A long fiber reinforced polyetheretherketone composite material and its preparation method
By treating PEEK composites with long fibers and nano-modifiers, the problem of insufficient mechanical properties of short fiber reinforced PEEK composites was solved, achieving efficient fiber length retention and interfacial bonding, thereby improving the mechanical properties and production efficiency of the material.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- CHONGQING UNIV
- Filing Date
- 2023-05-19
- Publication Date
- 2026-07-31
AI Technical Summary
Existing short fiber reinforced PEEK composites have poor mechanical properties, the fiber length is severely reduced during extrusion injection molding, and the interfacial bonding performance is not ideal, which limits their application in high-end fields such as aerospace.
Long fiber reinforced PEEK composite material is used. The reinforcing fibers are functionalized by nano-modifiers and combined with polyetherimide (PEI) modified long fiber masterbatch. The solution method is used to prepare and injection mold the composite material, thereby improving the fiber length retention rate and interfacial properties.
It significantly improves the fiber length retention rate and interfacial properties of PEEK composite materials, thereby greatly improving their mechanical properties, reducing production costs, and making them suitable for recycled fiber raw materials.
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Figure CN116376220B_ABST
Abstract
Description
Technical Field
[0001] This invention belongs to the field of fiber-reinforced thermoplastic resin composites, and provides a long fiber-reinforced polyether ether ketone composite material with excellent mechanical properties and its preparation method. Background Technology
[0002] Fiber-reinforced thermoplastic composites possess numerous advantages, including excellent mechanical properties (such as high fracture toughness, high impact resistance, and high damage tolerance), high heat resistance, easy repair, and recyclability, leading to their widespread application in aerospace, military equipment, automotive, and electronics industries. Currently, high-performance thermoplastic composites used in the aerospace industry primarily utilize polyetheretherketone (PEEK), polyetherimide (PEI), and polyphenylene sulfide as matrix materials, with high-performance fibers such as carbon fiber, glass fiber, and basalt fiber as reinforcement. PEEK, as a semi-crystalline polymer, has a glass transition temperature of 143℃ and a melting point of approximately 340℃, making it the best-performing specialty engineering plastic currently available. Continuous fiber-reinforced PEEK composites exhibit excellent mechanical properties but suffer from high manufacturing costs, low production efficiency, and difficulty in molding irregular and complex structures. Short fiber-reinforced PEEK composites can be manufactured using traditional extrusion injection molding processes, offering advantages such as high production efficiency and the ability to mold complex structures. However, compared to continuous fiber-reinforced PEEK composites, short fiber-reinforced PEEK composites have inferior mechanical properties, thus limiting their application in high-end fields such as aerospace.
[0003] The poor mechanical properties of short-fiber reinforced PEEK composites are due to the severe reduction in fiber length during extrusion injection molding. In recent years, it has been proposed to prepare long-fiber reinforced plastic masterbatches through pultrusion, which can effectively increase the retained fiber length in injection-molded composites, thereby improving their mechanical properties. However, preparing long-fiber reinforced PEEK masterbatches using pultrusion faces several challenges: 1) Pultrusion equipment is expensive and requires a large area; 2) PEEK has extremely high processing temperatures and high viscosity after melting, making it difficult to impregnate the fiber bundles; 3) PEEK is highly hydrophobic and lacks active functional groups. Furthermore, the surface chemicals of the fibers commonly used to reinforce PEEK are inactive, making it difficult to form chemical bonds between the reinforcing fibers and PEEK resin, resulting in unsatisfactory interfacial layer properties. Therefore, finding simple and effective methods to improve fiber length, the impregnation effect of PEEK resin on fibers, and the interfacial properties between PEEK resin and reinforcing fibers is of great significance for expanding the application of PEEK composites in aerospace and other fields. Summary of the Invention
[0004] Purpose of the invention: To address the problems of short fiber retention length and poor interfacial bonding performance in existing discontinuous fiber reinforced PEEK composite materials, this invention provides a long fiber reinforced PEEK composite material with good interfacial and mechanical properties, and its preparation method.
[0005] Technical solution: The present invention relates to a long fiber reinforced PEEK composite material with excellent mechanical properties and its preparation method.
[0006] (A) The long fiber reinforced PEEK composite material of the present invention is composed of the following components in parts by weight: 100 parts of polyether ether ketone (PEEK), 10-40 parts of polyetherimide (PEI), 1-100 parts of reinforcing fiber and 0.01-1 parts of nano-modifier.
