A porous shapeable artificial bone repair material and a method for preparing the same

Abstract

The application relates to the technical field of biomedical materials, and particularly discloses a porous plastic artificial bone repair material and a preparation method thereof. The porous plastic artificial bone repair material is prepared from raw materials including a polymer solution and inorganic substances; the polymer solution is composed of a caprolactone monomer-containing copolymer and a solvent; the caprolactone monomer-containing copolymer is prepared by adding an initiator and a catalyst to monomer raw materials after mixing to generate a copolymerization reaction; the monomer raw materials are composed of a caprolactone monomer and other monomers, and the addition amount of the caprolactone monomer is 30-50%. The porous plastic artificial bone repair material is sponge-like at room temperature, can be arbitrarily shaped, can rebound after being pressed, can be filled to be full for various defects, can be closely combined with the edges of the defects after being implanted, has a porous structure, is convenient to implant, has excellent bone conduction, and can be used for filling and repairing various bone defects in orthopedic surgery.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of biomedical materials, more specifically, it relates to a porous shapeable artificial bone repair material and a preparation method thereof. BACKGROUND

[0002] At present, in the treatment of bone defects caused by various reasons, bone implants are often used to fill the bone defect site in orthopedic surgery. The filling material provides biomechanical support for the defect site and participates in bone regeneration. Artificial bone repair materials are artificial biological materials that replace or repair bone tissue defects, and mainly play a role through osteogenesis, bone conduction and bone induction mechanisms.

[0003] At present, artificial bone repair materials generally have block, granular and injectable types. Block artificial bone repair materials can be used to fill bone defects after trimming, but their shape still cannot accurately match the shape of the defect. Granular materials can be filled in bone defects of various shapes, but the overall granular accumulation is prone to collapse and cannot stably maintain the bone regeneration space. The injectable type is generally composed of bone repair particles and viscous carriers. After mixing, a shapeable mass is formed, which is then injected into the bone defect area, greatly facilitating the implantation operation. However, the viscous carrier generally degrades within a short period of time. Therefore, in addition to the convenience of operation, the injectable artificial bone repair material also has the problem of easy collapse of granular materials.

[0004] Patent No. CN110801537A proposes a shapeable artificial bone composite material composed of a degradable polymer and inorganic particles dispersed in the polymer, which is prepared by dissolving, mixing, drying and vacuum drying. The artificial bone composite material is in a shapeable plasticine state at 25-40℃ and has fluidity at 40-60℃. This design makes the artificial bone composite material have shapeability and injectability, thereby facilitating the application of the artificial bone composite material in the field of orthopedics. The plasticine material is convenient to use and can be completely filled.

[0005] However, for the related technology in the above, the artificial bone composite material is in a shapeable plasticine state at 25-40℃, which is higher than the normal operating room temperature, that is, the artificial bone composite material needs to be heated to soften before use, which increases the operation time. As for the artificial bone composite material having fluidity at 40-60℃, it will cause soft tissue burns. In addition, the artificial bone composite material is a non-porous material, and for artificial bone repair materials, a porous structure is necessary. The porous structure is beneficial to early tissue integration and provides a path for the diffusion and circulation of growth factors and nutrients, ensuring that new blood vessels grow into the deep part of the material, thereby achieving the slow replacement of the implanted material by the new tissue. In summary, the porous structure is a core design element for the realization of biological activity, mechanical adaptability and functionalization of artificial bone repair materials.

[0006] Therefore, there is an urgent need to propose a solution to solve the above technical problems. SUMMARY

[0007] In order to make the artificial bone repair material have the unique performance of being arbitrarily shaped according to the shape of the bone defect and being able to rebound after being pressed, and to be closely attached to the edge of the defect after being implanted into the bone defect area, while having a porous structure, so as to facilitate the implantation operation and have excellent bone conduction, the application provides a porous shapeable artificial bone repair material and a preparation method thereof.

[0008] In a first aspect, the application provides a porous shapeable artificial bone repair material, which adopts the following technical solution:

[0009] A porous shapeable artificial bone repair material is made of raw materials comprising:

[0010] A high molecular solution and an inorganic substance;

[0011] The high molecular solution is composed of a caprolactone monomer-containing copolymer and a solvent;

[0012] The caprolactone monomer-containing copolymer is prepared by copolymerization of monomer raw materials after adding an initiator and a catalyst;

[0013] The monomer raw materials are composed of a caprolactone monomer and other monomers, and the addition amount of the caprolactone monomer is 30-50%.

