Preparation method and application of a biomedical-grade sulfonated polyether ether ketone material

Abstract

The application discloses a kind of biomedical grade sulfonated polyether ether ketone materials and preparation method and application thereof, belong to the field of biomedical polymer materials.The composite material with directly synthesized sulfonated polyether ether ketone (SPEEK) as matrix, sulfonic acid group content 1~20%, melt index 10~200g / 10min, and add 1~20% hydroxyapatite, 0~30% glass fiber and 0~30% carbon fiber.The SPEEK is treated by the depth purification process of liquid nitrogen cryogenic crushing, deionized water cleaning, alcohol reflux cleaning and ultrasonic cleaning, free fluorine≤50 ppm, total solvent≤1000 ppm.The composite material can be processed into plate, bar and various shapes of human organ products by 3D printing, injection molding or extrusion molding, for the repair and replacement of skull, joint, skeleton and other organs.The high-purity sulfonated polyether ether ketone material involved in the application has the advantages of uniform and orderly sulfonic acid group distribution, excellent biocompatibility, self-antibacterial and anti-inflammatory, beneficial to postoperative recovery and anti-infection.

Description

Technical Field

[0001] This invention belongs to the field of biomedical polymer materials technology, specifically relating to a biomedical material composed of sulfonated polyether ether ketone (SPEEK) and hydroxyapatite (HA) obtained by direct synthesis, its preparation method, and its application in the repair and replacement of human hard tissues. Background Technology

[0002] Polyetheretherketone (PEEK), as a high-performance specialty engineering plastic, has shown great potential in the field of bone implants due to its excellent mechanical properties, good biocompatibility, chemical resistance, and X-ray permeability. Unlike traditional metal implant materials with an elastic modulus exceeding 100 GPa, PEEK and its composites have an adjustable elastic modulus close to that of human cortical bone (approximately 20 GPa), which can effectively reduce the risk of osteoporosis and bone resorption caused by stress shielding effects. However, PEEK materials themselves have significant limitations: their bioactivity is low, and their surface is bioinert, which is not conducive to cell adhesion, proliferation, and differentiation. After implantation, they are prone to inflammatory responses, leading to fibrous encapsulation and affecting the long-term stability of the implant. In addition, PEEK materials do not possess antibacterial properties, and there is a risk of bacterial infection during the implantation surgery and postoperative recovery process.

[0003] To improve the bioactivity of PEEK, existing technologies have attempted to introduce hydroxyapatite (HA) into the PEEK matrix. Hydroxyapatite, as a major inorganic component of human bones and teeth, possesses excellent bioactivity and osteoconductivity. However, the interfacial bonding strength between hydroxyapatite and PEEK is limited. When the amount of hydroxyapatite added is high, it easily forms agglomerates in the matrix, leading to stress concentration and a significant decrease in the mechanical properties of the composite material.

[0004] Sulfonation is one way to improve the performance of PEEK. Traditionally, the preparation of sulfonated polyether ether ketones mainly involves post-sulfonation treatment of PEEK in highly polar reagents such as concentrated sulfuric acid. For example, patent CN121041514A discloses a surface-modified polyether ether ketone, its preparation method, and its application, which discloses sulfonation treatment of a polyether ether ketone substrate in concentrated sulfuric acid. However, this post-sulfonation process suffers from problems such as difficulty in controlling the degree of sulfonation, poor batch stability, and uneven distribution of sulfonic acid groups. Although some studies in recent years have attempted to introduce sulfonic acid functional groups during polymerization, there is currently no systematic solution for how to apply such high-performance SPEEK materials to the biomedical field and meet the stringent standards for implantation in the human body through rigorous purification processes.

