CN108324998A - The preparation method of polyurethane multichannel endovascular stent and coating liquid used - Google Patents

The preparation method of polyurethane multichannel endovascular stent and coating liquid used Download PDF

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Publication number
CN108324998A
CN108324998A CN201810355433.7A CN201810355433A CN108324998A CN 108324998 A CN108324998 A CN 108324998A CN 201810355433 A CN201810355433 A CN 201810355433A CN 108324998 A CN108324998 A CN 108324998A
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polyurethane
coating liquid
multichannel
preparation
stent
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CN108324998B (en
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张琪
张超
叶开天
张依
张华�
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SICHUAN ZHIJIANG ADVANCED MATERIALS Co Ltd
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SICHUAN ZHIJIANG ADVANCED MATERIALS Co Ltd
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    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS 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
    • A61L31/00Materials 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
    • A61L31/12Composite materials, i.e. containing one material dispersed in a matrix of the same or different material
    • A61L31/125Composite materials, i.e. containing one material dispersed in a matrix of the same or different material having a macromolecular matrix
    • A61L31/126Composite materials, i.e. containing one material dispersed in a matrix of the same or different material having a macromolecular matrix containing carbon fillers
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS 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
    • A61L27/00Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/40Composite materials, i.e. containing one material dispersed in a matrix of the same or different material
    • A61L27/44Composite materials, i.e. containing one material dispersed in a matrix of the same or different material having a macromolecular matrix
    • A61L27/443Composite materials, i.e. containing one material dispersed in a matrix of the same or different material having a macromolecular matrix with carbon fillers
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS 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
    • A61L27/00Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/50Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS 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
    • A61L27/00Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/50Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • A61L27/507Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials for artificial blood vessels
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS 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
    • A61L27/00Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/50Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • A61L27/58Materials at least partially resorbable by the body
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS 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
    • A61L31/00Materials 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
    • A61L31/14Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS 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
    • A61L31/00Materials 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
    • A61L31/14Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • A61L31/148Materials at least partially resorbable by the body
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS 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
    • A61L2430/00Materials or treatment for tissue regeneration
    • A61L2430/20Materials or treatment for tissue regeneration for reconstruction of the heart, e.g. heart valves

Abstract

The invention discloses a kind of coating liquid for endovascular stent surface, preparation method is:Fluorinated graphene is added in the perfluoro alkane as solvent, it is ultrasonic under room temperature, polyurethane is then added, 12h~for 24 hours is stirred at 20 DEG C~100 DEG C, the polyurethane solutions as coating liquid are made.The present invention further simultaneously discloses the preparation method of the polyurethane multichannel endovascular stent carried out using above-mentioned coating liquid, includes the following steps:Select the metal die to match with shape of blood vessel or intravascular stent as frame body;Coating liquid is injected into being controlled by micro-injection pump in electrostatic spinning apparatus and capacity is in the syringe of 5~10ml, coating liquid sprays under the action of electrostatic force from the needle point of syringe, electrostatic spinning is carried out to frame body, frame body surface is set to have polyurethane film, to obtain polyurethane multichannel endovascular stent.Method using the present invention can make the flexibility of intravascular stent more preferable.

Description

The preparation method of polyurethane multichannel endovascular stent and coating liquid used
Technical field
The present invention relates to a kind of polyurethane multichannel endovascular stent and preparation method thereof, specifically a kind of method of electrostatic spinning The method for preparing polyurethane multichannel endovascular stent.
Background technology
With the improvement of people's living standard, the incidence of angiocardiopathy is higher and higher.It is to cause dead weight Want one of reason.It is reported that the whole world has 3,000,000 people to receive angiocarpy bracket implant surgery every year.With endovascular treatment skill The development of art, endovascular stent implantation have become one of the main method for the treatment of angiocardiopathy, and the system after stenter to implant Row complication, such as acute/subacute thrombosis, in-stent restenosis have attracted more and more attention from people, especially holder Interior restenosis becomes the problem of can not avoiding.
