Medical 3D printing material

Abstract

The invention provides a 3D bone printing material which comprises biological bone meal with biological activity and bone cement, the biological bone meal is prepared from one or more of autogenous bone, allogeneic bone or animal bone, the bone cement comprises powder and liquid, the mass ratio of the biological bone meal to the bone cement is 1: 1-1: 12, and the mass ratio of the bone cement powder to the bone cement liquid is 0.5: 1-1.5: 1.

Description

Technical Field

[0001] This invention belongs to the field of medical devices, specifically relating to a type of medical 3D printing material and its application method. Background Technology

[0002] Currently, some commercially available implantable devices are made of non-degradable metal materials. When these non-degradable metal devices are implanted into the human body, some metals may cause allergic reactions, leading to local inflammation and pain. At the same time, although most metals have good biocompatibility, in some rare cases, the patient's body may produce an immune response and reject the implant.

[0003] Over time, these non-degradable metal implants may experience wear or metal fatigue after prolonged use. Regular medical follow-ups are required during implantation to ensure that the implant functions properly and is free from inflammation.

[0004] After non-degradable metal devices are implanted in the human body, patients may go to certain extreme environments (e.g., extremely cold or hot environments). Because metal has good thermal conductivity, it may cause local discomfort in the human body.

[0005] However, bone powder and bone cement are materials used in the medical field, commonly employed in bone repair and reconstruction surgeries. As a bone graft material (bone filler), it can be used to fill bone defects and promote the formation and integration of new bone. Bone powder can serve as a substitute for autologous bone (the patient's own bone) in the treatment of fractures, bone defects, and other bone-related diseases. Some specially treated bone powders possess osteoinductive properties, guiding and promoting bone formation, which is highly valuable for bone regeneration and repair. However, achieving a precise match between bone powder / bone cement and the patient's implantation remains a challenge, especially for complex and irregular implants. Meanwhile, hydrogels made from calcium phosphate polymer composites, silicate-based materials, silk protein-based materials, polymer composites, gelatin, and sodium alginate-based mixtures are all biomaterials suitable for bone regeneration and repair. These biomaterials offer improved mechanical properties while retaining good biodegradability and can be molded using various methods, including 3D printing. Furthermore, these materials maintain good spatial structure and mechanical properties in the early stages of degradation and exhibit excellent osteoconductivity, effectively repairing bone defects.

[0006] Alternatively, allogeneic bone grafting can be used. However, allogeneic bone is a type of allogeneic transplantation and is generally divided into two types: structural bone grafting and filling bone grafting. It can be used in the fields of fracture repair and soft tissue repair. At the same time, its sources are wide and its usage is not limited. When performing structural bone grafting, it is necessary to find a structure similar to the bone removed from the patient. After bone grafting, patients may experience rejection, absorption of allogeneic bone, and slowed healing.

[0007] Meanwhile, the choice of implants in traditional cosmetic surgery is often limited, making it difficult to fully meet the needs of patients. 3D printing technology, however, can customize implants based on the patient's facial features and requirements. Customized implants not only improve surgical outcomes but also reduce postoperative rejection. Furthermore, facial reconstruction surgery is complex and has uncertain results; 3D printing technology can precisely print the necessary implants based on three-dimensional data of the injured area, restoring the patient's facial structure.

[0008] Current 3D printing technology typically uses bone powder materials that require complex processing such as sterilization, degreasing, and deproteinization, and the biocompatibility of these materials with patients needs improvement. Therefore, achieving a precise match between bone powder and bone cement for implantation into patient injuries remains a challenge, especially for complex and irregular implants. It is necessary to select bone powder with better bioactivity to improve the bioactivity and biocompatibility of the resulting prosthesis. Summary of the Invention

[0009] This invention aims to solve the aforementioned problems by using a novel printing material in a 3D printer. Considering the precise matching of the printed prosthesis with the patient's injury, bone powder with better biocompatibility and bioactivity is required.

