Polyetheretherketone / graphene oxide / polydopamine-coated zirconia composite material, its preparation method and application

Abstract

The present invention discloses a polyetheretherketone / graphene oxide / polydopamine-coated zirconia composite material, its preparation method and application. First, dopamine and nano-zirconia are polymerized in a Tris-HCl solution through an in-situ polymerization method to form a polydopamine coating layer on the surface of zirconia, and polydopamine-coated zirconia nanoparticles are prepared. Subsequently, polydopamine-coated nano-zirconia particles, graphene oxide and polyetheretherketone are sequentially added to water, and stirred and mixed to obtain granular polyetheretherketone / graphene oxide / polydopamine-coated zirconia composite material. The material prepared by the present invention has excellent mechanical properties and good biocompatibility. At the same time, the photothermal effect of polydopamine endows the material system with the functions of photothermal bone promotion and photothermal antibacterial, and it is applied to the preparation of bone repair scaffolds to solve the problems that existing polyetheretherketone scaffold materials cannot have both high strength, good bioactivity, poor osteogenic performance and no antibacterial property.

Description

Technical Field

[0001] The present invention belongs to the technical field of biomedical materials, and particularly relates to a polyetheretherketone / graphene oxide / polydopamine-coated zirconia composite material, a preparation method thereof, and an application thereof. Background Art

[0002] With the continuous acceleration of population aging in China, the elderly are at a higher risk of suffering from osteoporosis and osteoarthritis. Coupled with bone tissue injuries caused by traffic accidents and sports injuries, higher requirements are put forward for bone repair scaffolds. Developing biomedical composite artificial bone repair materials with high strength and good biocompatibility is an urgent and major need for tissue and organ repair in the development of clinical medicine in China.

[0003] Due to the excellent mechanical properties and good chemical resistance of polyetheretherketone, it shows broad application prospects in hard tissue repair and orthopedic surgery. However, the mechanical strength of polyetheretherketone is relatively low, making it difficult to meet the requirements of hard tissue repair materials. Moreover, due to its inherent biological inertness, it is difficult to form good bone integration with the surrounding implanted site. In addition, polyetheretherketone materials do not have the ability to inhibit bacterial growth, and are prone to severe bacterial infection after implantation, ultimately leading to implantation failure. Nano-zirconia is often used to improve the mechanical properties and biocompatibility of polyetheretherketone composites due to its good biocompatibility and bone induction characteristics. However, in the preparation process of polyetheretherketone / zirconia composites, due to the high surface energy and easy agglomeration of nano-zirconia particles, the mechanical properties of the composites are often greatly reduced, making it difficult to meet the application requirements. Therefore, how to prepare a polyetheretherketone / nano-zirconia biocomposite material with both good mechanical properties and good biological activity, promoting bone regeneration and antibacterial properties, remains a difficult problem. Summary of the Invention

[0004] The present invention is proposed to solve the problems that existing polyetheretherketone scaffold materials cannot have both high strength, good biological activity, poor osteogenic performance, and no antibacterial property. The purpose is to provide a polyetheretherketone / graphene oxide / polydopamine-coated zirconia composite material, a preparation method thereof, and an application thereof.

[0005] The present invention is achieved through the following technical solutions:

[0006] A polyetheretherketone / graphene oxide / polydopamine-coated zirconia composite material, wherein the polydopamine-coated zirconia and graphene oxide are uniformly dispersed in a polyetheretherketone matrix by an aqueous solution dispersion method; the polydopamine-coated zirconia and graphene oxide are attached to the polyetheretherketone matrix through intermolecular forces; the intermolecular forces are π-π conjugate interactions and hydrogen bonds; the thickness of the polydopamine coating layer of the polydopamine-coated zirconia is 2 nm to 8 nm, preferably, the thickness of the polydopamine coating layer of the polydopamine-coated zirconia is 4.37 ± 1.36 nm; the mass ratio of polyetheretherketone, graphene oxide and polydopamine-coated zirconia in the composite material is: 10:1:89, 10:3:87 or 10:5:85; the composite material has the ability to chelate calcium ions, and the composite material has the functions of photothermal osteogenesis and photothermal antibacterial.

