Fiber-reinforced thermoplastic resin-based composite material based on dynamic reversible interface action as well as preparation method and recycling method of fiber-reinforced thermoplastic resin-based composite material

Abstract

The invention discloses a fiber-reinforced thermoplastic resin-based composite material based on dynamic reversible interface interaction and a preparation method and a recycling method thereof. The fiber-reinforced thermoplastic resin-based composite material comprises a modified thermoplastic resin matrix and a modified fiber reinforcement which are compounded with each other, the modified thermoplastic resin matrix and the modified fiber reinforcement are bonded and connected through dynamic bonds with dynamic reversible interface interaction. Through construction of dynamic reversible interface interaction in the fiber-reinforced thermoplastic resin-based composite material, infiltration compounding and interface bonding between a fiber reinforcement and a high-viscosity thermoplastic resin melt can be enhanced, and interface debonding and total-value recycling of the fiber reinforcement in the composite material recycling process can be effectively promoted; therefore, the bottleneck problems of poor wettability in the forming process, low bonding fastness at a heterogeneous interface, insufficient mechanical properties, low waste recovery value and the like confronted by the development of the fiber-reinforced thermoplastic composite material are effectively solved.

Description

Technical Field

[0001] This invention relates to the field of thermoplastic resin-based composite materials technology, and more specifically, to a fiber-reinforced thermoplastic resin-based composite material based on dynamic reversible interfacial interactions, its preparation method, and its recycling method. Background Technology

[0002] Fiber-reinforced resin matrix composites (FRPCs), a type of material composed of continuous fiber reinforcements and a resin matrix through a specific process, have gradually replaced traditional metallic and inorganic non-metallic materials in defense, aerospace, automotive, rail transportation, energy, chemical, construction, transportation, and sports and entertainment fields due to their advantages such as high specific strength, high specific modulus, low density, excellent corrosion resistance, high impact and fatigue resistance, and ease of structural and functional design. However, the rapid development and large-scale application of FRPCs globally have placed a significant burden on resources and the environment due to their high manufacturing cost, heavy reliance on petrochemical resources, the insoluble and non-melting nature of the thermosetting resin matrix, its high degree of cross-linking, and the significant challenges in recycling and degrading related waste. Thermosetting FRPCs, due to their slow molding cycle time, severe associated pollution, high product brittleness, and difficulties in repair, recycling, and reuse, are destined to have their future development and application severely limited. Vigorously promoting the application and development of thermoplastic FRPC composites can not only significantly improve the toughness and repairability of FRPC materials, thereby further ensuring the stability of the materials and extending their service life, but also improve the production efficiency of FRPC materials, reduce emissions of waste gas, wastewater, and solid waste, and achieve efficient recycling and reuse. This will broaden the application fields of FRPCs while promoting the realization of the production concept of "green economy, low-carbon environmental protection, and sustainable development." Composite materials made by combining high-performance thermoplastic resins (such as polyphenylene sulfide, polyamide, polyetheretherketone, and polyaryletherketone) with carbon fibers have already begun to emerge in fields such as aerospace, wind turbine blades, automobile manufacturing, medical devices, and building materials.

[0003] In achieving high performance, multifunctionality, low cost, and sustainability in continuous carbon fiber reinforced thermoplastic resin matrix composites, the interfacial interaction between the fiber reinforcement and the resin matrix plays a crucial role. The interface essentially refers to the transition region between the fiber reinforcement and the resin matrix, manifested as the transition between different chemical compositions and different physical properties. The strong interfacial adhesion between the fiber reinforcement and the resin matrix promotes mutual wetting during the composite process of incompatible two phases, thereby avoiding internal structural defects in the composite material and reducing stress concentration and weak points in mechanical properties. Furthermore, the strong interaction at the two-phase interface also facilitates the effective transfer of external loads between the resin matrix and the fiber reinforcement and prevents interfacial detachment under external loads. For traditional fiber-reinforced thermosetting composites, the good flowability of the resin precursor (mainly small molecules, uncrosslinked) and the high chemical activity of the related molecular structure provide a basis for good wetting between the resin and the fiber and the formation of interfacial interactions. However, the thermoplastic resin matrix, especially non-polar thermoplastic resin, has a chemically inert molecular structure and high melt viscosity (large molecular chains), which not only makes it difficult to achieve full wetting and bonding between the resin and the fiber reinforcement during the composite molding process, but also makes it difficult to provide effective interfacial interactions, resulting in frequent interfacial delamination between the resin and the fiber.

[0004] Interfacial interactions play a crucial role in promoting complete separation between fiber reinforcements and the resin matrix (especially thermoplastic resin matrix) during the recycling of FRPC waste, thus enabling the full-value recovery of the fiber reinforcement. During the service life of FRPC materials, strong interfacial adhesion between the resin matrix and fiber reinforcement is a prerequisite for ensuring the material's mechanical strength and service reliability; conversely, this strong interfacial adhesion also hinders the separation of fibers from the resin matrix during FRPC waste recycling. Currently, to ensure the interfacial adhesion strength and mechanical properties of FRPC materials during use, researchers have temporarily abandoned the approach of designing and constructing "separation-promoting" interfaces to achieve separation between the fiber reinforcement and the resin matrix. Instead, they primarily focus on modifying the molecular structure of the resin matrix to achieve pyrolysis, dissolution, and dynamic reversible bond formation and breaking, thereby completing the degradation of the resin matrix and the full recovery of the fiber reinforcement. However, the pollutants released during thermal degradation, the huge energy consumption, the frequent replacement cycle and high price of special solvents, and the great damage to the mechanical strength of the resin matrix caused by the construction of dynamic reversible bonds also demonstrate the limitations of achieving the recycling and reuse of FRPCs materials through the design of the molecular structure of the resin matrix.

[0005] Therefore, bottlenecks such as poor wettability between high-viscosity thermoplastic melts and fiber reinforcements, weak interfacial interactions, and low recycling value of related wastes have always limited the development and application of continuous fiber reinforced thermoplastic composites.

[0006] In view of this, the present invention is proposed. Summary of the Invention

[0007] The purpose of this invention is to provide a fiber-reinforced thermoplastic resin-based composite material based on dynamic reversible interfacial interactions, as well as its preparation and recycling methods, to improve the above-mentioned technical problems.

[0008] This invention is implemented as follows: In a first aspect, the present invention provides a fiber-reinforced thermoplastic resin-based composite material, comprising a modified thermoplastic resin matrix and a modified fiber reinforcement compounded together, wherein the modified thermoplastic resin matrix and the modified fiber reinforcement are connected by dynamic bonding having dynamic reversible interfacial interactions.

[0009] In an optional embodiment, the dynamic bond includes at least one of the following: Diels-Alder bond, ester bond, disulfide bond, imine bond, siloxane bond, benzyl ether bond, borate ester bond, and acylhydrazone bond.

[0010] In an optional embodiment, the modified thermoplastic resin matrix corresponds to at least one of the modified thermoplastic resins, including polypropylene, polyethylene, polyphenylene sulfide, polycarbonate, polyamide, polyetheretherketone, polyaryletherketone, and polyetherimide.

[0011] In an optional embodiment, the modified fiber reinforcement includes at least one of glass fiber, basalt fiber, carbon fiber, quartz fiber and silicon carbide fiber.

[0012] In a second aspect, the present invention provides a method for preparing a fiber-reinforced thermoplastic resin-based composite material as described in any of the foregoing embodiments, comprising: A first active group is constructed on the surface of the fiber reinforcement to obtain the modified fiber reinforcement; A second active group is introduced into the molecular structure of a thermoplastic resin to obtain a modified thermoplastic resin, which is then subjected to morphological processing. The modified thermoplastic resin after morphological processing is pre-composite with the modified fiber reinforcement to obtain a mixed preform; The hybrid preform is then hot-pressed together.

[0013] In an optional embodiment, constructing a first active group on the surface of the fiber reinforcement includes: first pre-oxidizing the fiber reinforcement, and then dehydrating and condensing it with the oxygen-containing functional groups on the surface of the fiber reinforcement using a silane coupling agent.

[0014] In an optional embodiment, the pre-oxidation treatment involves soaking the fiber reinforcement in concentrated sulfuric acid or concentrated nitric acid.

[0015] In an optional embodiment, the fiber reinforcement is desized before pre-oxidation treatment to remove the sizing agent from the surface.

[0016] In an optional embodiment, the silane coupling agent includes at least one of urea-amino silane coupling agents, amino silane coupling agents, succinic anhydride silane coupling agents, and isocyanate silane coupling agents.

[0017] In an alternative embodiment, the introduction of a second active group into the molecular structure of the thermoplastic resin can be achieved by copolymerization modification or side-linking.

[0018] In an optional embodiment, the overall grafting rate of the second active group of the modified thermoplastic resin reaches 5wt%~20wt%.

[0019] In an optional embodiment, the morphology processing includes processing into granules, fibers, or films; and / or, the pre-composite method is lay-up or winding; and / or, the mass ratio of the modified thermoplastic resin to the modified fiber reinforcement in the pre-composite process is (2~5):(5~8).

[0020] In an optional embodiment, the morphology processing is carried out by melt spinning to prepare long fibers, wherein the density of the long fibers reaches 2~20 dtex and the breaking strength of the monofilaments reaches 3cN / dtex~5cN / dtex.

[0021] In an optional embodiment, the ambient pH value of the hot-pressed composite is controlled to be 2~9, the hot-pressing temperature is 120℃~400℃, the external load is 0.5MPa~8MPa, the hot-pressing time is 10min~120min, and the holding time is 5h~24h.

[0022] Thirdly, the present invention provides a method for recycling fiber-reinforced thermoplastic resin-based composite materials as described in any of the foregoing embodiments, which promotes the interface detachment between the modified thermoplastic resin and the modified fiber reinforcement by introducing external reverse bond-breaking conditions.

[0023] In optional implementations, external reverse bond-breaking conditions include pH changes, temperature changes, or light-stimulated responses.

[0024] The present invention has the following beneficial effects: By modifying both the thermoplastic resin fiber and the fiber reinforcement separately, they are dynamically bonded together, thus establishing a dynamically reversible "bonding-strengthening-debonding" interfacial mechanism between the thermoplastic resin and the fiber reinforcement. This allows for reversible control of the interfacial interactions within the composite material. This design not only promotes uniform resin wetting of the fibers during molding, enhancing interfacial bonding strength and ensuring sufficient impregnation, uniform molding, and structural stability during service, but also triggers reverse interfacial debonding during recycling, effectively achieving low-damage fiber debonding and high-value recycling. Furthermore, by rationally controlling the chemical type, topological structure, and spatial distribution characteristics of the dynamically reversible interface, its influence on the wetting behavior, interfacial bonding / debonding response characteristics, service reliability, and recycling performance of thermoplastic composites can be systematically revealed. This maximizes the synergistic effect of such interfaces throughout the entire lifecycle of composite materials, ensuring stable processing, reliable service, and efficient recycling.

