A composite material hybrid scaffold for bone repair and preparation method thereof

Abstract

The present invention relates to the field of biomedical materials, and in particular to a composite material hybrid scaffold for bone repair and a preparation method thereof. The method comprises the following steps: (1) using zinc-magnesium alloy powder as raw material, obtaining a zinc-magnesium alloy scaffold by 3D printing using a selective laser melting method; (2) ball-milling and mixing bioactive glass powder and modified mullite whiskers to obtain a mixed powder, 3D printing the mixed powder into a shape, and filling the zinc-magnesium alloy scaffold to obtain a composite scaffold material; (3) dissolving silk fibroin and breviscapine in a solvent to prepare a spinning solution, electrospinning the surface of the composite scaffold material to obtain a silk fibroin barrier membrane, and washing and drying the membrane. The composite material hybrid scaffold obtained by the present invention has a significantly lower degradation rate than that of magnesium alloy, achieving effective bone formation space support, and has good biocompatibility and bone formation efficiency.

Description

Technical Field

[0001] The present invention relates to the field of biomedical materials, and in particular to a composite material hybrid scaffold for bone repair and a preparation method thereof. Background Art

[0002] Bone defects are a major disease facing humanity and are extremely common in clinical practice. Currently, there are three types of bone transplants in clinical practice, namely autologous bone transplants, allogeneic bone transplants, and artificial bone transplants. Autologous bone transplants are limited in source and may cause secondary damage; allogeneic bone transplants have risks such as rejection and viral transmission. Currently, bone tissue engineering has gradually become one of the most promising clinical application methods for treating bone defects. Artificial bone scaffolds need to maintain bone formation space and gradually degrade as new bone grows in. Degradation that is too fast or too slow is not conducive to bone formation. Zinc-magnesium alloys, which are mainly zinc and have a small amount of magnesium added, have the characteristics of controllable degradation, and the 3D printing process is easy to implement. At the same time, they have excellent mechanical properties, which are conducive to the maintenance of bone formation space and are considered to be "revolutionary medical implant materials."

[0003] Artificial bone graft materials must possess not only biocompatibility but also mechanical compatibility. A single scaffold configuration and single material make it difficult to achieve gradual degradation with new bone ingrowth, nor to achieve biomechanical compatibility and optimal osteogenesis. For large bone defects, artificial bone grafts using hybrid composite scaffolds are a research area in bone tissue engineering. Summary of the Invention

[0004] In order to overcome the deficiencies of the prior art, one of the objectives of the present invention is to provide a method for preparing a composite material hybrid scaffold for bone repair, which method has strong feasibility and is conducive to industrial production.

[0005] The second purpose of the present invention is to provide a composite hybrid scaffold for bone repair. The composite hybrid scaffold comprises three levels of structure: the primary structure is a laser-melted 3D-printed zinc-magnesium alloy scaffold with a porous network configuration, which has good mechanical properties and can support the defective bone formation space; the secondary structure is internal filling particles, which are a mixed powder of bioactive glass and modified mullite whiskers 3D-printed into porous small particles through digital light processing. The stacked and interlocked particles serve as the filler of the primary scaffold structure, have bioactivity, guide bone regeneration, and synergistically degrade while the primary structure degrades; the tertiary structure is a silk fibroin piezoelectric barrier film covering the scaffold surface, which can shield the in-growth of epithelial cells and fibroblasts and promote the in-growth of new bone tissue by osteoblasts.

[0006] One of the purposes of the present invention is achieved by the following technical solution:

[0007] A method for preparing a composite material hybrid scaffold for bone repair comprises the following steps:

[0008] (1) Using zinc-magnesium alloy powder as raw material, a zinc-magnesium alloy stent was obtained by 3D printing using selective laser melting;

[0009] (2) ball-milling the bioactive glass powder and the modified mullite whisker to obtain a mixed powder; 3D printing the mixed powder to obtain filling particles, and filling the filling particles into the zinc alloy stent to obtain a composite stent material;

[0010] (3) Dissolving silk fibroin and breviscapine in a solvent to prepare a spinning solution, electrospinning is performed on the surface of the composite scaffold material to form a silk fibroin barrier membrane, and washing and drying to obtain the composite material mixed structure scaffold for bone repair.