[0007] The reinforcing fiber is at least one of carbon fiber, glass fiber, and basalt fiber.
[0008] The nanomodifier is at least one of carbon nanotubes (CNT), graphene oxide (GO), and nano-silica (SiO2).
[0009] The nanomodifier is functionalized and contains at least one of amino, hydroxyl, or carboxyl functional groups, but is not limited to these.
[0010] (B) The preparation method of the long fiber reinforced PEEK composite material of the present invention mainly includes the following steps:
[0011] (1) Fiber pretreatment. The reinforcing fibers were immersed in acetone and refluxed at 60-80 °C for 12-24 h. After washing with deionized water, they were dried at 100-120 °C to remove the commercial sizing agent on the surface of the reinforcing fibers. Then, the reinforcing fibers were immersed in a strong acid or strong alkali at 30-70 °C for 120-240 min, followed by washing with deionized water until neutral, and drying at 100-120 °C.
[0012] (2) Preparation of long fiber masterbatch. The pretreated reinforcing fibers were cut into long fibers of 10-40 mm. The nano-modifier was uniformly dispersed in an organic solvent to obtain a nano-modifier solution with a concentration of 0.0001-0.01 g / mL. PEI resin was added to the organic solvent and stirred at 40-90℃ until the PEI was completely dissolved to obtain a PEI solution with a concentration of 0.1-0.3 g / mL. Then, the long fibers and nano-modifier solution of the prescribed amount were sequentially added to the PEI solution, and stirred thoroughly to ensure uniform dispersion of the nano-modifier and reinforcing fibers. The mixture was spread into a 2-4 mm thin layer, dried using a gradient drying method, then granulated using a pulverizer, and dried again at 120-150℃ for 1-4 h to obtain the PEI-modified long fiber masterbatch.
[0013] (3) Injection molding of composite material. Mix 100 parts of PEEK powder with a particle size of 10~100 μm with the above-mentioned long fiber masterbatch in the formulation, and then use an injection molding machine for injection molding. The temperature of the injection molding machine from the feed port to the nozzle is 360~390℃, and the mold temperature is 180~200℃ to obtain the final long fiber reinforced PEEK composite material.
[0014] The reinforcing fiber mentioned in step (1) is a newly produced continuous fiber bundle or a recycled discontinuous fiber.
[0015] The strong acid mentioned in step (1) is at least one of concentrated nitric acid, concentrated sulfuric acid, and concentrated hydrochloric acid; the strong base is a 0.1~1 mol / L sodium hydroxide solution.
[0016] The organic solvent mentioned in step (2) is at least one of N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAc), dichloromethane (CH2Cl2), and N-methylpyrrolidone (NMP).
[0017] The gradient drying process described in step (2) is 40~100℃ for 10~20 h, 120~160℃ for 5~10 h, and 180~220℃ for 1~5 h.
[0018] In the granulation process described in step (2), the diameter of the granule sieve is 10-20 mm, and the fiber length distribution in the masterbatch obtained after granulation is 5-20 mm.
[0019] The innovations of this invention compared to existing technologies are as follows:
[0020] (1) This invention provides a long fiber reinforced PEEK composite material with the following characteristics: A. Compared with traditional short fiber reinforced PEEK composite materials, the fiber retention length in this PEEK composite material can be increased by more than double, resulting in a significant reinforcing effect. B. PEI and PEEK have similar molecular structures. By preparing PEI-modified long fiber masterbatch and introducing PEI into the PEEK resin, the wetting properties of the PEEK resin for the fibers can be significantly improved. C. The PEI content in the PEEK composite material is as high as 10~40 phr. Since the glass transition temperature of PEI is higher than that of PEEK, it can significantly improve the mechanical properties of the PEEK composite material near the glass transition temperature (140~170 ℃). D. The introduction of nano-modifiers can not only improve the wetting properties between the fibers and PEI and PEEK, but also increase the mechanical interlocking force between the fibers and the matrix, thereby significantly improving the interfacial properties of the composite material. In summary, this PEEK composite material has a high fiber length retention rate and good interfacial properties, thus greatly improving the mechanical properties of the PEEK composite material.
