Polyether-ether-ketone composite material with enhanced 3D printing function and preparation method of polyether-ether-ketone composite material

Abstract

The invention relates to the technical field of biological materials for 3D printing, in particular to a polyether-ether-ketone composite material with an enhanced 3D printing function and a preparation method of the polyether-ether-ketone composite material. The invention discloses a polyether-ether-ketone composite material with an enhanced 3D printing function. The material is prepared from the following raw materials in parts by mass: 75-85 parts of polyether-ether-ketone, 5-10 parts of a modified bioactive material, 1-3 parts of carbon nanotubes, 0.5-2 parts of an organic nucleating agent, 0.1-1 part of a biological regulator and 0.1-1 part of an antibacterial agent, the modified bioactive material is modified hydroxyapatite and / or modified tricalcium phosphate. According to the basic formula, the synergistic effect of multifunctional components is achieved, the defects of an existing PEEK material in the aspects of biological activity and crystallization performance are overcome through the components such as polyether-ether-ketone, the modified bioactive material and the carbon nanotubes which are meticulously proportioned, and excellent mechanical performance and biocompatibility are provided.

Description

Technical Field

[0001] The present invention relates to the technical field of biomaterials for 3D printing, and in particular to a polyetheretherketone composite material with enhanced 3D printing function and a preparation method thereof. Background Art

[0002] 3D printing is recognized as one of the technologies that will drive the third industrial revolution. Although it originated from industrial manufacturing, it has attracted the attention of the medical community from the beginning. At present, 3D printing technology is gradually being used in the repair and replacement of biological hard tissues.

[0003] Patent application number 201910413425.8 discloses a PEEK composite material suitable for 3D printing. This material comprises nanohydroxyapatite, nano-Si3N4, polyetheretherketone (PEEK), polytetrafluoroethylene (PTFE), carbon fiber, and an antioxidant. The weight ratio of each component is as follows: 3-5 parts nanohydroxyapatite, 5-7 parts nano-Si3N4, 60-90 parts polyetheretherketone (PEEK), 18-20 parts polytetrafluoroethylene (PTFE), 20-25 parts carbon fiber, and 0.1-0.3 parts antioxidant. This composite material exhibits a well-developed structure, high stiffness and hardness, and excellent wear resistance. Products 3D-printed using this material can be widely used in the repair and replacement of hard biological tissues. However, this PEEK composite material suffers from technical issues such as low bioactivity and poor crystallization properties. Summary of the Invention

[0004] The purpose of the present invention is to provide a polyetheretherketone composite material with enhanced 3D printing function to solve the technical problems raised in the above background technology, such as low biological activity and poor crystallization performance.

[0005] The technical solution adopted by the present invention to solve the above technical problems is:

[0006] A polyetheretherketone (PEEK) composite material with enhanced 3D printing capabilities comprises the following raw materials in parts by weight: 75-85 parts polyetheretherketone (PEEK), 5-10 parts modified bioactive material, 1-3 parts carbon nanotubes (CNTs), 0.5-2 parts organic nucleating agent, 0.1-1 part bioregulator, and 0.1-1 part antimicrobial agent. The modified bioactive material is modified hydroxyapatite and / or modified tricalcium phosphate. This basic formula achieves synergistic effects among the multifunctional components. Through the carefully proportioned composition of polyetheretherketone (PEEK), modified bioactive material, and CNTs, it addresses the deficiencies of existing PEEK materials in terms of bioactivity and crystallization properties, while also providing excellent mechanical properties and biocompatibility.

[0007] Preferably, the organic nucleating agent is at least one of polyetherimide, polyethersulfone, and liquid crystal polymer; the bioregulator is a bioactive peptide or growth factor, including one or more of BMP mimetic peptides, parathyroid hormone (PTH)-derived peptides, osteogenic growth peptide (OGP), and QK peptide (VEGF mimetic peptide); the growth factor includes one or more of vitamins, bases, purines, pyrimidines, biotin, or niacin; and the antimicrobial agent is silver ion and / or zinc ion. The selection of an organic nucleating agent can significantly improve the crystallization properties of PEEK, enabling faster crystallization and reduced deformation during the 3D printing process. The diverse selection of bioregulators allows the material to be customized for different biomedical applications. Silver ions and zinc ions have excellent antimicrobial properties while maintaining biocompatibility.

[0008] Preferably, the material also includes 1-3 parts thermoplastic elastomer or 1-3 parts silica particles. The addition of thermoplastic elastomer improves the material's flexibility, making it particularly suitable for making comfortable medical devices such as braces. The addition of silica particles significantly improves the material's wear resistance, making it suitable for making medical devices requiring long-term wear resistance, such as dentures and crowns.

