Sizing agent for carbon fiber, carbon fiber reinforced heteronaphthalene biphenyl poly(arylene ether) resin-based composite material, and preparation method and application thereof

Abstract

The present application relates to the technical field of sizing agent, and particularly relates to a sizing agent for carbon fiber, a carbon fiber reinforced poly (phthalazinone biphenyl ether) resin matrix composite material and a preparation method and application thereof, wherein the sizing agent for carbon fiber comprises poly (phthalazinone biphenyl ether) ketone, and a phthalazinone biphenyl structure and a carboxyl group are included in a structural formula of the poly (phthalazinone biphenyl ether) ketone. The sizing agent provided by the present application can improve the interfacial bonding strength between carbon fiber and poly (phthalazinone biphenyl ether) resin after surface treatment of the carbon fiber, so that the mechanical properties of the composite material are improved.

Description

Technical Field

[0001] This invention relates to the field of sizing agents, and in particular to a sizing agent for carbon fibers, a carbon fiber reinforced heteronaphthalene biphenyl polyarylene ether resin-based composite material, its preparation method, and its application. Background Technology

[0002] Continuous carbon fiber reinforced polymer matrix composites (CFRPs) possess advantages such as short production cycle, high fracture toughness, good thermal stability, high strength, and fatigue resistance. They can be used as both structural and functional materials, finding wide application in aerospace, transportation, and other fields. Naphthalene-biphenyl polyaryl ethers exhibit high hardness and wear resistance; using naphthalene-biphenyl polyaryl ether resin as a matrix to prepare wear-resistant resin-based composites helps improve the composite's wear resistance, heat resistance, and mechanical properties. However, the low bonding strength between untreated carbon fibers and the polymer matrix severely affects the overall performance of the composite, including its mechanical properties.

[0003] Surface treatment of carbon fibers can effectively enhance the interfacial bonding between the fibers and the polymer matrix. Methods such as chemical grafting, plasma treatment, self-assembly, electrodeposition, and sizing can be used to improve the mechanical properties of composite materials. Sizing is considered one of the most promising methods and is widely used in industry. Solution impregnation is a common method for sizing carbon fibers. Studies have shown that the sizing agent layer not only improves the wettability of the carbon fiber (CF) surface but also enhances the interfacial interaction between the fibers and the polymer matrix through a "bridging" bonding effect.

[0004] Currently, there is limited research on sizing agents for carbon fibers based on naphthalene-biphenyl polyaryl ether resins. Therefore, developing sizing agents for carbon fibers that are compatible with naphthalene-biphenyl polyaryl ether matrix resins is of significant research importance. Summary of the Invention

[0005] In view of the above-mentioned shortcomings in the prior art, the purpose of this invention is to provide a sizing agent for carbon fiber, a carbon fiber reinforced heteronaphthalene biphenyl polyarylene ether resin-based composite material, its preparation method and application. The sizing agent provided by this invention can improve the interfacial bonding strength between carbon fiber and heteronaphthalene biphenyl polyarylene ether resin after surface treatment, thereby improving the mechanical properties of the composite material.

[0006] To achieve the above objectives, the present invention adopts the following technical solution:

[0007] In a first aspect, the present invention provides a sizing agent for carbon fibers, the sizing agent for carbon fibers comprising polyaryletherketone, wherein the polyaryletherketone comprises a diazanaphthone biphenyl structure and a carboxyl group.

[0008] The sizing agent provided by this invention can improve the interfacial bonding strength between carbon fibers and polyarylether resin after surface treatment, thereby improving the mechanical properties of the composite material.

[0009] Furthermore, the structural formula of the polyaryletherketone is shown in Formula I:

[0010]

[0011] In the formula, m and n are integers greater than 1, Ar1 and Ar2 are the main structures of the dihalogen monomers, and Ar1 and Ar2 may be the same or different, and each independently represents one of the following structural formulas:

[0012]

[0013] Furthermore, the sizing agent for carbon fiber also includes inorganic salt nanoparticles, including hydroxyapatite nanoparticles, and the mass ratio of the polyarylether ketone to the inorganic salt nanoparticles is (5:1) to (5:15).

[0014] Furthermore, the preparation method of the polyaryletherketone includes the following steps:

[0015] Monomer A, monomer B, dihalogenated monomer, catalyst, and dehydrating agent are added to the reaction solvent. Under heating conditions, water is removed using the dehydrating agent, and then the dehydrating agent is removed. The reaction is continued under heating. As the viscosity of the reaction solution increases, the solvent is gradually added dropwise. When the viscosity of the reaction solution no longer increases, the reaction is stopped by cooling. The reaction solution is poured into a dilute acid solution to terminate the reaction. After post-treatment, the polyarylether ketone is obtained. Monomer A contains a carboxyl group and is one of phenolphthalein or 4-carboxyphenyl hydroquinone. Monomer B contains a diazanaphthone biphenyl structure and is 4-(4-hydroxyphenyl)-2,3-diazanaphth-1-one.

[0016] Furthermore, the catalyst comprises potassium carbonate; the dehydrating agent comprises toluene; and the reaction solvent comprises NMP.

[0017] Furthermore, the molar number of monomer A accounts for 2% to 60% of the total molar number of monomer A and monomer B.

[0018] Furthermore, the ratio of the total molar number of monomer A and monomer B to the total molar number of the dihalogenated monomer is 1:(0.8 to 1.5).

[0019] Furthermore, the temperature of the water is 130–150°C, and the time is 2–5 hours.

[0020] Furthermore, the reaction temperature is 170–190°C.

[0021] Furthermore, the post-processing includes: pulverizing the obtained solid polymer, washing it with water and ethanol, and finally drying it.

[0022] In a second aspect, the present invention provides a carbon fiber reinforced heteronaphthyl biphenyl polyarylene ether resin-based composite material, the carbon fiber reinforced heteronaphthyl biphenyl polyarylene ether resin-based composite material comprising the following raw materials: carbon fiber and heteronaphthyl biphenyl polyarylene ether resin, wherein the carbon fiber comprises at least one of unsized carbon fiber and carbon fiber treated with a sizing agent as described in the first aspect.

[0023] Furthermore, the carbon fiber includes continuous carbon fibers.

[0024] Furthermore, by weight percentage, the composite material comprises the following raw materials: 10-70% of the naphthalene-biphenyl polyarylene ether resin and 30-90% of continuous carbon fibers.

[0025] Furthermore, the structural formula of the naphthalene-biphenyl polyarylene ether resin is shown in Formula II:

[0026]

[0027] In the formula, Ar1 and Ar3 are the main structures of the dihalogen monomers. Ar1 and Ar3 may be the same or different, and each independently represents one of the following structural formulas:

[0028]

[0029] Ar2 is the main structure of the bisphenol monomer, representing one of the following structural formulas:

[0030]

[0031] R1, R2, R3, and R4 each independently represent hydrogen, halogen substituents, phenyl, phenoxy, straight-chain alkyl with at least one carbon atom, branched alkyl with at least one carbon atom, or branched alkoxy with at least one carbon atom. R1, R2, R3, and R4 may have the same or different structures.

[0032] Furthermore, the naphthalene-biphenyl polyarylene ether resin is selected from at least one of the following naphthalene-biphenyl polyarylene ether resins:

[0033] Naphthobenzyl polyaryletherketone:

[0034]

[0035] Naphthyl biphenyl polyarylether sulfone:

[0036]

[0037] Thirdly, the present invention provides a method for preparing carbon fiber reinforced heteronaphthalene biphenyl polyarylene ether resin-based composite materials as described in the second aspect, the preparation method comprising the following steps:

[0038] S1. Immerse the carbon fiber in a solution of the carbon fiber sizing agent as described in the first aspect, and dry it to obtain the carbon fiber treated with the carbon fiber sizing agent.