[0007] A preparation method of a polyetheretherketone / graphene oxide / polydopamine-coated zirconia composite material, comprising the following steps:

[0008] (Ⅰ) Under stirring, add nano-zirconia to a Tris-HCl solution, ultrasonically disperse, then add dopamine hydrochloride to the dispersed solution, continuously react under stirring, and perform centrifugal separation. The obtained solid is freeze-dried to obtain polydopamine-coated zirconia nanoparticles;

[0009] (Ⅱ) Add the polydopamine-coated nano-zirconia particles, graphene oxide and polyetheretherketone obtained in step (Ⅰ) to water in sequence, ultrasonically disperse, stir and mix, perform centrifugal separation, and the obtained solid is freeze-dried to obtain granular polyetheretherketone / graphene oxide / polydopamine-coated zirconia composite material.

[0010] In the above technical solution, the concentration of the Tris-HCl solution is 8 mmol / L to 12 mmol / L, preferably 10 mmol / L; the mass ratio of the nano-zirconia to dopamine hydrochloride is 1:1 to 3:1, preferably 2:1; the concentration of dopamine hydrochloride is 0.002 g / mL to 0.006 g / mL, preferably 0.004 g / mL; both the nano-zirconia and dopamine hydrochloride are added to the Tris-HCl solution in powder form.

[0011] In the above technical solution, in step (Ⅰ), after adding nano-zirconia, ultrasonically disperse for 15 min to 30 min to improve the dispersion of nano-zirconia in the aqueous solution and ensure that dopamine can be uniformly coated on the surface of the nanoparticles during the self-polymerization process; after adding dopamine hydrochloride, continuously react at room temperature under stirring for 24 h, the centrifugal rotation speed is 8000 rpm, centrifuge 6 to 8 times, and freeze-dry for 12 h to 24 h.

[0012] In the above technical solution, the mass ratio of polydopamine-coated nano-zirconia particles, graphene oxide, and polyetheretherketone in step (II) is: 10:1:89, 10:3:87, or 10:5:85.

[0013] In the above technical solution, the mass concentration of polydopamine-coated nano-zirconia particles in water in step (II) is 8% - 12%, preferably 10%.

[0014] In the above technical solution, in step (II), ultrasonic dispersion is carried out for 15 min - 30 min, stirring and mixing is carried out for 4 h, the centrifugation speed is 8000 rpm, centrifugation is carried out 6 - 8 times, and freeze-drying is carried out for 12 h - 24 h.

[0015] Application of a polyetheretherketone / graphene oxide / polydopamine-coated zirconia composite material in a bone repair scaffold.

[0016] A preparation method of a polyetheretherketone / graphene oxide / polydopamine-coated zirconia composite material bone repair scaffold. The polyetheretherketone / graphene oxide / polydopamine-coated zirconia composite material is ball-milled and injection-molded to obtain the polyetheretherketone / graphene oxide / polydopamine-coated zirconia composite material bone repair scaffold.

[0017] In the above technical solution, the ball-milling rate is 200 rpm - 500 rpm, and the duration is 4 h - 6 h.

[0018] The beneficial effects of the present invention are:

[0019] The present invention provides a polyetheretherketone / graphene oxide / polydopamine-coated zirconia composite material. Dopamine and nano-zirconia are polymerized in a Tris-HCl solution by an in-situ polymerization method to form a polydopamine coating layer on the surface of zirconia, and polydopamine-coated zirconia nanoparticles are prepared. Graphene oxide and polyetheretherketone powder are added to an aqueous solution to promote the dispersion of polydopamine-coated zirconia in the polyetheretherketone material, enhance the interfacial bonding between the two, improve the mechanical properties of the polyetheretherketone composite material, and improve the bioactivity of the composite material. At the same time, the introduced polydopamine coating layer endows the material system with a good photothermal effect. The prepared material has excellent mechanical properties, good biocompatibility, osteogenic ability, and antibacterial properties. Applying it to the preparation of a bone repair scaffold is expected to provide a high-performance biomedical composite material for fields such as hard tissue bone repair and medical beauty. Description of the Drawings

[0020] Figure 1 It is a TEM photograph of the polydopamine-coated zirconia nanocomposite material prepared by the present invention and a distribution diagram of the particle size of the nanoparticles and the thickness of the polydopamine coating layer;

[0021] Figure 2 XRD patterns of the polyetheretherketone / graphene oxide / polydopamine-coated zirconia composites of Examples 1 to 3 of the present invention, the pure polyetheretherketone material of Comparative Example 1, and the polyetheretherketone / zirconia nanocomposite of Comparative Example 2;

