CN105771003B - A method of biodegradable polymer self-expanding type blood vessel dilator is prepared based on 3D printing technique - Google Patents
A method of biodegradable polymer self-expanding type blood vessel dilator is prepared based on 3D printing technique Download PDFInfo
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- CN105771003B CN105771003B CN201610232704.0A CN201610232704A CN105771003B CN 105771003 B CN105771003 B CN 105771003B CN 201610232704 A CN201610232704 A CN 201610232704A CN 105771003 B CN105771003 B CN 105771003B
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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
- A61L31/12—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material
- A61L31/125—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material having a macromolecular matrix
- A61L31/128—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material having a macromolecular matrix containing other specific inorganic fillers not covered by A61L31/126 or A61L31/127
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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
- A61L31/16—Biologically active materials, e.g. therapeutic substances
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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
- A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
- A61L2300/20—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices containing or releasing organic materials
-
- 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
- A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
- A61L2300/20—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices containing or releasing organic materials
- A61L2300/23—Carbohydrates
- A61L2300/236—Glycosaminoglycans, e.g. heparin, hyaluronic acid, chondroitin
-
- 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
- A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
- A61L2300/20—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices containing or releasing organic materials
- A61L2300/252—Polypeptides, proteins, e.g. glycoproteins, lipoproteins, cytokines
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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
- A61L2400/00—Materials characterised by their function or physical properties
- A61L2400/16—Materials with shape-memory or superelastic properties
-
- 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
- A61L2430/00—Materials or treatment for tissue regeneration
- A61L2430/22—Materials or treatment for tissue regeneration for reconstruction of hollow organs, e.g. bladder, esophagus, urether, uterus
Abstract
The present invention relates to a kind of methods for preparing biodegradable polymer self-expanding type blood vessel dilator based on 3D printing technique.Specific steps are as follows: synthesis has good biocompatibility, biodegradability polylactic acid base shape memory polyurethane/Fe3O4Composite material is prepared into intravascular stent by Fused Deposition Modeling technology by nanocomposite.In addition speed is repaired to improve blood vessel endothelium, sirolimus, heparin or endothelial growth factors etc. is selectively introduced in rack surface by electrostatic spinning.The shape memory function of substrate of the present invention increases " time " dimension, forms in conjunction with 3D printing, assigns bracket 4D and forms concept；Utilize Fe3O4Magnetothermal effect recovery of shape can occur with remote excitation shape-memory polymer, so that intravascular stent is voluntarily expanded, when stenter to implant, balloon expandable is not needed, the axial shortening of bracket when avoiding balloon expandable, radial rebound when withdrawing from, minimize the damage of blood vessel, and Fe3O4Introducing also solve the problem of polymer support developability difference.
Description
Technical field
The invention belongs to high molecular materials and biomedical devices field, and in particular to one kind is prepared based on 3D printing technique
The method of biodegradable polymer self-expanding type blood vessel dilator.
