PEEK composite material with biocompatibility and preparation method thereof

Abstract

The invention discloses a PEEK composite material with biocompatibility and a preparation method thereof, and belongs to the technical field of PEEK composite materials. The PEEK composite material is prepared from the following raw materials in parts by mass: 100 parts of sulfonated polyether ether ketone, 20 to 40 parts of furan heterocyclic polyarylethersulfone ketone and 5 to 15 parts of Ti3C2TX-SF modified carbon fibers, the furan heterocyclic polyarylether sulphone ketone is a product synthesized through a reaction of 6-(4-hydroxy-3-methoxyphenyl) pyridazine-3 (2H)-ketone, 4, 4 '-difluorodiphenyl sulfone and furyl difluorodiphenyl ketone. The Ti3C2TX-SF modified carbon fiber is obtained by dipping a polydopamine modified carbon fiber in a silk fibroin modified Ti3C2TX material dispersion liquid for surface modification treatment. According to the antibacterial PEEK composite material disclosed by the invention, sulfonated polyetheretherketone is taken as a matrix, and furan heterocyclic polyarylethersulfone ketone and Ti3C2TX-SF modified carbon fibers are added, so that the PEEK composite material has excellent antibacterial performance.

Description

Technical Field

[0001] This invention belongs to the field of PEEK composite material technology, specifically relating to a biocompatible PEEK composite material and its preparation method. Background Technology

[0002] With the increasingly stringent requirements of advanced manufacturing for material performance, traditional metal materials and general-purpose plastics can no longer meet the demanding requirements in terms of lightweighting, high temperature resistance, corrosion resistance, and long service life. Against this backdrop, the semi-crystalline thermoplastic polymer polyether ether ketone (PEEK) has emerged, whose aromatic rings and ketone bonds in its molecular structure endow it with extremely high mechanical strength, thermal stability, and chemical stability.

[0003] Due to the excellent properties of PEEK, polyetheretherketone (PEEK) composites are widely used in aerospace, precision manufacturing, and medical fields, especially in orthopedics, dentistry, and spinal surgery. PEEK itself has good biocompatibility, exhibiting excellent biocompatibility both in vivo and in vitro, including low cytotoxicity, good blood compatibility, and high resistance to gamma rays and electron beam radiation.

[0004] Although PEEK possesses a certain degree of biocompatibility, its surface hydrophobicity and bioinertness still limit its further application in the medical field, exhibiting performance deficiencies compared to traditional materials such as titanium alloys. To improve the bioinertness of PEEK materials, introducing other materials into the PEEK matrix to prepare PEEK composites is a common method. Currently, the materials introduced are mostly biocompatible inorganic materials such as carbon fiber, glass fiber, and hydroxyapatite. These PEEK composites can meet the biocompatibility and mechanical property requirements of medical materials, but their antibacterial properties are difficult to achieve in the complex environment of diverse bacterial communities. Therefore, improving the antibacterial properties of PEEK composites is an urgent problem to be solved. Summary of the Invention

[0005] This invention provides a biocompatible PEEK composite material and its preparation method, which can solve the problem of weak antibacterial ability of PEEK composite materials in the prior art.

[0006] The objective of this invention can be achieved through the following technical solutions: A biocompatible PEEK composite material, comprising the following raw materials by weight: 100 parts sulfonated polyether ether ketone, 20-40 parts furan heterocyclic polyaryl ether sulfone ketone, 5-15 parts Ti3C2T X -SF modified carbon fiber; The furanyl heterocyclic polyarylene ether sulfone ketone is a product synthesized by reaction of 6-(4-hydroxy-3-methoxyphenyl)pyridazine-3(2H)-one, 4,4′-difluorodiphenyl sulfone and furanyldifluorodiphenyl ketone; The Ti3C2T X -SF modified carbon fiber is made by impregnating polydopamine-modified carbon fiber with silk fibroin-modified Ti3C2T. X Obtained by surface modification treatment in a material dispersion; The structural formula of furanyl difluorobenzophenone is as follows: .

