Glass fiber composite material for 3D printing and method for producing the same

Abstract

The application relates to the field of high-performance composites, in particular to a glass fiber composite material for 3D printing and a preparation method thereof. The glass fiber composite material for 3D printing is characterized by comprising the following raw material components in parts by weight: modified glass fiber blend 10-30 parts, PEI 30-80 parts, PPSU 10-50 parts, plasticizer 3-5 parts, compatibilizer 5-8 parts and processing aid 1-5 parts; the modified glass fiber blend is prepared by blending TPSiV after glass fibers are treated with a wetting activator and an interface strengthening agent in sequence; and the effective component of the wetting activator is a reactive polyether functional polymer. The modified glass fiber blend, PEI and PPSU have synergistic effects, the interface bonding strength between the glass fibers and the resin matrix is excellent, the composite material has high strength, high rigidity and good toughness, and can resist complex external force impact and vibration.

Description

Technical Field

[0001] This application relates to the field of high-performance composites, and more specifically, to a glass fiber composite material for 3D printing and a method for preparing the same. Background Technology

[0002] In recent years, drone technology has developed rapidly, demonstrating enormous application value in numerous fields such as aerial photography, surveying and mapping, logistics and distribution, and agricultural plant protection. As the application scenarios for drones continue to expand, the performance requirements for drone components are also increasing. Drones need to fly in complex environments, facing various external impacts, vibrations, and different climatic conditions; therefore, their components must possess characteristics such as high strength, high rigidity, good heat resistance, and dimensional stability. 3D printing technology, as an advanced manufacturing technology, offers advantages such as rapid prototyping, the ability to achieve complex structural designs, and personalized customization, providing a new approach to the manufacturing of drone components. Through 3D printing, drone components that meet specific design requirements can be manufactured quickly, shortening the R&D cycle and reducing production costs. However, traditional 3D printing materials often fail to meet the strength and rigidity requirements of drone components; therefore, developing a high-performance material for 3D printing is of significant practical importance. Glass fiber composites, with their excellent mechanical properties such as high strength and high modulus, have become one of the ideal choices for 3D printing materials for drone components.

[0003] In the field of 3D printing, research on glass fiber composites has made some progress. A common preparation method involves combining glass fibers with a thermoplastic resin matrix, then using specific processes to create filaments or granules suitable for 3D printing. Commonly used thermoplastic resin matrices include acrylonitrile-butadiene-styrene copolymer (ABS) and polyamide (PA). During preparation, a melt blending method is typically used, where the glass fibers and resin matrix are mixed uniformly at high temperatures, and then extruded to form filaments or granules. Some studies have also treated the surface of the glass fibers to improve their interfacial bonding with the resin matrix, thereby enhancing the overall performance of the composite material. Furthermore, to improve flowability and print quality during 3D printing, additives such as lubricants and plasticizers are often added.

[0004] Despite the progress made in the application of glass fiber composites for 3D printing, some significant shortcomings remain. Regarding the interfacial bonding between the glass fiber and the resin matrix, although surface treatment has been performed, the interfacial bond strength is still not ideal. During the use of drone components, when subjected to external forces, debonding can easily occur between the glass fiber and the resin matrix, leading to a decrease in the material's mechanical properties and affecting the reliability and lifespan of the components. Summary of the Invention

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

[0006] Firstly, a glass fiber composite material for 3D printing comprises the following raw material components in parts by weight: 10-30 parts of modified glass fiber blend.

[0007] PEI: 30-80 copies

[0008] PPSU: 10-50 servings

[0009] Plasticizer: 3-5 parts

[0010] Compatibilizer: 5-8 parts

[0011] Processing aids: 1-5 parts;

[0012] The modified glass fiber blend is prepared by sequentially treating glass fibers with a wetting activator and an interface strengthening agent, and then blending them with TPSiV. The effective component of the wetting activator is a reactive polyether functionalized polymer. The effective component of the interface strengthening agent is a mixture of multiple components including 1,3-bis(3-methacryloyloxypropyl)tetra(trimethylsiloxy)disiloxane, side-chain acrylate modified silicone oil, and organopolyborosilicate.

[0013] By adopting the above technical solution, this glass fiber composite material achieves a comprehensive improvement in mechanical properties, heat resistance, and 3D printing performance through a unique modification process and component combination. It is particularly suitable for manufacturing drone parts and has broad application prospects. The specific preparation process of the modified glass fiber blend involves treating the glass fiber sequentially with a wetting activator and an interface strengthening agent before blending it with TPSiV. This step-by-step treatment ensures that each step fully utilizes its potential.

