CN112274705A - 3D printing porous support material and preparation method thereof - Google Patents
3D printing porous support material and preparation method thereof Download PDFInfo
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- 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
- A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
- A61L31/14—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
- A61L31/146—Porous materials, e.g. foams or sponges
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- 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
- A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
- A61L31/04—Macromolecular materials
- A61L31/041—Mixtures of macromolecular compounds
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- 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
- A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
- A61L31/14—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
- A61L31/141—Plasticizers
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- 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
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- 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
- B33Y70/00—Materials specially adapted for additive manufacturing
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- 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
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/26—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a solid phase from a macromolecular composition or article, e.g. leaching out
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2201/00—Foams characterised by the foaming process
- C08J2201/04—Foams characterised by the foaming process characterised by the elimination of a liquid or solid component, e.g. precipitation, leaching out, evaporation
- C08J2201/044—Elimination of an inorganic solid phase
- C08J2201/0444—Salts
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2305/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2301/00 or C08J2303/00
- C08J2305/08—Chitin; Chondroitin sulfate; Hyaluronic acid; Derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2339/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Derivatives of such polymers
- C08J2339/04—Homopolymers or copolymers of monomers containing heterocyclic rings having nitrogen as ring member
- C08J2339/06—Homopolymers or copolymers of N-vinyl-pyrrolidones
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2405/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2401/00 or C08J2403/00
- C08J2405/08—Chitin; Chondroitin sulfate; Hyaluronic acid; Derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2439/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Derivatives of such polymers
- C08J2439/04—Homopolymers or copolymers of monomers containing heterocyclic rings having nitrogen as ring member
- C08J2439/06—Homopolymers or copolymers of N-vinyl-pyrrolidones
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2467/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
Abstract
The invention belongs to the technical field of polymer biomedical materials, and particularly relates to a preparation method of a 3D printing porous scaffold material, which comprises the following steps: dissolving chitosan in lactic acid solution, adding ethanol, and preparing into an alcohol-water mixed solution of lactic acid chitosan; carrying out vacuum drying on the alcohol-water mixed solution of the lactic acid chitosan to prepare the lactic acid chitosan; mixing polylactic acid, polyvinylpyrrolidone, plasticizer, lubricant and calcium carbonate according to a certain mass part, melting the mixture with lactic acid chitosan, stirring, uniformly mixing, drawing by an extruder, and drawing into polymer filament material with the diameter of 1.75 mm; printing the polymer silk material into a bracket by a 3D printer; dissolving chitosan in dilute hydrochloric acid or lactic acid to prepare a dilute solution, placing the stent in the dilute solution for reaction, washing, placing the stent in sodium bicarbonate water for soaking, washing and vacuum drying to prepare a porous stent material; simple manufacturing process, high yield and easy industrialization.
Description
Technical Field
The invention belongs to the technical field of polymer biomedical materials, and particularly relates to a 3D printing porous scaffold material and a preparation method thereof.
Background
Three-dimensional rapid prototyping printing is abbreviated as 3D printing and is also referred to as additive manufacturing. Is a method which is completely opposite to the traditional material processing method and is manufactured by adding materials layer by layer based on three-dimensional CAD model data. Fused deposition printing (FDM) is a method in which a hot-melt nozzle is used to melt a plastic fiber material, extrude the molten plastic fiber material from the nozzle, and then solidify and mold the molten plastic fiber material after the molten plastic fiber material is deposited at a designated position. The process has the advantages of low price, small volume and relatively small difficulty in production and operation.
Polylactic acid (PLA) is mainly derived from renewable resources and is an environment-friendly plastic. PLA is an amorphous material with low strength and poor dimensional stability, which makes it very deformable, which makes 3D printing difficult. And the polylactic acid has poor toughness and is easy to brittle fracture. There are many methods for modifying modified polylactic acid materials.
Chitosan is obtained by performing N-deacetylation treatment on chitin, is the only natural alkaline polysaccharide discovered so far, has good biocompatibility, biodegradability, safe and nontoxic degradation products, wide antibacterial, hemostatic and analgesic effects and unique biological activity for selectively promoting epidermal cell growth. However, chitosan is difficult to process due to strong hydrogen bonding between molecules, and thus improving its processing performance by breaking hydrogen bonding is also one of the hot spots of research.
Polyvinylpyrrolidone (PVP), a non-ionic polymer, has the general properties of water-soluble polymers, such as colloid protection, film-forming property, cohesiveness, hygroscopicity, solubilization or coacervation, and is the most excellent in solubility and physiological compatibility. PVP has excellent physiological inertia, does not participate in human metabolism, has excellent biocompatibility and does not cause any stimulation to skin, mucous membrane, eyes and the like. Therefore, it is pharmaceutically acceptable and can be used in contact with human body.
