Hydroxyapatite carbon fiber material and bone repair biological composite material and preparation method and application

Abstract

The present application belongs to the technical field of carbon fiber composite materials, and provides a hydroxyapatite carbon fiber material and a preparation method thereof. The carbon fiber cloth is reacted with an organic template to obtain a carbon fiber cloth with an organic phase, and then the carbon fiber cloth is sequentially immersed in a soluble phosphate solution, a calcium-containing compound solution and a surfactant-containing simulated body fluid to obtain the hydroxyapatite carbon fiber material. The present application also provides a hydroxyapatite bone repair biological composite material and a preparation method thereof. It is found for the first time that cationic, nonionic and zwitterionic surfactants can accelerate the mineralization rate of hydroxyapatite, hydrogen bonds are generated between the hydroxyapatite and a polyaryletherketone resin matrix, the binding force between the hydroxyapatite and the polyaryletherketone matrix is stronger, the hydroxyapatite is not easy to fall off, a uniform and ordered hydroxyapatite bone repair biological composite material with excellent mechanical properties, high biological activity and biocompatibility is obtained, the mechanical strength and biological environment required for the hydroxyapatite to fully match and be implanted into the human body are met, and the application range of the hydroxyapatite is expanded.

Description

Technical Field

[0001] This invention relates to the field of carbon fiber composite materials technology, and in particular to a hydroxyapatite carbon fiber material, a bone repair biocomposite material, its preparation method, and its application. Background Technology

[0002] Currently, the materials commonly used in medicine for repairing bone defects, bone replacement, bone grafting, and in clinical orthopedic surgery are mainly stainless steel and titanium alloys, often referred to as the "gold standard" in the industry. These materials are widely used in clinical medicine due to their low cost, high mechanical strength, meeting the strength and modulus requirements of human bones and joints, and stability. However, with prolonged use, their shortcomings have gradually become apparent. For example, stainless steel has poor corrosion resistance in the human body, a high wear rate, and may even release toxic metal ions, posing a threat to human health. After implantation, the weight of metal materials increases the burden of walking; the high elastic modulus and radiation shielding properties of metal materials can cause stress shielding and visual field defects during examinations, interfering with results; and long-term retention of metal materials in the body can lead to the release of metal ions, harming human health. To overcome the shortcomings of metal materials, non-metallic materials are needed to further improve their service life and effectiveness in medicine.

[0003] Polyaryletherketones (PAEKs) are a rapidly developing class of novel thermoplastic polymers, occupying a leading position in the plastics industry. Because PAEKs combine the advantages of metallic materials with the disadvantages they exhibit in human applications, they have become a hot research topic in the medical field. PAEKs possess high heat resistance, acid and alkali resistance, chemical corrosion resistance, excellent radiation resistance, and abrasion resistance. Research results indicate that PAEKs also possess excellent biocompatibility and biosafety; their limited development is due to their bioinertness and low mechanical strength.

[0004] Fiber-reinforced polyaryletherketone (PAEK) composites can improve the performance of PAEK. Studies have shown that polyacrylonitrile-based carbon fibers (CFs) have better reinforcing effects compared to other carbon fibers (CFs). Currently, due to bottlenecks in the manufacturing process, short CFs are mostly used to reinforce PAEK, which cannot achieve optimal mechanical strength. Furthermore, long carbon fibers suffer from poor dispersibility, and reinforced PAEK composites exhibit bioinertness. Hydroxyapatite (HA) is the main inorganic component of human and animal bones, accounting for more than 60% of bone mass. It possesses excellent bioactivity and biocompatibility and has become a novel bone substitute in recent years. Introducing HA into fiber-reinforced PAEK composites not only increases the mechanical properties of the composite material to be compatible with human bone but also fully demonstrates the excellent bioactivity and biocompatibility of HA-containing composites, broadening its application range.

[0005] Currently, there are many methods for preparing hydroxyapatite. Among them, Guo Yaping et al. (patent number CN 103394124 B) first used the impregnation-coating method to generate a bioglass coating on the surface of a metal substrate after high-temperature calcination. Then, they used a hydrothermal method to grow ordered rod-shaped hydroxyapatite in simulated body fluid, with a minimum growth time of 24 hours. The prepared composite coating not only has excellent mechanical properties and strength but also good bioactivity and biocompatibility. Yan Yuhua et al. (patent number 200410012852.9) first modified the surface of glass fiber and then used a precipitation method to impregnate it in simulated body fluid to grow needle-shaped hydroxyapatite. They concluded that a growth time of at least 120 hours is required to prepare hydroxyapatite with excellent properties. The prepared composite material has high bioactivity and good bone integration. Qiao Fei et al. (Patent No. 200710068442.X) used a biomimetic mineralization method to grow hydroxyapatite (HA) on the surface of fibers. This experiment required a minimum of 336 hours of immersion in simulated body fluid to generate hydroxyapatite, with optimal performance achieved when the immersion time reached 672 hours. The composite material prepared using this method improved the bioactivity and biocompatibility of fiber (CF) and solved the problems of uneven HA dispersion and easy agglomeration, further improving the mechanical properties of the composite material. However, the main drawbacks of using hydrothermal and chemical reaction methods to prepare HA are: HA tends to deposit at the bottom of the material during the preparation process, easily agglomerating, resulting in poor HA dispersion and a small specific surface area, thus reducing the mechanical properties of the subsequent composite material. Furthermore, the excessively long growth time of HA in simulated body fluid in existing methods leads to unreasonable resource allocation and waste of human and material resources. HA also suffers from low grafting rates and unsatisfactory grafting effects during short growth periods.

