A carbon fiber material with biological activity, a preparation method thereof, and a composite material and application thereof

Abstract

The present application belongs to the technical field of polyether ether ketone composite materials, and provides a carbon fiber material with biological activity, a preparation method and a composite material and application thereof.The present application first uses a sizing method combined with a biomimetic method to prepare a carbon fiber reinforced polyether ether ketone composite material, first coats a uniform water-based carboxyl-containing sizing agent layer on a carbon fiber cloth, then immerses the carbon fiber cloth in a simulated body fluid as an organic template of hydroxyapatite, grows a hydroxyapatite bioactive coating layer by using the biomimetic method, and then uses a molding method to prepare the carbon fiber reinforced polyether ether ketone composite material.The method of the present application not only improves the interface performance of the carbon fiber reinforced polyether ether ketone composite material and improves the mechanical strength of the carbon fiber reinforced polyether ether ketone composite material, but also simultaneously endows the carbon fiber reinforced polyether ether ketone composite material with good biological activity and biocompatibility.

Description

Technical Field

[0001] This invention relates to the field of polyetheretherketone composite materials, and more particularly to a bioactive carbon fiber material, its preparation method, composite material, and its applications. Background Technology

[0002] Currently, the osseointegration and orthopedic implant industry is constantly seeking technological innovation, hoping to provide patients with maximum convenience and comfort. The implementation of new technologies requires novel materials as support. In recent years, polymers have shown the greatest promise for application in osseointegration and orthopedic implants. However, the performance of most polymers currently on the market is far from sufficient to withstand the physiological loads within the human body, meaning they cannot be used as load-bearing materials in the body for extended periods. Researchers have turned their attention to composite materials, among which carbon fiber reinforced polyaryletherketone composites stand out from numerous candidate materials due to their excellent wear resistance, corrosion resistance, and good X-ray transmittance, making them the most promising leading material in new orthopedic integration materials. Carbon fiber itself possesses characteristics such as light weight, high strength, and good durability. Most importantly, carbon fiber can remain in the human body for several years without triggering any immune response. However, due to the smooth graphite structure and highly stable non-polar structure of carbon fiber, it cannot be well bonded with polyaryletherketone (PAEK) resin matrices to prepare carbon fiber / PAEK composites. On the other hand, numerous biological experiments, such as in vivo quantitative histology and in vitro cell culture experiments, have demonstrated that PAEK resin matrices possess good biocompatibility. However, in the presence of saline solution, only PAEK resins are unaffected by the ionic effects of the saline solution, meaning that their smoothness, wear resistance, rigidity, mechanical strength, and elastic modulus are almost undamaged. Crucially, their swelling rate in saline solution is very low, which establishes PAEK resin's highly sought-after position in the current field of orthopedic repair and implant materials. However, using PAEK alone as a carrier does not yet provide sufficient mechanical strength to meet the requirements for stable bone growth in the human body. In conclusion, there is an urgent need to improve the inert surface of carbon fiber and develop a carbon fiber-reinforced PAEK biocomposite material with mechanical properties adapted to the growth environment required by human bones. Furthermore, it should possess certain bioactivity to ensure its application in the human body without rejection. The key to solving the aforementioned problems in osseointegration and orthopedic implant materials lies in finding a perfect combination of these two.

[0003] To address the issue of poor bonding between inert carbon fiber and polyetheretherketone (PEEK) resin matrix, researchers have conducted extensive studies. Currently, the most effective method is surface modification of the carbon fiber, including chemical modification, electrophoretic deposition-electropolymerization, vacuum phosphating, plasma treatment, sizing, and biomineralization. For example, Zou Huwei et al. (patent number CN 112323482 B) combined electrophoretic deposition and electropolymerization. First, graphene oxide was electrophoretically deposited onto the carbon fiber surface, then electropolymerized in situ to generate a polymer. Following a series of washing and drying processes, a modified carbon fiber composite material was obtained. A series of related tests demonstrated that the modified carbon fiber surface had an increased number of active functional groups, resulting in stronger wettability with the resin matrix and improved mechanical properties of the composite material. However, this technique requires the preparation of large quantities of electrophoretic solution and more sophisticated equipment, leading to a significant increase in preparation costs. Furthermore, the high energy consumption during the preparation process limits its large-scale application. Yang Hongbin et al. (Patent No. CN 111304909 B) used vacuum phosphating to modify unsized carbon fibers, significantly improving the surface wettability and electrochemical activity of the modified carbon fibers, laying the foundation for subsequent preparation of carbon fiber composites. However, because the preparation process involves adding untreated carbon fibers and a phosphorus source into a sealed vacuum container and subjecting them to heat treatment at 700–900°C for 1–2 hours, the requirements for operating equipment and personnel are too high, making it unsuitable for large-scale industrial production. Jiang Jianjun et al. (Patent No. CN 106283601 A) used plasma spraying technology to spray nano-graphene sol onto the surface of carbon fibers, thereby preparing high-performance carbon fiber composites. Although this method alters the inert chemical environment of the carbon fiber surface, its target audience is limited, the technical requirements for operators are high, and the equipment storage conditions are also quite demanding, thus preventing it from standing out in the market. Ao Yuhui et al. (Patent No. CN 113563577 A) prepared carbon fiber composites by modifying carbon fibers using a sizing method. Test results showed that this modification method effectively improved the hydrophilicity of the carbon fiber surface and significantly increased the mechanical strength of the carbon fiber composites without damaging the fiber's intrinsic strength. The preparation cost is low, and the equipment requirements and operator skill requirements are minimal, making it suitable for industrial production. However, a drawback is that while this method greatly improves the mechanical strength of the composites and meets the needs of industrial production, it does not impart sufficient bioactivity to the carbon fiber / polyetheretherketone composites, thus hindering their application in the medical industry.Qiao Fei et al. (Patent No. CN 100494275 C) used a biomimetic mineralization method to grow a hydroxyapatite coating on the surface of carbon fibers to reinforce polylactic acid materials. This method, by preparing a bioactive hydroxyapatite coating, endows the composite material with biocompatibility and bioactivity. However, it also has drawbacks. This method uses a polymer as an organic template to prepare hydroxyapatite, which may lead to rejection reactions when applied to the human body. Furthermore, it requires a four-week mineralization time to grow hydroxyapatite, resulting in a long preparation time and significantly increasing time costs. In addition, the mechanical properties of the prepared composite material do not adequately meet the strength requirements of orthopedic implants. Although some relatively mature modification treatments on the market can effectively improve the chemical environment of carbon fiber surfaces and meet the performance requirements of corresponding carbon fiber composites in different fields, they each have their shortcomings and cannot achieve the goal of large-scale application in the fields of osseointegration and orthopedic implants.