[0025] Therefore, the structural design of this fiber-reinforced thermoplastic resin matrix composite is expected to significantly promote the development of fiber-reinforced thermoplastic resin matrix composites towards high performance, low cost and sustainability, and provide key material support and technical foundation for their large-scale application in high-end fields such as automotive lightweighting, aerospace structural components, key components of intelligent robots and low-altitude aircraft manufacturing. Attached Figure Description

[0026] To more clearly illustrate the technical solutions of the embodiments of the present invention, the accompanying drawings used in the embodiments will be briefly introduced below. It should be understood that the following drawings only show some embodiments of the present invention and should not be regarded as a limitation on the scope. For those skilled in the art, other related drawings can be obtained based on these drawings without creative effort.

[0027] Figure 1 This is a schematic diagram illustrating the construction of dynamic reversible bonding at the interface between the thermoplastic resin matrix and the fiber reinforcement in an embodiment of the present invention. Figure 2 This is a schematic diagram illustrating a method for constructing the first active group on the surface of the fiber reinforcement according to an embodiment of the present invention; Figure 3 This diagram illustrates the process of introducing a second active group into the molecular structure of the thermoplastic resin matrix according to an embodiment of the present invention. Figure 4 These are morphological comparison images of the fiber-reinforced thermoplastic resin-based composite material of Example 14 of the present invention before recycling, after recycling, and after secondary composite molding. Detailed Implementation

[0028] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. Where specific conditions are not specified in the embodiments, conventional conditions or conditions recommended by the manufacturer shall apply. Reagents or instruments whose manufacturers are not specified are all conventional products that can be purchased commercially.

[0029] The following is a detailed description of a fiber-reinforced thermoplastic resin-based composite material based on dynamic reversible interfacial interaction, its preparation method, and its recycling method provided by the present invention.

[0030] Some embodiments of the present invention also provide a fiber-reinforced thermoplastic resin matrix composite material, comprising a modified thermoplastic resin matrix and a modified fiber reinforcement that are compounded together, wherein the modified thermoplastic resin matrix and the modified fiber reinforcement are connected by dynamic bonding with dynamic reversible interfacial interactions.

[0031] By separately modifying the thermoplastic resin matrix and fiber reinforcement, a dynamic and reversible interface is constructed between them. During the material molding process, this interface is strengthened through positive bonding, significantly improving the wettability of the thermoplastic resin to the fiber reinforcement and the interfacial bonding strength, thereby effectively enhancing the molding stability and service reliability of the composite material. In the recycling stage of fiber-reinforced thermoplastic polymer composites (FRTPCs), a reverse bond breaking mechanism is triggered to induce controlled dissociation at the interface, promoting efficient separation between the resin matrix and the fiber reinforcement, achieving rapid removal of the thermoplastic resin and complete retention and full-value recovery of the fiber reinforcement. This technical strategy, from the perspective of interface design, systematically solves the key bottleneck problems currently faced in the development and application of fiber-reinforced thermoplastic composites, including poor resin wettability during molding, low interfacial bonding strength, insufficient overall mechanical properties, and low recycling rate of waste materials, which are generally only capable of being downgraded and recycled. It provides a practical and feasible technical path for the sustainable development of high-performance composite materials.

[0032] It should be noted that the schematic diagram of the dynamic reversible bonding at the interface between the thermoplastic resin matrix and the fiber reinforcement is shown in the figure below. Figure 1 As shown.

[0033] Specifically, in some embodiments, the dynamic bond includes, but is not limited to, at least one of the following: Diels-Alder bond, ester bond, disulfide bond, benzyl ether bond, imine bond, siloxane bond, borate ester bond, and acylhydrazone bond. Preferably, the dynamic bond may be selected as a benzyl ether bond, ester bond, or amide bond.

[0034] In some embodiments, the modified thermoplastic resin matrix corresponds to at least one of the modified thermoplastic resins, including but not limited to polypropylene, polyethylene, polyphenylene sulfide, polycarbonate, polyamide, polyetheretherketone, polyaryletherketone, and polyetherimide.

[0035] In some embodiments, the modified fiber reinforcement includes, but is not limited to, at least one of glass fiber, basalt fiber, carbon fiber, quartz fiber and silicon carbide fiber.

[0036] In particular, when polyphenylene sulfide or polypropylene is chosen as the thermoplastic resin and carbon fiber is chosen as the fiber reinforcement, the resulting continuous carbon fiber reinforced polyphenylene sulfide composites and continuous carbon fiber reinforced polypropylene composites can construct a dynamic "bonding-bond breaking and peeling" reversible interfacial network, which can effectively solve the problems of poor wettability, weak interfacial interaction, insufficient mechanical properties, and recycling value of carbon fiber reinforced nonpolar thermoplastic composites. For example, the performance of carbon fiber plain weave reinforced polyphenylene sulfide composites can reach: tensile strength greater than 1000 MPa, interlaminar shear strength greater than 60 MPa, interfacial shear strength greater than 50 MPa, and mechanical property loss of recycled and remolded composites within 10%; the performance of carbon fiber plain weave reinforced polypropylene composites can reach: tensile strength greater than 600 MPa, interlaminar shear strength greater than 50 MPa, interfacial shear strength greater than 40 MPa, and mechanical property loss of recycled and remolded composites within 10%.

[0037] Some embodiments of the present invention also provide a method for preparing a fiber-reinforced thermoplastic resin-based composite material as described in any of the foregoing embodiments, comprising: constructing a first active group on the surface of the fiber reinforcement to obtain a modified fiber reinforcement; the specific construction method can be found in [reference needed]. Figure 2 As shown; a second active group is introduced into the molecular structure of a thermoplastic resin to obtain a modified thermoplastic resin. The process of introducing the second active group is described in [reference needed]. Figure 3 As shown, the modified thermoplastic resin is then subjected to morphological processing; the morphologically processed modified thermoplastic resin is pre-composite with the modified fiber reinforcement to obtain a mixed preform; the mixed preform is then hot-pressed.

[0038] Based on Knoevenagel condensation, benzyl ether bonds, ester bonds, and various amide bonds as templates for constructing dynamic reversible interfacial interactions, corresponding active groups are introduced into the surface of the fiber reinforcement and the molecular structure of the resin matrix. After the two are pre-composite to obtain a composite preform, the construction of dynamic reversible interfacial interactions inside the composite material is completed in the final hot-pressing composite process, thereby realizing the positive uniform wetting and interfacial strengthening of fiber-reinforced thermoplastic composite materials, as well as the reverse interfacial debonding and fiber peeling for reuse.

[0039] Specifically, some embodiments of the present invention provide a method for preparing fiber-reinforced thermoplastic resin-based composite materials, which includes the following steps: S1. Fiber reinforcement pretreatment.

[0040] The fiber reinforcement and solvent are mixed evenly in proportion at room temperature. The solution is changed after soaking the fiber reinforcement for 1 to 3 days, and this process is repeated for 6 to 14 days to wash away the sizing agent on the surface of the fiber fabric. Then, the fiber reinforcement is placed in an oven at 50℃ to 100℃ and dried for 1 to 12 hours to obtain the desized fiber reinforcement.

[0041] The original sizing agent applied to the fibers at the factory is designed to meet the processing requirements of spinning, weaving, etc. This original sizing agent forms a dense physical film on the fiber surface, covering it and preventing the silane coupling agent from directly contacting the fiber matrix. Therefore, it needs to be removed first. Specifically, the solvent used in the immersion of the fiber reinforcement includes one or more of ethanol, acetone, and deionized water.

[0042] The desized fiber reinforcement is then immersed in concentrated sulfuric acid or concentrated nitric acid for a certain period of time to obtain fiber-reinforced fabric with pre-oxidized surface treatment. For inert fibers such as carbon fiber and aramid fiber: during the pre-oxidation process, the carbon-carbon bonds on the fiber surface are oxidized to generate polar groups such as hydroxyl (-OH), carboxyl (-COOH), and carbonyl (-C=O). These groups are the anchoring sites for silane coupling agents. The silanol (-Si-OH) generated after the hydrolysis of the alkoxy group (-OR) of silane can undergo dehydration condensation with these groups to form stable Si-OC covalent bonds. For glass fiber: pre-oxidation can remove surface-adsorbed water molecules and trace organic impurities, while activating the silanol (-Si-OH) on the glass surface, enhancing its reactivity with silane coupling agents. In addition, pre-oxidation can create tiny etch pits on the fiber surface, increasing the specific surface area of ​​the fiber and increasing the adsorption sites of the silane coupling agent. The polar groups introduced by pre-oxidation can improve the surface energy of the fiber surface, enhance the spreading and wetting effect of the silane coupling agent hydrolysate on the fiber surface, and avoid the problem of uneven silane coating caused by surface hydrophobicity.

[0043] S2. Construction of active groups on the surface of fiber reinforcement.

[0044] By utilizing the dehydration condensation between various silane coupling agents (including but not limited to urea-amino silane coupling agents, amino silane coupling agents, succinic anhydride silane coupling agents, and isocyanate silane coupling agents) and oxygen-containing functional groups on the surface of the fiber reinforcement, the construction of isocyanate-based active groups (such as cyanate groups, urea-amino groups, amino groups, and succinic anhydride groups) on the fiber reinforcement surface can be achieved. The grafting density of various active groups on the fiber reinforcement surface can be controlled by changing the mass fraction (1wt%~10wt%) of various silane coupling agents in a water / ethanol mixed solvent. After soaking the fiber fabric for a certain period of time (3~10h, 30~80℃), the fiber fabric is removed, washed, and dried. The loading of various silane coupling agents on the fiber fabric is calculated by weighing and controlled to be between 5wt% and 20wt%.

[0045] S3. Introduction of active groups into the molecular structure of the resin matrix.

[0046] Based on copolymerization modification and side grafting, a second active group (such as a primary amine group, maleic anhydride group, or long-chain terminal amine group) is introduced into the molecular structure of conventional thermoplastic resins (such as polypropylene, polyphenylene sulfide, polyamide, and polyether ether ketone). The overall grafting rate of the active group is ensured to reach 5wt%~20wt%, for example, 5wt%, 6wt%, 8wt%, 10wt%, 12wt%, 15wt%, 18wt%, or 20wt%.

[0047] S4. Preparation and hot pressing of fiber-reinforced thermoplastic composite preforms.

[0048] The modified thermoplastic resin is processed to achieve various morphological conditions, including processing into granules, fibers, or films. Pre-composite bonding of the modified resin matrix and fiber reinforcement is achieved through methods such as lay-up and winding, followed by hot-pressing composite under specific conditions to achieve positive bonding with dynamic and reversible interfacial interactions.

