CN109289094A - A kind of vascular stent material and preparation method thereof - Google Patents
A kind of vascular stent material and preparation method thereof Download PDFInfo
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- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
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- 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
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- A—HUMAN NECESSITIES
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- 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
- A61L31/06—Macromolecular materials obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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- A—HUMAN NECESSITIES
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- 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
- A61L31/148—Materials at least partially resorbable by the body
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
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- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
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Abstract
The invention discloses a kind of preparation methods of vascular stent material, include the following steps: the preparation of (one) chloromaleic acid imines end group polycaprolactone, (2) preparation of copolymer, (3) chitosan-modified copolymer, (4) synthesis of furyl polyesters condensation polymer, the molding of (five) bracket.The invention also discloses the vascular stent materials being prepared according to the preparation method.Preparation method is simple for vascular stent material disclosed by the invention, prepares cheap；The vascular stent material good biocompatibility being prepared, mechanical mechanics property and degradability are excellent, safe and reliable.
Description
Technical field
The invention belongs to three classes the field of medical instrument technology, are related to the extensible implantation class prosthese of one kind more particularly to one
Kind intravascular stent and preparation method thereof.
Background technique
Currently, bracket interventional procedure is one of the main means for treating cardiovascular disease, mainly draw applied to vascular diseases
Rise vessel lumen is narrow or embolotherapy, it is unobstructed to achieve the purpose that improvement or treatment disease so as to improve blood flow.Bracket is situated between
The therapeutic effect for entering art depends on the selection of vascular stent material.The ideal vascular stent material of performance is to improve success rate of operation
And therapeutic effect, mitigate the powerful guarantee of patient suffering.
Timbering material commonly used in the prior art mainly includes non-degradable vascular stent material and degradable blood vessel bracket
Material.Non-degradable vascular stent material mainly has stainless steel, cobalt, tantalum and Nitinol, these metallic stent materials are in human body
Interior non-degradable needs to increase the degree of risk for causing restenosis in permanent retention body, easily causes vascular damaged, and easily
Lead to thrombosis.Degradable blood vessel bracket material is non-stimulated to human body, can reduce advanced stage in-stent restenosis risk, not influence
Lesion subsequent processing does not generate tail shadow, significantly reduces patient to the psychological pressure of implant, it is suitable to shorten antiplatelet drug
Use duration.But the degradable blood vessel bracket mechanical property of materials in the prior art is insufficient, intensity, oxidation resistent susceptibility and toughness compared with
Difference, degradation in vivo speed is too fast, is unfavorable for blood vessel recovery, and certain inflammatory reaction can be generated in degradation process.
Therefore, it develops one kind and takes into account that mechanical mechanics property, good degradation property, biocompatibility are excellent, and use is safe
Reliable vascular stent material is imperative.
Summary of the invention
In order to overcome the defects of the prior art, the present invention is intended to provide a kind of good biocompatibility, mechanical mechanics property
Vascular stent material excellent with degradability, safe and reliable, effectively to solve traditional degradable blood vessel bracket material
More or less existing mechanical mechanics property is insufficient, and intensity, oxidation resistent susceptibility and toughness are poor, and degradation in vivo speed is too
Fastly, it is unfavorable for blood vessel recovery, and the technical issues of certain inflammatory reaction can be generated in degradation process, while providing its preparation
Method.
The present invention is realized by the following scheme: a kind of preparation method of vascular stent material, includes the following steps:
I that succinimide end group polycaprolactone and the chloro- 1,3- butadiene of (E, Z) -1,4- two be dissolved in high boiling solvent is anti-
It answers, prepares chloromaleic acid imines end group polycaprolactone；
II by chloromaleic acid imines end group polycaprolactone, D- glucose saccharic acid 2- propylene -1- ester, 2- methyllactic acid allyl
Ester, initiator, which are added in N-Methyl pyrrolidone, to react, and obtains copolymer；
III modifies copolymer with chitosan in acetic acid solution；
IV 2,5-furandicarboxylic acid, ethylene glycol are added in dimethyl sulfoxide, with dicyclohexylcarbodiimide, 4- dimethylamino
Pyridine reaction, synthesizes furyl polyesters condensation polymer；
The molding of V bracket: chitosan-modified copolymer, furyl polyesters condensation polymer are dissolved in mixed solvent, then carried out
Electrostatic spinning obtains vascular stent material.