[0014] The wetting activator treatment gives the glass fiber surface good wettability, providing an ideal basis for the adsorption and reaction of the interface strengthening agent; the interface strengthening agent treatment constructs a multi-layered, high-strength interface structure on the glass fiber surface, which greatly enhances the interfacial bonding force between the glass fiber and the resin matrix; after blending with TPSiV, its unique sea-island structure gives the blend excellent flexibility and processing performance, and its excellent heat resistance, chemical resistance, environmental protection properties, good adhesion and recyclability further improve the overall performance of the composite material.

[0015] The reactive polyether functionalized wetting activator and interface reinforcing agent work together to form a transition layer with good wettability and reactivity on the glass fiber surface, which enhances 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, meets the usage requirements of UAV parts in complex environments, and enhances the flight performance, safety and overall reliability of the UAV.

[0016] Preferably, the weight ratio of the 1,3-bis(3-methacryloyloxypropyl)tetra(trimethylsiloxy)disiloxane, the side-chain acrylate-modified silicone oil, and the organopolyborosilicate is 3:(0.5-1):(0.1-0.5).

[0017] By adopting the above technical solution, 1,3-bis(3-methacryloyloxypropyl)tetra(trimethylsiloxy)disiloxane, side-chain acrylate modified silicone oil, and organopolyborosilicate are used to prepare modified glass fiber blends in a weight ratio of 3:(0.5-1):(0.1-0.5). The three components can form a "point-surface-bond" synergistic system through structural complementarity and functional division in the surface modification of glass fibers, which significantly improves the interfacial bonding force, weather resistance, and compatibility with the matrix between glass fibers and resin matrix. It is especially suitable for glass fiber pretreatment of high-performance composite materials. By combining modified glass fiber blends with PEI, PPSU, and other components, the composite material possesses excellent mechanical properties, effectively resisting complex external impacts and vibrations, ensuring the structural integrity and reliability of parts; it also exhibits superior heat resistance, remaining stable at high temperatures without softening or deforming, meeting the usage requirements of drones in extreme environments; and it boasts outstanding 3D printing performance, avoiding head clogging and filament breakage issues, ensuring continuous and efficient printing, high surface quality of the finished products, and low shrinkage, meeting the assembly precision requirements of drone parts.

[0018] Preferably, the reactive polyether functionalized polymer is composed of multiple components including trimethylolhexyl lactone crosslinked polymer, branched polyether modified polysiloxane, and polyethylene glycol diglycidyl ether.

[0019] By adopting the above technical solutions, the trimethylolpropionic acid crosslinking polymer, branched polyether modified polysiloxane, and polyethylene glycol diglycidyl ether work together to enhance the compatibility and interfacial bonding between glass fiber and resin matrix. The modified glass fiber blend forms strong chemical bonds and physical anchoring with PEI and PPSU, significantly improving the overall strength, rigidity, and toughness of the composite material and optimizing its impact resistance. This enables the composite material to have excellent stability at high temperatures and maintain dimensional accuracy. It also allows the composite material to exhibit excellent flowability during 3D printing, avoiding problems such as nozzle clogging and filament breakage, ensuring the continuity and efficiency of printing. The printed products have high surface quality and minimal shrinkage, meeting the precision requirements of UAV component assembly.

[0020] Preferably, the weight ratio of the trimethylolpropionic acid crosslinker, the branched polyether modified polysiloxane, and the polyethylene glycol diglycidyl ether is 1:(1-2):(3-5).

[0021] By adopting the above technical solution, the trimethylolpropionic acid crosslinking 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). This further enhances the synergistic effect of the three components, strengthening the compatibility and interfacial bonding between the glass fiber and the resin matrix. Combined with the synergistic effect of the modified glass fiber blend with PEI and PPSU, the strength, rigidity, and toughness of the composite material are improved, effectively resisting complex external impacts and vibrations, ensuring the structural integrity and reliability of UAV components, and improving flight performance and safety. The composite material exhibits excellent heat resistance; combining a high-performance thermoplastic resin matrix, a unique interfacial reinforcement structure of modified glass fiber blends, and TPSiV's excellent heat resistance, ensuring stability in high-temperature environments, maintaining dimensional accuracy, and expanding the application range and service life of drones. Furthermore, the good processing performance of TPSiV, the good compatibility between various raw materials, and the surface treatment of glass fibers by wetting activators and interfacial strengtheners result in good printing flowability of the composite material, avoiding problems such as clogging and filament breakage, improving production efficiency, reducing costs, and producing high-quality printed products with low shrinkage, meeting the assembly precision requirements of drone components, and enhancing overall performance and reliability.