However, in the prior art, the pore-forming of the scaffold material is difficult, so that the invention overcomes the defects of the prior art in practical application by compounding the polylactic acid and the chitosan into the porous scaffold material. The scaffold material can be widely used in the fields of biomedicine, tissue engineering, biological patches and the like.
Disclosure of Invention
Based on the above disadvantages and shortcomings of the prior art, it is an object of the present invention to at least solve one or more of the above problems of the prior art, in other words, to provide a method for preparing a 3D printed porous scaffold material that meets one or more of the above requirements.
The invention also aims to provide a porous support material for 3D printing.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a 3D printing porous scaffold material comprises the following steps:
(1) dissolving chitosan in lactic acid solution, adding ethanol, and preparing into an alcohol-water mixed solution of lactic acid chitosan;
(2) carrying out vacuum drying on the alcohol-water mixed solution of the lactic acid chitosan to prepare the lactic acid chitosan;
(3) mixing polylactic acid, polyvinylpyrrolidone, plasticizer, lubricant and calcium carbonate according to a certain mass part, melting the mixture with lactic acid chitosan, stirring, uniformly mixing, drawing by an extruder, and drawing into polymer filament material with the diameter of 1.75 mm;
(4) printing the polymer silk material into a bracket by a 3D printer;
(5) dissolving chitosan in dilute hydrochloric acid or lactic acid to prepare a dilute solution, placing the stent in the dilute solution for reaction, washing, soaking in sodium bicarbonate water, washing and vacuum drying to prepare the porous stent material.
Preferably, the polylactic acid is 20-60 parts, the polyvinylpyrrolidone is 25-60 parts, the plasticizer is 0-4 parts, the lubricant is 0.2-4 parts, the calcium carbonate is 30-60 parts, the lactic acid is 0.5-2 parts, and the chitosan is 40-80 parts.
Preferably, the melting temperature is 150-225 ℃.
Preferably, the molecular weight of the chitosan is 40-70 ten thousand daltons, and the deacetylation degree is more than 85%.
Preferably, the vacuum drying temperature is 40-50 ℃.
Preferably, the plasticizer is one or more of dibutyl sebacate, tributyl citrate, epoxidized soybean oil or polyethylene glycol 400.
Preferably, the lubricant is one or more of stearic acid, calcium stearate, zinc stearate or glyceryl stearate.
Preferably, the calcium carbonate is colloidal calcium carbonate, and the particle size is 5-10 μm.
Preferably, the concentration of the dilute hydrochloric acid or the lactic acid is 0.1-1 mol/L, and the concentration of the sodium bicarbonate water is 0.1-1 mol/L.
The invention also provides a 3D printing porous scaffold material prepared by the preparation method of any one of the schemes.
Compared with the prior art, the invention has the beneficial effects that:
the invention introduces plasticizer to improve the toughness of polylactic acid, acidifies chitosan to destroy hydrogen bonds of the polylactic acid, improves the processability of chitosan, enables the chitosan to be melt-processable, uses calcium carbonate as a pore-forming agent, mixes the calcium carbonate and polyvinylpyrrolidone into a stent, and enables the calcium carbonate to fully react with acid (hydrochloric acid or lactic acid) due to the swelling of PVP in an acidic aqueous solution, thereby forming pores and forming the porous stent material.
The polylactic acid and the lactic acid chitosan are blended to enhance the mechanical strength of the polylactic acid, and the chitosan enhances the processing performance of the polylactic acid through lactic acid conversion, so that the polylactic acid can be melt and processed.
The invention can be manufactured in a personalized way, has simple manufacturing process and high yield, and is easy to industrialize.
Drawings
FIG. 1 is a microscopic scanning electron microscope image of a cross section of a stent prepared by the present invention.
Detailed Description
In order to more clearly illustrate the embodiments of the present invention, the following will describe specific embodiments of the present invention. It is obvious that the following description is only some examples of the invention, from which other embodiments can be derived without inventive effort for a person skilled in the art.
The first embodiment is as follows:
the embodiment provides a preparation method of a 3D printing porous scaffold material, which comprises the following steps:
(1) 5g of chitosan, 4mL of lactic acid and 50mL of distilled water are mixed, mechanically stirred and dissolved, after dissolution, 50mL of 95% ethanol is added, stirring and mixing are continued, and an alcohol-water mixed solution of lactic acid chitosan is prepared, wherein the molecular weight of the chitosan is 40 ten thousand daltons, and the degree of deacetylation is 90%.
(2) Vacuum drying at 40 deg.C, removing water and ethanol, and preparing into dried lactic acid chitosan.
(3) 30 parts of polylactic acid, 40 parts of polyvinylpyrrolidone (K30), 1 part of epoxidized soybean oil, 0.1 part of stearic acid, 50 parts of colloidal calcium carbonate (with the particle size of 10 mu m) and 40 parts of lactylated chitosan are melted and blended in an extruder at 175 ℃ and are drawn into polymer wires with the diameter of 1.75 mm.
