A micrometer calcium silicate / polyether ether ketone composite material and a preparation method thereof
By preparing and surface-treating micron-sized calcium silicate-polyetheretherketone (PEEK) composite materials, the problems of bioactivity and mechanical properties of PEEK intervertebral fusion device materials were solved, resulting in a composite material with high bioactivity and good adhesion.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- SHANGHAI REACH MEDICAL INSTR
- Filing Date
- 2024-11-14
- Publication Date
- 2026-06-19
AI Technical Summary
Existing polyetheretherketone (PEEK) interbody fusion cage materials have poor bioactivity and insufficient osteogenic properties. Furthermore, the surface coating of bioactive materials is prone to detachment, or the preparation of porous structures leads to a decline in mechanical properties.
A method for preparing micron-sized calcium silicate and polyether ether ketone composite materials was adopted, which improved bioactivity and adhesion by melt extrusion granulation combined with surface treatment, including dopamine modification, protein solution modification and porous chitosan modification.
A composite material with excellent mechanical properties, high cell adhesion rate, and excellent biological activity was prepared. The surface treatment layer was tightly bonded to the matrix and was not easy to fall off.
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Figure CN119371805B_ABST
Abstract
Description
Technical Field
[0001] This invention relates to the field of polymer composite materials technology, and specifically discloses a micron-sized calcium silicate / polyether ether ketone composite material and its preparation method. Background Technology
[0002] Due to increased life expectancy and changes in lifestyle habits, the number of people suffering from spinal-related diseases is gradually increasing. Currently, the most common treatment is spinal interbody fusion, which involves implanting a spinal fusion device during surgery. Polyetheretherketone (PEEK) has good biocompatibility, a low coefficient of friction, and good corrosion resistance. Furthermore, its elastic modulus is close to that of cortical bone, so it does not cause bone resorption or interfacial loosening after implantation, making it an ideal material for interbody fusion devices.
[0003] However, polyetheretherketone (PEEK) exhibits poor bioactivity and osteogenic properties, failing to achieve bone fusion, a problem that urgently needs improvement. Current techniques often involve spraying bioactive materials onto the PEEK surface to enhance its osteogenic capacity, but this method suffers from coating detachment issues. Furthermore, preparing porous PEEK structures leads to a decrease in mechanical properties. Therefore, researching a PEEK-based composite material with both good mechanical properties and high bioactivity is of great significance. Summary of the Invention
[0004] The purpose of this invention is to provide a micron-sized calcium silicate / polyetheretherketone composite material and its preparation method, so as to solve the problems raised in the prior art.
[0005] To achieve the above objectives, the present invention provides the following technical solution: a method for preparing micron-sized calcium silicate / polyetheretherketone composite material, comprising the following steps: taking polyetheretherketone granules, drying, melting at 370~390℃, degassing, adding calcium silicate powder and mixing and vacuuming, extruding filaments with a diameter of 1.5~2mm, blowing off moisture, cutting into granules of 2.8~3.5mm, and screening through a vibrating screen to obtain micron-sized calcium silicate / polyetheretherketone composite material.
[0006] More optimally, the mass ratio of the polyetheretherketone granules to the calcium silicate powder is (6~7):(3~4).
[0007] In a more optimized manner, the preparation of the calcium silicate powder refers to the prior art and specifically includes the following steps: Take calcium nitrate tetrahydrate and sodium metasilicate nonahydrate, and prepare calcium nitrate aqueous solution and sodium metasilicate aqueous solution with concentrations adjusted to 0.5~1mol / L respectively; add 0.5~1.5 parts of polyethylene glycol (PEG-600) to 300 parts of calcium nitrate aqueous solution, and then add 300 parts of sodium metasilicate aqueous solution dropwise to generate a precipitate; wash the precipitate with deionized water, add 200~300 parts of dimethylformamide, heat and evaporate water while stirring, then extract to remove dimethylformamide, dry the obtained product at 50~70℃, calcine at 900℃, cool and pass through a 400-mesh sieve to obtain calcium silicate powder.
