Polyether-ether-ketone composite repair material as well as preparation method and application thereof

Abstract

The invention discloses a polyetheretherketone composite repair material which comprises a polyetheretherketone matrix and polydopamine coated polytetrafluoroethylene dispersed in the polyetheretherketone matrix, the preparation method comprises the following steps: firstly, wetting and premixing polytetrafluoroethylene micro powder and dopamine in an organic solvent system; then introducing into an alkaline buffer solution, initiating an oxidation self-polymerization reaction at normal temperature, so that dopamine is directionally deposited on the surface of the polytetrafluoroethylene micro powder to form a polydopamine coating layer, then compounding with polyether-ether-ketone powder under a ball milling condition, and promoting the dispersion of the polydopamine coated polytetrafluoroethylene micro powder in polyether-ether-ketone, so as to obtain the polydopamine coated polytetrafluoroethylene micro powder. The polyether-ether-ketone-based composite material system with high interface stability and function synergistic response is constructed. And molding is further combined with processes such as gradient melt extrusion and the like, so that the polyether-ether-ketone-based composite restoration with mechanical properties matched with temporomandibular joint discs, excellent tribological properties and photo-thermal antibacterial activity can be prepared.

Description

Technical Field

[0001] The present invention belongs to the technical field of biomedical materials, and in particular relates to a polyetheretherketone composite repair material and a preparation method and application thereof. Background Art

[0002] Temporomandibular (TMJ) disorders are common and frequently encountered conditions in the oral system, leading to problems such as malocclusion, pain, and impaired movement. Current treatments for TMJ disorders primarily involve repairing the TMJ disc. However, tissue engineering scaffolds with mechanical properties that match those of the TMJ disc remain scarce. Therefore, the development of tissue engineering scaffolds with mechanical properties matching those of the TMJ disc is crucial for the clinical treatment of TMJ disorders.

[0003] Polyetheretherketone (PEEK) materials have an elastic modulus close to that of human cortical bone, excellent mechanical properties and corrosion resistance, and their implants are widely used in clinical practice for orthopedics and various hard tissue repairs. However, the mechanical properties of PEEK are inconsistent with those of temporomandibular joint discs, and their self-lubricating properties are poor. Polytetrafluoroethylene (PTFE) has excellent self-lubricating properties, wear resistance and good biocompatibility. However, due to its hydrophobic surface and chemical inertness, it is difficult to form a uniform and continuous coating on the surface of PTFE to give it surface activity. In addition, due to the non-polar molecular structure of PTFE, the poor interfacial affinity between PEEK and PTFE molecules during the material composite process will lead to continuous interfacial stratification and voids in the composite material, which in turn affects the regulation of the composite material performance. Summary of the Invention

[0004] The main purpose of the present invention is to provide a polyetheretherketone composite repair material to address the problems of difficulty in forming a continuous and stable coating on the surface of polytetrafluoroethylene, as well as the poor matching of the mechanical properties of traditional polyetheretherketone materials with joint tissue, insufficient self-lubricating properties and lack of antibacterial function. First, a polydopamine coating layer is constructed on the surface of polytetrafluoroethylene, and then it is compounded with polyetheretherketone to prepare a polyetheretherketone-based composite repair material with mechanical properties compatible with the temporomandibular joint disc, excellent tribological properties and photothermal antibacterial activity.

[0005] To achieve the above purpose, the technical solution adopted by the present invention is: A polyetheretherketone (PEEK) composite repair material comprises a PEEK matrix and polydopamine-coated polytetrafluoroethylene (PTFE) dispersed therein; the polydopamine coating has a film-like or nano-particle stacking structure, with complete coating and no obvious exposed areas; the particle size of the PEEK-coated PTFE is 5-15 μm; the PEEK-coated PTFE adheres to the PEEK matrix through intermolecular forces, resulting in good interfacial bonding.

[0006] In the above solution, the polydopamine-coated polytetrafluoroethylene accounts for 5-30% of the mass of the polyetheretherketone matrix.