Further, a kind of preparation method of vascular stent material, includes the following steps:
The preparation of I chloromaleic acid imines end group polycaprolactone: under nitrogen or atmosphere of inert gases, by succinimide
End group polycaprolactone and-two chloro-1,3-butadiene of (E, Z)-Isosorbide-5-Nitrae, which are dissolved in high boiling solvent, forms solution, after solution is added
Into the there-necked flask equipped with reflux condensing tube, electric mixer, reflux is stirred to react 10-12 hours at 120-130 DEG C, back spin
Solvent is evaporated off, obtains chloromaleic acid imines end group polycaprolactone；
The preparation of II copolymer: chloromaleic acid imines end group polycaprolactone, the D- glucose that will be prepared by step I
Saccharic acid 2- propylene -1- ester, 2- methyllactic acid allyl ester, initiator are added in N-Methyl pyrrolidone, in nitrogen or indifferent gas
Be stirred to react at 70-80 DEG C and be stirred to react 4-6 hours under body atmosphere, after settle out in acetone, the polymer to settle out is placed in very
It dries to constant weight at 70-80 DEG C of empty drying box, obtains copolymer；
III chitosan-modified copolymer: the copolymer, the chitosan that are prepared by step II are added to mass fraction
In the acetic acid solution of 5-10%, to be stirred to react at 50-60 DEG C 8-10 hours, ammonium hydroxide is added afterwards, adjusts solution to neutrality, after
Revolving removes solvent, then washes crude product 3-5 times with ethyl alcohol, is finally placed in 90-100 DEG C of drying of vacuum oven to constant weight, obtains
Chitosan-modified copolymer；
The synthesis of IV furyl polyesters condensation polymer: after 2,5-furandicarboxylic acid, ethylene glycol are added in dimethyl sulfoxide, then
Thereto plus dicyclohexylcarbodiimide, 4-dimethylaminopyridine, it is stirred 1-2 hours under the conditions of ice-water bath under nitrogen atmosphere,
It is stirred to react at 150-170 DEG C 18-22 hours, after reaction, settles out in acetone again, the polymer to settle out is placed in very
It is dried 15-20 hours at 70-80 DEG C in empty drying box, obtains furyl polyesters condensation polymer；
The molding of V bracket: it is prepared by the chitosan-modified copolymer being prepared by step III, by step IV
To furyl polyesters condensation polymer be dissolved in the mixed solvent, be heated to 150-180 DEG C, be stirred at reflux 20-30 minutes, it is rear cooling
To room temperature, mixed solution is obtained, then mixed solution is subjected to electrostatic spinning, obtains vascular stent material.
Preferably, the polycaprolactone of succinimide end group described in step I ,-two chloro-1,3-butadiene of (E, Z)-Isosorbide-5-Nitrae, height
The mass ratio of boiling point solvent is 20:1:(40-50).
Preferably, the high boiling solvent is in dimethyl sulfoxide, n,N-Dimethylformamide, N-Methyl pyrrolidone
It is one or more of.
Preferably, the end group of chloromaleic acid imines described in step II polycaprolactone, D- glucose saccharic acid 2- propylene -1- ester,
2- methyllactic acid allyl ester, initiator, N-Methyl pyrrolidone mass ratio be 2:1:1:(0.02-0.04): (20-25).
Preferably, the initiator is selected from least one of azodiisobutyronitrile, azobisisoheptonitrile.
Preferably, the inert gas is selected from one of helium, neon, argon gas.
Preferably, copolymer described in step III, chitosan, acetic acid solution mass ratio be 1:(0.5-0.8): (8-
12)。
Preferably, 2,5-furandicarboxylic acid described in step IV, ethylene glycol, dimethyl sulfoxide, dicyclohexylcarbodiimide, 4-
The mass ratio of dimethylamino naphthyridine is 2.5:1:(15-20): (0.4-0.6): 0.3.
Preferably, the quality of chitosan-modified copolymer described in step V, furyl polyesters condensation polymer, organic solvent
Than for 1:2:(10-15).
Preferably, the mixed solvent is that tetrahydrofuran, water, acetic acid 5:5:1 in mass ratio are mixed.
Preferably, the parameter of the electrostatic spinning is as follows: spinning voltage 5-15KV, fltting speed 0.5-2mL/h, receive away from
From for 15-35cm.
A kind of vascular stent material is prepared using the preparation method of above-mentioned vascular stent material.