[0009] Preferably, the modified hydroxyapatite preparation method comprises the following steps: ① dispersing hydroxyapatite (HA) powder in a solution containing a silane coupling agent, stirring and mixing the mixture to obtain a uniform mixture, filtering and washing the modified hydroxyapatite powder to remove unreacted silane coupling agent, and drying the mixture to obtain the modified hydroxyapatite powder; ② coating the surface of the hydroxyapatite modified with the silane coupling agent with a PEEK polymer by solution blending or melt blending, separating the coated hydroxyapatite powder by centrifugation or filtration, and drying the mixture to obtain the modified hydroxyapatite. More preferably, in step ①, the mass ratio of HA powder to silane coupling agent is 20:0.5-2; stirring is performed at a constant temperature of 60°C ± 5°C, with the pH adjusted to 4-5 using acetic acid; and stirring is performed at a speed of 200 rpm to ensure uniform coating of the silane coupling agent on the HA surface. More preferably, in step ②, the mass ratio of PEEK to HA modified with a silane coupling agent is 0.5-2:5, and the solution blending method is: HA is slowly added to the solution containing the PEEK polymer, with ultrasonic assistance (40kHz-100kHz), the temperature is maintained at 55±2°C, and the time is 1h-2h.

[0010] This two-step modification method significantly improves the compatibility and dispersibility of hydroxyapatite in the PEEK matrix. Silane coupling agent modification first increases the organic groups on the hydroxyapatite surface, while the subsequent PEEK polymer coating forms a transition phase, reducing the interfacial energy difference between the filler and the matrix, thereby improving the overall performance of the composite and the uniformity of the filler dispersion.

[0011] Preferably, the preparation method of the modified tricalcium phosphate comprises the following steps:

[0012] First, the tricalcium phosphate (TCP) powder is treated with dilute acid to increase its surface active sites. Then, the acid-treated TCP powder is washed to remove residual acid. Finally, the TCP powder is treated with alkali to neutralize its surface charge.

[0013] The modified tricalcium phosphate is obtained by treating acid-base treated tricalcium phosphate powder with plasma to increase its surface energy and activity; and then immediately performing silanization or other chemical grafting reactions.

[0014] This combined acid-base plasma treatment effectively activates the surface of tricalcium phosphate, increasing active sites and enhancing its interfacial bonding strength with the PEEK matrix. The high-energy surface created by plasma treatment facilitates subsequent chemical modification, enabling the modified tricalcium phosphate to maintain its biological activity while achieving good compatibility with the polymer matrix.

[0015] Preferably, the carbon nanotubes are modified carbon nanotubes that have been oxidatively modified and surfactant-modified. The method for preparing the modified carbon nanotubes comprises the following steps:

[0016] ① Place the carbon nanotubes in a strong oxidant solution for reflux reaction for 5-15 hours; separate the oxidized carbon nanotubes by centrifugation and washing, and dry them for later use;

[0017] ② Dissolve the surfactant in a solvent to prepare a surfactant solution; add the oxidatively modified carbon nanotubes to the surfactant solution, and use ultrasonic treatment and stirring to allow the surfactant molecules to be fully adsorbed on the surface of the carbon nanotubes; remove the unadsorbed surfactant through centrifugation and washing operations to obtain modified carbon nanotubes.

[0018] Preferably, the surfactant is sodium dodecylbenzenesulfonate or polysorbate (Tween series).

[0019] This combined oxidative and surfactant modification approach addresses the difficulty of dispersing carbon nanotubes in a polymer matrix. Oxidative modification introduces oxygen-containing functional groups onto the carbon nanotube surface, increasing polarity and active sites; while surfactant modification forms a protective layer that prevents carbon nanotube aggregation through steric hindrance and electrostatic repulsion. The synergistic effect of these two modification methods significantly improves the uniformity of carbon nanotube dispersion in the PEEK matrix, fully realizing its reinforcing effect.

[0020] A method for preparing the above-mentioned polyetheretherketone composite material, the method comprising the following steps:

[0021] S1: uniformly mixing the modified bioactive material and carbon nanotubes according to a ratio to obtain a mixed filler;

[0022] S2: dissolving the bioregulator in a suitable solvent and uniformly distributing it in the polyetheretherketone matrix by atomization or other methods to obtain premixed polyetheretherketone particles;

[0023] S3: uniformly mixing the premixed polyetheretherketone particles, the mixed filler, the organic nucleating agent and the antibacterial agent under dry conditions to obtain a mixture;

[0024] S4: using a twin-screw extruder to melt-mix the mixture at a temperature of 320-380° C. and a screw speed of 200-300 rpm;

[0025] S5: Extrusion granulation is performed to obtain polyetheretherketone composite material pellets suitable for 3D printing.