[0014] By adopting the above technical solution, in the application of the above raw materials, the caprolactone monomer-containing copolymer in the high molecular solution has shape memory characteristics due to the caprolactone monomer, and its glass transition temperature is close to the body temperature of human body, so that the artificial bone repair material can be softened and shaped by body temperature when implanted, and the original shape is restored due to the crystallization area after removing external force. In addition, the melting point of caprolactone is about -15℃, and the glass transition temperature of polycaprolactone formed after copolymerization is about -60℃, and the melting point is 58-64℃, which is similar to rubber at room temperature, and becomes flowable after slight heating. At the same time, by introducing other monomers to improve the glass transition temperature of the copolymer, the artificial bone repair material is shapeable at room temperature but does not spontaneously deform.

[0015] After the high molecular solution is compounded with the inorganic substance, connected pores are formed by solvent evaporation, which can provide a migration channel for bone cells, ensure mechanical strength, and facilitate cell infiltration and vascularization. In addition, the porous structure reduces the density of the material, making it easier to compress and deform when shaping, and forming mechanical interlocking with the bone defect surface after implantation to realize the combination of mechanical support and biological activity.

[0016] The content of the caprolactone monomer in the control monomer is 30-50%, and it is found through research that the proportion is controlled to make the obtained copolymer have suitable glass transition temperature and degradation performance. The more the content of the caprolactone monomer, the lower the glass transition temperature of the obtained copolymer, and the longer the degradation time. The degradation rate of the copolymer at the above-mentioned proportion matches the bone regeneration speed, avoids the premature loss of mechanical properties, and at the same time, in combination with the porous structure itself, provides sufficient space for new bone formation.

[0017] In summary, the porous shapeable artificial bone repair material is sponge-like at room temperature, can be arbitrarily shaped and can rebound after being pressed, can achieve full filling for various defects, and can be closely combined with the edge of the defect after implantation, and at the same time has a porous structure, so it is convenient for implantation operation and has excellent bone conduction, and can be used for filling and repairing various bone defects in orthopedic surgery.

[0018] Preferably, the inorganic content is 10-60% of the mass of the porous shapeable artificial bone repair material.

[0019] By adopting the above technical solution, when the content of the hydroxyapatite is less than 10%, it is not enough to neutralize the acidic products released in the degradation process of the copolymer component of the obtained artificial bone repair material, which will produce acidic inflammation and cause bone resorption; when the content of the hydroxyapatite is higher than 60%, the hydroxyapatite cannot be completely wrapped by the polymer, the obtained artificial bone repair material will fall off powder, and there will be local stress accumulation in the material due to too many inorganic particles, resulting in poor mechanical properties of the material. Therefore, by selecting the above content range of inorganic matter, the obtained artificial bone repair material can provide a good osteogenic environment after being implanted into the bone defect area.

[0020] Preferably, the concentration of the polymer solution is 5-10%.

[0021] By adopting the above technical solution, when the concentration is lower than the above range, the distance between the polymer chains increases, the intermolecular force weakens, resulting in too low viscosity of the solution, and the inorganic matter in the solution is easy to settle; when the concentration is higher than the above range, the viscosity of the solution is too high, which will lead to incomplete dissolution of the copolymer containing the caprolactone monomer, and will easily cause biological compatibility hazards; and the polymer solution with the above concentration range can have better application stability when applied.

[0022] Preferably, the solvent is a high freezing point solvent, which is one or a combination of 1,4-dioxane and dimethyl sulfoxide.

[0023] By adopting the technical scheme, 1,4-dioxane is a non-protic polar solvent, and its freezing point is about 12 DEG C, so that it remains liquid at room temperature; dimethyl sulfoxide has the characteristic of "universal solvent", and its freezing point is about 18 DEG C, so that it remains liquid at room temperature; the solvent is selected to be a solvent with high freezing point, and 1,4-dioxane and dimethyl sulfoxide are selected to be used, so that better vacuum freeze-drying effect can be obtained in subsequent application process.

[0024] Preferably, the other monomer is a combination of one or both of lactide monomers and glycolide monomers.

[0025] By adopting the technical scheme, the main role of adding lactide or glycolide is to improve the thermal conversion temperature and adjust the degradation time, so that a plurality of types of porous plastic artificial bone repair materials are obtained, and the overall application performance is better.

