ingredient of the interface strengthener is composed of 1,3-bis(3-methacryloxypropyl)tetrakis(trimethylsiloxy)disiloxane and side chain acrylate modified silicone oil in a weight ratio of 3.5:1.5.

[0037] Preparation Example 5 Preparation Example 5 is different from Preparation Example 3 in that the effective ingredients of the interface strengthener are composed of 1,3-bis(3-methacryloxypropyl)tetrakis(trimethylsiloxy)disiloxane side chain acrylate modified silicone oil, side chain acrylate modified silicone oil, and organic polyborosilazane in a weight ratio of 3:0.5:0.5.

[0038] Preparation Comparative Example Preparation Comparative Example 1 The difference between Preparation Comparative Example 1 and Preparation Example 1 is that the process is different, and only the wetting activator is used to wet-activate the glass fiber, as follows: Glass fiber filaments with a diameter of 20 microns are conveyed to a tank containing a wetting activator at a rate of 1 m / min, so that the glass fiber filaments are fully in contact with the wetting activator for 5 minutes for wetting activation treatment, and then continue to be conveyed to a 60°C oven for 2 minutes to evaporate the solvent on the surface and dry the surface. The glass fiber filaments are then sheared to obtain glass fibers with a length of 50 microns. The glass fibers are then mixed evenly with TPSiV in a molten state at a temperature of 180°C, cooled to 25°C, crushed, and sieved through 50 mesh to obtain a modified glass fiber blend.

[0039] Preparation Comparative Example 2 The difference between Preparation Example 2 and Preparation Example 1 is that the process is different. Only the interface strengthener is used for treatment. The specific process is as follows: Glass fiber filaments with a diameter of 20 microns were conveyed to a tank containing an interfacial strengthener at a rate of 1 m / min, so that they were fully in contact with the interfacial strengthener for 5 minutes, and then continued to be conveyed to a 120°C oven for 1 minute to volatilize the diluent on the surface, and then entered the shearing device for shearing to obtain glass fibers with a length of 50 microns. The fibers were then mixed evenly with TPSiV in a molten state at a temperature of 180°C, cooled to 25°C, crushed, and sieved through 50 mesh to obtain a modified glass fiber blend.

[0040] Preparation Comparative Example 3 The difference between Preparation Example 3 and Preparation Example 1 is that the process is different, and no copolymerization with TPSiV is performed. The specific process is as follows: Glass fiber filaments with a diameter of 20 microns are conveyed to a tank containing a wetting activator at a rate of 1 m / min, so that the glass fiber filaments are fully in contact with the wetting activator for 5 minutes for wetting activation treatment, and then continue to be conveyed to a 60°C oven for 2 minutes to evaporate the solvent on the surface and dry the surface. Then, they are continued to be conveyed to a tank containing an interfacial strengthener and fully in contact with the interfacial strengthener for 5 minutes. Then, they are continued to be conveyed to a 120°C oven for 1 minute to evaporate the diluent on the surface, and then enter the shearing device for shearing. The shearing obtains glass fibers with a length of 50 microns as modified glass fiber blends.

[0041] Preparation Comparative Example 4 The difference between Preparation Comparative Example 4 and Preparation Example 1 is that the active ingredient of the interface strengthener is silane coupling agent KH550. Example

[0042] Example 1 A glass fiber composite material for 3D printing is prepared by the following method: According to parts by weight, 10 kg of modified glass fiber blend obtained in Preparation Example 1, 30 kg of PEI, 50 kg of PPSU, 3 kg of plasticizer, 8 kg of compatibilizer, and 5 kg of processing aid were weighed and mixed evenly, and then fed into a twin-screw extruder (the maximum setting temperature was 360 ° C, and the temperature of the extrusion die was 300 ° C. This temperature setting can fully mix the materials and avoid decomposition of some raw materials at higher temperatures) for melt extrusion and cooling to 25 ° C to obtain a glass fiber composite material for 3D printing.