[0004] Therefore, developing a carbon fiber reinforced polyetheretherketone composite material that simultaneously possesses good interfacial bonding, bioactivity, and biocompatibility, is non-toxic and harmless, and is easy to industrially produce, so as to maximize its role in the osseointegration and orthopedic implant industry and expand production as soon as possible, is of great significance for benefiting patients. Summary of the Invention

[0005] The purpose of this invention is to overcome the shortcomings of existing technologies by providing a bioactive carbon fiber material, its preparation method, composite material, and its applications. The composite material of this invention overcomes the problem in existing carbon fiber / polyetheretherketone (PEEK) composite materials that cannot simultaneously achieve good mechanical properties and bioactivity; at the same time, it further reduces preparation costs and simplifies process operation, broadening the application range of carbon fiber / PEEK composite materials and enabling their large-scale application in various industries, especially in the osseointegration and orthopedic implant industries.

[0006] To achieve the above-mentioned objectives, the present invention provides the following technical solution:

[0007] This invention provides a method for preparing a bioactive carbon fiber material, comprising the following steps:

[0008] 1) Under an inert atmosphere, the first monomer and the carboxyl-containing bisphenol monomer are subjected to water separation reaction and condensation reaction in sequence, and then boiled in water to obtain the main sizing agent.

[0009] The first monomer is a fluorinated ketone monomer or an ether nitrile monomer;

[0010] 2) Mix the emulsifier, cosolvent, and sizing agent main sizing material, and add water dropwise to the mixture until the two phases are transformed to obtain an aqueous carbon fiber sizing agent;

[0011] 3) The desized carbon fiber is sized with an aqueous carbon fiber sizing agent and then dried to obtain a carbon fiber material containing an aqueous carboxyl sizing agent.

[0012] 4) Carbon fiber materials containing water-based carboxyl sizing agents are sequentially impregnated in soluble phosphate solution, calcium compound solution, and simulated body fluid containing surfactant to obtain bioactive carbon fiber materials.

[0013] Preferably, in step 1), the molar ratio of the first monomer to the carboxyl-containing bisphenol monomer is 0.9–1.1:0.9–1.1;

[0014] Step 1) The carboxyl-containing bisphenol monomer is one or more of 4-carboxyphenylhydroquinone, 4-carboxyphenylbiphenyl, 4-carboxyphenylresorcinol, 4,4-bis(4-hydroxyphenyl)valeric acid and phenolphthalein; the fluorinated ketone monomer is 4,4-difluorobenzophenone; and the ether nitrile monomer is 2,6-dichlorobenzonitrile.

[0015] Preferably, the temperature of the water separation reaction in step 1) is 120-140°C and the time of the water separation reaction is 1.5-6 hours; the temperature of the polycondensation reaction is 180-220°C and the time of the polycondensation reaction is 6-30 hours.

[0016] The drying temperature in step 3) is 100-200℃, and the drying time is 30-60 minutes.

[0017] Preferably, the emulsifier in step 2) is dodecyltrimethylammonium bromide, tetradecyltrimethylammonium bromide, octadecyltrimethylammonium bromide, hexadecyltrimethylammonium bromide, or bis(dodecyldimethylammonium bromide); the cosolvent is dichloromethane or chloroform.

[0018] The mass ratio of emulsifier, co-solvent, and sizing agent in the main slurry is 0.4–0.6:0.8–1.2:100.

[0019] Preferably, in step 4), the mass concentration of soluble phosphate in the soluble phosphate solution is 25-90%, the mass concentration of calcium compound in the calcium compound solution is 25-80%, and the mass fraction of surfactant in the simulated body fluid containing surfactant is 2-25%.

[0020] The soluble phosphate is one or more of sodium dihydrogen phosphate, dipotassium hydrogen phosphate, and ammonium phosphate; the calcium-containing compound is one or more of calcium chloride, calcium lignosulfonate, and calcium salicylate; and the surfactant is a cationic surfactant, a nonionic surfactant, or an amphoteric surfactant.

[0021] Preferably, in step 4), the temperatures of the soluble phosphate solution, the calcium compound solution, and the simulated body fluid containing surfactant are independently 15–90°C; the immersion time in the soluble phosphate solution and the calcium compound solution is independently 5–65 min, and the immersion time in the simulated body fluid containing surfactant is 12–30 min.

[0022] Preferably, the cationic surfactant is a quaternary ammonium salt type cationic surfactant; the nonionic surfactant is a polyol type nonionic surfactant or a polyether type nonionic surfactant; and the amphoteric surfactant is a betaine type amphoteric surfactant or an organic acid sodium type amphoteric surfactant.

[0023] The present invention also provides a bioactive carbon fiber material prepared by the aforementioned preparation method.

[0024] The present invention also provides a carbon fiber reinforced polyether ether ketone composite material, wherein the raw materials for preparing the carbon fiber reinforced polyether ether ketone composite material include bioactive carbon fiber material and polyether ether ketone in a mass ratio of 43-55:40-53.

[0025] The present invention also provides the application of the aforementioned carbon fiber reinforced polyetheretherketone composite material in the medical industry.