[0007] Polyetheretherketone (PEEK) has a stable structure, but its surface inertness makes it difficult to react directly with other materials. This invention uses sulfonated PEEK instead of conventional PEEK, introducing hydrophilic sulfonic acid groups into the main chain of the sulfonated PEEK. This provides active sites for reaction with other materials, and the sulfonic acid groups can disrupt bacterial cell membranes through electrostatic interactions, exhibiting antibacterial properties. Based on the sulfonated PEEK matrix, furan-heterocyclic polyarylene ether sulfone ketone is added. Unlike other polyarylene ether ketone compounds, its molecular chain structure contains furan rings, pyridazine rings, methoxy groups, and sulfone groups, giving the polymer better hydrophilicity and antibacterial properties. Furan-heterocyclic polyarylene ether sulfone ketone also possesses excellent heat resistance. While ensuring the thermal stability of the PEEK material, furan-heterocyclic polyarylene ether sulfone ketone serves as a functional bridging material. With good compatibility with the PEEK matrix, the polar groups on the molecular chain interact with Ti3C2T... X -SF-modified carbon fibers form a multi-hydrogen bond network structure, promoting the formation of Ti3C2T X -SF-modified carbon fibers are uniformly dispersed in the system. Ti3C2T X -SF modified carbon fiber as the reinforcing phase, Ti3C2T X Ti3C2T is a novel two-dimensional material with antibacterial activity. Silk fibroin (SF) is a natural material with excellent biocompatibility and biodegradability. X The bonding force between Ti3C2T and polydopamine-modified carbon fibers is not strong, and they are prone to detachment and aggregation during processing, resulting in a less than expected antibacterial effect and affecting the overall mechanical properties of the material. This invention first uses Ti3C2T... X When combined with silk fibroin (SF) and then bonded to polydopamine (PDA)-modified carbon fibers, the amino and carboxyl functional groups on the silk fibroin molecular chain can react with the PDA layer to form Ti3C2T X -SF is firmly grafted onto the carbon fiber surface in the form of covalent bonds, ensuring the stability of the composite material during processing.

[0008] Furthermore, the preparation steps of the sulfonated polyether ether ketone are as follows: PEEK powder was added to concentrated sulfuric acid and heated to 50-70℃. The mixture was stirred at a constant temperature for 4-6 hours. After the reaction was completed, it was added to an ice-water mixture, stirred evenly, and allowed to stand overnight. The mixture was then washed with deionized water until neutral and dried to obtain sulfonated polyether ether ketone.

[0009] Furthermore, the concentrated sulfuric acid has a mass fraction of 98%; The ratio of PEEK powder to concentrated sulfuric acid is 2-5g:100mL.

[0010] Furthermore, the preparation steps of the furan heterocyclic polyaryl ether sulfone ketone are as follows: 6-(4-hydroxy-3-methoxyphenyl)pyridazine-3(2H)-one, 4,4′-difluorodiphenyl sulfone, furanyldifluorobenzophenone, potassium carbonate, sulfolane, and toluene were added to a flask. The mixture was heated to 135-140℃ under a nitrogen atmosphere and stirred at a constant temperature for 2-3 hours. The temperature was then increased to 150-160℃ and stirred for 8-12 hours. After the reaction was completed, sulfolane was added and stirred to dilute the mixture to form a solution. The solution was then poured into a dilute hydrochloric acid solution at 50-80℃ to precipitate the precipitate. The precipitate was washed with water and dried to obtain furanyl heterocyclic polyarylene ether sulfone ketone.

[0011] Further, the molar ratio of 6-(4-hydroxy-3-methoxyphenyl)pyridazine-3(2H)-one, 4,4′-difluorodiphenyl sulfone, and furanyldifluorobenzophenone is 2.0-2.1:1:1; The molar ratio of potassium carbonate to 6-(4-hydroxy-3-methoxyphenyl)pyridazine-3(2H)-one is 1.4-1.6:1; the ratio of 6-(4-hydroxy-3-methoxyphenyl)pyridazine-3(2H)-one to sulfolane is 20-50 g: 250 mL; and the volume ratio of sulfolane to toluene is 1-1.6:5.

[0012] This invention increases the proportion of bio-based raw materials in the preparation of furan-based heterocyclic polyarylene ether sulfones. 6-(4-hydroxy-3-methoxyphenyl)pyridazine-3(2H)-one is a guaiacol derivative, and furanyl difluorobenzophenone is a derivative containing a furan ring, both derived from bio-based compounds, significantly improving the product's biocompatibility. The prepared product's molecular chain structure contains furan rings, pyridazine rings, methoxy groups, and sulfone groups, giving it both excellent antibacterial properties and high thermal stability. The increased polar groups allow the furan-based heterocyclic polyarylene ether sulfone to act as an intermediate material, compatible with sulfonated polyether ether ketones and Ti3C2T. X -SF modified carbon fiber adjusts the overall antibacterial properties, mechanical properties and thermal stability of the material.

[0013] The reaction formula for preparing the furan heterocyclic polyarylene ether sulfone ketone is as follows: .

[0014] Furthermore, the preparation steps of the furanyl difluorobenzophenone are as follows: 2,5-furandicarboxylic acid chloride and fluorobenzene were added to a flask, stirred and dissolved, and then placed in an ice bath. Aluminum chloride was slowly added dropwise. After the addition was complete, the mixture was stirred until homogeneous. The temperature was raised to 70-75℃ and stirred for 10-12 hours. The mixture was then cooled to room temperature and poured into a methanol solution. The precipitate was filtered, dried, and recrystallized to obtain furanyl difluorobenzophenone.

[0015] Furthermore, the molar ratio of 2,5-furandicarboxylic acid chloride to fluorobenzene is 1:3.0-3.2; The molar ratio of aluminum chloride to 2,5-furandicarboxylic acid chloride is 2.8-3.0:1.

[0016] The reaction formula for the preparation of furanyl difluorobenzophenone is as follows: .