Background technique
Cardiovascular disease is most one of prevalent disease that can lead to death that the whole world faces, wherein obliterative vascular disease
It is arch-criminal.It is at present percutaneous coronary implantable intravascular stent in the treatment to the most effective treatment method of Most patients, passes
The metallic support of system easily causes to form thrombus in bracket as a kind of foreign matter, and it is narrow again that subsequent endometrial hyperplasia will also result in blood vessel
It is narrow, lead to adverse cardiac events, mortality reaches 40% or more, especially to the cardiovascular patient of paediatrics, needs
Subsequent procedures remove bracket, can bring the secondary injury to patient.Degradable absorption intravascular stent perplexs without advanced thrombus, avoids
Inflammatory reaction, therefore, the degradable development for absorbing intravascular stent and application are considered as the revolution of interventional therapy.Earliest
The material for being used for degradable blood vessel bracket is magnesium alloy, but magnesium alloy bracket degradation rate is too fast, and it is large-scale to limit it
Clinical application.And biodegradable polymer (such as: polylactic acid-based homopolymer and copolymer) degradation speed is adjustable, cell phase
Capacitive is good, good mechanical property, and thrombus, foreign body reaction and neointimal hyperplasia phenomenon are formed after implantable intravascular can be inhibited,
Endothelialization is more complete, and therefore, the research and application of biodegradable polymer coronary stent are very active.But at present
Degradable absorbing polymeric intravascular stent implantation process is more complicated, it is still desirable to balloon-system auxiliary expansion, when balloon expandable
Axial shortening can occur for bracket, generate the Relative sliding between bracket and blood vessel, lead to the damage of blood vessel, sacculus is removed
After out, bracket can generate radial rebound, make bracket and blood vessel poor contact, there are Detecting Residual Stenosis.In addition, polymer does not have
Developability need to add metal flag using the dipping in iodine solution or at both ends to increase developability.Therefore, developing has self expandable
And the degradable polymer blood vessel stent with developability certainly will will bring changing again for intravascular stent.
Currently, the forming method of degradable polymer blood vessel stent mainly has the side such as solution casting, braiding, laser engraving
Method, the forming method that 3D printing combination electrostatic spinning, surface spray also have been reported that.The shape of bracket is relatively more fixed, is largely
Tubulose and screw type, shape is limited, is difficult to realize personalized designs.3D printing forming technique is according to CAD
(CAD) data such as model or computed tomography (CT), by the accurate 3D accumulation of material and curing molding, quickly manufacture is appointed
The novel digital forming technique of meaning complicated shape 3D object, with precision height, speed is fast, material and manufacturing cost are low, can spirit
It is living to realize the features such as personalized.By development in more than 30 years, the especially in recent years development of processing technology advanced by leaps and bounds, 3D printing
Technology has penetrated into all trades and professions, such as prepares model with 3D printing method, using 3D printing hydrogel, liposome, cell and
Basis material prepares tissue, and the degradable polymers such as polylactic acid and polycaprolactone material can prepare bone by 3D printing
Tissue engineering bracket.The 3D printing technique of comparative maturity mainly includes photocuring stereosopic printing (SLA), fused glass pellet at present
(FDM), selective laser sintering (SLS) and three-dimensional spray printing (3DP) etc., wherein being relatively more suitable for thermoplasticity biological medical polymer
The 3D printing technique of material is FDM.Thermoplastic polymer with shape memory function can select FDM mode 3D printing skill
Art prepares the structure of designed original shape, then further according to needing the transition temperature in material deformed above, cooling rapidly
Fixed temporary shapes simultaneously save, it can be made to be returned to original shape by heating or other mode of excitation when needed,
One, structure " time " dimension is imparted on the basis of 3D printing, here it is the research hotspots just started at present -- " 4D is beaten
Print " is named " 4D molding ".
Summary of the invention
The purpose of the present invention is to provide one kind to prepare biodegradable polymer self-expanding blood based on 3D printing technique
The method of pipe holder.Prepared intravascular stent not only possesses good biocompatibility, biodegradability, and passes through
Externally-applied magnetic field is remotely controlled can be achieved self-expanding near body temperature, avoid the use of sacculus, will be right during stent-expansion
The near minimum level of the damage of vascular wall.