[0008] In a more optimized manner, the micron-sized calcium silicate / polyetheretherketone composite material is surface-treated to obtain a surface-treated micron-sized calcium silicate / polyetheretherketone composite material, specifically including the following steps:
[0009] Step 1: Take micron-sized calcium silicate / polyetheretherketone composite material, pretreat it, soak it in dopamine Tris-HCl solution, control the pH to 8~9, and polymerize for 20~24h to obtain PDA modified composite material;
[0010] Step 2: Soak porous calcium silicate in protein solution, add β-mercaptoethanol, let stand at room temperature for 12-15 hours, filter and dry to obtain modified calcium silicate;
[0011] Step 3: Take porous chitosan, add acetic acid aqueous solution, stir evenly, add methacrylic anhydride, stir at 40~45℃ in the dark for 10~12h, wash and dry to obtain modified porous chitosan.
[0012] Step 4: Take modified calcium silicate and modified porous chitosan, add them to ethanol and stir evenly to obtain a treatment solution. Adjust the pH to 8-9, add photoinitiator, stir evenly, immerse the PDA modified composite material in it, treat it under ultraviolet light for 20-30 minutes, soak it for 2-3 hours, and dry it to obtain the surface-treated micronized calcium silicate / polyether ether ketone composite material.
[0013] More optimally, the pretreatment is sulfonation treatment, specifically the following process: take micron-sized calcium silicate / polyether ether ketone composite material, immerse it in 98% concentrated sulfuric acid and stir for 5-8 minutes, wash and dry to obtain sulfonated composite material.
[0014] Ideally, the concentration of the dopamine Tris-HCl solution is 2-5 mg / mL.
[0015] More preferably, the protein solution contains bovine serum albumin at a concentration of 200-300 mg / ml; and β-mercaptoethanol is added at a concentration of 200-300 mM.
[0016] An optimized method for preparing the protein solution is as follows: take TCEP solution, adjust the pH value to 4-6, and mix it with bovine serum albumin solution to obtain the protein solution.
[0017] In a more optimized manner, the preparation of the porous calcium silicate refers to the prior art and specifically includes the following steps: taking calcium nitrate tetrahydrate and sodium metasilicate nonahydrate, and preparing calcium nitrate aqueous solution and sodium metasilicate aqueous solution with concentrations adjusted to 0.5~1mol / L respectively; adding dodecyltrimethylammonium chloride and polyacrylamide to 300 parts of sodium metasilicate aqueous solution, stirring evenly to obtain sodium silicate aqueous solution containing surfactant; adding 300 parts of calcium nitrate aqueous solution dropwise to obtain emulsion, aging at 4~5℃ for 20~24h, filtering, washing, and drying at 50~70℃ to obtain porous calcium silicate.
[0018] In a more optimized manner, the amount of dodecyltrimethylammonium chloride added is 10-15% of the mass of sodium metasilicate nonahydrate; the amount of polyacrylamide added is 2-4% of the mass of sodium metasilicate nonahydrate.
[0019] In a more optimized manner, the modified porous chitosan comprises the following raw materials, by mass parts: 2-3 parts porous chitosan and 5-8 parts methacrylic anhydride.
[0020] In a more optimized manner, the preparation of the porous chitosan refers to the prior art and specifically includes the following steps: adding chitosan to a 2 vol% aqueous acetic acid solution to obtain a 2% (w / w) chitosan-acetic acid aqueous solution;
[0021] Add 3-5 parts of anhydrous calcium chloride to 20 parts of deionized water, add 1-2 parts of PEG-600, disperse evenly, and obtain a calcium chloride solution;
[0022] At room temperature, 40-50 parts of liquid paraffin and 0.5-1 part of Span-80 are mixed evenly, and chitosan acetic acid aqueous solution and calcium chloride solution are added. The mixture is heated to 55-60℃ and stirred for 1-2 hours. 2-3 parts of 25wt% glutaraldehyde aqueous solution are added, and the pH is adjusted to 9-10. The mixture is heated to 70-75℃ and reacted for 2-3 hours. Acetone is added and ultrasonic demulsification is performed for 5-8 minutes. After vacuum filtration, the product is washed successively with petroleum ether, ethanol and deionized water. After vacuum drying, porous chitosan is obtained.
[0023] Ideally, the chitosan Mw = 120000 g / mol and the molar ratio of chitosan to anhydrous calcium chloride is 1:(8~10).
[0024] Ideally, the concentration of the treatment solution is 3-5 mg / mL; the mass ratio of modified calcium silicate to modified porous chitosan in the treatment solution is 1:(3-4).
[0025] Ideally, the amount of photoinitiator used is 0.05% (W / V) of the treatment liquid volume.