[0005] Existing patent CN119264414A proposes a method for uniformly and orderly introducing sulfonic acid groups at the molecular level through direct synthesis. However, the finished product disclosed by this method is still an industrial substrate, containing certain levels of impurities, incompletely reacted monomers, and low-molecular-weight products, which do not affect industrial applications. There is currently no corresponding high-precision purification technology to meet the stringent standards of the biopharmaceutical industry. This has resulted in a lack of research on the application of this type of SPEEK material in the biomedical field, especially regarding its combination with bioactive components such as hydroxyapatite and subsequent deep purification for use in the preparation of human implants. No such technical solution has been disclosed to date. Summary of the Invention

[0006] (a) Purpose of the invention

[0007] This invention addresses the technical problems of existing PEEK-based bone repair materials, such as insufficient bioactivity, lack of antibacterial properties, uneven distribution of sulfonic acid groups in traditional sulfonation processes, and difficulty in achieving the required purity for medical applications. Furthermore, existing industrial-grade SPEEK has low purity and lacks corresponding research and application in the biomedical field. This invention provides a biomedical-grade sulfonated polyether ether ketone material, its preparation method, and its applications.

[0008] (II) Technical Solution

[0009] To achieve the above objectives, the present invention provides the following technical solution:

[0010] A sulfonated polyether ether ketone (SPEEK) biomedical composite material, using sulfonated polyether ether ketone (SPEEK) prepared by direct synthesis as the matrix material, wherein the sulfonic acid groups on its molecular chain are uniformly and orderly distributed.

[0011] A method for preparing biomedical grade sulfonated polyetheretherketone material, the method comprising the following steps:

[0012] S1 Sulfonated Polyether Ether Ketone Selection: Select directly synthesized industrially produced sulfonated polyether ether ketone powder, wherein the sulfonated polyether ether ketone has a sulfonic acid group content of 1~20% and a melt index of 10~300g / 10min.

[0013] S2 Cryogenic Grinding: Sulfonated polyether ether ketone powder is pulverized to 300~1000 mesh using a liquid nitrogen cryogenic pulverizer at -60℃.

[0014] S3 Deionized Water Washing: The pulverized powder is placed in deionized water at 80℃, stirred for 1 hour, centrifuged, and washed repeatedly 5 times.

[0015] S4 Alcohol Reflux Washing: The powder treated with S3 was refluxed and washed 3 times, 1 hour each time, and separated by centrifugation to obtain the de-alcoholized powder.

[0016] S5 Ultrasonic Assisted Cleaning: Clean again with deionized water and ultrasonic machine for 30 minutes, then separate by centrifugation, then clean again and separate by centrifugation again, repeat 3 times.

[0017] S6 Low-Temperature Vacuum Drying: Finally, the obtained powder is dried under low-temperature vacuum to obtain free fluorine ≤50 ppm.

[0018] High-purity sulfonated polyether ether ketone powder with total solvent ≤1000 ppm, including diphenyl sulfone ≤50 ppm and DMSO ≤200 ppm.

[0019] Under the aforementioned low-temperature vacuum conditions, the temperature is 70~90℃, the vacuum degree is above -50, and the drying time is 10-15 hours.

[0020] Furthermore, in step S1, the melt index of the sulfonated polyether ether ketone is 20~30 g / 10 min.

[0021] Furthermore, the water-soluble low-carbon alcohols mentioned in step S4 refer to alcohols with fewer than four carbon atoms.

[0022] Preferably, the low-carbon alcohols mentioned in step S4 refer to anhydrous ethanol, methanol, n-propanol, or isopropanol.

[0023] Furthermore, the sulfonated polyether ether ketone has a sulfonic acid group content of 3-10%.

[0024] Preferably, the sulfonated polyether ether ketone has a sulfonic acid group content of 4%.

[0025] Furthermore, the preparation method further includes the following steps:

[0026] Material compounding: The obtained high-purity sulfonated polyether ether ketone is compounded by mixing the obtained high-purity sulfonated polyether ether ketone with medical-grade hydroxyapatite, medical-grade glass fiber and / or medical-grade carbon fiber in a certain proportion to obtain a compound material. The medical-grade hydroxyapatite, medical-grade glass fiber and / or medical-grade carbon fiber are in the following mass percentages: 1~20% hydroxyapatite, 0~30% glass fiber and / or 0~30% carbon fiber, and the remainder is high-purity sulfonated polyether ether ketone powder.