[0017] Furthermore, the Ti3C2T X The preparation steps for SF modified carbon fiber are as follows: Step 1: Preparation of Ti3C2T X -SF material: a single layer of Ti3C2T X Nanosheets and silk fibroin were dispersed in deionized water to obtain a suspension. EDC and DMAP were added to the suspension as catalysts. Under a nitrogen atmosphere, the system was stirred at 60-70℃ for 2-3 hours to obtain silk fibroin-modified Ti3C2T. X The material, namely Ti3C2T X -SF material; Step 2: Preparation of polydopamine-modified carbon fibers: Prepare a dopamine hydrochloride solution, immerse the carbon fibers in the dopamine hydrochloride solution, sonicate for 0.5-1 h, add Tris buffer to adjust the pH to 8.5, stir at room temperature for 5-6 h, wash and dry to obtain polydopamine-modified carbon fibers. Step 3: Preparation of Ti3C2T X -SF modified carbon fiber: Polydopamine-modified carbon fiber was dispersed in deionized water to obtain a dispersion, and Ti3C2T X -SF material was added to the dispersion and stirred at room temperature for 12-24 hours. After filtration, washing, and drying, Ti3C2T was obtained. X -SF modified carbon fiber.

[0018] Single-layer Ti3C2T X Nanosheets tend to aggregate in polymer matrices and have weak adhesion to carbon fiber surfaces. However, under the catalysis of EDC and DMAP, the carboxyl groups on the silk fibroin molecular chains bond with monolayer Ti3C2T... XThe hydroxyl groups (-OH) on the surface of the nanosheets undergo esterification to yield Ti3C2T. X -SF material, SF chemical grafting on monolayer Ti3C2T X Compared to physically adsorbed structures, nanosheets exhibit a more robust surface adhesion. Dopamine self-polymerizes and deposits on the carbon fiber surface to obtain polydopamine-modified carbon fibers. The carbon fiber surface contains a polydopamine layer, and the abundant amino, carboxyl, and hydroxyl groups on the SF molecular chain enable it to form strong covalent / non-covalent bonds with the PDA layer. (Ti3C2T) X -SF material is anchored on carbon fiber to obtain Ti3C2T X -SF modified carbon fiber. The modified carbon fiber has a rougher surface, and the organic layers of polydopamine and silk fibroin can form a hydrogen bond network with the polymer, thereby improving interfacial compatibility. Ti3C2T X -SF modified carbon fiber has good biocompatibility and can endow the material with excellent antibacterial and mechanical properties.

[0019] Furthermore, the monolayer Ti3C2T X The nanosheets were prepared by chemical etching and had a diameter of 1-10 μm.

[0020] Furthermore, in step 1, the monolayer Ti3C2T X The mass ratio of nanosheets, silk fibroin, and deionized water is 5:(1.0-2.5):100.

[0021] Furthermore, the mass ratio of the EDC to the DMAP is 1:1; The EDC is a single-layer Ti3C2T X 10-20% of the mass of nanosheets.

[0022] Furthermore, the concentration of the dopamine hydrochloride solution is 0.01-0.03 mol / L.

[0023] Furthermore, the concentration of the Tris buffer is 0.01 mol / L.

[0024] Furthermore, in step 3, the concentration of polydopamine-modified carbon fibers in the dispersion is 20-50 g / L; The Ti3C2T X -The mass ratio of SF material to polydopamine-modified carbon fiber is 15-25:100.

[0025] This invention also provides a method for preparing a biocompatible PEEK composite material, which includes the following steps: Step 1: Prepare the raw materials according to the proportions, including sulfonated polyether ether ketone, furan heterocyclic polyarylene ether sulfone ketone, and Ti3C2T. X- SF modified carbon fiber is mixed to obtain a mixture; Step 2: Melt extrusion granulation of the mixture to obtain PEEK composite material.

[0026] The beneficial effects of this invention are: (1) This invention addresses the problem of poor antibacterial performance of polyether ether ketone composites by combining polyether ether ketone bulk modification and the addition of reinforcing materials. Sulfonated polyether ether ketone is used as the matrix material. The hydrophilic sulfonic acid groups introduced on its main chain not only provide reactive sites for binding with reinforcing materials but also disrupt the structure of bacterial cell membranes through electrostatic adsorption, thus endowing the material with basic antibacterial capabilities. This invention designs and synthesizes furan heterocyclic polyarylene ether sulfone ketone. The polymer molecular chain contains functional groups such as furan rings, pyridazine heterocycles, and methoxy groups, enhancing the hydrophilicity and antibacterial activity of the material. This invention utilizes the two-dimensional material Ti3C2T with excellent antibacterial properties... X Ti3C2T was prepared by chemically bonding it firmly to the surface of carbon fibers. X -SF modified carbon fiber, Ti3C2T X - SF modified carbon fiber, together with sulfonated polyether ether ketone and furan heterocyclic polyarylether sulfone ketone, forms an antibacterial network from the matrix to the reinforcing material. PEEK composite materials have excellent antibacterial and mechanical properties.