A method of biodegradable polymer self-expanding type blood vessel dilator being prepared based on 3D printing technique, comprising following
Step:
(1) synthesis of Biodegradable polylactic acids base shape memory polyurethane
With molar ratio 5:5 to 9:1'sD,LLactide (D,L- LA) withe-Caprolactone (e-It CL is) raw material, through ring-opening polymerisation
Prepare random copolymer PCLA, PCLA again with hexamethylene diisocyanate (HDI) and the poly- tetrahydro of flexible oligomer
Furans (PTMEG) chain extension is prepared into Biodegradable polylactic acids base shape memory polyurethane (PCLAUs), wherein HDI and PCLA
Molar ratio is 1.05:1 to 1.2:1, and the dosage of PTMEG is the 5% to 10% of system gross mass；
(2) Biodegradable polylactic acids base shape memory polyurethane/Fe3O4The synthesis of nanocomposite
By the method for solution blending by the PCLAUs that step (1) obtains and the magnetic Fe that surface modification is crossed3O4Nanoparticle
It carries out compound, is prepared into PCLAUs/Fe3O4Nanocomposite；It is studied with differential scanning calorimetry (DSC)D,LLactide (D, L- LA) withe-Caprolactone (e-CL) the hot property of random copolymer passes through adjustingD,LLactide (D,L- LA) withe-Caprolactone
(e-CL) the ratio of component regulates and controls the T of random copolymerg, it is made to be slightly above body temperature；
(3) Biodegradable polylactic acids base shape memory polyurethane/Fe3O4The extrusion molding of nanocomposite
The Biodegradable polylactic acids base shape memory polyurethane for being obtained step (2) using desktop type extruder/
Fe3O4 nanocomposite is extruded into the filiform of 1.75mm or 3.00mm；Extrusion temperature is arranged at 140 DEG C ~ 160 DEG C；
(4) 3D printing of intravascular stent
Using FDM type 3D printer, the step of establishing (3) is obtained into pipe holder model and is printed as intravascular stent；Blood vessel branch
It is 27.000 ~ 37.085mm that frame moulded dimension, which is set as length, and outer diameter is 2.000 ~ 3.566mm, and monofilament is with a thickness of 0.100 ~ 0.3
00mm；
(5) preparation of medication coat
The PCLAUs that step (1) is obtained, using DMF as solvent, using electrostatic spinning technique, in the blood that step (4) obtains
Pipe holder surface is selectively introducing drug or growth factor, and the drug is sirolimus or heparin, and growth factor is raw for endothelium
The long factor；
(6) deformation and storage of intravascular stent
It is radially compressed at required shape after the intravascular stent with medication coat that step (5) obtains is heated to 80 DEG C
Shape, is quickly cooled to 24 DEG C, and lower than 24 °C at a temperature of store.
(7) reply of intravascular stent
After intravascular stent implantable intravascular under the assistance of seal wire that step (6) obtains, under the action of externally-applied magnetic field, magnetic
Thermal excitation is voluntarily expanded, and is bonded in blood vessel, support blood vessels.
In the present invention, print temperature described in step (4) is set as 140 ~ 155 DEG C, and printer head extrusion speed is 20 ~
45mm/min。
In the present invention, voluntarily expansion pattern is externally-applied magnetic field excitation described in step (7), and expansion temperature is body
Temperature.
Intravascular stent prepared by the present invention have the advantage that the shape memory function of (1) substrate increase one " when
Between " dimension, it is formed in conjunction with 3D printing, assigns bracket 4D and form concept；(2) Fe is utilized3O4Magnetothermal effect can be with remote excitation shape
Recovery of shape occurs for shape memory polymer, expands intravascular stent voluntarily, when stenter to implant, does not need balloon expandable, avoids
The axial shortening of bracket when balloon expandable, radial rebound when withdrawing from, minimize the damage of blood vessel, and Fe3O4's
Introducing also solves the problem of polymer support developability difference;(3) application of 3D printing technique can quickly and accurately prepare individual character
Change 4D intravascular stent;(4) surface electrostatic spinning layer, which can according to need, introduces different drug or growth factor, improves blood vessel
Long-term patency.
Detailed description of the invention
Fig. 1 is the intravascular stent planar structure that embodiment 1SolidWorks is established.Its planar structure is by " u "-shaped unit group
At, it can be achieved that radial contraction, and axially retain constant.Wherein length be 27.000 ~ 37.085mm, outer diameter be 2.000 ~
3.566mm。
Fig. 2 is that the intravascular stent plan view that embodiment 1SolidWorks is established stretches entity.Planar structure is stretched
0.3mm is obtained, i.e. the thickness of realization intravascular stent is set as 0.3mm.