[0027] Molding and processing: The high-purity sulfonated polyether ether ketone or the compounded material obtained in step S6 is processed into products of the desired shape by 3D printing, injection molding or extrusion molding.

[0028] The compound material comprises the following components by mass percentage:

[0029] Sulfonated polyether ether ketone (SPEEK): matrix material, with a sulfonic acid group content of 1~20%, preferably 3~10%, and most preferably 4%; melt index of 10~300 g / 10 min, preferably 20~30 g / 10 min.

[0030] Medical-grade hydroxyapatite (HA) or hospital-grade nano-hydroxyapatite (nHA): 1~20%, preferably 5~15%;

[0031] Hospital-grade glass fiber: 0~30%, preferably 5~20%;

[0032] Medical-grade carbon fiber: 0~30%, preferably 5~20%;

[0033] All percentages above are by mass; the balance is sulfonated polyether ether ketone powder.

[0034] Furthermore, the hydroxyapatite is nano-hydroxyapatite with a particle size of 20~100nm.

[0035] Furthermore, the carbon fiber is a short-cut carbon fiber with a length of 50~500μm, or a continuous carbon fiber.

[0036] Furthermore, the compound material may also contain 0.5% to 5% by mass of a bioactive component, wherein the bioactive component is selected from one or more of bioactive glass, chitosan, and strontium-doped hydroxyapatite.

[0037] After the above purification process, the free fluorine content is required to be ≤50 ppm, the total solvent content ≤1000 ppm, of which diphenyl sulfone ≤50 ppm and DMSO ≤200 ppm. Small molecule impurities are dissolved and removed by anhydrous ethanol, which fully meets the testing standards for high-purity sulfonated PEEK medical-grade powder according to YY / T 0660-2008. This is the current national standard for basic PEEK and the core basis for domestic medical device registration. Detailed Implementation

[0040] To achieve the above objectives, the present invention provides the following technical solution:

[0041] A sulfonated polyether ether ketone (SPEEK) biomedical composite material is disclosed, using SPEEK prepared by direct synthesis as the matrix material, wherein the sulfonic acid groups on the molecular chain are uniformly and orderly distributed. The SPEEK is synthesized using the method described in patent application publication number CN119264414A. The high-purity SPEEK material obtained by the preparation method involved in this invention has the advantages of uniform and orderly distribution of sulfonic acid groups, excellent impact resistance, excellent biocompatibility, self-antibacterial and anti-inflammatory properties, and benefits for postoperative recovery and infection resistance.

[0042] A method for preparing biomedical grade sulfonated polyetheretherketone material, the method comprising the following steps:

[0043] S1 Sulfonated Polyether Ether Ketone Selection: Industrially produced sulfonated polyether ether ketone powder synthesized directly is selected, wherein the sulfonic acid group content of the sulfonated polyether ether ketone is 1~20%, and the melt index is 10~300g / 10min; the material selection is indeed ingenious, and the industrially produced sulfonated polyether ether ketone material produced by this specified method has excellent mechanical properties, with tensile strength, elongation at break, and flexural strength all superior to polyether ether ketone, and its impact strength is more than twice that of polyether ether ketone.

[0044] S2 Cryogenic Grinding: Sulfonated polyether ether ketone powder is pulverized to 300-1000 mesh using a liquid nitrogen cryogenic grinder at -60℃. This process emphasizes a specific crushing method; conventional material crushing processes can generally only process materials to around 50-60 mesh, which cannot meet our subsequent processing requirements. Therefore, it is necessary to use liquid nitrogen for crushing in a deep cooling environment. The purpose of this treatment is to facilitate the cleaning of solvents and fluoride salts encapsulated inside the particles.

[0045] S3 Deionized Water Washing: The pulverized powder is placed in deionized water at 80℃, stirred for 1 hour, centrifuged, and the washing process is repeated 5 times. The purpose of centrifugation is to remove solvent and salt impurities from the inside of the tiny particles as much as possible, resulting in a more thorough cleaning. Based on our material processing experience, powder can be seen to have ultra-fine pores and other spatial structures under a high-powered microscope. The components of impurities, such as solvents and salts, can remain inside these tiny pores. Therefore, the above process is performed to thoroughly clean and remove impurities.