[0049] For example, the modified thermoplastic resin obtained above is melt-spun into long fibers. By adjusting the relevant spinning process and hot stretching parameters, the linear density of the obtained fibers reaches 2~20 dtex, and the single filament breaking strength reaches 3 cN / dtex~5 cN / dtex. Next, based on the fabric co-winding process, the modified fiber fabric and modified resin fiber are wound together according to the requirement of resin to fiber fabric mass ratio of 2:8~5:5 to obtain a mixed preform of modified fiber reinforcement / modified resin fiber. 5~20 layers of the preform are laid up and stacked and placed in a hot press. By adjusting the ambient temperature and pH value, the dynamic bonding reaction between the first active group on the fiber fabric and the second active group on the resin matrix fiber is promoted. During the hot pressing process, not only is the composite laminate prepared, but also the dynamic reversible interfacial interaction is constructed. During the hot-pressing reaction, the ambient pH value is controlled at 2~9, the hot-pressing temperature is set at 120℃~400℃, the external load is set at 0.5MPa~8MPa, the hot-pressing time is set at 10min~120min, and the holding time is set at 5h~24h.

[0050] Furthermore, some embodiments of the present invention also provide a method for recycling fiber-reinforced thermoplastic resin-based composite materials as described in any of the foregoing embodiments, which promotes the interface detachment between the modified thermoplastic resin and the modified fiber reinforcement by introducing external reverse bond-breaking conditions.

[0051] In some implementations, the external reverse bond-breaking conditions include pH changes, temperature changes, or light-induced responses.

[0052] The features and performance of the present invention will be further described in detail below with reference to embodiments.

[0053] Example 1 S1. Desizing treatment of basalt plain weave fabric.

[0054] Basalt plain weave fabric and solvent were uniformly mixed at a ratio of 1:10 at room temperature (25℃). The basalt plain weave fabric was soaked in the solution for 7 days, changing the solution every 3 days to wash away the sizing agent on the surface of the fabric. Next, the basalt plain weave fabric was rinsed multiple times with deionized water to remove the used solvent, and then dried in an 80℃ forced-air drying oven for 12 hours to obtain desized basalt plain weave fabric. The solvents included ethanol and acetone, mixed at a volume ratio of 3:1.

[0055] S2, basalt plain weave fabric surface pre-oxidation.

[0056] The desized basalt fiber plain weave fabric was placed in concentrated nitric acid and treated at 40°C for 12 hours. It was then washed with deionized water until neutral and dried at 80°C for 12 hours.

[0057] S3, primary amine groups are constructed on the surface of pre-oxidized basalt plain weave fabric.

[0058] 1 wt% KH550 was added to a mixed solvent of water and ethanol in a 1:1 mass ratio. After complete hydrolysis at room temperature for 2 hours, the pre-oxidized basalt plain weave fabric was impregnated in the solvent, and the impregnation reaction was continued at 80°C for 4 hours. Finally, after washing with deionized water, the primary amine modified basalt plain weave fabric was dried at 80°C for 12 hours to complete the dehydration and drying process.

[0059] S4. Preparation of maleic anhydride modified polypropylene particles.

[0060] During the high-temperature melt extrusion process, the twin-screw shear temperature is set to 190℃, and the feeding is completed according to the mass ratio of maleic anhydride to polypropylene particles of 2:8 to complete the preparation of maleic anhydride-grafted polypropylene particles.

[0061] S5, a composite of primary amine-modified basalt plain weave fabric and maleic anhydride-modified polypropylene fiber.

[0062] Maleic anhydride-modified polypropylene granules were prepared into maleic anhydride-modified polypropylene fiber filaments using a conventional melt spinning process. Based on a mass ratio of 3:7 between maleic anhydride-modified polypropylene fiber and primary amine-modified basalt plain weave fabric, the maleic anhydride-modified polypropylene fiber and primary amine-modified basalt plain weave fabric were intertwined to obtain a maleic anhydride-modified polypropylene fiber / primary amine-modified basalt fiber preform.

[0063] S6, maleic anhydride modified polypropylene fiber / primary amine modified basalt fiber preform composite hot pressing molding.

[0064] The hot-pressing process was used to lay up and stack the obtained maleic anhydride modified polypropylene fiber / primary amine modified basalt plain weave fabric preforms and place them in 160℃. The pH value of the environment was adjusted to 5 with glacial acetic acid, and then hot-pressed at 3MPa for 15min and held for 12h. The resulting primary amine modified basalt fiber reinforced maleic anhydride modified polypropylene composite material was obtained.

[0065] Example 2 S1. Desizing treatment of basalt plain weave fabric.

[0066] Basalt plain weave fabric and solvent were uniformly mixed at a ratio of 1:10 at room temperature (25℃). The basalt plain weave fabric was soaked in the solution for 7 days, changing the solution every 3 days to wash away the sizing agent on the surface of the fabric. Next, the basalt plain weave fabric was rinsed multiple times with deionized water to remove the used solvent, and then dried in an 80℃ forced-air drying oven for 12 hours to obtain desized basalt plain weave fabric. The solvents included ethanol and acetone, mixed at a volume ratio of 3:1.

[0067] S2, basalt plain weave fabric surface pre-oxidation.

[0068] The desized basalt fiber plain weave fabric was placed in concentrated nitric acid and treated at 40°C for 12 hours. It was then washed with deionized water until neutral and dried at 80°C for 12 hours.

[0069] S3, primary amine groups are constructed on the surface of pre-oxidized basalt plain weave fabric.

[0070] 3 wt% KH550 was added to a mixed solvent of water and ethanol in a 1:1 mass ratio. After complete hydrolysis at room temperature for 2 hours, the pre-oxidized basalt plain weave fabric was impregnated in the solvent, and the impregnation reaction was continued at 80°C for 4 hours. Finally, after washing with deionized water, the primary amine modified basalt plain weave fabric was dried at 80°C for 12 hours to complete the dehydration and drying process.

[0071] S4. Preparation of maleic anhydride modified polypropylene particles.

[0072] During the high-temperature melt extrusion process, the twin-screw shear temperature is set to 190℃, and the feeding is completed according to the mass ratio of maleic anhydride to polypropylene particles of 2:8 to complete the preparation of maleic anhydride-grafted polypropylene particles.

[0073] S5, a composite of primary amine-modified basalt plain weave fabric and maleic anhydride-modified polypropylene fiber.

[0074] Maleic anhydride-modified polypropylene granules were prepared into maleic anhydride-modified polypropylene fiber filaments using a conventional melt spinning process. Based on a mass ratio of 3:7 between maleic anhydride-modified polypropylene fiber and primary amine-modified basalt plain weave fabric, the maleic anhydride-modified polypropylene fiber and primary amine-modified basalt plain weave fabric were intertwined to obtain a maleic anhydride-modified polypropylene fiber / primary amine-modified basalt fiber preform.

[0075] S6, maleic anhydride modified polypropylene fiber / primary amine modified basalt fiber preform composite hot pressing molding.

[0076] The hot-pressing process was used to lay up and stack the obtained maleic anhydride modified polypropylene fiber / primary amine modified basalt plain weave fabric preforms and place them in 160℃. The pH value of the environment was adjusted to 5 with glacial acetic acid, and then hot-pressed at 3MPa for 15min and held for 12h. The resulting primary amine modified basalt fiber reinforced maleic anhydride modified polypropylene composite material was obtained.

[0077] Example 3 S1. Desizing treatment of basalt plain weave fabric.

[0078] Basalt plain weave fabric and solvent were uniformly mixed at a ratio of 1:10 at room temperature (25℃). The basalt plain weave fabric was soaked in the solution for 7 days, changing the solution every 3 days to wash away the sizing agent on the surface of the fabric. Next, the basalt plain weave fabric was rinsed multiple times with deionized water to remove the used solvent, and then dried in an 80℃ forced-air drying oven for 12 hours to obtain desized basalt plain weave fabric. The solvents included ethanol and acetone, mixed at a volume ratio of 3:1.

[0079] S2, basalt plain weave fabric surface pre-oxidation.

[0080] The desized basalt fiber plain weave fabric was placed in concentrated nitric acid and treated at 40°C for 12 hours. It was then washed with deionized water until neutral and dried at 80°C for 12 hours.

[0081] S3, primary amine groups are constructed on the surface of pre-oxidized basalt plain weave fabric.

[0082] 5 wt% KH550 was added to a mixed solvent of water and ethanol in a 1:1 mass ratio. After complete hydrolysis at room temperature for 2 hours, the pre-oxidized basalt plain weave fabric was impregnated in the solvent, and the impregnation reaction was continued at 80°C for 4 hours. Finally, after washing with deionized water, the primary amine modified basalt plain weave fabric was dried at 80°C for 12 hours to complete the dehydration and drying process.

[0083] S4. Preparation of maleic anhydride modified polypropylene particles.

[0084] During the high-temperature melt extrusion process, the twin-screw shear temperature is set to 190℃, and the feeding is completed according to the mass ratio of maleic anhydride to polypropylene particles of 2:8 to complete the preparation of maleic anhydride-grafted polypropylene particles.

[0085] S5, a composite of primary amine-modified basalt plain weave fabric and maleic anhydride-modified polypropylene fiber.

[0086] Maleic anhydride-modified polypropylene granules were prepared into maleic anhydride-modified polypropylene fiber filaments using a conventional melt spinning process. Based on a mass ratio of 3:7 between maleic anhydride-modified polypropylene fiber and primary amine-modified basalt plain weave fabric, the maleic anhydride-modified polypropylene fiber and primary amine-modified basalt plain weave fabric were intertwined to obtain a maleic anhydride-modified polypropylene fiber / primary amine-modified basalt fiber preform.

[0087] S6, maleic anhydride modified polypropylene fiber / primary amine modified basalt fiber preform composite hot pressing molding.

[0088] The hot-pressing process was used to lay up and stack the obtained maleic anhydride modified polypropylene fiber / primary amine modified basalt plain weave fabric preforms and place them in 160℃. The pH value of the environment was adjusted to 5 with glacial acetic acid, and then hot-pressed at 3MPa for 15min and held for 12h. The resulting primary amine modified basalt fiber reinforced maleic anhydride modified polypropylene composite material was obtained.

[0089] Example 4 S1. Desizing treatment of basalt plain weave fabric.

[0090] Basalt plain weave fabric and solvent were uniformly mixed at a ratio of 1:10 at room temperature (25℃). The basalt plain weave fabric was soaked in the solution for 7 days, changing the solution every 3 days to wash away the sizing agent on the surface of the fabric. Next, the basalt plain weave fabric was rinsed multiple times with deionized water to remove the used solvent, and then dried in an 80℃ forced-air drying oven for 12 hours to obtain desized basalt plain weave fabric. The solvents included ethanol and acetone, mixed at a volume ratio of 3:1.

[0091] S2, basalt plain weave fabric surface pre-oxidation.

[0092] The desized basalt fiber plain weave fabric was placed in concentrated nitric acid and treated at 40°C for 12 hours. It was then washed with deionized water until neutral and dried at 80°C for 12 hours.

[0093] S3, primary amine groups are constructed on the surface of pre-oxidized basalt plain weave fabric.

