CN114904048A

CN114904048A - Polyether-ether-ketone base composite material and preparation method and application thereof

Info

Publication number: CN114904048A
Application number: CN202210741889.3A
Authority: CN
Inventors: 张洪玉; 王海蟒; 胡刻铭
Original assignee: Tsinghua University
Current assignee: Tsinghua University
Priority date: 2022-06-28
Filing date: 2022-06-28
Publication date: 2022-08-16
Anticipated expiration: 2042-06-28
Also published as: CN114904048B

Abstract

The invention relates to a polyether-ether-ketone base composite material and a preparation method and application thereof. The polyetheretherketone substrate composite comprises a polyetheretherketone substrate comprising a first surface and a second surface, the first and second surfaces being interconnected to form the entire outer surface of the polyetheretherketone substrate; the first surface is sequentially provided with a polydopamine layer and a polydopamine-modified nano hydroxyapatite layer, and the second surface is provided with a gel layer; the gel layer is prepared by carrying out gelation reaction on polyethylene glycol bisacrylamide and 2-methacryloyloxyethyl phosphorylcholine. The polyether-ether-ketone base composite material has good lubricity, compressive strength and osteogenesis capacity.

Description

Polyether-ether-ketone base composite material and preparation method and application thereof

Technical Field

The invention relates to the technical field of biological materials, in particular to a polyether-ether-ketone substrate composite material and a preparation method and application thereof.

Background

Osteochondral tissue is complex in structure and can withstand a certain degree of external force, but cartilage does not heal itself even after slight damage. The structure and function of the joint depend on the vitality of the cartilage, and arthritis and other diseases are very easy to occur if the cartilage is not available. Osteochondral defects are therefore a very common and problematic problem, with lesions ranging from articular cartilage to subchondral bone.

The current challenges in treating osteochondral defects are mainly: there are significant differences in the composition, structure and cells of articular cartilage and subchondral bone. In addition, the avascular nature of cartilage greatly limits its regenerative capacity. Given the heterogeneity of osteochondral regions, the design of a bi-layer scaffold may better integrate significantly different structural and mechanical properties into the overall material.

However, it is difficult for the conventional double-layered scaffold to simultaneously satisfy the requirements for the lubricity, mechanical properties and osteogenesis ability in the osteochondral repair.

Disclosure of Invention

Based on the polyether-ether-ketone base composite material, the preparation method and the application thereof are provided.

In a first aspect of the invention, there is provided a polyetheretherketone substrate composite comprising a polyetheretherketone substrate comprising a first surface and a second surface, the first and second surfaces being interconnected to form the entire outer surface of the polyetheretherketone substrate;

the first surface is sequentially provided with a polydopamine layer and a polydopamine-modified nano hydroxyapatite layer, and the second surface is provided with a gel layer; the gel layer is prepared by carrying out polymerization reaction on polyethylene glycol bisacrylamide and 2-methacryloyloxyethyl phosphorylcholine.

In one embodiment, the molar ratio of the polyethylene glycol bisacrylamide to the 2-methacryloyloxyethyl phosphorylcholine is 1 (0.5-2).

In a second aspect of the present invention, a method for preparing a composite material with a polyetheretherketone substrate is provided, comprising the following steps:

obtaining a polyetheretherketone substrate comprising a first surface and a second surface, the first surface and the second surface being interconnected to form an overall outer surface of the polyetheretherketone substrate;

modifying the first surface with polydopamine;

reacting nano hydroxyapatite with dopamine to prepare poly-dopamine modified nano hydroxyapatite;

contacting the first surface modified with polydopamine-modified nano-hydroxyapatite for reaction;

dissolving polyethylene glycol bisacrylamide, 2-methacryloyloxyethyl phosphorylcholine and a photoinitiator in water to prepare a gel precursor solution;

and contacting the second surface with a gel precursor solution to carry out polymerization.

In one embodiment, the step of obtaining a polyetheretherketone substrate comprises:

mixing polyether-ether-ketone with sodium chloride, and grinding the mixture until the particle size is less than 300 microns;

compressing, molding and sintering the ground material;

and polishing, cleaning and drying the sintered material to prepare the polyether-ether-ketone substrate.

In one embodiment, the step of modifying the first surface with polydopamine comprises:

adding dopamine hydrochloride into a Tris-HCl solution to prepare a modification solution;

and contacting the first surface with the modification solution, and performing polydopamine modification on the first surface.