[0006] Therefore, the research has yielded a hydroxyapatite carbon fiber material and a bone repair biocomposite material that improves the dispersibility and specific surface area of ​​HA, shortens its growth time, and enhances its mechanical properties and bioactivity. This is of great significance. Summary of the Invention

[0007] The purpose of this invention is to overcome the shortcomings of existing technologies by providing a hydroxyapatite carbon fiber material, a bone repair biocomposite material, its preparation method, and its applications. This invention solves the problems of poor mechanical properties and uneven dispersion of long fibers in current composite materials, which limit their application range. This invention uses carbon fiber cloth to reinforce polyaryletherketone to prepare composite materials, which not only further improves the mechanical properties but also addresses the issues of poor bioactivity and biocompatibility of the composite material.

[0008] To achieve the above-mentioned objectives, the present invention provides the following technical solution:

[0009] This invention provides a method for preparing hydroxyapatite carbon fiber material, comprising the following steps:

[0010] 1) React carbon fiber cloth and organic template to obtain carbon fiber cloth with organic phase;

[0011] 2) The carbon fiber cloth with organic phase was sequentially immersed in a soluble phosphate solution, a calcium compound solution, and a simulated body fluid containing a surfactant to obtain hydroxyapatite carbon fiber material.

[0012] The simulated body fluid containing surfactants is anionic surfactant-type simulated body fluid, cationic surfactant-type simulated body fluid, nonionic surfactant-type simulated body fluid, or zwitterionic surfactant-type simulated body fluid.

[0013] Preferably, in step 1), the mass ratio of organic template to carbon fiber cloth is 6-10:20-22; the organic template is an aqueous solution of organic template; the mass fraction of organic template in the aqueous solution of organic template is 1-30%;

[0014] The organic template is dopamine, silk fibroin, sericin, spider silk, L-dopamine, polycaprolactone, polylactic acid, chitosan, gelatin or collagen;

[0015] The reaction temperature is 10–90°C, and the reaction time is 5–60 min.

[0016] Preferably, in step 2), the soluble phosphate is one or more of sodium dihydrogen phosphate, disodium hydrogen phosphate, sodium phosphate, potassium dihydrogen phosphate, dipotassium hydrogen phosphate, potassium phosphate, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, and ammonium phosphate.

[0017] The calcium-containing compounds are one or more of the following: calcium chloride, calcium carbonate, calcium propionate, calcium citrate, calcium lignosulfonate, calcium alginate, tricalcium phosphate, calcium methacrylate, calcium salicylate, and octacalcium phosphate.

[0018] The soluble phosphate solution contains 30-90% soluble phosphate by mass, the calcium compound solution contains 30-80% calcium compound by mass, and the simulated body fluid containing surfactant contains 2-30% surfactant by mass.

[0019] Preferably, the temperatures of the soluble phosphate solution, the calcium compound solution, and the simulated body fluid containing surfactant are independently 10–90°C, the immersion time of the carbon fiber cloth constructing the organic phase in the soluble phosphate solution and the calcium compound solution is independently 5–60 min, and the immersion time in the simulated body fluid containing surfactant is 12–16 min.

[0020] Preferably, the anionic surfactant in the anionic surfactant-type simulated body fluid is a sulfonate, sulfate, or sulfate ester; the cationic surfactant in the cationic surfactant-type simulated body fluid is an amine salt or quaternary ammonium salt; the nonionic surfactant in the nonionic surfactant-type simulated body fluid is a polyoxyethylene type, polyol type, alkanolamide type, polyether type, or amine oxide type; and the amphoteric surfactant in the zwitterionic surfactant-type simulated body fluid is a betaine type or sodium organic acid type.

[0021] Preferably, the anionic surfactant is a succinate sulfonate, alkylbenzene sulfonate, alkyl sulfonate, sodium dodecyl sulfate, alkylnaphthalene sulfonate, petroleum sulfonate, alkylolamide, alkylsulfonic acid acetamide, alkyl succinate sulfonate, alkanolamine alkylbenzene sulfonate, naphthenate, alkylphenol sulfonate, or polyoxyethylene monolaurate.

[0022] The cationic surfactant is octadecyl diester quaternary ammonium salt, octadecylamine polyoxyethylene ether bisquaternary ammonium salt, hexadecyl alcohol polyoxyethylene ether dimethyl octyl ammonium chloride, hexadecyl trimethyl ammonium bromide, cationic gemini emulsifier, or dodecyl polyoxyethylene ammonium bromide.