[0007] The above-mentioned method for preparing a polyetheretherketone composite repair material comprises the following steps: 1) Adding polytetrafluoroethylene micropowder to an organic solvent under stirring, ultrasonically dispersing the mixture, then adding dopamine hydrochloride, performing a first continuous reaction under stirring, centrifuging, and drying the resulting solid to obtain polytetrafluoroethylene micropowder with dopamine adhered to the surface; 2) adding the obtained polytetrafluoroethylene micropowder with dopamine attached to its surface to an alkaline buffer solution, ultrasonically dispersing the micropowder, then adding dopamine hydrochloride, performing a second continuous reaction under stirring, centrifuging, and drying to obtain polydopamine-coated polytetrafluoroethylene micropowder; 3) The obtained polydopamine-coated polytetrafluoroethylene micropowder and polyetheretherketone are subjected to high-speed ball milling to obtain a granular polyetheretherketone composite repair material.

[0008] In the above scheme, in step 1), the mass ratio of polytetrafluoroethylene micropowder to dopamine hydrochloride is 1:1~3.

[0009] In the above solution, the organic solvent can be selected from anhydrous ethanol, isopropyl alcohol and acetone.

[0010] In the above scheme, in step 1), the ultrasonic dispersion time is 15 to 30 minutes, which improves the dispersibility of the polytetrafluoroethylene powder in the anhydrous ethanol solution and ensures the uniform adhesion of dopamine hydrochloride on the polytetrafluoroethylene surface.

[0011] In the above scheme, the first continuous reaction time is 18~24 h, and the stirring rate is 500~800 rpm.

[0012] In the above scheme, the alkaline buffer solution can be a Tris-HCl solution with a pH value of 7.5-8.5.

[0013] Furthermore, the concentration of the Tris-HCl solution is 8-13 mmol / L.

[0014] In the above scheme, in step 2), the mass ratio of the polytetrafluoroethylene micropowder with dopamine adhered to the surface to dopamine hydrochloride is 1-4:1, preferably 1.8-2.2:1; the polytetrafluoroethylene micropowder with dopamine adhered to the surface and dopamine hydrochloride are both added to the Tris-HCl solution in powder form.

[0015] In the above scheme, in step 2), after adding polytetrafluoroethylene micropowder with dopamine attached to the surface, ultrasonic dispersion is carried out for 15 to 30 minutes to improve the dispersibility of the polytetrafluoroethylene micropowder with dopamine attached to the surface in the aqueous solution and ensure that dopamine hydrochloride can be evenly coated on the surface of the polytetrafluoroethylene micropowder during the self-polymerization process.

[0016] In the above scheme, the time of the second continuous reaction is 18-24 h, and the stirring rate is 500-800 rpm.

[0017] In the above scheme, the centrifugal speed used is 8000~10000 rpm, the centrifugation is performed 4~6 times in step 1), and the centrifugation is performed 6~8 times in step 2); and the freeze-drying is performed for 12~16 hours.

[0018] In the above scheme, in step 2), the concentration of dopamine hydrochloride in the buffer solution is 0.001~0.004 g / mL.

[0019] In the above scheme, in step 3), the mass ratio of polydopamine-coated polytetrafluoroethylene micropowder to polyetheretherketone is 5:95~30:70.

[0020] In the above scheme, the ball milling mixing time is 2 to 4 hours, the ball milling speed is 300 to 400 rpm, and the ball-to-material ratio is 1:1 to 3:1.

[0021] The present invention also provides a use of the polyetheretherketone composite repair material in preparing a temporomandibular joint disc repair material.

[0022] Furthermore, the application method includes: melt-extruding the polyetheretherketone composite repair material and injection molding to obtain a polyetheretherketone composite temporomandibular joint disc repair material for temporomandibular joint disc repair.

[0023] In the above scheme, in the melt extrusion step, the temperature of each section of the extrusion zone is gradually increased between 360 and 380°C. The specific temperature zones are controlled as follows: feeding section: 320-340°C; plasticizing section: 340-360°C; melting section: 360-380°C; die head temperature: 360-370°C; injection molding mold and barrel temperatures are 160-180°C and 360-400°C, respectively.

[0024] In the above scheme, the screw speed of the main machine for melt extrusion is 20~60 rpm.

