CN116262815A - Polyester resin, bone tissue engineering scaffold and preparation method thereof - Google Patents
Polyester resin, bone tissue engineering scaffold and preparation method thereof Download PDFInfo
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- CN116262815A CN116262815A CN202111538637.2A CN202111538637A CN116262815A CN 116262815 A CN116262815 A CN 116262815A CN 202111538637 A CN202111538637 A CN 202111538637A CN 116262815 A CN116262815 A CN 116262815A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
- A61F2/00—Filters implantable into blood vessels; Prostheses, i.e. artificial substitutes or replacements for parts of the body; Appliances for connecting them with the body; Devices providing patency to, or preventing collapsing of, tubular structures of the body, e.g. stents
- A61F2/02—Prostheses implantable into the body
- A61F2/28—Bones
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/14—Macromolecular materials
- A61L27/18—Macromolecular materials obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
- A61L27/56—Porous materials, e.g. foams or sponges
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
- A61L27/58—Materials at least partially resorbable by the body
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
- B29C64/10—Processes of additive manufacturing
- B29C64/106—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material
- B29C64/112—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material using individual droplets, e.g. from jetting heads
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
- B29C64/30—Auxiliary operations or equipment
- B29C64/386—Data acquisition or data processing for additive manufacturing
- B29C64/393—Data acquisition or data processing for additive manufacturing for controlling or regulating additive manufacturing processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y10/00—Processes of additive manufacturing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y80/00—Products made by additive manufacturing
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
- A61F2/00—Filters implantable into blood vessels; Prostheses, i.e. artificial substitutes or replacements for parts of the body; Appliances for connecting them with the body; Devices providing patency to, or preventing collapsing of, tubular structures of the body, e.g. stents
- A61F2/02—Prostheses implantable into the body
- A61F2/28—Bones
- A61F2002/2835—Bone graft implants for filling a bony defect or an endoprosthesis cavity, e.g. by synthetic material or biological material
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
- A61F2/00—Filters implantable into blood vessels; Prostheses, i.e. artificial substitutes or replacements for parts of the body; Appliances for connecting them with the body; Devices providing patency to, or preventing collapsing of, tubular structures of the body, e.g. stents
- A61F2/02—Prostheses implantable into the body
- A61F2/30—Joints
- A61F2002/30001—Additional features of subject-matter classified in A61F2/28, A61F2/30 and subgroups thereof
- A61F2002/30003—Material related properties of the prosthesis or of a coating on the prosthesis
- A61F2002/3006—Properties of materials and coating materials
- A61F2002/30062—(bio)absorbable, biodegradable, bioerodable, (bio)resorbable, resorptive
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
- A61F2/00—Filters implantable into blood vessels; Prostheses, i.e. artificial substitutes or replacements for parts of the body; Appliances for connecting them with the body; Devices providing patency to, or preventing collapsing of, tubular structures of the body, e.g. stents
- A61F2/02—Prostheses implantable into the body
- A61F2/30—Joints
- A61F2/30767—Special external or bone-contacting surface, e.g. coating for improving bone ingrowth
- A61F2002/3093—Special external or bone-contacting surface, e.g. coating for improving bone ingrowth for promoting ingrowth of bone tissue
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
- A61F2/00—Filters implantable into blood vessels; Prostheses, i.e. artificial substitutes or replacements for parts of the body; Appliances for connecting them with the body; Devices providing patency to, or preventing collapsing of, tubular structures of the body, e.g. stents
- A61F2/02—Prostheses implantable into the body
- A61F2/30—Joints
- A61F2/3094—Designing or manufacturing processes
- A61F2002/30985—Designing or manufacturing processes using three dimensional printing [3DP]
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- A61L2430/00—Materials or treatment for tissue regeneration
- A61L2430/02—Materials or treatment for tissue regeneration for reconstruction of bones; weight-bearing implants
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2230/00—Compositions for preparing biodegradable polymers
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Abstract
The invention discloses a polyester resin, a bone tissue engineering scaffold and a preparation method thereof, which are prepared by esterification and polycondensation of alpha-ketoglutaric acid and 1, 2-propanediol. The material of the invention is nontoxic and degradable, and the degradation product alpha-ketoglutarate can indirectly promote bone growth by participating in tricarboxylic acid circulation and synthesizing bone collagen. In addition, the bone tissue engineering scaffold prepared by adopting the material can be prepared by 3D printing through low-temperature solution deposition, has multistage pores, is safe and nontoxic, and can meet the requirements of tissue cell growth on pore diameters with different sizes.