[0022] Preferably, the diameter of the glass fiber is 1-100 micrometers.

[0023] By adopting the above technical solution, the diameter range of this glass fiber can be better matched with other raw materials. When preparing glass fiber composite materials for 3D printing, it helps the modified glass fiber blend to be fully mixed with raw materials such as PEI and PPSU, further improving the mechanical properties, heat resistance properties 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 head blockage and filament breakage during 3D printing, and ensures the surface quality and dimensional accuracy of the printed products.

[0024] Preferably, 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 surface drying, they are treated with an interface strengthening agent, sheared to obtain glass fibers, and then mixed evenly with molten TPSiV to obtain the modified glass fiber blend.

[0025] By adopting the above technical solution, the step-by-step processing method ensures that each step plays its precise role. The wetting and activating agent treatment gives the glass fiber surface good wettability, creating ideal conditions for the adsorption and reaction of the interface strengthening agent, allowing the interface strengthening agent to cover the glass fiber surface more evenly. The interface strengthening agent treatment constructs a multi-layered, high-strength interface structure on the glass fiber surface, greatly enhancing the interfacial bonding force between the glass fiber and the resin matrix, effectively preventing the glass fiber from being pulled out and slipping when the composite material is under stress. When mixed evenly with molten TPSiV, the unique sea-island structure of TPSiV gives the blend excellent flexibility and processing performance. At the same time, its excellent heat resistance, chemical resistance, environmental protection characteristics, good adhesion and recyclability further improve the comprehensive performance of the composite material, making the composite material perform well in terms of mechanical properties, heat resistance and 3D printing performance. Specifically, it has high strength, high rigidity, good toughness, good stability in high temperature environment, high dimensional accuracy, good fluidity during 3D printing, avoids the problem of clogging and filament breakage, high surface quality of products and low shrinkage.

[0026] Preferably, the plasticizer is triphenyl phosphate and / or polypropylene adipate.

[0027] By employing the above technical solution, a combination of modified glass fiber blend, PEI, PPSU, plasticizer, compatibilizer, and processing aids is used. The modified glass fiber blend is prepared by sequentially treating glass fibers with a wetting activator and an interface strengthening agent before blending them with TPSiV. This approach improves the overall mechanical and heat resistance properties of the material, enhances the interfacial bonding strength between the glass fiber and the resin matrix, and improves the material's 3D printing performance. Using triphenyl phosphate and / or polypropylene adipate as plasticizers further optimizes the material's plasticity and flexibility, making it easier to mold during processing and improving production efficiency and product quality.

[0028] Preferably, the compatibilizer is SEBS-g-MAH and / or PTW.

[0029] By adopting the above technical solution, using SEBS-g-MAH and / or PTW as compatibilizers in glass fiber composites for 3D printing containing modified glass fiber blends, PEI, PPSU, plasticizers, and processing aids can improve the compatibility between raw materials, further enhance the overall performance of the composite material, make the composite material flow better during the 3D printing process, avoid problems such as clogging and filament breakage, ensure the continuity and efficiency of printing, and at the same time, the printed products have higher surface quality, lower shrinkage, and higher dimensional accuracy, meeting the requirements of UAVs for component assembly precision and improving the overall performance and reliability of UAVs.

[0030] Preferably, the processing aid is one or a mixture of more than one of the following: release agent, lubricant, antioxidant, UV stabilizer, heat stabilizer, and antibacterial agent.

[0031] By adopting the above technical solution, in the glass fiber composite material for 3D printing composed of modified glass fiber blends, PEI, PPSU, plasticizers, compatibilizers, and processing aids, one or more of the following processing aids are used: release agent, lubricant, antioxidant, UV stabilizer, heat stabilizer, and antibacterial agent. The release agent allows the composite material to be smoothly ejected from the mold after molding, improving production efficiency and product quality. The lubricant improves the fluidity of the material during processing, reduces friction, and makes extrusion and other processing processes smoother. The antioxidant prevents the material from being oxidized during processing and use, extending the material's service life. The heat stabilizer works together to avoid thermal decomposition of some raw materials during high-temperature extrusion or 3D printing, improving the stability of production quality and maintaining good quality even under long-term high-temperature use. The UV stabilizer enhances the material's resistance to ultraviolet rays, reducing the impact of ultraviolet rays on material performance. The antibacterial agent inhibits bacterial growth, making the composite material suitable for applications with hygiene requirements. Overall, the processing and performance of the composite material are improved.