[0025] The principles of the present invention include: The present invention provides a polyetheretherketone composite repair material. First, in order to solve the problem that the surface of polytetrafluoroethylene is highly hydrophobic and difficult to form a continuous coating layer, a "two-step coating method" is innovatively introduced to achieve efficient deposition and uniform film formation of polydopamine. The specific steps include: firstly wetting and premixing polytetrafluoroethylene micropowder and dopamine in an organic solvent system, so that the dopamine molecules can be initially wetted and adsorbed on the surface of the polytetrafluoroethylene micropowder with the assistance of the organic solvent, thereby reducing its surface tension and improving the interfacial affinity; then transferring the material to an alkaline buffer solution, inducing an oxidative self-polymerization reaction at room temperature, so that dopamine is directionally deposited on the surface of the polytetrafluoroethylene micropowder to form a polydopamine coating layer, and preparing polytetrafluoroethylene micropowder continuously coated with polydopamine. Then, it was compounded with polyetheretherketone powder under ball milling conditions, and the dispersion of polydopamine-coated polytetrafluoroethylene micropowder in polyetheretherketone was promoted. Through the coordinated control of the four-stage process of pretreatment + polymerization + drying + compounding, a polyetheretherketone-based composite material system with high interface stability and functional synergistic response was constructed, which enhanced the interfacial affinity between the two, regulated the mechanical properties of the polyetheretherketone composite material, and improved the friction performance of the obtained composite material. At the same time, the introduced polydopamine coating gave the material system a good photothermal effect.

[0026] The prepared composite material has excellent tribological properties, outstanding photothermal and antibacterial properties, and mechanical properties matching those of the temporomandibular joint disc, and is expected to become an ideal repair material for the temporomandibular joint disc.

[0027] Compared with the prior art, the present invention has the following beneficial effects: 1) To address the high inertness of the PTFE surface, a combined coating strategy of "organic premixing + aqueous polymerization" was proposed. This innovative approach pre-wetted the PTFE micropowder with an organic solvent before dopamine self-polymerization, enhancing the initial adsorption capacity of polydopamine on the PTFE surface. In-situ polymerization was then performed in an alkaline buffer system, improving the integrity and stability of the polydopamine coating and effectively resolving the surface modification challenges of PTFE. 2) Optimizing melt extrusion process parameters to ensure that the functional layer is not damaged during the molding process while effectively promoting the interface fusion between it and the matrix to ensure the overall performance of the resulting composite material; 3) Through structural design and interface regulation, the mechanical properties of polyetheretherketone material are adapted to the temporomandibular joint disc, and the lubrication, friction reduction and photothermal antibacterial functions of the material system are synergistically performed under a physiological friction environment. BRIEF DESCRIPTION OF THE DRAWINGS

[0028] Figure 1 TEM photos of the polydopamine-coated polytetrafluoroethylene micropowder prepared in Example 2 and the polydopamine-coated polytetrafluoroethylene micropowder prepared in Comparative Example 3.

[0029] Figure 2 The present invention provides an FT-IR spectrum of the polyetheretherketone composite material prepared for repairing the temporomandibular joint disc.

[0030] Figure 3 These are the mechanical property graphs of the polyetheretherketone composite materials for repairing the temporomandibular joint disc in Examples 1 to 3, the pure polyetheretherketone material in Comparative Example 1, and the polytetrafluoroethylene / polyetheretherketone composite material in Comparative Example 2.

[0031] Figure 4 Thermal performance spectra of the polyetheretherketone composite materials for repairing the temporomandibular joint disc in Examples 1 to 3, the pure polyetheretherketone material in Comparative Example 1, and the polytetrafluoroethylene / polyetheretherketone composite material in Comparative Example 2.

[0032] Figure 5 These are the tribological performance graphs of the polyetheretherketone composite material for repairing the temporomandibular joint disc in Example 2 of the present invention, the pure polyetheretherketone material in Comparative Example 1, and the polytetrafluoroethylene / polyetheretherketone composite material in Comparative Example 2.

[0033] Figure 6 These are the biocompatibility graphs of the polyetheretherketone composite material for repairing the temporomandibular joint disc in Example 2 of the present invention, the pure polyetheretherketone material in Comparative Example 1, and the polytetrafluoroethylene / polyetheretherketone composite material in Comparative Example 2.

[0034] Figure 7 These are the photothermal response performance graphs of the polyetheretherketone composite material for repairing the temporomandibular joint disc in Example 2 of the present invention, the pure polyetheretherketone material in Comparative Example 1, and the polytetrafluoroethylene / polyetheretherketone composite material in Comparative Example 2.