[0026] Compared with the prior art, the beneficial effects achieved by the present invention are as follows: calcium silicate is added to polyetheretherketone (PEEK). Calcium silicate has excellent bioactivity and biocompatibility. By using melt extrusion granulation and injection molding technology, and by optimizing the process and adjusting the ratio of PEEK / calcium silicate (too little calcium silicate will result in little improvement in bioactivity, while too much will result in uneven dispersion and decreased mechanical properties), calcium silicate is evenly dispersed in PEEK, thus obtaining a composite material with excellent mechanical properties, good cell adhesion rate, and excellent bone bioactivity.
[0027] To further improve the surface bioactivity of the composite material, a surface treatment was performed. The treatment solution included modified calcium silicate and modified porous chitosan in a mass ratio of 1:(3~4). The modified calcium silicate was obtained by modifying porous calcium silicate with protein solution and β-mercaptoethanol. The porous structure helps to improve surface roughness and adhesion. The protein solution contains bovine serum albumin, which can improve biocompatibility and adhesion. β-mercaptoethanol is a disulfide bond reducing agent, which makes it easier for bovine serum albumin to coat porous calcium silicate. After reducing the disulfide bonds to thiol groups, it can react with modified porous chitosan containing double bonds in subsequent steps, and crosslinking improves adhesion. The modified porous chitosan is a porous chitosan modified with methacrylic anhydride. Chitosan itself has good biocompatibility and antibacterial ability. After modification and grafting of double bonds, it can crosslink with modified calcium silicate under ultraviolet light in subsequent steps, improving adhesion on the surface of the composite material and making it less likely to fall off.
[0028] The surface of the composite material is also modified with dopamine self-polymerization, which gives it excellent adhesion. Furthermore, the catechol groups are oxidized to quinone structures under alkaline conditions, interacting with thiol and amino groups in the modified calcium silicate and modified porous chitosan, further enhancing the bonding strength. The treatment solution contains a photoinitiator, which crosslinks the modified calcium silicate and modified porous chitosan during UV treatment, improving both bonding and adhesion. In other words, during surface treatment, the modified calcium silicate and modified porous chitosan in the treatment solution are bonded to the surface of the composite material through multiple mechanisms, making them tightly attached and resistant to detachment.
[0029] The concentration of the treatment solution needs to be controlled at 3~5mg / mL. Too high a concentration will lead to excessive modified calcium silicate and modified porous chitosan, which will be easy to fall off and may cause inflammatory reactions. In addition, too many porous structures on the surface will also lead to easy surface damage.
[0030] In summary, this invention employs a process of first obtaining polyetheretherketone / calcium silicate composite material through melt extrusion, followed by surface treatment. This process ensures the mechanical properties of the composite material itself and enhances its bioactivity. At the same time, the surface-treated layer is tightly bonded to the matrix and is not easily detached, and does not lead to a decrease in surface properties. Attached Figure Description
[0031] Figure 1 The image shows a surface SEM image of the micron-sized calcium silicate / polyetheretherketone composite material in Example 1.
[0032] Figure 2 This is a cross-sectional SEM image of the micron-sized calcium silicate / polyetheretherketone composite material in Example 1. Detailed Implementation
[0033] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.
[0034] Unless otherwise specified, all the following quantities are parts by weight.
[0035] Preparation of porous chitosan: Chitosan was added to a 2 vol% aqueous acetic acid solution to obtain a 2% (w / w) chitosan-acetic acid aqueous solution; 4 parts of anhydrous calcium chloride were added to 20 parts of deionized water, and 1 part of PEG-600 was added and dispersed evenly to obtain a calcium chloride solution; at room temperature, 50 parts of liquid paraffin and 1 part of Span-80 were mixed evenly, and the above chitosan-acetic acid aqueous solution and calcium chloride solution were added. The mixture was heated to 55°C and stirred for 1 h, 3 parts of 25 wt% glutaraldehyde aqueous solution were added, the pH was adjusted to 9, the mixture was heated to 70°C and reacted for 2 h, acetone was added and ultrasonic demulsification was performed for 8 min, and the product was filtered under reduced pressure and washed successively with petroleum ether, ethanol and deionized water. After vacuum drying, porous chitosan was obtained; the chitosan Mw = 120000 g / mol, and the molar ratio of chitosan to anhydrous calcium chloride was 1:8;
[0036] Preparation of calcium silicate powder: Calcium nitrate tetrahydrate and sodium metasilicate nonahydrate were prepared into 0.5 mol / L aqueous solutions of calcium nitrate and sodium metasilicate, respectively. One part of polyethylene glycol was added to 300 parts of calcium nitrate aqueous solution, followed by the dropwise addition of 300 parts of sodium metasilicate aqueous solution, resulting in a precipitate. The precipitate was washed with deionized water, and 300 parts of dimethylformamide were added. The water was evaporated by heating while stirring, and then the dimethylformamide was removed by extraction. The resulting product was dried at 60°C and then calcined at 900°C. After cooling, the product was passed through a 400-mesh sieve to obtain calcium silicate powder.