[0010] The first aspect of the present invention relates to a 3D bone printing material comprising bioactive bone powder and bone cement, wherein the bioactive bone powder is made from one or more of autologous bone, allogeneic bone or animal bone, and the bone cement comprises powder and liquid, wherein the mass ratio of bioactive bone powder to bone cement is 1:1 to 1:12, and the mass ratio of bone cement powder to bone cement liquid is 0.5:1 to 1.5:1.

[0011] 3D bone printing materials use bioactive bone powder as raw materials, exhibiting excellent biocompatibility with biological tissues. The retention of bioactive cells facilitates better bone ingrowth and integration with surrounding bone tissue, reducing immune rejection and improving the biocompatibility of 3D bone printing materials. Furthermore, it helps reduce the bioinertia between bone cement materials and bone tissue. Under appropriate proportions, this makes the printing process more controllable, resulting in a more stable bone structure after printing.

[0012] In some preferred embodiments, the mass ratio of bio-bone powder to bone cement is 1:3 to 1:10, and the mass ratio of bone cement powder to bone cement liquid is 0.8:1 to 1.2:1. Therefore, by adjusting the ratio of bone powder to bone cement, and the ratio of powder to liquid in the bone cement, the porosity, extrusion performance, and density of the printed prosthesis, etc., of the printing material can be adjusted.

[0013] In some preferred embodiments, the mass ratio of bio-bone powder to bone cement is 1:4 to 1:10, and the mass ratio of bone cement powder to bone cement liquid is 0.9:1 to 1.1:1. Therefore, by adjusting the ratio of bone powder to bone cement, and the ratio of powder to liquid in the bone cement, the porosity, extrusion performance, and density of the printed prosthesis, etc., of the printing material can be adjusted.

[0014] In some preferred embodiments, the bio-bone powder is preferably made from autologous bone. This makes it more suitable for implantation in patients with injuries.

[0015] In some embodiments, bio-bone powder is obtained by removing the periosteum from fresh bone after extraction and then grinding it into powder. This simple process maximizes the preservation of the bone powder's cellular viability.

[0016] In some embodiments, the bone cement powder may include polymethyl methacrylate (PMMA), and the bone cement liquid may include PMMA monomer. PMMA bone cement is a traditional acrylate-based bone cement that, through a polymerization reaction between the powder and liquid components, can achieve rapid setting at room temperature.

[0017] In some embodiments, the 3D bone printing material may also include additives, which may include one or more of the following: developers, polylactic acid, biodegradable polyester, solubilizers, and artificial bone powder. This improves the material's imaging performance, solubility, biodegradability, biocompatibility, and enhances its mechanical properties.

[0018] In some preferred embodiments, the developer may include barium sulfate or zirconium oxide; the biodegradable polyester may include one or more of polyurethane, polycaprolactone, polyglycolic acid, polyanhydride, polyphosphate, polycarbonate, polyhydroxybutyrate, polydioxanone, and polyglycolic acid; the solubilizer may include polyvinylpyrrolidone; and the artificial bone powder may include hydroxyapatite, tricalcium phosphate, calcium phosphate composites, bioglass, collagen, and lactic acid-glycolic acid copolymer. This improves the material's imaging performance, solubility, biodegradability, biocompatibility, and enhances its mechanical properties.

[0019] In some implementations, the additive may be 0-5% by mass. Appropriate additives are selected based on the location and type of bone to be printed, thereby improving the biocompatibility of the printed material.

[0020] A second aspect of the present invention relates to a method for 3D bone printing, using a 3D bone printing material as described in the first aspect of this application, comprising the following steps:

[0021] S1: Mix bone cement powder and bone cement liquid in a certain proportion to form a mixed slurry S;

[0022] S2: Mix the biological bone powder and the mixed slurry S obtained from S1 to form a mixed slurry M;

[0023] S3: Store the mixed slurry M frozen at a low temperature;

[0024] S4: Extrude the frozen mixed paste M for printing, keeping the temperature of the mixed paste M no higher than 20°C before extrusion;

[0025] S5: Heat and solidify the extruded mixed slurry M to achieve rapid material molding.