Fig. 3 is the intravascular stent model that embodiment 1SolidWorks is established.Planar stretch entity is crimped and is stood
Body structure, in this stereochemical structure, hollow out degree can reach 70% or more.
The temporary shapes of 1 intravascular stent radial compression of the position Fig. 4 embodiment.Intravascular stent is radially contracted, and keeps interim
Shape invariance facilitates storage.
Fig. 5 is self expandable under 1 intravascular stent magnetic thermal excitation of embodiment to permanent shape.Under the action of externally-applied magnetic field, magnetic
Thermal excitation is voluntarily expanded, and is bonded in blood vessel, support blood vessels.
Specific embodiment
The following examples are further illustrations of the invention, it is not intended to limit the scope of the invention.
Embodiment 1.
(1) synthesis of Biodegradable polylactic acids base shape memory polyurethane
With molar ratio 7:3'sD,LLactide (D,L- LA) withe-Caprolactone (e-It CL is) raw material, through ring-opening polymerisation
Prepare random copolymer PCLA, PCLA again with hexamethylene diisocyanate (HDI) and the poly- tetrahydro of flexible oligomer
Furans (PTMEG) chain extension is prepared into Biodegradable polylactic acids base shape memory polyurethane (PCLAUs), wherein HDI and PCLA
Molar ratio is 1.2:1, and the dosage of PTMEG is the 10% of system gross mass；
(2) Biodegradable polylactic acids base shape memory polyurethane (PCLAUs)/Fe3O4The synthesis of nanocomposite
By the method for solution blending by the PCLAUs that step (1) obtains and the magnetic Fe that surface modification is crossed3O4Nanoparticle
It carries out compound, is prepared into PCLAUs/Fe3O4Nanocomposite；Wherein, magnetic Fe3O4Nanoparticle oleic acid (Oleic
Acid it) is surface-treated.In compound system, magnetic Fe3O4Nanoparticle mass fraction is 3%.
(3) Biodegradable polylactic acids base shape memory polyurethane/Fe3O4The extrusion molding of nanocomposite
The Biodegradable polylactic acids base shape memory polyurethane for being obtained step (2) using desktop type extruder/
Fe3O4 nanocomposite is extruded into the filiform of 1.75mm or 3.00mm；Extrusion temperature is arranged at 140 DEG C ~ 160 DEG C；
(4) 3D printing of intravascular stent
Using FDM type 3D printer, the step of establishing (3) is obtained into pipe holder model and is printed as intravascular stent；Blood vessel branch
It is 27.000 ~ 37.085mm that frame moulded dimension, which is set as length, and outer diameter is 2.000 ~ 3.566mm, and monofilament is with a thickness of 0.100 ~ 0.3
00mm；
(5) preparation of medication coat
The PCLAUs that step (1) is obtained, using DMF as solvent, using electrostatic spinning technique, in the blood that step (4) obtains
Pipe holder surface is selectively introducing drug or growth factor, and the drug is sirolimus or heparin, and growth factor is raw for endothelium
The long factor；
(6) deformation and storage of intravascular stent
It is radially compressed at required shape after the intravascular stent with medication coat that step (5) obtains is heated to 80 DEG C
Shape, is quickly cooled to 24 DEG C, and lower than 24 °C at a temperature of store.
(7) reply of intravascular stent
After intravascular stent implantable intravascular under the assistance of seal wire that step (6) obtains, under the action of externally-applied magnetic field, magnetic
Thermal excitation is voluntarily expanded, and is bonded in blood vessel, support blood vessels.
Embodiment 2.