[0037] Preparation of porous calcium silicate: Calcium nitrate tetrahydrate and sodium metasilicate nonahydrate were prepared into 0.5 mol / L aqueous solutions of calcium nitrate and sodium metasilicate, respectively. Dodecyltrimethylammonium chloride and polyacrylamide were added to 300 parts of the sodium metasilicate aqueous solution and stirred until homogeneous to obtain a sodium silicate aqueous solution containing a surfactant. 300 parts of the calcium nitrate aqueous solution were added dropwise to obtain an emulsion, which was aged at 4℃ for 20 h, filtered, washed, and dried at 60℃ to obtain porous calcium silicate. The amount of dodecyltrimethylammonium chloride added was 12% of the mass of sodium metasilicate nonahydrate; the amount of polyacrylamide added was 3% of the mass of sodium metasilicate nonahydrate.
[0038] Preparation of protein solution: Take TCEP solution, adjust the pH to 5, and mix it with bovine serum albumin solution to obtain protein solution; the protein solution contains bovine serum albumin at a concentration of 200 mg / ml;
[0039] Example 1: Polyetheretherketone (PEEK) granules were dried in a drying machine at 150°C for 4 hours, then melted in a twin-screw extruder at 370-390°C. After degassing, calcium silicate powder was added and mixed in the twin-screw extruder, and a vacuum was applied. The mixture was extruded through a die and rapidly cooled and hardened into Φ1.8mm filaments using a water chiller. The filaments were dried by blowing moisture with an air knife and then cut into Φ1.8x3.15mm granules using a pelletizer. The granules were then screened using a vibrating screen to obtain micron-sized calcium silicate / PEEK composite material. The mass ratio of PEEK granules to calcium silicate powder was 7:3.
[0040] Example 2: The micron-sized calcium silicate / polyether ether ketone composite material prepared in Example 1 was subjected to surface treatment: S1: The micron-sized calcium silicate / polyether ether ketone composite material was immersed in 98% concentrated sulfuric acid and stirred at 500 rpm / min for 5 min. It was then removed and placed in deionized water to terminate the reaction. Then, it was washed in acetone and deionized water for 30 min each, and dried at 60°C to obtain the sulfonated composite material.
[0041] S2: Take the sulfonated composite material, soak it in a 4 mg / mL dopamine Tris-HCl solution, control the pH to 8.5, and polymerize for 24 h to obtain the PDA-modified composite material;
[0042] S3: Soak porous calcium silicate in protein solution, add 250mM β-mercaptoethanol, let stand at room temperature for 12h, filter and dry to obtain modified calcium silicate;
[0043] S4: Take 3 parts of porous chitosan, add 100 parts of 4% v / v acetic acid aqueous solution, heat and stir at 60℃ for 12h, add 8 parts of methacrylic anhydride, stir at 40℃ in the dark for 12h, wash and dry to obtain modified porous chitosan.
[0044] S5: Take modified calcium silicate and modified porous chitosan in a mass ratio of 1:4, add them to ethanol to obtain a treatment solution with a concentration of 4 mg / mL, adjust the pH to 8, add photoinitiator 1173, stir evenly, immerse the PDA modified composite material in it, treat it under ultraviolet light at 360 nm for 30 min, then soak it for 3 h, and dry it to obtain the surface-treated micron-sized calcium silicate / polyether ether ketone composite material.
[0045] Example 3: The micron-sized calcium silicate / polyether ether ketone composite material prepared in Example 1 was subjected to surface treatment: S1: The micron-sized calcium silicate / polyether ether ketone composite material was immersed in 98% concentrated sulfuric acid and stirred at 500 rpm / min for 5 min. It was then removed and placed in deionized water to terminate the reaction. Then, it was washed in acetone and deionized water for 30 min each, and dried at 60°C to obtain the sulfonated composite material.