[0026] The molding material obtained by the above method has good extrusion and molding properties, and can be precisely printed into various bone prosthesis structures as needed, especially more complex bone prosthesis structures, which have broad application prospects in clinical practice.

[0027] In some implementations, the cryopreservation temperature is -20 to 0°C. This slows down the material curing process and ensures the stability of the material properties during printing.

[0028] In some preferred embodiments, the cryopreservation temperature is preferably -18 to -12°C. This slows down the material curing rate and ensures the stability of the material properties during the printing process.

[0029] In some preferred embodiments, the cryopreservation temperature is preferably -15°C. This slows down the material curing process and ensures the stability of the material properties during printing.

[0030] In some embodiments, the heating temperature described in S5 is 30–120°C. This accelerates the chemical reaction of the materials in the mixture, speeds up the curing process, and ultimately allows the mixture to accumulate into a mold.

[0031] In some embodiments, the heating temperature in S5 is preferably 60–80°C. This accelerates the chemical reaction of the materials in the mixture, speeds up the curing process, and ultimately allows the mixture to accumulate into a mold.

[0032] In some embodiments, the heating temperature in S5 is preferably 70°C. This accelerates the chemical reaction of the materials in the mixture, speeds up the curing process, and ultimately allows the mixture to accumulate into a mold.

[0033] The 3D printing material according to the present invention has the following beneficial effects:

[0034] By mixing bioactive bone powder, bone cement powder, bone cement liquid, and additives in a specific ratio, the printing material can maintain good bioactivity after being used by a 3D printer. It has good biocompatibility, excellent 3D printing molding effect and structural stability, and can print complex and irregular fine structures. At the same time, it can promote bone regeneration and improve biocompatibility after implantation, and can be widely used in the fields of bone repair and plastic surgery. Attached Figure Description

[0035] Figure 1 The sample was printed according to the method of Example 11 using the 3D printing material of the present invention. Detailed Implementation

[0036] The present invention will be further illustrated below with reference to specific embodiments. It should be understood that the following detailed description of the technical solutions of the present invention using embodiments will help to further understand the advantages and effects of the technical solutions of the present invention. The embodiments do not limit the scope of protection of the present invention, which is determined by the claims.

[0037] In a first aspect, the present invention provides a 3D bone printing material comprising bioactive bone powder and bone cement, wherein the bioactive bone powder is made from one or more of autologous bone, allogeneic bone or animal bone, and the bone cement comprises powder and liquid, wherein the mass ratio of bioactive bone powder to bone cement is 1:1 to 1:12, and the mass ratio of bone cement powder to bone cement liquid is 0.5:1 to 1.5:1.

[0038] 3D-printed bone prostheses are porous scaffold structures built from bone cement powder and liquid. Bioactive bone powder resides within these porous structures, resulting in a bioactive composition. This invention utilizes bioactive bone powder as a raw material, exhibiting excellent biocompatibility with biological tissues and retaining bioactive cells. This allows for the induction of osteoblast growth, facilitating bone ingrowth and integration with surrounding bone tissue, promoting secondary bone growth, enhancing the biocompatibility of 3D bone printing materials, and reducing the bioinertia between bone cement materials and bone tissue.

[0039] By adjusting the solid-liquid ratio of bone cement powder and liquid, the extrusion properties and porosity of the material can be modified. Furthermore, the content of bio-bone powder in the material can be adjusted according to the load-bearing characteristics and bone density requirements of the printed bone structure.