[0094] 7wt% KH550 was added to a mixed solvent of water and ethanol in a 1:1 mass ratio. After complete hydrolysis at room temperature for 2 hours, the pre-oxidized basalt plain weave fabric was impregnated in the solvent, and the impregnation reaction was continued at 80℃ for 4 hours. Finally, after washing with deionized water, the primary amine modified basalt plain weave fabric was dried at 80℃ for 12 hours to complete the dehydration and drying process.

[0095] S4. Preparation of maleic anhydride modified polypropylene particles.

[0096] During the high-temperature melt extrusion process, the twin-screw shear temperature is set to 190℃, and the feeding is completed according to the mass ratio of maleic anhydride to polypropylene particles of 2:8 to complete the preparation of maleic anhydride-grafted polypropylene particles.

[0097] S5, a composite of primary amine-modified basalt plain weave fabric and maleic anhydride-modified polypropylene fiber.

[0098] Maleic anhydride-modified polypropylene granules were prepared into maleic anhydride-modified polypropylene fiber filaments using a conventional melt spinning process. Based on a mass ratio of 3:7 between maleic anhydride-modified polypropylene fiber and primary amine-modified basalt plain weave fabric, the maleic anhydride-modified polypropylene fiber and primary amine-modified basalt plain weave fabric were intertwined to obtain a maleic anhydride-modified polypropylene fiber / primary amine-modified basalt fiber preform.

[0099] S6, maleic anhydride modified polypropylene fiber / primary amine modified basalt fiber preform composite hot pressing molding.

[0100] The hot-pressing process was used to lay up and stack the obtained maleic anhydride modified polypropylene fiber / primary amine modified basalt plain weave fabric preforms and place them in 160℃. The pH value of the environment was adjusted to 5 with glacial acetic acid, and then hot-pressed at 3MPa for 15min and held for 12h. The resulting primary amine modified basalt fiber reinforced maleic anhydride modified polypropylene composite material was obtained.

[0101] Example 5 S1. Desizing treatment of basalt plain weave fabric.

[0102] Basalt plain weave fabric and solvent were uniformly mixed at a ratio of 1:10 at room temperature (25℃). The basalt plain weave fabric was soaked in the solution for 7 days, changing the solution every 3 days to wash away the sizing agent on the surface of the fabric. Next, the basalt plain weave fabric was rinsed multiple times with deionized water to remove the used solvent, and then dried in an 80℃ forced-air drying oven for 12 hours to obtain desized basalt plain weave fabric. The solvents included ethanol and acetone, mixed at a volume ratio of 3:1.

[0103] S2, basalt plain weave fabric surface pre-oxidation.

[0104] The desized basalt fiber plain weave fabric was placed in concentrated nitric acid and treated at 40°C for 12 hours. It was then washed with deionized water until neutral and dried at 80°C for 12 hours.

[0105] S3. Isocyanate groups are constructed on the surface of pre-oxidized basalt plain weave fabric.

[0106] 1 wt% of 3-isocyanate-propyltriethoxysilane was added to a mixed solvent of water and ethanol in a 1:1 mass ratio. After complete hydrolysis at room temperature for 2 hours, the pre-oxidized basalt plain weave fabric was impregnated in the solution, and the impregnation reaction was continued at 80°C for 4 hours. Finally, after washing with deionized water, the isocyanate-modified basalt plain weave fabric was dried at 80°C for 12 hours to complete the dehydration and drying process.

[0107] S4. Preparation of amine-modified polyphenylene sulfide particles.

[0108] The polymerization of amine-modified polyphenylene sulfide was completed using 95 parts of p-dichlorobenzene, 5 parts of 2,5-dichloroaniline, and an appropriate amount of sodium sulfide as raw materials, under the action of a catalyst and NMP.

[0109] S5. Isocyanate-modified basalt plain weave fabric and amine-modified polyphenylene sulfide fiber are entangled and composite.

[0110] Amine-modified polyphenylene sulfide (PPS) granules were prepared into PPS fiber filaments using a conventional melt spinning process. Based on a mass ratio of 3:7 between PPS fiber and isocyanate-modified basalt plain weave fabric, the PPS fiber and isocyanate-modified basalt plain weave fabric were intertwined to obtain a PPS fiber / isocyanate-modified basalt fiber preform.

[0111] S6, Amine-modified polyphenylene sulfide fiber / isocyanate-modified basalt fiber preform composite hot pressing molding.

[0112] The obtained amine-modified polyphenylene sulfide fiber / isocyanate-modified basalt plain weave fabric preforms were laid up and stacked in 260℃, and the pH value of the environment was adjusted to 5 with glacial acetic acid. The preforms were then hot-pressed at 5MPa for 30 minutes and held for 12 hours. The resulting product was an isocyanate-modified basalt fiber reinforced amine-modified polyphenylene sulfide composite material.

[0113] Example 6 S1. Desizing treatment of basalt plain weave fabric.

[0114] Basalt plain weave fabric and solvent were uniformly mixed at a ratio of 1:10 at room temperature (25℃). The basalt plain weave fabric was soaked in the solution for 7 days, changing the solution every 3 days to wash away the sizing agent on the surface of the fabric. Next, the basalt plain weave fabric was rinsed multiple times with deionized water to remove the used solvent, and then dried in an 80℃ forced-air drying oven for 12 hours to obtain desized basalt plain weave fabric. The solvents included ethanol and acetone, mixed at a volume ratio of 3:1.

[0115] S2, basalt plain weave fabric surface pre-oxidation.

[0116] The desized basalt fiber plain weave fabric was placed in concentrated nitric acid and treated at 40°C for 12 hours. It was then washed with deionized water until neutral and dried at 80°C for 12 hours.

[0117] S3. Isocyanate groups are constructed on the surface of pre-oxidized basalt plain weave fabric.

[0118] 3 wt% of 3-isocyanate-propyltriethoxysilane was added to a mixed solvent of water and ethanol in a 1:1 mass ratio. After complete hydrolysis at room temperature for 2 hours, the pre-oxidized basalt plain weave fabric was impregnated in the solvent, and the impregnation reaction was continued at 80°C for 4 hours. Finally, after washing with deionized water, the isocyanate-modified basalt plain weave fabric was dried at 80°C for 12 hours to complete the dehydration and drying process.

[0119] S4. Preparation of amine-modified polyphenylene sulfide particles.

[0120] The polymerization of amine-modified polyphenylene sulfide was completed using 95 parts of p-dichlorobenzene, 5 parts of 2,5-dichloroaniline, and an appropriate amount of sodium sulfide as raw materials, under the action of a catalyst and NMP.

[0121] S5. Isocyanate-modified basalt plain weave fabric and amine-modified polyphenylene sulfide fiber are entangled and composite.

[0122] Amine-modified polyphenylene sulfide (PPS) granules were prepared into PPS fiber filaments using a conventional melt spinning process. Based on a mass ratio of 3:7 between PPS fiber and isocyanate-modified basalt plain weave fabric, the PPS fiber and isocyanate-modified basalt plain weave fabric were intertwined to obtain a PPS fiber / isocyanate-modified basalt fiber preform.

[0123] S6, Amine-modified polyphenylene sulfide fiber / isocyanate-modified basalt fiber preform composite hot pressing molding.

[0124] The obtained amine-modified polyphenylene sulfide fiber / isocyanate-modified basalt plain weave fabric preforms were laid up and stacked in 260℃, and the pH value of the environment was adjusted to 5 with glacial acetic acid. The preforms were then hot-pressed at 5MPa for 30 minutes and held for 12 hours. The resulting product was an isocyanate-modified basalt fiber reinforced amine-modified polyphenylene sulfide composite material.

[0125] Example 7 S1. Desizing treatment of basalt plain weave fabric.

[0126] Basalt plain weave fabric and solvent were uniformly mixed at a ratio of 1:10 at room temperature (25℃). The basalt plain weave fabric was soaked in the solution for 7 days, changing the solution every 3 days to wash away the sizing agent on the surface of the fabric. Next, the basalt plain weave fabric was rinsed multiple times with deionized water to remove the used solvent, and then dried in an 80℃ forced-air drying oven for 12 hours to obtain desized basalt plain weave fabric. The solvents included ethanol and acetone, mixed at a volume ratio of 3:1.

[0127] S2, basalt plain weave fabric surface pre-oxidation.

[0128] The desized basalt fiber plain weave fabric was placed in concentrated nitric acid and treated at 40°C for 12 hours. It was then washed with deionized water until neutral and dried at 80°C for 12 hours.

[0129] S3. Isocyanate groups are constructed on the surface of pre-oxidized basalt plain weave fabric.

[0130] 5 wt% of 3-isocyanate-propyltriethoxysilane was added to a mixed solvent of water and ethanol in a 1:1 mass ratio. After complete hydrolysis at room temperature for 2 hours, the pre-oxidized basalt plain weave fabric was impregnated in the solution, and the impregnation reaction was continued at 80°C for 4 hours. Finally, after washing with deionized water, the isocyanate-modified basalt plain weave fabric was dried at 80°C for 12 hours to complete the dehydration and drying process.

[0131] S4. Preparation of amine-modified polyphenylene sulfide particles.

[0132] The polymerization of amine-modified polyphenylene sulfide was completed using 95 parts of p-dichlorobenzene, 5 parts of 2,5-dichloroaniline, and an appropriate amount of sodium sulfide as raw materials, under the action of a catalyst and NMP.

[0133] S5. Isocyanate-modified basalt plain weave fabric and amine-modified polyphenylene sulfide fiber are entangled and composite.

[0134] Amine-modified polyphenylene sulfide (PPS) granules were prepared into PPS fiber filaments using a conventional melt spinning process. Based on a mass ratio of 3:7 between PPS fiber and isocyanate-modified basalt plain weave fabric, the PPS fiber and isocyanate-modified basalt plain weave fabric were intertwined to obtain a PPS fiber / isocyanate-modified basalt fiber preform.

[0135] S6, Amine-modified polyphenylene sulfide fiber / isocyanate-modified basalt fiber preform composite hot pressing molding.

[0136] The obtained amine-modified polyphenylene sulfide fiber / isocyanate-modified basalt plain weave fabric preforms were laid up and stacked in 260℃, and the pH value of the environment was adjusted to 5 with glacial acetic acid. The preforms were then hot-pressed at 5MPa for 30 minutes and held for 12 hours. The resulting product was an isocyanate-modified basalt fiber reinforced amine-modified polyphenylene sulfide composite material.

[0137] Example 8 S1. Desizing treatment of basalt plain weave fabric.

[0138] Basalt plain weave fabric and solvent were uniformly mixed at a ratio of 1:10 at room temperature (25℃). The basalt plain weave fabric was soaked in the solution for 7 days, changing the solution every 3 days to wash away the sizing agent on the surface of the fabric. Next, the basalt plain weave fabric was rinsed multiple times with deionized water to remove the used solvent, and then dried in an 80℃ forced-air drying oven for 12 hours to obtain desized basalt plain weave fabric. The solvents included ethanol and acetone, mixed at a volume ratio of 3:1.

[0139] S2, basalt plain weave fabric surface pre-oxidation.