[0046] S2: Take the sulfonated composite material, soak it in a 5 mg / mL dopamine Tris-HCl solution, control the pH to 8.5, and polymerize for 24 h to obtain the PDA-modified composite material;
[0047] S3: Soak porous calcium silicate in protein solution, add 200mM β-mercaptoethanol, let stand at room temperature for 12h, filter and dry to obtain modified calcium silicate;
[0048] S4: Take 2 parts of porous chitosan, add 100 parts of 4% v / v acetic acid aqueous solution, heat and stir at 60℃ for 12h, add 5 parts of methacrylic anhydride, stir at 40℃ in the dark for 12h, wash and dry to obtain modified porous chitosan.
[0049] S5: Take modified calcium silicate and modified porous chitosan in a mass ratio of 1:3, add them to ethanol to obtain a treatment solution with a concentration of 4 mg / mL, adjust the pH to 8, add photoinitiator 1173, stir evenly, immerse the PDA modified composite material in it, treat it under ultraviolet light at 360 nm for 30 min, then soak it for 3 h, and dry it to obtain the surface-treated micron-sized calcium silicate / polyether ether ketone composite material.
[0050] Comparative Example 1 (no photoinitiator added, no ultraviolet light treatment, the rest of the methods and steps are the same as in Example 2): Take the micron-sized calcium silicate / polyether ether ketone composite material obtained in Example 1 and perform surface treatment: S1: Take the micron-sized calcium silicate / polyether ether ketone composite material, immerse it in 98% concentrated sulfuric acid, stir at 500 rpm / min for 5 min, take it out and place it in deionized water to terminate the reaction, then wash it in acetone and deionized water for 30 min respectively, and dry it at 60℃ to obtain sulfonated composite material;
[0051] S2: Take the sulfonated composite material, soak it in a 4 mg / mL dopamine Tris-HCl solution, control the pH to 8.5, and polymerize for 24 h to obtain the PDA-modified composite material;
[0052] S3: Soak porous calcium silicate in protein solution, add 250mM β-mercaptoethanol, let stand at room temperature for 12h, filter and dry to obtain modified calcium silicate;
[0053] S4: Take 3 parts of porous chitosan, add 100 parts of 4% v / v acetic acid aqueous solution, heat and stir at 60℃ for 12h, add 8 parts of methacrylic anhydride, stir at 40℃ in the dark for 12h, wash and dry to obtain modified porous chitosan.
[0054] S5: Take modified calcium silicate and modified porous chitosan in a mass ratio of 1:4, add them to ethanol to obtain a treatment solution with a concentration of 4 mg / mL, adjust the pH to 8, stir evenly, immerse the PDA modified composite material in it, soak for 3 hours, dry, and obtain the surface-treated micronized calcium silicate / polyether ether ketone composite material.
[0055] Comparative Example 2 (using micron-sized calcium silicate / polyether ether ketone composite material instead of PDA modified composite material, the remaining methods and steps are the same as in Example 2): Take the micron-sized calcium silicate / polyether ether ketone composite material obtained in Example 1 and perform surface treatment: S1: Immerse porous calcium silicate in protein solution, add 250mM β-mercaptoethanol, let stand at room temperature for 12h, filter and dry to obtain modified calcium silicate;
[0056] S2: Take 3 parts of porous chitosan, add 100 parts of 4% v / v acetic acid aqueous solution, heat and stir at 60℃ for 12h, add 8 parts of methacrylic anhydride, stir at 40℃ in the dark for 12h, wash and dry to obtain modified porous chitosan.
[0057] S3: Take modified calcium silicate and modified porous chitosan in a mass ratio of 1:4, add them to ethanol to obtain a treatment solution with a concentration of 4 mg / mL, adjust the pH to 8, add photoinitiator 1173, stir evenly, immerse the micron-sized calcium silicate / polyether ether ketone composite material in it, treat it under ultraviolet light at 360 nm for 20~30 min, soak it for 3 h, and dry it to obtain the surface-treated micron-sized calcium silicate / polyether ether ketone composite material.