[0032] Secondly, a method for preparing a glass fiber composite material for 3D printing includes the following steps: weighing modified glass fiber blend, PEI, PPSU, plasticizer, compatibilizer and processing aid according to weight parts, mixing them evenly, melting and extruding, and cooling to obtain a glass fiber composite material for 3D printing.

[0033] By adopting the above technical solution, modified glass fiber blends, PEI, PPSU, plasticizers, compatibilizers, and processing aids are mixed evenly according to their weight proportions, then melt-extruded, cooled, and granulated to obtain glass fiber composite materials for 3D printing. This composite material possesses excellent mechanical properties, effectively resisting external impacts and vibrations, ensuring the structural integrity and reliability of drone components, and improving the flight performance and safety of drones. It also exhibits excellent heat resistance, maintaining good stability in high-temperature environments and preserving dimensional accuracy over long periods, meeting the usage requirements of drones in extreme environments. Furthermore, it boasts outstanding 3D printing performance, with good flowability during printing, avoiding problems such as nozzle clogging and filament breakage, ensuring printing continuity and efficiency, producing high-quality products with low shrinkage, and meeting the stringent requirements of drone component assembly precision.

[0034] In summary, this application includes at least one of the following beneficial technical effects:

[0035] 1. Modified glass fiber blends synergistically enhance the effects of PEI and PPSU. The excellent interfacial bonding strength between glass fiber and resin matrix results in high strength, high rigidity, and good toughness of the composite material, which can resist complex external impacts and vibrations, ensuring the structural integrity and reliability of UAV components and improving flight performance and safety.

[0036] 2. Using PEI and PPSU as resin matrices, combined with the unique interfacial reinforcement structure of modified glass fiber blends 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 UAVs in extreme environments.

[0037] 3. Due to the good processing performance of TPSiV, the excellent compatibility of various raw materials, and the effective surface treatment of glass fiber, the composite material exhibits excellent flowability during 3D printing, avoiding head clogging and filament breakage, ensuring continuous and efficient printing, and improving production efficiency; the printed products have high surface quality, require no complex post-processing, have low shrinkage, and high dimensional accuracy, meeting the assembly precision requirements of UAV parts. Detailed Implementation

[0038] The present application will be further described in detail below with reference to the embodiments.

[0039] Source of raw materials:

[0040] TPSiV: Candolin nylon matrix TPSiV 1180;

[0041] PEI (polyetherimide): molecular weight (Mn) 30,000-500,000;

[0042] PPSU: Brand and model: Solvay PPSU R-5000 (USA);

[0043] Organopolyborosilicate: a liquid precursor polymer composed of repeating Si-N and Si-NB units, which can be used as a thermosetting resin. It can be cross-linked and cured in air or an inert atmosphere at 120-180℃. The molecular weight (Mn) is 700-900; the viscosity at 25℃ is 11000-21000cp.

[0044] Side-chain acrylate modified silicone oil: Rana White, product number LNB-1013;

[0045] Trimethylolhexyl lactone crosslinking polymer: Maidehao model MDH;

[0046] Branched polyether modified polysiloxane: Brand and model IOTAIOTA13541;

[0047] Polyethylene glycol diglycidyl ether: CAS No. 39443-66-8.

[0048] Preparation example of modified glass fiber blends

[0049] Preparation Example 1

[0050] A modified glass fiber blend is prepared by the following method:

[0051] The wetting activator is obtained by dissolving a reactive polyether functionalized polymer in a 70% (w / w) ethanol solution, wherein the amount of the reactive polyether functionalized polymer is 30 g / L.

[0052] The interface strengthening agent is obtained by dispersing 50 g / L of active ingredient and 1 g / L of benzoyl peroxide in a diluent, which is a mixture of toluene and acetone at a weight ratio of 1:9.