[0021] (2) This invention provides a novel method for preparing long fiber reinforced PEEK composite materials. Compared with the traditional process of extrusion granulation followed by injection molding, the composite material prepared by this method has a higher fiber length retention rate (because its masterbatch does not undergo an extrusion process), thus significantly improving its performance. Compared with the existing process of granulation via pultrusion followed by injection molding, it has the following advantages: A. It does not require a large, expensive pultrusion production line, resulting in low cost; B. By using a solution method to prepare PEI-modified long fiber masterbatch, a high content of modified PEI resin can be introduced while the fiber is surface-treated and modified, which is fundamentally different from traditional fiber sizing treatment; C. This method can use recycled continuous or discontinuous fibers as raw materials. Attached Figure Description
[0022] Figure 1 The flowchart below shows the preparation process of the long fiber reinforced polyetheretherketone composite material according to the present invention.
[0023] Figure 2 This is a SEM image of the PEI-modified long fiber masterbatch prepared in Example 3 of the present invention.
[0024] Figure 3 Load-displacement diagrams of the long fiber reinforced polyetheretherketone composite materials prepared in Example 5 and Comparative Example 2 of this invention. Detailed Implementation
[0025] The present invention will be described below with reference to specific embodiments. These embodiments are merely specific descriptions of the claims of the present invention, and the claims include, but are not limited to, the embodiments.
[0026] Unless otherwise specified, all reagents and materials described in the following examples are commercially available, and all experimental methods are conventional unless otherwise specified. In the following examples, CF, GF, and BF represent carbon fiber, glass fiber, and basalt fiber, respectively, and x nanofiller / y reinforcing fiber / z PEI / 100PEEK represents the composition of long fiber reinforced polyetheretherketone composites, where x, y, and z represent the percentage content of the corresponding components.
[0027] Example 1: Preparation of 1CNT / 1CF / 10PEI / 100PEEK composite material, carried out according to the following steps:
[0028] (1) Fiber pretreatment. CF was soaked in acetone and extracted by reflux at 80°C for 24 h. After washing with deionized water, it was dried at 120°C to remove the commercial sizing agent on the surface of CF. Then, CF was soaked in concentrated nitric acid at 30°C for 240 min, followed by washing with deionized water until neutral, and drying at 120°C for later use.
[0029] (2) Preparation of long fiber masterbatch. Pretreated CF was cut into 20 mm long fibers; CNTs containing hydroxyl and carboxyl functional groups were uniformly dispersed in the organic solvent DMF to obtain a CNT solution with a concentration of 0.01 g / mL; PEI resin was added to the DMF organic solvent and stirred at 70 °C until the PEI was completely dissolved to obtain a PEI solution with a concentration of 0.1 g / mL. Then, 1000 mL of CNT (1 part) solution and 1 part of long fiber were sequentially added to 1000 mL of PEI (10 parts) solution, and stirred thoroughly to ensure uniform dispersion of CNTs and CF. The mixture was spread into a 2 mm thin layer and subjected to gradient drying at 100 °C for 20 h, 160 °C for 5 h, and 200 °C for 4 h. Granulation was then performed using a pulverizer (sieve diameter 10 mm), and the mixture was dried again at 150 °C for 4 h to obtain the PEI-modified long fiber masterbatch.
[0030] (3) Injection molding of composite material. 100 parts of PEEK powder with a particle size of 10 μm are mixed evenly with the PEI modified long fiber masterbatch obtained in step (2) above, and then injection molded using an injection molding machine. The temperature of the injection molding machine from the feed port to the nozzle is 360-370-375-380-385 ℃, and the mold temperature is 180 ℃, so as to obtain the final long fiber reinforced PEEK composite material.
[0031] Example 2: Preparation of 0.01GO / 100GF / 20PEI / 100PEEK composite material, carried out according to the following steps:
[0032] (1) Fiber pretreatment. GF was soaked in acetone and extracted by reflux at 80°C for 24 h. After washing with deionized water, it was dried at 100°C to remove the commercial sizing agent on the surface of GF. Then, GF was soaked in concentrated sulfuric acid at 70°C for 120 min, followed by washing with deionized water until neutral, and drying at 100°C for later use.
[0033] (2) Preparation of long fiber masterbatch. Pretreated GF was cut into 40 mm long fibers; amino-functionalized GO was uniformly dispersed in the organic solvent DMAc to obtain a GO solution with a concentration of 0.001 g / mL; PEI resin was added to the organic solvent DMAc and stirred at 90°C until the PEI was completely dissolved to obtain a PEI solution with a concentration of 0.2 g / mL. Then, 100 mL of GO (0.01 parts) solution and 100 parts of long fibers were sequentially added to 1000 mL of PEI (20 parts) solution, and stirred thoroughly to ensure uniform dispersion of GO and GF. The mixture was spread into a 4 mm thin layer and dried in a gradient at 100°C for 15 h, 160°C for 8 h, and 200°C for 3 h. Granulation was then performed using a pulverizer (sieve diameter 20 mm), and the mixture was dried again at 140°C for 4 h to obtain the PEI-modified long fiber masterbatch.