[0011] Furthermore, in step (2), the preparation method of the modified mullite whiskers is as follows:

[0012] The mullite whiskers are dispersed in toluene, 3-aminopropyltriethoxysilane is added and stirred, and then washed with toluene and dried to obtain the product.

[0013] Furthermore, the mass ratio of the mullite whiskers to 3-aminopropyltriethoxysilane is 1:(6-7.5), and the stirring time is 10-14 hours.

[0014] Furthermore, the mullite whiskers of the present invention have a diameter of 0.2-3 μm and a length of 5-200 μm.

[0015] Furthermore, in step (1), the content of magnesium in the zinc-magnesium based alloy powder is 0.8-2 wt%.

[0016] Furthermore, in step (2), the mass ratio of the bioactive glass powder to the modified mullite whiskers is 1:(0.03-0.12).

[0017] Furthermore, in step (2), the ball milling mixing time is 3-4 hours.

[0018] Furthermore, in step (2), the bioactive glass powder is formed by mixing 58S bioactive glass and 45S bioactive glass in a mass ratio of 1:1; the particle size of the 58S bioactive glass powder is less than 15 μm, and the particle size of the 45S bioactive glass powder is less than 15 μm.

[0019] Furthermore, in step (3), the mass fraction of the silk fibroin in the spinning solution is 8-10%, and the mass fraction of the breviscapine in the spinning solution is 0.2-0.5%.

[0020] Furthermore, in step (3), the solvent is hexafluoroisopropanol.

[0021] The second object of the present invention is achieved by adopting the following technical solution:

[0022] The composite material mixed structure scaffold for bone repair is obtained according to the above preparation method.

[0023] Compared with the prior art, the present invention has the following beneficial effects:

[0024] 1. The present invention provides a composite hybrid scaffold for bone repair. This composite hybrid scaffold combines the unique advantages of multiple biodegradable materials to achieve a coordinated effect, constructing a comprehensive defect repair and reconstruction system from multiple perspectives, including mechanical retention support, bone volume maintenance, osteoconduction, and barrier piezoelectric osteogenesis. The specific strategies are as follows:

[0025] First, the present invention uses laser melting 3D printing technology, using zinc-magnesium-based alloy powder as raw material, to produce a zinc-magnesium alloy stent with a porous grid structure. This 3D printing process is not only easy to implement, but the resulting zinc-magnesium alloy stent exhibits excellent mechanical properties. Through a carefully designed porous grid structure, the stent can effectively maintain the overall macroscopic mechanical stability of the defect repair site. At the same time, the topological structure is optimized in combination with biomechanical principles, minimizing the amount of zinc-magnesium alloy powder used, thereby reducing the ion concentration and achieving optimal mechanical adaptability and biocompatibility.

[0026] Secondly, the bioactive glass selected in this invention exhibits excellent biocompatibility and high mechanical strength, and its degradation products can promote growth factor expression and enhance bone tissue growth. Based on the bioactive glass's degradability, bioactivity, and structural mechanical design, the present invention enhances the compatibility of its components by adding mullite whiskers modified with a silane coupling agent. This composite material is then assembled with a zinc-magnesium alloy stent to comprehensively regulate the degradation properties of the hybrid stent under in vivo biological stress environments.

[0027] Furthermore, the present invention also produces a silk fibroin barrier membrane through electrospinning. The resulting silk fibroin barrier membrane has a longer degradation cycle than the periosteum used clinically. More importantly, the addition of breviscapine during the membrane-forming process can trigger a conformational transition of the silk fibroin from a random coil to a β-pleated sheet, thereby increasing the longitudinal piezoelectric coefficient of the silk fibroin barrier membrane and enhancing its piezoelectric effect under stress response. This effectively shields epithelial cells and fibroblasts from growing into the scaffold over a longer period of time, strengthens the barrier effect, promotes guided bone regeneration within the scaffold, and further enhances its osteogenesis efficiency.