[0026] The beneficial effects of this invention include:

[0027] 1) This invention is the first to combine sizing and biomineralization methods, which not only improves the interfacial properties and mechanical strength of carbon fiber reinforced polyetheretherketone (PEEK) composites, but also endows them with good bioactivity and biocompatibility. Compared with commercially available short-cut carbon fiber composites, the composite material prepared by this invention solves the difficulties of uneven sizing agent coating and the inability to grow bioactive coatings. Furthermore, its mechanical strength and other properties are superior, enabling the composite material to be applied not only in defense industries such as aircraft and rockets, but also in civilian chemical industries such as automobiles and hydrogen storage tanks, and in medical fields such as medical devices. This greatly expands the application range of carbon fiber reinforced PEEK composites, striving to achieve the design concept of "multiple uses for one material, making the most of everything."

[0028] 2) This invention overcomes the drawback of poor bonding between carbon fiber and polyetheretherketone matrix by using a sizing method, greatly reducing production and usage costs and making it competitive enough for large-scale application in the existing market. It avoids the defects caused by modification methods such as chemical modification, electrophoretic deposition-electroplation combined modification, vacuum phosphating, and plasma treatment.

[0029] 3) This invention employs a biomineralization method, for the first time directly using a layer of carboxyl-containing aqueous sizing agent coated on carbon fiber cloth as a mineralization organic template. This allows for rapid and induced mineralization growth of a hydroxyapatite (HA) bioactive coating on the fiber surface, eliminating the need for additional polymeric growth sites and minimizing the use of petroleum-based pharmaceuticals. This overcomes the drawback of previous methods using organic polymers as mineralization organic templates for hydroxyapatite, which resulted in degradation due to high-temperature instability. This invention utilizes the sizing agent as a mineralization organic template, preventing decomposition during composite material preparation and significantly improving the overall performance of the composite material. The preparation method of this invention significantly increases the growth rate of the HA bioactive coating, requiring a very short preparation time, thus solving the problem of excessively long growth times for HA bioactive coatings in simulated body fluids. By reducing the growth time of the HA bioactive coating in simulated body fluids to 15 minutes, properties consistent with, or even superior to, commercially available HA bioactive coatings grown for 4 weeks can be obtained. For example, a moss-like morphology and uniformly dispersed HA bioactive mineralization layer can be artificially shaped on carbon fiber cloth, effectively increasing the specific surface area of ​​the HA bioactive mineralization layer. This not only significantly enhances the interfacial bonding force between carbon fiber and hydroxyapatite, and between carbon fiber and polyether ether ketone matrix, thus improving its mechanical properties, but also endows the composite material with good bioactivity and biocompatibility. This further reduces raw material costs and processes, making it a promising candidate for large-scale application in the medical industry to better serve patients.

[0030] 4) In the composite material prepared by this invention, intermolecular forces such as hydrogen bonds and van der Waals forces are generated between the carbon fiber and the polyether ether ketone matrix, resulting in a stronger bond with the polyether ether ketone matrix that is less prone to detachment. Furthermore, hydrogen bonds are also generated between the carbon fiber and hydroxyapatite. This yields a uniform and ordered carbon fiber reinforced polyether ether ketone composite material with excellent mechanical properties, bioactivity, biocompatibility, and osteoinductive properties. This material fully meets the mechanical strength and environmental requirements of the national defense and military industries and the civilian chemical industry, and it can also match the human bone modulus well, thus better meeting the application requirements of modern orthopedic medicine and expanding its application scope.

[0031] 5) The preparation method of the present invention is simple and easy to operate, non-toxic and pollution-free, meets the needs of green chemistry and sustainable development, and can be applied on a large scale in the market, bringing great development prospects for high-end, high-quality thermoplastic carbon fiber composite materials with certain bioactivity and biocompatibility that are lacking in the existing market. Attached Figure Description

[0032] Figure 1 This is a flowchart illustrating the sizing process of desizing carbon fiber using the water-based carbon fiber sizing agent of the present invention.

[0033] Figure 2SEM image of commercial T-300 carbon fiber cloth after slurry removal;

[0034] Figure 3 This is a SEM image of the carbon fiber material with an aqueous carboxyl sizing agent as described in Example 1.

[0035] Figure 4 This is a SEM image of the carbon fiber material with an aqueous carboxyl sizing agent containing an HA bioactive mineralization layer, as described in Example 1.

[0036] Figure 5 This is a morphology diagram of the carbon fiber material with an aqueous carboxyl sizing agent having an HA bioactive mineralization layer, as described in Example 1.

[0037] Figure 6 FTIR images of commercial T-300 carbon fiber cloth (UCF) for desizing, carbon fiber material (SCF) with aqueous carboxyl sizing agent of Example 1, and carbon fiber material (SCF-HA) with aqueous carboxyl sizing agent of Example 1 having HA bioactive mineralization layer.

[0038] Figure 7 XRD patterns of commercial T-300 carbon fiber cloth for desizing, and carbon fiber materials with aqueous carboxyl sizing agents having an HA bioactive mineralization layer in Examples 1 and 2.

[0039] Figure 8 This is an elemental distribution diagram of the carbon fiber material with an aqueous carboxyl sizing agent containing an HA bioactive mineralization layer, as described in Example 1.

[0040] Figure 9 The energy spectrum of the carbon fiber material with an aqueous carboxyl sizing agent having an HA bioactive mineralization layer in Example 2 is shown.

[0041] Figure 10 This is a photograph of the carbon fiber material with an aqueous carboxyl sizing agent containing an HA bioactive mineralization layer, as described in Example 1.

[0042] Figure 11 The images show the unsized carbon fiber reinforced polyether ether ketone composite material of Comparative Example 1 (A) and the human bone cell fluorescence staining image of the carbon fiber reinforced polyether ether ketone composite material of Example 1 (B).

[0043] Figure 12 The figures show the bioactivity and biocompatibility test results of the unsized carbon fiber reinforced polyether ether ketone composite material (UCF / PEEK) of Comparative Example 1 and the carbon fiber reinforced polyether ether ketone composite material (SCF-HA / PEEK) of Example 1. Detailed Implementation

[0044] This invention provides a method for preparing a bioactive carbon fiber material, comprising the following steps:

[0045] 1) Under an inert atmosphere, the first monomer and the carboxyl-containing bisphenol monomer are subjected to water separation reaction and condensation reaction in sequence, and then boiled in water to obtain the main sizing agent.