Description
Technical Field
The invention relates to the field of degradable polyester and 3D printing, in particular to a polyester resin, a bone tissue engineering bracket and a preparation method thereof.
Background
At present, the clinical field of medicine mostly adopts polyester such as PLA or PBS to prepare porous support materials, and patent CN112274705A uses chitosan to modify polylactic acid, and after the support is printed by a 3D printer, the chitosan is removed by dilute hydrochloric acid. Patent CN108727571a invented a modified polyester 3D printing material based on PBS and 3D printing with FDM. At present, the technical problem to be solved is to develop a 3D printing resin which is degradable and the degradation product has the function of promoting bone growth.
Disclosure of Invention
A polyester with degradation products capable of promoting bone growth is prepared by polymerizing alpha-ketoglutarate and 1, 2-propylene glycol, can be dissolved in a 1, 4-dioxane solvent, is prepared into a solution, and then is subjected to low-temperature 3D printing, so that a bone tissue engineering scaffold with multistage pores can be prepared, and the degraded alpha-ketoglutarate can promote bone growth.
According to one aspect of the present application, there is provided a polyester resin having a structure represented by formula I:
a formula I;
wherein n represents a polymerization degree, and n is 50-1000; molecular weight of 1X 10 4 ~2×10 5 。
The intrinsic viscosity of the polyester resin is 0.2-0.8dL/g.
According to another aspect of the present application, there is provided a method for preparing the above polyester resin, comprising at least the steps of:
and mixing a raw material containing alpha-ketoglutaric acid and 1, 2-propylene glycol with a catalyst, and reacting to obtain the polyester resin.
The catalyst is selected from tetrabutyl titanate, tetraisopropyl titanate, zinc acetate, antimony trioxide and the like.
The molar ratio of the alpha-ketoglutaric acid to the 1, 2-propanediol is 1:1 to 5;
the molar ratio of the catalyst volume to the alpha-ketoglutaric acid is 30-50 microliter/1 mol;
the reaction is carried out in an inert gas atmosphere;
the inactive gas is selected from at least one of nitrogen, helium or argon;
the reaction process comprises the steps of heating to 150-170 ℃ at a heating rate of 5 ℃/min and keeping for 2-10 hours; then the temperature is raised to 170-200 ℃ at the temperature rising rate of 5 ℃/min and kept for 2-10 hours.
According to another aspect of the present application, there is provided a method for preparing a bone tissue engineering scaffold, comprising at least the steps of:
printing the resin solution into a bone tissue engineering scaffold by a low-temperature solution 3D printer;
the resin solution contains polyester resin and solvent;
the polyester resin is selected from the polyester resins or the polyester resins prepared by the preparation method.
The solvent is selected from 1, 4-dioxane;
the content of the polyester resin in the resin solution is 10-30% g/ml.
The bone tissue engineering scaffold is subjected to freeze drying.
The freeze-drying comprises freeze-drying by dry ice or liquid nitrogen;
the freeze drying comprises freeze drying in a freeze dryer for not less than 48 hours
According to another aspect of the present application, there is provided a bone tissue engineering scaffold characterized by being prepared by the above-described preparation method;
having multiple levels of pores;
the pore diameter is the diameter of a large pore with the diameter of 100-500 micrometers and the diameter of a small pore with the diameter of 0.1-10 micrometers; the specific surface area is 0.1-0.5 m 2 /g。
The beneficial effects of this application are: is a bone tissue engineering scaffold with multiple levels of pores, and the degraded alpha-ketoglutarate can promote bone growth.