[0046] S4 Alcohol Reflux Washing: The powder treated with S3 is refluxed and washed three times, one hour each time, and then separated by centrifugation to obtain the de-alcoholized powder. The purpose of this step is to thoroughly clean the unreacted monomers and small molecules produced by the reaction, ensuring that the final product meets biomedical requirements.

[0047] S5 Ultrasonic Assisted Cleaning: Clean again with deionized water and an ultrasonic cleaner for 30 minutes, then separate by centrifugation. Repeat the cleaning and centrifugation process three times. Through the cavitation impact of ultrasound, trace impurities are cleaned again, achieving the requirement of controlling solvent impurities and fluoride salt impurities to below 50 ppm.

[0048] S6 Low-Temperature Vacuum Drying: Finally, the obtained powder is dried under low-temperature vacuum to obtain free fluorine ≤50 ppm.

[0049] The SPEEK powder is a high-purity sulfonated polyether ether ketone powder with a total solvent content of ≤1000 ppm, including diphenyl sulfone ≤50 ppm and DMSO ≤200 ppm. Due to the high moisture content of the SPEEK treated in the above steps, the drying time is relatively long. To minimize its oxidation and discoloration in air, the temperature is controlled at 70~90℃, the vacuum degree is above -50, and the drying time is 10-15 hours.

[0050] Furthermore, in step S1, the melt index of the sulfonated polyether ether ketone is 20~30 g / 10 min.

[0051] Furthermore, the water-soluble low-carbon alcohols mentioned in step S4 refer to alcohols with fewer than four carbon atoms.

[0052] Preferably, the low-carbon alcohols mentioned in step S4 refer to anhydrous ethanol, methanol, n-propanol, or isopropanol.

[0053] Furthermore, the sulfonated polyether ether ketone has a sulfonic acid group content of 3-10%.

[0054] Preferably, the sulfonated polyether ether ketone has a sulfonic acid group content of 4%.

[0055] Furthermore, the preparation method further includes the following steps:

[0056] Material Blending: The obtained high-purity sulfonated polyether ether ketone is blended with medical-grade hydroxyapatite, medical-grade glass fiber, and / or medical-grade carbon fiber in a specific ratio to obtain a blended material.

[0057] The mass percentage is: 1~20% hydroxyapatite, 0~30% glass fiber and / or 0~30% carbon fiber, with the remainder being high-purity sulfonated polyether ether ketone powder.

[0058] Molding and processing: The high-purity sulfonated polyether ether ketone or the compounded material obtained in step S6 is processed into products of the desired shape by 3D printing, injection molding or extrusion molding.

[0059] The compound material comprises the following components by mass percentage:

[0060] Sulfonated polyether ether ketone (SPEEK): matrix material, with a sulfonic acid group content of 1~20%, preferably 3~10%, and most preferably 4%; melt index of 10~300 g / 10 min, preferably 20~30 g / 10 min.

[0061] Medical-grade hydroxyapatite (HA) or hospital-grade nano-hydroxyapatite (nHA): 1~20%, preferably 5~15%;

[0062] Hospital-grade glass fiber: 0~30%, preferably 5~20%;

[0063] Medical-grade carbon fiber: 0~30%, preferably 5~20%;

[0064] All percentages above are by mass; the balance is sulfonated polyether ether ketone powder.

[0065] Furthermore, the hydroxyapatite is nano-hydroxyapatite with a particle size of 20~100nm.

[0066] Furthermore, the carbon fiber is a short-cut carbon fiber with a length of 50~500μm, or a continuous carbon fiber.

[0067] Furthermore, the compound material may also contain 0.5% to 5% by mass of a bioactive component, wherein the bioactive component is selected from one or more of bioactive glass, chitosan, and strontium-doped hydroxyapatite.