[0023] The nonionic surfactant is a fatty acid monoglyceride, a fatty acid monostearate, a fatty acid sorbitan, a polysorbate, a polyoxyethylene fatty acid ester, a polyoxyethylene fatty alcohol ether, a polyoxyethylene-polyoxypropylene copolymer, or a Prolactin.

[0024] The zwitterionic surfactants are lauryl betaine, sodium dodecylaminopropionate, alkyl dimethyl betaine, alkyl dimethyl hydroxypropyl phosphate betaine, alkyl di(aminoethyl)glycine, sodium N-hydroxymethylglycinate, disodium iminodipropionate, betaine, citrate betaine, cocamidopropyl betaine, sodium lauroylamphoteric acid, or lauroamide propyl betaine.

[0025] The present invention also provides a hydroxyapatite carbon fiber material prepared by the preparation method described above, wherein the mass ratio of organic template, carbon fiber and hydroxyapatite in the hydroxyapatite carbon fiber material is 6-10:20-22:20-24.

[0026] The present invention also provides a hydroxyapatite bone repair biocomposite material containing hydroxyapatite carbon fiber material, which is prepared by hydroxyapatite carbon fiber material and polyaryletherketone in a mass ratio of 46-56:42-50; wherein the polyaryletherketone is polyetheretherketoneketone, polyetherketoneketone, polyetheretherketone, polyetherketone, or polyetherketoneetherketoneketone.

[0027] The present invention also provides a method for preparing the hydroxyapatite bone repair biocomposite material, wherein hydroxyapatite carbon fiber material and polyaryletherketone are compounded to obtain a prepreg; the prepreg is hot-pressed to obtain the hydroxyapatite bone repair biocomposite material.

[0028] The present invention also provides the application of the aforementioned hydroxyapatite bone repair biocomposite material in the repair of bone tissue defects.

[0029] The beneficial effects of this invention include the following:

[0030] 1) The hydroxyapatite of this invention is induced to mineralize and grow on the organic phase surface of carbon fiber cloth, with a significantly improved growth rate. Various morphologies of uniformly dispersed hydroxyapatite (HA) mineralization layers are grown on the carbon fiber cloth, increasing the specific surface area of ​​the HA mineralization layer. The composite material prepared by this invention using a biomineralization method exhibits hydrogen bonding between hydroxyapatite and the polyaryletherketone resin matrix, resulting in stronger adhesion and reduced detachment. This yields a uniform, ordered hydroxyapatite bone repair biocomposite material with excellent mechanical properties, bioactivity, biocompatibility, and osteoinductive properties. This material fully meets the mechanical strength and biological environmental requirements for implantation into the human body, better satisfying the application requirements of modern orthopedic medicine and expanding its application scope.

[0031] 2) The preparation method of the present invention is not only simple and easy to operate with low production cost, but also has a very short preparation time. It solves the problem of excessive growth time of HA in simulated body fluid. The growth time of HA in simulated body fluid is shortened to 15 minutes, which can prepare a high-performance hydroxyapatite mineralization layer. This greatly improves the growth rate of HA, reduces energy consumption, unreasonable resource allocation and waste of personnel and material resources. Moreover, no organic solvents are involved, and almost no waste is generated, which meets the needs of green chemistry and large-scale applications.

[0032] 3) In this invention, simulated body fluids containing different types of surfactants promote and accelerate HA growth. Cationic surfactants, amphoteric surfactants, and nonionic surfactants can accelerate the biomineralization rate of hydroxyapatite on the carbon fiber surface. Attached Figure Description

[0033] Figure 1 Here is a SEM image of the hydroxyapatite mineralization layer obtained in Example 1;

[0034] Figure 2 Here is a SEM image of the hydroxyapatite mineralization layer obtained in Example 2;

[0035] Figure 3 Here is a SEM image of the hydroxyapatite mineralization layer obtained in Example 3;

[0036] Figure 4 EDS image of the hydroxyapatite mineralization layer obtained in Example 1;

[0037] Figure 5 The image shows the XRD pattern of the hydroxyapatite mineralized layer obtained in Example 1.

[0038] Figure 6 The figures show the bioactivity and biocompatibility test results of the carbon fiber reinforced polyether ether ketone composite material containing an organic-inorganic structure in Example 1 and the control group. The control group is a composite material prepared by directly combining commercial carbon fiber with polyether ether ketone after desizing. Detailed Implementation

[0039] This invention provides a method for preparing hydroxyapatite carbon fiber material, comprising the following steps:

[0040] 1) React carbon fiber cloth and organic template to obtain carbon fiber cloth with organic phase;

[0041] 2) The carbon fiber cloth with organic phase was sequentially immersed in a soluble phosphate solution, a calcium compound solution, and a simulated body fluid containing a surfactant to obtain hydroxyapatite carbon fiber material.

[0042] The simulated body fluid containing surfactants is anionic surfactant-type simulated body fluid, cationic surfactant-type simulated body fluid, nonionic surfactant-type simulated body fluid, or zwitterionic surfactant-type simulated body fluid.