In one embodiment, the step of reacting nano-hydroxyapatite with dopamine comprises:

mixing the nano hydroxyapatite with the modification solution, and performing polydopamine modification on the surface of the nano hydroxyapatite to perform polymerization reaction; the resulting product was then washed and lyophilized.

In one embodiment, the step of contacting the first surface modified with polydopamine-modified nano-hydroxyapatite to perform a reaction comprises:

dispersing the nano-hydroxyapatite modified by the polydopamine in water to prepare a dispersion liquid;

and soaking the first surface modified with polydopamine in the dispersion liquid for reaction.

In one embodiment, the step of contacting the second surface with a gel precursor solution to effect polymerization comprises:

and applying the gel precursor solution to the second surface, and carrying out polymerization reaction under the condition of ultraviolet light.

In a third aspect of the invention, a biological scaffold is provided, which comprises the polyetheretherketone-based composite material of the first aspect or the polyetheretherketone-based composite material prepared by the preparation method of the second aspect.

In one embodiment, the biological scaffold is an osteochondral defect replacement scaffold.

According to the composite material with the polyether-ether-ketone substrate, the polydopamine modified nano-hydroxyapatite is arranged on the first surface of the polyether-ether-ketone substrate, the polyethylene glycol bisacrylamide (PEGDAA) and the 2-Methacryloyloxyethyl Phosphorylcholine (MPC) are subjected to polymerization reaction to prepare the gel layer on the second surface, and the structures of the layers cooperate with each other to form an integrated material, so that excellent lubricity, compressive strength and osteogenesis capacity can be comprehensively realized, the bionic structure of cartilage-subchondral bone is well simulated, and the composite material can be used as a substitute support for osteochondral defect parts and used for substitute treatment of osteochondral defect. In addition, the polyetheretherketone base composite material also has good biocompatibility.

Meanwhile, the preparation method of the polyether-ether-ketone substrate composite material is simple in steps and mild in conditions, and toxic substances which are difficult to remove are not introduced in the process, so that the preparation method is more suitable for application in the aspect of biomedicine.

Drawings

FIG. 1 is a graph showing the results of a lubricity test of the composite material of example 1 of the present invention;

FIG. 2 is a graph showing the results of mechanical strength tests of the composite material of example 1 of the present invention;

FIG. 3 is a graph showing the results of the biocompatibility test of the composite material of example 1 of the present invention;

FIG. 4 is a graph showing the results of the osteogenic ability test of the composite material of example 1 of the present invention;

FIG. 5 is a graph showing the results of biomineralization activity tests on the composite material of example 1 of the present invention.

Detailed Description

The polyetheretherketone-based composite material of the present invention, its method of preparation and its use are described in further detail in the following with reference to specific examples. The present invention may be embodied in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.

Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.

In the present invention, "first aspect", "second aspect", "third aspect" and the like are used for descriptive purposes only and are not to be construed as indicating or implying a relative importance or quantity, nor are they to be construed as implicitly indicating the importance or quantity of the technical feature indicated. Also, "first," "second," "third," etc. are for non-exhaustive enumeration description purposes only and should not be construed as constituting a closed limitation to the number.

In the present invention, the technical features described in the open type include a closed technical solution composed of the listed features, and also include an open technical solution including the listed features.

In the present invention, the numerical intervals are regarded as continuous, and include the minimum and maximum values of the range and each value between the minimum and maximum values, unless otherwise specified. Further, when a range refers to an integer, each integer between the minimum and maximum values of the range is included. Further, when multiple range describing features or characteristics are provided, the ranges may be combined. In other words, unless otherwise indicated, all ranges disclosed herein are to be understood to encompass any and all subranges subsumed therein.

The percentage contents referred to in the present invention mean, unless otherwise specified, mass percentages for solid-liquid mixing and solid-solid phase mixing, and volume percentages for liquid-liquid phase mixing.

The percentage concentrations referred to in the present invention refer to the final concentrations unless otherwise specified. The final concentration refers to the ratio of the additive component in the system to which the component is added.

The temperature parameter in the present invention is not particularly limited, and may be a constant temperature treatment or a treatment within a certain temperature range. The constant temperature process allows the temperature to fluctuate within the accuracy of the instrument control.

The room temperature in the present invention is generally 4 ℃ to 30 ℃, preferably 20. + -. 5 ℃.