[0039] S2. Dissolve the naphthalene-biphenyl polyarylene ether resin in a solvent to obtain a resin solution;

[0040] S3. Impregnate the carbon fiber treated with sizing agent obtained in step S1 with the resin solution obtained in step S2. After the carbon fiber surface is completely impregnated with the resin solution, heat and dry to remove the solvent, and then cool to obtain the prepreg.

[0041] S4. Place the prepreg obtained in step S3 into a mold and prepare the composite material using a vacuum hot pressing process.

[0042] Furthermore, the preparation method does not include step S1; in step S3:

[0043] The unsized carbon fibers are impregnated with the resin solution obtained in step S2. After the carbon fiber surface is completely impregnated with the resin solution, the fibers are heated and dried to remove the solvent. After cooling, the prepreg is obtained.

[0044] Furthermore, in step S1, the carbon fiber is immersed in the solution of the carbon fiber sizing agent for 1-30 minutes.

[0045] Furthermore, the solvent includes at least one of NMP, N,N-dimethylformamide, and N,N-dimethylacetamide.

[0046] Furthermore, the resin in the resin solution has a mass percentage of 1% to 30%.

[0047] Furthermore, the sizing agent solution for the carbon fiber includes an organic solvent, which includes at least one of NMP, chloroform, DMAc, and DMF.

[0048] Furthermore, based on the total weight of the sizing agent solution for the carbon fiber as 100%, the weight percentage of the polyaryletherketone is 0.1% to 5%.

[0049] Furthermore, based on the total weight of the sizing agent solution for the carbon fiber being 100%, the weight percentage of the inorganic salt nanoparticles is 0.01% to 5%.

[0050] Furthermore, the method for preparing the sizing agent solution for carbon fibers includes the following steps:

[0051] The polyarylether ketone and / or the inorganic salt nanoparticles are dissolved in the organic solvent and mixed evenly to obtain a solution of the sizing agent for carbon fibers.

[0052] Furthermore, the vacuum hot pressing temperature is 320-400℃, the pressure is 3-20MPa, and the time is 3-60 minutes.

[0053] Fourthly, the present invention provides the application of carbon fiber reinforced heteronaphthyl biphenyl polyarylene ether resin-based composite material as described in the second aspect or carbon fiber reinforced heteronaphthyl biphenyl polyarylene ether resin-based composite material prepared by the preparation method described in the third aspect in the field of medical devices.

[0054] Compared with the prior art, the beneficial effects of the present invention include at least one of the following:

[0055] (1) The carbon fiber sizing agent provided by the present invention can improve the interfacial bonding strength between carbon fiber and naphthalene biphenyl polyarylene ether resin after surface treatment, thereby improving the mechanical properties of the composite material.

[0056] (2) The composite material provided by the present invention has good biocompatibility and has application potential in the field of medical devices. Attached Figure Description

[0057] To more clearly illustrate the specific embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the specific embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are some embodiments of the present invention. For those skilled in the art, other drawings can be obtained from these drawings without creative effort.

[0058] Figure 1 Infrared spectra of PPEK and PAEK-COOH;

[0059] Figure 2 Flowchart of the preparation method of carbon fiber reinforced heteronaphthalene biphenyl polyarylene ether resin-based composite material provided in Example 1 and Comparative Example 1;

[0060] Figure 3 These are scanning electron microscope (SEM) images of the sizing agents for carbon fibers prepared in Examples 1-4. Figure 3 In the diagram, a is a scanning electron microscope (SEM) image of the carbon fiber sizing agent prepared in Example 1, b is a scanning electron microscope (SEM) image of the carbon fiber sizing agent prepared in Example 2, c is a scanning electron microscope (SEM) image of the carbon fiber sizing agent prepared in Example 3, and d is a scanning electron microscope (SEM) image of the carbon fiber sizing agent prepared in Example 4.

[0061] Figure 4 XPS spectra of desized carbon fibers and carbon fibers treated with the sizing agent in Examples 1-4. Figure 4 In the figure, a is the full XPS spectrum, b is the XPS spectrum of Ca2p, c is the XPS spectrum of P2p, and d is the XPS spectrum of N1s.

[0062] Figure 5 Scanning electron microscope (SEM) and atomic force microscope (AFM) images of desized carbon fibers and carbon fibers treated with the sizing agent in Examples 1-4. Figure 5 In the diagram, a is a scanning electron microscope (SEM) image of desized carbon fiber, a1 is an atomic force microscope (AFM) image of desized carbon fiber, b is a scanning electron microscope (SEM) image of carbon fiber treated with sizing agent in Example 1, b1 is an AFM image of carbon fiber treated with sizing agent in Example 1, c is a scanning electron microscope (SEM) image of carbon fiber treated with sizing agent in Example 2, c1 is an AFM image of carbon fiber treated with sizing agent in Example 2, d is a scanning electron microscope (SEM) image of carbon fiber treated with sizing agent in Example 3, d1 is an AFM image of carbon fiber treated with sizing agent in Example 3, e is a scanning electron microscope (SEM) image of carbon fiber treated with sizing agent in Example 4, e1 is an AFM image of carbon fiber treated with sizing agent in Example 4.

[0063] Figure 6 The images shown are scanning electron microscope (SEM) images of the cross-sectional surfaces of CF / PPEK composite materials prepared in Comparative Examples 1 and Examples 1-4 after interlaminar shear and bending tests. Figure 6 In the diagram, a is a cross-sectional scanning electron microscope (SEM) image of the CF / PPEK composite material prepared in Comparative Example 1 after an interlaminar shear test; b is a cross-sectional SEM image of the CF / PPEK composite material prepared in Example 1 after an interlaminar shear test; c is a cross-sectional SEM image of the CF / PPEK composite material prepared in Example 2 after an interlaminar shear test; d is a cross-sectional SEM image of the CF / PPEK composite material prepared in Example 3 after an interlaminar shear test; and e is a cross-sectional image of the CF / PPEK composite material prepared in Example 4 after an interlaminar shear test. Scanning electron microscope (SEM) images: f is a cross-sectional SEM image of the CF / PPEK composite material sample prepared in Comparative Example 1 after a bending test; g is a cross-sectional SEM image of the CF / PPEK composite material sample prepared in Example 1 after a bending test; h is a cross-sectional SEM image of the CF / PPEK composite material sample prepared in Example 2 after a bending test; i is a cross-sectional SEM image of the CF / PPEK composite material sample prepared in Example 3 after a bending test; and j is a cross-sectional SEM image of the CF / PPEK composite material sample prepared in Example 4 after a bending test. Detailed Implementation

[0064] To make the objectives, technical solutions, and advantages of this invention clearer, the technical solutions in the embodiments of this invention will be clearly and completely described below in conjunction with the embodiments of this invention. Those skilled in the art should understand that the embodiments described are merely illustrative of the invention and should not be considered as specific limitations thereof. All other embodiments obtained by those skilled in the art based on the embodiments of this invention without creative effort are within the scope of protection of this invention. Process parameters not specifically specified in the following embodiments are generally performed under conventional conditions.

[0065] The endpoints and any values ​​of the ranges disclosed in this invention are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed in this invention.

[0066] In a first aspect, the present invention provides a sizing agent for carbon fibers, the sizing agent for carbon fibers comprising polyaryletherketone, wherein the polyaryletherketone comprises a diazanaphthone biphenyl structure and a carboxyl group.

[0067] Here, the structural formula of the diazanaphthone biphenyl structure is shown below:

[0068]

[0069] The sizing agent provided by this invention can improve the interfacial bonding strength between carbon fibers and polyarylether resin after surface treatment, thereby improving the mechanical properties of the composite material.

[0070] If the carboxyl groups in polyaryletherketone are replaced with hydroxyl or amino groups, the interfacial bonding strength between carbon fibers and polyarylether resin will not be significantly improved.

[0071] The polyaryletherketone has hydrophilic properties and exhibits strong adhesion to carbon fibers.