[0043] In step 1) of the present invention, the mass ratio of organic template to carbon fiber cloth is preferably 6-10:20-22, more preferably 7-9:20.5-21.5, and even more preferably 8:21; the organic template is preferably an aqueous solution of organic template; the mass fraction of organic template in the aqueous solution of organic template is preferably 1-30%, more preferably 3-25%, and even more preferably 5-15%;

[0044] The preferred organic templates are dopamine, silk fibroin, sericin, spider silk, L-dopamine, polycaprolactone, polylactic acid, chitosan, gelatin, or collagen.

[0045] The reaction temperature is preferably 10–90°C, more preferably 20–80°C, and even more preferably 30–70°C; the reaction time is preferably 5–60 min, more preferably 10–50 min, and even more preferably 15–40 min.

[0046] In this invention, the carbon fiber cloth in step 1) is preferably a completely desizing carbon fiber cloth. During the reaction between the carbon fiber cloth and the organic template, the carbon fiber cloth is completely immersed in the organic template aqueous solution. The carbon fiber cloth that forms the organic phase is the carbon fiber cloth whose surface forms the organic phase.

[0047] In step 2) of this invention, the soluble phosphate is preferably one or more of sodium dihydrogen phosphate, disodium hydrogen phosphate, sodium phosphate, potassium dihydrogen phosphate, dipotassium hydrogen phosphate, potassium phosphate, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, and ammonium phosphate.

[0048] The calcium-containing compound is preferably one or more of calcium chloride, calcium carbonate, calcium propionate, calcium citrate, calcium lignosulfonate, calcium alginate, tricalcium phosphate, calcium methacrylate, calcium salicylate, and octacalcium phosphate.

[0049] The soluble phosphate solution preferably contains 30-90% by mass, more preferably 40-80%, and even more preferably 50-70% by mass; the calcium compound solution preferably contains 30-80% by mass, more preferably 40-70%, and even more preferably 50-60% by mass; and the simulated body fluid containing surfactant preferably contains 2-30% by mass, more preferably 5-25%, and even more preferably 10-20% by mass.

[0050] In this invention, the temperatures of the soluble phosphate solution, the calcium compound solution, and the simulated body fluid containing surfactant are preferably 10–90°C, more preferably 20–80°C, and even more preferably 30–70°C; the immersion times of the carbon fiber cloth constructing the organic phase in the soluble phosphate solution and the calcium compound solution are preferably 5–60 min, more preferably 10–55 min, and even more preferably 15–50 min; the immersion time in the simulated body fluid containing surfactant is preferably 12–16 min, more preferably 13–15 min, and even more preferably 14 min.

[0051] In this invention, the soluble phosphate solution is preferably a tris(hydroxymethyl)aminomethane solution of soluble phosphate, and the calcium-containing compound solution is preferably a tris(hydroxymethyl)aminomethane solution containing calcium compounds; the tris(hydroxymethyl)aminomethane solution is preferably an aqueous solution of tris(hydroxymethyl)aminomethane, wherein the mass fraction of tris(hydroxymethyl)aminomethane in the aqueous solution is preferably 1.2-1.7%, more preferably 1.4-1.5%; the pH value of the aqueous solution of tris(hydroxymethyl)aminomethane is preferably 7-9, more preferably 7.45-8.50.

[0052] In this invention, after the carbon fiber cloth for constructing the organic phase is immersed in a soluble phosphate solution, it is washed with water and then immersed in a calcium compound solution. After the calcium compound solution is immersed, the carbon fiber cloth for constructing the organic phase is washed again.

[0053] In this invention, the anionic surfactant in the anionic surfactant-type simulated body fluid is preferably a sulfonate, sulfate, or sulfate ester; more preferably, it is a succinate sulfonate, alkylbenzene sulfonate, alkyl sulfonate, sodium dodecyl sulfate, alkylnaphthalene sulfonate, petroleum sulfonate, alkylolamide, alkylsulfonic acid acetamide, alkyl succinate sulfonate, alkanolamine alkylbenzene sulfonate, naphthenate, alkylphenol sulfonate, or polyoxyethylene monolaurate.

[0054] In this invention, the cationic surfactant in the cationic surfactant-type simulated body fluid is preferably an amine salt or a quaternary ammonium salt; more preferably, it is octadecyl diester quaternary ammonium salt YH-866, octadecylamine polyoxyethylene ether bisquaternary ammonium salt, hexadecyl alcohol polyoxyethylene ether dimethyl octyl ammonium chloride, hexadecyl trimethyl ammonium bromide, cationic gemini emulsifier 31770, or dodecyl polyoxyethylene ammonium bromide.

[0055] In this invention, the nonionic surfactant in the nonionic surfactant-type simulated body fluid is preferably of polyoxyethylene type, polyol type, alkanolamide type, polyether type, or amine oxide type, and more preferably fatty acid monoglycerides, glyceryl monostearate, fatty acid sorbitan (Span type), polysorbate (Tween type), polyoxyethylene fatty acid ester (Mize), polyoxyethylene fatty alcohol ether (Benze), polyoxyethylene-polyoxypropylene copolymer (Poloxamer), or Pluronic; the Pluronic is preferably Pluronic F68.