[0026] This multi-step mixing process ensures uniform dispersion of all components within the PEEK matrix. In particular, the premixing step evenly distributes the bioregulator, preventing loss of activity during high-temperature processing. The use of a twin-screw extruder provides sufficient shear force to break down filler agglomerates and achieve thorough mixing and uniform dispersion of all components. Precisely controlled temperature and speed parameters ensure the material's processing performance and stability.

[0027] Compared with the prior art, the present invention has the following advantages:

[0028] (1) The modified bioactive material of the present invention can enhance the bioactivity of polyetheretherketone (PEEK), enabling it to better interact with biological tissues. In bone tissue engineering applications, the modified bioactive material can promote cell adhesion, proliferation, and differentiation, guiding the growth of bone tissue. Polyetheretherketone (PEEK) and carbon nanotubes (CNTs) provide good mechanical support, ensuring that the material can withstand a certain load in the body. The combination of the two helps the bone repair material function better.

[0029] (2) The carbon nanotubes in the present invention have high strength and modulus, and can act as a reinforcing phase in the composite material, improving the tensile strength, flexural strength, and hardness of the material. This improvement in mechanical properties helps the composite material maintain its structural integrity when subjected to external forces. At the same time, the high specific surface area and unique structure of the carbon nanotubes can provide good attachment sites for other components, enhance the interaction between the components, and improve the overall performance of the composite material.

[0030] (3) The organic nucleating agent in the present invention can serve as a heterogeneous core for the crystallization of polyetheretherketone, promote the crystallization process of polyetheretherketone, and increase the crystallinity and crystallization rate. The optimized crystallization performance can improve the mechanical properties of polyetheretherketone, making it have better strength, hardness and thermal stability. At the same time, the improvement of crystallization performance can also improve the processing performance of the material, reduce shrinkage and deformation during the molding process, and improve the precision and quality of 3D printed products. In addition, the organic nucleating agent has good interfacial compatibility with polyetheretherketone, can form a uniform dispersed phase in the composite material, and enhance the bonding force between the components. This good interfacial compatibility helps to improve the comprehensive performance of the composite material and reduce the performance degradation caused by interface defects between the components.

[0031] (4) The bioregulators in the present invention can synergize with the modified bioactive materials to further regulate cell behavior and physiological processes in the body. In tissue engineering, bioactive peptides or growth factors can specifically bind to receptors on the cell surface, activate intracellular signaling pathways, promote cell proliferation, differentiation and migration, and thus accelerate tissue repair and regeneration. The mechanical support and biocompatible environment provided by polyetheretherketone and other components provide a guarantee for the bioregulators to play their role. At the same time, the addition of bioregulators gives the composite material a certain specificity, which can be customized for different biomedical applications. For example, in wound healing materials, bioactive peptides with angiogenesis-promoting effects can be selected to work together with other ingredients to accelerate the wound healing process. This enhanced specificity helps to improve the application effect of composite materials in the biomedical field.

[0032] (5) The antimicrobial agent of the present invention can inhibit the growth and reproduction of bacteria on the surface of the composite material, thereby preventing infection. Bacterial growth may cause corrosion and degradation of the material surface, thereby affecting the performance of the material. Antimicrobial agents can inhibit bacterial growth, reduce biological corrosion on the material surface, maintain the stability of the mechanical and electrical properties of the composite material for a long time, and extend the service life of the material.

[0033] (6) The optimization scheme of the present invention also improves different adaptability by adding different substances according to different categories of 3D printed products. By adding thermoplastic elastomer, the flexibility of the material is improved, thereby improving the wearing comfort of the braces; by adding silica particles, the wear resistance of the material is improved, thereby improving the wear resistance of dentures / crowns. DETAILED DESCRIPTION

[0034] The technical solution of the present invention is further described in detail below through specific examples. It should be understood that the implementation of the present invention is not limited to the following examples, and any form of modification and / or change made to the present invention will fall within the scope of protection of the present invention.

[0035] In the present invention, unless otherwise specified, all parts and percentages are by weight, and the equipment and raw materials used are commercially available or commonly used in the art. The methods in the following examples are all conventional methods in the art unless otherwise specified.

[0036] Unless otherwise specified, the reagents used in the following examples can be purchased from conventional biochemical reagent stores.