[0068] After the above purification process, the free fluorine content is required to be ≤50 ppm, the total solvent content ≤1000 ppm, of which diphenyl sulfone ≤50 ppm and DMSO ≤200 ppm, and small molecule impurities are dissolved and removed by anhydrous ethanol, fully meeting the standards.

[0069] Mandatory Recommended Standards for the Pharmaceutical Industry (Required for Registration):

[0070] YY / T 0660-2008 (Basic PEEK National Standard, Core Basis for Domestic Medical Device Registration)

[0071] YY / T 2008-2026 (2026 latest version, special project for additive PEEK powder, with solvent residue appendix)

[0072] Example 1

[0073] This embodiment provides a sulfonated polyether ether ketone / nanohydroxyapatite / carbon fiber composite material and its preparation method.

[0074] (1) Provision of sulfonated polyether ether ketone: SPEEK powder directly synthesized, with sulfonic acid group content of 4% and melt index of 25.

[0075] (2) Deep purification: The SPEEK powder was pulverized to 500 mesh in a liquid nitrogen cryogenic pulverizer at -60℃. The pulverized powder was stirred in deionized water at 80℃ for 1 hour, centrifuged, and repeated 5 times; then refluxed with anhydrous ethanol 3 times, 1 hour each time, and centrifuged; finally, ultrasonically cleaned in deionized water for 30 minutes, repeated 3 times, and centrifuged; and dried under low temperature vacuum. The free fluorine residue was <50 ppm, the total solvent residue was ≤1000 ppm, of which diphenyl sulfone was ≤50 ppm and DMSO was ≤200 ppm.

[0076] (3) Preparation of composite material: Take 80 parts of purified SPEEK powder, 10 parts of nano hydroxyapatite (particle size 50nm) and 10 parts of short carbon fiber (length 200μm) (all by mass), mix them evenly to obtain composite powder.

[0077] (4) Molding and processing: The mixed powder obtained in step (3) is printed using selective laser sintering (SLS) 3D printing technology, or it is first extruded into a special filament and then printed using fused deposition modeling (FDM) 3D printing technology. The printing temperature is 400℃, the chamber temperature is 120℃, and the printing layer thickness is 0.2mm to prepare standard test strips and skull repair models.

[0078] SLS - Selective Laser Sintering Type:

[0079] Raw materials: polymer powder, metal powder; principle: high-power laser scanning, local high temperature melts and binds the powder particles together, the powder melts and sintersties into shape, and the excess powder acts as a support.

[0080] FDM - Fused Deposition Modeling:

[0081] Raw material: 1.75mm~2.85mm filament plastic wire; Principle: The heated nozzle melts and extrudes the wire, which is then layered and molded into shape.

[0082] The raw materials for the SLS and FDM printing methods mentioned above are not directly interchangeable. Powder cannot be directly printed using the FDM method, and filaments cannot be directly used for SLS printing.

[0083] After the finished product Sample 1 was generated in Example 1, it was sent to a professional testing institution for testing (Report No.: SHA03-26079112-CS-02, Report issued by: Shanghai Micro-Spectrum Testing Technology Group Co., Ltd.).

[0084] The test results are as follows: (Refer to Table 1)

[0085]

[0086] Table 1: Test Results of Sample 1

[0087] Note: 1. 1 mg / kg = 1 ppm = 0.0001%.

[0088] 2. ND = Not detected (less than the method detection limit).

[0089] 3. The DMSO content was determined by GC-MS external standard method.

[0090] 4. DMSOCAS No.: 67-68-5.

[0091] Example 2

[0092] This embodiment provides a sulfonated polyether ether ketone / hydroxyapatite / glass fiber composite material and its preparation method.

[0093] (1) Provision and deep purification of sulfonated polyether ether ketone: Same as in Example 1.

[0094] (2) Preparation of composite material: Take 75 parts of purified SPEEK powder, 10 parts of hydroxyapatite and 15 parts of glass fiber (all by weight), mix them evenly to obtain a mixed powder.

[0095] (3) Molding and processing: The mixed powder obtained in step (2) is granulated and processed by injection molding process. The injection temperature is 400℃ and the mold temperature is 180℃ to prepare standard test strips and artificial joint parts.