[0046] The first monomer is a fluorinated ketone monomer or an ether nitrile monomer;

[0047] 2) Mix the emulsifier, cosolvent, and sizing agent main sizing material, and add water dropwise to the mixture until the two phases are transformed to obtain an aqueous carbon fiber sizing agent;

[0048] 3) The desized carbon fiber is sized with an aqueous carbon fiber sizing agent and then dried to obtain a carbon fiber material containing an aqueous carboxyl sizing agent.

[0049] 4) Carbon fiber materials containing water-based carboxyl sizing agents are sequentially impregnated in soluble phosphate solution, calcium compound solution, and simulated body fluid containing surfactant to obtain bioactive carbon fiber materials.

[0050] In this invention, the inert atmosphere in step 1) is preferably a nitrogen atmosphere or an argon atmosphere.

[0051] In this invention, the molar ratio of the first monomer and the carboxyl-containing bisphenol monomer in step 1) is preferably 0.9-1.1:0.9-1.1, and more preferably 1:1;

[0052] Step 1) The carboxyl-containing bisphenol monomer is preferably one or more of 4-carboxyphenylhydroquinone, 4-carboxyphenylbiphenyl, 4-carboxyphenylresorcinol, 4,4-bis(4-hydroxyphenyl)valeric acid and phenolphthalein; the fluorinated ketone monomer is preferably 4,4-difluorobenzophenone; and the ether nitrile monomer is preferably 2,6-dichlorobenzonitrile.

[0053] In this invention, the temperature of the water separation reaction in step 1) is preferably 120-140°C, more preferably 125-135°C, and even more preferably 130°C; the time of the water separation reaction is preferably 1.5-6 hours, more preferably 3-5 hours, and even more preferably 4 hours; the water separation reaction continues until no water flows out; the temperature of the polycondensation reaction is preferably 180-220°C, more preferably 190-210°C, and even more preferably 200°C; the time of the polycondensation reaction is preferably 6-30 hours, more preferably 8-25 hours, and even more preferably 10-20 hours.

[0054] In this invention, the sizing agent main slurry is poured into deionized water for boiling and washing. The boiling and washing temperature is preferably 100℃, and the boiling and washing time is preferably 2 hours. The deionized water is changed 6 times during the boiling and washing process to ensure that inorganic salts and other impurities in the sizing agent main slurry are completely removed.

[0055] In this invention, the emulsifier in step 2) is preferably dodecyltrimethylammonium bromide, tetradecyltrimethylammonium bromide, octadecyltrimethylammonium bromide, hexadecyltrimethylammonium bromide, or bis(dodecyldimethylammonium bromide); the cosolvent is preferably dichloromethane or chloroform.

[0056] The mass ratio of emulsifier, co-solvent, and sizing agent in the main slurry is preferably 0.4-0.6:0.8-1.2:100, more preferably 0.45-0.55:0.9-1.1:100, and even more preferably 0.5:1.0:100.

[0057] In step 2) of this invention, an emulsifier and a co-solvent are added to the main sizing agent to carry out a two-phase conversion, so that the system is converted from oil-in-water type to water-in-oil type, thereby successfully preparing a water-based carbon fiber sizing agent suitable for polyether ether ketone matrix.

[0058] In this invention, the drying temperature in step 3) is preferably 100-200°C, more preferably 120-180°C, and even more preferably 140-150°C. The drying time is preferably 30-60 min, more preferably 40-50 min, and even more preferably 45 min.

[0059] In this invention, the flowchart for the water-based carbon fiber sizing agent to sizing desizing carbon fiber is as follows: Figure 1 As shown.

[0060] In this invention, the mass concentration of soluble phosphate in the soluble phosphate solution in step 4) is preferably 25-90%, more preferably 35-80%, and even more preferably 45-70%; the mass concentration of calcium compound in the calcium compound solution is preferably 25-80%, more preferably 35-70%, and even more preferably 45-60%; and the mass fraction of surfactant in the simulated body fluid containing surfactant is preferably 2-25%, more preferably 6-22%, and even more preferably 10-20%.

[0061] In this invention, the soluble phosphate is preferably one or more of sodium dihydrogen phosphate, dipotassium hydrogen phosphate, and ammonium phosphate; the calcium-containing compound is preferably one or more of calcium chloride, calcium lignosulfonate, and calcium salicylate; and the surfactant is preferably a cationic surfactant, a nonionic surfactant, or an amphoteric surfactant.

[0062] In this invention, the solvent in the soluble phosphate solution and the calcium-containing compound solution is preferably an aqueous solution of tris(hydroxymethyl)aminomethane, wherein the mass fraction of tris(hydroxymethyl)aminomethane in the aqueous solution is preferably 1.3-1.8%, more preferably 1.4-1.6%; and the pH value of the aqueous solution of tris(hydroxymethyl)aminomethane is preferably 6-10, more preferably 7.45-8.51.

[0063] In this invention, the temperatures of the soluble phosphate solution, the calcium compound solution, and the simulated body fluid containing surfactant in step 4) are preferably 15–90°C, more preferably 25–80°C, and even more preferably 35–70°C; the immersion times in the soluble phosphate solution and the calcium compound solution are preferably 5–65 min, more preferably 10–50 min, and even more preferably 15–45 min; and the immersion times in the simulated body fluid containing surfactant are preferably 12–30 min, more preferably 15–25 min, and even more preferably 18–20 min.

[0064] In this invention, after the carbon fiber material containing an aqueous carboxyl sizing agent is impregnated in a soluble phosphate solution, it is preferable to clean the carbon fiber material and then impregnate it in a calcium compound solution; after impregnation in the calcium compound solution, it is preferable to clean the carbon fiber material and then impregnate it in a simulated body fluid containing a surfactant.

[0065] In this invention, the cationic surfactant is preferably a quaternary ammonium salt, more preferably an octadecyl diester quaternary ammonium salt, benzyl chloride onium salt, or amide-based gemini quaternary ammonium salt; the nonionic surfactant is preferably a polyol or polyether, more preferably polytrimethylene ether glycol, polyoxyethylene fatty alcohol ether, or polyether polyol CF-60; the amphoteric surfactant is preferably a betaine or sodium organic acid, more preferably dodecyl dimethyl betaine, food-grade betaine, dodecyl betaine, disodium lauryl sulfosuccinate monoester, or monolauryl phosphate MAP.