[0043] The compatibilizer is PTW (ethylene-acrylate-methyl glycidyl ester terpolymer, brand model is French Arkema PTW); the plasticizer is dioctyl terephthalate; the processing aids are antioxidant 1010, ultraviolet absorber UV-326, calcium stearate, zinc stearate, and antibacterial agent (nanosilver) in a weight ratio of 1:1:1:1:1.

[0044] Example 2-3 The difference between Example 2-3 and Example 1 is that the amounts of raw materials used are different, as shown in Table 1; Table 1 Amount of raw materials used in Examples 1-3 (parts by weight) Examples 4-8 The difference between Examples 4-8 and Example 2 is that the sources of the modified glass fiber blends are different, as shown in Table 2; Table 2 Sources of modified glass fiber blends of Example 2 and Examples 4-8 Example Sources of Modified Glass Fiber Blends Example 4 Preparation Example 2 Example 5 Preparation Example 3 Example 6 Preparation Example 4 Example 7 Preparation Example 5 Example 8 Preparation Example 6 Comparative Example Comparative Examples 1-4 The difference between Comparative Examples 1-4 and Example 1 is that the sources of the modified glass fiber blends are different, as shown in Table 3; Table 3 Sources of modified glass fiber blends of Comparative Examples 1-4 Preparation Example Sources of Modified Glass Fiber Blends Preparation Example 1 Preparation Comparative Example 1 Preparation Example 2 Preparation Comparative Example 2 Preparation Example 3 Preparation Comparative Example 3 Preparation Example 4 Preparation Comparative Example 4 Performance Testing The glass fiber composite materials obtained in Examples 1-7 and Comparative Examples 1-4 were 3D printed at a temperature of 360° C., a hot bed temperature of 140° C., and a printing speed of 60 mm / s, and experimental samples for the following experiments were obtained.

[0045] Detection method / test method Elongation at break and tensile strength: tested with reference to ASTM D638-14.

[0046] Impact toughness: Refer to ASTM D256 to test the notched impact strength. The test conditions are 2mm V-notch, temperature is 25℃, and the thickness of the test sample is 3.2mm. The higher the notched impact strength, the better the impact toughness.

[0047] High temperature resistance test: Place the test sample in an oven at 195°C for 7 days, take it out and place it at room temperature for 24 hours, then test the tensile strength using the test method and calculate the tensile strength residual rate (equal to the tensile strength after the high temperature resistance test divided by the tensile strength before the high temperature resistance test, multiplied by 100%).

[0048] The above experimental data are shown in the following table; Table 4 Experimental data of Examples 1-8 and Comparative Examples 1-4 Combined with the experimental results of Examples 1-7 and Comparative Examples 1-4 and Table 4, the following analysis was performed; 1. Example 1 and Comparative Examples 1-4, Example 1 corresponds to the modified glass fiber blend of Preparation Example 1, and Comparative Examples 1-4 correspond to the modified glass fiber blends of Preparation Examples 1-4. It can be seen from Table 4 that the notched impact strength, tensile strength, elongation at break, and tensile strength residual rate of Comparative Examples 1-4 are all lower than those of Example 1, indicating that the specific preparation process of the modified glass fiber blend of the present application constructs a multi-level, high-strength interface structure on the surface of the glass fiber, greatly enhancing the interfacial bonding force between the glass fiber and the resin matrix; after blending with TPSiV, the comprehensive performance of the composite material is further improved, so that the final product obtains better mechanical properties and heat resistance, meets the use requirements of drone components in complex environments, and improves the flight performance, safety and overall reliability of the drone.

[0049] 2. Example 2 and Example 5, Example 2 uses the modified glass fiber blend of Preparation Example 1, and Example 5 uses the modified glass fiber blend of Preparation Example 3. The difference lies in the composition of the reactive polyether functionalized polymer. From the experimental results, it can be seen that the notched impact strength, tensile strength, elongation at break and tensile strength residual rate of Example 2 are all lower than those of Example 5, indicating that Example 5 uses a reactive polyether functionalized polymer composed of trimethylol hexyl lactone cross-linked polymer, branched polyether modified polysiloxane, and polyethylene glycol diglycidyl ether, which has a better synergistic effect, thereby enabling the final material to obtain better comprehensive performance.