[0035] Figure 8 This is a graph showing the in vitro photothermal antibacterial and antibacterial rates of the polyetheretherketone composite material for repairing the temporomandibular joint disc of Example 2 of the present invention, the pure polyetheretherketone material of Comparative Example 1, the polytetrafluoroethylene / polyetheretherketone composite material of Comparative Example 2, and the blank control group. DETAILED DESCRIPTION

[0036] For a better understanding of the present invention, the following examples are provided to further illustrate the present invention, but the present invention is not limited to the following examples.

[0037] In the following examples, the average particle size of the polyetheretherketone used was 15 μm; The density of the polytetrafluoroethylene powder used was 2.15 g / mL and the average particle size was 12 μm.

[0038] Example 1 A polyetheretherketone composite repair material, the preparation method of which comprises the following steps: 1) Prepare 1 L of anhydrous ethanol and add 4 g of polytetrafluoroethylene powder to the solution at a mass ratio of 1:1 under stirring at room temperature. Then, ultrasonically disperse the solution for 15 minutes. Then, add 4 g of dopamine hydrochloride powder. Continue the reaction at room temperature for 24 hours (600 rpm), centrifuge at 8000 rpm five times, and freeze-dry for 12 hours to obtain polytetrafluoroethylene powder with dopamine attached to its surface. 2) Prepare 1 L of 10 mmol / L Tris-HCl solution (pH 8.5). Add 4 g of polytetrafluoroethylene powder with dopamine attached to the surface to the Tris-HCl solution at a mass ratio of 1:1 while stirring at room temperature (600 rpm). Then, ultrasonically disperse for 15 min. Then, add 4 g of dopamine hydrochloride powder. The reaction is continued at room temperature with stirring (600 rpm) for 24 h. Centrifuge at 8000 rpm six times, and freeze-dry for 12 h to obtain polydopamine-coated polytetrafluoroethylene powder. 3) 30 g of polydopamine-coated polytetrafluoroethylene powder (30 wt%) and 70 g of polyetheretherketone powder (70 wt%) were added to a planetary ball mill with a ball-to-material ratio of 1:1. The mixture was ball-milled at 400 rpm for 4 h to obtain a polyetheretherketone composite material for temporomandibular joint disc repair.

[0039] The composite material obtained in this example was melt-extruded at 360°C, during which the temperature zone gradient was controlled (feeding section 340°C; plasticizing section 360°C; melting section 370°C; die section 360°C), and the main screw speed of the melt extrusion was 40 rpm; then, the composite material was injection molded at 180°C (the injection molding mold and barrel temperatures were 180°C and 380°C, respectively), to obtain a polyetheretherketone composite temporomandibular joint disc repair material for temporomandibular joint disc repair.

[0040] Example 2 A polyetheretherketone composite repair material, the preparation method of which comprises the following steps: 1) Prepare 1 L of anhydrous ethanol and add 4 g of polytetrafluoroethylene powder to the solution at a mass ratio of 1:1 under stirring at room temperature. Then, ultrasonically disperse the solution for 15 minutes. Then, add 4 g of dopamine hydrochloride powder. The mixture is stirred at room temperature for 24 hours (600 rpm), centrifuged five times at 8000 rpm, and freeze-dried for 12 hours to obtain polytetrafluoroethylene powder with dopamine attached to its surface. 2) Prepare 1 L of 10 mmol / L Tris-HCl solution (pH 8.5). Under room temperature stirring (600 rpm), add 4 g of polytetrafluoroethylene powder with dopamine attached to its surface at a mass ratio of 2:1. Then, ultrasonically disperse the solution for 15 minutes. Then, add 2 g of dopamine hydrochloride powder to the dispersed solution. Continue the reaction at room temperature with stirring for 24 hours. Centrifuge at 8000 rpm six times, and freeze-dry for 12 hours to obtain polydopamine-coated polytetrafluoroethylene powder. 3) 30 g of polydopamine-coated polytetrafluoroethylene powder (30 wt%) and 70 g of polyetheretherketone powder (70 wt%) were added to a planetary ball mill with a ball-to-material ratio of 1:1. The mixture was ball-milled at 400 rpm for 4 h to obtain a polyetheretherketone composite material for temporomandibular joint disc repair.

[0041] The composite material obtained in this example was melt-extruded at 360°C, during which the temperature zone gradient was controlled (feeding section 340°C; plasticizing section 360°C; melting section 370°C; die section 360°C), the main screw speed of the melt extrusion was 40 rpm, and then injection molded at 180°C (the injection molding mold and barrel temperatures were 180°C and 380°C, respectively), to obtain a polyetheretherketone composite temporomandibular joint disc repair material for temporomandibular joint disc repair.