[0066] In this invention, carbon fiber materials containing an aqueous carboxyl sizing agent are sequentially impregnated in a soluble phosphate solution, a calcium compound solution, and a simulated body fluid containing a surfactant to biomineralize and grow a hydroxyapatite bioactive coating. Subsequently, a carbon fiber / polyetheretherketone composite material with excellent mechanical properties and bioactivity is obtained by molding.

[0067] The present invention also provides a bioactive carbon fiber material prepared by the aforementioned preparation method.

[0068] The present invention also provides a carbon fiber reinforced polyether ether ketone composite material, wherein the raw materials for preparing the carbon fiber reinforced polyether ether ketone composite material include bioactive carbon fiber material and polyether ether ketone in a mass ratio of 43-55:40-53.

[0069] In this invention, the preferred mass ratio of bioactive carbon fiber material to polyetheretherketone is 45-52:43-50, and more preferably 46-48:47-49.

[0070] In this invention, the carbon fiber reinforced polyether ether ketone composite material is prepared by compression molding. The carbon fiber material with a bioactive water-containing carboxyl sizing agent is combined with polyether ether ketone to obtain a prepreg. The prepreg is then compression molded to obtain the carbon fiber reinforced polyether ether ketone composite material.

[0071] In this invention, the prepreg is preferably molded in a mold coated with a release agent; the release agent is preferably Weiling brand C-3 type release agent produced by Shanghai Xuling New Material Technology Co., Ltd.

[0072] In this invention, the compression molding pressure is preferably 2-10 MPa, more preferably 5-8 MPa; the compression molding temperature is preferably 375-410℃, more preferably 380-400℃; and the compression molding time is preferably 25-35 min, more preferably 28-30 min.

[0073] In the molding process of this invention, the carbon fiber layup direction is 0° or 180° compared to the polyetheretherketone film.

[0074] This invention also provides the application of the aforementioned carbon fiber reinforced polyetheretherketone composite material in the medical industry, preferably in the repair of bone tissue defects.

[0075] This invention employs a method combining sizing and biomineralization to improve the bioactivity and osseointegration properties of carbon fiber composites, overcoming the challenges of poor bonding between carbon fibers and the polyetheretherketone (PEEK) matrix and lack of bioactivity. This invention is the first to use a sizing agent as a mineralization organic template and the first to combine sizing with biomineralization, improving the interfacial properties and mechanical strength of carbon fiber-reinforced PEEK composites while simultaneously endowing them with excellent bioactivity and biocompatibility. The method of this invention forms a strong bond between hydroxyapatite and the carbon fibers and matrix. Compared to existing composites that cannot simultaneously achieve good mechanical properties and bioactivity, this method significantly shortens the mineralization time of hydroxyapatite, resulting in hydrogen and chemical bonds between the carbon fiber interfacial layer, the carbon fiber surface, and the PEEK matrix, leading to superior interfacial properties. Furthermore, the preparation is simple, non-toxic, and easy for industrial production, greatly meeting the urgent need for new materials in the orthopedic industry and possessing a wide range of applications.

[0076] The technical solutions provided by the present invention will be described in detail below with reference to the embodiments, but they should not be construed as limiting the scope of protection of the present invention.

[0077] In this embodiment, the release agent is Weiling brand C-3 type release agent produced by Shanghai Xuling New Material Technology Co., Ltd.

[0078] Example 1

[0079] Under nitrogen protection, 4-carboxyphenyl biphenyl hydroquinone and 4,4-difluorobenzophenone in a molar ratio of 1:1 were sequentially added to a 500 mL three-necked flask (equipped with a water separator, reflux condenser and mechanical stirrer) for a gradient polycondensation reaction. The temperature was first raised to 125 °C and the water separation reaction was carried out for 3 hours until no water flowed out of the water separator. Then, the temperature was gradually increased from 125 °C to 200 °C at a rate of 10 °C / min and the polycondensation reaction was carried out for 7 hours. The resulting sizing agent slurry was poured into deionized water to completely immerse the slurry and boiled at 100 °C for 2 hours, during which the deionized water was changed 6 times to fully remove inorganic salts and other impurities from the sizing agent slurry. Subsequently, using a high-speed shearing machine (speed 2000 r / min), dodecyltrimethylammonium bromide (0.5% by mass of the main sizing agent), chloroform (1% by mass of the main sizing agent), and the main sizing agent were added to a beaker via a reverse inversion method. Deionized water was added dropwise at a rate of 2 drops per second using a separatory funnel until the system changed from an oil-in-water type to an oil-in-water type, yielding an aqueous carbon fiber sizing agent. 30g of completely desizing T-300 carbon fiber cloth was immersed in a sizing tank for sizing treatment using the aqueous carbon fiber sizing agent. The sizing amount was controlled at 0.6%. The sized T-300 carbon fiber cloth was then dried at 100℃ for 30 min to obtain carbon fiber material containing the aqueous carboxyl sizing agent.

[0080] 7.06 g of tris(hydroxymethyl)aminomethane (Tris) was added to a beaker containing 500 mL of deionized water, and the pH was adjusted to 7.45 and 8.50 respectively with 2 mol / L dilute hydrochloric acid to obtain Tris solutions.

[0081] The carbon fiber material with an aqueous carboxyl sizing agent was immersed in a Tris solution of sodium dihydrogen phosphate (pH=8.50) (sodium dihydrogen phosphate mass concentration in Tris solution was 35%) and kept at 35℃ for 12 min. The carbon fiber material with an aqueous carboxyl sizing agent was removed, washed with deionized water, and then immersed in a Tris solution of calcium chloride (pH=7.45) (calcium chloride mass concentration in Tris solution was 35%) and kept at 38℃ for 12 min. The carbon fiber material with an aqueous carboxyl sizing agent was removed, washed with deionized water, and then immersed in a simulated body fluid containing dodecyl dimethyl betaine (dodecyl dimethyl betaine mass fraction in simulated body fluid was 4%) and kept at 37.5℃ for 15 min to obtain a carbon fiber material with an aqueous carboxyl sizing agent and a moss-like HA bioactive mineralization layer.