[0140] The desized basalt fiber plain weave fabric was placed in concentrated nitric acid and treated at 40°C for 12 hours. It was then washed with deionized water until neutral and dried at 80°C for 12 hours.

[0141] S3. Isocyanate groups are constructed on the surface of pre-oxidized basalt plain weave fabric.

[0142] 7 wt% of 3-isocyanate-propyltriethoxysilane was added to a mixed solvent of water and ethanol in a 1:1 mass ratio. After complete hydrolysis at room temperature for 2 hours, the pre-oxidized basalt plain weave fabric was impregnated in the solution, and the impregnation reaction was continued at 80°C for 4 hours. Finally, after washing with deionized water, the isocyanate-modified basalt plain weave fabric was dried at 80°C for 12 hours to complete the dehydration and drying process.

[0143] S4. Preparation of amine-modified polyphenylene sulfide particles.

[0144] The polymerization of amine-modified polyphenylene sulfide was completed using 95 parts of p-dichlorobenzene, 5 parts of 2,5-dichloroaniline, and an appropriate amount of sodium sulfide as raw materials, under the action of a catalyst and NMP.

[0145] S5. Isocyanate-modified basalt plain weave fabric and amine-modified polyphenylene sulfide fiber are entangled and composite.

[0146] Amine-modified polyphenylene sulfide (PPS) granules were prepared into PPS fiber filaments using a conventional melt spinning process. Based on a mass ratio of 3:7 between PPS fiber and isocyanate-modified basalt plain weave fabric, the PPS fiber and isocyanate-modified basalt plain weave fabric were intertwined to obtain a PPS fiber / isocyanate-modified basalt fiber preform.

[0147] S6, Amine-modified polyphenylene sulfide fiber / isocyanate-modified basalt fiber preform composite hot pressing molding.

[0148] The obtained amine-modified polyphenylene sulfide fiber / isocyanate-modified basalt plain weave fabric preforms were laid up and stacked in 260℃, and the pH value of the environment was adjusted to 5 with glacial acetic acid. The preforms were then hot-pressed at 5MPa for 30 minutes and held for 12 hours. The resulting product was an isocyanate-modified basalt fiber reinforced amine-modified polyphenylene sulfide composite material.

[0149] Example 9 S1. Desizing treatment of carbon fiber plain weave fabric.

[0150] Carbon fiber plain weave fabric and solvent were uniformly mixed at a ratio of 1:10 at room temperature (25℃). The carbon fiber plain weave fabric was soaked in the solution for 7 days, changing the solution every 3 days to wash away the sizing agent on the surface of the fabric. Next, the carbon fiber plain weave fabric was rinsed multiple times with deionized water to remove the used solvent, and then dried in an 80℃ forced-air drying oven for 12 hours to obtain desized carbon fiber plain weave fabric. The solvents included ethanol and acetone, mixed at a volume ratio of 3:1.

[0151] S2, pre-oxidation of carbon fiber plain weave fabric surface.

[0152] The desized carbon fiber plain weave fabric was placed in concentrated nitric acid and treated at 40°C for 12 hours. It was then washed with deionized water until neutral and dried at 80°C for 12 hours.

[0153] Primary amine groups are constructed on the surface of S3 pre-oxidized carbon fiber plain weave fabric.

[0154] 1 wt% KH550 was added to a mixed solvent of water and ethanol in a 1:1 mass ratio. After complete hydrolysis at room temperature for 2 hours, the pre-oxidized carbon fiber plain weave fabric was immersed in the solution, and the immersion reaction was continued at 80°C for 4 hours. Finally, after washing with deionized water, the primary amine modified carbon fiber plain weave fabric was dried at 80°C for 12 hours to complete the dehydration and drying process.

[0155] S4. Preparation of maleic anhydride modified polypropylene particles.

[0156] During the high-temperature melt extrusion process, the twin-screw shear temperature is set to 190℃, and the feeding is completed according to the mass ratio of maleic anhydride to polypropylene particles of 2:8 to complete the preparation of maleic anhydride-grafted polypropylene particles.

[0157] S5, a composite of primary amine modified carbon fiber plain weave fabric and maleic anhydride modified polypropylene fiber.

[0158] Maleic anhydride-modified polypropylene granules were prepared into maleic anhydride-modified polypropylene fiber filaments using a conventional melt spinning process. Based on a mass ratio of 3:7 between maleic anhydride-modified polypropylene fiber and primary amine-modified carbon fiber plain weave fabric, the maleic anhydride-modified polypropylene fiber and primary amine-modified carbon fiber plain weave fabric were intertwined to obtain a maleic anhydride-modified polypropylene fiber / primary amine-modified carbon fiber preform.

[0159] S6, maleic anhydride modified polypropylene fiber / primary amine modified carbon fiber preform composite hot pressing molding.

[0160] The obtained maleic anhydride-modified polypropylene fiber / primary amine-modified carbon fiber plain weave fabric preform was laid up and stacked in 160℃, and the pH value of the environment was adjusted to 5 with glacial acetic acid. It was then hot-pressed at 3MPa for 15min and held for 12h. The resulting primary amine-modified carbon fiber reinforced maleic anhydride-modified polypropylene composite material was obtained.

[0161] Example 10 S1. Desizing treatment of carbon fiber plain weave fabric.

[0162] Carbon fiber plain weave fabric and solvent were uniformly mixed at a ratio of 1:10 at room temperature (25℃). The carbon fiber plain weave fabric was soaked in the solution for 7 days, changing the solution every 3 days to wash away the sizing agent on the surface of the fabric. Next, the carbon fiber plain weave fabric was rinsed multiple times with deionized water to remove the used solvent, and then dried in an 80℃ forced-air drying oven for 12 hours to obtain desized carbon fiber plain weave fabric. The solvents included ethanol and acetone, mixed at a volume ratio of 3:1.

[0163] S2, pre-oxidation of carbon fiber plain weave fabric surface.

[0164] The desized carbon fiber plain weave fabric was placed in concentrated nitric acid and treated at 40°C for 12 hours. It was then washed with deionized water until neutral and dried at 80°C for 12 hours.

[0165] S3, primary amine groups are constructed on the surface of pre-oxidized carbon fiber plain weave fabric.

[0166] 3 wt% KH550 was added to a mixed solvent of water and ethanol in a 1:1 mass ratio. After complete hydrolysis at room temperature for 2 hours, the pre-oxidized carbon fiber plain weave fabric was impregnated in the solvent, and the impregnation reaction was continued at 80°C for 4 hours. Finally, after washing with deionized water, the primary amine modified carbon fiber plain weave fabric was dried at 80°C for 12 hours to complete the dehydration and drying process.

[0167] S4. Preparation of maleic anhydride modified polypropylene particles.

[0168] During the high-temperature melt extrusion process, the twin-screw shear temperature is set to 190℃, and the feeding is completed according to the mass ratio of maleic anhydride to polypropylene particles of 2:8 to complete the preparation of maleic anhydride-grafted polypropylene particles.

[0169] S5, a composite of primary amine modified carbon fiber plain weave fabric and maleic anhydride modified polypropylene fiber.

[0170] Maleic anhydride-modified polypropylene granules were prepared into maleic anhydride-modified polypropylene fiber filaments using a conventional melt spinning process. Based on a mass ratio of 3:7 between maleic anhydride-modified polypropylene fiber and primary amine-modified carbon fiber plain weave fabric, the maleic anhydride-modified polypropylene fiber and primary amine-modified carbon fiber plain weave fabric were intertwined to obtain a maleic anhydride-modified polypropylene fiber / primary amine-modified carbon fiber preform.

[0171] S6, maleic anhydride modified polypropylene fiber / primary amine modified carbon fiber preform composite hot pressing molding.

[0172] The obtained maleic anhydride-modified polypropylene fiber / primary amine-modified carbon fiber plain weave fabric preform was laid up and stacked in 160℃, and the pH value of the environment was adjusted to 5 with glacial acetic acid. It was then hot-pressed at 3MPa for 15min and held for 12h. The resulting primary amine-modified carbon fiber reinforced maleic anhydride-modified polypropylene composite material was obtained.

[0173] Example 11 S1. Desizing treatment of carbon fiber plain weave fabric.

[0174] Carbon fiber plain weave fabric and solvent were uniformly mixed at a ratio of 1:10 at room temperature (25℃). The carbon fiber plain weave fabric was soaked in the solution for 7 days, changing the solution every 3 days to wash away the sizing agent on the surface of the fabric. Next, the carbon fiber plain weave fabric was rinsed multiple times with deionized water to remove the used solvent, and then dried in an 80℃ forced-air drying oven for 12 hours to obtain desized carbon fiber plain weave fabric. The solvents included ethanol and acetone, mixed at a volume ratio of 3:1.

[0175] S2, pre-oxidation of carbon fiber plain weave fabric surface.

[0176] The desized carbon fiber plain weave fabric was placed in concentrated nitric acid and treated at 40°C for 12 hours. It was then washed with deionized water until neutral and dried at 80°C for 12 hours.

[0177] S3, primary amine groups are constructed on the surface of pre-oxidized carbon fiber plain weave fabric.

[0178] 5 wt% KH550 was added to a mixed solvent of water and ethanol in a 1:1 mass ratio. After complete hydrolysis at room temperature for 2 hours, the pre-oxidized carbon fiber plain weave fabric was impregnated in the solvent, and the impregnation reaction was continued at 80°C for 4 hours. Finally, after washing with deionized water, the primary amine modified carbon fiber plain weave fabric was dried at 80°C for 12 hours to complete the dehydration and drying process.

[0179] S4. Preparation of maleic anhydride modified polypropylene particles.

[0180] During the high-temperature melt extrusion process, the twin-screw shear temperature is set to 190℃, and the feeding is completed according to the mass ratio of maleic anhydride to polypropylene particles of 2:8 to complete the preparation of maleic anhydride-grafted polypropylene particles.

[0181] S5, a composite of primary amine modified carbon fiber plain weave fabric and maleic anhydride modified polypropylene fiber.

[0182] Maleic anhydride-modified polypropylene granules were prepared into maleic anhydride-modified polypropylene fiber filaments using a conventional melt spinning process. Based on a mass ratio of 3:7 between maleic anhydride-modified polypropylene fiber and primary amine-modified carbon fiber plain weave fabric, the maleic anhydride-modified polypropylene fiber and primary amine-modified carbon fiber plain weave fabric were intertwined to obtain a maleic anhydride-modified polypropylene fiber / primary amine-modified carbon fiber preform.

[0183] S6, maleic anhydride modified polypropylene fiber / primary amine modified carbon fiber preform composite hot pressing molding.

[0184] The obtained maleic anhydride-modified polypropylene fiber / primary amine-modified carbon fiber plain weave fabric preform was laid up and stacked in 160℃, and the pH value of the environment was adjusted to 5 with glacial acetic acid. It was then hot-pressed at 3MPa for 15min and held for 12h. The resulting primary amine-modified carbon fiber reinforced maleic anhydride-modified polypropylene composite material was obtained.

[0185] Example 12 S1. Desizing treatment of carbon fiber plain weave fabric.