The invention provides a polyetheretherketone substrate composite material, which comprises a polyetheretherketone substrate, wherein the polyetheretherketone substrate comprises a first surface and a second surface, and the first surface and the second surface are connected with each other to form the whole outer surface of the polyetheretherketone substrate;

the first surface is sequentially provided with a polydopamine layer and a polydopamine-modified nano hydroxyapatite layer, and the second surface is provided with a gel layer; the gel layer is prepared by carrying out polymerization reaction on polyethylene glycol bisacrylamide (PEGDAA) and 2-Methacryloyloxyethyl Phosphorylcholine (MPC).

In one specific example, the molar ratio of the polyethylene glycol bisacrylamide (PEGDAA) to the 2-Methacryloyloxyethyl Phosphorylcholine (MPC) is 1 (0.5-2). Specifically, the molar ratio of polyethylene glycol bisacrylamide (PEGDAA) and 2-Methacryloyloxyethyl Phosphorylcholine (MPC) includes, but is not limited to: 1:0.5, 1:1, 1:1.5, 1:1.8, 1:1.9, 1: 2. At a molar ratio > 1:2, the gel is susceptible to swelling and even breaking due to excessive water absorption, resulting in failure of the bond to the substrate.

In one specific example, the polyethylene glycol bisacrylamide (PEGDAA) has a molecular weight of 3kDa to 4 kDa. Specifically, the molecular weight of the polyethylene glycol bisacrylamide (PEGDAA) includes, but is not limited to: 3kDa, 3.1kDa, 3.2kDa, 3.3kDa, 3.4kDa, 3.5kDa, 3.6kDa, 3.7kDa, 3.8kDa, 3.9kDa and 4 kDa.

The invention also provides a preparation method of the polyether-ether-ketone substrate composite material, which comprises the following steps:

s1: obtaining a polyetheretherketone substrate comprising a first surface and a second surface, the first surface and the second surface being interconnected to form an overall outer surface of the polyetheretherketone substrate;

s2: modifying the first surface with polydopamine;

s3: reacting nano hydroxyapatite with dopamine to prepare poly-dopamine modified nano hydroxyapatite;

s4: contacting the first surface modified with polydopamine-modified nano-hydroxyapatite for reaction;

s5: dissolving polyethylene glycol bisacrylamide (PEGDAA), 2-Methacryloyloxyethyl Phosphorylcholine (MPC) and a photoinitiator in water to prepare a gel precursor solution;

s6: and contacting the second surface with a gel precursor solution to carry out polymerization.

It is understood that the aforementioned numbers of S1-S5 are for the purpose of more clearly illustrating the scheme of the present invention, and are not intended as a limitation on the order of the preparation steps.

Specifically, in step S1:

in one specific example, the step of obtaining a polyetheretherketone substrate comprises:

mixing polyether-ether-ketone with a pore-forming agent, and grinding until the particle size is less than 300 microns;

compressing, molding and sintering the ground material;

In one specific example, the pore former is sodium chloride.

In a specific example, the mass ratio of the polyether-ether-ketone to the sodium chloride is 3 (5-10).

In one specific example, the compression molding pressure is 2MPa to 6 MPa.

In one specific example, the conditions of sintering include: the sintering temperature is 360-370 ℃, and the sintering time is 4-8 hours.

In one specific example, the number of sandpaper used for polishing is 1800 mesh to 2200 mesh.

In one specific example, the main purpose of the cleaning is to substantially remove sodium chloride, and in particular, the step of cleaning comprises: firstly, ultrasonically cleaning for 4-8 hours in ethanol, and then cleaning for 40-60 hours in deionized water.

In one specific example, the drying conditions include: the temperature is 45-55 ℃ and the time is 40-60 hours.

In one specific example, the polyetheretherketone substrate is a porous structure with through voids.

Specifically, in step S2:

in one specific example, the step of modifying the first surface with polydopamine comprises:

It will be appreciated that the polydopamine is modified to be a self-polymerisation of dopamine to form a polydopamine coating on said first surface.

In one specific example, the concentration of the Tris-HCl solution is 0.3M-0.7M, pH and is 8-9. Further, the concentration of the dopamine hydrochloride is 1.5-2.5 mg/mL.

In one specific example, the polymerization conditions include: the temperature is room temperature, and the time is 20-30 hours.

Specifically, in step S3:

in one specific example, the step of reacting nano-hydroxyapatite with dopamine comprises:

mixing the nano hydroxyapatite with the modification solution, performing polydopamine modification on the surface of the nano hydroxyapatite, and then cleaning and freeze-drying the obtained product.