[0053] Glass fiber filaments with a diameter of 20 micrometers are fed into a tank containing a wetting activator at a rate of 1 m / min, allowing the glass fiber filaments to fully contact the wetting activator for 5 minutes for wetting and activation treatment. They are then fed into a 60°C oven for 2 minutes to allow the solvent on the surface to evaporate and the surface to dry. They are then fed into a tank containing an interface strengthening agent, allowing them to fully contact the interface strengthening agent for 5 minutes. They are then fed into a 120°C oven for 1 minute to allow the diluent on the surface to evaporate. They are then fed into a shearing device for shearing to obtain glass fibers with a length of 50 micrometers. These fibers are then mixed evenly with TPSiV in a molten state at a temperature of 180°C, cooled to 25°C, pulverized, and sieved through a 50-mesh sieve to obtain a modified glass fiber blend. The weight ratio of the 50-micrometer glass fiber to TPSiV is 10:1.

[0054] The reactive polyether functionalized polymer is composed of trimethylolhexyl lactone crosslinked polymer and polyethylene glycol diglycidyl ether in a weight ratio of 1:3; the effective component of the interface reinforcing agent is composed of 1,3-bis(3-methacryloyloxypropyl)tetra(trimethylsiloxy)disiloxane and organopolyborosilicate in a weight ratio of 3:1.

[0055] Preparation Example 2

[0056] The difference between Preparation Example 2 and Preparation Example 1 is that the reactive polyether functionalized polymer is composed of branched polyether modified polysiloxane and polyethylene glycol diglycidyl ether in a weight ratio of 1:3.

[0057] Preparation Example 3

[0058] The difference between Preparation Example 3 and Preparation Example 1 is that the reactive polyether functionalized polymer is composed of trimethylolhexyl lactone crosslinked polymer, branched polyether modified polysiloxane, and polyethylene glycol diglycidyl ether in a weight ratio of 1:1:3.

[0059] Preparation Example 4

[0060] The difference between Preparation Example 4 and Preparation Example 3 is that the effective component of the interface strengthening agent is composed of 1,3-bis(3-methacryloyloxypropyl)tetra(trimethylsiloxy)disiloxane and side-chain acrylate modified silicone oil in a weight ratio of 3.5:1.5.

[0061] Preparation Example 5

[0062] The difference between Preparation Example 5 and Preparation Example 3 is that the effective component of the interface strengthening agent is composed of 1,3-bis(3-methacryloyloxypropyl)tetra(trimethylsiloxy)disiloxane side-chain acrylate modified silicone oil, side-chain acrylate modified silicone oil, and organopolyborosilicate in a weight ratio of 3:0.5:0.5.

[0063] Preparation of comparative examples

[0064] Preparation of Comparative Example 1

[0065] The difference between Comparative Example 1 and Preparation Example 1 lies in the process; only a wetting activator is used to wet and activate the glass fibers, as detailed below:

[0066] Glass fiber filaments with a diameter of 20 micrometers are fed into a tank containing a wetting activator at a rate of 1 m / min, allowing the glass fiber filaments to fully contact the wetting activator for 5 minutes for wetting and activation treatment. Then, they are fed into a 60°C oven for 2 minutes to allow the solvent on the surface to evaporate and the surface to dry. Then, they are sheared by a shearing device to obtain glass fibers with a length of 50 micrometers. These fibers are then mixed evenly with TPSiV in a molten state at a temperature of 180°C, cooled to 25°C, pulverized, and sieved through a 50-mesh sieve to obtain a modified glass fiber blend.

[0067] Preparation of Comparative Example 2

[0068] The difference between Comparative Example 2 and Comparative Example 1 lies in the process; only an interface strengthening agent is used for treatment. The specific process is as follows:

[0069] Glass fiber filaments with a diameter of 20 micrometers are fed into a tank containing an interface strengthening agent at a rate of 1 m / min, allowing them to fully contact the interface strengthening agent for 5 minutes. They are then fed into a 120°C oven for 1 minute to allow the surface diluent to evaporate. After that, they are sheared by a shearing device to obtain glass fibers with a length of 50 micrometers. These fibers are then mixed evenly with TPSiV in a molten state at a temperature of 180°C, cooled to 25°C, pulverized, and sieved through a 50-mesh sieve to obtain a modified glass fiber blend.