After stenter to implant human body in the blood environment, metallic support uses for a long time in blood environment, there are thrombus and Corrode two main problems.Determine that one of the key factor of endovascular stent performance quality is timbering material.Currently used for system The material for making endovascular stent mainly has metal, high molecular material etc..The more a wide range of coronary artery bracket of clinical application is metal material Material, the excellent mechanical property of metal material can meet the requirement of environment, but the blood of the corrosion and induction of metallic support in blood Bolt problem can destroy substrate performance and physiological environment.Compared with bare metal stent, overlay film frame is to the damage of blood vessel and intravascular The stimulation of film is light, has the characteristics such as thrombus source is small, inflammatory reaction is slight and endometrial hyperplasia is few, reduces the restenosis of blood vessel Rate.
CN1410132A discloses a kind of polyurethane and intravascular stent and its system made of polyhydroxyalkanoate blend Preparation Method belongs to biomedical engineering field.The intravascular stent is by polyurethane (PU) and polyhydroxyalkanoate (PHA) blend It is made;The intravascular stent is made of porous inner membrance, solid outer membrane and reinforcing rib, and reinforcing rib is with belt-shaped form wound on outer membrane surface layer;It should Intravascular stent is more main in addition to good biocompatibility, anticoagulant property, cell adhesion and degradation speed appropriate It is to make the mechanical strength of intravascular stent and suture strength have to increase substantially.
CN102198024A discloses a kind of intravascular stent, cylindrical structure, and being parallel to axis direction on barrel has one A fracture, intravascular stent use common alloy material or memory alloy material;It is coated with solid on all surface of intravascular stent Membranoid substance or coating, membranoid substance or coating are polyurethane, varicosity polyurethane or polyurethane.The intravascular stent is unfavorable for platelet aggregation Collection, it is not easy to form thrombus, cell ingrowth can be promoted and form vascular endothelial cell layer, have excellent biocompatibility, No rejection reduces hyperplasia, no foreign body sensation, without sensitization, applied widely, while saving precious metal, reduces product cost.
CN103301513A is related to the preparation method with the intravascular stent of pharmaceutical grade immobilised enzymes coating.Including following step Suddenly, A. prepares the buffer solution of medical enzyme preparation;B. it coats;C. the intravascular stent with pharmaceutical grade enzyme coating is prepared.It can be used for The immobilised enzymes holder of surgical interventional therapy, it is convenient to prepare, and condition is simple, safe and reliable.It is obtained to be controlled for surgery intervention The immobilised enzymes holder for the treatment of, with good biocompatibility, high, more medical than the injection enzyme of reactivity high catalytic efficiency 2000 again with On, there is extensive potential applicability in clinical practice;Clinical thrombus can be used in, improve blood circulation, treatment inflammation and degradation blood The effect of uric acid in liquid.
CN106366285A discloses a kind of preparation and application of intravascular stent, poly- using homemade temperature-sensitive memory-type Object and 3D printing technique are closed to weave angiocarpy bracket, temperature-sensitive memory-type polymer is temperature-sensitive memory polyurethane material, point Son amount is 8,000-200,000 dalton, and glass transition temperature is 35~45 DEG C.The preparation method of the intravascular stent is simple, production Object is controllable, and prepared temperature-sensitive memory polyurethane material has the glass transition temperature higher than body temperature, meets requirement; Can be the customized intravascular stent of patient, application method according to operation needs under the conditions of low-grade fever using 3D printing technique Simply, storage is convenient.
US8313524 (B2) discloses a kind of self sealss blood vessel graft, includes substrate with sealant layer and several Optional extra play.Base material can be expanded PTFE, and the material for fluid sealant and extra play is polyurethane.
US5219662 (A) discloses a kind of polyurethane material and can be used as vasotransplantation or artificial heart component, has and people The preferable biocompatibility of body.
US8357767 (B2), US4156066 (A) disclose a kind of polyurethane or polyurethane/urea compositions, have tension Intensity is more than 10MPa, and elasticity modulus is more than 400MPa, and elongation at break is more than the performances such as 30%.The composition can be used for biology In medicine intravascular stent, orthopaedic implant, drug delivery coating or organizational project.