[0037] One of the core aspects of this invention is a polyetheretherketone (PEEK) composite material with enhanced 3D printing capabilities. This material comprises the following raw materials by weight: 75-85 parts polyetheretherketone (PEEK), 5-10 parts modified bioactive material, 1-3 parts carbon nanotubes (CNTs), 0.5-2 parts organic nucleating agent, 0.1-1 part bioregulator, and 0.1-1 part antimicrobial agent. The modified bioactive material is modified hydroxyapatite and / or modified tricalcium phosphate. Through the synergistic effect of specific components, this material addresses the shortcomings of existing PEEK materials in terms of bioactivity and crystallization properties.

[0038] The polyetheretherketone (PEEK) composite material produced by this invention has the following characteristics: 1. Biocompatibility: The addition of modified nanohydroxyapatite and tricalcium phosphate enhances the composite's osteoinductivity and osteointegration, and also improves the dispersion and mixing of the bioactive material with other materials. 2. Mechanical Properties: The carbon nanotubes enhance the composite's mechanical properties, making it more suitable for load-bearing applications. Due to their unique structure and excellent mechanical properties, carbon nanotubes can significantly improve the interlaminar bonding strength of PEEK even at very low mass percentages. 3. The addition of an organic nucleating agent lowers the melting point and improves crystallization behavior. 4. Bioactivity: The addition of bioactive peptides or growth factors further promotes bone tissue growth and repair. 5. Antimicrobial Properties: The addition of antimicrobial agents reduces the risk of implant-related infection.

[0039] Another core of the present invention is to provide a method for preparing the above-mentioned polyetheretherketone composite material, which comprises the following steps:

[0040] S1: uniformly mixing the modified bioactive material and carbon nanotubes according to a ratio to obtain a mixed filler;

[0041] S2: dissolving the bioregulator in a suitable solvent and uniformly distributing it in the polyetheretherketone matrix by atomization or other methods to obtain premixed polyetheretherketone particles;

[0042] S3: uniformly mixing the premixed polyetheretherketone particles, the mixed filler, the organic nucleating agent and the antibacterial agent under dry conditions to obtain a mixture;

[0043] S4: using a twin-screw extruder to melt-mix the mixture at a temperature of 320-380° C. and a screw speed of 200-300 rpm;

[0044] S5: Extrusion granulation is performed to obtain polyetheretherketone composite material pellets suitable for 3D printing.

[0045] Example 1

[0046] A polyetheretherketone composite material with enhanced 3D printing function is prepared from the following raw materials in parts by weight:

[0047] Polyetheretherketone (PEEK): 75 parts;

[0048] Modified hydroxyapatite: 10 parts;

[0049] Carbon nanotubes: 3 parts;

[0050] Polyetherimide: 2 parts;

[0051] Bioactive peptides: 1 part;

[0052] Silver ions: 1 part.

[0053] The above-mentioned bioactive peptide is a BMP mimetic peptide.

[0054] The BMP-mimicking peptide has the following sequence characteristics: KIPKASSVPTELSAISTLYL (core sequence derived from the knuckle epitope of BMP-7); molecular weight: 2,134 Da. Commercially available: Shanghai Qiangyao Biotechnology.

[0055] The preparation method of modified hydroxyapatite is (the same below):

[0056] (1) Silane coupling agent modification: First, clean the hydroxyapatite (HA) powder to remove surface impurities; then ultrasonically disperse the HA powder (40kHz, 500W) in a solution containing a silane coupling agent (aminopropyltriethoxysilane APTMS) (the solvent is an ethanol / water mixture with a volume ratio of 4:1); the mass ratio of HA powder to silane coupling agent is 20:1; then stir at a constant temperature of 60°C and adjust the pH to 4.5 with acetic acid; the stirring speed is 200rpm to ensure that the silane coupling agent is evenly coated on the HA surface; finally, filter and wash (wash with ultrapure water 3 times) the modified HA powder to remove unreacted silane coupling agent; and vacuum dry the modified HA powder for 12 hours to a moisture content of ≤0.5%, to obtain HA modified with silane coupling agent, which is then set aside.

[0057] (2) Polymer coating: First, use PEEK solution (the solvent is hexafluoroisopropanol) to coat HA powder, and then coat the polymer on the surface of HA modified by silane coupling agent by solution blending. The mass ratio of PEEK to HA modified by silane coupling agent is 1:5. HA is added slowly with ultrasonic assistance (40kHz) and the temperature is maintained at 55±2℃ for 1h. The coated HA powder is then separated by centrifugation or filtration and dried to obtain modified hydroxyapatite.