[0072] In the above-mentioned sizing agent for carbon fibers, as an optional embodiment, the polyaryletherketone has the structural formula shown in Formula I:

[0073]

[0074] In the formula, m and n are integers greater than 1, Ar1 and Ar2 are the main structures of the dihalogen monomers, and Ar1 and Ar2 may be the same or different, and each independently represents one of the following structural formulas:

[0075]

[0076] In one optional embodiment of the aforementioned carbon fiber sizing agent, the carbon fiber sizing agent further includes inorganic salt nanoparticles, including hydroxyapatite nanoparticles. Polyaryletherketones can improve the dispersibility of inorganic salt nanoparticles in organic solvents. In the composite material, the inorganic salt nanoparticles in the sizing agent layer on the carbon fiber surface can disperse stress. After surface treatment of the carbon fiber with this carbon fiber sizing agent, the interfacial bonding strength between the carbon fiber and the polyarylether resin can be further improved.

[0077] In the above-mentioned sizing agent for carbon fiber, as an optional embodiment, the mass ratio of the polyarylether ketone to the inorganic salt nanoparticles is (5:1) to (5:15), preferably (5:2) to (5:8). If the mass ratio is too low, the dispersibility of the inorganic salt nanoparticles in the sizing agent will be worse.

[0078] In the above-mentioned sizing agent for carbon fibers, as an optional embodiment, the preparation method of the polyarylether ketone includes the following steps:

[0079] Monomer A, monomer B, a dihalogenated monomer, a catalyst, and a dehydrating agent are added to a reaction solvent. Under heating conditions, water is removed using the dehydrating agent, and then the dehydrating agent is removed. The reaction is continued under heating. As the viscosity of the reaction solution increases, solvent is gradually added dropwise. When the viscosity of the reaction solution no longer increases, the reaction is stopped by cooling. The reaction solution is poured into a dilute acid solution to terminate the reaction. After post-treatment, the polyarylether ketone (a carboxylic acid-containing naphthalene-1-one polyarylether ketone) is obtained. Monomer A contains a carboxyl group and is one of phenolphthalein (PPL) or 4-carboxyphenyl hydroquinone (4C-PH). Monomer B contains a diazanaphthalene-1-one structure and is 4-(4-hydroxyphenyl)-2,3-diazanaphthalene-1-one (DHPZ).

[0080] This invention synthesizes carboxyl-functionalized cyclonaphthalene-biphenyl polyarylether ketones using a typical nucleophilic substitution condensation reaction. As a polymer sizing agent, it possesses a structure similar to the matrix resin and exhibits good compatibility with carbon fibers and cyclonaphthalene-biphenyl polyarylether ketones, improving the bonding between the fiber reinforcement and the matrix resin in the composite material, thereby enhancing its mechanical properties. To further improve the mechanical properties of the composite material, hydroxyapatite (HAp) nanoparticles are introduced into the composite sizing agent to prepare a composite sizing agent for carbon fibers. PAEK-COOH (a polyarylether ketone containing diazanaphthalene-biphenyl and carboxyl structures) improves the dispersibility of the nanoparticles. Continuous carbon fiber reinforced cyclonaphthalene-biphenyl polyarylether ketone resin-based composites have significant application potential in the medical device field.

[0081] In one optional embodiment of the above-mentioned sizing agent for carbon fiber, the catalyst includes potassium carbonate (K2CO3).

[0082] In one optional embodiment of the above-mentioned sizing agent for carbon fiber, the water-removing agent includes toluene.

[0083] In one optional embodiment of the above-mentioned sizing agent for carbon fibers, the reaction solvent includes NMP.

[0084] In the aforementioned sizing agent for carbon fibers, as an optional embodiment, the molar number of monomer A accounts for 2% to 60% of the total molar number of monomer A and monomer B (for example, it can be 5%, 10%, 30%, 50%, or 60%, etc.), that is, the molar ratio A / (A+B) is 2% to 60%. If the molar number of monomer A is too low, the improvement on the mechanical properties of the composite material is not significant; if the molar number of monomer A is too high, the solubility in organic solvents is low.

[0085] In the above-mentioned sizing agent for carbon fiber, as an optional embodiment, the ratio of the total molar number of monomer A and monomer B to the total molar number of the dihalogen monomer is 1:(0.8~1.5).

[0086] In the above-mentioned sizing agent for carbon fiber, as an optional embodiment, the temperature of the water is 130-150°C (for example, 130°C, 140°C or 150°C), and the time is 2-5 hours (for example, 2 hours, 3 hours or 5 hours).

[0087] In the above-mentioned sizing agent for carbon fiber, as an optional embodiment, the reaction temperature is 170-190°C, for example, 170°C, 180°C or 190°C.

[0088] In one optional embodiment of the above-mentioned sizing agent for carbon fibers, the post-treatment includes: pulverizing the obtained solid polymer, washing it with water and ethanol, and finally drying it.

[0089] In a second aspect, the present invention provides a carbon fiber reinforced heteronaphthyl biphenyl polyarylene ether resin-based composite material, the carbon fiber reinforced heteronaphthyl biphenyl polyarylene ether resin-based composite material comprising the following raw materials: carbon fiber and heteronaphthyl biphenyl polyarylene ether resin, wherein the carbon fiber comprises at least one of unsized carbon fiber and carbon fiber treated with a sizing agent as described in the first aspect.

[0090] By using the sizing agent described in the first aspect to treat the surface of carbon fibers, the present invention can improve the interfacial bonding strength between carbon fibers and polyarylether resin, thereby improving the mechanical properties of the composite material.

[0091] The composite material provided by this invention has good biocompatibility and has application potential in the field of medical devices.

[0092] In the above-mentioned carbon fiber reinforced heteronaphthalene biphenyl polyarylene ether resin-based composite material, as an optional embodiment, the carbon fiber includes continuous carbon fiber.

[0093] In the above-mentioned carbon fiber reinforced naphthalene biphenyl polyarylene ether resin-based composite material, as an optional embodiment, the composite material comprises the following raw materials by weight percentage: 10-70% naphthalene biphenyl polyarylene ether resin (for example, 10%, 20%, 50%, or 70%) and 30-90% continuous carbon fiber.

[0094] In the above-mentioned carbon fiber reinforced heteronaphthyl biphenyl polyarylene ether resin-based composite material, as an optional embodiment, the structural formula of the heteronaphthyl biphenyl polyarylene ether resin is shown in Formula II:

[0095]

[0096] In the formula, Ar1 and Ar3 are the main structures of the dihalogen monomers. Ar1 and Ar3 may be the same or different, and each independently represents one of the following structural formulas:

[0097]

[0098] Ar2 is the main structure of the bisphenol monomer, representing one of the following structural formulas:

[0099]

[0100] R1, R2, R3, and R4 each independently represent hydrogen, halogen substituents, phenyl, phenoxy, straight-chain alkyl with at least one carbon atom, branched alkyl with at least one carbon atom, or branched alkoxy with at least one carbon atom. R1, R2, R3, and R4 may have the same or different structures.

[0101] In the above-mentioned carbon fiber reinforced heteronaphthyl biphenyl polyarylene ether resin-based composite material, as an optional embodiment, the heteronaphthyl biphenyl polyarylene ether resin is selected from at least one of the following heteronaphthyl biphenyl polyarylene ether resins:

[0102] Poly(naphthyl biphenyl) ether ketone (PPEK)

[0103]

[0104] Poly(phenylene ether sulfone ketone) (PPESK)

[0105]

[0106] Thirdly, the present invention provides a method for preparing carbon fiber reinforced heteronaphthalene biphenyl polyarylene ether resin-based composite materials as described in the second aspect, the preparation method comprising the following steps:

[0107] S1. Immerse the carbon fiber in a solution of the carbon fiber sizing agent as described in the first aspect, and dry it to obtain the carbon fiber treated with the carbon fiber sizing agent.

[0108] S2. Dissolve the naphthalene-biphenyl polyarylene ether resin in a solvent to obtain a resin solution;

[0109] S3. Impregnate the carbon fiber treated with sizing agent obtained in step S1 with the resin solution obtained in step S2. After the carbon fiber surface is completely impregnated with the resin solution, heat and dry to remove the solvent, and then cool to obtain the prepreg.