(4) Modeling by computer modeling software (three-dimensional modeling software such as 3DMAX, UG, CAD, Solidworks, Zbrush, Maya, Blend and the like), slicing by the slicing software, and printing the liver stent material with a three-dimensional structure.
(5) Weighing 0.5g of chitosan, dissolving in 0.5mol/L dilute hydrochloric acid to prepare 1L of dilute solution, placing the printed stent in the prepared dilute solution, controlling the temperature below 20 ℃ all the time through ice-water bath, taking out the stent after reacting for 1 hour, soaking in 0.5mol/L sodium bicarbonate water for 0.5 hour, washing in distilled water for three times, standing and washing for 4 hours each time, taking out the stent, and drying in vacuum at 40 ℃ to prepare the polylactic acid/chitosan composite stent material with a porous structure.
Example two:
the embodiment provides a preparation method of a 3D printing porous scaffold material, which comprises the following steps:
(1) mixing 3g of chitosan, 4mL of lactic acid and 40mL of distilled water, mechanically stirring for dissolving, adding 60mL of absolute ethyl alcohol after dissolving, continuously stirring and uniformly mixing to prepare an alcohol-water mixed solution of lactic acid chitosan, wherein the molecular weight of the chitosan is 70 ten thousand daltons, and the degree of deacetylation is 95%.
(2) Vacuum drying at 45 deg.C, removing water and ethanol, and preparing into dried lactic acid chitosan.
(3) 50 parts of polylactic acid, 25 parts of polyvinylpyrrolidone (K60), 0.1 part of calcium stearate, 40 parts of colloidal calcium carbonate (with the particle size of 10 mu m) and 45 parts of lactic acid chitosan are melted and blended in an extruder at 190 ℃ and are drawn into polymer wires with the diameter of 1.75 mm.
(4) Modeling by computer modeling software (3DMAX, UG, CAD, Solidworks, Zbrush, Maya, Blend and other three-dimensional modeling software), slicing by the slicing software, and printing out the heart stent material with a three-dimensional structure.
(5) Weighing 0.2g of chitosan, dissolving in 0.8mol/L dilute hydrochloric acid to prepare 0.8L dilute solution, placing the printed stent in the prepared dilute solution, controlling the temperature below 20 ℃ all the time through ice-water bath, taking out the stent after reacting for 0.5 hour, soaking in 0.6mol/L baking soda water for 1 hour, then washing in distilled water for three times, standing and washing for 5 hours each time, then taking out the stent, and drying in vacuum at 40 ℃ to prepare the polylactic acid/chitosan composite stent material with a porous structure.
Example three:
the embodiment provides a preparation method of a 3D printing porous scaffold material, which comprises the following steps:
(1) mixing 2g of chitosan, 3mL of lactic acid and 30mL of distilled water, mechanically stirring for dissolving, adding 50mL of absolute ethyl alcohol after dissolving, continuously stirring and uniformly mixing to prepare an alcohol-water mixed solution of lactic acid chitosan, wherein the molecular weight of the chitosan is 60 ten thousand daltons, and the degree of deacetylation is 88%.
(2) Vacuum drying at 50 deg.C, removing water and ethanol, and preparing into dried lactic acid chitosan.
(3) 70 parts of polylactic acid, 30 parts of polyvinylpyrrolidone (K90), 1 part of polyethylene glycol (400), 0.1 part of glyceryl stearate, 60 parts of colloidal calcium carbonate (with the particle size of 5 mu m) and 55 parts of lactic acid chitosan are melted and blended in an extruder at 180 ℃ and are drawn into polymer filament materials with the diameter of 1.75 mm.
(4) Modeling by computer modeling software (3DMAX, UG, CAD, Solidworks, Zbrush, Maya, Blend and other three-dimensional modeling software), slicing by the slicing software, and printing out the heart stent material with a three-dimensional structure.
(5) Weighing 0.1g of chitosan, dissolving in 1mol/L of lactic acid to prepare 1L of dilute solution, placing the printed stent in the prepared dilute solution, controlling the temperature below 20 ℃ all the time through ice-water bath, taking out the stent after reacting for 1.5 hours, soaking in 1mol/L of baking soda water for 1.5 hours, washing in distilled water for three times, standing and washing for 6 hours each time, taking out the stent, and drying in vacuum at 45 ℃ to prepare the polylactic acid/chitosan composite stent material with a porous structure.