[0027] (2) Based on the problem of uneven dispersion of inorganic materials in polymer matrix in the prior art, the present invention designs and prepares Ti3C2T X -SF modified carbon fiber, with silk fibroin molecules chemically grafted onto a single layer of Ti3C2T via esterification. X On the surface of nanosheets, dopamine self-polymerizes and deposits on the carbon fiber surface, utilizing the abundant active groups on the SF molecular chain to form a strong covalent / non-covalent bond with the PDA layer, Ti3C2T X -SF material is anchored onto carbon fiber, Ti3C2T X - SF-modified carbon fibers can form hydrogen bond networks with polymers; on the other hand, furan heterocyclic polyarylene ether sulfone ketones are used as intermediate bridging materials, whose polar functional groups on the molecular chain can interact with sulfonated polyether ether ketones and Ti3C2T. X - The active groups on the surface of SF modified carbon fibers form a multi-hydrogen bond network structure, which improves interfacial compatibility and effectively promotes the uniform dispersion of modified carbon fibers in the matrix.

[0028] (3) This invention improves the material properties while optimizing the biocompatibility of the material, and prepares furan heterocyclic polyarylene ether sulfone ketone and Ti3C2T X -SF modified carbon fiber uses bio-based derivatives as raw materials, which improves the affinity of the material when in contact with biological tissues. Detailed Implementation

[0029] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0030] Preparation Example

[0031] Preparation Example 1

[0032] Preparation of sulfonated polyether ether ketone: Weigh 3g of PEEK powder and add it to 100mL of concentrated sulfuric acid (98% by mass). Heat the mixture to 60℃ and stir for 5 hours. After the reaction is complete, add the mixture to an ice-water mixture, stir evenly, and let stand overnight. Wash with deionized water until neutral and dry to obtain sulfonated polyether ether ketone with a sulfonation degree of 46.9%.

[0033] Preparation Example 2

[0034] Preparation of furanyl difluorobenzophenone: Weigh 192.98 g (1 mol) of 2,5-furandicarboxylic acid chloride and 288.31 g (3 mol) of fluorobenzene into a flask, stir to dissolve, and place in an ice bath. Slowly add 389.69 g (2.9 mol) of aluminum chloride. After the addition is completed in 30 min, stir until homogeneous, heat to 70 °C and stir for 12 h. Cool to room temperature, pour into methanol solution, filter to precipitate, dry, and recrystallize with toluene and n-hexane to obtain furanyl difluorobenzophenone.

[0035] Preparation of furan heterocyclic polyarylene ether sulfones: Weigh 21.8210 g (0.10 mol) 6-(4-hydroxy-3-methoxyphenyl)pyridazine-3(2H)-one, 12.7125 g (0.05 mol) 4,4′-difluorodiphenyl sulfone, 15.6135 g (0.05 mol) furanyldifluorobenzophenone, 20.7315 g (0.15 mol) potassium carbonate, 50 mL sulfolane, and 200 mL toluene into a flask. Under a nitrogen atmosphere, heat to 135 °C and stir for 3 h. Then heat to 160 °C and stir for 10 h. After the reaction is complete, add 100 mL sulfolane and stir to dilute and form a solution. Pour the solution into a 1 M dilute hydrochloric acid solution at 50 °C to precipitate. Filter to collect the precipitate, wash three times with hot water, and dry to obtain furanyl heterocyclic polyarylene ether sulfone ketone.

[0036] Preparation Example 3

[0037] Preparation of Ti3C2T X -SF modified carbon fiber: Step 1: Preparation of Ti3C2TX -SF material: Weigh out 50g of single-layer Ti3C2T X Nanosheets (prepared by chemical etching, with a diameter of 1-10 μm) and 20 g of silk fibroin were added to 1 L of deionized water and ultrasonically dispersed for 30 min to obtain a suspension. 5 g of EDC and 5 g of DMAP were added to the suspension as catalysts. Under a nitrogen atmosphere, the mixture was heated to 60 °C and stirred for 3 h to obtain silk fibroin-modified Ti3C2T. X The material, namely Ti3C2T X -SF material.

[0038] Step 2: Preparation of polydopamine-modified carbon fibers: Prepare a 0.01 mol / L dopamine hydrochloride solution, immerse the carbon fibers in the dopamine hydrochloride solution, sonicate for 1 h, add 0.01 mol / L Tris buffer to adjust the pH to 8.5, stir at room temperature for 6 h, wash with deionized water and dry to obtain polydopamine-modified carbon fibers.

[0039] Step 3: Preparation of Ti3C2T X -SF modified carbon fiber: Weigh 30g of polydopamine-modified carbon fiber and add it to 1L of deionized water. Sonicate for 30min to obtain a dispersion. Weigh 6g of Ti3C2T X -SF material was added to the dispersion, stirred at room temperature for 24 hours, filtered, washed with deionized water, and dried to obtain Ti3C2T. X -SF modified carbon fiber.