[0028] 2. The present invention also provides a method for preparing the composite material hybrid scaffold for bone repair, which has strong feasibility and effectively improves the material performance. BRIEF DESCRIPTION OF THE DRAWINGS

[0029] Figure 1 This is an exploded schematic diagram of the composite material hybrid bracket of the present invention;

[0030] Figure 2 This is a Micro-CT scan result obtained after the composite material hybrid stent of the present invention was implanted in an animal body for 3 months;

[0031] Figure 3 This is a diagram showing the histological evaluation results of the composite material hybrid stent of the present invention obtained 3 months after implantation in animals;

[0032] Reference numerals:

[0033] 1 is a zinc-magnesium alloy stent, 2 is a filling particle, and 3 is a silk fibroin barrier membrane. DETAILED DESCRIPTION

[0034] Below, in conjunction with the accompanying drawings and specific embodiments, the present invention is further described. It should be noted that, under the premise of no conflict, the various embodiments described below or the various technical features can be arbitrarily combined to form new embodiments. Specific conditions not specified in the embodiments are carried out according to conventional conditions or conditions recommended by the manufacturer. Reagents or instruments used, unless otherwise specified, are conventional products obtained through commercial channels.

[0035] The bioactive glass powder of the present invention is prepared by mixing 58S bioactive glass and 45S bioactive glass in a mass ratio of 1:1, wherein the particle size of the 58S bioactive glass powder is less than 15 μm, and the particle size of the 45S bioactive glass powder is less than 15 μm.

[0036] The diameter of the mullite whisker in the present invention is 0.2-3µm, and the length is 5-200µm.

[0037] The zinc-magnesium-based powder material of the present invention is produced using an aerosol method. First, an automatic feeding system precisely controls the zinc-magnesium ratio, with the magnesium content being 1 wt%. Electromagnetic induction is then used to rapidly melt the material, with a power of 500 kW and a frequency of 10 kHz, raising the melting temperature to 450°C. After the molten metal flows through a nozzle, high-pressure inert argon gas (oxygen content <50 ppm, gas pressure of 8 MPa, and gas flow rate ≥ Mach 1.5) is simultaneously ejected from the nozzle at high speed, breaking the metal stream into tiny droplets. The droplets then exchange heat with the cooling gas, rapidly solidifying into powder particles, which are then collected.

[0038] Preparation Example 1:

[0039] A modified mullite whisker, the preparation method is as follows:

[0040] According to the usage ratio of mullite whiskers, toluene and 3-aminopropyltriethoxysilane of 100 mg:45 mL:700 mg, the mullite whiskers were dispersed in toluene, and 3-aminopropyltriethoxysilane was added. After stirring for 12 hours, the mixture was washed with toluene and then vacuum dried at 50°C for 12 hours.

[0041] Preparation Example 2:

[0042] A modified mullite whisker, the preparation method is as follows:

[0043] According to the usage ratio of mullite whiskers, toluene and 3-aminopropyltriethoxysilane of 100 mg:40 mL:600 mg, the mullite whiskers were dispersed in toluene, and 3-aminopropyltriethoxysilane was added. After stirring for 10 hours, the mixture was washed with toluene and then vacuum dried at 50°C for 12 hours.

[0044] Preparation Example 3:

[0045] A modified mullite whisker, the preparation method is as follows:

[0046] According to the usage ratio of mullite whiskers, toluene and 3-aminopropyltriethoxysilane of 100 mg:50 mL:750 mg, the mullite whiskers were dispersed in toluene, and then 3-aminopropyltriethoxysilane was added. After stirring for 14 hours, the mixture was washed with toluene and then vacuum dried at 50°C for 12 hours.

[0047] Example 1:

[0048] A method for preparing a composite material hybrid scaffold for bone repair comprises the following steps:

[0049] (1) A zinc-magnesium alloy stent 1 was obtained by 3D printing of zinc-magnesium alloy powder (with a magnesium content of 1 wt%) under argon protection throughout the process by selective laser melting. The process parameters were: laser power 80 W, scanning speed 110 mm / s, and printing layer thickness 60 μm. The zinc-magnesium alloy stent 1 was used as the primary structure of the composite hybrid stent.

[0050] (2) In an argon atmosphere, the bioactive glass powder and the modified mullite whiskers obtained in Preparation Example 1 were mixed in a ball mill at a speed of 250 rpm for 3.5 hours to obtain a mixed powder; wherein the mass ratio of the bioactive glass powder to the modified mullite whiskers was 1:0.09; then, the mixed powder was 3D printed using DLP digital light processing technology with the following process parameters: exposure time 2.2 seconds, printing layer thickness 50 μm, to obtain filling particles 2; the filling particles 2 were filled into the zinc-magnesium alloy stent 1 as a secondary structure to obtain a composite stent material;