[0042] Example 3 A preparation method of a polyetheretherketone composite repair material comprises the following steps: 1) Prepare 1 L of anhydrous ethanol and add 4 g of polytetrafluoroethylene powder to the solution at a mass ratio of 1:1 under stirring at room temperature. Then, ultrasonically disperse the solution for 15 minutes. Then, add 4 g of dopamine hydrochloride powder. Continue the reaction at room temperature for 24 hours (600 rpm), centrifuge at 8000 rpm five times, and freeze-dry for 12 hours to obtain polytetrafluoroethylene powder with dopamine attached to its surface. 2) Prepare 1 L of 10 mmol / L Tris-HCl solution (pH 8.5). Add 4 g of polytetrafluoroethylene powder with dopamine attached to its surface to the Tris-HCl solution at a mass ratio of 4:1 under room temperature stirring (600 rpm). Then, ultrasonically disperse for 15 min. Then, add 1 g of dopamine hydrochloride powder. The reaction is continued under room temperature stirring (600 rpm) for 24 h. Centrifuge at 8000 rpm six times and freeze-dry for 12 h to obtain polydopamine-coated polytetrafluoroethylene powder. 3) 30 g of polydopamine-coated polytetrafluoroethylene powder (30 wt%) and 70 g of polyetheretherketone powder (70 wt%) were added to a planetary ball mill with a ball-to-material ratio of 1:1. The mixture was ball-milled at 400 rpm for 4 h to obtain a polyetheretherketone composite material for temporomandibular joint disc repair.

[0043] The composite material obtained in this example was melt-extruded at 360°C, during which the temperature zone gradient was controlled (feeding section 340°C; plasticizing section 360°C; melting section 370°C; die section 360°C), and the main screw speed of the melt extrusion was 40 rpm; then, the composite material was injection molded at 180°C (the injection molding mold and barrel temperatures were 180°C and 380°C, respectively), to obtain a polyetheretherketone composite temporomandibular joint disc repair material for temporomandibular joint disc repair.

[0044] Comparative Example 1 A temporomandibular joint disc repair material prepared using pure polyetheretherketone powder is prepared by directly melt extrusion and injection molding using pure polyetheretherketone powder as raw material (excluding polydopamine-coated polytetrafluoroethylene) (the corresponding process conditions are the same as those in Example 1) to prepare a temporomandibular joint disc repair material.

[0045] Comparative Example 2 A polyetheretherketone composite repair material is prepared by a method substantially the same as that of Example 2, except that the polydopamine wrapping and modification process described in steps 1) and 2) is not performed.

[0046] Comparative Example 3 A polyetheretherketone composite repair material is prepared by a method substantially the same as that of Example 2, except that the premixing process of dopamine and polytetrafluoroethylene in step 1) is omitted, and pure polytetrafluoroethylene powder is directly mixed in an alkaline buffer solution in step 2).

[0047] Comparative Example 4 A polyetheretherketone composite repair material, the preparation method of which is roughly the same as that of Example 2, except that no temperature gradient control is performed during the melt extrusion process, and the temperature of each section of the extrusion process is set to 360°C.

[0048] The polydopamine coated polytetrafluoroethylene micropowder prepared in Example 2 of the present invention and the polydopamine coated polytetrafluoroethylene micropowder prepared in Comparative Example 3 were subjected to TEM test. The test results are as follows: Figure 1 As shown, Figure 1 a and b represent Example 2 and Comparative Example 3, respectively.

[0049] Depend on Figure 1It can be seen that the surface of the polytetrafluoroethylene micropowder in Example 2 is coated with a continuous and uniform polydopamine layer. The polydopamine coating is generally film-like, and there is a small amount of nano-scale particle accumulation structure. The coating is complete and there is no obvious exposed area; while the coating effect in Comparative Example 3 is not good; and further extending the continuous reaction time in Comparative Example 3 to 48h, it is still impossible to achieve continuous and uniform coating of the polytetrafluoroethylene micropowder.