[0096] After the finished product Sample 2 was generated in Example 2, it was sent to a professional testing institution for testing (Report No.: SHA03-26079112-CS-03, Report issued by: Shanghai Micro-Spectrum Testing Technology Group Co., Ltd.).

[0097] The test results are as follows: (Refer to Table 2)

[0098]

[0099] Table 2: Test Results of Sample 2

[0100] Note: 1. 1 mg / kg = 1 ppm = 0.0001%.

[0101] 2. ND = Not detected (less than the method detection limit).

[0102] 3. The DMSO content was determined by GC-MS external standard method.

[0103] 4. DMSOCAS No.: 67-68-5.

[0104] Example 3

[0105] This embodiment provides a sulfonated polyether ether ketone / nano-hydroxyapatite composite material and its preparation method.

[0106] (1) Provision and deep purification of sulfonated polyether ether ketone: Same as in Example 1.

[0107] (2) Preparation of composite material: Take 90 parts of purified SPEEK powder and 10 parts of nano hydroxyapatite (particle size 30nm) (both by mass), mix them evenly to obtain a mixed powder.

[0108] (3) Molding process: The mixed powder obtained in step (2) is granulated and extruded to prepare plates and rods. The extrusion temperature is 400℃ and the extrusion speed is 5m / min.

[0109] After the finished product Sample 3 was generated in Example 3, it was sent to a professional testing institution for testing (Report No.: SHA03-26079112-CS-04, Report issued by: Shanghai Micro-Spectrum Testing Technology Group Co., Ltd.).

[0110] The test results are as follows: (Refer to Table 3)

[0111]

[0112] Table 3: Test Results of Sample 3

[0113] Note: 1. 1 mg / kg = 1 ppm = 0.0001%.

[0114] 2. ND = Not detected (less than the method detection limit).

[0115] 3. The DMSO content was determined by GC-MS external standard method.

[0116] 4. DMSOCAS No.: 67-68-5.

[0117] The sulfonated polyether ether ketone material obtained through the above specific embodiments does indeed meet the expected specifications of free fluorine ≤50 ppm, total solvent ≤1000 ppm, of which diphenyl sulfone ≤50 ppm and DMSO ≤200 ppm, and can meet the medical grade specifications and requirements.

[0118] Example 4

[0119] This embodiment provides a sulfonated polyether ether ketone / nano-hydroxyapatite / carbon fiber / glass fiber composite material and its preparation method.

[0120] (1) Provision and deep purification of sulfonated polyether ether ketone: Same as in Example 1.

[0121] (2) Preparation of composite material: Take 70 parts of purified SPEEK powder, 10 parts of nano hydroxyapatite, 10 parts of short carbon fiber and 10 parts of glass fiber (all by mass), mix them evenly to obtain a mixed powder.

[0122] (3) Molding and processing: Same as the 3D printing process in Example 1.

[0123] Comparative Example 1

[0124] The difference from Example 1 is that SPEEK (4% sulfonation degree) treated with conventional concentrated sulfuric acid was used, without deep purification process, and other conditions were the same.

[0125] Comparative Example 2

[0126] The difference from Example 1 is that unsulfonated polyether ether ketone (PEEK) is used instead of sulfonated polyether ether ketone, while other conditions are the same.

[0127] Comparative Example 3

[0128] The difference from Example 1 is that hydroxyapatite is not added, while other conditions are the same.

[0129] Comparative Example 4

[0130] The difference from Example 1 is that the sulfonic acid group content is 25% (outside the scope of this invention), while other conditions are the same.

[0131] Performance testing

[0132] (1) Mechanical property testing

[0133] The composite material standard specimens prepared in Examples 1-4 and Comparative Examples 1-4 were subjected to mechanical property tests according to ASTM standards, including tensile strength, flexural strength, flexural modulus and impact strength.