[0056] In this invention, the zwitterionic surfactant in the simulated body fluid is preferably betaine-type or sodium organic acid-type, and more preferably lauryl betaine, sodium dodecylaminopropionate, alkyl dimethyl betaine, alkyl dimethyl hydroxypropyl phosphate betaine, alkyl di(aminoethyl)glycine, sodium N-hydroxymethylglycinate, disodium iminodipropionate, betaine, citrate betaine, cocamidopropyl betaine, sodium lauroamphoacetate, or lauramidopropyl betaine.

[0057] In this invention, carbon fiber cloth with an organic phase is immersed in a simulated body fluid containing a surfactant, and hydroxyapatite is rapidly grown on the surface of the organic phase of the carbon fiber using a biomineralization method, while controlling its growth morphology. Among the surfactant types, cationic surfactants, amphoteric surfactants, and nonionic surfactants can not only control the growth morphology of the inorganic phase - hydroxyapatite on the organic phase of the carbon fiber, but also accelerate its mineralization growth rate.

[0058] The present invention also provides a hydroxyapatite carbon fiber material prepared by the preparation method described above, wherein the mass ratio of organic template, carbon fiber and hydroxyapatite in the hydroxyapatite carbon fiber material is 6-10:20-22:20-24.

[0059] In this invention, the preferred mass ratio of organic template, carbon fiber and hydroxyapatite is 7-9:20.5-21.5:21-23, and more preferably 8:21:22.

[0060] The present invention also provides a hydroxyapatite bone repair biocomposite material containing hydroxyapatite carbon fiber material, which is prepared by hydroxyapatite carbon fiber material and polyaryletherketone in a mass ratio of 46-56:42-50; wherein the polyaryletherketone is polyetheretherketoneketone, polyetherketoneketone, polyetheretherketone, polyetherketone, or polyetherketoneetherketoneketone.

[0061] In this invention, the preferred mass ratio of hydroxyapatite carbon fiber material to polyaryletherketone is 48-55:43-49, and more preferably 49-54:44-48.

[0062] In the hydroxyapatite bone repair biocomposite material of the present invention, the mass ratio of organic template, carbon fiber, hydroxyapatite and polyaryletherketone is preferably 6-10:20-22:20-24:42-50, more preferably 7-9:20.5-21.5:21-23:43-49, and even more preferably 8:21:22:44-48.

[0063] The present invention also provides a method for preparing the hydroxyapatite bone repair biocomposite material, wherein hydroxyapatite carbon fiber material and polyaryletherketone are compounded to obtain a prepreg; the prepreg is hot-pressed to obtain the hydroxyapatite bone repair biocomposite material.

[0064] During the hot pressing process of the prepreg described in this invention, the prepreg is placed 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. The mass fraction of each component in the release agent is as follows: emulsion 10-15%, methyl silicone oil emulsion 15-20%, modified silicone oil emulsion 5-8%, deionized water 50-55%, emulsifier 4.5-6.0%, additive 0.5-1.0%, and preservative 0.3-0.5%.

[0065] In the hot pressing process described in this invention, the pressure is preferably 2-10 MPa, more preferably 5-8 MPa; the temperature is preferably 375-410℃, more preferably 380-400℃; and the time is preferably 25-35 min, more preferably 28-30 min.

[0066] In the hot pressing process of this invention, the carbon fiber layup direction is 0° compared to the polyaryletherketone film.

[0067] The present invention also provides the application of the aforementioned hydroxyapatite bone repair biocomposite material in the repair of bone tissue defects.

[0068] 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.

[0069] In this embodiment, the release agent is Weiling brand C-3 type release agent produced by Shanghai Xuling New Material Technology Co., Ltd.

[0070] Example 1

[0071] 20g of completely desizing T-300 carbon fiber cloth was placed in a 500mL beaker containing 6g of spider silk protein and 300mL of deionized water. The mixture was magnetically stirred until fully dissolved, and then heated to 15℃ to allow the carbon fiber cloth to fully soak and react for 15 minutes, thereby constructing an organic phase structure on its surface.

[0072] 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.

[0073] The organic phase structure on the surface of carbon fibers was immersed in a Tris solution of sodium dihydrogen phosphate (pH = 8.50) (sodium dihydrogen phosphate concentration in Tris solution was 40%), heated to 30°C, and held at 30°C for 10 min. The organic phase structure was then removed, washed with deionized water, and then immersed in a Tris solution of calcium carbonate (pH = 7.45) (calcium carbonate concentration in Tris solution was 40%), heated to 35°C, and held at 35°C for 13 min. Afterward, it was washed with deionized water. The organic phase structure was then immersed in a simulated body fluid containing octadecylamine polyoxyethylene ether bisquaternary ammonium salt (octadecylamine polyoxyethylene ether bisquaternary ammonium salt mass fraction in simulated body fluid was 5%) at 37°C for 15 min, resulting in a carbon fiber material with a petal-like HA mineralization layer.