The beneficial effects of adopting the technical scheme are that
1) preparation method of vascular stent material provided by the invention, simple to operation, reaction condition is mild, and raw material is easy
, cheap, Clinical practicability is good.
2) vascular stent material provided by the invention efficiently solves traditional degradable blood vessel bracket material and more or less deposits
Mechanical mechanics property it is insufficient, intensity, oxidation resistent susceptibility and toughness are poor, and degradation in vivo speed is too fast, are unfavorable for blood
Pipe restores, and the technical issues of certain inflammatory reaction can be generated in degradation process, has good biocompatibility, Mechanics of Machinery
Performance and degradability are excellent, safe and reliable advantage.
3) vascular stent material provided by the invention is formed using addition polymers and condensation polymer co-blended spinning, has taken into account two kinds
The advantage of polymer, the two compatibility is good, but retains suitable voidage, in addition respectively good mechanical mechanics property, increases
It is strong its in practical applications a possibility that and success rate.
4) vascular stent material provided by the invention combines these biocompatibilities of chitosan, polycaprolactone, ethylene glycol
Well, it the advantages of Biodegradable material, shows lower haemolytic index, enhances safety, effectively reduce clinical application
In limited by high immunogenicity reaction, reduce the failure of transplanting, and each structure increases material with chemistry key connection
Stability；Furans, maleic acid structure are introduced, the mechanical property of material, each ingredient and structure synergistic effect is improved, improves
The comprehensive performance of timbering material.
Specific embodiment
In order to make those skilled in the art more fully understand technical solution of the present invention, and make features described above of the invention,
Purpose and advantage are more clear understandable, and the present invention will be further explained with reference to the examples below.Embodiment is only used for
It is bright the present invention rather than limit the scope of the invention.
Terminal maleimide group polycaprolactone described in the following embodiments of the present invention is previously prepared, preparation method reference:
Zhang,M.J.；Liu,H.H.；Shao,W.；Miao,K.；Zhao,Y.L.Synthesisand propertiesofmultic
leavableamphiphilicdendriticcomblikeandtoothbrushlikecopolymerscomprisingalt
ernatingPEGandPCLgrafts.Macromolecules,2013,46,1325-1336；Other raw materials are from upper Haiquan
Sunrise foreign trade Co., Ltd.
Embodiment 1
A kind of preparation method of vascular stent material, includes the following steps:
The preparation of I chloromaleic acid imines end group polycaprolactone: under nitrogen atmosphere, succinimide end group is gathered in oneself
Ester 20g and-two chloro-1,3-butadiene 1g of (E, Z)-Isosorbide-5-Nitrae, which are dissolved in dimethyl sulfoxide 40g, forms solution, after solution is added to dress
In the there-necked flask for having reflux condensing tube, electric mixer, flowing back and be stirred to react 10 hours at 120 DEG C, solvent is evaporated off in back spin,
Obtain chloromaleic acid imines end group polycaprolactone；
The preparation of II copolymer: chloromaleic acid imines end group polycaprolactone 10g, the D- that will be prepared by step I
Glucose saccharic acid 2- propylene -1- ester 5g, 2- methyllactic acid allyl ester 5g, azodiisobutyronitrile 0.1g are added to N-Methyl pyrrolidone
In 100g, be stirred to react at 70 DEG C and be stirred to react 4 hours under nitrogen atmosphere, after settle out in acetone, the polymer that will be settled out
It is placed at 70 DEG C of vacuum oven and dries to constant weight, obtain copolymer；
III chitosan-modified copolymer: the copolymer 1 0g, the chitosan 5g that are prepared by step II are added to quality
It in the acetic acid solution 80g that score is 5%, is stirred to react at 50 DEG C 8 hours, ammonium hydroxide is added afterwards, adjust solution to neutrality, back spin
Solvent is evaporated off, then is washed crude product 3 times with ethyl alcohol, is finally placed in 90 DEG C of dryings of vacuum oven to constant weight, obtains chitosan and repair
Adorn copolymer；
The synthesis of IV furyl polyesters condensation polymer: dimethyl sulfoxide is added in 2,5- furandicarboxylic acid 25g, ethylene glycol 10g
After in 150g, then add dicyclohexylcarbodiimide 4g, 4-dimethylaminopyridine 3g thereto, under nitrogen atmosphere ice-water bath condition
Lower stirring 1 hour, then be stirred to react at 150 DEG C 18 hours, after reaction, settle out in acetone, the polymer that will be settled out
It is placed in a vacuum drying oven at 70 DEG C and dries 15 hours, obtain furyl polyesters condensation polymer；
The molding of V bracket: it is prepared by the chitosan-modified copolymer 1 0g being prepared by step III, by step IV
Obtained furyl polyesters condensation polymer 20g is dissolved in mixed solvent 100g, is heated to 150 DEG C, is stirred at reflux 20 minutes, rear cold
But to room temperature, mixed solution is obtained, then mixed solution is subjected to electrostatic spinning, obtains vascular stent material.