[0022] Figure 3 Thermal property patterns of the polyetheretherketone / graphene oxide / polydopamine-coated zirconia composites of Examples 1 to 3 of the present invention, the pure polyetheretherketone material of Comparative Example 1, and the polyetheretherketone / zirconia nanocomposite of Comparative Example 2;

[0023] Figure 4 Mechanical property patterns of the polyetheretherketone / graphene oxide / polydopamine-coated zirconia composites of Examples 1 to 3 of the present invention, the pure polyetheretherketone material of Comparative Example 1, and the polyetheretherketone / zirconia nanocomposite of Comparative Example 2;

[0024] Figure 5 In vitro biocompatibility patterns of the polyetheretherketone / graphene oxide / polydopamine-coated zirconia composites of Examples 1 to 3 of the present invention, the pure polyetheretherketone material of Comparative Example 1, and the polyetheretherketone / zirconia nanocomposite of Comparative Example 2;

[0025] Figure 6 SEM photos of the in vitro osteogenesis of the polyetheretherketone / graphene oxide / polydopamine-coated zirconia composite of Example 1 of the present invention, the pure polyetheretherketone material of Comparative Example 1, and the polyetheretherketone / zirconia nanocomposite of Comparative Example 2;

[0026] Figure 7 Antibacterial property diagrams and antibacterial rate diagrams of the polyetheretherketone / graphene oxide / polydopamine-coated zirconia composite of Example 1 of the present invention, the pure polyetheretherketone material of Comparative Example 1, the polyetheretherketone / zirconia nanocomposite of Comparative Example 2, and the blank control group.

[0027] For those of ordinary skill in the art, other related drawings can be obtained based on the above drawings without creative efforts. Detailed Embodiments

[0028] In order to enable those skilled in the art to better understand the technical solutions of the present invention, the technical solutions of the present invention will be further described below with reference to the accompanying drawings of the specification and through specific embodiments.

[0029] Example 1

[0030] A preparation method of a polyetheretherketone / graphene oxide / polydopamine-coated zirconia composite bone repair scaffold specifically includes the following steps:

[0031] (i) Prepare 1 L of Tris-HCl solution with a concentration of 10 mmol / L. Under stirring at room temperature, first add 8 g of nano-zirconia powder to the solution according to a mass ratio of 2:1. Subsequently, ultrasonically disperse for 15 min. Then add 4 g of dopamine hydrochloride powder to the dispersed solution and continuously react for 24 h under stirring at room temperature. Centrifuge at 8000 rpm for 6 times and freeze-dry for 12 h to obtain polydopamine-coated zirconia nanoparticles;

[0032] (ii) Add polydopamine-coated nano-zirconia particles, graphene oxide, and polyetheretherketone with mass fractions of 10%, 1%, and 89% respectively, with specific masses of 20 g, 2 g, and 178 g, into an aqueous solution. Ultrasonically disperse for 15 min, stir and mix for 4 h, centrifuge at 8000 rpm for 6 times, and freeze-dry for 12 h to obtain granular polyetheretherketone / graphene oxide / polydopamine-coated zirconia composite material;

[0033] (iii) Ball-mill and disperse the obtained composite material at 400 rpm for 4 h and then injection-mold to obtain a polyetheretherketone / graphene oxide / polydopamine-coated zirconia composite bone repair scaffold.

[0034] Example 2

[0035] A preparation method of a polyetheretherketone / graphene oxide / polydopamine-coated zirconia composite bone repair scaffold specifically includes the following steps:

[0036] (i) Prepare 1 L of Tris-HCl solution with a concentration of 10 mmol / L. Under stirring at room temperature, first add 8 g of nano-zirconia powder to the solution according to a mass ratio of 2:1. Subsequently, ultrasonically disperse for 15 min. Then add 4 g of dopamine hydrochloride powder to the dispersed solution and continuously react for 24 h under stirring at room temperature. Centrifuge at 8000 rpm for 6 times and freeze-dry for 12 h to obtain polydopamine-coated zirconia nanoparticles;

[0037] (ii) Add polydopamine-coated nano-zirconia particles, graphene oxide, and polyetheretherketone with mass fractions of 10%, 3%, and 87% respectively, with specific masses of 20 g, 6 g, and 174 g, into an aqueous solution. Ultrasonically disperse for 15 min, stir and mix for 4 h, centrifuge at 8000 rpm for 6 times, and freeze-dry for 12 h to obtain granular polyetheretherketone / graphene oxide / polydopamine-coated zirconia composite material;

[0038] (iii) Ball-mill and disperse the obtained composite material at 400 rpm for 4 h and then injection-mold to obtain a polyetheretherketone / graphene oxide / polydopamine-coated zirconia composite bone repair scaffold.