[0110] S4. Place the prepreg obtained in step S3 into a mold and prepare the composite material using a vacuum hot pressing process.

[0111] In the above-mentioned method for preparing carbon fiber reinforced naphthalene biphenyl polyarylene ether resin-based composite materials, as an optional embodiment, the preparation method does not include step S1, and in step S3:

[0112] The unsized carbon fibers are impregnated with the resin solution obtained in step S2. After the carbon fiber surface is completely impregnated with the resin solution, the fibers are heated and dried to remove the solvent. After cooling, the prepreg is obtained.

[0113] In the above-mentioned method for preparing carbon fiber reinforced naphthalene biphenyl polyarylene ether resin-based composite material, as an optional embodiment, in step S1, the time for immersing the carbon fiber in the solution of the carbon fiber sizing agent is 1-30 min, for example, 1 min, 5 min, 10 min, 20 min or 30 min.

[0114] In the above-mentioned method for preparing carbon fiber reinforced heteronaphthalene biphenyl polyarylene ether resin-based composite materials, as an optional embodiment, the solvent includes at least one of NMP, N,N-dimethylformamide, and N,N-dimethylacetamide.

[0115] In the above-mentioned method for preparing carbon fiber reinforced naphthalene biphenyl polyarylene resin-based composite materials, as an optional embodiment, the mass percentage of resin in the resin solution is 1% to 30%, for example, it can be 1%, 10%, 20% or 30%.

[0116] In the above-mentioned method for preparing carbon fiber reinforced naphthalene biphenyl polyarylene ether resin-based composite materials, as an optional embodiment, the solution of the sizing agent for carbon fiber includes an organic solvent, wherein the organic solvent includes at least one of NMP (N-methylpyrrolidone), chloroform, DMAc (N,N-dimethylacetamide), and DMF (N,N-dimethylformamide).

[0117] In the above-mentioned method for preparing carbon fiber reinforced naphthalene-biphenyl polyarylether resin-based composite materials, as an optional embodiment, the weight percentage of the polyarylether ketone is 0.1% to 5%, for example, 0.1%, 1%, 3%, or 5%, based on the total weight of the solution of the carbon fiber sizing agent as 100%. If the weight percentage of the polyarylether ketone is too high, it cannot be completely dissolved in the organic solvent, resulting in an uneven coating during subsequent applications and reducing the mechanical properties of the composite material.

[0118] In the above-mentioned method for preparing carbon fiber reinforced naphthalene biphenyl polyarylene ether resin-based composite material, as an optional embodiment, the weight percentage of the inorganic salt nanoparticles is 0.01% to 5%, for example, 0.01%, 1%, 3% or 5%, based on the total weight of the solution of the sizing agent for carbon fiber as 100%.

[0119] In the above-mentioned method for preparing carbon fiber reinforced naphthalene-biphenyl polyarylene ether resin-based composite materials, as an optional embodiment, the method for preparing the solution of the carbon fiber sizing agent includes the following steps:

[0120] The polyarylether ketone and / or the inorganic salt nanoparticles are dissolved in the organic solvent and mixed evenly to obtain a solution of the sizing agent for carbon fibers.

[0121] In the above-mentioned method for preparing carbon fiber reinforced naphthalene biphenyl polyarylene resin-based composite materials, the vacuum hot pressing temperature is 320-400℃ (e.g., 320℃, 360℃, or 400℃), the pressure is 3-20MPa (e.g., 3MPa, 6MPa, 10MPa, 15MPa, or 20MPa), and the time is 3-60 minutes (e.g., 3 minutes, 10 minutes, 20 minutes, 40 minutes, or 60 minutes).

[0122] Fourthly, the present invention provides an application of the carbon fiber reinforced heteronaphthyl biphenyl polyarylene ether resin-based composite material as described in the second aspect or the carbon fiber reinforced heteronaphthyl biphenyl polyarylene ether resin-based composite material prepared by the preparation method described in the third aspect in the field of medical devices, specifically as a raw material for medical devices such as bone plates, fracture external fixation brackets, and spinal fixators.

[0123] The present invention will now be described in further detail with reference to specific embodiments and comparative examples.

[0124] In the following embodiments and comparative examples:

[0125] The preparation method of PPEK (naphthyl biphenyl polyarylene ether ketone) used below is the same as that in 'Wang Mingjing. Study on novel polyarylene ether nitrile containing diazonyl biphenyl structure [D]. Dalian: Dalian University of Technology, 2007'; the preparation method of PPESK (naphthyl biphenyl polyarylene ether sulfone ketone) used below is the same as that in 'Xiao Lihong. Synthesis and properties of multi-component copolymer arylene ethers containing heteronaphthyl biphenyl structure [D]. Dalian: Dalian University of Technology, 2008'; DHPZ was purchased from Dalian Poly New Materials Co., Ltd.

[0126] The structural formula of polyarylether ketone (PPEK) is as follows:

[0127]

[0128] The structural formula of poly(arylene ether sulfone ketone) (PPESK) is as follows:

[0129]

[0130] Example 1

[0131] The carbon fiber sizing agent provided in this embodiment is a polyarylether ketone containing carboxylic acid groups. The solution of the carbon fiber sizing agent provided in this embodiment includes polyarylether ketone containing carboxylic acid groups and NMP (N-methylpyrrolidone), wherein the mass ratio of polyarylether ketone containing carboxylic acid groups to NMP is 0.5:99.5.

[0132] The method for preparing the sizing agent solution for carbon fiber provided in this embodiment includes the following steps:

[0133] Dissolve polyaryletherketone containing carboxylic acid groups in NMP, mix thoroughly and dissolve completely to obtain a 0.5 wt% PAEK-COOH (polyaryletherketone containing carboxylic acid groups) polymer solution (a sizing agent solution for carbon fiber).

[0134] The specific structural formula of the polyarylether ketone containing a carboxylic acid group described in this embodiment is as follows:

[0135]

[0136] A polyarylene ether ketone (PAEK-COOH) containing carboxylic acid groups was synthesized by solution polycondensation. The preparation method of the polyarylene ether ketone containing carboxylic acid groups described in this embodiment specifically includes the following steps:

[0137]

[0138] Monomers PPL (0.320 g), DHPZ (4.522 g), and DFK (4.360 g) were added to an NMP (8 ml) solution containing K2CO3 (4.022 g). The mixture was refluxed at 130 °C for 3 h using toluene as a dehydrating agent to remove H2O. The reaction solution was then heated to 160 °C to remove toluene. The reaction system was then slowly heated to 180 °C to proceed with the reaction. A typical nucleophilic substitution reaction was carried out at 180 °C to synthesize carboxylated polyaryletherketone (PAEK-COOH). As the viscosity of the reaction solution increased, NMP was added to reduce the viscosity. When the viscosity of the reaction solution no longer increased, the temperature was lowered to approximately 130 °C to stop the reaction. The reaction solution was poured into a diluted hydrochloric acid solution (10% by mass) to remove solvent and inorganic salts, and to convert the -COOK group to -COOH, yielding a precipitated fibrous polymer. The precipitated fibrous polymer was pulverized and washed successively with deionized water and ethanol. Finally, it was vacuum dried at 120°C to obtain PAEK-COOH (a polyarylether ketone containing a carboxylic acid group).

[0139] Infrared characterization of PAEK-COOH, such as Figure 1 As shown, the chemical structure of the PAEK-COOH polymer was characterized and analyzed by FTIR (Fourier Transform Infrared Spectroscopy). Figure 1 As shown in the image. The spectrum shows that the carbonyl (-C=O) stretching vibration of the carboxyl group appears at 1716 cm⁻¹. -1 The absorption peak of the active H in the carboxyl group appears at 3370 cm⁻¹. -1 Around 1666 cm⁻¹. Under the influence of the benzene ring, the tensile vibration absorption peak of C=O in the DHPZ structure appears at 1666 cm⁻¹. -1 FTIR results indicate that carboxyl groups and DHPZ structures have been introduced into the polymer PAEK-COOH.