[0134] The results showed that the composite materials of Examples 1-4 all exhibited good mechanical properties. The addition of carbon fibers significantly improved the tensile and flexural strength of the materials. Comparative Example 1, due to the use of a traditional post-sulfonation process without deep purification, had uneven distribution of sulfonic acid groups and poor interfacial bonding, resulting in significantly lower mechanical properties than the examples. Comparative Example 2, lacking sulfonation treatment, had weak interfacial bonding between SPEEK and hydroxyapatite, leading to decreased mechanical properties. Comparative Example 4, with its excessively high sulfonic acid group content, experienced increased brittleness and decreased mechanical properties.

[0135] (2) Purity detection

[0136] Fluoride and solvent residues were tested on the SPEEK raw materials of Example 1 and Comparative Example 1. The results showed that after deep purification, the free fluoride in Example 1 was ≤50 ppm, and the total solvent was ≤1000 ppm, of which diphenyl sulfone was ≤50 ppm and DMSO was ≤200 ppm. Comparative Example 1, which was not deeply purified, had fluoride residues >50 ppm, which did not meet the safety requirements for medical implant materials.

[0137] (3) Biocompatibility test

[0138] Cytotoxicity tests, skin irritation tests, and sensitization tests were performed according to the GB / T 16886 / ISO 10993 series of standards. The composite materials prepared in Examples 1-4 were co-cultured with osteoblasts (MC3T3-E1), and cell viability was detected using the CCK-8 assay.

[0139] The results showed that the composite materials in Examples 1-4 all exhibited cell viability greater than 90%, no cytotoxicity, and good biocompatibility. Comparative Example 1, due to its high residual solvent and fluoride content, had cell viability of only 70-85%, posing a certain risk of cytotoxicity.

[0140] (4) Antibacterial performance test

[0141] The antibacterial properties of the composite materials prepared in Examples 1-4 and Comparative Examples 1-3 against Staphylococcus aureus (ATCC 25923) and Escherichia coli (ATCC 25922) were tested using the inhibition zone method.

[0142] The results showed that the composite materials in Examples 1-4 all exhibited obvious inhibition zones and had good antibacterial effects against both test strains. The antibacterial effect of Comparative Example 2 (unsulfonated) was significantly weaker than that of the Examples, and the antibacterial effect of Comparative Example 3 (without hydroxyapatite) also decreased.

[0143] (5) Animal implantation experiments

[0144] The composite material prepared in Example 1 was processed into a bone plate shape and implanted into a femoral defect model in New Zealand white rabbits. Animals were sacrificed at 4, 8, and 12 weeks post-surgery, and the implant and surrounding tissues were removed for histological observation.

[0145] The results showed that no obvious inflammatory reaction was observed around the implant, new bone tissue grew along the implant surface, and osseointegration was good. No signs of infection were observed during the postoperative recovery period, confirming the material's self-antibacterial and anti-inflammatory properties and good osseointegration ability.

[0146] Industrial applicability

[0147] The present invention provides a biomedical-grade sulfonated polyether ether ketone (PEEK) material, and a composite material based on PEEK incorporating hydroxyapatite, glass fiber, and / or carbon fiber. This material can be processed into sheets, rods, and implants of various complex shapes using various molding processes such as 3D printing, injection molding, and extrusion. It is suitable for clinical applications such as skull repair, artificial joint replacement, and bone replacement. The material exhibits good biocompatibility, self-antibacterial and anti-inflammatory properties, and mechanical properties, which are beneficial for postoperative recovery and infection control, demonstrating broad clinical application prospects and industrial production value.

[0148] The above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention in any way. Although the present invention has been disclosed above with reference to preferred embodiments, it is not intended to limit the present invention. Any person skilled in the art can make some changes or modifications to the above-disclosed technical content to create equivalent embodiments without departing from the scope of the present invention. Any simple modifications, equivalent changes, and modifications made to the above embodiments based on the present invention without departing from the scope of the present invention are within the scope of the present invention.