US2009118761 (A1) discloses one kind for blocking angiomatous endovascular device, which includes polymer Case member can be made of bioactivity and Biocompatible Polyurethane glycol glycosaminoglycan copolymer and liquid embolizing agent.
Fluorinated graphene surface energy reduces, hydrophobicity enhances, while also having the characteristics that high temperature resistant, chemical property are stablized, It may be used as tunnel obstacle or the insulator or barrier material as high quality, it can also be used to light emitting diode and display, The fields such as interface, novel nano electronic device, lubriation material are with a wide range of applications.
New derivatives of the fluorinated graphene as graphene had not only maintained the performance of graphene high intensity, but also because of fluorine original The introducing of son brings novel interface and the physical and chemical performances such as surface energy reduction, hydrophobicity enhancing and Bandgap extension.Meanwhile Fluorinated graphene high temperature resistant, chemical property are stablized, and show the property of similar polytetrafluoroethylene (PTFE), are referred to as " two-dimentional Teflon Dragon ".
Fluorinated graphene can be easily transferred on various substrates, especially the Young's modulus of fluorinated graphene and continue Strain can be up to 100N/m and 15% respectively, can be realized with flexible, anti-impact if being transferred into flexible substrate It hits and flexible optoelectronic sensitive detection parts the features such as light weight.
But the report of endovascular stent surface coating to be used for currently without fluorinated graphene.
Invention content
The technical problem to be solved in the present invention is to provide a kind of preparation method of polyurethane multichannel endovascular stent and institutes Coating liquid.
In order to solve the above technical problem, the present invention provides a kind of coating liquids for endovascular stent surface (that is, being used for The polyurethane solutions of endovascular stent surface coating), the preparation method of the coating liquid is:
Fluorinated graphene is added in the perfluoro alkane as solvent, ultrasonic under room temperature (10~30 DEG C) (400~ Then polyurethane is added in 600w) 15h~30h, 12h~for 24 hours (to make polyurethane be dissolved in perfluor is stirred at 20 DEG C~100 DEG C In alkane), the polyurethane solutions as coating liquid are made;
The solid-liquid ratio of fluorinated graphene and perfluoro alkane is 0.1~0.6g/ml, and the solid-liquid ratio of polyurethane and perfluoro alkane is 1~30g/ml.
The improvement of the coating liquid for endovascular stent surface as the present invention, it is characterized in that:
The perfluoro alkane is perfluor hexane, perfluorocyclohexane, PF 5070;
The polyurethane is thermoplastic polyurethane TPU;
The fluorinated graphene is the number of plies≤20,0.8~5.0nm of thickness, 2.0~5.0 μm of grain size, fluorine content 20- 40wt.%.
The present invention is also while to provide the polyurethane multichannel carried out using above-mentioned coating liquid (polyurethane solutions) intravascular The preparation method of holder, includes the following steps:
(1), frame body is selected;
The frame body is the metal die or intravascular stent to match with shape of blood vessel;
(2) prepared by intravascular stent:
By coating liquid (polyurethane solutions) inject electrostatic spinning apparatus in by micro-injection pump control and capacity be 5~ In the syringe of 10ml, coating liquid (polyurethane solutions) sprays under the action of electrostatic force from the needle point of syringe, to frame body (gold Belong to mold or intravascular stent) electrostatic spinning is carried out, so that frame body surface is had polyurethane film, to obtain polyurethane multichannel blood vessel Inner support (that is, multichannel band film intravascular stent).
The improvement of the preparation method of polyurethane multichannel endovascular stent as the present invention:
Step (2) electrostatic spinning process condition is:Polyurethane solutions of the control micro-injection pump to make needle point spray Flow velocity is 1~5ml/h (motor rotary speed of micro-injection pump is about 1500~2000r/min at this time);Control power supply voltage be 10~25KV, it is 10~25cm to receive distance (distance of needle point to frame body), and temperature is 10~30 DEG C, relative humidity 20~ 40%.