[0058] Comparative Example 3 (increased treatment solution concentration, other methods and steps are the same as in Example 2): Take the micron-sized calcium silicate / polyether ether ketone composite material obtained in Example 1 and perform surface treatment: S1: Take the micron-sized calcium silicate / polyether ether ketone composite material, immerse it in 98% concentrated sulfuric acid, stir at 500 rpm / min for 5 min, take it out and place it in deionized water to terminate the reaction, then wash it in acetone and deionized water for 30 min respectively, and dry it at 60℃ to obtain sulfonated composite material;
[0059] S2: Take the sulfonated composite material, soak it in a 4 mg / mL dopamine Tris-HCl solution, control the pH to 8.5, and polymerize for 24 h to obtain the PDA-modified composite material;
[0060] S3: Soak porous calcium silicate in protein solution, add 250mM β-mercaptoethanol, let stand at room temperature for 12h, filter and dry to obtain modified calcium silicate;
[0061] S4: Take 3 parts of porous chitosan, add 100 parts of 4% v / v acetic acid aqueous solution, heat and stir at 60℃ for 12h, add 8 parts of methacrylic anhydride, stir at 40℃ in the dark for 12h, wash and dry to obtain modified porous chitosan.
[0062] S5: Take modified calcium silicate and modified porous chitosan in a mass ratio of 1:4, add them to ethanol to obtain a treatment solution with a concentration of 8 mg / mL, adjust the pH to 8, add photoinitiator 1173, stir evenly, immerse the PDA modified composite material in it, treat it under ultraviolet light at 360 nm for 30 min, soak it for 3 h, and dry it to obtain the surface-treated micron-sized calcium silicate / polyether ether ketone composite material.
[0063] Comparative Example 4 (using calcium silicate powder instead of porous calcium silicate, with the remaining steps being the same as in Example 2): The micron-sized calcium silicate / polyether ether ketone composite material prepared in Example 1 was subjected to surface treatment: S1: The micron-sized calcium silicate / polyether ether ketone composite material was immersed in 98% concentrated sulfuric acid and stirred at 500 rpm / min for 5 min. It was then removed and placed in deionized water to terminate the reaction. Then, it was washed in acetone and deionized water for 30 min each, and dried at 60°C to obtain the sulfonated composite material.
[0064] S2: Take the sulfonated composite material, soak it in a 4 mg / mL dopamine Tris-HCl solution, control the pH to 8.5, and polymerize for 24 h to obtain the PDA-modified composite material;
[0065] S3: Soak calcium silicate powder in protein solution, add 250mM β-mercaptoethanol, let stand at room temperature for 12h, filter and dry to obtain modified calcium silicate;
[0066] S4: Take 3 parts of porous chitosan, add 100 parts of 4% v / v acetic acid aqueous solution, heat and stir at 60℃ for 12h, add 8 parts of methacrylic anhydride, stir at 40℃ in the dark for 12h, wash and dry to obtain modified porous chitosan.
[0067] S5: Take modified calcium silicate and modified porous chitosan in a mass ratio of 1:4, add them to ethanol to obtain a treatment solution with a concentration of 4 mg / mL, adjust the pH to 8, add photoinitiator 1173, stir evenly, immerse the PDA modified composite material in it, treat it under ultraviolet light at 360 nm for 30 min, then soak it for 3 h, and dry it to obtain the surface-treated micron-sized calcium silicate / polyether ether ketone composite material.
[0068] Unless otherwise specified, the experimental methods used in the above embodiments are conventional methods; the raw materials used are commercially available unless otherwise specified, and their sources are as follows: calcium nitrate tetrahydrate (CAS: 13477-34-4); sodium metasilicate nonahydrate (CAS: 13517-24-3); polyethylene glycol (PEG-600, Wuhan Xindadi Environmental Protection Materials Co., Ltd.); dimethylformamide (CAS: 68-12-2); polyetheretherketone granules (KA679524, Jieshikai); acetone (CAS: 67-64-1); dopamine (CAS: 51-61-6); dodecyltrimethylammonium chloride (CAS: 112-00-5); polyacrylamide (S31321, Shanghai Yuanye); chitosan (Mw=120000). g / mol, Shanghai Koraman Reagent Co., Ltd.); Acetic acid (CAS: 64-19-7); Anhydrous calcium chloride (S24110, Shanghai Yuanye); Liquid paraffin (S68179, Shanghai Yuanye); Span-80 (CAS: 1338-43-8); Glutaraldehyde (CAS: 111-30-8); Petroleum ether (CAS: 8030-30-6); Ethanol (CAS: 64-17-5); β-mercaptoethanol (GOY-0957P, Shanghai Guyan); Methacrylic anhydride (CAS: 760-93-0); TCEP solution (ZY131056, Zeye Biotechnology); Bovine serum albumin solution (H47988, Hubei Aipudi Biotechnology Co., Ltd.); Photoinitiator 1173 (CAS: 7473-98-5).