[0050] The polyetheretherketone composite material for repairing the temporomandibular joint disc obtained in Example 2 was subjected to FT-IR analysis and compared with the composite material of Comparative Example 2 and the composite material of Comparative Example 3. The test results are as follows: Figure 2 As shown, Figure 2 a, b, and c represent Example 2, Comparative Example 2, and Comparative Example 3, respectively. In the infrared absorption spectrum, the 3442 cm-1 corresponding to the NH group in Example 2 was observed. -1 The tensile vibration peak at 300 nm can be attributed to the -NH2 functional group of the polydopamine coating, while the corresponding vibration peak does not appear in the composite materials of Comparative Example 2 and Comparative Example 3, indicating that the modification method of dopamine self-polymerization successfully forms a polydopamine coating on the surface of the polytetrafluoroethylene micropowder.

[0051] The mechanical properties of the polyetheretherketone composite materials obtained in Examples 1 to 3 of the present invention were analyzed and compared with the pure polyetheretherketone material obtained in Comparative Example 1, the composite material obtained in Comparative Example 2, the composite material obtained in Comparative Example 3 and the polyetheretherketone composite material obtained in Comparative Example 4. The test results are as follows: Figure 3 As shown in (a) and (b), Figure 3 a, b, c, d, e, and f represent Comparative Example 1, Comparative Example 2, Comparative Example 3, and Examples 1 to 3, respectively.

[0052] Depend on Figure 3 It can be seen that the tensile strength and flexural strength of the composite material obtained in Example 2 reached 73.63 ± 0.69 MPa and 81.1 ± 3.8 MPa, respectively, which is very consistent with the test data on the mechanical properties of the temporomandibular joint disc in existing studies. The material obtained in Example 4 was not subjected to temperature gradient control, and showed poor mechanical strength, and it was impossible to prepare test samples for performance testing.

[0053] The polyetheretherketone composite materials obtained in Examples 1 to 3 of the present invention were subjected to TG and DSC analysis and compared with the pure polyetheretherketone material of Comparative Example 1 and the polytetrafluoroethylene / polyetheretherketone composite material with a mass fraction of 30% of Comparative Example 2. The test results are as follows: Figure 4 As shown in (a) and (b), Figure 4 a, b, c, d, and e represent Comparative Example 1, Comparative Example 2, and Examples 1 to 3, respectively.

[0054] Depend on Figure 4 (a) It can be seen that the introduction of polytetrafluoroethylene in the composite materials of Examples 1 to 3 and Comparative Example 2 accelerates the thermal degradation process of the materials. This is because in the initial stage (room temperature to 540°C), the thermal decomposition of polytetrafluoroethylene dominates. After exceeding 600°C, the aromatic rings in the polyetheretherketone main chain begin to break, and the remaining aromatic structures undergo cross-linking or polymerization to form stable carbonaceous residues. At 800°C, the thermal residual mass of the composite materials of Examples 1 to 2 is higher than that of the polyetheretherketone material. This is because polydopamine can reduce the decomposition rate of polytetrafluoroethylene to a certain extent, thereby reducing the overall degradation rate. Figure 4 (b) It can be seen that the polydopamine layer interacts with the PTFE molecular chains, altering the arrangement of the PTFE molecular segments. This indirectly affects the local crystallinity and melting behavior of the PTFE, shifting the melting peaks of both PTFE and PEEK to higher temperatures. These results demonstrate the improved thermal stability of the resulting composite, ensuring its suitability for high-temperature processing, repeated sterilization, and long-term implantation.

[0055] The tribological test was conducted on the polyetheretherketone composite material for repairing the temporomandibular joint disc of Example 2 of the present invention, and compared with the pure polyetheretherketone material of Comparative Example 1 and the polytetrafluoroethylene / polyetheretherketone composite material with a mass fraction of 30% of Comparative Example 2. The test results are as follows: Figure 5 shown. Figure 5 (a) and (b) represent the friction coefficient diagram and wear rate diagram of the material, respectively. Figure 5 a, b, and c represent Comparative Example 1, Comparative Example 2, and Example 2, respectively.

[0056] Depend on Figure 5 (a) It can be seen that in the initial stage of the friction test, the composite material of Comparative Example 2 and the composite material of Example 2 were observed to have similar friction coefficients. However, as the friction time increased, the composite material of Example 2 showed a lower friction coefficient. The composite materials of Comparative Example 2 and Example 2 both showed a significant decrease in friction coefficient compared to the composite material of Comparative Example 1. After the friction test, the wear rate of the composite materials was calculated. Figure 5 As shown in (b), the wear rate of the composite material of Example 2 is 3.54×10 -7 mm 3 / nm, which is significantly lower than that of Comparative Example 1 (6.18×10 -7 mm 3 / nm) and the composite material of comparative example 2 (4.58×10 -7 mm 3 These results indicate that the introduction of the polydopamine layer effectively improves the tribological properties of the composite material.