[0039] Example 3

[0040] A preparation method of a polyetheretherketone / graphene oxide / polydopamine-coated zirconia composite bone repair scaffold, specifically including the following steps:

[0041] (ⅰ) Prepare 1 L of a 10 mmol / L Tris-HCl solution. Under stirring at room temperature, first add 8 g of nano-zirconia powder to the solution according to a mass ratio of 2:1, then ultrasonically disperse for 15 min. Subsequently, add 4 g of dopamine hydrochloride powder to the dispersed solution and continuously react under stirring at room temperature for 24 h. Centrifuge at 8000 rpm for 6 times and freeze-dry for 12 h to obtain polydopamine-coated zirconia nanoparticles;

[0042] (ⅱ) Add polydopamine-coated nano-zirconia particles, graphene oxide, and polyetheretherketone to an aqueous solution according to mass fractions of 10%, 5%, and 85% respectively, with specific masses of 20 g, 10 g, and 170 g respectively. Ultrasonically disperse for 15 min, stir and mix for 4 h, centrifuge at 8000 rpm for 6 times, and freeze-dry for 12 h to obtain granular polyetheretherketone / graphene oxide / polydopamine-coated zirconia composite materials;

[0043] (ⅲ) Ball-mill and disperse the obtained composite materials at 400 rpm for 4 h and then injection-mold to obtain a polyetheretherketone / graphene oxide / polydopamine-coated zirconia composite bone repair scaffold.

[0044] To further verify the performance of the bone repair scaffold prepared from the polyetheretherketone / graphene oxide / polydopamine-coated zirconia composite material of this application, the following comparative examples are set:

[0045] Comparative Example 1

[0046] Using the same preparation conditions as in step (ⅲ) of Example 1, extrude and injection-mold with pure polyetheretherketone particles (without graphene oxide and polydopamine-coated zirconia) as the material to prepare a bone repair scaffold.

[0047] Comparative Example 2

[0048] Using the same preparation conditions as in step (ⅲ) of Example 1, extrude and injection-mold with polyetheretherketone and nano-zirconia according to a mass ratio of 9:1 (without graphene oxide and polydopamine) as the material to prepare a bone repair scaffold.

[0049] Perform TEM analysis on the polydopamine-coated zirconia nanoparticles (b) used in Examples 1 to 3 of the present invention and compare them with unpolymerized and modified zirconia nanoparticles (a) to characterize the thickness and uniformity of the polydopamine coating layer. The test results are as Figure 1As shown, the particle size of the zirconia nanoparticles and the thickness of the polydopamine coating layer are both evenly distributed, indicating that the dopamine self-polymerization modification method used successfully formed a polydopamine coating layer with a uniform thickness on the surface of the nano-zirconia, and the thickness is 4.37 ± 1.36 nm.

[0050] XRD analysis was performed on the polyetheretherketone / graphene oxide / zirconia dioxide composite materials of Examples 1 to 3 of the present invention, and they were compared with the pure polyetheretherketone material of Comparative Example 1 and the nano-zirconia / polyetheretherketone composite material of Comparative Example 2 with a mass fraction of 10%. The test results are as Figure 2 shown, Figure 2 where a, b, c, d, and e in

[0051] are respectively represented as Comparative Example 1, Comparative Example 2, and Examples 1 to 3. Figure 2 It can be seen that the main diffraction peaks of the XRD patterns of the polyetheretherketone / graphene oxide / zirconia dioxide composite materials of Examples 1 to 3 are all composed of the superimposition of the characteristic diffraction peaks of polyetheretherketone and zirconia dioxide, and the positions of each main diffraction peak did not change significantly, nor was there the generation of new diffraction peaks, indicating that in each example and the comparative examples containing nano-zirconia, the two are physically mixed and there is no change in the lattice constant.