[0070] Preparation of Comparative Example 3

[0071] The difference between Comparative Example 3 and Preparation Example 1 lies in the process; it does not involve copolymerization with TPSiV. The specific process is as follows:

[0072] Glass fiber filaments with a diameter of 20 micrometers are fed into a tank containing a wetting activator at a rate of 1 m / min, allowing the glass fiber filaments to fully contact the wetting activator for 5 minutes for wetting and activation treatment. Then, they are fed into a 60°C oven for 2 minutes to allow the solvent on the surface to evaporate and the surface to dry. They are then fed into a tank containing an interface strengthening agent, allowing them to fully contact the interface strengthening agent for 5 minutes. They are then fed into a 120°C oven for 1 minute to allow the diluent on the surface to evaporate. Finally, they are fed into a shearing device for shearing, and the sheared glass fibers with a length of 50 micrometers are obtained as modified glass fiber blends.

[0073] Preparation of Comparative Example 4

[0074] The difference between Comparative Example 4 and Example 1 is that the effective component of the interface strengthening agent is silane coupling agent KH550.

[0075] Example

[0076] Example 1

[0077] A glass fiber composite material for 3D printing is prepared by the following method:

[0078] According to the weight proportions, 10 kg of modified glass fiber blend, 30 kg of PEI, 50 kg of PPSU, 3 kg of plasticizer, 8 kg of compatibilizer, and 5 kg of processing aid obtained in Preparation Example 1 were weighed and mixed evenly. The mixture was then fed into a twin-screw extruder (the maximum set temperature was 360°C, and the temperature of the extrusion die was 300°C. This temperature setting can ensure that the materials are fully mixed evenly and avoid the decomposition of some raw materials at higher temperatures) for melt extrusion. The mixture was then cooled to 25°C to obtain a glass fiber composite material for 3D printing.

[0079] The compatibilizer is PTW (ethylene-acrylate-methyl glycidyl ester terpolymer, brand name: Arkema PTW, France); the plasticizer is dioctyl terephthalate; the processing aids are antioxidant 1010, ultraviolet absorber UV-326, calcium stearate, zinc stearate, and antibacterial agent (nano silver) in a weight ratio of 1:1:1:1:1.

[0080] Example 2-3

[0081] The difference between Examples 2-3 and Example 1 is that the amount of raw materials used is different, as shown in Table 1.

[0082] Table 1. Raw material usage (parts by weight) for Examples 1-3

[0083]

[0084]

[0085] Examples 4-8

[0086] The difference between Examples 4-8 and Example 2 is that the source of the modified glass fiber blends is different, as shown in Table 2.

[0087] Table 2. Sources of the modified glass fiber blends in Examples 2 and 4-8

[0088] 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

[0089] Comparative Example

[0090] Comparative Examples 1-4

[0091] The difference between Comparative Examples 1-4 and Example 1 is that the source of the modified glass fiber blends is different, as shown in Table 3.

[0092] Table 3 shows the sources of the modified glass fiber blends in Comparative Examples 1-4.

[0093] Preparation Example Sources of modified glass fiber blends Preparation Example 1 Preparation of Comparative Example 1 Preparation Example 2 Preparation of Comparative Example 2 Preparation Example 3 Preparation of Comparative Example 3 Preparation Example 4 Preparation of Comparative Example 4

[0094] 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 heated bed temperature of 140°C, and a printing speed of 60 mm / s to test the performance. The resulting experimental samples were used in the following experiments.

[0095] Detection methods / test methods

[0096] Elongation at break and tensile strength: Tested according to ASTM D638-14.

[0097] Impact toughness: Notched impact strength was tested according to ASTM D256. The test conditions were a 2mm V-notch, a temperature of 25℃, and a sample thickness of 3.2mm. The higher the notched impact strength, the better the impact toughness.

[0098] High temperature resistance test: After placing the test sample in an oven at 195℃ for 7 days, take it out and place it at room temperature for 24 hours. Then, test the tensile strength according to the test method and calculate the tensile strength residual rate (which is equal to the tensile strength after the high temperature resistance test divided by the tensile strength before the high temperature resistance test, and then multiplied by 100%).

[0099] The experimental data are shown in the table below;

[0100] Table 4. Experimental data of Examples 1-8 and Comparative Examples 1-4

[0101]

[0102] Based on the experimental results of Examples 1-7, Comparative Examples 1-4, and Table 4, the following analysis is performed;

[0103] 1. Examples 1 and Comparative Examples 1-4: Example 1 corresponds to the modified glass fiber blend prepared in Example 1, and Comparative Examples 1-4 correspond to the modified glass fiber blend prepared in Comparative Examples 1-4. As can be seen from Table 4, the notched impact strength, tensile strength, elongation at break, and residual tensile strength of Comparative Examples 1-4 are all lower than those of Example 1. This indicates that the specific preparation process of the modified glass fiber blend of this application constructs a multi-layered, high-strength interface structure on the surface of the glass fiber, which greatly enhances 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 usage requirements of UAV components in complex environments, and improves the flight performance, safety, and overall reliability of the UAV.