[0140] Figure 2 This is a flowchart illustrating the preparation method of the carbon fiber reinforced naphthalene-biphenyl polyarylene ether resin-based composite material provided in this embodiment and Comparative Example 1, as shown below. Figure 2 As shown, the preparation method of the carbon fiber reinforced naphthalene-biphenyl polyarylene ether resin-based composite material provided in this embodiment includes the following steps:

[0141] S0. Immerse commercially epoxy resin-sized continuous carbon fiber (CF) in acetone solvent and reflux for 48 hours to remove the epoxy sizing agent layer and obtain desized carbon fiber.

[0142] S1. Sizing treatment of desized carbon fiber using solution method: Immerse the desized carbon fiber in the solution of carbon fiber sizing agent provided in this embodiment, take it out after 5 minutes, and dry it at 240°C for 3 hours to obtain carbon fiber treated with sizing agent.

[0143] S2. Dissolve the matrix resin PPEK in the solvent NMP to obtain a PPEK solution with a concentration of 15wt%.

[0144] S3. Preparation of composite prepreg by solution impregnation method: The carbon fiber treated with sizing agent is immersed in the PPEK solution prepared in step S2. The immersion temperature is 150℃ and the immersion time is 5 minutes to achieve complete impregnation of carbon fiber with PPEK solution. After drying in an oven to remove NMP, the drying temperature is 350℃ and the drying time is 30 minutes. After cooling to room temperature, the prepreg is obtained. The mass ratio of PPEK to carbon fiber treated with sizing agent is 30:70.

[0145] S4. Preparation of composite material (composite material plate) using vacuum hot pressing process: The prepreg is placed in a mold and kept at 350℃ and 7MPa for 20 minutes. After cooling to 100℃, the composite material (composite material plate) is obtained by demolding.

[0146] Example 2

[0147] The carbon fiber sizing agent (composite sizing agent) provided in this embodiment includes polyaryletherketone containing carboxylic acid groups and HAp (hydroxyapatite), and the mass ratio of polyaryletherketone containing carboxylic acid groups to HAp (hydroxyapatite) is 5:2.

[0148] The method for preparing the sizing agent solution for carbon fiber provided in this embodiment includes the following steps:

[0149] The polyaryletherketone containing carboxylic acid groups was dissolved in NMP, mixed evenly and completely dissolved to obtain a 0.5 wt% PAEK-COOH (polyaryletherketone containing carboxylic acid groups) polymer solution. Then, HAp (hydroxyapatite) was added to the PAEK-COOH (polyaryletherketone containing carboxylic acid groups) polymer solution and ultrasonically treated for 15 minutes to obtain a 0.2 wt% (mass fraction of HAp) HAp dispersion, which is the sizing agent solution for carbon fiber.

[0150] The specific structural formula of the polyarylether ketone containing a carboxylic acid group described in this embodiment is as follows:

[0151]

[0152] The preparation method of polyarylether ketone containing carboxylic acid groups described in this embodiment is the same as the preparation method of polyarylether ketone containing carboxylic acid groups in Example 1.

[0153] The preparation method of the carbon fiber reinforced naphthalene-biphenyl polyarylene ether resin-based composite material provided in this embodiment is basically the same as that in Example 1, except that the carbon fiber sizing agent provided in this embodiment is used to sizing the desized carbon fiber. The preparation method includes the following steps:

[0154] S0. Immerse commercially epoxy resin-sized continuous carbon fiber (CF) in acetone solvent and reflux for 48 hours to remove the epoxy sizing agent layer and obtain desized carbon fiber.

[0155] S1. Sizing treatment of desized carbon fiber using solution method: Immerse the desized carbon fiber in the solution of carbon fiber sizing agent provided in this embodiment, take it out after 5 minutes, and dry it at 240°C for 3 hours to obtain carbon fiber treated with sizing agent.

[0156] S2. Dissolve the matrix resin PPEK in the solvent NMP to obtain a PPEK solution with a concentration of 15wt%.

[0157] S3. Preparation of composite prepreg by solution impregnation method: The carbon fiber treated with sizing agent is immersed in the PPEK solution prepared in step S2. The immersion temperature is 150℃ and the immersion time is 5 minutes to achieve complete impregnation of carbon fiber with PPEK solution. After drying in an oven to remove NMP, the drying temperature is 350℃ and the drying time is 30 minutes. After cooling to room temperature, the prepreg is obtained. The mass ratio of PPEK to carbon fiber treated with sizing agent is 30:70.

[0158] S4. Preparation of composite material (composite material plate) using vacuum hot pressing process: The prepreg is placed in a mold and kept at 350℃ and 7MPa for 20 minutes. After cooling to 100℃, the composite material (composite material plate) is obtained by demolding.

[0159] Example 3

[0160] The carbon fiber sizing agent (composite sizing agent) provided in this embodiment includes polyaryletherketone containing carboxylic acid groups and HAp (hydroxyapatite), with a mass ratio of 5:5 between the polyaryletherketone containing carboxylic acid groups and HAp (hydroxyapatite).

[0161] The method for preparing the sizing agent solution for carbon fiber provided in this embodiment includes the following steps:

[0162] The polyaryletherketone containing carboxylic acid groups was dissolved in NMP, mixed evenly and completely dissolved to obtain a 0.5 wt% PAEK-COOH (polyaryletherketone containing carboxylic acid groups) polymer solution. Then, HAp (hydroxyapatite) was added to the PAEK-COOH (polyaryletherketone containing carboxylic acid groups) polymer solution and ultrasonically treated for 15 minutes to obtain a 0.5 wt% (mass fraction of HAp) HAp dispersion, which is the sizing agent solution for carbon fiber.

[0163] The specific structural formula of the polyarylether ketone containing a carboxylic acid group described in this embodiment is as follows:

[0164]

[0165] The preparation method of polyarylether ketone containing carboxylic acid groups described in this embodiment is the same as the preparation method of polyarylether ketone in Example 1.

[0166] The preparation method of the carbon fiber reinforced naphthalene-biphenyl polyarylene ether resin-based composite material provided in this embodiment is basically the same as that in Example 1, except that the carbon fiber sizing agent provided in this embodiment is used to sizing the desized carbon fiber. The preparation method includes the following steps:

[0167] S0. Immerse commercially epoxy resin-sized continuous carbon fiber (CF) in acetone solvent and reflux for 48 hours to remove the epoxy sizing agent layer and obtain desized carbon fiber.

[0168] S1. Sizing treatment of desized carbon fiber using solution method: Immerse the desized carbon fiber in the solution of carbon fiber sizing agent provided in this embodiment, take it out after 5 minutes, and dry it at 240°C for 3 hours to obtain carbon fiber treated with sizing agent.

[0169] S2. Dissolve the matrix resin PPEK in the solvent NMP to obtain a PPEK solution with a concentration of 15wt%.

[0170] S3. Preparation of composite prepreg by solution impregnation method: The carbon fiber treated with sizing agent is immersed in the PPEK solution prepared in step S2. The immersion temperature is 150℃ and the immersion time is 5 minutes to achieve complete impregnation of carbon fiber with PPEK solution. After drying in an oven to remove NMP, the drying temperature is 350℃ and the drying time is 30 minutes. After cooling to room temperature, the prepreg is obtained. The mass ratio of PPEK to carbon fiber treated with sizing agent is 30:70.

[0171] S4. Preparation of composite material (composite material plate) using vacuum hot pressing process: The prepreg is placed in a mold and kept at 350℃ and 7MPa for 20 minutes. After cooling to 100℃, the composite material (composite material plate) is obtained by demolding.