[0040] Preparation Example 4

[0041] Preparation of Ti3C2T X -SF modified carbon fiber: Step 1: Preparation of Ti3C2T X -SF material: Weigh out 50g of single-layer Ti3C2T X Nanosheets (prepared by chemical etching, with a diameter of 1-10 μm) and 10 g of silk fibroin were added to 1 L of deionized water and ultrasonically dispersed for 30 min to obtain a suspension. 5 g of EDC and 5 g of DMAP were added to the suspension as catalysts. Under a nitrogen atmosphere, the mixture was heated to 60 °C and stirred for 3 h to obtain silk fibroin-modified Ti3C2T. X The material, namely Ti3C2T X -SF material.

[0042] Step 2: Preparation of polydopamine-modified carbon fibers: Prepare a 0.01 mol / L dopamine hydrochloride solution, immerse the carbon fibers in the dopamine hydrochloride solution, sonicate for 1 h, add 0.01 mol / L Tris buffer to adjust the pH to 8.5, stir at room temperature for 6 h, wash with deionized water and dry to obtain polydopamine-modified carbon fibers.

[0043] Step 3: Preparation of Ti3C2T X -SF modified carbon fiber: Weigh 30g of polydopamine-modified carbon fiber and add it to 1L of deionized water. Sonicate for 30min to obtain a dispersion. Weigh 6g of Ti3C2T X -SF material was added to the dispersion, stirred at room temperature for 24 hours, filtered, washed with deionized water, and dried to obtain Ti3C2T. X -SF modified carbon fiber.

[0044] Preparation Example 5

[0045] Preparation of Ti3C2T X -SF modified carbon fiber: Step 1: Preparation of Ti3C2T X -SF material: Weigh out 50g of single-layer Ti3C2T X Nanosheets (prepared by chemical etching, with a diameter of 1-10 μm) and 25 g of silk fibroin were added to 1 L of deionized water and ultrasonically dispersed for 30 min to obtain a suspension. 5 g of EDC and 5 g of DMAP were added to the suspension as catalysts. Under a nitrogen atmosphere, the mixture was heated to 60 °C and stirred for 3 h to obtain silk fibroin-modified Ti3C2T. X The material, namely Ti3C2T X -SF material.

[0046] Step 2: Preparation of polydopamine-modified carbon fibers: Prepare a 0.01 mol / L dopamine hydrochloride solution, immerse the carbon fibers in the dopamine hydrochloride solution, sonicate for 1 h, add 0.01 mol / L Tris buffer to adjust the pH to 8.5, stir at room temperature for 6 h, wash with deionized water and dry to obtain polydopamine-modified carbon fibers.

[0047] Step 3: Preparation of Ti3C2T X -SF modified carbon fiber: Weigh 30g of polydopamine-modified carbon fiber and add it to 1L of deionized water. Sonicate for 30min to obtain a dispersion. Weigh 6g of Ti3C2T X -SF material was added to the dispersion, stirred at room temperature for 24 hours, filtered, washed with deionized water, and dried to obtain Ti3C2T. X -SF modified carbon fiber.

[0048] Preparation Example 6

[0049] Preparation of Ti3C2T X -SF modified carbon fiber: Step 1: Preparation of Ti3C2T X -SF material: Weigh out 50g of single-layer Ti3C2T XNanosheets (prepared by chemical etching, with a diameter of 1-10 μm) and 10 g of silk fibroin were added to 1 L of deionized water and ultrasonically dispersed for 30 min to obtain a suspension. 5 g of EDC and 5 g of DMAP were added to the suspension as catalysts. Under a nitrogen atmosphere, the mixture was heated to 60 °C and stirred for 3 h to obtain silk fibroin-modified Ti3C2T. X The material, namely Ti3C2T X -SF material.

[0050] Step 2: Preparation of polydopamine-modified carbon fibers: Prepare a 0.01 mol / L dopamine hydrochloride solution, immerse the carbon fibers in the dopamine hydrochloride solution, sonicate for 1 h, add 0.01 mol / L Tris buffer to adjust the pH to 8.5, stir at room temperature for 6 h, wash with deionized water and dry to obtain polydopamine-modified carbon fibers.

[0051] Step 3: Preparation of Ti3C2T X -SF modified carbon fiber: Weigh 30g of polydopamine-modified carbon fiber and add it to 1L of deionized water. Sonicate for 30min to obtain a dispersion. Weigh 4.5g of Ti3C2T X -SF material was added to the dispersion, stirred at room temperature for 24 hours, filtered, washed with deionized water, and dried to obtain Ti3C2T. X -SF modified carbon fiber.

[0052] Preparation Example 7

[0053] Preparation of Ti3C2T X -SF modified carbon fiber: Step 1: Preparation of Ti3C2T X -SF material: Weigh out 50g of single-layer Ti3C2T X Nanosheets (prepared by chemical etching, with a diameter of 1-10 μm) and 10 g of silk fibroin were added to 1 L of deionized water and ultrasonically dispersed for 30 min to obtain a suspension. 5 g of EDC and 5 g of DMAP were added to the suspension as catalysts. Under a nitrogen atmosphere, the mixture was heated to 60 °C and stirred for 3 h to obtain silk fibroin-modified Ti3C2T. X The material, namely Ti3C2T X -SF material.