The preparation method of polyurethane multichannel endovascular stent as the present invention is further improved:
The metal die or intravascular stent are obtained by 3D printing.
The capacity of syringe is 5~10ml.
The present invention has the following technical effect that:
(1) present invention can carry out variously-shaped intravascular stent (metal die) using electrostatic spinning apparatus the plating on surface Film;Concise in technology, it is easy to operate;
(2) more preferably, intravascular stent surface covers the poly- ammonia containing fluorinated graphene to the biocompatibility of polyurethane and human body After ester so that the flexibility of intravascular stent is more preferable;
(3) polyurethane film containing fluorinated graphene being related to, can be not only used for the overlay film of intravascular stent, and can be with It is used as the covering material of various hearts and Vascular implantation instrument.
Specific implementation mode
The present invention is described further with reference to embodiments.It should be noted that following embodiments cannot function as pair The limitation of the scope of the present invention, any spirit improved all without prejudice to the present invention made on the basis of the present invention.
The preparation method of embodiment 1, a kind of polyurethane multichannel endovascular stent (a diameter of 6mm, length 20mm), according to It is secondary to follow the steps below:
(1), it is the intravascular stent of 20mm as frame body to select a diameter of 6mm, length.
(2), the preparation of polyurethane solutions:
By 0.6g fluorinated graphenes (fluorinated graphene be the number of plies≤20,0.8~5.0nm of thickness, 2.0~5.0 μm of grain size, Fluorine content 20-40wt.%) it is added in 1ml perfluor hexanes, ultrasound (400W) 30h under room temperature, TPU (thermoplastic polies are then added Urethane) 10g, stirs for 24 hours in 100 DEG C, so that TPU is dissolved in perfluoro alkane, obtain the polyurethane solutions as coating liquid.
(3), prepared by intravascular stent:
Conventional electrostatic spinning apparatus is selected, includes the syringe by micro-injection pump control and capacity for 5~10ml, it is electric Source anode output end is connected with the syringe needle of syringe, and power cathode output end connects with metal receiving axis, frame body (metal die or Intravascular stent) it is arranged in metal receiving axis.
By in the syringe of the 10ml in polyurethane solutions 6ml injection electrostatic spinning apparatus, pass through control micro-injection pump To make needle point spray polyurethane solutions flow velocity be 3ml/h (at this point, the motor rotary speed of micro-injection pump is about 2000r/ Min), control environment temperature is 10~30 DEG C, relative humidity 20~40%;Control power supply voltage be 15KV, setting receive away from From for 25cm.
Polyurethane solutions spray under the action of electrostatic force from needle point, by the syringe needle of syringe to metal die or blood vessel Holder carries out electrostatic spinning, to make intravascular stent surface form one layer of uniform film, obtains a kind of multichannel band film blood vessel branch Frame.
The preparation method of embodiment 2, a kind of polyurethane multichannel endovascular stent (a diameter of 3mm, length 30mm), according to It is secondary to follow the steps below:
(1), it is the intravascular stent of 30mm as frame body to select a diameter of 3mm, length.
(2), the preparation of polyurethane solutions:
Fluorinated graphene 0.3g is added in 1ml perfluorocyclohexanes, ultrasound (500w) 30h, is then added TPU under room temperature (thermoplastic polyurethane) 10g stirs 20h in 80 DEG C, so that TPU is dissolved in perfluorocyclohexane, obtain molten as the polyurethane of coating liquid Liquid.
(3), prepared by intravascular stent:
By in the syringe of the 10ml in polyurethane solutions 8ml injection electrostatic spinning apparatus, pass through control micro-injection pump To make the flow velocity of the polyurethane solutions of needle point ejection be 2ml/h, control environment temperature is 10~30 DEG C, relative humidity 20~ 40%;The voltage for controlling power supply is 10KV, and it is 25cm that setting, which receives distance,.To obtain a kind of multichannel band film intravascular stent.