[0040] In some preferred embodiments, the mass ratio of bone cement powder to bone cement liquid is 0.8:1 to 1.2:1. By controlling the solid-liquid ratio of bone cement powder and liquid, not only can the bone cement have good bonding and flow properties, but it can also have good extrusion properties. This makes the printing material suitable for 3D printing equipment. Simultaneously, by adjusting the ratio, the porosity of the scaffold structure of the printed material can be controlled, thereby adjusting the density of the printed material, and also adjusting its curing time as a binder, which is more conducive to the control of the printing process. In some preferred embodiments, the mass ratio of bio-bone powder to bone cement is 1:3 to 1:10. Since the functions of bones in different locations are different, the required load-bearing capacity, strength, and bone density of bones are also different. In addition to being controlled by a porous scaffold structure, this can also be adjusted by the content of bone powder present in the porous structure. Changes in bone powder content also affect the flowability, extrusion, and formability of the bone printing material, thereby affecting the stability of the formed bone structure.

[0041] In some preferred embodiments, the mass ratio of bone cement powder to bone cement liquid is 0.9:1 to 1.1:1. When the solid-liquid ratio of the bone cement is too high, the material is too viscous and cannot be easily molded; when the solid-liquid ratio of the bone cement is too low, the resulting slurry is too thin and difficult to mold. In some preferred embodiments, the mass ratio of biological bone powder to bone cement is 1:4 to 1:10. When the bone powder content is too low, the bone density is low and the bioinertness of the bone cement material cannot be effectively reduced; when the bone powder content is too high, the material is not stable enough due to the influence of the bonding properties of the bone cement.

[0042] In some preferred embodiments, the bio-bone powder is preferably made from autologous bone. When autologous bone is used as the raw material, patients are less likely to experience immune rejection compared to bone powder from other sources, making the transplantation process safer and with a higher success rate. Furthermore, the autologous bone used is generally bone in the human body that serves only a decorative purpose and does not affect normal bodily functions.

[0043] In some embodiments, bio-bone powder is obtained by removing the periosteum from fresh bone after extraction and then grinding it into powder. Currently, the bone powder used in commonly used 3D bone printing often requires complex processing, including but not limited to degreasing and deproteinization under high temperature, high pressure, and various chemical reagents. These processes are not only complex but also cause the resulting bone powder to lose its biological activity. Using the material of this invention, bio-active bone powder can be obtained through a simple process of removing the periosteum and grinding, maximizing the preservation of the bone powder's cellular activity. Using this bio-active bone powder eliminates the need for separate culturing of active bone marrow cells and the addition of corresponding nutrients; simple processing is sufficient to activate the bone's biological activity, promote secondary bone growth, and form a more stable bone structure. The operation is simple, safe, and fast. This simple and rapid processing method improves the efficiency of 3D bone printing, buying valuable treatment time for patients with acute bone injuries.

[0044] In some implementations, the particle size of the bio-bone meal is controlled between 50 and 200 μm. Considering the issue of uniformity after mixing bone meal and bone cement, a reasonable selection of the bone meal particle size is necessary. A mismatch in particle sizes leads to decreased mixing uniformity, thereby resulting in a decline in mechanical properties.

[0045] In some embodiments, the bone cement powder may include polymethyl methacrylate (PMMA), and the bone cement liquid may include PMMA monomer. This invention selects PMMA bone cement as a binder. PMMA bone cement is a traditional acrylate-based bone cement, and through the polymerization reaction between the powder and liquid components, it can achieve rapid setting at room temperature.

[0046] In some embodiments, the 3D bone printing material may also include additives, which may include one or more of the following: developers, polylactic acid, biodegradable polyester, solubilizers, and artificial bone powder. Thus, by selectively adding these additives, the imaging performance, solubility, biodegradability, biocompatibility, and mechanical properties of the material can be improved.