(1) synthesis of Biodegradable polylactic acids base shape memory polyurethane
With molar ratio 8:2'sD,LLactide (D,L- LA) withe-Caprolactone (e-It CL is) raw material, through ring-opening polymerisation
Prepare random copolymer PCLA, PCLA again with hexamethylene diisocyanate (HDI) and the poly- tetrahydro of flexible oligomer
Furans (PTMEG) chain extension is prepared into Biodegradable polylactic acids base shape memory polyurethane (PCLAUs), wherein HDI and PCLA
Molar ratio is 1.04:1, and the dosage of PTMEG is the 10% of system gross mass；
(2) Biodegradable polylactic acids base shape memory polyurethane (PCLAUs)/Fe3O4The synthesis of nanocomposite
By the method for solution blending by the PCLAUs that step (1) obtains and the magnetic Fe that surface modification is crossed3O4Nanoparticle
It carries out compound, is prepared into PCLAUs/Fe3O4Nanocomposite；Wherein, magnetic Fe3O4Nanoparticle oleic acid (Oleic
Acid it) is surface-treated.In compound system, magnetic Fe3O4Nanoparticle mass fraction is 6%.
(3) Biodegradable polylactic acids base shape memory polyurethane/Fe3O4The extrusion molding of nanocomposite
The Biodegradable polylactic acids base shape memory polyurethane (PCLAUs) prepared in step (2) /Fe3O4 nanometer is answered
Condensation material shreds into 0.5*0.5*0.2(unit: cm) it is granular.The mould head of 1.75mm is mounted on desktop type extruder,
Extrusion temperature is set as 150 DEG C, and booting preheats 10min, starts to squeeze out, and removes the non-uniform part of material head.By composite materials
It is extruded into the filiform of 1.75mm.
(3) Biodegradable polylactic acids base shape memory polyurethane/Fe3O4The extrusion molding of nanocomposite
The Biodegradable polylactic acids base shape memory polyurethane for being obtained step (2) using desktop type extruder/
Fe3O4 nanocomposite is extruded into the filiform of 1.75mm or 3.00mm；Extrusion temperature is arranged at 140 DEG C ~ 160 DEG C；
(4) 3D printing of intravascular stent
Using FDM type 3D printer, the step of establishing (3) is obtained into pipe holder model and is printed as intravascular stent；Blood vessel branch
It is 27.000 ~ 37.085mm that frame moulded dimension, which is set as length, and outer diameter is 2.000 ~ 3.566mm, and monofilament is with a thickness of 0.100 ~ 0.3
00mm；
(5) preparation of medication coat
The PCLAUs that step (1) is obtained, using DMF as solvent, using electrostatic spinning technique, in the blood that step (4) obtains
Pipe holder surface is selectively introducing drug or growth factor, and the drug is sirolimus or heparin, and growth factor is raw for endothelium
The long factor；
(6) deformation and storage of intravascular stent
It is radially compressed at required shape after the intravascular stent with medication coat that step (5) obtains is heated to 80 DEG C
Shape, is quickly cooled to 24 DEG C, and lower than 24 °C at a temperature of store.
(7) reply of intravascular stent
After intravascular stent implantable intravascular under the assistance of seal wire that step (6) obtains, under the action of externally-applied magnetic field, magnetic
Thermal excitation is voluntarily expanded, and is bonded in blood vessel, support blood vessels.
Embodiment 3.
(1) synthesis of Biodegradable polylactic acids base shape memory polyurethane
With molar ratio 9:1'sD,LLactide (D,L- LA) withe-Caprolactone (e-It CL is) raw material, through ring-opening polymerisation
Prepare random copolymer PCLA, PCLA again with hexamethylene diisocyanate (HDI) and the poly- tetrahydro of flexible oligomer
Furans (PTMEG) chain extension is prepared into Biodegradable polylactic acids base shape memory polyurethane (PCLAUs), wherein HDI and PCLA
Molar ratio is 1.10:1, and the dosage of PTMEG is the 10% of system gross mass；
(2) Biodegradable polylactic acids base shape memory polyurethane (PCLAUs)/Fe3O4The synthesis of nanocomposite
By the method for solution blending by the PCLAUs that step (1) obtains and the magnetic Fe that surface modification is crossed3O4Nanoparticle
It carries out compound, is prepared into PCLAUs/Fe3O4Nanocomposite；Wherein, magnetic Fe3O4Nanoparticle oleic acid (Oleic
Acid it) is surface-treated.In compound system, magnetic Fe3O4Nanoparticle mass fraction is 9%.