[0026] Preferably, the initiator is dodecanol, and the catalyst is stannous octoate.

[0027] By adopting the technical scheme, dodecanol has the advantages of precise molecular weight control and biocompatibility guarantee, and stannous octoate has the advantages of high catalytic activity and inhibition of side reactions, and the selection of the two can bring synergistic effect, so as to ensure the structural regularity of the copolymer.

[0028] Preferably, the inorganic substance is one or a combination of several of the commonly used inorganic implant materials in orthopedics, such as calcium phosphate and bioactive glass.

[0029] By adopting the technical scheme, calcium phosphate and bioactive glass can induce hydroxyapatite deposition and accelerate bone integration, so as to bring better bone conduction and biological activity, and meet the complex bone defect repair requirements; at the same time, after mixing the above inorganic substance with the polymer solution, the porous plastic artificial bone repair material with excellent stability can be obtained after subsequent pore forming.

[0030] Preferably, the porous plastic artificial bone repair material has a through porous structure, the porosity is > 60%, and the pore size is 50-200 mu m.

[0031] By adopting the technical scheme, the porosity > 60% provides sufficient space for osteoblasts and vascular endothelial cells, accelerates bone tissue ingrowth, and ensures the mechanical properties and degradation balance of the artificial bone repair material; the pore size is 50-200 mu m, so as to simulate the pore characteristics of natural cancellous bone, promote the directional differentiation of mesenchymal stem cells, and the porous structure with the pore size can also ensure the material diffusion efficiency.

[0032] In the second aspect, the application provides a preparation method of a porous plastic artificial bone repair material, which adopts the following technical scheme:

[0033] A method for preparing a porous shapeable artificial bone repair material, comprising the following steps:

[0034] (1) Preparing raw materials containing a polymer solution and inorganic substances according to a proportion;

[0035] (2) Adding inorganic substances to the polymer solution for stirring to obtain a suspension; pouring the suspension into a mold for vacuum freeze drying to obtain the porous shapeable artificial bone repair material.

[0036] Preferably, in the operation of vacuum freeze drying in step (2), the following operations are sequentially performed:

[0037] The pre-freezing temperature for vacuum freeze drying is -40-0°C, and the time is 0.5-4h;

[0038] The temperature for the first drying in the vacuum freeze drying is -40--20°C, and the time is 15-72h;

[0039] The temperature for the second drying in the vacuum freeze drying is 20-40°C, and the time is 10-72h.

[0040] By using the above technical solution, in the above vacuum freeze drying process, in the pre-freezing process, the selection of the above temperature and time can form uniform micron-sized ice crystals, avoid mechanical defects caused by large pore structures, and prevent subsequent drying collapse; then in the first drying stage, the selection of the above temperature and time can control the slow sublimation rate to form through pores, balance the energy consumption and drying efficiency, and avoid material shrinkage; finally in the second drying stage, the selection of the above temperature and time can remove bound water and avoid the collapse of the polymer skeleton, and maintain the integrity of the three-dimensional network. In this way, a porous shapeable artificial bone repair material with excellent quality and stability can be obtained.

[0041] In summary, the present application has the following beneficial effects:

[0042] 1. The porous shapeable artificial bone repair material of the present application is sponge-like at room temperature, can be arbitrarily shaped and can rebound after being pressed, can achieve full filling for various defects, and can be closely combined with the edge of the defect after implantation, and has a porous structure, so it is convenient for implantation operation and has excellent bone conduction, and can be used for filling and repairing various bone defects in orthopedic surgery;

[0043] 2. The porous shapeable artificial bone repair material of the present application has high porosity and a through porous structure. High porosity is beneficial for the transfer of small molecule nutrients and the discharge of metabolic products, and the through pore structure is beneficial for cell migration, vascular formation and bone integration;

[0044] 3、The porous shapeable artificial bone repair material in the preparation of the application has a simple process and can be easily industrialized. In addition, it does not require special equipment such as high temperature and high pressure, and is safe and low in cost. BRIEF DESCRIPTION OF DRAWINGS

[0045] Figure 1 is a microscopic image of the porous shapeable artificial bone repair material in Example 1 of the application. DETAILED DESCRIPTION

[0046] The application will be further described in detail below in combination with preparation examples, examples and comparative examples.

[0047] The raw materials used in each of the preparation examples, examples and comparative examples of the application are commercially available, except as otherwise specified.