The mixed solvent is that tetrahydrofuran, water, acetic acid 5:5:1 in mass ratio are mixed.
The parameter of the electrostatic spinning is as follows: spinning voltage 5KV, fltting speed 0.5mL/h, and receiving distance is 15cm.
A kind of vascular stent material is prepared using the preparation method of above-mentioned vascular stent material.
Embodiment 2
A kind of preparation method of vascular stent material, includes the following steps:
The preparation of I chloromaleic acid imines end group polycaprolactone: under helium atmosphere, succinimide end group is gathered in oneself
Ester 20g and-two chloro-1,3-butadiene 1g of (E, Z)-Isosorbide-5-Nitrae, which are dissolved in n,N-Dimethylformamide 42g, forms solution, after by solution
It is added in the there-necked flask that reflux condensing tube, electric mixer are housed, reflux is stirred to react 10.5 hours at 123 DEG C, back spin
Solvent is evaporated off, obtains chloromaleic acid imines end group polycaprolactone；
The preparation of II copolymer: chloromaleic acid imines end group polycaprolactone 10g, the D- that will be prepared by step I
Glucose saccharic acid 2- propylene -1- ester 5g, 2- methyllactic acid allyl ester 5g, azobisisoheptonitrile 0.13g are added to N- crassitude
In ketone 105g, be stirred to react at 72 DEG C and be stirred to react 4.5 hours under helium atmosphere, after settle out in acetone, it is poly- by what is settled out
Conjunction object, which is placed at 73 DEG C of vacuum oven, to dry to constant weight, and obtains copolymer；
III chitosan-modified copolymer: the copolymer 1 0g, the chitosan 6g that are prepared by step II are added to quality
It in the acetic acid solution 95g that score is 6%, is stirred to react at 53 DEG C 8.5 hours, is added ammonium hydroxide afterwards, adjust solution to neutrality, after
Revolving removes solvent, then is washed crude product 4 times with ethyl alcohol, is finally placed in 93 DEG C of dryings of vacuum oven to constant weight, obtains chitosan
Modify copolymer；
The synthesis of IV furyl polyesters condensation polymer: dimethyl sulfoxide is added in 2,5- furandicarboxylic acid 25g, ethylene glycol 10g
After in 165g, then add dicyclohexylcarbodiimide 4.5g, 4-dimethylaminopyridine 3g thereto, under nitrogen atmosphere ice-water bath item
It stirs 1.3 hours, then is stirred to react at 155 DEG C 18.5 hours under part, after reaction, settled out in acetone, by what is settled out
Polymer, which is placed in a vacuum drying oven at 73 DEG C, to be dried 16.5 hours, and furyl polyesters condensation polymer is obtained；
The molding of V bracket: it is prepared by the chitosan-modified copolymer 1 0g being prepared by step III, by step IV
Obtained furyl polyesters condensation polymer 20g is dissolved in mixed solvent 125g, is heated to 165 DEG C, is stirred at reflux 23 minutes, rear cold
But to room temperature, mixed solution is obtained, then mixed solution is subjected to electrostatic spinning, obtains vascular stent material.
The mixed solvent is that tetrahydrofuran, water, acetic acid 5:5:1 in mass ratio are mixed.
The parameter of the electrostatic spinning is as follows: spinning voltage 8KV, fltting speed 1mL/h, and receiving distance is 20cm.
A kind of vascular stent material is prepared using the preparation method of above-mentioned vascular stent material.