It is understood that the polydopamine is modified into self-polymerization of dopamine to form a polydopamine coating on the surface of the nano-hydroxyapatite.

In one specific example, the polymerization conditions include: the temperature is room temperature, and the time is 10-20 hours.

Specifically, in step S4:

in one specific example, the step of contacting the first surface modified with polydopamine-modified nano-hydroxyapatite to perform a reaction comprises:

It is understood that the reaction here is based on the interaction and adsorption of oxidative covalent polymerization and non-covalent self-assembly between the polydopamine on the first surface and the polydopamine modified on the nano-hydroxyapatite.

In one specific example, the reaction conditions include: the temperature is room temperature, and the time is 20-30 hours.

Specifically, in step S5:

in one specific example, the molar ratio of the polyethylene glycol diacrylate (PEGDAA) to the 2-Methacryloyloxyethyl Phosphorylcholine (MPC) is 1 (0.5-2). Specifically, the molar ratio of polyethylene glycol bisacrylamide (PEGDAA) and 2-Methacryloyloxyethyl Phosphorylcholine (MPC) includes, but is not limited to: 1:0.5, 1:1, 1:1.5, 1:1.8, 1:1.9, 1: 2.

In one specific example, in the gel precursor solution, the mass percentage of polyethylene glycol bisacrylamide (PEGDAA) is 15 to 25%, and the mass percentage of the photoinitiator is 0.3 to 0.5%.

In one specific example, the polyethylene glycol bisacrylamide (PEGDAA) has a molecular weight of 3kDa to 4 kDa. Specifically, the molecular weight of the polyethylene glycol bisacrylamide (PEGDAA) includes, but is not limited to: 3kDa, 3.1kDa, 3.2kDa, 3.3kDa, 3.4kDa, 3.5kDa, 3.6kDa, 3.7kDa, 3.8kDa, 3.9kDa, 4 kDa.

In one specific example, the photoinitiator is I2959.

Specifically, in step S6:

in one specific example, the step of contacting the second surface with a gel precursor solution to effect polymerization comprises:

It will be appreciated that gelation of the gel precursor is achieved by this polymerisation reaction to form a gel layer at the second surface. Meanwhile, during the polymerization reaction, radicals are generated on the polyetheretherketone substrate, and the PEGDAA and the MPC are polymerized to form a cross-linked network under the initiation of the photoinitiator, so that the gel layer is firmly combined with the porous polyetheretherketone substrate by combining mechanical interlocking and ultraviolet initiation.

In one specific example, the conditions under which the polymerization reaction is carried out under ultraviolet light conditions include: high strengthThe degree is 80-120 mW/cm ² The time is 3-8 minutes. The gel can be cracked due to too high ultraviolet irradiation intensity or too long ultraviolet irradiation time, the structure can be damaged, and the gel cannot be polymerized due to too low ultraviolet irradiation intensity or too short ultraviolet irradiation time.

In one specific example, after the polymerization reaction is finished, the method further comprises the step of soaking the material in deionized water, wherein the purpose is to fully swell the gel in water and remove unreacted monomers. Further, the soaking time can be 20-30 h.

The invention also provides a biological scaffold which comprises the polyetheretherketone base composite material or the polyetheretherketone base composite material prepared by the preparation method.

In one specific example, the biological scaffold is a osteochondral defect replacement scaffold.

The following specific examples are, unless otherwise specified, all of the examples are commercially available products.

Example 1

The embodiment is a preparation method of a lubricating gel-functionalized PEEK substrate composite material for osteochondral defects, which comprises the following steps:

(1) mixing polyether-ether-ketone and sodium chloride in a mass ratio of 3: 7, uniformly mixing, and grinding by a mortar until the particle size is less than 300 microns; putting the mixed powder into a stainless steel mold, and performing compression molding on the powder by a compressor applying 4 MPa; then placing the compression-molded block in a muffle furnace, and sintering for 6 hours at 365 ℃; polishing the sintered PEEK sheet by using 2000-mesh sand paper, ultrasonically cleaning the PEEK sheet in ethanol for 6 hours, and then cleaning the PEEK sheet in deionized water for 48 hours to fully filter sodium chloride; and finally, drying the PEEK in an oven at 50 ℃ for 48 hours to obtain the porous substrate with through gaps.