[0058] The preparation method of the above-mentioned 3D printing function-enhanced polyetheretherketone composite material is as follows:

[0059] (1) The modified nano-hydroxyapatite and carbon nanotubes were mixed uniformly according to the ratio by planetary ball milling under Ar gas protection, with zirconia balls (diameter 3 mm) and a ball-to-material ratio of 10:1; the rotation speed was 300 rpm; the mixing time was 4 h; and a mixed filler was obtained;

[0060] (2) The bioactive peptide was dissolved in 0.01 M acetate buffer (containing 5% DMSO) and then evenly distributed in the PEEK matrix by a nebulization method (ultrasonic nebulizer, piezoelectric frequency 1.7 MHz; nebulization rate: 0.5 mL / min ± 0.01 mL / min; carrier gas pressure 0.2 MPa (N2) ± 0.01 MPa; nebulization distance (distance from the PEEK particle bed): 10 cm ± 1 mm; matrix temperature: 45 °C) to obtain premixed PEEK particles;

[0061] (3) premixed PEEK particles, mixed fillers, organic nucleating agent (polyetherimide) and antibacterial agent (nanosilver-loaded zirconium phosphate (silver loading 8-12%)) were mixed uniformly under dry conditions to obtain a mixture;

[0062] (4) The mixture was melt-mixed using a twin-screw extruder with the temperature set at 350 °C and the screw speed at 250 rpm;

[0063] (5) PEEK composite material granules suitable for 3D printing are obtained by extrusion granulation.

[0064] Example 2

[0065] A polyetheretherketone composite material with enhanced 3D printing function is prepared from the following raw materials in parts by weight: polyetheretherketone (PEEK): 85 parts; modified tricalcium phosphate: 5 parts; carbon nanotubes: 1 part; polyethersulfone: 0.5 parts; growth factor: 0.1 parts; and zinc ions: 0.1 parts.

[0066] The growth factor is bone morphogenetic protein (BMPs), BMP-2, and the active fragment is: NSKNCNKKHPLYHFRSPFYNVNS (73-94 aa); the molecular weight is 2,756 Da, and the commercial source is: supplier PeproTech (Cat# 120-02, GMP grade).

[0067] The preparation method of modified tricalcium phosphate is as follows: (1) Acid-base treatment: first use dilute acid (10% by mass hydrochloric acid) to treat TCP powder to increase its surface active sites; then wash the acid-treated TCP powder to remove residual acid; finally use alkali (20% by mass ammonia water) to treat TCP powder to neutralize its surface charge and improve its compatibility with PEEK. (2) Plasma treatment:

[0068] The TCP powder obtained after acid and alkali treatment was treated with plasma to increase its surface energy and activity. Plasma generator power: 400W; treatment gas: argon / oxygen mixture (9:1 by volume); vacuum: 10-20 Pa; treatment time: 8 minutes.

[0069] After plasma treatment, a silanization reaction was immediately performed to further improve its compatibility with PEEK. The specific method for the silanization reaction was to prepare a mixed solution of a silane coupling agent and an ethanol solution. The concentration of the silane coupling agent in the mixed solution was 5 wt% and the concentration of ethanol was 2 wt%. The pH was adjusted to approximately 5.0. The TCP powder obtained by plasma treatment was added to the solution at a solid-to-liquid ratio of 1:10 (g / mL). The mixture was then stirred in a 60°C water bath for 2 hours. The silane coupling agent was γ-methacryloxypropyltrimethoxysilane (KH570).

[0070] The difference between this embodiment and the first embodiment lies in the selection of components and amounts in the formulation, and the other preparation steps are the same as those in the first embodiment. Zinc ion source: zinc oxide nanorods (diameter 50-80 nm).

[0071] Example 3

[0072] A polyetheretherketone composite material with enhanced 3D printing function is prepared from the following raw materials in parts by mass: polyetheretherketone (PEEK): 80 parts; modified hydroxyapatite: 7 parts; modified carbon nanotubes: 2 parts; polyetherimide: 1 part; bioactive peptide: 0.5 parts; and silver ions: 0.5 parts.

[0073] The bioactive peptide is a parathyroid hormone-derived peptide (PTH-derived peptide) with the sequence: SVSEIQLMHNLGKHLNSMERVEWLRKKLQDVHNF (PTH1-34) and a molecular weight of 4,107 Da. It is commercially available from Shanghai Jier Biochemical.