Embodiment 3
A kind of preparation method of vascular stent material, includes the following steps:
The preparation of I chloromaleic acid imines end group polycaprolactone: under neon atmosphere, succinimide end group is gathered in oneself
Ester 20g and-two chloro-1,3-butadiene 1g of (E, Z)-Isosorbide-5-Nitrae, which are dissolved in N-Methyl pyrrolidone 45g, forms solution, after solution is added
Enter into the there-necked flask equipped with reflux condensing tube, electric mixer, flows back and be stirred to react 11 hours at 125 DEG C, back spin is evaporated off
Solvent is removed, chloromaleic acid imines end group polycaprolactone is obtained；
The preparation of II copolymer: chloromaleic acid imines end group polycaprolactone 20g, the D- that will be prepared by step I
Glucose saccharic acid 2- propylene -1- ester 10g, 2- methyllactic acid allyl ester 10g, azodiisobutyronitrile 0.3g are added to N- crassitude
In ketone 230g, be stirred to react at 75 DEG C and be stirred to react 5 hours under neon atmosphere, after settle out in acetone, the polymerization that will be settled out
Object is placed at 75 DEG C of vacuum oven and dries to constant weight, and obtains copolymer；
III chitosan-modified copolymer: the copolymer 1 0g, the chitosan 6.5g that are prepared by step II are added to matter
It measures in the acetic acid solution 105g that score is 7%, is stirred to react at 56 DEG C 9 hours, is added ammonium hydroxide afterwards, adjust solution to neutrality,
Solvent is evaporated off in back spin, then is washed crude product 4 times with ethyl alcohol, is finally placed in 96 DEG C of dryings of vacuum oven to constant weight, it is poly- to obtain shell
Sugar-modified copolymer；
The synthesis of IV furyl polyesters condensation polymer: dimethyl sulfoxide is added in 2,5- furandicarboxylic acid 25g, ethylene glycol 10g
After in 180g, then add dicyclohexylcarbodiimide 5g, 4-dimethylaminopyridine 3g thereto, under nitrogen atmosphere ice-water bath condition
Lower stirring 1.6 hours, then be stirred to react at 160 DEG C 20 hours, after reaction, settle out in acetone, the polymerization that will be settled out
Object, which is placed in a vacuum drying oven at 75 DEG C, to be dried 18 hours, and furyl polyesters condensation polymer is obtained；
The molding of V bracket: it is prepared by the chitosan-modified copolymer 1 0g being prepared by step III, by step IV
Obtained furyl polyesters condensation polymer 20g is dissolved in mixed solvent 130g, is heated to 170 DEG C, is stirred at reflux 26 minutes, rear cold
But to room temperature, mixed solution is obtained, then mixed solution is subjected to electrostatic spinning, obtains vascular stent material.
The mixed solvent is that tetrahydrofuran, water, acetic acid 5:5:1 in mass ratio are mixed.
The parameter of the electrostatic spinning is as follows: spinning voltage 10KV, fltting speed 1.2mL/h, and receiving distance is 25cm.
A kind of vascular stent material is prepared using the preparation method of above-mentioned vascular stent material.
Embodiment 4
A kind of preparation method of vascular stent material, includes the following steps:
The preparation of I chloromaleic acid imines end group polycaprolactone: under argon atmosphere, succinimide end group is gathered in oneself
Ester 20g and-two chloro-1,3-butadiene 1g of (E, Z)-Isosorbide-5-Nitrae, which are dissolved in high boiling solvent 48g, forms solution, after solution is added to
Equipped with reflux condensing tube, electric mixer there-necked flask in, flow back and be stirred to react 11.5 hours at 128 DEG C, back spin is evaporated off
Solvent obtains chloromaleic acid imines end group polycaprolactone；The high boiling solvent is dimethyl sulfoxide, N, N- dimethyl formyl
The mixture that amine, N-Methyl pyrrolidone 1:2:1 in mass ratio are mixed；
The preparation of II copolymer: chloromaleic acid imines end group polycaprolactone 20g, the D- that will be prepared by step I
Glucose saccharic acid 2- propylene -1- ester 10g, 2- methyllactic acid allyl ester 10g, initiator 0.35g are added to N-Methyl pyrrolidone
In 245g, be stirred to react at 78 DEG C and be stirred to react 5.5 hours under argon atmosphere, after settle out in acetone, the polymerization that will be settled out
Object is placed at 78 DEG C of vacuum oven and dries to constant weight, and obtains copolymer；The initiator is azodiisobutyronitrile, azo two different heptan
Nitrile 3:5 in mass ratio is mixed；
III chitosan-modified copolymer: the copolymer 1 0g, the chitosan 7.8g that are prepared by step II are added to matter
It measures in the acetic acid solution 115g that score is 9%, is stirred to react at 58 DEG C 9.5 hours, ammonium hydroxide is added afterwards, adjust solution into
Property, solvent is evaporated off in back spin, then is washed crude product 5 times with ethyl alcohol, is finally placed in 95 DEG C of dryings of vacuum oven to constant weight, obtains shell
Glycan modifies copolymer；
The synthesis of IV furyl polyesters condensation polymer: dimethyl sulfoxide is added in 2,5- furandicarboxylic acid 25g, ethylene glycol 10g
After in 194g, then add dicyclohexylcarbodiimide 5.8g, 4-dimethylaminopyridine 3g thereto, under nitrogen atmosphere ice-water bath item
It stirs 1.8 hours, then is stirred to react at 168 DEG C 21.5 hours under part, after reaction, settled out in acetone, by what is settled out
Polymer, which is placed in a vacuum drying oven at 79 DEG C, to be dried 19 hours, and furyl polyesters condensation polymer is obtained；
The molding of V bracket: it is prepared by the chitosan-modified copolymer 1 0g being prepared by step III, by step IV
Obtained furyl polyesters condensation polymer 20g is dissolved in mixed solvent 145g, is heated to 178 DEG C, is stirred at reflux 29 minutes, rear cold
But to room temperature, mixed solution is obtained, then mixed solution is subjected to electrostatic spinning, obtains vascular stent material.