[0186] Carbon fiber plain weave fabric and solvent were uniformly mixed at a ratio of 1:10 at room temperature (25℃). The carbon fiber plain weave fabric was soaked in the solution for 7 days, changing the solution every 3 days to wash away the sizing agent on the surface of the fabric. Next, the carbon fiber plain weave fabric was rinsed multiple times with deionized water to remove the used solvent, and then dried in an 80℃ forced-air drying oven for 12 hours to obtain desized carbon fiber plain weave fabric. The solvents included ethanol and acetone, mixed at a volume ratio of 3:1.

[0187] S2, pre-oxidation of carbon fiber plain weave fabric surface.

[0188] The desized carbon fiber plain weave fabric was placed in concentrated nitric acid and treated at 40°C for 12 hours. It was then washed with deionized water until neutral and dried at 80°C for 12 hours.

[0189] S3, primary amine groups are constructed on the surface of pre-oxidized carbon fiber plain weave fabric.

[0190] 7wt% KH550 was added to a mixed solvent of water and ethanol in a 1:1 mass ratio. After complete hydrolysis at room temperature for 2 hours, the pre-oxidized carbon fiber plain weave fabric was impregnated in the solvent, and the impregnation reaction was continued at 80℃ for 4 hours. Finally, after washing with deionized water, the primary amine modified carbon fiber plain weave fabric was dried at 80℃ for 12 hours to complete the dehydration and drying process.

[0191] S4. Preparation of maleic anhydride modified polypropylene particles.

[0192] During the high-temperature melt extrusion process, the twin-screw shear temperature is set to 190℃, and the feeding is completed according to the mass ratio of maleic anhydride to polypropylene particles of 2:8 to complete the preparation of maleic anhydride-grafted polypropylene particles.

[0193] S5, a composite of primary amine modified carbon fiber plain weave fabric and maleic anhydride modified polypropylene fiber.

[0194] Maleic anhydride-modified polypropylene granules were prepared into maleic anhydride-modified polypropylene fiber filaments using a conventional melt spinning process. Based on a mass ratio of 3:7 between maleic anhydride-modified polypropylene fiber and primary amine-modified carbon fiber plain weave fabric, the maleic anhydride-modified polypropylene fiber and primary amine-modified carbon fiber plain weave fabric were intertwined to obtain a maleic anhydride-modified polypropylene fiber / primary amine-modified carbon fiber preform.

[0195] S6, maleic anhydride modified polypropylene fiber / primary amine modified carbon fiber preform composite hot pressing molding.

[0196] The obtained maleic anhydride-modified polypropylene fiber / primary amine-modified carbon fiber plain weave fabric preform was laid up and stacked in 160℃, and the pH value of the environment was adjusted to 5 with glacial acetic acid. It was then hot-pressed at 3MPa for 15min and held for 12h. The resulting primary amine-modified carbon fiber reinforced maleic anhydride-modified polypropylene composite material was obtained.

[0197] Example 13 S1. Desizing treatment of carbon fiber plain weave fabric.

[0198] Carbon fiber plain weave fabric and solvent were uniformly mixed at a ratio of 1:10 at room temperature (25℃). The carbon fiber plain weave fabric was soaked in the solution for 7 days, changing the solution every 3 days to wash away the sizing agent on the surface of the fabric. Next, the carbon fiber plain weave fabric was rinsed multiple times with deionized water to remove the used solvent, and then dried in an 80℃ forced-air drying oven for 12 hours to obtain desized carbon fiber plain weave fabric. The solvents included ethanol and acetone, mixed at a volume ratio of 3:1.

[0199] S2, pre-oxidation of carbon fiber plain weave fabric surface.

[0200] The desized carbon fiber plain weave fabric was placed in concentrated nitric acid and treated at 40°C for 12 hours. It was then washed with deionized water until neutral and dried at 80°C for 12 hours.

[0201] S3, isocyanate groups are constructed on the surface of pre-oxidized carbon fiber plain weave fabric.

[0202] 1 wt% of 3-isocyanate-propyltriethoxysilane was added to a mixed solvent of water and ethanol in a 1:1 mass ratio. After complete hydrolysis at room temperature for 2 hours, the pre-oxidized carbon fiber plain weave fabric was impregnated in the solvent, and the impregnation reaction was continued at 80°C for 4 hours. Finally, after washing with deionized water, the isocyanate-modified carbon fiber plain weave fabric was dried at 80°C for 12 hours to complete the dehydration and drying process.

[0203] S4. Preparation of amine-modified polyphenylene sulfide particles.

[0204] The polymerization of amine-modified polyphenylene sulfide was completed using 95 parts of p-dichlorobenzene, 5 parts of 2,5-dichloroaniline, and an appropriate amount of sodium sulfide as raw materials, under the action of a catalyst and NMP.

[0205] S5, isocyanate-modified carbon fiber plain weave fabric and amine-modified polyphenylene sulfide fiber entanglement composite.

[0206] Amine-modified polyphenylene sulfide (PPS) granules were prepared into PPS fiber filaments using a conventional melt spinning process. Based on a mass ratio of 3:7 between PPS fiber and isocyanate-modified carbon fiber plain weave fabric, the PPS fiber and isocyanate-modified carbon fiber plain weave fabric were intertwined to obtain an PPS fiber / isocyanate-modified carbon fiber preform.

[0207] S6, Amine-modified polyphenylene sulfide fiber / isocyanate-modified carbon fiber preform composite hot pressing molding.

[0208] The obtained amine-modified polyphenylene sulfide fiber / isocyanate-modified carbon fiber plain weave fabric preform was laid up and stacked in 260℃, and the pH value of the environment was adjusted to 5 with glacial acetic acid. It was then hot-pressed at 5MPa for 30min and held for 12h. The resulting isocyanate-modified carbon fiber reinforced amine-modified polyphenylene sulfide composite material was obtained.

[0209] Example 14 S1. Desizing treatment of carbon fiber plain weave fabric.

[0210] Carbon fiber plain weave fabric and solvent were uniformly mixed at a ratio of 1:10 at room temperature (25℃). The carbon fiber plain weave fabric was soaked in the solution for 7 days, changing the solution every 3 days to wash away the sizing agent on the surface of the fabric. Next, the carbon fiber plain weave fabric was rinsed multiple times with deionized water to remove the used solvent, and then dried in an 80℃ forced-air drying oven for 12 hours to obtain desized carbon fiber plain weave fabric. The solvents included ethanol and acetone, mixed at a volume ratio of 3:1.

[0211] S2, pre-oxidation of carbon fiber plain weave fabric surface.

[0212] The desized carbon fiber plain weave fabric was placed in concentrated nitric acid and treated at 40°C for 12 hours. It was then washed with deionized water until neutral and dried at 80°C for 12 hours.

[0213] S3, isocyanate groups are constructed on the surface of pre-oxidized carbon fiber plain weave fabric.

[0214] 3 wt% of 3-isocyanate-propyltriethoxysilane was added to a mixed solvent of water and ethanol in a 1:1 mass ratio. After complete hydrolysis at room temperature for 2 hours, the pre-oxidized carbon fiber plain weave fabric was impregnated in the solvent, and the impregnation reaction was continued at 80°C for 4 hours. Finally, after washing with deionized water, the isocyanate-modified carbon fiber plain weave fabric was dried at 80°C for 12 hours to complete the dehydration and drying process.

[0215] S4. Preparation of amine-modified polyphenylene sulfide particles.

[0216] The polymerization of amine-modified polyphenylene sulfide was completed using 95 parts of p-dichlorobenzene, 5 parts of 2,5-dichloroaniline, and an appropriate amount of sodium sulfide as raw materials, under the action of a catalyst and NMP.

[0217] S5, isocyanate-modified carbon fiber plain weave fabric and amine-modified polyphenylene sulfide fiber entanglement composite.

[0218] Amine-modified polyphenylene sulfide (PPS) granules were prepared into PPS fiber filaments using a conventional melt spinning process. Based on a mass ratio of 3:7 between PPS fiber and isocyanate-modified carbon fiber plain weave fabric, the PPS fiber and isocyanate-modified carbon fiber plain weave fabric were intertwined to obtain an PPS fiber / isocyanate-modified carbon fiber preform.

[0219] S6, Amine-modified polyphenylene sulfide fiber / isocyanate-modified carbon fiber preform composite hot pressing molding.

[0220] The obtained amine-modified polyphenylene sulfide fiber / isocyanate-modified carbon fiber plain weave fabric preform was laid up and stacked in 260℃, and the pH value of the environment was adjusted to 5 with glacial acetic acid. It was then hot-pressed at 5MPa for 30min and held for 12h. The resulting isocyanate-modified carbon fiber reinforced amine-modified polyphenylene sulfide composite material was obtained.

[0221] Example 15 S1. Desizing treatment of carbon fiber plain weave fabric.

[0222] Carbon fiber plain weave fabric and solvent were uniformly mixed at a ratio of 1:10 at room temperature (25℃). The carbon fiber plain weave fabric was soaked in the solution for 7 days, changing the solution every 3 days to wash away the sizing agent on the surface of the fabric. Next, the carbon fiber plain weave fabric was rinsed multiple times with deionized water to remove the used solvent, and then dried in an 80℃ forced-air drying oven for 12 hours to obtain desized carbon fiber plain weave fabric. The solvents included ethanol and acetone, mixed at a volume ratio of 3:1.

[0223] S2, pre-oxidation of carbon fiber plain weave fabric surface.

[0224] The desized carbon fiber plain weave fabric was placed in concentrated nitric acid and treated at 40°C for 12 hours. It was then washed with deionized water until neutral and dried at 80°C for 12 hours.

[0225] S3, isocyanate groups are constructed on the surface of pre-oxidized carbon fiber plain weave fabric.

[0226] 5 wt% of 3-isocyanate-propyltriethoxysilane was added to a mixed solvent of water and ethanol in a 1:1 mass ratio. After complete hydrolysis at room temperature for 2 hours, the pre-oxidized carbon fiber plain weave fabric was impregnated in the solvent, and the impregnation reaction was continued at 80°C for 4 hours. Finally, after washing with deionized water, the isocyanate-modified carbon fiber plain weave fabric was dried at 80°C for 12 hours to complete the dehydration and drying process.

[0227] S4. Preparation of amine-modified polyphenylene sulfide particles.

[0228] The polymerization of amine-modified polyphenylene sulfide was completed using 95 parts of p-dichlorobenzene, 5 parts of 2,5-dichloroaniline, and an appropriate amount of sodium sulfide as raw materials, under the action of a catalyst and NMP.

[0229] S5, isocyanate-modified carbon fiber plain weave fabric and amine-modified polyphenylene sulfide fiber entanglement composite.

[0230] Amine-modified polyphenylene sulfide (PPS) granules were prepared into PPS fiber filaments using a conventional melt spinning process. Based on a mass ratio of 3:7 between PPS fiber and isocyanate-modified carbon fiber plain weave fabric, the PPS fiber and isocyanate-modified carbon fiber plain weave fabric were intertwined to obtain an PPS fiber / isocyanate-modified carbon fiber preform.