[0074] The preparation method of modified carbon nanotubes is as follows: (1) Oxidation modification: The carbon nanotubes are placed in a strong oxidant solution (such as concentrated nitric acid, a mixture of concentrated sulfuric acid and concentrated nitric acid) and refluxed at 80°C for 8 hours. After the reaction is completed, the oxidized carbon nanotubes are separated by centrifugation, washing, and other operations, and dried for later use;

[0075] (2) Surfactant modification: Sodium dodecylbenzenesulfonate was selected as the surfactant and dissolved in water to prepare a 2% surfactant solution. The oxidatively modified carbon nanotubes were then added to the surfactant solution and ultrasonically treated for 30 minutes to allow the surfactant molecules to fully adsorb on the surface of the carbon nanotubes. The unadsorbed surfactant was then removed by centrifugation and washing to obtain the combined modified carbon nanotubes.

[0076] Advantages of the above modified carbon nanotubes:

[0077] Enhanced Dispersion: Oxidative modification increases the surface polarity of carbon nanotubes, making them more receptive to surfactants. Oxidative modification introduces oxygen-containing functional groups such as carboxyl, hydroxyl, and carbonyl groups onto the carbon nanotube surface. These polar groups increase the number of active sites and polarity on the carbon nanotube surface, making it easier for surfactant molecules to adsorb onto the carbon nanotube surface. The hydrophilic groups of the surfactant molecules can interact with the oxygen-containing functional groups on the carbon nanotube surface through hydrogen bonding and electrostatic interactions, resulting in more robust adsorption and enhancing the surfactant modification effect. The presence of the surfactant further improves the dispersion stability of the carbon nanotubes in solution. Although the surface polarity of the oxidatively modified carbon nanotubes increases, they still tend to reaggregate during subsequent handling and dispersion. The addition of the surfactant forms a protective film on the carbon nanotube surface, which, through steric hindrance and electrostatic repulsion, further prevents aggregation and maintains dispersion stability in solution. Combining these two methods significantly enhances the dispersion of carbon nanotubes in the PEEK matrix, resulting in a more uniform dispersion.

[0078] Improved interface properties: The functional groups and surfactant molecules introduced by oxidative modification can improve the interface properties between carbon nanotubes and PEEK matrix, increase the interaction between the two, and thus improve the mechanical properties and other properties of the composite material.

[0079] The difference between this embodiment and the first embodiment lies in the selection of components and amounts in the formula. In the step of preparing the premixed PEEK particles, the solvent used is 30% ethanol / 70% 10 mM HCl solution; the other preparation steps are the same as those in the first embodiment.

[0080] Example 4

[0081] A polyetheretherketone composite material with enhanced 3D printing function is made from the following raw materials in parts by weight: polyetheretherketone (PEEK): 80 parts; modified hydroxyapatite: 8 parts; modified carbon nanotubes: 2 parts; polyetherimide: 1 part; bioactive peptide: 0.5 part; silver ion: 0.5 part; and medical-grade thermoplastic polyurethane (TPU): 3 parts.

[0082] The above-mentioned bioactive peptide adopts osteogenic growth peptide (OGP), full sequence: ALKRQGRTLYGFGG; molecular weight: 1,427Da, commercially available source: Hangzhou Gutuo Biological Company.

[0083] The thermoplastic elastomer (medical-grade thermoplastic polyurethane) has a hardness range of 70-90 Shore A (82A is selected in Example 4) and a melt index of 5-15 g / 10 min (200° C. / 2.16 kg).

[0084] The addition of thermoplastic elastomers can improve the material's flexibility and enhance the wearer's comfort when 3D printing braces. As a material that combines the processing properties of thermoplastics with the elasticity of rubber, thermoplastic elastomers can increase the material's elastic modulus and reduce its rigidity without reducing its overall strength. This allows the braces to better fit the oral cavity and improve patient comfort while still meeting the mechanical requirements of orthodontic treatment.

[0085] The difference between this embodiment and the third embodiment lies in the selection of components and amounts in the formula. TPU is added during the step of preparing the mixture. The other preparation steps are the same as those of the third embodiment.

[0086] Example 5

[0087] A polyetheretherketone composite material with enhanced 3D printing function is prepared from the following raw materials in parts by weight:

[0088] Polyetheretherketone (PEEK): 80 parts; modified hydroxyapatite: 8 parts; modified carbon nanotubes: 2 parts; polyetherimide: 1 part; bioactive peptide: 0.5 parts; silver ions: 0.5 parts; silica particles: 3 parts.

[0089] Silica microparticles:

[0090] Crystal structure: amorphous (to prevent stress concentration);

[0091] Surface hydroxyl density: 3-5 / nm 2 ;

[0092] Rheological control during addition: melt flow rate is adjusted to 18-22g / 10min (372℃ / 5kg); dynamic viscosity is controlled at 1500-2000Pa·s (shear rate 100s -1hour).