The mixed solvent is that tetrahydrofuran, water, acetic acid 5:5:1 in mass ratio are mixed.
The parameter of the electrostatic spinning is as follows: spinning voltage 13KV, fltting speed 1.8mL/h, and receiving distance is 33cm.
A kind of vascular stent material is prepared using the preparation method of above-mentioned vascular stent material.
Embodiment 5
A kind of preparation method of vascular stent material, includes the following steps:
The preparation of I chloromaleic acid imines end group polycaprolactone: under nitrogen atmosphere, succinimide end group is gathered in oneself
Ester 20g and-two chloro-1,3-butadiene 1g of (E, Z)-Isosorbide-5-Nitrae, which are dissolved in N-Methyl pyrrolidone 50g, forms solution, after solution is added
Enter into the there-necked flask equipped with reflux condensing tube, electric mixer, flows back and be stirred to react 12 hours at 130 DEG C, back spin is evaporated off
Solvent is removed, chloromaleic acid imines end group polycaprolactone is obtained；
The preparation of II copolymer: chloromaleic acid imines end group polycaprolactone 10g, the D- that will be prepared by step I
Glucose saccharic acid 2- propylene -1- ester 5g, 2- methyllactic acid allyl ester 5g, azobisisoheptonitrile 0.2g are added to N-Methyl pyrrolidone
In 125g, be stirred to react at 80 DEG C and be stirred to react 6 hours under nitrogen atmosphere, after settle out in acetone, the polymer that will be settled out
It is placed at 80 DEG C of vacuum oven and dries to constant weight, obtain copolymer；
III chitosan-modified copolymer: the copolymer 1 0g, the chitosan 8g that are prepared by step II are added to quality
It in the acetic acid solution 120g that score is 10%, is stirred to react at 60 DEG C 10 hours, is added ammonium hydroxide afterwards, adjust solution to neutrality,
Solvent is evaporated off in back spin, then is washed crude product 5 times with ethyl alcohol, is finally placed in 100 DEG C of dryings of vacuum oven to constant weight, it is poly- to obtain shell
Sugar-modified copolymer；
The synthesis of IV furyl polyesters condensation polymer: dimethyl sulfoxide is added in 2,5- furandicarboxylic acid 25g, ethylene glycol 10g
After in 200g, then add dicyclohexylcarbodiimide 6g, 4-dimethylaminopyridine 3g thereto, under nitrogen atmosphere ice-water bath condition
Lower stirring 2 hours, then be stirred to react at 170 DEG C 22 hours, after reaction, settle out in acetone, the polymer that will be settled out
It is placed in a vacuum drying oven at 80 DEG C and dries 20 hours, obtain furyl polyesters condensation polymer；
The molding of V bracket: it is prepared by the chitosan-modified copolymer 1 0g being prepared by step III, by step IV
Obtained furyl polyesters condensation polymer 20g is dissolved in mixed solvent 150g, is heated to 180 DEG C, is stirred at reflux 30 minutes, rear cold
But to room temperature, mixed solution is obtained, then mixed solution is subjected to electrostatic spinning, obtains vascular stent material.
The mixed solvent is that tetrahydrofuran, water, acetic acid 5:5:1 in mass ratio are mixed.