[0034] (3) Injection molding of composite material. 100 parts of PEEK powder with a particle size of 80 μm are mixed evenly with the PEI modified long fiber masterbatch obtained in step (2) above, and then injection molded using an injection molding machine. The temperature of the injection molding machine from the feed port to the nozzle is 360-375-380-385-390℃, and the mold temperature is 200℃, thus obtaining the final long fiber reinforced PEEK composite material.
[0035] Example 3: Preparation of 0.8CNT / 50CF / 40PEI / 100PEEK composite material, carried out according to the following steps:
[0036] (1) Fiber pretreatment. CF was soaked in acetone and extracted by reflux at 70°C for 18 h. After washing with deionized water, it was dried at 120°C to remove the commercial sizing agent on the surface of CF. Then, CF was soaked in 0.5 mol / L sodium hydroxide solution at 60°C for 120 min, followed by washing with deionized water until neutral, and drying at 120°C for later use.
[0037] (2) Preparation of long fiber masterbatch. Pretreated CF was cut into 30 mm long fibers; CNTs with carboxyl functional groups were uniformly dispersed in the organic solvent CH2Cl2 to obtain a CNT solution with a concentration of 0.01 g / mL; PEI resin was added to the organic solvent CH2Cl2 and stirred at 40°C until the PEI was completely dissolved to obtain a PEI solution with a concentration of 0.2 g / mL. Then, 800 mL of CNT (0.8 parts) solution and 50 parts of long fibers were sequentially added to 2000 mL of PEI (40 parts) solution, and stirred thoroughly to ensure uniform dispersion of CNTs and CF. The mixture was spread into a 3 mm thin layer and dried in a gradient at 40°C for 10 h, 120°C for 5 h, and 180°C for 2 h. Granulation was then performed using a pulverizer (sieve diameter 20 mm), and the mixture was dried again at 120°C for 1 h to obtain the PEI-modified long fiber masterbatch.
[0038] (3) Injection molding of composite material. 100 parts of PEEK powder with a particle size of 50 μm are mixed evenly with the PEI modified long fiber masterbatch obtained in step (2) above, and then injection molded using an injection molding machine. The temperature of the injection molding machine from the feed port to the nozzle is 360-375-380-385-385℃, and the mold temperature is 190℃, thus obtaining the final long fiber reinforced PEEK composite material.
[0039] Example 4: Preparation of 0.5SiO2 / 40BF / 30PEI / 100PEEK composite material, carried out according to the following steps:
[0040] (1) Fiber pretreatment. The BF was soaked in acetone and refluxed at 60°C for 24 h. After washing with deionized water, it was dried at 110°C to remove the commercial sizing agent on the surface of the BF. Then, the BF was soaked in 1 mol / L sodium hydroxide solution at 60°C for 180 min, followed by washing with deionized water until neutral, and drying at 110°C for later use.
[0041] (2) Preparation of long fiber masterbatch. Pretreated BF was cut into 20 mm long fibers; SiO2 with carboxyl functional groups was uniformly dispersed in NMP organic solvent to obtain a SiO2 solution with a concentration of 0.01 g / mL; PEI resin was added to NMP organic solvent and stirred at 90°C until the PEI was completely dissolved to obtain a PEI solution with a concentration of 0.2 g / mL. Then, 500 mL of SiO2 (0.5 parts) solution and 40 parts of long fibers were sequentially added to 1500 mL of PEI (30 parts) solution, and stirred thoroughly to ensure uniform dispersion of SiO2 and BF. The mixture was spread into a 4 mm thin layer and dried in a gradient at 100°C for 10 h, 160°C for 10 h, and 220°C for 5 h. Granulation was then performed using a pulverizer (sieve diameter 10 mm), and the mixture was dried again at 150°C for 4 h to obtain the PEI-modified long fiber masterbatch.
[0042] (3) Injection molding of composite material. 100 parts of PEEK powder with a particle size of 100 μm are mixed evenly with the PEI modified long fiber masterbatch obtained in step (2) above, and then injection molded using an injection molding machine. The temperature of the injection molding machine from the feed port to the nozzle is 360-375-380-380-385℃, and the mold temperature is 195℃, thus obtaining the final long fiber reinforced PEEK composite material.