[0231] S6, Amine-modified polyphenylene sulfide fiber / isocyanate-modified carbon fiber preform composite hot pressing molding.

[0232] The obtained amine-modified polyphenylene sulfide fiber / isocyanate-modified carbon fiber plain weave fabric preform was laid up and stacked in 260℃, and the pH value of the environment was adjusted to 5 with glacial acetic acid. It was then hot-pressed at 5MPa for 30min and held for 12h. The resulting isocyanate-modified carbon fiber reinforced amine-modified polyphenylene sulfide composite material was obtained.

[0233] Example 16 S1. Desizing treatment of carbon fiber plain weave fabric.

[0234] Carbon fiber plain weave fabric and solvent were uniformly mixed at a ratio of 1:10 at room temperature (25℃). The carbon fiber plain weave fabric was soaked in the solution for 7 days, changing the solution every 3 days to wash away the sizing agent on the surface of the fabric. Next, the carbon fiber plain weave fabric was rinsed multiple times with deionized water to remove the used solvent, and then dried in an 80℃ forced-air drying oven for 12 hours to obtain desized carbon fiber plain weave fabric. The solvents included ethanol and acetone, mixed at a volume ratio of 3:1.

[0235] S2, pre-oxidation of carbon fiber plain weave fabric surface.

[0236] The desized carbon fiber plain weave fabric was placed in concentrated nitric acid and treated at 40°C for 12 hours. It was then washed with deionized water until neutral and dried at 80°C for 12 hours.

[0237] S3, isocyanate groups are constructed on the surface of pre-oxidized carbon fiber plain weave fabric.

[0238] 7 wt% of 3-isocyanate-propyltriethoxysilane was added to a mixed solvent of water and ethanol in a 1:1 mass ratio. After complete hydrolysis at room temperature for 2 hours, the pre-oxidized carbon fiber plain weave fabric was impregnated in the solvent, and the impregnation reaction was continued at 80°C for 4 hours. Finally, after washing with deionized water, the isocyanate-modified carbon fiber plain weave fabric was dried at 80°C for 12 hours to complete the dehydration and drying process.

[0239] S4. Preparation of amine-modified polyphenylene sulfide particles.

[0240] The polymerization of amine-modified polyphenylene sulfide was completed using 95 parts of p-dichlorobenzene, 5 parts of 2,5-dichloroaniline, and an appropriate amount of sodium sulfide as raw materials, under the action of a catalyst and NMP.

[0241] S5, isocyanate-modified carbon fiber plain weave fabric and amine-modified polyphenylene sulfide fiber entanglement composite.

[0242] Amine-modified polyphenylene sulfide (PPS) granules were prepared into PPS fiber filaments using a conventional melt spinning process. Based on a mass ratio of 3:7 between PPS fiber and isocyanate-modified carbon fiber plain weave fabric, the PPS fiber and isocyanate-modified carbon fiber plain weave fabric were intertwined to obtain an PPS fiber / isocyanate-modified carbon fiber preform.

[0243] S6, Amine-modified polyphenylene sulfide fiber / isocyanate-modified carbon fiber preform composite hot pressing molding.

[0244] The obtained amine-modified polyphenylene sulfide fiber / isocyanate-modified carbon fiber plain weave fabric preform was laid up and stacked in 260℃, and the pH value of the environment was adjusted to 5 with glacial acetic acid. It was then hot-pressed at 5MPa for 30min and held for 12h. The resulting isocyanate-modified carbon fiber reinforced amine-modified polyphenylene sulfide composite material was obtained.

[0245] Comparative Example 1 S1. Desizing treatment of basalt plain weave fabric.

[0246] Basalt plain weave fabric and solvent were uniformly mixed at a ratio of 1:10 at room temperature (25℃). The basalt plain weave fabric was soaked in the solution for 7 days, changing the solution every 3 days to wash away the sizing agent on the surface of the fabric. Next, the basalt plain weave fabric was rinsed multiple times with deionized water to remove the used solvent, and then dried in an 80℃ forced-air drying oven for 12 hours to obtain desized basalt plain weave fabric. The solvents included ethanol and acetone, mixed at a volume ratio of 3:1.

[0247] S2, basalt plain weave fabric and polypropylene fiber entanglement composite.

[0248] Polypropylene granules were prepared into polypropylene fiber filaments using a conventional melt spinning process. Based on a mass ratio of 3:7 between polypropylene fiber and basalt plain weave fabric, the polypropylene fiber and basalt plain weave fabric were intertwined to obtain a polypropylene fiber / basalt fiber preform.

[0249] S3, polypropylene fiber / basalt fiber preform composite hot pressing molding.

[0250] The obtained polypropylene fiber / basalt plain weave fabric preform is laid up and stacked using a hot pressing process. It is then placed in 160℃, hot-pressed at 3MPa for 15 minutes, and held under pressure for 12 hours. The resulting basalt fiber reinforced polypropylene composite material is then obtained.

[0251] Comparative Example 2 S1. Desizing treatment of basalt plain weave fabric.

[0252] Basalt plain weave fabric and solvent were uniformly mixed at a ratio of 1:10 at room temperature (25℃). The basalt plain weave fabric was soaked in the solution for 7 days, changing the solution every 3 days to wash away the sizing agent on the surface of the fabric. Next, the basalt plain weave fabric was rinsed multiple times with deionized water to remove the used solvent, and then dried in an 80℃ forced-air drying oven for 12 hours to obtain desized basalt plain weave fabric. The solvents included ethanol and acetone, mixed at a volume ratio of 3:1.

[0253] S2, basalt plain weave fabric and polyphenylene sulfide fiber entanglement composite.

[0254] Polyphenylene sulfide (PPS) granules were prepared into PPS fiber filaments using a conventional melt spinning process. Based on a mass ratio of PPS fiber to basalt plain weave fabric of 3:7, the PPS fiber and basalt plain weave fabric were intertwined to obtain a PPS fiber / basalt fiber preform.

[0255] S3, polyphenylene sulfide fiber / basalt fiber preform composite hot pressing molding.

[0256] The obtained polyphenylene sulfide fiber / basalt plain weave fabric preform is laid up and stacked using a hot pressing process. It is then placed in 260℃, hot-pressed at 5MPa for 30 minutes, and held under pressure for 12 hours. The resulting basalt fiber reinforced polyphenylene sulfide composite material is then obtained.

[0257] Comparative Example 3 S1. Desizing treatment of carbon fiber plain weave fabric.

[0258] Carbon fiber plain weave fabric and solvent were uniformly mixed at a ratio of 1:10 at room temperature (25℃). The carbon fiber plain weave fabric was soaked in the solution for 7 days, changing the solution after every 3 days to wash off the sizing agent on the surface of the fabric. Next, the carbon fiber plain weave fabric was rinsed multiple times with deionized water to remove the used solvent, and then placed in an 80℃ forced-air drying oven for 12 hours to obtain desized carbon fiber plain weave fabric. The solvents included ethanol and acetone, mixed at a volume ratio of 3:1.

[0259] S2, a composite of carbon fiber plain weave fabric and polypropylene fiber.

[0260] Polypropylene granules were prepared into polypropylene fiber filaments using a conventional melt spinning process. Based on a mass ratio of 3:7 between polypropylene fiber and carbon fiber plain weave fabric, the polypropylene fiber and carbon fiber plain weave fabric were intertwined to obtain a polypropylene fiber / carbon fiber preform.

[0261] S3, polypropylene fiber / carbon fiber preform composite hot pressing molding.

[0262] The obtained polypropylene fiber / carbon fiber plain weave fabric preform is laid up and stacked using a hot pressing process. It is then placed in 160℃, hot-pressed at 3MPa for 15 minutes, and held under pressure for 12 hours. The carbon fiber reinforced polypropylene composite material is then obtained.

[0263] Comparative Example 4 S1. Desizing treatment of carbon fiber plain weave fabric.

[0264] Carbon fiber plain weave fabric and solvent were uniformly mixed at a ratio of 1:10 at room temperature (25℃). The carbon fiber plain weave fabric was soaked in the solution for 7 days, changing the solution every 3 days to wash away the sizing agent on the surface of the fabric. Next, the carbon fiber plain weave fabric was rinsed multiple times with deionized water to remove the used solvent, and then dried in an 80℃ forced-air drying oven for 12 hours to obtain desized carbon fiber plain weave fabric. The solvents included ethanol and acetone, mixed at a volume ratio of 3:1.

[0265] S2, the entanglement and composite of carbon fiber plain weave fabric and polyphenylene sulfide fiber.

[0266] Polyphenylene sulfide granules were prepared into polyphenylene sulfide fiber filaments using a conventional melt spinning process. Based on the mass ratio of polyphenylene sulfide fiber to carbon fiber plain weave fabric of 3:7, the polyphenylene sulfide fiber and carbon fiber plain weave fabric were intertwined to obtain a polyphenylene sulfide fiber / carbon fiber preform.

[0267] S3, polyphenylene sulfide fiber / carbon fiber preform composite hot pressing molding.

[0268] The obtained polyphenylene sulfide fiber / carbon fiber plain weave fabric preform is laid up and stacked in 260℃, hot-pressed at 5MPa for 30min, and held for 12h. The carbon fiber reinforced polyphenylene sulfide composite material is then obtained.

[0269] Comparative Example 5 S1. Desizing treatment of basalt plain weave fabric.

[0270] Basalt plain weave fabric and solvent were uniformly mixed at a ratio of 1:10 at room temperature (25℃). The basalt plain weave fabric was soaked in the solution for 7 days, changing the solution every 3 days to wash away the sizing agent on the surface of the fabric. Next, the basalt plain weave fabric was rinsed multiple times with deionized water to remove the used solvent, and then dried in an 80℃ forced-air drying oven for 12 hours to obtain desized basalt plain weave fabric. The solvents included ethanol and acetone, mixed at a volume ratio of 3:1.

[0271] S2. Pre-oxidation treatment of basalt plain weave fabric surface.

[0272] The desized basalt fiber plain weave fabric was placed in concentrated nitric acid and treated at 40°C for 12 hours. It was then washed with deionized water until neutral and dried at 80°C for 12 hours.

[0273] S3, pre-oxidized basalt plain weave fabric and polypropylene fiber entanglement composite.

[0274] Polypropylene granules were prepared into polypropylene fiber filaments using a conventional melt spinning process. Based on a mass ratio of 3:7 between polypropylene fiber and pre-oxidized basalt plain weave fabric, the polypropylene fiber and pre-oxidized basalt plain weave fabric were intertwined to obtain a polypropylene fiber / pre-oxidized basalt fiber preform.

[0275] S4, polypropylene fiber / pre-oxidized basalt fiber preform composite hot pressing molding.

[0276] The obtained polypropylene fiber / pre-oxidized basalt plain weave fabric preform is laid up and stacked using a hot pressing process. It is then placed in 160℃, hot-pressed at 3MPa for 15min, and held under pressure for 12h. The pre-oxidized basalt fiber reinforced polypropylene composite material is then obtained.