(3) Biodegradable polylactic acids base shape memory polyurethane/Fe3O4The extrusion molding of nanocomposite
The Biodegradable polylactic acids base shape memory polyurethane (PCLAUs) prepared in step (2) /Fe3O4 nanometer is answered
Condensation material shreds into 0.5*0.5*0.2(unit: cm) it is granular.The mould head of 1.75mm is mounted on desktop type extruder,
Extrusion temperature is set as 150 DEG C, and booting preheats 10min, starts to squeeze out, and removes the non-uniform part of material head.By composite materials
It is extruded into the filiform of 3.00mm.
(3) Biodegradable polylactic acids base shape memory polyurethane/Fe3O4The extrusion molding of nanocomposite
The Biodegradable polylactic acids base shape memory polyurethane for being obtained step (2) using desktop type extruder/
Fe3O4 nanocomposite is extruded into the filiform of 1.75mm or 3.00mm；Extrusion temperature is arranged at 140 DEG C ~ 160 DEG C；
(4) 3D printing of intravascular stent
Using FDM type 3D printer, the step of establishing (3) is obtained into pipe holder model and is printed as intravascular stent；Blood vessel branch
It is 27.000 ~ 37.085mm that frame moulded dimension, which is set as length, and outer diameter is 2.000 ~ 3.566mm, and monofilament is with a thickness of 0.100 ~ 0.3
00mm；
(5) preparation of medication coat
The PCLAUs that step (1) is obtained, using DMF as solvent, using electrostatic spinning technique, in the blood that step (4) obtains
Pipe holder surface is selectively introducing drug or growth factor, and the drug is sirolimus or heparin, and growth factor is raw for endothelium
The long factor；
(6) deformation and storage of intravascular stent
It is radially compressed at required shape after the intravascular stent with medication coat that step (5) obtains is heated to 80 DEG C
Shape, is quickly cooled to 24 DEG C, and lower than 24 °C at a temperature of store.
(7) reply of intravascular stent
After intravascular stent implantable intravascular under the assistance of seal wire that step (6) obtains, under the action of externally-applied magnetic field, magnetic
Thermal excitation is voluntarily expanded, and is bonded in blood vessel, support blood vessels.
Claims (2)
1. a kind of method for preparing biodegradable polymer self-expanding type blood vessel dilator based on 3D printing technique, feature include
Following steps:
(1) synthesis of Biodegradable polylactic acids base shape memory polyurethane
With molar ratio 5:5 to 9:1'sD,LLactide (D,L- LA) and ε-Caprolactone (ε-CL it is) raw material, is prepared through ring-opening polymerisation
Random copolymer PCLA, PCLA expand with hexamethylene diisocyanate (HDI) and flexible oligomer polytetrahydrofuran (PTMEG) again
Chain is prepared into Biodegradable polylactic acids base shape memory polyurethane (PCLAUs), and wherein the molar ratio of HDI and PCLA is 1.05:
The dosage of 1 to 1.2:1, PTMEG are the 5% to 10% of system gross mass；
(2) Biodegradable polylactic acids base shape memory polyurethane (PCLAUs)/Fe3O4The synthesis of nanocomposite
By the method for solution blending by the PCLAUs that step (1) obtains and the magnetic Fe that surface modification is crossed3O4Nanoparticle carries out
It is compound, it is prepared into PCLAUs/Fe3O4Nanocomposite；It is studied with differential scanning calorimetry (DSC)D,LLactide (D,L-
) and ε LA-Caprolactone (ε-CL) the hot property of random copolymer passes through adjustingD,LLactide (D,L- LA) and ε-Caprolactone (ε-
CL) the ratio of component regulates and controls the T of random copolymerg, it is made to be slightly above body temperature；
(3) Biodegradable polylactic acids base shape memory polyurethane/Fe3O4The extrusion molding of nanocomposite