[0048] Preparation examples of raw materials and / or intermediates.

[0049] Preparation Example 1

[0050] A copolymer containing caprolactone monomers is prepared by the following operation,

[0051] The monomer raw material is placed in a reaction container, then the initiator and catalyst are added, heated to 140°C, and reacted for 24h under stirring to obtain a crude polymer; then the crude polymer is taken out, dissolved in dichloromethane, then the solution is poured into methanol to precipitate, filtered to obtain the filtrate; finally, the obtained filtrate is vacuum dried at 40°C for 12h to obtain the copolymer containing caprolactone monomers.

[0052] Note: The ratio of monomer raw material, catalyst and initiator is 100g: 0.5mL: 150μL; the initiator is dodecanol, the catalyst is stannous octoate, and the monomer raw material is composed of lactide and caprolactone in a mass ratio of 1:1.

[0053] Preparation Example 2

[0054] A copolymer containing caprolactone monomers, which is different from Preparation Example 1, is that the monomer raw material is composed of lactide, caprolactone and glycolide in a mass ratio of 1:1:1.

[0055] Preparation Example 3

[0056] A copolymer containing caprolactone monomers, which is different from Preparation Example 1, is that the monomer raw material is composed of lactide and caprolactone in a mass ratio of 7:3.

[0057] Preparation Example 4

[0058] A copolymer containing caprolactone monomers, which is different from Preparation Example 1, is that the monomer raw material is composed of lactide and caprolactone in a mass ratio of 9:1.

[0059] The copolymer containing caprolactone monomer obtained in Preparation Example 1-4 has the number average molecular weight, glass transition temperature and in vitro degradation results shown in Table 1 below.

[0060] Table 1 Performance parameters of Preparation Examples 1-4

[0061] Performance number Number average molecular weight Glass transition temperature In vitro degradation Preparation Example 1 98893 4.22℃ About 5% weight loss at 3 months; 81% weight loss at 6 months Preparation Example 2 101880 10.63℃ About 23% weight loss at 3 months; over 90% weight loss at 6 months Preparation Example 3 85970 10.75℃ About 12% weight loss at 3 months; over 90% weight loss at 6 months Preparation Example 4 90401 36.7℃ About 7% weight loss at 3 months; 87% weight loss at 6 months

[0062] The four copolymers have similar molecular weights, but due to the different monomer contents, the glass transition temperatures and in vitro degradation times are different. In Preparation Example 4, the glass transition temperature is already above room temperature due to the excessively low caprolactone content, and a bone repair material that can be shaped at room temperature cannot be obtained. In addition, when the caprolactone content is 50% (Preparation Example 1), there is still about 20% undegraded after 6 months. Although the in vivo degradation time of the material is often faster than the in vitro degradation time due to the more complex in vivo environment, to ensure that the degradation time of the bone repair material matches the bone formation period, the caprolactone content should not be higher than 50%.

[0063] Example 1

[0064] A porous shapeable artificial bone repair material is prepared from raw material polymer solution and inorganic matter, and is prepared by the following steps:

[0065] (1) Prepare raw materials containing polymer solution and inorganic matter according to the ratio;

[0066] (2) Add inorganic matter to the polymer solution and stir to obtain a suspension; pour the suspension into a mold and perform vacuum freeze drying to obtain a porous shapeable artificial bone repair material.

[0067] Note: In the above operation, the polymer solution is composed of a copolymer containing caprolactone monomer and a solvent, the copolymer containing caprolactone monomer is obtained in Preparation Example 1, the solvent is 1,4-dioxane, and the concentration of the polymer solution is 7.5%. The inorganic matter is hydroxyapatite, and the inorganic matter content is 35% of the mass of the porous shapeable artificial bone repair material. In step (2), the vacuum freeze drying operation is as follows:

[0068] The pre-freezing temperature for vacuum freeze drying is -40 to 0°C, and the time is 0.5 to 4h;

[0069] The temperature for the first drying in vacuum freeze drying is -40 to -20°C, and the time is 15 to 72h;

[0070] The temperature for the second drying in vacuum freeze drying is 20 to 40°C, and the time is 10 to 72h;

[0071] However, in this example, the operation is as follows:

[0072] The pre-freezing temperature for vacuum freeze drying was -15°C, and the time was 2 hours.

[0073] The temperature for the first drying in vacuum freeze drying was -20°C, and the time was 48 hours.