Claims

1. A method for preparing a biomedical grade sulfonated polyetheretherketone material, characterized in that, The preparation method includes the following steps: S1 Sulfonated Polyether Ether Ketone Selection: Select directly synthesized industrially produced sulfonated polyether ether ketone powder, wherein the sulfonated polyether ether ketone has a sulfonic acid group content of 1~20% and a melt index of 10~300g / 10min. S2 Cryogenic Grinding: Sulfonated polyether ether ketone powder is pulverized to 300~1000 mesh using a liquid nitrogen cryogenic pulverizer at -60℃. S3 Deionized Water Washing: The pulverized powder is placed in deionized water at 80℃, stirred for 1 hour, centrifuged, and washed repeatedly 5 times. S4 Alcohol Reflux Washing: The powder treated with S3 was refluxed and washed 3 times, 1 hour each time, and separated by centrifugation to obtain the de-alcoholized powder. S5 Ultrasonic Assisted Cleaning: Clean again with deionized water and ultrasonic machine for 30 minutes, then separate by centrifugation, then clean again and separate by centrifugation again, repeat 3 times. S6 Low-temperature vacuum drying: Finally, the obtained powder is dried under low-temperature vacuum to obtain high-purity sulfonated polyether ether ketone powder with free fluorine ≤50 ppm, total solvent ≤1000 ppm, of which diphenyl sulfone ≤50 ppm and DMSO ≤200 ppm; under the low-temperature vacuum conditions, the temperature is 70~90℃, the vacuum degree is above -50, and the drying time is 10-15 hours.

2. The method for preparing biomedical-grade sulfonated polyetheretherketone material according to claim 1, characterized in that, The preparation method includes the following steps: Material compounding: The obtained high-purity sulfonated polyether ether ketone is compounded by mixing the obtained high-purity sulfonated polyether ether ketone with medical-grade hydroxyapatite, medical-grade glass fiber and / or medical-grade carbon fiber in a certain proportion to obtain a compound material. The medical-grade hydroxyapatite, medical-grade glass fiber and / or medical-grade carbon fiber are in the following mass percentages: 1~20% hydroxyapatite, 0~30% glass fiber and / or 0~30% carbon fiber, and the remainder is high-purity sulfonated polyether ether ketone powder. Molding and processing: The high-purity sulfonated polyether ether ketone or the compounded material obtained in step S6 is processed into products of the desired shape by 3D printing, injection molding or extrusion molding.

3. The method for preparing biomedical-grade sulfonated polyetheretherketone material according to claim 1, characterized in that, The melt index of sulfonated polyether ether ketone in step S1 is 20~30 g / 10 min.

4. The method for preparing biomedical-grade sulfonated polyetheretherketone material according to claim 1, characterized in that, The water-soluble low-carbon alcohols mentioned in step S4 refer to anhydrous ethanol, methanol, n-propanol, or isopropanol.

5. The method for preparing biomedical-grade sulfonated polyetheretherketone material according to claim 1, characterized in that: The sulfonated polyether ether ketone has a sulfonic acid group content of 3-10%.

6. The method for preparing biomedical-grade sulfonated polyetheretherketone material according to claim 5, characterized in that: The sulfonated polyether ether ketone has a sulfonic acid group content of 4%.

7. The method for preparing biomedical-grade sulfonated polyetheretherketone material according to claim 2, characterized in that: The amount of medical-grade hydroxyapatite added is 5-15%; the medical-grade hydroxyapatite is nano-hydroxyapatite with a particle size of 20-100nm.

8. The method for preparing biomedical-grade sulfonated polyetheretherketone material according to claim 2, characterized in that: The amount of medical-grade glass fiber added is 5-20%, and the amount of medical-grade carbon fiber added is 5-20%; the medical-grade carbon fiber is short-cut carbon fiber with a length of 50-500μm, or it is continuous carbon fiber.

9. An application of a biomedical grade sulfonated polyetheretherketone material, characterized in that, The application of the biomedical grade sulfonated polyether ether ketone material prepared according to any one of claims 1-8 in the preparation of human bone repair implants.

10. The application of the biomedical grade sulfonated polyetheretherketone material according to claim 9, characterized in that: The implants include skull repair bodies, artificial joints, bone substitutes, bone screws, bone plates, or interbody fusion devices.

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