[0054] Step 2: Preparation of polydopamine-modified carbon fibers: Prepare a 0.01 mol / L dopamine hydrochloride solution, immerse the carbon fibers in the dopamine hydrochloride solution, sonicate for 1 h, add 0.01 mol / L Tris buffer to adjust the pH to 8.5, stir at room temperature for 6 h, wash with deionized water and dry to obtain polydopamine-modified carbon fibers.

[0055] Step 3: Preparation of Ti3C2T X-SF modified carbon fiber: Weigh 30g of polydopamine-modified carbon fiber and add it to 1L of deionized water. Sonicate for 30min to obtain a dispersion. Weigh 7.5g of Ti3C2T X -SF material was added to the dispersion, stirred at room temperature for 24 hours, filtered, washed with deionized water, and dried to obtain Ti3C2T. X -SF modified carbon fiber.

[0056] Example 1

[0057] Preparation of biocompatible PEEK composite materials: Step 1: Prepare 100 parts by weight of the sulfonated polyether ether ketone prepared in Preparation Example 1, 30 parts by weight of the furan heterocyclic polyarylene ether sulfone ketone prepared in Preparation Example 2, and 10 parts by weight of the Ti3C2T prepared in Preparation Example 3. X -SF modified carbon fiber, incorporating sulfonated polyether ether ketone, furan heterocyclic polyarylene ether sulfone ketone, and Ti3C2T X -SF modified carbon fiber is mixed to obtain a mixture.

[0058] Step 2: The mixture is fed into a screw extruder, and the melting temperature is set as follows: Zone 1 320-340℃, Zone 2 350-360℃, Zone 3 360-370℃. The mixture is melt-extruded and granulated to obtain the PEEK composite material.

[0059] Example 2

[0060] The only difference from Example 1 is that the mass fraction of furan heterocyclic polyarylene ether sulfone ketone prepared in Preparation Example 2 is adjusted to 20 parts, while the other conditions and steps are the same as in Example 1.

[0061] Example 3

[0062] The only difference from Example 1 is that the mass fraction of furan heterocyclic polyarylene ether sulfone ketone prepared in Preparation Example 2 is adjusted to 40 parts, while the other conditions and steps are the same as in Example 1.

[0063] Example 4

[0064] The only difference from Example 1 is that the Ti3C2T prepared in Preparation Example 4 was used. X - Example 3: Preparation of Ti3C2T by SF-modified carbon fiber as an equivalent mass substitute X -SF modified carbon fiber, other conditions and steps are the same as in Example 1.

[0065] Example 5

[0066] The only difference from Example 1 is that the Ti3C2T prepared in Preparation Example 5 was used. X - Example 3: Preparation of Ti3C2T by SF-modified carbon fiber as an equivalent mass substitute X -SF modified carbon fiber, other conditions and steps are the same as in Example 1.

[0067] Example 6

[0068] The only difference from Example 1 is that the Ti3C2T prepared in Preparation Example 6 was used. X - Example 3: Preparation of Ti3C2T by SF-modified carbon fiber as an equivalent mass substitute X -SF modified carbon fiber, other conditions and steps are the same as in Example 1.

[0069] Example 7

[0070] The only difference from Example 1 is that the Ti3C2T prepared in Preparation Example 7 was used. X - Example 3: Preparation of Ti3C2T by SF-modified carbon fiber as an equivalent mass substitute X -SF modified carbon fiber, other conditions and steps are the same as in Example 1.

[0071] Example 8

[0072] The only difference from Example 1 is that the Ti3C2T prepared in Preparation Example 3 is used instead. X - The mass fraction of SF modified carbon fiber was adjusted to 5 parts, and other conditions and steps were the same as in Example 1.

[0073] Example 9

[0074] The only difference from Example 1 is that the Ti3C2T prepared in Preparation Example 3 is used instead. X - The mass fraction of SF modified carbon fiber was adjusted to 15 parts, and other conditions and steps were the same as in Example 1.

[0075] Comparative Example 1

[0076] The only difference from Example 1 is that the polyether ether ketone is not sulfonated.

[0077] Preparation of biocompatible PEEK composite materials: Step 1: Prepare 100 parts by weight of polyetheretherketone, 30 parts by weight of furan heterocyclic polyarylene ether sulfone ketone prepared in Preparation Example 2, and 10 parts by weight of Ti3C2T prepared in Preparation Example 3. X -SF modified carbon fiber, incorporating polyetheretherketone, furan heterocyclic polyarylethersulfone ketone, and Ti3C2T X -SF modified carbon fiber is mixed to obtain a mixture.

[0078] Step 2: The mixture is fed into a screw extruder, and the melting temperature is set as follows: Zone 1 320-340℃, Zone 2 350-360℃, Zone 3 360-370℃. The mixture is melt-extruded and granulated to obtain the PEEK composite material.