[0057] The polyetheretherketone composite material for repairing the temporomandibular joint disc of Example 2 of the present invention was subjected to in vitro biocompatibility analysis and compared with the pure polyetheretherketone material of Comparative Example 1 and the polytetrafluoroethylene / polyetheretherketone composite material with a mass fraction of 30% of Comparative Example 2. The test results are as follows: Figure 6 shown. Figure 6 a, b, and c represent Comparative Example 1, Comparative Example 2, and Example 2, respectively.

[0058] Depend on Figure 6 It can be seen that as the culture time increases, the cells on the surface of the composite material of Example 2 proliferate more significantly than those on the surfaces of the composite materials of Comparative Examples 1 and 2. This demonstrates that the composite material is non-toxic to cells and has good biocompatibility.

[0059] The photothermal conversion performance of the polyetheretherketone composite material for repairing the temporomandibular joint disc of Example 2 of the present invention was tested and compared with the pure polyetheretherketone material of Comparative Example 1 and the polytetrafluoroethylene / polyetheretherketone composite material with a mass fraction of 30% of Comparative Example 2. The test results are as follows: Figure 7 The wavelength of the selected near-infrared light source is 808nm. Figure 7 (a), (b), (c), and (d) represent the temperature rise of the material under near-infrared light of different power densities under wet conditions, and the temperature rise under wet conditions of 0.5 W / cm 2 Photothermal cycle stability spectrum of the polyetheretherketone composite material for repairing temporomandibular joint disc under near-infrared light irradiation with different power density and drying conditions; Real-time temperature rise spectrum of the polyetheretherketone composite material for repairing temporomandibular joint disc under near-infrared light irradiation with different power density and drying conditions; Photothermal cycle stability spectrum of the polyetheretherketone composite material for repairing temporomandibular joint disc under near-infrared light irradiation with different power density. Figure 7 a, b, and c represent Comparative Example 1, Comparative Example 2, and Example 2, respectively.

[0060] Depend on Figure 7 (a) It can be seen that the composite material of Example 2 shows the best photothermal conversion ability under the three power densities of near-infrared light irradiation, and the temperature rise after 15 minutes of irradiation reaches 22.3±0.1°C, 33.8±0.2°C and 46.4±0.2°C respectively. Figure 7 As shown in (b), after 5 photothermal cycles (each lasting 30 minutes), the composite material of Example 2 can still maintain its photothermal conversion ability, showing good photothermal cycle stability. Figure 7 (c) It can be seen that the photothermal conversion of the composite material of Example 2 under dry conditions also depends on the power density. 2After 15 minutes of near-infrared light irradiation, the maximum temperatures reached 64.5 ± 0.2°C, 75.2 ± 0.1°C, 110.2 ± 0.2°C and 166.6 ± 0.3°C, respectively. Figure 7 (d) shows the temperature increase and decrease of the composite material of Example 2 during five photothermal cycles, indicating that it has good photothermal cycling stability under dry conditions.

[0061] The polyetheretherketone composite material for repairing the temporomandibular joint disc of Example 2 of the present invention was tested for in vitro photothermal antibacterial activity, and compared with the pure polyetheretherketone material of Comparative Example 1, the polytetrafluoroethylene / polyetheretherketone composite material with a mass fraction of 30% of Comparative Example 2, and a blank control group containing no material. The test results are as follows: Figure 8 The test bacteria selected were Gram-positive Staphylococcus aureus ( S. aureus ) and Gram-negative Escherichia coli ( E. coli ). Figure 8 (a) and (b) in the figure respectively represent the inhibition rate maps against Staphylococcus aureus and Escherichia coli. Figure 8 a, b, c, and d represent the blank control group, comparative example 1, comparative example 2, and embodiment 2, respectively.

[0062] Depend on Figure 8 As can be seen, Example 2 exhibited the best antibacterial effect, achieving 99.6 ± 0.1% and 92.5 ± 0.2% inhibition rates against Staphylococcus aureus and Escherichia coli, respectively, both without near-infrared light (NIR-) and with near-infrared light (NIR+). Notably, even without NIR irradiation, Example 2 achieved inhibition rates of 48.1 ± 6.4% and 31.7 ± 2.5% against Staphylococcus aureus and Escherichia coli, respectively. This can be attributed to the polydopamine layer disrupting the integrity of the bacterial cell membrane through electrostatic interactions and protein chelation.