[0277] Comparative Example 6 S1. Desizing treatment of basalt plain weave fabric.

[0278] Basalt plain weave fabric and solvent were uniformly mixed at a ratio of 1:10 at room temperature (25℃). The basalt plain weave fabric was soaked in the solution for 7 days, changing the solution every 3 days to wash away the sizing agent on the surface of the fabric. Next, the basalt plain weave fabric was rinsed multiple times with deionized water to remove the used solvent, and then dried in an 80℃ forced-air drying oven for 12 hours to obtain desized basalt plain weave fabric. The solvents included ethanol and acetone, mixed at a volume ratio of 3:1.

[0279] S2. Pre-oxidation treatment of basalt plain weave fabric surface.

[0280] The desized basalt fiber plain weave fabric was placed in concentrated nitric acid and treated at 40°C for 12 hours. It was then washed with deionized water until neutral and dried at 80°C for 12 hours.

[0281] S3, pre-oxidized basalt plain weave fabric and polyphenylene sulfide fiber entanglement composite.

[0282] Polyphenylene sulfide granules were prepared into polyphenylene sulfide fiber filaments using a conventional melt spinning process. Based on the mass ratio of polyphenylene sulfide fiber to pre-oxidized basalt plain weave fabric of 3:7, the polyphenylene sulfide fiber and pre-oxidized basalt plain weave fabric were intertwined to obtain a polyphenylene sulfide fiber / pre-oxidized basalt fiber preform.

[0283] S4, polyphenylene sulfide fiber / pre-oxidized basalt fiber preform composite hot pressing molding.

[0284] The obtained polyphenylene sulfide fiber / pre-oxidized basalt plain weave fabric preform is laid up and stacked in 260℃, hot-pressed at 5MPa for 30min, and held for 12h. The pre-oxidized basalt fiber reinforced polyphenylene sulfide composite material is then obtained by hot pressing.

[0285] Comparative Example 7 S1. Desizing treatment of carbon fiber plain weave fabric.

[0286] Carbon fiber plain weave fabric and solvent were uniformly mixed at a ratio of 1:10 at room temperature (25℃). The carbon fiber plain weave fabric was soaked in the solution for 7 days, changing the solution after every 3 days to wash off the sizing agent on the surface of the fabric. Next, the carbon fiber plain weave fabric was rinsed multiple times with deionized water to remove the used solvent, and then placed in an 80℃ forced-air drying oven for 12 hours to obtain desized carbon fiber plain weave fabric. The solvents included ethanol and acetone, mixed at a volume ratio of 3:1.

[0287] S2, Pre-oxidation treatment of carbon fiber plain weave fabric surface.

[0288] The desized carbon fiber plain weave fabric was placed in concentrated nitric acid and treated at 40°C for 12 hours. It was then washed with deionized water until neutral and dried at 80°C for 12 hours.

[0289] S3, pre-oxidized carbon fiber plain weave fabric and polypropylene fiber winding composite.

[0290] Polypropylene granules were prepared into polypropylene fiber filaments using a conventional melt spinning process. Based on a mass ratio of 3:7 between polypropylene fiber and pre-oxidized carbon fiber plain weave fabric, the polypropylene fiber and pre-oxidized carbon fiber plain weave fabric were intertwined to obtain a polypropylene fiber / pre-oxidized carbon fiber preform.

[0291] S4, polypropylene fiber / pre-oxidized carbon fiber preform composite hot pressing molding.

[0292] The obtained polypropylene fiber / pre-oxidized carbon fiber plain weave fabric preform is laid up and stacked using a hot pressing process. It is then placed in 160℃, hot-pressed at 3MPa for 15min, and held under pressure for 12h. The pre-oxidized carbon fiber reinforced polypropylene composite material is then obtained.

[0293] Comparative Example 8 S1. Desizing treatment of carbon fiber plain weave fabric.

[0294] Carbon fiber plain weave fabric and solvent were uniformly mixed at a ratio of 1:10 at room temperature (25℃). The carbon fiber plain weave fabric was soaked in the solution for 7 days, changing the solution every 3 days to wash away the sizing agent on the surface of the fabric. Next, the carbon fiber plain weave fabric was rinsed multiple times with deionized water to remove the used solvent, and then dried in an 80℃ forced-air drying oven for 12 hours to obtain desized carbon fiber plain weave fabric. The solvents included ethanol and acetone, mixed at a volume ratio of 3:1.

[0295] S2, Pre-oxidation treatment of carbon fiber plain weave fabric surface.

[0296] The desized carbon fiber plain weave fabric was placed in concentrated nitric acid and treated at 40°C for 12 hours. It was then washed with deionized water until neutral and dried at 80°C for 12 hours.

[0297] S3, pre-oxidized carbon fiber plain weave fabric and polyphenylene sulfide fiber entanglement composite.

[0298] Polyphenylene sulfide granules were prepared into polyphenylene sulfide fiber filaments using a conventional melt spinning process. Based on the mass ratio of polyphenylene sulfide fiber to pre-oxidized carbon fiber plain weave fabric of 3:7, the polyphenylene sulfide fiber and pre-oxidized carbon fiber plain weave fabric were intertwined to obtain a polyphenylene sulfide fiber / pre-oxidized carbon fiber preform.

[0299] S4, polyphenylene sulfide fiber / pre-oxidized carbon fiber preform composite hot pressing molding.

[0300] The obtained polyphenylene sulfide fiber / pre-oxidized carbon fiber plain weave fabric preform is laid up and stacked in 260℃, hot-pressed at 5MPa for 30min, and held for 12h. The pre-oxidized carbon fiber reinforced polyphenylene sulfide composite material is then obtained.

[0301] The tensile strength, tensile modulus, flexural strength, flexural modulus, and interfacial shear strength of all the comparative examples and embodiments described above were tested, and the results are shown in Table 1.

[0302] Table 1. Mechanical properties of fiber-reinforced thermoplastic resin-based composites

[0303] All the comparative examples and embodiments described above were immersed in a sodium hydroxide solution with pH=13 at 40°C for 24 hours. The peeling of the fiber reinforcement in the composite material was recorded; and the recovered fiber reinforcement was then subjected to secondary composite molding with the corresponding resin fiber (see steps S5 and S6 of Example 1), and its tensile strength, tensile modulus, flexural strength, and flexural modulus were recorded. The relevant results are shown in Table 2. The morphology of the fiber-reinforced thermoplastic resin-based composite material of Example 14 before and after recycling, as well as during secondary composite molding, is shown in Table 2. Figure 4 As shown.

[0304] Table 2. Deschistolysis of fiber reinforcement during recycling and mechanical properties of the secondary recycled composite materials

[0305] The above description is merely a preferred embodiment of the present invention and is not intended to limit the invention. Various modifications and variations can be made to the present invention by those skilled in the art. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the scope of protection of the present invention.

Claims

1. A fiber-reinforced thermoplastic resin-based composite material based on dynamic reversible interfacial interactions, characterized in that, It comprises a modified thermoplastic resin matrix and a modified fiber reinforcement that are composite with each other, wherein the modified thermoplastic resin matrix and the modified fiber reinforcement are connected by dynamic bonds with dynamic reversible interfacial interactions.

2. The fiber-reinforced thermoplastic resin-based composite material according to claim 1, characterized in that, The dynamic bond includes at least one of the following: Diels-Alder bond, ester bond, benzyl ether bond, disulfide bond, imine bond, siloxane bond, borate ester bond, and hydrazone bond.

3. The fiber-reinforced thermoplastic resin-based composite material according to claim 1 or 2, characterized in that, The modified thermoplastic resin matrix corresponds to at least one of the following thermoplastic resins: polypropylene, polyethylene, polyphenylene sulfide, polycarbonate, polyamide, polyetheretherketone, polyaryletherketone, and polyetherimide.

4. The fiber-reinforced thermoplastic resin-based composite material according to claim 1 or 2, characterized in that, The modified fiber reinforcement includes at least one of glass fiber, basalt fiber, carbon fiber, quartz fiber, and silicon carbide fiber.

5. A method for preparing a fiber-reinforced thermoplastic resin-based composite material as described in any one of claims 1 to 4, characterized in that, It includes: A first active group is constructed on the surface of the fiber reinforcement to obtain the modified fiber reinforcement; A second active group is introduced into the molecular structure of a thermoplastic resin to obtain a modified thermoplastic resin, which is then subjected to morphological processing. The modified thermoplastic resin after morphological processing is pre-composite with the modified fiber reinforcement to obtain a mixed preform; The hybrid preform is then hot-pressed together.

6. The method for preparing the fiber-reinforced thermoplastic resin-based composite material according to claim 5, characterized in that, Constructing the first active group on the surface of the fiber reinforcement includes: first pre-oxidizing the fiber reinforcement, and then dehydrating and condensing it with the oxygen-containing functional groups on the surface of the fiber reinforcement using a silane coupling agent; Preferably, the pre-oxidation treatment involves soaking the fiber reinforcement in concentrated sulfuric acid or concentrated nitric acid. Preferably, the fiber reinforcement is desized before pre-oxidation treatment to remove the sizing agent from the surface; Preferably, the silane coupling agent includes at least one of urea-amino silane coupling agents, amino silane coupling agents, succinic anhydride silane coupling agents, and isocyanate silane coupling agents.

7. The method for preparing fiber-reinforced thermoplastic resin-based composite materials according to claim 5, characterized in that, Introducing a second active group into the molecular structure of a thermoplastic resin can be achieved through copolymerization modification or side-linking. Preferably, the overall grafting rate of the second active group of the modified thermoplastic resin reaches 5wt%~20wt%.

8. The method for preparing the fiber-reinforced thermoplastic resin-based composite material according to any one of claims 5 to 7, characterized in that, The morphology processing includes processing into granules, fibers, or films; and / or, the pre-composite method is lay-up or winding; and / or, the mass ratio of the modified thermoplastic resin to the modified fiber reinforcement in the pre-composite process is (2~5):(5~8). Preferably, the morphology processing is carried out by melt spinning to prepare long fibers, wherein the density of the long fibers reaches 2~20 dtex and the breaking strength of the single filament reaches 3cN / dtex~5cN / dtex.

9. The method for preparing the fiber-reinforced thermoplastic resin-based composite material according to any one of claims 5 to 7, characterized in that, The ambient pH value of the hot-pressed composite is controlled at 2~9, the hot-pressing temperature is 120℃~400℃, the external load is 0.5MPa~8MPa, the hot-pressing time is 10min~120min, and the holding time is 5h~24h.

10. A method for recycling the fiber-reinforced thermoplastic resin-based composite material as described in any one of claims 1 to 4, characterized in that, The interface detachment between the modified thermoplastic resin and the modified fiber reinforcement is promoted by introducing external reverse bond breaking conditions. Preferably, the external reverse bond breaking conditions include pH change, temperature change or light stimulation response.

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