[0079] Comparative Example 2

[0080] The only difference from Example 1 is that furan heterocyclic polyarylether sulfone ketone is not added.

[0081] Preparation of biocompatible PEEK composite materials: Step 1: Prepare 100 parts by weight of the sulfonated polyether ether ketone prepared in Preparation Example 1 and 10 parts by weight of the Ti3C2T prepared in Preparation Example 3. X -SF modified carbon fiber, combining sulfonated polyetheretherketone and Ti3C2T X -SF modified carbon fiber is mixed to obtain a mixture.

[0082] Step 2: The mixture is fed into a screw extruder, and the melting temperature is set as follows: Zone 1 320-340℃, Zone 2 350-360℃, Zone 3 360-370℃. The mixture is melt-extruded and granulated to obtain the PEEK composite material.

[0083] Comparative Example 3

[0084] The only difference from Example 1 is that carbon fiber is used instead of Ti3C2T. X -SF modified carbon fiber.

[0085] Preparation of biocompatible PEEK composite materials: Step 1: Prepare 100 parts by weight of sulfonated polyether ether ketone prepared in Preparation Example 1, 30 parts by weight of furan heterocyclic polyarylene ether sulfone ketone prepared in Preparation Example 2, and 10 parts by weight of carbon fiber. Mix the sulfonated polyether ether ketone, furan heterocyclic polyarylene ether sulfone ketone, and carbon fiber to obtain a mixture.

[0086] Step 2: The mixture is fed into a screw extruder, and the melting temperature is set as follows: Zone 1 320-340℃, Zone 2 350-360℃, Zone 3 360-370℃. The mixture is melt-extruded and granulated to obtain the PEEK composite material.

[0087] The performance of the PEEK composite materials prepared in Examples 1-9 and Comparative Examples 1-3 was tested, and the results are shown in Table 1.

[0088] Antibacterial properties: The antibacterial rate (Staphylococcus aureus and Escherichia coli) was tested according to the standard GB / T 31402-2023 Determination of antibacterial activity of plastics and other non-porous materials.

[0089] Mechanical properties: Tensile strength was tested in accordance with the standard GB / T 1040.2-2006 Determination of tensile properties of plastics - Part 2: Test conditions for molded and extruded plastics, at a speed of 2 mm / s.

[0090] Hydrophilicity: The water contact angle was tested using an SL2008 water contact meter.

[0091] Table 1

[0092] As shown in Table 1, Examples 1-3 combined with Comparative Example 2 demonstrate that the addition of furan heterocyclic polyarylene ether sulfone ketone to the composite material improves both tensile strength and antibacterial properties. Furthermore, considering the results of Examples 1, 4, and 5, the amount of silk fibroin modification affects the preparation of Ti3C2T. X - SF modified carbon fiber containing Ti3C2T X Regarding the bonding stability on the carbon fiber surface, the composite material of Example 1 exhibits higher tensile strength than those of Examples 4 and 5, and also demonstrates higher antibacterial activity and better hydrophilicity. The PEEK composite material prepared in these embodiments of the invention not only possesses excellent antibacterial properties but also exhibits good mechanical properties and hydrophilicity, which is beneficial for its application in the medical field.

[0093] It should be noted that, in this document, relational terms such as "first" and "second" are used only to distinguish one entity or operation from another, and do not necessarily require or imply any such actual relationship or order between these entities or operations. Furthermore, the terms "comprising," "including," or any other variations thereof are intended to cover non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements includes not only those elements but also other elements not expressly listed, or elements inherent to such process, method, article, or apparatus.

[0094] Although embodiments of the invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made to these embodiments without departing from the principles and spirit of the invention, the scope of which is defined by the appended claims and their equivalents.

Claims

1. A biocompatible PEEK composite material, characterized in that, By weight, it includes the following raw materials: 100 parts sulfonated polyether ether ketone, 20-40 parts furan heterocyclic polyaryl ether sulfone ketone, 5-15 parts Ti3C2T X -SF modified carbon fiber; The furanyl heterocyclic polyarylene ether sulfone ketone is a product synthesized by reaction of 6-(4-hydroxy-3-methoxyphenyl)pyridazine-3(2H)-one, 4,4′-difluorodiphenyl sulfone and furanyldifluorodiphenyl ketone; The Ti3C2T X -SF modified carbon fiber is made by impregnating polydopamine-modified carbon fiber with silk fibroin-modified Ti3C2T. X Obtained by surface modification treatment in a material dispersion; The structural formula of furanyl difluorobenzophenone is as follows: 。 2. The biocompatible PEEK composite material according to claim 1, characterized in that, The preparation steps of the sulfonated polyether ether ketone are as follows: PEEK powder was added to concentrated sulfuric acid and heated to 50-70℃. The mixture was stirred at a constant temperature for 4-6 hours. After the reaction was completed, it was added to an ice-water mixture, stirred evenly, and allowed to stand overnight. The mixture was then washed with deionized water until neutral and dried to obtain sulfonated polyether ether ketone.