[0051] (3) Silk fibroin and breviscapine were dissolved in hexafluoroisopropanol to prepare a spinning solution, wherein the mass fraction of silk fibroin in the spinning solution was 9%, and the mass fraction of breviscapine in the spinning solution was 0.4%; 5 mL of the spinning solution was drawn into a 10 mL glass syringe and placed in an electrospinning device, and electrospinning was performed on the surface of the composite scaffold material in step (2) in a low vacuum environment at 40°C, and the silk fibroin barrier membrane 3 formed on the surface of the composite scaffold material was recorded as a tertiary structure; wherein the syringe needle model was G20, the DC voltage at the syringe needle was 15 kV, the spinning speed was 2.0 mL / h, and the spinning distance was 15 cm; then the spun composite scaffold material was washed with deionized water 3 times, and vacuum dried to obtain the composite material hybrid scaffold.

[0052] This embodiment 1 also provides a composite material hybrid scaffold for bone repair, which is prepared by the above preparation method. The structural decomposition diagram of the composite material hybrid scaffold for bone repair is shown as follows: Figure 1 shown.

[0053] Example 2:

[0054] A method for preparing a composite material hybrid scaffold for bone repair comprises the following steps:

[0055] (1) The specific steps are the same as those in Example 1;

[0056] (2) In an argon atmosphere, the bioactive glass powder and the modified mullite whiskers obtained in Preparation Example 2 were mixed in a ball mill at a speed of 240 rpm for 4 hours to obtain a mixed powder; wherein the mass ratio of the bioactive glass powder to the modified mullite whiskers was 1:0.03; then, the mixed powder was 3D printed using DLP digital light processing technology with the following process parameters: exposure time 2.2 seconds, printing layer thickness 50 μm, to obtain filling particles 2; the filling particles 2 were filled into the zinc-magnesium alloy stent 1 as a secondary structure to obtain a composite stent material;

[0057] (3) Dissolve silk fibroin and breviscapine in hexafluoroisopropanol to prepare a spinning solution, wherein the mass fraction of silk fibroin in the spinning solution is 8%, and the mass fraction of breviscapine in the spinning solution is 0.2%; use a 10 mL glass syringe to draw 5 mL of the spinning solution, place it in an electrospinning device, and perform electrospinning on the surface of the composite scaffold material in step (2) in a low vacuum environment at 40°C, and record the silk fibroin barrier film 3 formed on the surface of the composite scaffold material as a tertiary structure; wherein the syringe needle model is G20, the DC voltage at the syringe needle is 15 kV, the spinning speed is 2.0 mL / h, and the spinning distance is 15 cm; then wash the spun composite scaffold material with deionized water three times, and obtain the composite material hybrid scaffold after vacuum drying.

[0058] This embodiment 2 also provides a composite material hybrid scaffold for bone repair, which is prepared using the above preparation method.

[0059] Example 3:

[0060] A method for preparing a composite material hybrid scaffold for bone repair comprises the following steps:

[0061] (1) The specific steps are the same as those in Example 1;

[0062] (2) In an argon atmosphere, the bioactive glass powder and the modified mullite whiskers obtained in Preparation Example 3 were mixed in a ball mill at a speed of 260 rpm for 3 h to obtain a mixed powder; wherein the mass ratio of the bioactive glass powder to the modified mullite whiskers was 1:0.12; then, the mixed powder was 3D printed using DLP digital light processing technology with the following process parameters: laser power of 85 W, scanning speed of 120 mm / s, and printing layer thickness of 50 μm to obtain filling particles 2; the filling particles 2 were filled into the zinc-magnesium alloy stent 1 as a secondary structure to obtain a composite stent material;

[0063] (3) Dissolve silk fibroin and breviscapine in hexafluoroisopropanol to prepare a spinning solution; wherein, the mass fraction of silk fibroin in the spinning solution is 10%, and the mass fraction of breviscapine in the spinning solution is 0.5%; draw 5 mL of the spinning solution with a 10 mL glass syringe, place it in an electrospinning device, and electrospin on the surface of the composite scaffold material in step (2) in a low vacuum environment at 40°C, and record the silk fibroin barrier film 3 formed on the surface of the composite scaffold material as a tertiary structure; wherein, the syringe needle model is G20, the DC voltage at the syringe needle is 15 kV, the spinning speed is 2.0 mL / h, and the spinning distance is 15 cm; then wash the spun composite scaffold material with deionized water three times, and obtain the composite material hybrid scaffold after vacuum drying.