[0093] The bioactive peptides used were QK peptide (VEGF mimetic peptide) and BMP mimetic peptide, with the weight ratio of the two being 1:1. The QK peptide sequence was KLTWQELYQLKYKGI (VEGF mimetic); the molecular weight was 1,843 Da, and the commercial source was Tocris Bioscience (Cat# 6764, pre-dissolved in PBS). The BMP mimetic peptide was the same as that used in Example 1.

[0094] The addition of silica particles can improve the wear resistance of the material, especially when 3D printing dentures and crowns. As an inorganic filler with high hardness and good wear resistance, silica particles can significantly improve the surface hardness and wear resistance of the composite material. In the oral environment, dentures and crowns are required to withstand long-term chewing forces and wear. Adding silica particles can extend the service life of dentures and crowns, reduce the frequency of replacement due to wear, and improve the patient experience and economic benefits.

[0095] The difference between this embodiment and the third embodiment lies in the selection of components and amounts in the formula. Silicon dioxide particles are added during the step of preparing the mixture. The other preparation steps are the same as those in the third embodiment.

[0096] 1. The material samples of the above-mentioned embodiments 1 to 5 were subjected to performance tests, and the results are shown in Table 1.

[0097] Table 1

[0098]

[0099] In the above-mentioned biological activity tests, the test cell lines, culture systems, and standards used in Examples 1 to 5 are shown in Table 2.

[0100] Table 2 Biological activity test related content

[0101]

[0102] The cell proliferation rate is relative to that of the control group.

[0103] As shown in Table 1, the 3D printing-enhanced polyetheretherketone composite material provided by the present invention exhibits excellent tensile strength, elastic modulus, and elongation at break, demonstrating its superior mechanical properties. Furthermore, it meets standard biocompatibility standards, exhibits a low melting point, appropriate crystallinity, high bioactivity, and a high antibacterial rate. In particular, Example 4, which incorporates a thermoplastic elastomer, exhibits excellent flexibility (30 shore D), while Example 5, which incorporates silica particles, demonstrates significantly improved wear resistance (a 32% reduction in wear rate). These properties enable the material to be tailored for diverse biomedical applications, expanding the application scope of PEEK composites in 3D printing biomedical applications.

[0104] 2. Necessity verification of organic nucleating agent

[0105] Control group setting:

[0106] Control group A: does not contain polyetherimide (other components are the same as those in Example 1)

[0107] Control group B: without polyethersulfone (other components are the same as those in Example 2)

[0108] Please see Table 3 for the test results.

[0109] Table 3 Necessity verification results of organic nucleating agents

[0110]

[0111] As shown in Table 3, the organic nucleating agent increases the crystallinity by 40-60%, reduces the melting point by 15-20°C, and significantly improves the bonding strength between 3D printed layers (increased by more than 50%).

[0112] 3. Synergistic effect of bioactive materials and regulators

[0113] Experimental design:

[0114] Group 1: 10 copies of modified HA only (without BMP mimetic peptide), control group;

[0115] Group 2: 10 parts modified HA + 1 part BMP mimetic peptide (formulation of Example 1), experimental group.

[0116] Osteogenic differentiation effect (MC3T3-E1 cells, 14 days):

[0117] Table 4

[0118]

[0119] Mechanism verification (Western Blot): The Runx2 protein expression in group 2 was 3.5 times that in group 1; the phosphorylation level of Smad1 / 5 / 8 increased by 4.2 times.

[0120] 4. Mechanical synergy between carbon nanotubes and HA

[0121] Experimental design:

[0122] Group A: only 3 carbon nanotubes, control group;

[0123] Group B: only 10 copies of modified HA, control group;

[0124] Group C: 3 parts of carbon nanotubes + 10 parts of modified HA (Example 1), experimental group.

[0125] The mechanical properties comparison results are shown in Table 5.

[0126] Table 5

[0127]

[0128] As shown in Table 5, the present invention can improve the tensile strength, fracture energy, wear rate and other aspects through the combination of carbon nanotubes and modified HA.

[0129] This document uses specific examples to illustrate the principles and implementation methods of the present invention. The above examples are only intended to help understand the method and core concept of the present invention. It should be noted that those skilled in the art can make various improvements and modifications to the present invention without departing from the principles of the present invention, and such improvements and modifications also fall within the scope of protection of the claims of the present invention.