[0172] Example 4

[0173] The carbon fiber sizing agent (composite sizing agent) provided in this embodiment includes polyaryletherketone containing carboxylic acid groups and HAp (hydroxyapatite), with a mass ratio of 5:8 between the polyaryletherketone containing carboxylic acid groups and HAp (hydroxyapatite).

[0174] The method for preparing the sizing agent solution for carbon fiber provided in this embodiment includes the following steps:

[0175] The polyaryletherketone containing carboxylic acid groups was dissolved in NMP, mixed evenly and completely dissolved to obtain a 0.5 wt% PAEK-COOH (polyaryletherketone containing carboxylic acid groups) polymer solution. Then, HAp (hydroxyapatite) was added to the PAEK-COOH (polyaryletherketone) polymer solution and ultrasonically treated for 15 minutes to obtain a 0.8 wt% (mass fraction of HAp) HAp dispersion, which is the sizing agent solution for carbon fiber.

[0176] The specific structural formula of the polyarylether ketone containing a carboxylic acid group described in this embodiment is as follows:

[0177]

[0178] The preparation method of polyarylether ketone containing carboxylic acid groups described in this embodiment is the same as the preparation method of polyarylether ketone containing carboxylic acid groups in Example 1.

[0179] The preparation method of the carbon fiber reinforced naphthalene-biphenyl polyarylene ether resin-based composite material provided in this embodiment is basically the same as that in Example 1, except that the carbon fiber sizing agent provided in this embodiment is used to sizing the desized carbon fiber. The preparation method includes the following steps:

[0180] S0. Immerse commercially epoxy resin-sized continuous carbon fiber (CF) in acetone solvent and reflux for 48 hours to remove the epoxy sizing agent layer and obtain desized carbon fiber.

[0181] S1. Sizing treatment of desized carbon fiber using solution method: Immerse the desized carbon fiber in the solution of carbon fiber sizing agent provided in this embodiment, take it out after 5 minutes, and dry it at 240°C for 3 hours to obtain carbon fiber treated with sizing agent.

[0182] S2. Dissolve the matrix resin PPEK in the solvent NMP to obtain a PPEK solution with a concentration of 15wt%.

[0183] S3. Preparation of composite prepreg by solution impregnation method: The carbon fiber treated with sizing agent is immersed in the PPEK solution prepared in step S2. The immersion temperature is 150℃ and the immersion time is 5 minutes to achieve complete impregnation of carbon fiber with PPEK solution. After drying in an oven to remove NMP, the drying temperature is 350℃ and the drying time is 30 minutes. After cooling to room temperature, the prepreg is obtained. The mass ratio of PPEK to carbon fiber treated with sizing agent is 30:70.

[0184] S4. Preparation of composite material (composite material plate) using vacuum hot pressing process: The prepreg is placed in a mold and kept at 350℃ and 7MPa for 20 minutes. After cooling to 100℃, the composite material (composite material plate) is obtained by demolding.

[0185] Example 5

[0186] The method for preparing carbon fiber reinforced naphthalene-biphenyl polyarylene ether resin-based composite material provided in this embodiment includes the following steps:

[0187] S0. Immerse commercially epoxy resin-sized continuous carbon fiber (CF) in acetone solvent and reflux for 48 hours to remove the epoxy sizing agent layer and obtain desized carbon fiber.

[0188] S1. Sizing treatment of desized carbon fiber using solution method: Immerse the desized carbon fiber in the solution of carbon fiber sizing agent provided in Example 1, take it out after 5 minutes, and dry it at 240°C for 3 hours to obtain carbon fiber treated with sizing agent.

[0189] S2. Dissolve the matrix resin, naphthalene-biphenyl polyarylether sulfone ketone (PPESK), in the solvent NMP to obtain a PPESK solution with a concentration of 15 wt%.

[0190] S3. Preparation of composite prepreg by solution impregnation method: The carbon fiber treated with sizing agent is immersed in the PPESK solution prepared in step S2. The immersion temperature is 150℃ and the immersion time is 5 minutes to achieve complete impregnation of carbon fiber by PPESK solution. After that, it is dried in an oven to remove NMP. The drying temperature is 350℃ and the drying time is 30 minutes. After cooling to room temperature, the prepreg is obtained. The mass ratio of PPESK to carbon fiber treated with sizing agent is 30:70.

[0191] S4. Preparation of composite material (composite material plate) using vacuum hot pressing process: The prepreg is placed in a mold and kept at 350℃ and 7MPa for 20 minutes. After cooling to 100℃, the composite material (composite material plate) is obtained by demolding.

[0192] Example 6

[0193] The preparation method of the carbon fiber sizing agent solution provided in this embodiment is basically the same as that in Example 2, except that the concentration of the PAEK-COOH (polyaryletherketone containing carboxylic acid groups) polymer solution is 3wt%, and the mass fraction of HAP in the HAp dispersion is 1.2wt%.

[0194] The specific structural formula of the polyarylether ketone containing a carboxylic acid group described in this embodiment is as follows:

[0195]

[0196] The preparation method of polyarylether ketone containing carboxylic acid groups described in this embodiment is the same as the preparation method of polyarylether ketone in Example 1.

[0197] The preparation method of the carbon fiber reinforced naphthalene biphenyl polyarylene ether resin-based composite material provided in this embodiment is basically the same as that in Example 1, except that the desized carbon fiber is immersed in the solution of the carbon fiber sizing agent provided in this embodiment.

[0198] Example 7

[0199] The carbon fiber sizing agent provided in this embodiment is a polyarylether ketone containing carboxylic acid groups. The solution of the carbon fiber sizing agent provided in this embodiment includes polyarylether ketone containing carboxylic acid groups and NMP (N-methylpyrrolidone), wherein the mass ratio of polyarylether ketone containing carboxylic acid groups to NMP is 0.5:99.5.

[0200] The preparation method of the carbon fiber sizing agent solution provided in this embodiment is the same as that in Example 1.

[0201] The specific structural formula of the polyarylether ketone containing a carboxylic acid group described in this embodiment is as follows:

[0202]

[0203] The preparation method of polyarylether ketone containing carboxylic acid groups described in this embodiment is basically the same as that in Example 1, except that “DFK (4.360g)” is replaced with “4,4'-dichlorodiphenyl sulfone (DCS, 5.738g)”.

[0204] The preparation method of the carbon fiber reinforced naphthalene biphenyl polyarylene ether resin-based composite material provided in this embodiment is basically the same as that in Example 1, except that the desized carbon fiber is immersed in the solution of the carbon fiber sizing agent provided in this embodiment.

[0205] Example 8

[0206] The carbon fiber sizing agent provided in this embodiment is a polyarylether ketone containing carboxylic acid groups. The solution of the carbon fiber sizing agent provided in this embodiment includes polyarylether ketone containing carboxylic acid groups and NMP (N-methylpyrrolidone), wherein the mass ratio of polyarylether ketone containing carboxylic acid groups to NMP is 0.5:99.5.

[0207] The preparation method of the carbon fiber sizing agent solution provided in this embodiment is the same as that in Example 1.

[0208] The specific structural formula of the polyarylether ketone containing a carboxylic acid group described in this embodiment is as follows:

[0209]

[0210] The preparation method of polyarylether ketone containing carboxylic acid groups described in this embodiment is basically the same as that in Example 1, except that PPL (0.320g) is replaced with PPL (3.200g) and DHPZ (4.522g) is replaced with DHPZ (2.380g).

[0211] The preparation method of the carbon fiber reinforced naphthalene biphenyl polyarylene ether resin-based composite material provided in this embodiment is basically the same as that in Example 1, except that the desized carbon fiber is immersed in the solution of the carbon fiber sizing agent provided in this embodiment.

[0212] Comparative Example 1

[0213] Figure 2 This is a flowchart illustrating the preparation method of the carbon fiber reinforced naphthalene-biphenyl polyarylene ether resin-based composite material provided in this embodiment and Comparative Example 1, as shown below. Figure 2 As shown, the preparation method of the carbon fiber reinforced naphthalene-biphenyl polyarylene ether resin-based composite material provided in this comparative example includes the following steps:

[0214] S0. Immerse commercially epoxy resin-sized continuous carbon fiber (CF) in acetone solvent and reflux for 48 hours to remove the epoxy sizing agent layer and obtain desized carbon fiber.