[0074] Carbon fiber material containing an HA mineralization layer was composited with polyetheretherketone (PEEK) at a mass ratio of 50:45 to prepare a prepreg. The prepreg was then cut into appropriate sizes (12cm*8cm) and placed in a mold coated with a release agent. Compared with the PEEK film, the carbon fiber layup direction was 0°, and a hot pressing process was performed (pressure 5MPa, temperature 385℃, time 30min) to obtain a carbon fiber reinforced PEEK composite material with an organic-inorganic structure. The mass fractions of the release agent components were: emulsion 13%, methyl silicone oil emulsion 20%, modified silicone oil emulsion 8%, deionized water 52%, emulsifier 5.5%, additive 1.0%, and preservative 0.5%.

[0075] Example 2

[0076] 60g of completely desizing T-300 carbon fiber cloth was placed in a 500mL beaker containing 24g of dopamine and 300mL of deionized water. The mixture was magnetically stirred until fully dissolved, and then heated to 30℃ to allow the carbon fiber cloth to fully soak and react for 30 minutes, thereby constructing an organic phase structure on its surface.

[0077] 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.

[0078] The organic phase structure on the surface of carbon fibers was immersed in a Tris solution of diammonium hydrogen phosphate (pH = 8.50) (50% by mass of diammonium hydrogen phosphate in the Tris solution), heated to 38°C, and held at 38°C for 45 min. The organic phase structure was then removed, washed with deionized water, and then immersed in a Tris solution of calcium methacrylate (pH = 7.45) (50% by mass of calcium methacrylate in the Tris solution), heated to 42°C, and held at 42°C for 22 min. Afterward, it was washed with deionized water. The organic phase structure was then immersed in a simulated body fluid containing polysorbate 80 (8% by mass of polysorbate 80 in the simulated body fluid) at 40°C for 45 min, yielding a carbon fiber material with a fish-scale-like HA mineralization layer.

[0079] Carbon fiber material containing an HA mineralization layer was composited with polyetherketoneketone (PEKK) at a mass ratio of 52:44 to prepare a prepreg. The prepreg was then cut into appropriate sizes (12cm*8cm) and placed in a mold coated with a release agent. Compared with the PEVKK film, the carbon fiber layup direction was 0° and a hot pressing process was performed (pressure 6MPa, temperature 390℃, time 28min) to obtain a carbon fiber reinforced PEVKK composite material with an organic-inorganic structure. The mass fractions of the release agent components were: emulsion 15%, methyl silicone oil emulsion 18%, modified silicone oil emulsion 5%, deionized water 55%, emulsifier 5.5%, additive 1.0%, and preservative 0.5%.

[0080] Example 3

[0081] 90g of completely desizing T-300 carbon fiber cloth was placed in a 500mL beaker containing 36g of chitosan and 300mL of deionized water. The mixture was magnetically stirred until fully dissolved, and then heated to 55℃ to allow the carbon fiber cloth to fully soak and react for 60 minutes, thereby constructing an organic phase structure on its surface.

[0082] 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.

[0083] The organic phase structure on the surface of carbon fibers was immersed in a Tris solution of potassium phosphate (pH = 8.50) (potassium phosphate concentration in Tris solution was 60%), heated to 60°C, and held at 60°C for 50 min. The organic phase structure was then removed, washed with deionized water, and then immersed in a Tris solution of calcium salicylate (pH = 7.45) (calcium salicylate concentration in Tris solution was 55%), heated to 55°C, and held at 55°C for 30 min. Afterward, it was washed with deionized water. The organic phase structure was then immersed in a simulated body fluid containing sodium N-hydroxymethylglycinate (sodium N-hydroxymethylglycinate concentration in simulated body fluid was 12%) at 50°C for 32 min, yielding a carbon fiber material with a wheat-ear-shaped HA mineralized layer.

[0084] Carbon fiber material containing an HA mineralization layer was composited with polyetheretherketone ketone (PEEKK) at a mass ratio of 52:47 to prepare a prepreg. The prepreg was then cut into appropriate sizes (12cm*8cm) and placed in a mold coated with a release agent. Compared with the PEEKK film, the carbon fiber layup direction was 0°, and a hot pressing process was performed (pressure 5MPa, temperature 390℃, time 29min) to obtain a carbon fiber reinforced PEEKK composite material with an organic-inorganic structure. The mass fractions of the release agent components were: emulsion 13%, methyl silicone oil emulsion 19%, modified silicone oil emulsion 6%, deionized water 55%, emulsifier 5.8%, additive 0.9%, and preservative 0.3%.

[0085] Example 4

[0086] 150g of completely desizing T-300 carbon fiber cloth was placed in a 500mL beaker containing 60g of polycaprolactone and 300mL of deionized water. The mixture was magnetically stirred until fully dissolved, and then heated to 37℃ to allow the carbon fiber cloth to fully soak and react for 75 minutes, thereby constructing an organic phase structure on its surface.