[0082] Carbon fiber material with an aqueous carboxyl sizing agent containing an HA bioactive mineralization layer was compounded with polyetheretherketone (PEEK) at a mass ratio of 55:40 to obtain a prepreg. The prepreg was then cut into 12cm×8cm pieces and placed into a mold (made of P20 steel) coated with 10g of release agent for compression molding. During the compression molding process, the carbon fiber layup direction was 0° relative to the PEEK film, the pressure was 6MPa, the temperature was 386℃, and the time was 25min, resulting in a carbon fiber reinforced PEEK composite material.

[0083] Example 2

[0084] Under argon protection, 4,4-bis(4-hydroxyphenyl)valeric acid and 2,6-dichlorobenzonitrile in a molar ratio of 1:1 were sequentially added to a 1000 mL three-necked flask (equipped with a water separator, reflux condenser, and mechanical stirrer) for a gradient polycondensation reaction. The temperature was first raised to 140 °C and the water separation reaction was carried out for 5 hours until no water flowed out of the water separator. Then, the temperature was gradually increased from 140 °C to 190 °C at a rate of 10 °C / min and the polycondensation reaction was carried out for 12 hours. The resulting sizing agent slurry was poured into deionized water to completely immerse the slurry and boiled at 100 °C for 2 hours, during which the deionized water was changed 6 times to fully remove inorganic salts and other impurities from the sizing agent slurry. Subsequently, using a high-speed shearing machine (speed 2000 r / min), cetyltrimethylammonium bromide (0.5% by mass of the main sizing agent), dichloromethane (1% by mass of the main sizing agent), and the main sizing agent were added to a beaker via a reverse inversion method. Deionized water was added dropwise at a rate of 2 drops per second using a separatory funnel until the system changed from an oil-in-water type to an oil-in-water type, yielding an aqueous carbon fiber sizing agent. 160g of completely desizing T-300 carbon fiber cloth was immersed in a sizing tank for sizing treatment using the aqueous carbon fiber sizing agent. The sizing amount was controlled at 0.6%. The sized T-300 carbon fiber cloth was then dried at 190℃ for 60 min to obtain carbon fiber material containing the aqueous carboxyl sizing agent.

[0085] 7.06 g of tris(hydroxymethyl)aminomethane (Tris) was added to a beaker containing 500 mL of deionized water, and the pH was adjusted to 7.45 and 8.50 respectively with 2 mol / L dilute hydrochloric acid to obtain Tris solutions.

[0086] The carbon fiber material with an aqueous carboxyl sizing agent was immersed in a Tris solution of dipotassium hydrogen phosphate (pH = 8.50) (the mass concentration of dipotassium hydrogen phosphate in the Tris solution was 45%) and kept at 52°C for 52 min. The carbon fiber material with an aqueous carboxyl sizing agent was removed, washed with deionized water, and then immersed in a Tris solution of calcium salicylate (pH = 7.45) (the mass concentration of calcium salicylate in the Tris solution was 58%) and kept at 60°C for 35 min. The carbon fiber material with an aqueous carboxyl sizing agent was removed, washed with deionized water, and then immersed in a simulated body fluid containing DMDHEU gemini quaternary ammonium salt (the mass fraction of DMDHEU gemini quaternary ammonium salt in the simulated body fluid was 14%) and kept at 55°C for 26 min to obtain a carbon fiber material with an HA bioactive mineralization layer.

[0087] Carbon fiber material with an aqueous carboxyl sizing agent containing an HA bioactive mineralization layer was compounded with polyetheretherketone (PEEK) at a mass ratio of 53:49 to obtain a prepreg. The prepreg was then cut into 12cm×8cm pieces and placed into a mold (made of P20 steel) coated with 10g of release agent for compression molding. During the compression molding process, the carbon fiber layup direction was 180° relative to the PEEK film, the pressure was 10MPa, the temperature was 385℃, and the time was 35min, resulting in a carbon fiber reinforced PEEK composite material.

[0088] Example 3

[0089] Under nitrogen protection, phenolphthalein and 4,4-difluorobenzophenone in a molar ratio of 0.9:1 were sequentially added to a 600mL three-necked flask (equipped with a water separator, reflux condenser, and mechanical stirrer) for a gradient polycondensation reaction. The temperature was first raised to 130℃ and the water separation reaction was carried out for 4 hours until no water flowed out of the water separator. Then, the temperature was gradually increased from 130℃ to 210℃ at a rate of 10℃ / min and the polycondensation reaction was carried out for 15 hours. The resulting sizing agent slurry was poured into deionized water to completely immerse the slurry and boiled at 100℃ for 2 hours, during which the deionized water was changed 6 times to fully remove inorganic salts and other impurities from the sizing agent slurry. Subsequently, using a high-speed shearing machine (speed 2000 r / min), didodecyl dimethyl ammonium bromide (0.45% by mass of the main sizing agent), dichloromethane (1.1% by mass of the main sizing agent), and the main sizing agent were added to a beaker via a reverse inversion method. Deionized water was added dropwise at a rate of 2 drops / second using a separatory funnel until the system changed from an oil-in-water type to an oil-in-water type, yielding an aqueous carbon fiber sizing agent. 90g of completely desizing T-300 carbon fiber cloth was immersed in a sizing tank for sizing treatment using the aqueous carbon fiber sizing agent. The sizing amount was controlled at 0.6%. The sized T-300 carbon fiber cloth was then dried in an oven at 150℃ for 45 min to obtain carbon fiber material containing the aqueous carboxyl sizing agent.

[0090] 7.06 g of tris(hydroxymethyl)aminomethane (Tris) was added to a beaker containing 500 mL of deionized water, and the pH was adjusted to 7.45 and 8.50 respectively with 2 mol / L dilute hydrochloric acid to obtain Tris solutions.