[0052] TG and DSC analysis were performed on the polyetheretherketone / graphene oxide / zirconia dioxide composite materials of Examples 1 to 3 of the present invention, and they were compared with the pure polyetheretherketone material of Comparative Example 1 and the nano-zirconia / polyetheretherketone composite material of Comparative Example 2 with a mass fraction of 10%. The test results are respectively as Figure 3 (a) and (b) shown, Figure 3 where a, b, c, d, and e in

[0053] are respectively represented as Comparative Example 1, Comparative Example 2, and Examples 1 to 3. Figure 3It can be seen that in the TG spectra of the polyetheretherketone / graphene oxide / polydopamine-coated zirconia composites of Examples 1 to 3, as the content of graphene oxide increases, the thermal decomposition temperature and the final carbon yield of the composites gradually increase. The maximum thermal degradation temperature reaches the maximum value of 343.48 °C in Example 3, i.e., when the content of graphene oxide is 5%, indicating that the modification of zirconia by dopamine coating and the addition of graphene oxide can improve the thermal stability of the composites. At the same time, the DSC spectra of the polyetheretherketone / graphene oxide / polydopamine-coated zirconia composites of Examples 1 to 3 show that as the content of graphene oxide increases, the crystallization temperature of the composites gradually increases, and the crystallinity first increases and then slightly decreases. The crystallinity reaches the maximum value of 40.16% in Example 1, i.e., when the content of graphene oxide is 1%, which is much higher than 29.75% of Comparative Example 1 and 30.45% of Comparative Example 2. This is mainly because the coating modification of dopamine and the addition of graphene oxide improve the binding ability between nano-zirconia and the polyetheretherketone matrix, promote the dispersion of nano-zirconia in the polyetheretherketone matrix, and improve the crystallization performance and thermal stability of the composites.

[0054] The mechanical properties of the polyetheretherketone / graphene oxide / polydopamine-coated zirconia composites of Examples 1 to 3 of the present invention were analyzed and compared with the pure polyetheretherketone material of Comparative Example 1 and the nano-zirconia / polyetheretherketone composite material of Comparative Example 2 with a mass fraction of 10%. The test results are as Figure 4 shown. Figure 4 (a) and (b) respectively show the tensile strength and surface hardness data graphs of the polyetheretherketone / graphene oxide / polydopamine-coated zirconia composites with different graphene oxide contents. Figure 4 In which a, b, c, d, and e respectively represent Comparative Example 1, Comparative Example 2, and Examples 1 to 3.

[0055] From Figure 4 (a), it can be seen that with the addition of graphene oxide and the coating modification of polydopamine, the tensile strength of the composite material first increases and then decreases. When the coating modification of polydopamine and the content of graphene oxide are 1%, the tensile strength of the composite material reaches the maximum value of 102.39 ± 3.97 MPa, which is 8.53% higher than the tensile strength of the pure polyetheretherketone material (94.34 ± 5.87 MPa). When the content of graphene oxide is 3% and 5%, the tensile strength of the composite material slightly decreases. This is because as the content of graphene oxide increases, agglomeration occurs, which becomes a stress concentration point during the tensile process and fractures first, resulting in a decrease in the tensile strength of the material. From Figure 4As can be seen from (b), with the addition of graphene oxide and the modification by polydopamine coating, the surface hardness of the composite material gradually increases and reaches a maximum value of 86.3 ± 0.51 HD when the content of graphene oxide is 5%. Compared with 80.22 ± 1.64 HD of the pure polyetheretherketone material, it is increased by 7.58% and there is no downward trend. The addition of graphene oxide and the modification by polydopamine coating significantly improve the hardness value of the composite material.

[0056] The in vitro biocompatibility of the polyetheretherketone / graphene oxide / polydopamine-coated zirconia composites of Examples 1 to 3 of the present invention was analyzed, and they were compared with the pure polyetheretherketone material of Comparative Example 1 and the nanometer zirconia / polyetheretherketone composite material of Comparative Example 2 with a mass fraction of 10%. The test results are as Figure 5 shown. Figure 5 In (a) and (b) respectively show the in vitro cytotoxicity and the cell adhesion diagram on the material surface of the polyetheretherketone / graphene oxide / polydopamine-coated zirconia composites with different graphene oxide contents. Figure 5 a, b, c, d, and e in it respectively represent Comparative Example 1, Comparative Example 2, and Examples 1 to 3.