The preparation method of embodiment 3, a kind of polyurethane multichannel endovascular stent (a diameter of 12mm, length 10mm), It follows the steps below successively:
(1), it is the intravascular stent of 10mm as frame body to select a diameter of 12mm, length.
(2), the preparation of polyurethane solutions:
Fluorinated graphene 0.2g is added in 1ml PF 5070s, ultrasound (600w) 20h, is then added TPU under room temperature (thermoplastic polyurethane) 20g stirs 16h in 60 DEG C, so that TPU is dissolved in PF 5070, obtain the polyurethane solutions as coating liquid.
(3), prepared by intravascular stent:
By in the syringe of the 10ml in polyurethane solutions 5ml injection electrostatic spinning apparatus, pass through control micro-injection pump To make the flow velocity of the polyurethane solutions of needle point ejection be 5ml/h, control environment temperature is 10~30 DEG C, relative humidity 20~ 40%;The voltage for controlling power supply is 25KV, and it is 15cm that setting, which receives distance,.To obtain a kind of multichannel band film intravascular stent.
The preparation method of embodiment 4, a kind of polyurethane multichannel endovascular stent (a diameter of 3mm, length 10mm), according to It is secondary to follow the steps below:
(1), it is the intravascular stent of 10mm as frame body to select a diameter of 3mm, length.
(2), the preparation of polyurethane solutions:
Fluorinated graphene 0.5g is added in 1ml perfluor hexanes, ultrasound (450w) 30h, is then added TPU under room temperature (thermoplastic polyurethane) 5g stirs 12h in 100 DEG C, so that TPU is dissolved in perfluor hexane, obtain the polyurethane solutions as coating liquid.
(3), prepared by intravascular stent:
By in the syringe of the 5ml in polyurethane solutions 3ml injection electrostatic spinning apparatus, by control micro-injection pump from And the flow velocity of the polyurethane solutions of needle point ejection is made to be 5ml/h, control environment temperature is 10~30 DEG C, relative humidity 20~ 40%;The voltage for controlling power supply is 15KV, and it is 15cm that setting, which receives distance,.To obtain a kind of multichannel band film intravascular stent.
Comparative example 1-1, the use for cancelling fluorinated graphene in 1 step of embodiment (2), that is, the dosage of fluorinated graphene It is 0;Remaining is equal to embodiment 1.
Comparative example 1-2, the amount of " fluorinated graphene " in 1 step of embodiment (2) is made into 1g by 0.6g;Remaining is equal to reality Apply example 1.
Comparative example 2-1, make the fluorinated graphene in 1 step of embodiment (2) into carbon nanotube, dosage is constant;Remaining etc. It is same as embodiment 1.
Comparative example 2-2, make the fluorinated graphene in 1 step of embodiment (2) into carbon fiber, dosage is constant;Remaining is equivalent In
Embodiment 1.
Comparative example 3 makes (2) the step of embodiment 1 into:
0.6g fluorinated graphenes, 10gTPU are added in 1ml perfluor hexanes, stirred at 100 DEG C for 24 hours, as plated film Liquid.
Experiment one, flexibility experiment,
Experimental method is:Vascular stent material is cut into the rectangle of long 10mm, width 6mm, in electronic universal tester One way tensile test is carried out on (CMT8502, Shenzhen), tensile speed 5mm/min, until sample is broken, test temperature is normal Temperature.
Acquired results are:It is shown in Table 1.
Table 1
Project Fracture strength, kPa Elongation at break, % Young's modulus, MPa
Embodiment 1 998.3±8.5 20.5±0.5 54.6±0.5
Comparative example 1-1 456.43±5.5 12.3±0.8 25.2±0.6
Comparative example 1-2 417.01±3.4 10.2±0.5 23.8±0.9
Comparative example 2-1 633.2±6.6 10.3±0.6 33.2±0.5
Comparative example 2-2 642.4±9.5 11.6±0.4 32.9±0.2
Comparative example 3 436.58±4.5 11.9±0.6 27.2±0.5
Embodiment 2 1004.6±5.9 22.8±0.7 65.5±0.3
Embodiment 3 998.9±9.5 25.8±0.2 55.3±0.5
Embodiment 4 1001.2±7.5 28.2±0.7 64.8±0.8
Note:Flexibility refers to object after stress deformation, the property being not easily broken.