[0104] 2. Examples 2 and 5 differ in that Example 2 uses the modified glass fiber blend prepared in Example 1, while Example 5 uses the modified glass fiber blend prepared in Example 3. The difference lies in the composition of the reactive polyether functionalized polymer. The experimental results show that the notched impact strength, tensile strength, elongation at break, and residual tensile strength of Example 2 are all lower than those of Example 5. This indicates that the reactive polyether functionalized polymer used in Example 5, composed of trimethylolpropionic acid hexyl lactone crosslinking polymer, branched polyether modified polysiloxane, and polyethylene glycol diglycidyl ether, has a better synergistic effect, thereby enabling the final material to obtain better comprehensive performance.

[0105] 3. Examples 5 and 7 differ in that Example 5 uses the modified glass fiber blend prepared in Example 3, while Example 7 uses the modified glass fiber blend prepared in Example 5. The difference lies in the composition of the effective component of the interface reinforcing agent. The experimental results show that the notched impact strength, tensile strength, elongation at break, and tensile strength residual of Example 5 are all lower than those of Example 7. This indicates that the effective component of the interface reinforcing agent used in Example 7 consists of 1,3-bis(3-methacryloyloxypropyl)tetra(trimethylsiloxy)disiloxane side-chain acrylate modified silicone oil, side-chain acrylate modified silicone oil, and organopolyborosilicate, which plays a better synergistic role, thereby enabling the final material to obtain better comprehensive performance.

[0106] This specific embodiment is merely an explanation of this application and is not intended to limit it. After reading this specification, those skilled in the art can make modifications to this embodiment without contributing any inventive step, but such modifications are protected by patent law as long as they fall within the scope of the claims of this application.

Claims

1. A glass fiber composite material for 3D printing, characterized in that, The raw materials consist of the following parts by weight: 10-30 parts of modified glass fiber blend PEI: 30-80 copies PPSU: 10-50 servings Plasticizer: 3-5 parts Compatibilizer: 5-8 parts Processing aids: 1-5 parts; The modified glass fiber blend is prepared by sequentially treating glass fibers with a wetting activator and an interface strengthening agent, and then blending them with TPSiV; the effective component of the wetting activator is a reactive polyether functionalized polymer; the effective component of the interface strengthening agent is a mixture of multiple components including 1,3-bis(3-methacryloyloxypropyl)tetra(trimethylsiloxy)disiloxane, side-chain acrylate modified silicone oil, and organopolyborosilicates. The reactive polyether functionalized polymer is composed of various components including trimethylolhexyl lactone crosslinked polymer, branched polyether modified polysiloxane, and polyethylene glycol diglycidyl ether.

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)tetra(trimethylsiloxy)disiloxane, the side-chain acrylate-modified silicone oil, and the organopolyborosilicate 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 weight ratio of the trimethylolhexyl lactone crosslinking polymer, the branched polyether modified polysiloxane, and the polyethylene glycol diglycidyl ether is 1:(1-2):(3-5).

4. A glass fiber composite material for 3D printing according to any one of claims 1, characterized in that: The glass fiber has a diameter of 1-100 micrometers.

5. A glass fiber composite material for 3D printing according to any one of claims 1-4, 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. After surface drying, they are treated with an interface strengthening agent, sheared to obtain glass fibers, and then mixed evenly with molten TPSiV to obtain a modified glass fiber blend.

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

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

8. A glass fiber composite material for 3D printing according to claim 1, characterized in that: The processing aid is one or a mixture of multiple of the following: release agent, lubricant, antioxidant, UV stabilizer, heat stabilizer, and antibacterial agent.

9. A method for preparing a glass fiber composite material for 3D printing as described in any one of claims 1-8, characterized in that, Includes the following steps: According to the weight parts, weigh the modified glass fiber blend, PEI, PPSU, plasticizer, compatibilizer and processing aid, mix them evenly, melt extrude and cool to obtain glass fiber composite material for 3D printing.

Images