[0050] 3. Example 5 and Example 7, Example 5 uses the modified glass fiber blend of Preparation Example 3, and Example 7 uses the modified glass fiber blend of Preparation Example 5. The difference lies in the composition of the effective ingredient of the interface strengthener. From the experimental results, it can be seen that the notched impact strength, tensile strength, elongation at break and tensile strength residual rate of Example 5 are lower than those of Example 7, indicating that the effective ingredient of the interface strengthener used in Example 7 is composed of 1,3-bis(3-methacryloxypropyl)tetra(trimethylsiloxy)disiloxane side chain acrylate modified silicone oil, side chain acrylate modified silicone oil, and organic polyborosilazane, which has a better synergistic effect, so that the final material obtains better comprehensive performance.

[0051] This specific embodiment is merely an explanation of the present application and is not a limitation of the present application. After reading this specification, those skilled in the art may make non-creative modifications to the present embodiment as needed, but as long as they are within the scope of the claims of the present application, they are protected by the patent law.

Claims

1. A glass fiber composite material for 3D printing, characterized in that: The invention comprises the following raw materials in parts by weight: 10-30 parts of modified glass fiber blend PEI: 30-80 parts PPSU: 10-50 parts Plasticizer: 3-5 parts Compatibilizer: 5-8 parts Processing aids: 1-5 parts; The modified glass fiber blend is prepared by sequentially treating glass fiber with a wetting activator and an interfacial strengthening agent, and then blending with TPSiV; the active ingredient of the wetting activator is a reactive polyether functional polymer; the active ingredient of the interfacial strengthening agent is a mixture of 1,3-bis(3-methacryloxypropyl)tetrakis(trimethylsiloxy)disiloxane, side-chain acrylate-modified silicone oil, and organic polyborosilazane.

2. The glass fiber composite material for 3D printing according to claim 1, characterized in that: The weight ratio of the 1,3-bis(3-methacryloyloxypropyl)tetrakis(trimethylsiloxy)disiloxane, the side chain acrylate modified silicone oil and the organic polyborosilazane is 3:(0.5-1):(0.1-0.5).

3. The glass fiber composite material for 3D printing according to claim 1, characterized in that: The reactive polyether functionalized polymer is a combination of trimethylol hexyl lactone cross-linked polymer, branched polyether modified polysiloxane, and polyethylene glycol diglycidyl ether.

4. The glass fiber composite material for 3D printing according to claim 1, characterized in that: The weight ratio of the trimethylol hexyl lactone crosslinked polymer, the branched polyether modified polysiloxane, and the polyethylene glycol diglycidyl ether is 1:(1-2):(3-5).

5. The glass fiber composite material for 3D printing according to any one of claim 1, characterized in that: The diameter of the glass fiber is 1-100 microns.

6. A glass fiber composite material for 3D printing according to any one of claims 1 to 5, characterized in that: The modified glass fiber blend is prepared by the following method: The glass fiber filaments are wetted and activated by a wetting activator, and after being surface dried, they are treated with an interface reinforcing agent, and the glass fibers are sheared to obtain glass fibers, which are then uniformly mixed with TPSiV in a molten state to obtain a modified glass fiber blend.

7. The glass fiber composite material for 3D printing according to claim 1, characterized in that: The plasticizer is triphenyl phosphate and / or polypropylene adipate.

8. The glass fiber composite material for 3D printing according to claim 1, characterized in that: The compatibilizer is SEBS-g-MAH and / or PTW.

9. The glass fiber composite material for 3D printing according to claim 1, characterized in that: The processing aid is a mixture of one or more of a release agent, a lubricant, an antioxidant, an anti-UV agent, a heat stabilizer and an antibacterial agent.

10. A method for preparing a glass fiber composite material for 3D printing according to any one of claims 1 to 9, characterized in that: The following steps are involved: The modified glass fiber blend, PEI, PPSU, plasticizer, compatibilizer, and processing aid were weighed and mixed evenly according to parts by weight, melt-extruded, and cooled to obtain a glass fiber composite material for 3D printing.

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