[0069] Experiment: Micronized calcium silicate / polyetheretherketone composite material prepared in Example 1 and surface-treated micronized calcium silicate / polyetheretherketone composite materials prepared in Examples 2-3 and Comparative Examples 1-4 were used; (1) Tensile strength was measured using a universal testing machine according to GB / T 1040.1-2018 standard; (2) Mouse embryonic osteoblast precursor cells (MC3T3-E1, Fudan University Cell Bank, Shanghai, China) were selected for cell experiments; Culture: MC3T3-E1 cells were cultured in DMEM medium (Gibco BRL, Thermo Fisher Scientific). In a Scientific (USA) medium containing 10 vol% fetal bovine serum, 100 U / mL penicillin, and 100 μg / mL streptomycin, the medium was placed in a CO2 incubator at 100% humidity, 5% CO2, and 37°C. The medium was changed every 3 days. Cell adhesion was tested by sterilizing the composite material sample with ethylene oxide and placing it in a sterile 24-well plate. Trypsin (0.25%) was added to the plate to digest the cells (1 minute), followed by the addition of cell culture medium to stop digestion. The sample was centrifuged, the supernatant was removed, and cell culture medium was added again, and the cells were counted. Cells were then seeded onto the material surface (cell density: 2 × 10⁻⁶). 4 Cells per well were cultured in a cell culture incubator for 24 hours. The liquid in the culture plate was then removed, and the sample was gently washed with sterile phosphate-buffered saline (PBS). Cells remaining on the material surface were collected, and the cell count was determined using a CyQUANT® assay kit (Life Technologies, Carlsbad, USA). Using the same method, cells were cultured in culture plates (TCP) without the material sample, and the cell count was determined after the same culture time, serving as a blank control group. Cell adhesion rate (%) = (number of cells on the material surface / number of cells in the blank control group) × 100%. Specific data are shown in the table below.
[0070] Tensile strength / MPa Cell adhesion rate / % Example 1 92.0 55.6 Example 2 96.6 73.2 Example 3 96.7 73.0 Comparative Example 1 92.6 62.5 Comparative Example 2 92.9 60.4 Comparative Example 3 92.3 69.5 Comparative Example 4 93.2 66.9
[0071] Conclusions: In Comparative Example 1, without the addition of a photoinitiator and without UV treatment, the performance decreased due to the absence of UV-induced crosslinking. In Comparative Example 2, replacing the PDA-modified composite material with a micron-sized calcium silicate / polyetheretherketone composite material significantly reduced adhesion. In Comparative Example 3, increasing the concentration of the treatment solution actually led to a decrease in performance due to factors such as adhesion, indicating that the concentration of the treatment solution is also important. In Comparative Example 4, replacing porous calcium silicate with calcium silicate powder reduced adhesion due to the reduced porous structure. In summary, the micron-sized calcium silicate / polyetheretherketone composite material prepared in this invention exhibits excellent mechanical properties and cell adhesion rate, meaning it possesses excellent activity.
[0072] It will be apparent to those skilled in the art that the present invention is not limited to the details of the exemplary embodiments described above, and that the invention can be implemented in other specific forms without departing from the spirit or essential characteristics of the invention. Therefore, the embodiments should be considered in all respects as exemplary and non-limiting, and the scope of the invention is defined by the appended claims rather than the foregoing description. Thus, it is intended that all variations falling within the meaning and scope of equivalents of the claims be included within the present invention.