[0074] The temperature for the second drying in vacuum freeze drying was 20°C, and the time was 30 hours.

[0075] Example 2

[0076] A porous moldable artificial bone repair material, which differs from Example 1 in that the concentration of the polymer solution was 5%.

[0077] Example 3

[0078] A porous moldable artificial bone repair material, which differs from Example 1 in that the concentration of the polymer solution was 10%.

[0079] Example 4

[0080] A porous moldable artificial bone repair material, which differs from Example 1 in that the concentration of the polymer solution was 4%.

[0081] Example 5

[0082] A porous moldable artificial bone repair material, which differs from Example 1 in that the concentration of the polymer solution was 11%.

[0083] Example 6

[0084] A porous moldable artificial bone repair material, which differs from Example 1 in that the inorganic matter content was 10% of the mass of the porous moldable artificial bone repair material.

[0085] Example 7

[0086] A porous moldable artificial bone repair material, which differs from Example 1 in that the inorganic matter content was 60% of the mass of the porous moldable artificial bone repair material.

[0087] Example 8

[0088] A porous moldable artificial bone repair material, which differs from Example 1 in that the inorganic matter content was 8% of the mass of the porous moldable artificial bone repair material.

[0089] Example 9

[0090] A porous moldable artificial bone repair material, which differs from Example 1 in that the inorganic matter content was 65% of the mass of the porous moldable artificial bone repair material.

[0091] Example 10

[0092] A porous moldable artificial bone repair material, which differs from Example 1 in that the copolymer containing caprolactone monomers is obtained in Preparation Example 2.

[0093] Example 11

[0094] A porous moldable artificial bone repair material, which differs from Example 1 in that the copolymer containing caprolactone monomers is obtained in Preparation Example 3.

[0095] Performance detection test

[0096] Test samples: The porous moldable artificial bone repair materials obtained in Examples 1-11 are used as test samples 1-11.

[0097] Test method: (1) Plasticity test: Take a piece of porous moldable artificial bone repair material (10*15 mm), knead it by hand at room temperature, and test whether it has moldability. Observe its resilience after kneading: ① Whether it has a tendency to return to its original shape after being kneaded to a specific shape; ② Whether it can return to its original shape.

[0098] (2) Porosity test: According to the drainage method in the literature (DOI: 10.7666 / d.y1918314.), test the porosity. The specific test process is as follows:

[0099] ① Take a piece of porous moldable artificial bone repair material (10*15 mm), accurately measure its diameter and height, and calculate the volume V0;

[0100] ② Accurately weigh the mass of the pure water filled in the specific gravity bottle W1, and the mass of the dried artificial bone repair material W0;

[0101] ③ Immerse the artificial bone repair material in the pure water in the specific gravity bottle, vacuumize, and fill the internal pores of the artificial bone repair material with pure water. Then fill the specific gravity bottle with water, and weigh to get the mass W2. The actual volume of the artificial bone repair material is:

[0102] V 实 = (W2-W1-W0) / p (p - density of pure water);

[0103] ④ Calculate the porosity of the artificial bone repair material:

[0104] P = (V0-Vactual) / V0 x 100%.

[0105] (3) Osteogenesis performance test: the osteogenesis performance of the porous plastic artificial bone repair material was tested using a sheep bone defect model. The defect site: distal femoral metaphysis and proximal tibial epiphysis, defect model size: 10*15mm, implantation time: 3M. Evaluation method: Micro-CT combined with histological section. At the same time, a blank control group was set up without implanting any material.

[0106] After the above tests were performed on the test samples 1-11, the test results were recorded in Table 2 below.

[0107] Table 2 Test results of test samples 1-11

[0108] Sample Moldability Porosity Osteogenic performance (new bone formation rate) Test sample 1 Moldable into any shape at room temperature, and returns to original shape after a short while 79.20% 58.6% Test sample 2 Moldable into any shape at room temperature, and returns to original shape after a short while 78.3% 56.7 Test sample 3 Moldable into any shape at room temperature, and returns to original shape after a short while 78.6 57.1 Test sample 4 Moldable into any shape at room temperature, and returns to original shape after a short while 75.1 51.8 Test sample 5 Moldable into any shape at room temperature, and returns to original shape after a short while 75.0 51.6 Test sample 6 Moldable into any shape at room temperature, and returns to original shape after a short while 78.1 56.3 Test sample 7 Moldable into any shape at room temperature, and returns to original shape after a short while 78.9 57.4 Test sample 8 Moldable into any shape at room temperature, and returns to original shape after a short while 75.4 52.3 Test sample 9 Moldable into any shape at room temperature, and returns to original shape after a short while 75.6 52.7 Test sample 10 Moldable into any shape at room temperature, and returns to original shape after a short while 81.62% 76.9% Test sample 11 Moldable into any shape at room temperature, and returns to original shape after a short while 80.06% 65.1% Blank control group / / 23.7%