[0047] In some preferred embodiments, the developer may include barium sulfate or zirconium oxide to enhance the image visibility of the 3D-printed bone prosthesis. In some preferred embodiments, polylactic acid (PLA) is polymerized from lactic acid from renewable resources (such as corn starch or sugarcane), exhibiting excellent biocompatibility and biodegradability. In some preferred embodiments, the biodegradable polyester may include one or more of polyurethane, polycaprolactone, polyglycolic acid, polyanhydride, polyphosphate, polycarbonate, polyhydroxybutyrate, polydioxanone, and polyglycolic acid, possessing good Young's modulus, making the mechanical properties of the 3D bone printing material more closely match those of native bone, while also effectively reducing stress shielding effects and preventing bone loss. In some preferred embodiments, the solubilizer may include polyvinylpyrrolidone (PVP), which is soluble in water and most organic solvents, exhibits excellent physiological inertness, does not participate in human metabolism, and possesses excellent biocompatibility. In some preferred embodiments, the artificial bone powder includes hydroxyapatite, tricalcium phosphate, calcium phosphate composites, bioglass, collagen, and lactic acid-glycolic acid copolymers. It can improve the regenerative capacity of bio-bone powder, which is beneficial to new bone growth. At the same time, it forms a good synergistic effect with bio-bone powder and bone cement, improves the mechanical properties and processing performance of the material, and improves the stability of the bone prosthesis formed after printing.

[0048] In some preferred embodiments, the mass percentage of the additive can be 0-5%. The appropriate type and amount of additive can be selected based on the specific location and type of the bone prosthesis to be printed, selectively improving the imaging performance, solubility, biodegradability, biocompatibility, and mechanical properties of the printed prosthesis material.

[0049] A second aspect of the present invention provides a method for 3D bone printing, using a 3D bone printing material as described in the first aspect of this application, comprising the following steps:

[0050] S1: Mix bone cement powder and bone cement liquid in a certain proportion to form a mixed slurry S;

[0051] Adjusting the solid-liquid ratio of powder and liquid binders can modify the flow properties, extrusion properties, and bonding properties of the binder, as well as regulate the curing time and porosity, thereby controlling the molding properties of the material.

[0052] S2: Mix the biological bone powder and the mixed slurry S obtained from S1 to form a mixed slurry M;

[0053] Bio-based bone powder is obtained by pulverizing fresh bone derived from the patient's own body, allogeneic bone, or animal bone after removing the periosteum, thus retaining a certain degree of bioactivity. To ensure uniformity during the mixing process, the particle size of the bone powder is typically 50–200 μm. By adjusting the ratio of bio-based bone powder to bone cement, the density and strength of the printed material can be controlled, and the flow properties of the mixed material can be adjusted, thereby affecting the molding performance of the material. This makes the printing process more controllable, allowing for the printing of more complex bone structures, and resulting in more stable printed bone structures.

[0054] In some preferred embodiments, additives are added to the mixed slurry M according to the performance requirements of the prosthesis and mixed evenly. The imaging performance, solubility, biodegradability, biocompatibility, and mechanical properties of the material can be adjusted by adding one or more of the following: developing agent, polylactic acid, biodegradable polyester, solubilizer, and artificial bone powder.

[0055] S3: Store the mixed slurry M frozen at a low temperature;

[0056] Preserving the mixed slurry in a frozen environment slows down the material's curing rate, ensuring the stability of its properties during printing. Freezing also helps improve the material's extrudability and flowability, making the extrusion process smoother.

[0057] S4: Extrude the frozen mixed paste M for printing, keeping the temperature of the mixed paste M no higher than 20°C before extrusion;

[0058] When the mixed slurry is removed from a frozen environment and placed at room temperature, the bone cement components in the slurry will undergo a polymerization reaction, generating heat. When the slurry temperature is too high, the reaction rate will accelerate, thus speeding up the material's curing. Because of the excessively rapid curing, the 3D printing nozzle can often become clogged; therefore, it is necessary to maintain a low temperature during the extrusion process. Using a cooling device to control the material temperature below 20°C before extrusion can alleviate the curing process.

[0059] S5: Heat and solidify the extruded mixed slurry M to achieve rapid material molding.

[0060] The mixed slurry extruded from the printhead remains in a fluid state, possessing a certain degree of fluidity. This can easily lead to deformation or collapse of the printed shape, deviating from the intended printing model. Therefore, it is necessary to rapidly cure and solidify the material to ensure the structure matches the intended model. Increasing the temperature can accelerate the curing reaction of the binder; therefore, the extruded material needs to be heated to expedite its curing process.