(2) Preparing a Tris-HCl solution with the concentration of 0.5M, pH-8.5, and adding dopamine hydrochloride according to the concentration of 2 mg/mL; soaking the porous substrate (except the upper surface) obtained in the step (1) in the solution for reaction for 24h, then washing the polydopamine coating which is not firmly adsorbed by deionized water, and drying in an oven at 50 ℃.

(3) Uniformly dispersing 1.2g of nano-hydroxyapatite in 300mL of Tris-HCl solution containing 2mg/mL of dopamine hydrochloride, reacting for 12 hours, centrifuging at 9000rpm, cleaning with deionized water, and freeze-drying to obtain the polydopamine-modified nano-hydroxyapatite powder.

(4) Uniformly dispersing 4mg/mL of the powder obtained in the step (3) in water by stirring under ultrasonic conditions, then immersing the material obtained in the step (2) (except the upper surface) in the solution for reaction for 24 hours, finally washing with deionized water and drying in an oven at 50 ℃.

(5) In an atmosphere of nitrogen, 20 wt% PEGDAA (molecular weight 3.4kDa), MPC (molar ratio PEGDAA: MPC 1:2), 0.5 wt% I2959 were completely dissolved in deionized water to obtain a gel precursor solution.

(6) Fixing PEEK substrate by a mould, dripping the gel precursor solution on the substrate without dopamine surface modification, opening an ultraviolet point light source, and controlling the intensity to be 100mW/cm ² And the preparation process is finished after 6 minutes.

(7) Finally, the material obtained in the step (6) is placed in deionized water for 24 hours, and the gel is fully swelled in the water, and unreacted monomers are removed.

Test example:

(1) lubricating performance

Experimental samples: samples with different MPC contents were prepared according to the gel preparation method of example 1 steps (5) - (6) with no MPC and with molar ratios PEGDAA: MPC of 2:1, 1:2, respectively.

The lubricating properties of the hydrogels were evaluated by Tribology experiments while observing a firm bond of the substrate to the hydrogel, and the friction tests were performed on a UMT-5 friction wear tester (Center for Tribology inc., USA) using a reciprocating mode. PTFE spheres with the diameter of 8mm are used as an upper sample, and a lower sample, namely the integrated material to be tested, is fixed in a watch glass through cyanoacrylate glue. The watch glass was filled with sufficient SBF solution as a lubricant to simulate a human environment. The test parameters of UMT-5 are: the stroke is 4mm, and the test time is 10 min.

The results are shown in FIG. 1. It can be seen that porous PEEK is a rough surface (coefficient of friction of 0.214) and that when the PEGDAA hydrogel is layered on top, the coefficient of friction is reduced to 0.063. After the introduction of the MPC, the coefficient of friction decreased from 0.038 to 0.022 as its content increased.

(2) Mechanical strength

Experimental samples: PEGDAA (without MPC) and PEGDAA-MPC (molar ratio 1:2) were tested in example (1).

The compression performance of the hydrogel of the test sample was evaluated using the compression mode of a universal material testing machine equipped with a 20kN pressure sensor. The hydrogel used for the compression test was formed into a cylindrical shape (diameter 14mm, height 15mm) using a mold. During the test, the pressing speed was always kept at 0.5mm/min until the hydrogel was broken, and a stress-strain curve was obtained.

The results are shown in FIG. 2. The PEGDAA-MPC has greater compressive strength and better elasticity.

(3) Biocompatibility

Experimental samples: PEEK used in example 1, PDA (polydopamine) prepared according to step (2) of example 1, and nHA (nano hydroxyapatite) used in example 1.

PEEK samples were soaked in 75% ethanol solution for 2 hours and then irradiated with uv light for more than 2 hours. Cell proliferation was determined using the CCK-8 assay. The MC3T3-E1 osteoblast suspension was suspended at 5X 10 per well ³ The density of individual cells was co-cultured with PEEK, PDA, and nHA in 96-well plates. After 1, 3 and 5 days of incubation, the medium was removed and washed gently three times with PBS. The incubation was continued for 2 hours, 100. mu.L of a working solution containing 10% CCK-8 was added to each well, and then the absorbance value was measured at 450nm using a microplate reader.

The results are shown in FIG. 3. At all three time points, the relative survival rate of the cells was above 80%, indicating that the material used was non-biotoxic, allowing the cells to proliferate within 5 days.