[0043] Example 5: Preparation of 0.2CNT / 20CF / 30PEI / 100PEEK composite material, performed according to the following steps:
[0044] (1) Fiber pretreatment. CF was soaked in acetone and extracted by reflux at 80 °C for 12 h. After washing with deionized water, it was dried at 100 °C to remove the commercial sizing agent on the surface of CF. Then, the carbon fibers were soaked in concentrated hydrochloric acid at 30 °C for 240 min, followed by washing with deionized water until neutral, and drying at 100 °C for later use.
[0045] (2) Preparation of long fiber masterbatch. The pretreated CF was cut into 10 mm long fibers; CNTs with hydroxyl and carboxyl functional groups were uniformly dispersed in V(DMF):V(CH2Cl2). A CNT solution with a concentration of 0.01 g / mL was obtained by mixing a solvent with a ratio of 1.0:4.0; PEI resin was added to a mixture of V(DMF):V(CH2Cl2). In a mixed solvent with a ratio of 1.0:4.0, the solution was stirred at 50°C until PEI was completely dissolved, yielding a PEI solution with a concentration of 0.3 g / mL. Then, 200 mL of CNT (0.2 parts) solution and 20 parts of long fibers were sequentially added to 1000 mL (30 parts) of the PEI solution, and stirred thoroughly to ensure uniform dispersion of CNTs and CF. The mixture was spread into a 3 mm thin layer and dried in a gradient at 50°C for 10 h, 130°C for 5 h, and 190°C for 2 h. Granulation was then performed using a pulverizer (10 mm sieve diameter), followed by drying at 150°C for 2 h to obtain the PEI-modified long fiber masterbatch.
[0046] (3) Injection molding of composite material. 100 parts of PEEK powder with a particle size of 30 μm are mixed evenly with the PEI modified long fiber masterbatch obtained in step (2) above, and then injection molded using an injection molding machine. The temperature of the injection molding machine from the feed port to the nozzle is 360-375-375-380-385℃, and the mold temperature is 190℃, thus obtaining the final long fiber reinforced PEEK composite material.
[0047] Comparative Example 1: Preparation of 0.5SiO2 / 40BF / 30PEI / 100PEEK composite material was carried out according to the following steps:
[0048] (1) Process BF according to step (1) of Example 4.
[0049] (2) After the same processing steps (1) of Example 4, BF was cut into fixed lengths of 20 mm and 400 g was taken. 5 g of SiO2 from step (2) of Example 4 was taken and mixed evenly with 300 g of PEI powder and 1000 g of PEEK powder (100 μm). 0.5SiO2 / 40BF / 30PEI / 100PEEK masterbatch was prepared by conventional extrusion process. The screw speed of the extruder was 150 r / min and the temperature from the hopper to the die of the extruder was 366-370-375-380-385℃.
[0050] (3) The 0.5SiO2 / 40BF / 30PEI / 100PEEK masterbatch prepared by extrusion process is dried at 150°C for 4 h, and injection molded using the injection molding parameters of Example 4 to obtain the 0.5SiO2 / 40BF / 30PEI / 100PEEK composite material.
[0051] Comparative Example 2: Preparation of 0.2CNT / 20CF / 30PEI / 100PEEK composite material was carried out according to the following steps:
[0052] (1) Process CF according to step (1) of Example 5.
[0053] (2) CF that has undergone the same processing as step (1) of Example 5 is cut into a fixed length of 10 mm and 200 g is taken. 2 g of CNT from step (2) of Example 5 is taken and mixed evenly with 300 g of PEI powder and 1000 g of PEEK powder (30 μm). 0.2CNT / 20CF / 30PEI / 100PEEK masterbatch is prepared by conventional extrusion process. The screw speed of the extruder is 150 r / min and the temperature from the hopper to the die of the extruder is 366-370-375-380-385℃.
[0054] (3) The 0.2CNT / 20CF / 30PEI / 100PEEK masterbatch prepared by extrusion process is dried at 150°C for 2 h, and injection molded using the injection molding parameters of Example 5 to obtain the 0.2CNT / 20CF / 30PEI / 100PEEK composite material.
[0055] Example of effect
[0056] This example examines the tensile properties of the composite materials prepared in Examples 1, 3, 5, and Comparative Example 2. The method involves tensile testing of injection-molded specimens according to ASTM D638-96 standard, with a loading speed of 2 mm / min. Five specimens were tested in each group, and the average value was taken. The test results are shown in Table 1 below.