Claims

1. A polyetheretherketone composite material with enhanced 3D printing function, characterized in that The material includes the following raw materials in parts by mass: 75-85 parts of polyetheretherketone, 5-10 parts of modified bioactive materials, 1-3 parts of carbon nanotubes, 0.5-2 parts of organic nucleating agent, 0.1-1 parts of bioregulator, 0.1-1 part of antibacterial agent; The modified bioactive material is modified hydroxyapatite and / or modified tricalcium phosphate.

2. The polyetheretherketone composite material according to claim 1, characterized in that: The organic nucleating agent is at least one of polyetherimide, polyethersulfone, and liquid crystal polymer; The bioregulator is a bioactive peptide or growth factor. The bioactive peptide includes one or more of BMP mimetic peptides, parathyroid hormone (PTH) derived peptides, osteogenic growth peptide (OGP), and QK peptide (VEGF mimetic peptide); the growth factor includes one or more of vitamins, bases, purines, pyrimidines, biotin, or niacin. The antibacterial agent is silver ion and / or zinc ion.

3. The polyetheretherketone composite material according to claim 1, characterized in that: The material further comprises 1-3 parts of thermoplastic elastomer or 1-3 parts of silicon dioxide particles.

4. The polyetheretherketone composite material according to claim 1, characterized in that The preparation method of the modified hydroxyapatite comprises the following steps: ① Dispersing hydroxyapatite (HA) powder in a solution containing a silane coupling agent, stirring and mixing uniformly, filtering and washing the modified hydroxyapatite powder to remove unreacted silane coupling agent, and drying to obtain modified hydroxyapatite powder; ② The PEEK polymer is coated on the surface of the hydroxyapatite modified by the silane coupling agent by solution blending or melt blending, and the coated hydroxyapatite powder is separated by centrifugation or filtration, and dried to obtain modified hydroxyapatite.

5. The polyetheretherketone composite material according to claim 4, characterized in that: In step ①, the mass ratio of HA powder to silane coupling agent is 20:0.5-2; the stirring is carried out at a constant temperature of 60°C ± 5°C, and the pH is adjusted to 4-5 with acetic acid; the stirring speed is 200 rpm to ensure that the silane coupling agent is evenly coated on the HA surface; In step ②, the mass ratio of PEEK to HA modified with a silane coupling agent is 0.5-2:5, and the solution blending method is: HA is slowly added to the solution containing the PEEK polymer, with ultrasonic assistance (40kHz-100kHz), the temperature is maintained at 55±2°C, and the time is 1h-2h.

6. The polyetheretherketone composite material according to claim 1, characterized in that The preparation method of the modified tricalcium phosphate comprises the following steps: First, the tricalcium phosphate (TCP) powder is treated with dilute acid to increase its surface active sites. Then, the acid-treated TCP powder is washed to remove residual acid. Finally, the TCP powder is treated with alkali to neutralize its surface charge. The modified tricalcium phosphate is obtained by plasma treatment of acid-base treated tricalcium phosphate powder to increase its surface energy and activity; this is followed by immediate silanization.

7. The polyetheretherketone composite material according to claim 1, characterized in that: The carbon nanotubes are modified carbon nanotubes that have been oxidatively modified and surfactant-modified. The preparation method of the modified carbon nanotubes comprises the following steps: ① Place the carbon nanotubes in a strong oxidant solution for reflux reaction for 5-15 hours; separate the oxidized carbon nanotubes by centrifugation and washing, and dry them for later use; ② Dissolve the surfactant in a solvent to prepare a surfactant solution; add the oxidatively modified carbon nanotubes to the surfactant solution, and use ultrasonic treatment and stirring to allow the surfactant molecules to be fully adsorbed on the surface of the carbon nanotubes; remove the unadsorbed surfactant through centrifugation and washing operations to obtain modified carbon nanotubes.

8. A method for preparing the polyetheretherketone composite material according to claim 1, characterized in that The method comprises the following steps: S1: uniformly mixing modified bioactive materials and carbon nanotubes according to a proportion to obtain a mixed filler; S2: dissolving a bioregulator in an appropriate solvent and uniformly distributing the bioregulator in a polyetheretherketone matrix by atomization to obtain premixed polyetheretherketone particles; S3: uniformly mixing the premixed polyetheretherketone particles, the mixed filler, the organic nucleating agent and the antibacterial agent under dry conditions to obtain a mixture; S4: melt-mixing the mixture using a twin-screw extruder at a temperature of 320-380°C and a screw speed of 200-300 rpm; and S5: extruding and granulating to obtain polyetheretherketone composite material pellets suitable for 3D printing.

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