3. The biocompatible PEEK composite material according to claim 1, characterized in that, The preparation steps of the furan heterocyclic polyaryl ether sulfone ketone are as follows: 6-(4-hydroxy-3-methoxyphenyl)pyridazine-3(2H)-one, 4,4′-difluorodiphenyl sulfone, furanyldifluorobenzophenone, potassium carbonate, sulfolane, and toluene were added to a flask. The mixture was heated to 135-140℃ under a nitrogen atmosphere and stirred at a constant temperature for 2-3 hours. The temperature was then increased to 150-160℃ and stirred for 8-12 hours. After the reaction was completed, sulfolane was added and stirred to dilute the mixture to form a solution. The solution was then poured into a dilute hydrochloric acid solution at 50-80℃ to precipitate the precipitate. The precipitate was washed with water and dried to obtain furanyl heterocyclic polyarylene ether sulfone ketone.

4. The biocompatible PEEK composite material according to claim 3, characterized in that, The molar ratio of 6-(4-hydroxy-3-methoxyphenyl)pyridazine-3(2H)-one, 4,4′-difluorodiphenyl sulfone, and furanyldifluorobenzophenone is 2.0-2.1:1:1; The molar ratio of potassium carbonate to 6-(4-hydroxy-3-methoxyphenyl)pyridazine-3(2H)-one is 1.4-1.6:1; the ratio of 6-(4-hydroxy-3-methoxyphenyl)pyridazine-3(2H)-one to sulfolane is 20-50 g: 250 mL; and the volume ratio of sulfolane to toluene is 1-1.6:

5.

5. The biocompatible PEEK composite material according to claim 3, characterized in that, The preparation steps of the furanyl difluorobenzophenone are as follows: 2,5-furandicarboxylic acid chloride and fluorobenzene were added to a flask, stirred and dissolved, and then placed in an ice bath. Aluminum chloride was slowly added dropwise. After the addition was complete, the mixture was stirred until homogeneous. The temperature was raised to 70-75℃ and stirred for 10-12 hours. The mixture was then cooled to room temperature and poured into a methanol solution. The precipitate was filtered, dried, and recrystallized to obtain furanyl difluorobenzophenone.

6. The biocompatible PEEK composite material according to claim 5, characterized in that, The molar ratio of 2,5-furandicarboxylic acid chloride to fluorobenzene is 1:3.0-3.

2.

7. The biocompatible PEEK composite material according to claim 1, characterized in that, The Ti3C2T X The preparation steps for SF modified carbon fiber are as follows: Step 1: Preparation of Ti3C2T X -SF material: a single layer of Ti3C2T X Nanosheets and silk fibroin were dispersed in deionized water to obtain a suspension. EDC and DMAP were added to the suspension as catalysts. Under a nitrogen atmosphere, the system was stirred at 60-70℃ for 2-3 hours to obtain silk fibroin-modified Ti3C2T. X The material, namely Ti3C2T X -SF material; Step 2: Preparation of polydopamine-modified carbon fibers: Prepare a dopamine hydrochloride solution, immerse the carbon fibers in the dopamine hydrochloride solution, sonicate for 0.5-1 h, add Tris buffer to adjust the pH to 8.5, stir at room temperature for 5-6 h, wash and dry to obtain polydopamine-modified carbon fibers. Step 3: Preparation of Ti3C2T X -SF modified carbon fiber: Polydopamine-modified carbon fiber was dispersed in deionized water to obtain a dispersion, and Ti3C2T X -SF material was added to the dispersion and stirred at room temperature for 12-24 hours. After filtration, washing, and drying, Ti3C2T was obtained. X -SF modified carbon fiber.

8. The biocompatible PEEK composite material according to claim 7, characterized in that, The monolayer Ti3C2T X The nanosheets were prepared by chemical etching and had a diameter of 1-10 μm. The monolayer Ti3C2T X The mass ratio of nanosheets, silk fibroin, and deionized water is 5:(1.0-2.5):100; the mass ratio of EDC and DMAP is 1:

1. The EDC is a single-layer Ti3C2T X 10-20% of the mass of nanosheets.

9. The biocompatible PEEK composite material according to claim 7, characterized in that, The concentration of the dopamine hydrochloride solution is 0.01-0.03 mol / L; The concentration of the Tris buffer solution is 0.01 mol / L; In step 3, the concentration of polydopamine-modified carbon fibers in the dispersion is 20-50 g / L; The Ti3C2T X -The mass ratio of SF material to polydopamine-modified carbon fiber is 15-25:

100.

10. A method for preparing a biocompatible PEEK composite material, characterized in that, The preparation of the PEEK composite material according to any one of claims 1-9 includes the following steps: Step 1: Prepare the raw materials according to the proportions, including sulfonated polyether ether ketone, furan heterocyclic polyarylene ether sulfone ketone, and Ti3C2T. X - SF modified carbon fiber is mixed to obtain a mixture; Step 2: Melt extrusion granulation of the mixture to obtain PEEK composite material.

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