(4) Capability of forming bone

Experimental sample: PEEK used in example 1, and a PEEK substrate (PEEK-PHA) modified with the polydopamine-modified nano hydroxyapatite powder prepared in step (4) of example 1.

In alpha-MEM MediumAlizarin red staining was performed to evaluate the osteogenic capacity of the different groups of samples. Samples were UV-sterilized, soaked in culture medium for 2 hours, and then incubated at 8X 10 per well ⁴ The density of individual cells was CO-cultured with the cell suspension at 37 ℃ with 5% CO for 7 days ₂ . Samples were rinsed three times with PBS at the indicated time intervals and fixed with 4% paraformaldehyde for 30 minutes at room temperature. After aspiration of the fixative, the sample was rinsed three times with PBS. Subsequently, the cells were stained with 0.2% alizarin red solution for 30 minutes. The specimens were rinsed three times with deionized water and dried in air and then observed with an optical microscope.

The results are shown in FIG. 4. The results of alizarin red staining of the samples after 7 days of osteoblast culture are shown, and the surface-modified PEEK (i.e., PEEK-PHA) produced many calcium nodules (dark gray in fig. 4, red in the original color) compared to the PEEK control group, confirming their osteogenic ability.

(5) Biomineralization Activity

Experimental samples: PEEK used in example 1, and a PEEK substrate (PEEK-PHA) modified with the polydopamine-modified nano hydroxyapatite powder prepared in step (4) of example 1.

Biomineralising activity was assessed by incubating samples in SBF-mimicking body fluids (almost equal to the ion concentration of human plasma) to produce bone-like apatite. Samples of PEEK and PEEK-PHA were immersed in 30mL of SBF solution at room temperature, incubated for 7 days, and then removed, rinsed with deionized water and freeze-dried. The surface mineralization products were observed by SEM.

The results are shown in fig. 5, where PEEK-PHA showed a large number of mineralization products compared to PEEK, indicating that the surface modification significantly increased the bioactivity of PEEK, improving the original bioinert.

The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.

The above-mentioned embodiments only express several embodiments of the present invention, so as to understand the technical solutions of the present invention specifically and in detail, but not to be understood as the limitation of the protection scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. It should be understood that the technical solutions provided by the present invention, which are obtained by logical analysis, reasoning or limited experiments, are within the scope of the appended claims. Therefore, the protection scope of the present invention should be subject to the content of the appended claims, and the description and the drawings can be used for explaining the content of the claims.

Claims

1. A peek substrate composite comprising a peek substrate comprising a first surface and a second surface interconnected to form an overall outer surface of the peek substrate;

the first surface is sequentially provided with a polydopamine layer and a polydopamine-modified nano-hydroxyapatite layer, and the second surface is provided with a gel layer; the gel layer is prepared by carrying out polymerization reaction on polyethylene glycol bisacrylamide and 2-methacryloyloxyethyl phosphorylcholine.

2. The polyetheretherketone-based composite material of claim 1, wherein the molar ratio of the polyethylene glycol bisacrylamide to the 2-methacryloyloxyethyl phosphorylcholine is 1 (0.5-2).

3. The preparation method of the polyether-ether-ketone substrate composite material is characterized by comprising the following steps of:

modifying the first surface with polydopamine;

4. The method of preparing a polyetheretherketone substrate composite according to claim 3, wherein the step of obtaining a polyetheretherketone substrate comprises:

compressing, molding and sintering the ground material;

5. The method of preparing a polyetheretherketone-based composite material according to claim 3 or 4, wherein the first surface modification of polydopamine comprises:

and contacting the first surface with the modification liquid, and performing polydopamine modification on the first surface.

6. The method for preparing a polyetheretherketone-based composite material according to claim 3 or 4, wherein the step of reacting nano-hydroxyapatite with dopamine comprises:

7. The method for preparing a polyetheretherketone-based composite material according to claim 3 or 4, wherein the step of contacting the first surface modified with polydopamine-modified nano-hydroxyapatite for reaction comprises:

8. The method of preparing a polyetheretherketone substrate composite according to claim 3 or 4, wherein the step of contacting the second surface with a gel precursor solution to effect a polymerisation reaction comprises:

9. A bioscaffold comprising the PEEK-based composite of claim 1 or 2 or the PEEK-based composite prepared by the method of any one of claims 3-8.

10. The bioscaffold of claim 9, wherein the bioscaffold is an osteochondral defect replacement scaffold.