Drawings
FIG. 1 is a FTIR spectrum of a polyester obtained in example 1;
fig. 2 is a photograph of a 3D-printed tissue engineering scaffold of the low temperature solution obtained in example 1.
The specific embodiment is as follows:
example 1
Alpha-ketoglutaric acid (100 mmol), 1, 2-propylene glycol (200 mmol) and tetrabutyl titanate (30 ul) are added into a three-neck flask, and esterification reaction is carried out for 4 hours under the protection of nitrogen gas and heated to 170 ℃ while stirring; the mixture was heated to 190℃and evacuated to carry out polymerization for 5 hours, to obtain polyester (. Alpha.KG-1, 2-pd).
10g of polyester was weighed and dissolved in 50ml of 1, 4-dioxane solvent to prepare a 20% g/ml solution. 5ml of the solution is placed in a printer nozzle at each time, the temperature of the printer nozzle is set to be 30 ℃, the temperature of a printing cavity is set to be minus 20 ℃, the distance between filling lines is 0.8mm, and the directions of the filling lines are 0 DEG and 90 DEG]Printing speed 10mm/s, extrusion speed 0.6mm 3 And/s, layer height of 0.1mm, printing forming size of 10x10x10mm. And immediately transferring the porous scaffold to a freeze dryer after printing, and performing vacuum-pumping freeze drying at-30 ℃ for 48 hours to obtain the polyester porous bone implantation scaffold.
FIG. 1 is a FTIR spectrum of a polyester obtained in example 1; as can be seen from the figure, 1750cm -1 Characteristic absorption peaks with ester bonds nearby;
fig. 2 is a photograph of a 3D-printed tissue engineering scaffold of the low temperature solution obtained in example 1, and the more obvious porous structure can be seen from the figure.
Example 2
Alpha-ketoglutaric acid (100 mmol), 1, 2-propylene glycol (200 mmol) and tetrabutyl titanate (30 ul) are added into a three-neck flask, and esterification reaction is carried out for 5 hours under the protection of nitrogen gas and heated to 160 ℃ while stirring; heating to 190 deg.c and vacuum pumping to polymerize for 6 hr to obtain polyester.
5g of polyester was weighed and dissolved in 50ml of 1, 4-dioxane solvent to prepare a 10% g/ml solution. Placing 5ml of the above solution into a printer nozzle at each time, setting the temperature of the printer nozzle at 30deg.C, the temperature of the printing chamber at-20deg.C, and filling the lines at a distance of 0.8mmCharging line direction [0 DEG, 90 DEG ]]Printing speed 10mm/s, extrusion speed 0.6mm 3 And/s, layer height of 0.1mm, printing forming size of 10x10x10mm. And immediately transferring the porous scaffold to a freeze dryer after printing, and performing vacuum-pumping freeze drying at-30 ℃ for 48 hours to obtain the polyester porous bone implantation scaffold.
Example 3
Alpha-ketoglutaric acid (100 mmol), 1, 2-propylene glycol (200 mmol) and tetrabutyl titanate (30 ul) are added into a three-neck flask, and esterification reaction is carried out for 5 hours under the protection of nitrogen gas and heated to 170 ℃ while stirring; heating to 200 ℃ and vacuumizing to carry out polymerization reaction for 3 hours to obtain the polyester.