Referring to fig. 1, the 3D printing porous scaffold material prepared by the method of the present invention has higher mechanical strength, polylactic acid is blended with lactylated chitosan, the chitosan increases its processability through lactylation, so that it can be melt-processed, the chitosan is blended with a plasticizer, a lubricant and a water-soluble polymer, and then is extruded and drawn, a scaffold is three-dimensionally printed, pores are formed through the reaction of calcium carbonate and dilute hydrochloric acid or lactic acid (the water-soluble polymer PVP can avoid the difficulty that calcium carbonate cannot contact dilute acid to react), the calcium carbonate is neutralized by baking soda after washing to remove acid, and the three-dimensional scaffold material with a porous structure is finally prepared after washing and drying. The invention has the advantages of personalized manufacture, biological safety and the like, and the manufacturing process is simple, the yield is high, and the industrialization is easy. Can be widely used in the fields of biomedicine, tissue engineering, biological patches and the like.
In the embodiment and the alternative scheme thereof, the polylactic acid can be randomly selected from 20-60 parts; the polyvinylpyrrolidone can be randomly selected from 25-60 parts; the plasticizer can be selected from 0-4 parts at will; the lubricant can be selected randomly from 0.2-4 parts; the calcium carbonate can be randomly selected from 30-60 parts; the lactic acid can be randomly selected from 0.5-2 parts; the chitosan can be randomly selected from 40-80 parts.
In the embodiment and the alternative scheme thereof, the melting temperature can be arbitrarily selected between 150 ℃ and 225 ℃; the vacuum drying temperature can be arbitrarily selected between 40 ℃ and 50 ℃.
In the above embodiments and alternatives, the plasticizer may be selected from dibutyl sebacate, tributyl citrate, epoxidized soybean oil, or polyethylene glycol 400.
In the above embodiments and alternatives thereof, the lubricant may be selected from stearic acid, calcium stearate, zinc stearate, or glyceryl stearate.
In the embodiment and the alternative scheme thereof, the concentration of the hydrochloric acid or the lactic acid can be randomly selected from 0.1-1 mol/L; the concentration of the small soda water can be arbitrarily selected from 0.1-1 mol/L.
The foregoing has outlined rather broadly the preferred embodiments and principles of the present invention and it will be appreciated that those skilled in the art may devise variations of the present invention that are within the spirit and scope of the appended claims.
Claims (10)
1. A preparation method of a porous scaffold material for 3D printing is characterized by comprising the following steps:
(1) dissolving chitosan in lactic acid solution, adding ethanol, and preparing into an alcohol-water mixed solution of lactic acid chitosan;
(2) carrying out vacuum drying on the alcohol-water mixed solution of the lactic acid chitosan to prepare the lactic acid chitosan;
(3) mixing polylactic acid, polyvinylpyrrolidone, plasticizer, lubricant and calcium carbonate according to a certain mass part, melting the mixture with lactic acid chitosan, stirring, uniformly mixing, drawing by an extruder, and drawing into polymer filament material with the diameter of 1.75 mm;
(4) printing the polymer silk material into a bracket by a 3D printer;
(5) dissolving chitosan in dilute hydrochloric acid or lactic acid to prepare a dilute solution, placing the stent in the dilute solution for reaction, washing, soaking in sodium bicarbonate water, washing and vacuum drying to prepare the porous stent material.
2. The preparation method of the porous scaffold material for 3D printing according to claim 1, wherein the polylactic acid is 20-60 parts, the polyvinylpyrrolidone is 25-60 parts, the plasticizer is 0-4 parts, the lubricant is 0.2-4 parts, the calcium carbonate is 30-60 parts, the lactic acid is 0.5-2 parts, and the chitosan is 40-80 parts.
3. The preparation method of the porous scaffold material for 3D printing according to claim 1, wherein the melting temperature is 150-225 ℃.
4. The preparation method of the porous scaffold material for 3D printing according to claim 1, wherein the chitosan molecular weight is 40-70 ten thousand daltons, and the degree of deacetylation is more than 85%.
5. The preparation method of the porous scaffold material for 3D printing according to claim 1, wherein the vacuum drying temperature is 40-50 ℃.
6. The preparation method of the porous scaffold material for 3D printing according to claim 1, wherein the plasticizer is one or more of dibutyl sebacate, tributyl citrate, epoxidized soybean oil or polyethylene glycol 400.
7. The preparation method of the porous scaffold material for 3D printing according to claim 1, wherein the lubricant is one or more of stearic acid, calcium stearate, zinc stearate or glyceryl stearate.
8. The preparation method of the porous scaffold material for 3D printing according to claim 1, wherein the calcium carbonate is colloidal calcium carbonate with a particle size of 5-10 μm.
9. The preparation method of the 3D printing porous scaffold material according to claim 1, wherein the concentration of the dilute hydrochloric acid or lactic acid is 0.1-1 mol/L, and the concentration of the small soda water is 0.1-1 mol/L.
10. A 3D printed porous scaffold material prepared by the method of any one of claims 1 to 9.
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