[0087] 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.

[0088] The organic phase structure on the surface of carbon fibers was immersed in a Tris solution of ammonium phosphate (pH = 8.50) (70% by mass concentration of ammonium phosphate in the Tris solution), heated to 50°C, and held at 50°C for 55 min. The organic phase structure was then removed, washed with deionized water, and then immersed in a Tris solution of calcium propionate (pH = 7.45) (65% by mass concentration of calcium propionate in the Tris solution), heated to 46°C, and held at 46°C for 80 min. Afterward, it was washed with deionized water. The organic phase structure was then immersed in a simulated body fluid containing sodium dodecyl sulfate (15% by mass fraction of sodium dodecyl sulfate) at 66°C for 85 min, yielding a carbon fiber material with a granular HA mineralized layer.

[0089] Carbon fiber material containing an HA mineralization layer was composited with polyetherketone at a mass ratio of 54:48 to prepare a prepreg. The prepreg was then cut into appropriate sizes (12cm*8cm) and placed in a mold coated with a release agent. Compared with the polyetherketone film, the carbon fiber layup direction was 0° and a hot pressing process was performed (pressure 5MPa, temperature 397℃, time 27min) to obtain a carbon fiber reinforced polyetherketone composite material with an organic-inorganic structure. The mass fractions of the release agent components were: emulsion 14%, methyl silicone oil emulsion 18%, modified silicone oil emulsion 7%, deionized water 54%, emulsifier 5.5%, additive 1.0%, and preservative 0.5%.

[0090] The mechanical properties of the carbon fiber reinforced polyaryletherketone composites containing organic-inorganic structures prepared in Examples 1-4 were tested. Each composite material was 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, the method of the present invention can both accelerate the growth rate of hydroxyapatite on carbon fiber cloth and enable the composite material to possess excellent mechanical properties.

[0091] Table 1. Mechanical property data of composite materials in Examples 1-4

[0092]

[0093]

[0094] The morphology of the hydroxyapatite mineralized layers obtained in Examples 1-3 was characterized, and the scanning electron microscope images are shown below. Figures 1-3 As shown. By Figure 1 It can be seen that the morphology of the HA mineralized layer obtained in Example 1 is a petal-like structure, which effectively increases the specific surface area of ​​the HA mineralized layer; Figure 2 It can be seen that the morphology of the HA mineralized layer obtained in Example 2 is a fish-scale structure, which effectively increases the specific surface area of ​​the HA mineralized layer; Figure 3 It is known that the morphology of the HA mineralized layer obtained in Example 3 is a wheat ear-like structure, which effectively increases the specific surface area of ​​the HA mineralized layer.

[0095] EDS and XRD analyses were performed on the HA mineralization layer of Example 1, and the results are as follows: Figure 4 , Figure 5 As shown. By Figure 4 , Figure 5 It can be seen that a hydroxyapatite mineralization layer was successfully formed on the surface of the carbon fiber.

[0096] The bioactivity and biocompatibility of the carbon fiber reinforced polyetheretherketone composite material containing an organic-inorganic structure from Example 1 were tested compared with the control group. The test results are as follows: Figure 6 As shown. By Figure 6 It can be seen that the composite material prepared in Example 1 has excellent bioactivity and biocompatibility compared with the control group (composite material prepared by directly combining commercial T-300 carbon fiber with polyether ether ketone after desizing).

[0097] The specific process method for bioactivity testing is as follows:

[0098] T-300 carbon fiber cloth (CF cloth) with an organic phase structure was immersed in simulated body fluids containing the aforementioned different surfactants for biomineralization. Subsequently, it was placed in a water bath at 37.5℃ for different growth times. The samples were then removed, bagged, and stored for later use. During the experiment, SEM observation showed that the HA content of the biomineralized CF cloth surface increased with increasing immersion time in the simulated body fluids, demonstrating that the prepared material possesses good bioactivity.

[0099] The specific process for biocompatibility testing is as follows:

[0100] 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 / well, place the UCF / PEEK composite material and CF-HA / PEEK composite material extracts in an incubator (37℃, 5% CO2) for 1 day, 3 days, and 5 days respectively. Add complete culture medium containing 10% CCK-8 to each well (incubate in the dark), and after 1 hour, use a microplate reader to detect the absorbance values ​​of each group at a wavelength of 450nm. The CCK-8 test results are as follows. Figure 6 As shown. By Figure 6It was found that with the extension of cell culture time, the absorbance value of cells in the CF-HA / PEEK composite extract was greater than that of the control group UCF / PEEK composite, and the absorbance of the CF-HA / PEEK composite showed an increasing trend (P<0.05). This indicates that the CF-HA / PEEK composite is non-cytotoxic, the cells in the extract continued to proliferate and grow, and the CF-HA / PEEK composite has good biocompatibility.