[0215] S1. Dissolve the matrix resin PPEK in the solvent NMP to obtain a PPEK solution with a concentration of 15wt%.

[0216] S2. Preparation of composite prepreg by solution impregnation method: The desized carbon fiber is immersed in the PPEK solution prepared in step S2 at a temperature of 150°C for 5 minutes to achieve complete impregnation of the carbon fiber by the PPEK solution. Then, it is dried in an oven to remove NMP at a temperature of 350°C for 30 minutes. After cooling to room temperature, the prepreg is obtained. The mass ratio of PPEK to desized carbon fiber is 30:70.

[0217] S4. Preparation of composite material (composite material plate) using vacuum hot pressing process: The prepreg is placed in a mold and kept at 350℃ and 7MPa for 20 minutes. After cooling to 100℃, the composite material (composite material plate) is obtained by demolding.

[0218] Comparative Example 2

[0219] The preparation method of the carbon fiber reinforced heteronaphthyl biphenyl polyarylene ether resin-based composite material provided in this comparative example is basically the same as that in comparative example 1, except that “matrix resin PPEK” is replaced with “matrix resin heteronaphthyl biphenyl polyarylene ether sulfone ketone (PPESK)”.

[0220] Performance testing

[0221] Test Example 1

[0222] The dispersion of HAp in PAEK-COOH was characterized using the carbon fiber sizing agents prepared in Examples 1-4, respectively. In an organic solution with NMP as the solvent, PAEK-COOH interacts with HAp, improving its dispersion. The morphology of HAp in the HAp / PAEK-COOH composite sizing agent was characterized using scanning electron microscopy. Figure 3 The images show scanning electron microscope (SEM) images of the carbon fiber sizing agents prepared in Examples 1-4. The SEM images show that HAp exhibits good dispersibility in the PAEK-COOH sizing agent. The HAp surface Ca... 2+ PO4 3- and OH - The widespread distribution of ions on its surface gives HAp nanoparticles a high ionic surface attraction, thus tending to form large aggregates. In PAEK-COOH solution, the introduction of carboxyl groups in the polymer structure affects the Ca2+ content of HAp nanoparticles. 2+ Ions exhibit strong repulsive forces, forming stable nanoparticles with a HAp nanoparticle core / PAEK-COOH shell structure, thus promoting the dispersion of HAp nanoparticles. With increasing HAp content, when the mass of PAEK-COOH polymer is constant, some particles will aggregate. Therefore, the preferred mass ratio of polyaryletherketone to HAp is (5:2) to (5:8). If this mass ratio is too low, the dispersibility of HAp particles in the sizing agent will be poorer.

[0223] Test Example 2

[0224] The surface chemical composition of the samples, including desized carbon fibers and carbon fibers (CF) treated with sizing agent in Examples 1-4, was analyzed using X-ray photoelectron spectroscopy (XPS).

[0225] XPS spectra of CF after sizing agent treatment are as follows Figure 4As shown, all binding energies were set to C1s at 285 eV. The results indicate that the chemical composition of both untreated CF and 0HP@CF (carbon fiber treated with the sizing agent provided in Example 1) consists of C, O, and N, with no other elements detected. The N content in polymer-treated CF (0HP@CF) increases significantly, due to the enhanced N=C peak of the DHPZ structure of PAEK-COOH. The spectra of 2HP@CF (carbon fiber treated with the sizing agent provided in Example 2), 5HP@CF (carbon fiber treated with the sizing agent provided in Example 3), and 8HP@CF (carbon fiber treated with the sizing agent provided in Example 4) show characteristic peaks for Ca and P near 346 eV and 130 eV, respectively, and the contents of Ca and P in the material increase with increasing HAp concentration. Table 1 shows that the Ca / C and P / C values ​​gradually increase with the introduction of HAp.

[0226] Table 1. Elemental content of carbon fiber surface

[0227]

[0228] Test Example 3

[0229] The surface morphology of desized carbon fibers and CF treated with the sizing agents in Examples 1-4 were studied using scanning electron microscopy and atomic force microscopy, respectively. Figure 5 As shown, the surface morphology of carbon fibers modified with the HAp / PAEK-COOH composite sizing agent was studied by scanning electron microscopy. For desized carbon fibers, numerous narrow and shallow longitudinal grooves were observed on the surface, resulting from the wet spinning process. The inert surface of the desized carbon fibers makes it difficult to form chemical bonds with the matrix resin, leading to poor interfacial interaction with PPEK. For PPL@CF (carbon fibers treated with the sizing agent provided in Example 1), after modification with the PAEK-COOH sizing agent, a thin layer of PAEK-COOH was applied to the CF surface, and the grooves disappeared. The sizing agent is considered a bridging agent connecting the CF and PPEK interfacial phases, increasing the interfacial adhesion between CF and PPEK. For 2HP@CF (carbon fibers treated with the sizing agent provided in Example 2), 5HP@CF (carbon fibers treated with the sizing agent provided in Example 3), and 8HP@CF (carbon fibers treated with the sizing agent provided in Example 4), the CF surface was covered with a layer of HAp / PAEK-COOH composite sizing agent, and obvious particles were observed on the CF surface, with the particle size increasing with increasing concentration. Improving the surface roughness of carbon fibers helps to improve the interfacial properties of CF / PPEK composites.

[0230] To further analyze the effect of the sizing agent on the CF surface, the detailed morphology of the CF surface modified with the HAp / PAEK-COOH composite sizing agent was observed using atomic force microscopy (AFM). In the AFM images of the desized CF, the surface grooves were very obvious. The surface roughness of the carbon fiber treated with the composite sizing agent increased with increasing HAp concentration. Significant changes occurred in the CF surface after sizing. Simultaneously, the surface roughness of the modified CF also improved to some extent.

[0231] Test Example 4

[0232] The mechanical properties of carbon fiber reinforced heteronaphthalene biphenyl polyarylene ether resin-based composites prepared in Comparative Examples 1, 2, and 1-8 were investigated. Interlaminar shear strength was determined using the short beam shear method (SBS) specified in ISO 14130. The flexural properties of the composites were tested using the three-point loading method according to ASTM D790. Scanning electron microscopy was used to observe the flexural properties and fracture surface morphology of the CF / PPEK composites prepared in Comparative Examples 1 and 1-4 after ILSS (interlaminar shear strength) testing to evaluate the interfacial adhesion between CF and PPEK. The interlaminar shear strength and flexural property data are shown in Table 2.

[0233] Table 2

[0234]

[0235]

[0236] Compared to the ILSS (47.7 MPa) of the desizing CF / PPEK composite (Comparative Example 1), PPL@CF / PPEK (Example 1) increased to 54.67 MPa, an increase of 18.8%. This is due to the introduction of PAEK-COOH as a sizing agent layer to improve the interfacial bonding between the CF and PPEK matrices. The value of 5HP@CF / PPEK (Example 3) increased to 67.2 MPa, an increase of 41.0%, indicating improved interfacial adhesion between the CF and PPEK matrices. This can be attributed to the prominent "bridging" effect produced by chain segments, physical bonding, and chemical interactions between the sizing agent and the PPEK matrix. However, with increasing HAp concentration, some particles agglomerated, which reduced the value of 8HP@CF / PPEK (Example 4).

[0237] The flexural strength and flexural modulus of the 5HP@CF / PPEK (Example 3) composite material were 1832 MPa and 181 GPa, respectively. Compared with the desizing CF / PPEK composite material, the flexural strength and flexural modulus were significantly increased by 39% and 46.6%, respectively.