[0061] The molding material obtained by the above method has good extrusion and molding properties, and can be precisely printed into various bone prosthesis structures as needed, especially more complex bone prosthesis structures, which have broad application prospects in clinical practice.

[0062] In some implementations, cryopreservation is carried out at temperatures ranging from -20°C to 0°C. Preserving the mixed slurry in a frozen environment slows down the material's curing rate, ensuring the stability of its properties during printing. Freezing also helps improve the material's extrudability and flowability, making the extrusion process smoother during printing.

[0063] In some preferred embodiments, the cryopreservation temperature is preferably -18 to -12°C. Freezing helps improve the extrudability and flowability of materials, but at excessively low temperatures, energy consumption is too high, and restoring the cryopreserved material to room temperature for printing is time-consuming. Therefore, a suitable cryopreservation temperature is required.

[0064] In some preferred embodiments, the cryopreservation temperature is preferably -15°C. Experiments have determined that this temperature condition provides the best preservation results.

[0065] In some embodiments, the heating temperature described in S5 is 30–120°C. Increasing the temperature can accelerate the chemical reaction of the materials in the mixture, thereby speeding up the curing process and ultimately allowing the mixture to accumulate into a mold.

[0066] In some preferred embodiments, the heating temperature in step S5 is preferably 60–80°C. By selecting a suitable reaction temperature to control the curing speed, the molding effect of the printed model can be controlled.

[0067] In some preferred embodiments, the heating temperature in step S5 is preferably 70°C. Experiments have determined that this temperature is most suitable for controlling the curing speed.

[0068] The following describes embodiments of this application. The embodiments described below are exemplary and are only used to explain this application, and should not be construed as limiting this application. Where specific techniques or conditions are not specified in the embodiments, they are performed according to the techniques or conditions described in the literature in the art or according to the product manual. Instruments whose manufacturers are not specified are conventional products that can be obtained commercially.

[0069] It should be noted that, unless otherwise specified, the embodiments and features described in this application can be combined with each other. The present invention will now be described in detail with reference to specific embodiments.

[0070] Unless otherwise specified, all raw materials or reagents used in the examples were purchased from Sinopharm Chemical Reagent Co., Ltd.

[0071] Unless otherwise specified, the reagents described shall be used directly without purification.

[0072] Raw material preparation

[0073] Preparation of biological bone meal:

[0074] The fresh bone after extraction is deperiostealed and then pulverized into powder particles of 50–200 μm.

[0075] The bone cement was purchased from Beijing Bangsai Technology Co., Ltd., model number JA-MV-20.

[0076] Example 1

[0077] An image of the little finger bone is generated using MRI magnetic resonance imaging technology, and finally, image slice data of the model to be printed is generated for the 3D printer to read.

[0078] Take 12g of bone cement powder and 8g of bone cement liquid, mix them to obtain mixed slurry S1. Take 12g of pulverized bovine bone powder and mix it with mixed slurry S1 to obtain mixed slurry M1. Add additives as needed and mix well. The resulting mixed slurry has poor fluidity and high viscosity. Store the final mixed slurry frozen at -15℃.

[0079] The frozen material is removed and placed in the printer's material reservoir at room temperature. The mixed slurry M1 is then delivered to the print head via a syringe. A temperature control component is added to the outside of the syringe to maintain the reaction temperature of the mixed slurry at 10°C. A piston in the syringe, controlled by a motor, extrudes the mixed slurry M1 from the print head onto the printing platform, which is maintained at 70°C, based on the model image slice data read by the 3D printer. This produces the desired printed model.

[0080] Examples 2-13

[0081] The mixed slurry was formed using the same method as in Example 1, except for the source of bone meal and the changes in the quality of bone meal, bone cement powder, and bone cement liquid. Specific changes are listed in Table 1.

[0082] Table 1

[0083]

[0084]

[0085] In Examples 2-13, the mixed slurry formed was used to print stable prosthetic structures based on MRI imaging patterns.