[0057] Table 1 Tensile properties of PEEK composite materials
[0058] Tensile strength (MPa) 112.8±2.1 232.2±4.9 181.1±5.1 107.3±3.9 Young's modulus (GPa) 4.3±0.4 25.4±0.3 12.1±0.4 5.8±0.4
[0059] Pure PEEK resin has a tensile strength of 103.1 MPa and a Young's modulus of 3.8 GPa. As shown in Table 1, the PEEK composite material prepared by extrusion injection molding in Comparative Example 2 showed only a 4.1% increase in tensile strength and a 52.6% increase in Young's modulus compared to pure PEEK resin. In Example 5, the PEEK composite material prepared using this invention showed a 75.6% increase in tensile strength and a 218.4% increase in Young's modulus compared to pure PEEK resin; compared to Comparative Example 2, the PEEK composite material prepared by extrusion injection molding showed a 68.7% increase in tensile strength and a 108.6% increase in Young's modulus. This indicates that the long fiber reinforced PEEK composite material prepared by this invention has excellent tensile properties. This is because the fiber length in the masterbatch is preserved, and the wettability and interfacial properties between the fibers and the matrix are improved, thereby enhancing the mechanical properties of the PEEK composite material.
Claims
1. A long fiber reinforced polyetheretherketone composite material, wherein the long fiber reinforced composite material is composed of 100 parts of polyetheretherketone, 10-40 parts of polyetherimide, 1-100 parts of reinforcing fiber, and 0.01-1 parts of nano-modifier by weight, and the preparation method includes the following steps: (1) Fiber pretreatment: The reinforcing fiber was soaked in acetone and refluxed at 60-80 °C for 12-24 h. After washing with deionized water, it was dried at 100-120 °C. Then, the reinforcing fiber was soaked in strong acid or strong alkali at 30-70 °C for 120-240 min. After washing with deionized water until neutral, it was dried at 100-120 °C. (2) Preparation of long fiber masterbatch: The pretreated reinforcing fibers are cut into long fibers of 10-40 mm; the nano-modifier is uniformly dispersed in an organic solvent to obtain a nano-modifier solution with a concentration of 0.0001-0.01 g / mL; PEI resin is added to the organic solvent and stirred at 40-90 °C until PEI is completely dissolved to obtain a PEI solution with a concentration of 0.1-0.3 g / mL; then, the long fibers and nano-modifier solution of the formulation are added to the PEI solution in sequence and stirred thoroughly to ensure that the nano-modifier and reinforcing fibers are evenly dispersed; the above mixture is spread into a thin layer of 2-4 mm and dried by gradient drying, then granulated by a pulverizer, and dried again at 120-150 °C for 1-4 h to obtain PEI modified long fiber masterbatch; (3) Injection molding of composite material: 100 parts of PEEK powder with a particle size of 10~100 μm are mixed evenly with the above-mentioned long fiber masterbatch in the formulation, and then injection molding is performed using an injection molding machine. The temperature of the injection molding machine from the feed port to the nozzle is 360~390 ℃, and the mold temperature is 180~200 ℃, so as to obtain the final long fiber reinforced PEEK composite material.
2. The long fiber reinforced polyetheretherketone composite material according to claim 1, characterized in that: The reinforcing fiber is at least one of carbon fiber, glass fiber, and basalt fiber; The nano-modifier is at least one of carbon nanotubes, graphene oxide, and nano-silica; The nanomodifier is functionalized and contains at least one of amino, hydroxyl, or carboxyl functional groups.
3. The long fiber reinforced polyether ether ketone composite according to claim 1, characterized in that, In step (1): The reinforcing fiber is a newly produced continuous fiber bundle or a recycled discontinuous fiber; The strong acid mentioned is at least one of concentrated nitric acid, concentrated sulfuric acid, and concentrated hydrochloric acid; The strong alkali is a 0.1~1 mol / L sodium hydroxide solution.
4. The long fiber reinforced polyetheretherketone composite material according to claim 1, characterized in that, In step (2): The organic solvent is at least one selected from N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAc), dichloromethane (CH2Cl2), and N-methylpyrrolidone (NMP); The gradient drying program is 40~100℃ for 10~20 h, 120~160℃ for 5~10 h, and 180~220℃ for 1~5 h; In the granulation process, the diameter of the granule sieve is 10-20 mm, and the length of the fibers in the long fiber masterbatch obtained after granulation is distributed between 5 and 20 mm.