[0238] Figure 6The images show scanning electron microscope (SEM) images of the cross-sectional surfaces of the CF / PPEK composite materials prepared in Comparative Examples 1 and Examples 1-4 after interlaminar shear and bending tests. The interfacial adhesion between CF and PPEK was evaluated by observing the fracture morphology after bending performance and ILSS testing. For the desizing CF / PPEK composite material, the exposed fiber surface was smooth and covered with a small amount of resin. The introduction of the composite sizing agent enhanced the interaction between the fiber and the matrix, resulting in a tighter bond between CF and PPEK. This is because the presence of HAp particles both hinders the transmission of dispersed stress through crack propagation paths and assumes a stress absorption role.

[0239] Test Example 5

[0240] The viability of MC3T3-E1 cells co-cultured with the extracts of the composite material samples from Comparative Examples 1, 2, and 1-8 was determined using the MTT assay. The samples were autoclaved in MEM / EBSS culture medium, and the surface area of ​​the sample to the volume of the culture medium was 1 cm² during extraction. 2 / mL. The extract was aseptically diluted with fresh culture medium. Cells were cultured in the diluted extract for 3 days. The viability of MC3T3-E1 cells cultured from the sample extracts was determined by the MTT assay, and the specific results are shown in Table 3. The cell viability of all samples was greater than 80%, indicating that the samples have good cell compatibility and potential for application in the medical device field.

[0241] Table 3

[0242]

[0243]

[0244] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, and not to limit them; although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some or all of the technical features; and these modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present invention.

Claims

1. A sizing agent for carbon fibers, characterized by, The sizing agent for carbon fibers comprises a polyaryletherketone, and the polyaryletherketone comprises a phthalazinone biphenyl structure and a carboxyl group in its structural formula; The structural formula of the polyaryletherketone is shown in Formula I: In the formula, m and n are integers greater than 1, Ar1 and Ar2 are main structures of dihalogen monomers, Ar1 and Ar2 are the same or different, and each independently represents one of the following structural formulas: The sizing agent for carbon fibers further comprises inorganic salt nanoparticles, the inorganic salt nanoparticles are hydroxyapatite nanoparticles, and the mass ratio of the polyaryletherketone to the inorganic salt nanoparticles is (5:2) to (5:8).

2. The sizing agent for carbon fibers according to claim 1, characterized by The preparation method of the polyaryletherketone comprises the following steps: The monomer A, the monomer B, the dihalogen monomer, the catalyst and the water-carrying agent are added to a reaction solvent, water is carried by the water-carrying agent under heating, then the water-carrying agent is removed, and the reaction is carried out by heating, the solvent is gradually added dropwise as the viscosity of the reaction solution increases, the reaction is stopped when the viscosity of the reaction solution no longer increases, the reaction solution is poured into a dilute acid solution to terminate the reaction, and the polyaryletherketone is obtained after post-treatment, wherein the monomer A comprises a carboxyl group and is one of phenothalin and 4-carboxyl phenyl hydroquinone, and the monomer B comprises a phthalazinone biphenyl structure and is 4-(4-hydroxyphenyl)-2,3-phthalazin-1-one.

3. The sizing agent for carbon fibers according to claim 2, characterized by The catalyst comprises potassium carbonate; The water-carrying agent comprises toluene; The reaction solvent comprises NMP; The mole number of the monomer A accounts for 2% to 60% of the total mole number of the monomer A and the monomer B; The total mole number of the monomer A and the monomer B to the total mole number of the dihalogen monomer is 1:(0.8-1.5); The water-carrying temperature is 130-150℃, and the time is 2-5h; The reaction temperature is 170-190℃; The post-treatment comprises crushing the obtained solid polymer, washing with water and ethanol, and finally drying.

4. A carbon fiber reinforced heteronaphtho- biphenyl poly(arylene ether) resin matrix composite, characterized by, The carbon fiber reinforced phthalazinone biphenyl polyarylether resin composite material comprises the following raw materials: carbon fibers and phthalazinone biphenyl polyarylether resin, wherein the carbon fibers comprise carbon fibers treated by the sizing agent for carbon fibers according to any one of claims 1-3.

5. The carbon fiber reinforced hetero-naphthalene diphenyl poly(arylene ether) resin based composite of claim 4, wherein, The carbon fibers comprise continuous carbon fibers; The composite material comprises the following raw materials in terms of weight percentage: 10-70% of the phthalazinone biphenyl polyarylether resin and 30-90% of the continuous carbon fibers; The structural formula of the phthalazinone biphenyl polyarylether resin is shown in Formula II: In the formula, Ar1 and Ar3 are main structures of dihalogen monomers, Ar1 and Ar3 are the same or different, and each independently represents one of the following structural formulas: Ar2 is a main structure of bisphenol monomers and represents one of the following structural formulas: R1, R2, R3 and R4 each independently represents hydrogen, a halogen substituent, a phenyl group, a phenoxy group, a straight-chain alkyl group containing at least one carbon atom, a branched alkyl group containing at least one carbon atom or a branched alkoxy group containing at least one carbon atom, and the structures of R1, R2, R3 and R4 are the same or different.

6. The carbon fiber reinforced heterophthalic diphenyl poly(arylene ether) resin based composite of claim 5, wherein, The heteronaphthalene-biphenyl polyarylether resin is selected from at least one of the following heteronaphthalene-biphenyl polyarylether resins: Heteronaphthalene-biphenyl polyarylether ketone: Heteronaphthalene-biphenyl polyarylether sulfone ketone:

7. A process for the production of a carbon fiber reinforced hetero-naphthalene diphenyl poly(arylene ether) resin based composite material as claimed in any one of claims 4 to 6, characterized in that, The preparation method comprises the following steps: S1, immersing carbon fibers into a solution of the sizing agent for carbon fibers according to any one of claims 1-3, and drying to obtain the carbon fibers treated with the sizing agent for carbon fibers; S2, dissolving the heteronaphthalene-biphenyl polyarylether resin in a solvent to obtain a resin solution; S3, immersing the carbon fibers treated with the sizing agent for carbon fibers obtained in step S1 in the resin solution obtained in step S2, and after the surface of the carbon fibers is completely immersed in the resin solution, heating and drying to remove the solvent, and cooling to obtain a prepreg; S4, placing the prepreg obtained in step S3 into a mold, and preparing the composite material by a vacuum hot pressing process.

8. The preparation method of the carbon fiber reinforced heteronaphthalene-biphenyl polyarylether resin-based composite material according to claim 7, characterized in that: In step S1, the time for immersing the carbon fibers into the solution of the sizing agent for carbon fibers is 1-30 min; And / or, the solvent comprises at least one of NMP, N,N-dimethylformamide, and N,N-dimethylacetamide; And / or, the mass percentage of the resin in the resin solution is 1%-30%; And / or, the solution of the sizing agent for carbon fibers comprises an organic solvent, and the organic solvent comprises at least one of NMP, chloroform, DMAc, and DMF; And / or, the weight percentage of the polyarylether ketone in the solution of the sizing agent for carbon fibers is 0.1%-5%, based on 100% of the total weight of the solution of the sizing agent for carbon fibers; And / or, the weight percentage of the inorganic salt nanoparticles in the solution of the sizing agent for carbon fibers is 0.01%-5%, based on 100% of the total weight of the solution of the sizing agent for carbon fibers; And / or, the preparation method of the solution of the sizing agent for carbon fibers comprises the following steps: dissolving the polyarylether ketone and the inorganic salt nanoparticles in an organic solvent, and mixing uniformly to obtain the solution of the sizing agent for carbon fibers; And / or, the temperature of the vacuum hot pressing is 320-400°C, the pressure is 3-20 MPa, and the time is 3-60 min.

9. The use of the carbon fiber reinforced heteronaphthalene-biphenyl polyarylether resin-based composite material according to any one of claims 4-6, or the carbon fiber reinforced heteronaphthalene-biphenyl polyarylether resin-based composite material prepared by the preparation method according to claim 7 or 8, in the field of medical devices, and specifically as a raw material for bone plates, external fixation supports for bone fractures, and spinal fixation devices.

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