[0064] This embodiment 3 also provides a composite material hybrid scaffold for bone repair, which is prepared using the above preparation method.

[0065] Comparative Example 1:

[0066] This comparative example 1 is basically the same as Example 1, except that the modified mullite whiskers are omitted in step (2); the rest are consistent with Example 1.

[0067] Comparative Example 2:

[0068] This comparative example 2 is basically the same as Example 1, except that the modified mullite whiskers are replaced with mullite whiskers in step (2); the rest are consistent with Example 1.

[0069] Comparative Example 3:

[0070] Comparative Example 3 is basically the same as Example 1, except that breviscapine is omitted in step (3); the rest remains the same as Example 1.

[0071] Test Example 1:

[0072] The composite materials of Examples 1-3 and Comparative Examples 1-3 were placed in Hank's simulated body fluid at 37°C. After immersion for 500 hours, the degradation rate of each group of samples was tested in millimeters per year (mm / a). The experimental results are shown in Table 1.

[0073] Table 1 Degradation rates of the composite materials obtained in Examples 1-3 and Comparative Examples 1-3

[0074] ;

[0075] The test results in Table 1 show that the degradation rate of the composite material for bone repair prepared by the present invention is slow and controllable. In Comparative Example 1 and Comparative Example 2, the degradation rate of the composite material obtained by omitting the modified mullite whiskers and replacing the modified mullite whiskers with mullite whiskers, respectively, is greatly increased. This indicates that the addition of mullite whiskers modified by a silane coupling agent can not only improve the compatibility between the components, but also regulate the degradation rate of the composite material hybrid scaffold.

[0076] Test Example 2:

[0077] In order to test the longitudinal piezoelectric coefficient D33 of the composite materials obtained in Examples 1-3 and Comparative Examples 1-3, a quasi-static piezoelectric constant measuring instrument was used to test the longitudinal piezoelectric coefficient of the composite materials under a scanning voltage of 0-10V; the test results are shown in Table 2.

[0078] Table 2 Longitudinal piezoelectric coefficients of the composite materials obtained in Examples 1-3 and Comparative Examples 1-3

[0079] ;

[0080] The above test results show that the longitudinal piezoelectric coefficient of the composite materials obtained in Examples 1-3 of the present invention is significantly better than that of Comparative Example 3. In Comparative Example 3, breviscapine was omitted when preparing the silk fibroin barrier membrane, and the piezoelectric coefficient decreased significantly, indicating that breviscapine can improve the longitudinal piezoelectric coefficient of the silk fibroin membrane. This may be because breviscapine can induce the transformation of the silk fibroin conformation from random coil to β-fold, thereby improving the longitudinal piezoelectric coefficient of the silk fibroin barrier membrane. Therefore, through the effect of breviscapine on improving the longitudinal piezoelectric coefficient of the silk fibroin barrier membrane, the piezoelectric effect of the composite material under stress response is enhanced, the differentiation and proliferation of bone cells are stimulated, and it can be used to repair bone defects.

[0081] Test Example 3:

[0082] In order to evaluate the osteogenic efficacy of the products obtained in Examples 1-3 of the present invention and Comparative Examples 1-3, an in vivo osteogenic experiment was conducted on animals.

[0083] New Zealand white rabbits were selected as experimental animals, weighing 2.5-3.0 kg, and provided by the Department of Animal Experimental Science, Peking University School of Medicine. The animals were randomly divided into Example 1 group, Example 2 group, Example 3 group, Comparative Example 1 group, Comparative Example 2 group, and Comparative Example 3 group. All experimental rabbits were anesthetized by inhalation of isoflurane, with an induction concentration of 2%-5% and a maintenance concentration of 1.5%-3%. The anesthesiologist monitored the rabbit's breathing and heart rate throughout the operation. The rabbit was placed in a prone position, and the surgical area was shaved and disinfected using a 10% povidone-iodine solution. A 4 cm sagittal incision was made on the scalp at the top of the skull, and the full-thickness skin flap was turned over to expose the intersection of the coronal suture and the sagittal suture. Four symmetrical circumferential grooves with a diameter of 6 mm and a depth of about 0.5 mm were made into cortical perforations. Then, in the corresponding groups, the products of Examples 1-3 and Comparative Examples 1-3 were implanted into the grooves and fixed vertically, and the wounds were closed in layers. After the operation, 40,000 U of conventional penicillin per kilogram body weight was injected intramuscularly for 3 days in the experimental rabbits.