[0086] In summary, the embodiments of this application provide a 3D bone printing material that combines bio-bone powder and bone cement as the main raw materials for 3D printing, resulting in a 3D printed bone material with excellent biocompatibility and osteogenic, osteoinductive, and osteoconductive properties. This provides an effective approach for the application of bio-bone powder in the field of bone graft materials.

[0087] It should be noted that this application is not limited to the above-described embodiments. The above embodiments are merely examples, and any embodiments with the same structure and effect as the technical concept within the scope of this application are included in the technical scope of this application. Furthermore, various modifications that can be conceived by those skilled in the art to the embodiments, and other ways of constructing by combining some of the constituent elements of the embodiments, without departing from the spirit of this application, are also included in the scope of this application.

Claims

1. A 3D bone printing material comprising bioactive biologic bone powder and bone cement, wherein, The biological bone powder is made of one or more of autologous bone, allogeneic bone or animal bone, the bone cement comprises a powder and a liquid, The mass ratio of the biological bone powder and the bone cement is 1:1-1:12, The mass ratio of the bone cement powder and the bone cement liquid is 0.5:1-1.5:

1.

2. The 3D bone printing material according to claim 1, wherein, The mass ratio of the biological bone powder and the bone cement is 1:3-1:10, The mass ratio of the bone cement powder and the bone cement liquid is 0.8:1-1.2:

1.

3. The 3D bone printing material according to claim 1, wherein, The mass ratio of the biological bone powder and the bone cement is 1:4-1:10, The mass ratio of the bone cement powder and the bone cement liquid is 0.9:1-1.1:

1.

4. The 3D bone printing material according to claim 1, wherein, The biological bone powder is made of autologous bone.

5. The 3D bone printing material according to claim 1, wherein, The biological bone powder is obtained by removing periosteum from fresh bone after excision and then powdering.

6. The 3D bone printing material according to claim 1, wherein, The bone cement powder comprises polymethyl methacrylate, and the bone cement liquid comprises methyl methacrylate monomer.

7. The 3D bone printing material according to claim 1, further comprising an additive, wherein the additive comprises one or more of a developing agent, polylactic acid, degradable polyester, a solubilizing agent, and artificial bone powder.

8. The 3D bone printing material according to claim 7, wherein, The developing agent comprises barium sulfate or zirconium oxide; The degradable polyester comprises one or more of polyurethane, polycaprolactone, polyglycolide, polyanhydride, polyphosphoester, polycarbonate, polyhydroxybutyrate, poly-p-dioxanone, and polyglycolic acid; The solubilizing agent comprises polyvinylpyrrolidone; The artificial bone powder comprises one or more of hydroxyapatite, tricalcium phosphate, calcium phosphate composite material, bioglass, collagen, and poly(lactic-co-glycolic acid).

9. The 3D bone printing material according to claim 7 or 8, wherein, The mass percentage of the additive is 0-5%.

10. A method for 3D bone printing, using the 3D bone printing material according to any one of claims 1-9, comprising the following steps: S1: mixing bone cement powder and bone cement liquid in a certain proportion to form a mixed slurry S; S2: mixing biological bone powder and the mixed slurry S obtained from S1 to form a mixed slurry M; S3: freezing and storing the mixed slurry M at low temperature; S4: extruding the frozen mixed slurry M for printing, and keeping the temperature of the mixed slurry M not higher than 20℃ before extrusion; S5: heating and curing the extruded mixed slurry M to realize rapid prototyping.

11. The method of claim 10, wherein, The temperature for low-temperature freezing and storage is -20-0℃.

12. The method of claim 11, wherein, The temperature for low-temperature freezing and storage is preferably -18--12℃.

13. The method of claim 12, wherein, The temperature for low-temperature freezing and storage is preferably -15℃.

14. The method of claim 10, wherein, The heating temperature in S5 is 30-120℃.

15. The method of claim 14, wherein, The heating temperature in S5 is preferably 60-80℃.

16. The method of claim 15, wherein, The heating temperature in S5 is preferably 70℃.

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