[0063] The present invention prepares polydopamine-coated polytetrafluoroethylene micropowder by in-situ polymerization, and prepares a polyetheretherketone composite material for repairing the temporomandibular joint disc by ball milling and blending. The polydopamine-coated polytetrafluoroethylene is attached to the polyetheretherketone matrix through hydrogen bonding and π-π stacking, thereby enhancing the interfacial bonding of the composite material. The mechanical strength of the material system is regulated to be compatible with the temporomandibular joint disc. The prepared material system has excellent tribological properties and excellent photothermal antibacterial properties, which solves the problems of the existing polyetheretherketone material not matching the mechanical properties of the temporomandibular joint disc, poor friction properties, and inability to achieve photothermal antibacterial properties. It is expected to become an ideal repair material for the temporomandibular joint disc.

[0064] The above description is only a specific embodiment of the present invention, but the protection scope of the present invention is not limited thereto. Those skilled in the art should understand that any changes or substitutions that can be easily thought of by those skilled in the art within the technical scope disclosed by the present invention fall within the protection scope and disclosure scope of the present invention.

Claims

1. A polyetheretherketone composite repair material, characterized in that: The invention comprises a polyetheretherketone matrix and polydopamine-coated polytetrafluoroethylene dispersed therein; wherein the polydopamine coating is in a film-like and / or nano-particle stacking structure.

2. The polyetheretherketone composite repair material according to claim 1, characterized in that The polydopamine-coated polytetrafluoroethylene accounts for 5-30% of the mass of the polyetheretherketone matrix.

3. The method for preparing the polyetheretherketone composite repair material according to any one of claims 1 to 2, characterized in that: The following steps are involved: 1) Under stirring, adding polytetrafluoroethylene micropowder to an organic solvent and ultrasonically dispersing the mixture, then adding dopamine hydrochloride, performing a first continuous reaction under stirring, centrifuging, and drying to obtain polytetrafluoroethylene micropowder with dopamine adhered to the surface; 2) adding the obtained polytetrafluoroethylene micropowder to an alkaline buffer solution, ultrasonically dispersing the micropowder, then adding dopamine hydrochloride, performing a second continuous reaction under stirring, centrifuging, and drying to obtain polydopamine-coated polytetrafluoroethylene micropowder; 3) The obtained polydopamine-coated polytetrafluoroethylene micropowder and polyetheretherketone are subjected to high-speed ball milling to obtain a granular polyetheretherketone composite repair material.

4. The preparation method according to claim 3, characterized in that In step 1), the mass ratio of polytetrafluoroethylene micropowder to dopamine hydrochloride is 1:1-3.

5. The preparation method according to claim 3, characterized in that The organic solvent can be selected from one or more of anhydrous ethanol, isopropanol, and acetone; the pH value of the alkaline buffer solution is 7.5-8.

5.

6. The preparation method according to claim 3, characterized in that The first continuous reaction time was 18-24 h, and the stirring rate was 500-800 rpm; the second continuous reaction time was 18-24 h, and the stirring rate was 500-800 rpm.

7. The preparation method according to claim 3, characterized in that The mass ratio of the polytetrafluoroethylene micropowder with dopamine adhered to the surface to dopamine hydrochloride is 1-4:

1.

8. The preparation method according to claim 3, characterized in that The mass ratio of polydopamine-coated polytetrafluoroethylene micropowder to polyetheretherketone is 5:95~30:

70.

9. Use of the polyetheretherketone composite repair material according to claim 1 or 2 or the polyetheretherketone composite repair material obtained by the preparation method according to claim 3 in preparing a temporomandibular joint disc repair, characterized in that: The method comprises the following steps: melting and extruding a polyetheretherketone composite repair material, and performing injection molding to obtain a repair object.

10. The use according to claim 9, characterized in that In the melt extrusion step, the temperature of each section of the extrusion zone is gradually increased between 360 and 380°C. The specific temperature zones are controlled as follows: feeding section: 320 to 340°C; plasticizing section: 340 to 360°C; Melting section: 360~380°C; Die temperature: 360~370°C.

Images