[0109] From the above Figure 1 It can be seen that the porous plastic artificial bone repair material has a through-hole structure, and the pore size is distributed in the range of 10-200μm.

[0110] It can be seen from the combination of Example 1 and Examples 10-11 and Table 2 that the porous plastic artificial bone repair material prepared can meet the requirements of porosity >60%, and can be kneaded into any shape at room temperature and can rebound to the original shape after a few minutes, having good plasticity and porous structure. At the same time, compared with the blank control group, it can be seen that the porous plastic artificial bone repair material prepared all shows excellent osteogenesis performance. Among them, the osteogenesis performance of Example 10 is better, and the reason is speculated to be that the obtained artificial bone repair material contains glycolide monomer, which has a faster degradation rate, providing sufficient space for new bone formation.

[0111] It can be seen from the combination of Example 1 and Examples 2-5 and Table 2 that the concentration of the polymer solution is 5-10%, which can provide a good osteogenesis environment for the obtained artificial bone repair material after being implanted into the bone defect area. When the concentration is lower or higher than the above range, the application performance will be obviously lost.

[0112] It can be seen from the combination of Example 1 and Examples 6-9 and Table 2 that when the inorganic content is 10-60% of the mass of the porous plastic artificial bone repair material, the porous plastic artificial bone repair material with excellent and stable application quality can be obtained. When the inorganic content is lower or higher than the above range, the application performance will be obviously lost.

[0113] This specific embodiment is only an explanation of the present application, and is not a limitation of the present application. Those skilled in the art can make modifications to the present embodiment without creative contribution after reading the present specification, but as long as the modifications are within the scope of the claims of the present application, they are protected by the patent law.

Claims

1. A porous, shapeable artificial bone repair material, characterized in that, It is made of raw materials including: a high polymer solution and inorganic substance; the high polymer solution is composed of a caprolactone monomer-containing copolymer and a solvent; the caprolactone monomer-containing copolymer is prepared by copolymerization of monomer raw materials after adding an initiator and a catalyst; the monomer raw materials are composed of a caprolactone monomer and other monomers, and the addition amount of the caprolactone monomer is 30-50%; the inorganic substance content is 10-60% of the mass of the porous plastic artificial bone repair material, and the inorganic substance is hydroxyapatite; the concentration of the high polymer solution is 5-10%, and after the high polymer solution is compounded with the inorganic substance, connected pores are formed by solvent evaporation; the other monomers are one or a combination of both of a propylene lactone monomer and a glycolide monomer.

2. The porous, shapeable bone repair material of claim 1, wherein: The solvent is a high freezing point solvent, which is one or a combination of several of 1,4-dioxane and dimethyl sulfoxide. ​ 3. The porous, shapeable bone repair material of claim 2, wherein: The initiator is dodecanol, and the catalyst is stannous octoate.

4. The porous, moldable bone repair material of claim 1, wherein: The porous plastic artificial bone repair material has a through-porous structure, a porosity >60%, and a pore size of 50-200 μm.

5. The method for preparing the porous, malleable artificial bone repair material according to claim 1, characterized in that: It includes the following steps: (1) preparing raw materials including a high polymer solution and inorganic substance according to the proportion; (2) adding inorganic substance to the high polymer solution for stirring to obtain a suspension; pouring the suspension into a mold for vacuum freeze drying to obtain a porous plastic artificial bone repair material.

6. The method for preparing the porous, malleable artificial bone repair material according to claim 5, characterized in that: In step (2), the operation of vacuum freeze drying is as follows: the pre-freezing temperature for vacuum freeze drying is -40-0 ℃, and the time is 0.5-4 h; the temperature for the first drying in vacuum freeze drying is -40--20 ℃, and the time is 15-72 h; the temperature for the second drying in vacuum freeze drying is 20-40 ℃, and the time is 10-72 h.

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