5g of polyester was weighed and dissolved in 50ml of 1, 4-dioxane solvent to prepare a 10% g/ml solution. 5ml of the solution is placed in a printer nozzle at each time, the temperature of the printer nozzle is set to be 30 ℃, the temperature of a printing cavity is set to be minus 20 ℃, the distance between filling lines is 0.8mm, and the directions of the filling lines are 0 DEG and 90 DEG]Printing speed 10mm/s, extrusion speed 0.6mm 3 And/s, layer height of 0.1mm, printing forming size of 10x10x10mm. And immediately transferring the porous scaffold to a freeze dryer after printing, and performing vacuum-pumping freeze drying at-30 ℃ for 48 hours to obtain the polyester porous bone implantation scaffold.
Example 4
Alpha-ketoglutaric acid (100 mmol), 1, 2-propylene glycol (200 mmol) and tetrabutyl titanate (30 ul) are added into a three-neck flask, and esterification reaction is carried out for 4 hours under the protection of nitrogen gas and heated to 170 ℃ while stirring; heating to 190 deg.c and vacuum pumping to polymerize for 5 hr to obtain polyester.
10g of polyester was weighed and dissolved in 50ml of 1, 4-dioxane solvent to prepare a 20% g/ml solution. 5ml of the solution is placed in a printer nozzle at each time, the temperature of the printer nozzle is set to be 30 ℃, the temperature of a printing cavity is set to be minus 25 ℃, the distance between filling lines is 0.8mm, and the directions of the filling lines are 0 DEG and 90 DEG]Printing speed 12mm/s, extrusion speed 0.6mm 3 And/s, layer height of 0.15mm, printing forming size of 10x10x10mm. And immediately transferring the porous scaffold to a freeze dryer after printing, and performing vacuum-pumping freeze drying at-30 ℃ for 60 hours to obtain the polyester porous bone implantation scaffold.
The foregoing description is only a few examples of the present application and is not intended to limit the present application in any way, and although the present application is disclosed in the preferred examples, it is not intended to limit the present application, and any person skilled in the art may make some changes or modifications to the disclosed technology without departing from the scope of the technical solution of the present application, and the technical solution is equivalent to the equivalent embodiments.
Claims (9)
2. A process for producing the polyester resin according to claim 1, comprising at least the steps of:
and mixing a raw material containing alpha-ketoglutaric acid and 1, 2-propylene glycol with a catalyst, and reacting to obtain the polyester resin.
3. The preparation method according to claim 2, wherein the catalyst is selected from tetrabutyl titanate, tetraisopropyl titanate, zinc acetate, antimony trioxide and the like.
4. The method of claim 2, wherein the molar ratio of α -ketoglutaric acid to 1, 2-propanediol is 1:1 to 5;
the molar ratio of catalyst volume to alpha-ketoglutaric acid is 30-50 microliter/1 mol.
5. The preparation method according to claim 2, wherein the reaction is carried out in an inert gas atmosphere;
the inactive gas is selected from at least one of nitrogen, helium or argon;
the reaction process comprises the steps of heating to 150-170 ℃ at a heating rate of 5 ℃/min and keeping for 2-10 hours; then the temperature is raised to 170-200 ℃ at the temperature rising rate of 5 ℃/min and kept for 2-10 hours.
6. The preparation method of the bone tissue engineering scaffold is characterized by at least comprising the following steps:
printing the resin solution into a bone tissue engineering scaffold by a low-temperature solution 3D printer;
the resin solution contains polyester resin and solvent;
the polyester resin is selected from the polyester resin according to claim 1 or the polyester resin produced by the production method according to any one of claims 2 to 5.
7. The method of claim 6, wherein the solvent is selected from the group consisting of 1, 4-dioxane;
the content of the polyester resin in the resin solution is 10-30% g/ml.
8. The method according to claim 6, wherein the bone tissue engineering scaffold is freeze-dried.
9. A bone tissue engineering scaffold characterized by being prepared by the preparation method of any one of claims 6 to 8;
having multiple levels of pores;
the pore diameter is the diameter of a large pore with the diameter of 100-500 micrometers and the diameter of a small pore with the diameter of 0.1-10 micrometers; the specific surface area is 0.1-0.5 m 2 /g。
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