[0084] (1) Three months after surgery, skull specimens were taken and Micro-CT scanning was performed to reconstruct and observe the volume of new bone. The experimental results are as follows: Figure 2 shown.

[0085] (2) The skull specimens taken out 3 months later were sliced ​​and stained with HE for histological observation to evaluate the osteogenesis effect. The results were as follows: Figure 3 shown.

[0086] Depend on Figure 2 The Micro-CT scans show that Examples 1-3 have better osteogenesis than Comparative Examples 1-3, with a large amount of new bone growing into the spaces between the scaffold particles. Among them, Comparative Example 3, after omitting Breviscapine, had the least amount of new bone.

[0087] Depend on Figure 3 It can be seen that the composite materials of Examples 1-3 form bone uniformly in vivo, and the bone volume is better than that of the products of Comparative Examples 1-3. Among them, Comparative Example 3 has a small amount of new bone tissue, but less than that of Example 1.

[0088] The above results indicate that the addition of breviscapine during the preparation of silk fibroin barrier membrane can trigger the transformation of silk fibroin conformation from random coil to β-fold, thereby increasing the longitudinal piezoelectric coefficient of the silk fibroin barrier membrane and enhancing its piezoelectric effect under stress response, which can further improve the osteogenic efficiency while shielding epithelial cells and fibroblasts.

[0089] The above embodiments are only preferred embodiments of the present invention and cannot be used to limit the scope of protection of the present invention. Any non-substantial changes and replacements made by technicians in this field on the basis of the present invention fall within the scope of protection required by the present invention.

Claims

1. A method for preparing a composite material hybrid scaffold for bone repair, characterized in that: The following steps are involved: (1) Using zinc-magnesium alloy powder as raw material, a zinc-magnesium alloy stent was obtained by 3D printing using selective laser melting; (2) ball-milling the bioactive glass powder and the modified mullite whisker to obtain a mixed powder; 3D printing the mixed powder to obtain filling particles; and filling the filling particles into the zinc-magnesium alloy stent to obtain a composite stent material; (3) dissolving silk fibroin and breviscapine in a solvent to prepare a spinning solution, electrospinning the solution on the surface of the composite scaffold material to form a silk fibroin barrier film, and washing and drying the solution to obtain the composite material hybrid scaffold for bone repair; The preparation method of the modified mullite whisker is as follows: The mullite whiskers are dispersed in toluene, 3-aminopropyltriethoxysilane is added and stirred, and then washed with toluene and dried to obtain the product.

2. The method for preparing a composite material hybrid scaffold for bone repair according to claim 1, characterized in that: The mass ratio of the mullite whiskers to 3-aminopropyltriethoxysilane is 1:(6-7.5), and the stirring time is 10-14 hours.

3. The method for preparing a composite material hybrid scaffold for bone repair according to claim 1, characterized in that: In step (1), the content of magnesium in the zinc-magnesium based alloy powder is 0.8-2 wt%.

4. The method for preparing a composite material hybrid scaffold for bone repair according to claim 1, characterized in that: In step (2), the mass ratio of the bioactive glass powder to the modified mullite whiskers is 1:(0.03-0.12).

5. The method for preparing a composite material hybrid scaffold for bone repair according to claim 1, characterized in that: In step (2), the ball milling mixing time is 3-4 hours.

6. The method for preparing a composite material hybrid scaffold for bone repair according to claim 1, characterized in that: In step (2), the bioactive glass powder is prepared by mixing 58S bioactive glass and 45S bioactive glass in a mass ratio of 1:1; the particle size of the 58S bioactive glass powder is less than 15 μm, and the particle size of the 45S bioactive glass powder is less than 15 μm.

7. The method for preparing a composite material hybrid scaffold for bone repair according to claim 1, characterized in that: In step (3), the mass fraction of the silk fibroin in the spinning solution is 8-10%, and the mass fraction of the breviscapine in the spinning solution is 0.2-0.5%.

8. The method for preparing a composite material hybrid scaffold for bone repair according to claim 1, characterized in that: In step (3), the solvent is hexafluoroisopropanol.

9. A composite material hybrid scaffold for bone repair, characterized in that: Prepared according to any one of claims 1 to 8.

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