[0091] The carbon fiber material with aqueous carboxyl sizing agent was immersed in a Tris solution of ammonium phosphate (pH=8.50) (the mass concentration of ammonium phosphate in the Tris solution was 60%) and kept at 65℃ for 40 min. The carbon fiber material with aqueous carboxyl sizing agent was removed, washed with deionized water, and then immersed in a Tris solution of calcium lignosulfonate (pH=7.45) (the mass concentration of calcium lignosulfonate in the Tris solution was 45%) and kept at 70℃ for 30 min. The carbon fiber material with aqueous carboxyl sizing agent was removed, washed with deionized water, and then immersed in a simulated body fluid containing polyether polyol CF-60 (the mass fraction of polyether polyol CF-60 in the simulated body fluid was 10%) and kept at 60℃ for 20 min to obtain a carbon fiber material with an HA bioactive mineralization layer.

[0092] Carbon fiber material with an aqueous carboxyl sizing agent containing an HA bioactive mineralization layer was compounded with polyetheretherketone (PEEK) at a mass ratio of 50:45 to obtain a prepreg. The prepreg was then cut into 12cm×8cm pieces and placed into a mold (made of P20 steel) coated with 10g of release agent for compression molding. During the compression molding process, the carbon fiber layup direction was 0° relative to the PEEK film, the pressure was 8MPa, the temperature was 395℃, and the time was 30min to obtain a carbon fiber reinforced PEEK composite material.

[0093] Comparative Example 1

[0094] Commercially available T-300 carbon fiber cloth that has been completely desizing was directly compounded with polyetheretherketone at a mass ratio of 55:40 to prepare a composite material. The process for preparing the composite material was the same as in Example 1.

[0095] Mechanical properties were tested on the carbon fiber reinforced polyetheretherketone (PEEK) composites prepared in Examples 1-3 and the composite material of Comparative Example 1. The composites of each example and the comparative example were tested five times, and the average value was taken. The mechanical property test results are shown in Table 1. As can be seen from Table 1, compared with the comparative example, the method of the present invention can effectively improve the interfacial properties between the CF and PEEK matrix, thus giving the composite material of the present invention excellent mechanical properties.

[0096] Table 1 Mechanical properties of composite materials in Examples 1-3 and Comparative Example 1

[0097]

[0098] Figures 2-4 The images shown are SEM images of commercial T-300 carbon fiber cloth after sizing removal, SEM images of carbon fiber material with aqueous carboxyl sizing agent of Example 1, and SEM images of carbon fiber material with aqueous carboxyl sizing agent of Example 1 having HA bioactive mineralization layer; from Figures 2-4 As can be seen, the sizing layer of Example 1 is uniformly coated on the carbon fiber, and the resulting HA mineralization layer has a moss-like structure. The method provided by the present invention effectively improves the specific surface area of ​​the HA bioactive mineralization layer, and greatly enhances the interfacial bonding force between carbon fiber and hydroxyapatite, and between carbon fiber and polyether ether ketone matrix.

[0099] The FTIR spectra of the carbon fiber material with aqueous carboxyl sizing agent and the carbon fiber material with HA bioactive mineralization layer in Example 1 are as follows: Figure 6 As shown, the elemental distribution diagram of the carbon fiber material with an aqueous carboxyl sizing agent containing an HA bioactive mineralization layer in Example 1 is as follows. Figure 8 As shown. By Figure 6 , Figure 8It can be seen that Example 1 successfully grew a hydroxyapatite mineralization layer on the surface of carbon fiber with an aqueous carboxyl sizing agent layer, and contained a large amount of calcium ions and phosphorus ions.

[0100] XRD analysis was performed on the aqueous carboxyl sizing agents and HA mineralization layers of Examples 1 and 2, and the results are as follows: Figure 7 As shown. By Figure 7 It can be seen that the preparation method of the present invention successfully grew a hydroxyapatite mineralization layer on the surface of carbon fiber with an aqueous carboxyl sizing agent layer.

[0101] Energy dispersive spectroscopy (EDS) analysis was performed on the aqueous carboxyl sizing agent and the HA mineralization layer of Example 2. The results are as follows: Figure 9 As shown. By Figure 9 It is known that the carbon fiber reinforced polyether ether ketone composite material prepared by the preparation method of the present invention meets the calcium-to-phosphorus ratio of human bone.

[0102] The bioactivity and biocompatibility of the carbon fiber reinforced polyetheretherketone (SCF-HA / PEEK) composite material of Example 1 and the unsized carbon fiber reinforced polyetheretherketone (UCF / PEEK) composite material of Comparative Example 1 were tested. The test results are as follows: Figure 12 As shown.

[0103] The specific process method for bioactivity testing is as follows:

[0104] T-300 carbon fiber cloth (CF cloth) with an organic phase structure was immersed in simulated body fluids containing different surfactants for biomineralization. The samples were then grown in a water bath at 37.5°C for different times. The samples were then removed, bagged, and stored for later use. SEM analysis revealed that the HA content of the biomineralized CF cloth increased with increasing immersion time in the simulated body fluids, demonstrating that the prepared material possesses good bioactivity.

[0105] The specific process for biocompatibility testing is as follows:

[0106] CCK-8 assay was performed: 3rd generation MC3T3-E1 cells were seeded in 24-well plates at a cell density of 5 × 10⁶ cells / well. 4 In each well, the extracts of UCF / PEEK composite material, aqueous carboxyl sizing agent, and HA mineralization layer-reinforced PEEK composite material (SCF-HA / PEEK) were placed in an incubator (37℃, 5% CO2) and cultured for 1, 3, 5, and 7 days, respectively. Complete culture medium containing 10% CCK-8 was added to each well (stored in the dark). After 1 hour, the absorbance values ​​of each group were measured using a microplate reader at a wavelength of 450 nm. The CCK-8 test results are as follows: Figure 12 As shown. By Figure 12It can be seen that, with the extension of cell culture time, the absorbance value of cells in the extract of the SCF-HA / PEEK composite material in Example 1 is greater than that of the UCF / PEEK composite material in Comparative Example 1, and the absorbance of the SCF-HA / PEEK composite material shows an increasing trend. This indicates that the SCF-HA / PEEK composite material is non-cytotoxic, the cells in the extract continuously proliferate and grow, and the SCF-HA / PEEK composite material has good biocompatibility. Figure 12 It can be seen that the composite material prepared in Example 1 has superior bioactivity and biocompatibility compared with Comparative Example 1.