[0101] 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 preparing hydroxyapatite carbon fiber material, characterized in that, It includes the following steps: 1) React carbon fiber cloth and organic template to obtain carbon fiber cloth with organic phase; 2) The carbon fiber cloth with organic phase was sequentially immersed in a soluble phosphate solution, a calcium compound solution, and a simulated body fluid containing a surfactant to obtain hydroxyapatite carbon fiber material; The simulated body fluid containing surfactants is anionic surfactant-type simulated body fluid, cationic surfactant-type simulated body fluid, nonionic surfactant-type simulated body fluid, or zwitterionic surfactant-type simulated body fluid; the cationic surfactant is octadecyl diester quaternary ammonium salt, octadecylamine polyoxyethylene ether bisquaternary ammonium salt, hexadecyl alcohol polyoxyethylene ether dimethyl octyl ammonium chloride, cationic gemini emulsifier, or dodecyl polyoxyethylene ammonium bromide. Organic templates include dopamine, sericin, spider silk, polycaprolactone, polylactic acid, chitosan, gelatin, or collagen. The mass fraction of surfactant in the simulated body fluid containing surfactant is 2-30%.

2. The preparation method according to claim 1, characterized in that, In step 1), the mass ratio of organic template to carbon fiber cloth is 6~10:20~22; the organic template is an aqueous solution of organic template; the mass fraction of organic template in the aqueous solution of organic template is 1~30%; The reaction temperature is 10~90℃, and the reaction time is 5~60min.

3. The preparation method according to claim 1 or 2, characterized in that, In step 2), the soluble phosphate is one or more of the following: sodium dihydrogen phosphate, disodium hydrogen phosphate, sodium phosphate, potassium dihydrogen phosphate, dipotassium hydrogen phosphate, potassium phosphate, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, and ammonium phosphate. The calcium-containing compound is one or more of calcium chloride, calcium propionate, calcium lignosulfonate, and calcium methacrylate; The mass concentration of soluble phosphate in soluble phosphate solutions is 30-90%, and the mass concentration of calcium compounds in calcium-containing compound solutions is 30-80%.

4. The preparation method according to claim 3, characterized in that, The temperatures of the soluble phosphate solution, the calcium compound solution, and the simulated body fluid containing surfactants were independently 10–90 °C. The immersion times of the carbon fiber cloth constructing the organic phase in the soluble phosphate solution and the calcium compound solution were independently 5–60 min, and the immersion time in the simulated body fluid containing surfactants was 12–16 min.

5. The preparation method according to claim 4, characterized in that, The anionic surfactants in the simulated body fluids of anionic surfactant type are sulfonates, sulfates, or sulfate esters; the nonionic surfactants in the simulated body fluids of nonionic surfactant type are polyoxyethylene type, polyol type, alkanolamide type, polyether type, or amine oxide type; and the amphoteric surfactants in the simulated body fluids of zwitterionic surfactant type are betaine type or sodium organic acid type.

6. The preparation method according to claim 5, characterized in that, Anionic surfactants are succinate sulfonates, alkylbenzene sulfonates, alkyl sulfonates, sodium dodecyl sulfate, alkylnaphthalene sulfonates, petroleum sulfonates, alkylsulfonic acid acetamides, alkyl succinate sulfonates, alkanolamine alkylbenzene sulfonates, naphthenates, or alkylphenol sulfonates; The nonionic surfactant is a fatty acid monoglyceride, a fatty acid monostearate, a fatty acid sorbitan, a polysorbate, a polyoxyethylene fatty acid ester, a polyoxyethylene fatty alcohol ether, or a polyoxyethylene-polyoxypropylene copolymer. The zwitterionic surfactants are lauryl betaine, sodium dodecylaminopropionate, alkyl dimethyl betaine, alkyl dimethyl hydroxypropyl phosphate betaine, alkyl di(aminoethyl)glycine, sodium N-hydroxymethylglycinate, disodium iminodipropionate, betaine, citrate betaine, cocamidopropyl betaine, sodium lauroylamphoteric acid, or lauroamide propyl betaine.

7. The hydroxyapatite carbon fiber material prepared by the preparation method according to any one of claims 1 to 6, characterized in that, In hydroxyapatite carbon fiber materials, the mass ratio of organic template, carbon fiber and hydroxyapatite is 6~10:20~22:20~24.

8. A hydroxyapatite bone repair biocomposite material comprising the hydroxyapatite carbon fiber material of claim 7, characterized in that, The hydroxyapatite bone repair biocomposite material is prepared from hydroxyapatite carbon fiber material and polyaryletherketone in a mass ratio of 46~56:42~50; wherein the polyaryletherketone is polyetheretherketoneketone, polyetherketoneketone, polyetheretherketone, polyetherketone or polyetherketoneetherketone.

9. The method for preparing the hydroxyapatite bone repair biocomposite material according to claim 8, characterized in that, Hydroxyapatite carbon fiber material is combined with polyaryletherketone to obtain a prepreg; the prepreg is then hot-pressed to obtain a hydroxyapatite bone repair biocomposite material.

10. The application of the hydroxyapatite bone repair biocomposite material according to claim 8 in the preparation of materials for repairing bone tissue defects.

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