Claims
1. A method for preparing a microcalcium silicate / polyether ether ketone composite material, characterized by: Includes the following steps: Take polyetheretherketone granules, dry them, melt them at 370~390℃, degas the air, add calcium silicate powder, mix them, vacuum them, extrude filaments with a diameter of 1.5~2mm, blow off the moisture, cut them into granules of 2.8~3.5mm, and screen them through a vibrating screen to obtain micron-sized calcium silicate / polyetheretherketone composite material. The mass ratio of the polyetheretherketone granules to the calcium silicate powder is (6~7):(3~4). The micron-sized calcium silicate / polyetheretherketone composite material is surface-treated to obtain the final surface-treated micron-sized calcium silicate / polyetheretherketone composite material, specifically including the following steps: Step 1: Take micron-sized calcium silicate / polyetheretherketone composite material, pretreat it, soak it in dopamine Tris-HCl solution, control the pH to 8~9, and polymerize for 20~24h to obtain PDA modified composite material; Step 2: Soak porous calcium silicate in protein solution, add β-mercaptoethanol, let stand at room temperature for 12-15 hours, filter and dry to obtain modified calcium silicate; Step 3: Take porous chitosan, add acetic acid aqueous solution, stir evenly, add methacrylic anhydride, stir at 40~45℃ in the dark for 10~12h, wash and dry to obtain modified porous chitosan. Step 4: Take modified calcium silicate and modified porous chitosan, add them to ethanol and stir evenly to obtain a treatment solution. Adjust the pH to 8-9, add photoinitiator, stir evenly, immerse the PDA modified composite material in it, treat it under ultraviolet light for 20-30 minutes, soak it for 2-3 hours, and dry it to obtain the surface-treated micronized calcium silicate / polyether ether ketone composite material. The concentration of the treatment solution is 3~5 mg / mL; the mass ratio of modified calcium silicate to modified porous chitosan in the treatment solution is 1:(3~4). The preparation of the porous calcium silicate includes the following steps: calcium nitrate tetrahydrate and sodium metasilicate nonahydrate are taken, and calcium nitrate aqueous solution and sodium metasilicate aqueous solution with concentrations adjusted to 0.5~1mol / L are prepared respectively; dodecyltrimethylammonium chloride and polyacrylamide are added to 300 parts of sodium metasilicate aqueous solution, and stirred evenly to obtain sodium metasilicate aqueous solution containing surfactant; 300 parts of calcium nitrate aqueous solution are added dropwise to obtain emulsion, aged at 4~5℃ for 20~24h, filtered, washed, and dried at 50~70℃ to obtain porous calcium silicate; The method for preparing the porous chitosan includes the following steps: adding chitosan to a 2 vol% aqueous acetic acid solution to obtain a 2% (w / w) chitosan-acetic acid aqueous solution; adding 3-5 parts of anhydrous calcium chloride to 20 parts of deionized water, adding 1-2 parts of PEG-600, dispersing evenly to obtain a calcium chloride solution. At room temperature, 40-50 parts of liquid paraffin and 0.5-1 part of Span-80 are mixed evenly, and chitosan acetic acid aqueous solution and calcium chloride solution are added. The mixture is heated to 55-60℃ and stirred for 1-2 hours. 2-3 parts of 25wt% glutaraldehyde aqueous solution are added, and the pH is adjusted to 9-10. The mixture is heated to 70-75℃ and reacted for 2-3 hours. Acetone is added and ultrasonic demulsification is performed for 5-8 minutes. After vacuum filtration, the product is washed successively with petroleum ether, ethanol and deionized water. After vacuum drying, porous chitosan is obtained.
2. The method for preparing a micron-sized calcium silicate / polyetheretherketone composite material according to claim 1, characterized in that: The pretreatment is sulfonation treatment, and the specific process is as follows: take micron-sized calcium silicate / polyether ether ketone composite material, immerse it in 98% concentrated sulfuric acid and stir for 5-8 minutes, wash and dry to obtain sulfonated composite material.
3. The method for preparing a micron-sized calcium silicate / polyetheretherketone composite material according to claim 1, characterized in that: The concentration of the dopamine Tris-HCl solution is 2~5 mg / mL.
4. The method for preparing a micron-sized calcium silicate / polyetheretherketone composite material according to claim 1, characterized in that: The protein solution contains bovine serum albumin at a concentration of 200-300 mg / ml; and β-mercaptoethanol is added at a concentration of 200-300 mM.
5. The method for preparing a micron-sized calcium silicate / polyetheretherketone composite material according to claim 1, characterized in that: The modified porous chitosan comprises the following raw materials, by mass: 2-3 parts porous chitosan and 5-8 parts methacrylic anhydride.
6. The micron-sized calcium silicate / polyetheretherketone composite material prepared by the preparation method of the micron-sized calcium silicate / polyetheretherketone composite material according to any one of claims 1 to 5.