To sum up, the timbering material prepared by the present invention is not easily broken after stress deformation, and flexibility is far above above-mentioned comparison Example.
Finally, it should also be noted that it is listed above be only the present invention several specific embodiments.Obviously, this hair Bright to be not limited to above example, acceptable there are many deformations.Those skilled in the art can be from present disclosure All deformations for directly exporting or associating, are considered as protection scope of the present invention.

Claims (5)

1. for the coating liquid on endovascular stent surface, it is characterized in that the preparation method of the coating liquid is:
Fluorinated graphene is added in the perfluoro alkane as solvent, ultrasound 15h~30h, is then added polyurethane under room temperature, 12h~for 24 hours is stirred at 20 DEG C~100 DEG C, and the polyurethane solutions as coating liquid are made;
The solid-liquid ratio of fluorinated graphene and perfluoro alkane is 0.1~0.6g/ml, the solid-liquid ratio of polyurethane and perfluoro alkane is 1~ 30g/ml。
2. the coating liquid according to claim 1 for endovascular stent surface, it is characterized in that:
The perfluoro alkane is perfluor hexane, perfluorocyclohexane, PF 5070;
The polyurethane is thermoplastic polyurethane TPU;
The fluorinated graphene is the number of plies≤20,0.8~5.0nm of thickness, 2.0~5.0 μm of grain size, fluorine content 20-40wt.%.
3. using the preparation method for the polyurethane multichannel endovascular stent that coating liquid as claimed in claim 1 or 2 carries out, It is characterized in including the following steps:
(1), frame body is selected;
The frame body is the metal die or intravascular stent to match with shape of blood vessel;
(2) prepared by intravascular stent:
It in the syringe of 5~10ml, will be plated by micro-injection pump control and capacity in coating liquid injection electrostatic spinning apparatus Film liquid sprays under the action of electrostatic force from the needle point of syringe, carries out electrostatic spinning to frame body, frame body surface is made to have poly- ammonia Ester film, to obtain polyurethane multichannel endovascular stent.
4. the preparation method of polyurethane multichannel endovascular stent according to claim 3, it is characterized in that:
Step (2) electrostatic spinning process condition is:Control micro-injection pump is to make the flow velocity of the polyurethane solutions of needle point ejection For 1~5ml/h;The voltage for controlling power supply is 10~25KV, and it is 10~25cm to receive distance, and temperature is 10~30 DEG C, relatively wet Degree 20~40%.
5. the preparation method of polyurethane multichannel endovascular stent according to claim 3 or 4, it is characterized in that:
The metal die or intravascular stent are obtained by 3D printing.
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Cited By (4)

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CN109181067A (en) * 2018-08-22 2019-01-11 四川之江高新材料股份有限公司 The preparation method of the polyethylene mixture containing fluorinated graphene for 3D printing
CN109206709A (en) * 2018-08-22 2019-01-15 四川之江高新材料股份有限公司 The preparation method of the powdered rubber polyethylene mixture modified containing fluorinated graphene for 3D printing
CN109206709B (en) * 2018-08-22 2021-05-28 四川之江高新材料股份有限公司 Preparation method of powdered rubber polyethylene mixture containing modified graphene fluoride for 3D printing
CN109181067B (en) * 2018-08-22 2021-06-08 四川之江高新材料股份有限公司 Preparation method of graphene fluoride-containing polyethylene mixture for 3D printing
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CN108948500B (en) * 2018-08-23 2020-12-29 之江(四川)高新材料应用技术研究院有限公司 Preparation method of polyethylene mixture containing polyurethane modified powder rubber for 3D printing
CN112274693A (en) * 2020-11-04 2021-01-29 中国科学院兰州化学物理研究所 Anti-infection intravascular stent and preparation method thereof

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