[0107] This invention is the first to employ a sizing method combined with biomineralization to prepare carbon fiber reinforced polyetheretherketone (PEEK) composites. First, a uniform layer of aqueous carboxyl sizing agent is coated onto carbon fiber fabric. This layer is then immersed in simulated body fluid as an organic template for hydroxyapatite. A biomineralization method is used to grow a bioactive hydroxyapatite coating, followed by molding to prepare the carbon fiber reinforced PEEK composite. This method directly uses the aqueous carboxyl sizing agent as the organic template for the bioactive hydroxyapatite coating, enabling rapid mineralization of hydroxyapatite directly on the fiber surface without the need for additional polymers as growth sites, thus minimizing the use of petroleum-based pharmaceuticals. This invention utilizes the sizing agent as an organic template, preventing decomposition during subsequent composite material preparation and significantly improving the overall performance of the composite. The composite prepared by this method not only significantly enhances the interfacial bonding between carbon fiber and hydroxyapatite, and between carbon fiber and the PEEK matrix, improving its mechanical properties, but also endows the composite with excellent bioactivity and biocompatibility, further reducing raw material costs and making it a promising candidate for large-scale application in the medical industry.

[0108] The above description is only a preferred embodiment of the present invention. It should be noted that for those skilled in the art, several improvements and modifications can be made without departing from the principle of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.

Claims

1. A method for producing a carbon fiber material having a biological activity, characterized by, The method comprises the following steps: 1) sequentially performing a water removal reaction and a polycondensation reaction on the first monomer and the carboxyl-containing bisphenol monomer under an inert atmosphere, and then performing a boiling washing in water to obtain a main sizing agent slurry; The first monomer is a fluorine-containing ketone monomer or an ether nitrile monomer; The carboxyl-containing bisphenol monomer in step 1) is one or more of 4-carboxyphenyl hydroquinone, 4-carboxyphenyl biphenol, 4-carboxyphenyl resorcinol, 4,4-bis(4-hydroxyphenyl) valeric acid and phenolphthalein; the fluorine-containing ketone monomer is 4,4-difluorobenzophenone; and the ether nitrile monomer is 2,6-dichlorobenzonitrile; 2) mixing an emulsifier, a cosolvent and the main sizing agent slurry, and adding water dropwise in the mixture until the two phases are converted to obtain an aqueous carbon fiber sizing agent; 3) performing sizing treatment on the desized carbon fiber with the aqueous carbon fiber sizing agent, and then drying to obtain a carbon fiber material containing the aqueous carboxyl sizing agent; 4) sequentially immersing the carbon fiber material containing the aqueous carboxyl sizing agent in a soluble phosphate solution, a calcium-containing compound solution and a surfactant-containing simulated body fluid to obtain a carbon fiber material with biological activity; The soluble phosphate is one or more of sodium dihydrogen phosphate, dipotassium hydrogen phosphate and ammonium phosphate; and the calcium-containing compound is one or more of calcium chloride, calcium lignosulfonate and calcium salicylate.

2. The production method according to claim 1, characterized by, The molar ratio of the first monomer to the carboxyl-containing bisphenol monomer in step 1) is 0.9-1.1:0.9-1.

1.

3. The production method according to claim 1 or 2, characterized by, The temperature of the water removal reaction in step 1) is 120-140℃, and the time of the water removal reaction is 1.5-6h; the temperature of the polycondensation reaction is 180-220℃, and the time of the polycondensation reaction is 6-30h. The temperature of the drying in step 3) is 100-200℃, and the time of the drying is 30-60min.

4. The production method according to claim 3, characterized by, The emulsifier in step 2) is dodecyltrimethylammonium bromide, tetradecyltrimethylammonium bromide, octadecyltrimethylammonium bromide, hexadecyltrimethylammonium bromide or didodecyldimethylammonium bromide; and the cosolvent is dichloromethane or trichloromethane. The mass ratio of the emulsifier, the cosolvent and the main sizing agent slurry is 0.4-0.6:0.8-1.2:

100.

5. The preparation method according to claim 4, characterized in that, The mass concentration of the soluble phosphate in the soluble phosphate solution in step 4) is 25-90%, the mass concentration of the calcium-containing compound in the calcium-containing compound solution is 25-80%, and the mass fraction of the surfactant in the surfactant-containing simulated body fluid is 2-25%. The surfactant is a cationic surfactant, a nonionic surfactant or a zwitterionic surfactant.

6. The production method according to claim 4 or 5, characterized by, The temperature of the soluble phosphate solution, the calcium-containing compound solution and the surfactant-containing simulated body fluid in step 4) is independently 15-90℃; the time of immersion in the soluble phosphate solution and the calcium-containing compound solution is independently 5-65min, and the time of immersion in the surfactant-containing simulated body fluid is 12-30min.

7. The preparation method according to claim 5, characterized in that, The cationic surfactant is a quaternary ammonium salt type cationic surfactant; the nonionic surfactant is a polyhydric alcohol type nonionic surfactant or a polyether type nonionic surfactant; and the zwitterionic surfactant is a betaine type zwitterionic surfactant or an organic acid sodium type zwitterionic surfactant.

8. The bioactive carbon fiber material prepared by the method of any one of claims 1-7.

9. A carbon fiber reinforced polyether ether ketone composite material, characterized by, The raw material for preparing the carbon fiber reinforced polyether ether ketone composite material comprises the bioactive carbon fiber material with the aqueous carboxyl-containing sizing agent and the polyether ether ketone in a mass ratio of 43-55:40-53; The bioactive carbon fiber material is the bioactive carbon fiber material of claim 8.

10. The carbon fiber reinforced polyether ether ketone composite material of claim 9 for use in the medical industry.

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