[0057] From Figure 5 (a), it can be seen that after the addition of graphene oxide and the modification by polydopamine coating, the cell survival rates on the 1st, 3rd, and 5th days are all above 90%, proving that the biocompatibility of the material is good. Figure 5 (b) shows the adhesion of mouse fibroblasts on the material surface. It can be seen that the cell morphology on the surface of the pure polyetheretherketone group is the worst, all being spherical. After the addition of nanometer zirconia, the cell morphology is improved and the cells have a certain degree of spreading, but no obvious pseudopodia are observed in both cases. However, after the composite of graphene oxide and the modification by polydopamine coating, obvious pseudopodia of the cells can be observed, and the state of cell spreading and adhesion is better, indicating that the composite modification can improve the affinity of the material for cells.

[0058] The in vitro mineralization performance of the polyetheretherketone / graphene oxide / polydopamine-coated zirconia composite material of Example 1 of the present invention was analyzed, and it was compared with the pure polyetheretherketone material of Comparative Example 1 and the nanometer zirconia / polyetheretherketone composite material of Comparative Example 2 with a mass fraction of 10%. The test results are as Figure 6 shown. Figure 6 a, b, and c in it respectively represent Comparative Example 1, Comparative Example 2, and Example 1.

[0059] From Figure 6It can be seen that the surface of the pure polyetheretherketone material, i.e., the material of Comparative Example 1, is relatively smooth, and almost no mineralized nodules are formed. After zirconia composite modification, some mineralized nodules are formed on the material surface. After modification with composite graphene oxide and polydopamine-coated zirconia, a large number of mineralized nodules are formed on the material surface, and the crystal morphology is stable. This is mainly because polydopamine can chelate calcium ions in body fluids and promote the mineralization of the material surface. The improvement of the in vitro mineralization ability of the material is beneficial to the bone integration of the bone implant material in vivo.

[0060] The in vitro photothermal antibacterial performance of the polyetheretherketone / graphene oxide / polydopamine-coated zirconia composite material of Example 1 of the present invention was analyzed, and its antibacterial situation after applying near-infrared light radiation was compared with that of the pure polyetheretherketone material of Comparative Example 1, the 10% mass fraction of nano-zirconia / polyetheretherketone composite material of Comparative Example 2, and the blank control group without material. The test results are as Figure 7 shown. The test bacteria selected were the Gram-positive bacterium Staphylococcus aureus (S. aureus) and the Gram-negative bacterium Escherichia coli (E. coli). Figure 7 In (a), (b), and (c) are respectively the optical photos of the photothermal antibacterial performance and the columnar graphs of the antibacterial rates corresponding to E. coli and S. aureus. Figure 7 In which a, b, c, and d represent the blank control group, Comparative Example 1, Comparative Example 2, and Example 1 respectively.

[0061] From Figure 7 it can be seen that under the condition of not applying near-infrared light irradiation (NIR-), Comparative Example 1 and Comparative Example 2 have no antibacterial property against Escherichia coli and Staphylococcus aureus, and to a certain extent, promote the reproduction of bacteria, while Example 1 has a certain antibacterial property under the condition of NIR-. Under the condition of applying near-infrared light irradiation (NIR+), Example 1 has excellent antibacterial properties against both bacteria, and the antibacterial rates are 99.43±0.65% and 95.45±5.15% respectively, and the antibacterial performance is good.

[0062] The present invention prepares polydopamine-coated zirconia nanoparticles with uniform coating thickness by in-situ polymerization, and uniformly disperses graphene oxide and polydopamine-coated zirconia nanoparticles in a polyether ether ketone matrix by an aqueous solution dispersion method. The mechanical properties of polyether ether ketone are enhanced by reinforcing with nanoparticles, and the interfacial bonding ability between the nanoparticles and the polyether ether ketone matrix is improved by intermolecular forces such as π-π conjugation interaction and hydrogen bonding. The polydopamine in the prepared composite scaffold has good biocompatibility, can chelate calcium ions in body fluids, and improve the ability of osteogenesis in vitro. At the same time, the polydopamine coating layer in the material system endows the material system with the ability of photothermal conversion, and has good photothermal promotion of bone regeneration and photothermal antibacterial ability, and is expected to become a bone repair implant material, acting on hard tissues such as the skull, tibia, and other joint parts.