The Biodegradable polylactic acids base shape memory polyurethane/Fe for being obtained step (2) using desktop type extruder3O4Nanometer
Composite material is extruded into the filiform of 1.75mm or 3.00mm；Extrusion temperature is arranged at 140 DEG C ~ 160 DEG C；
(4) 3D printing of intravascular stent
Using FDM type 3D printer, the Filamentous composite material that the step of establishing (3) obtains is printed as intravascular stent；Blood vessel branch
It is 27.000 ~ 37.085mm that frame moulded dimension, which is set as length, and outer diameter is 2.000 ~ 3.566mm, and monofilament is with a thickness of 0.100 ~ 0.3
00mm；
(5) preparation of medication coat
The PCLAUs that step (1) is obtained, using DMF as solvent, using electrostatic spinning technique, in the blood vessel branch that step (4) obtains
Frame surface is selectively introducing drug or growth factor, and the drug is sirolimus or heparin, and growth factor is endothelial growth factor
Son；
(6) deformation and storage of intravascular stent
It is radially compressed at required shape after the intravascular stent with medication coat that step (5) obtains is heated to 80 DEG C, it is fast
Speed is cooled to 24 DEG C, and lower than 24 °C at a temperature of store；
(7) reply of intravascular stent
After intravascular stent implantable intravascular under the assistance of seal wire that step (6) obtains, under the action of externally-applied magnetic field, magnetic heat shock
It expands, and is bonded in blood vessel, support blood vessels from row.
2. a kind of 3D printing technique that is based on according to claim 1 prepares biodegradable polymer self-expanding blood vessel branch
The method of frame, which is characterized in that print temperature described in step (4) is set as 140 ~ 155 DEG C, and printer head extrusion speed is
20~45mm/min。
Priority Applications (1)
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| CN106236338A (en) * | 2016-09-27 | 2016-12-21 | 吉林大学 | Negative poisson's ratio degradable shape-memory polymer intravascular stent increases material manufacture method |
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| CN106901880A (en) * | 2017-02-04 | 2017-06-30 | 同济大学 | Expand preparation and the application process of formula self expandable developable degradable polyurethane urethra rack in two ends |
| CN106823016A (en) * | 2017-02-04 | 2017-06-13 | 同济大学 | Based on degradable self expandable 4D intravascular stents of shape memory polyurethane and preparation method thereof |
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| CN108641074B (en) * | 2018-05-23 | 2021-01-29 | 重庆大学 | Biodegradable material and preparation method and application thereof |
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| KR102221074B1 (en) * | 2018-12-24 | 2021-03-02 | 부산대학교 산학협력단 | A stent comprising biodegradable polymer and nitinol and method for preparing thereof |
| CN110641012B (en) * | 2019-09-25 | 2021-07-02 | 青岛五维智造科技有限公司 | Micro-scale 3D printing preparation method and device for polymer fully-degradable intravascular stent and application of micro-scale 3D printing preparation method and device |
| CN111282019B (en) * | 2020-01-20 | 2021-07-16 | 浙江大学 | Medical titanium implant and preparation method thereof |
| CN111839810B (en) * | 2020-07-27 | 2021-07-06 | 北京理工大学 | Manufacturing method of intravascular stent |
| CN112500668B (en) * | 2020-11-23 | 2022-09-16 | 江苏大学 | Shape memory polymer structure capable of selectively responding and preparation method thereof |
| CN113198052A (en) * | 2021-04-14 | 2021-08-03 | 成都理工大学 | Ferroferric oxide/polytetrahydrofuran composite bone repair material and application thereof |
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