[0063] The applicant declares that 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 conceived by those skilled in the art within the technical scope disclosed by the present invention fall within the protection scope and the disclosure scope of the present invention.

Claims

1. A method for preparing a polyetheretherketone / graphene oxide / polydopamine-coated zirconia composite material, characterized in that: It includes the following steps: (Ⅰ) Under stirring, add nano-zirconia into Tris-HCl solution, perform ultrasonic dispersion, then add dopamine hydrochloride into the dispersed solution, continuously react under stirring, perform centrifugal separation, and freeze-dry the obtained solid to obtain polydopamine-coated zirconia nanoparticles; (Ⅱ) Add the polydopamine-coated nano-zirconia particles, graphene oxide, and polyetheretherketone obtained in step (Ⅰ) into water in sequence, perform ultrasonic dispersion, stir and mix, perform centrifugal separation, and freeze-dry the obtained solid to obtain granular polyetheretherketone / graphene oxide / polydopamine-coated zirconia composite material; The graphene oxide and polydopamine-coated zirconia are uniformly dispersed in the polyetheretherketone matrix by an aqueous solution dispersion method; the graphene oxide and polydopamine-coated zirconia are attached to the polyetheretherketone matrix by intermolecular forces; the intermolecular forces are π-π conjugate interaction and hydrogen bond; The thickness of the polydopamine coating layer of the polydopamine-coated zirconia is 2 nm to 8 nm; In the polyetheretherketone / graphene oxide / polydopamine-coated zirconia composite material, the mass ratio of polydopamine-coated zirconia, graphene oxide, and polyetheretherketone is: 10:1:89, 10:3:87, or 10:5:85; The polyetheretherketone / graphene oxide / polydopamine-coated zirconia composite material has the ability to chelate calcium ions.

2. The method for preparing a polyetheretherketone / graphene oxide / polydopamine-coated zirconia composite material according to claim 1, characterized in that: The concentration of the Tris-HCl solution is 8 mmol / L to 12 mmol / L, and the mass ratio of the nano-zirconia to dopamine hydrochloride is 1:1 to 3:1; the concentration of dopamine hydrochloride is 0.002 g / mL to 0.006 g / mL; both the nano-zirconia and dopamine hydrochloride are added into the Tris-HCl solution in powder state.

3. The method for preparing a polyetheretherketone / graphene oxide / polydopamine-coated zirconia composite material according to claim 1, characterized in that: In step (Ⅰ), after adding nano-zirconia, perform ultrasonic dispersion for 15 min to 30 min; after adding dopamine hydrochloride, continuously react at room temperature under stirring for 24 h, the centrifugal speed is 8000 rpm, centrifuge 6 to 8 times, and freeze-dry for 12 h to 24 h.

4. The method for preparing a polyetheretherketone / graphene oxide / polydopamine-coated zirconia composite material according to claim 1, characterized in that: In step (Ⅱ), the mass concentration of the polydopamine-coated zirconia particles in water is 8% to 12%.

5. The method for preparing a polyetheretherketone / graphene oxide / polydopamine-coated zirconia composite material according to claim 1, characterized in that: In step (Ⅱ), perform ultrasonic dispersion for 15 min to 30 min, stir and mix for 4 h, the centrifugal speed is 8000 rpm, centrifuge 6 to 8 times, and freeze-dry for 12 h to 24 h.

6. The application of the polyetheretherketone / graphene oxide / polydopamine-coated zirconia composite material prepared by the method according to any one of claims 1 to 5 in the preparation of a bone repair scaffold.

7. A method for preparing a polyetheretherketone / graphene oxide / polydopamine-coated zirconia composite material bone repair scaffold by applying the method according to any one of claims 1 to 5, characterized in that: Ball-mill the polyetheretherketone / graphene oxide / polydopamine-coated zirconia composite material and perform injection molding to obtain a polyetheretherketone / graphene oxide / polydopamine-coated zirconia composite bone repair scaffold.

8. The method for preparing a polyetheretherketone / graphene oxide / polydopamine-coated zirconia composite material bone repair scaffold according to claim 7, characterized in that: The ball-milling rate is 200 rpm to 500 rpm, and the duration is 4 h to 6 h.

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