The parameter of the electrostatic spinning is as follows: spinning voltage 15KV, fltting speed 2mL/h, and receiving distance is 35cm.
A kind of vascular stent material is prepared using the preparation method of above-mentioned vascular stent material.
Comparative example
Commercially available vascular stent material, main component are polylactic acid, are purchased from Zhejiang company.
The performance of vascular stent material obtained by embodiment 1-5 and comparative example is tested, test result is shown in Table 1, surveys
Method for testing is as follows:
(1) biocompatibility subcutaneously embeds test: the membrane material that the sample for sections observation is 10mmxl0mm.By film
It is taken out together with surrounding tissue, is placed in fixed in formalin solution, progress paraffin section, hematoxylin eosin staining, respectively at
40 times and 100 times of optical microphotograph microscopic observation surrounding materials inflammatory reactions.Sliced materials surrounding tissue in 3 random counter visuals field
Inflammatory cell quantity in unit area is averaged as the slice inflammatory cell quantity.
(2) degrade in vivo extension test: extension test uses the Instron5565 type static(al) material of Britain Instron company
Expect testing machine, inductor load capacity 500N.Setting tensile speed is 5mm/min, right in the environment of 25 DEG C, relative humidity 50%
Sample is tested.
(3) it hemolytic: is tested according to ISOTR7405.
Table 1
| Test item | Inflammatory cell quantity after 200 days | Tensile strength | Hemolytic |
| Unit | ×103It is a | MPa | % |
| Embodiment 1 | 1.0 | 45 | 0.05 |
| Embodiment 2 | 0.9 | 47 | 0.05 |
| Embodiment 3 | 0.8 | 49 | 0.04 |
| Embodiment 4 | 0.8 | 50 | 0.03 |
| Embodiment 5 | 0.6 | 52 | 0.02 |
| Comparative example | 3.5 | 25 | 0.45 |
As it can be seen from table 1 vascular stent material disclosed by the invention has more excellent mechanical property, blood compatibility
Property and biocompatibility.
The basic principles, main features and advantages of the present invention have been shown and described above.The technology of the industry
Personnel are it should be appreciated that the present invention is not limited to the above embodiments, and what is described in the above embodiment and the description is only the present invention
Principle, various changes and improvements may be made to the invention without departing from the spirit and scope of the present invention, these variation and
Improvement is both fallen in the range of claimed invention.The present invention claims protection scope by appended claims and its
Equivalent defines.
Claims (10)
1. a kind of preparation method of vascular stent material, which comprises the steps of:
Succinimide end group polycaprolactone and-two chloro-1,3-butadiene of (E, Z)-Isosorbide-5-Nitrae are dissolved in high boiling solvent reaction, system by I
Standby chloromaleic acid imines end group polycaprolactone；
II by chloromaleic acid imines end group polycaprolactone, D- glucose saccharic acid 2- propylene -1- ester, 2- methyllactic acid allyl ester, draw
Hair agent, which is added in N-Methyl pyrrolidone, reacts, and obtains copolymer；
III modifies copolymer with chitosan in acetic acid solution；
IV 2,5-furandicarboxylic acid, ethylene glycol are added in dimethyl sulfoxide, with dicyclohexylcarbodiimide, 4-dimethylaminopyridine
Reaction synthesizes furyl polyesters condensation polymer；
The molding of V bracket: chitosan-modified copolymer, furyl polyesters condensation polymer are dissolved in mixed solvent, then carry out electrostatic
Spinning obtains vascular stent material.
2. the preparation method of vascular stent material according to claim 1, which comprises the steps of:
The preparation of I chloromaleic acid imines end group polycaprolactone: under nitrogen or atmosphere of inert gases, by succinimide end group
Polycaprolactone and-two chloro-1,3-butadiene of (E, Z)-Isosorbide-5-Nitrae, which are dissolved in high boiling solvent, forms solution, after solution is added to dress
In the there-necked flask for having reflux condensing tube, electric mixer, flows back and be stirred to react 10-12 hours at 120-130 DEG C, back spin is evaporated off
Solvent is removed, chloromaleic acid imines end group polycaprolactone is obtained；
The preparation of II copolymer: chloromaleic acid imines end group polycaprolactone, the D- glucose saccharic acid that will be prepared by step I
2- propylene -1- ester, 2- methyllactic acid allyl ester, initiator are added in N-Methyl pyrrolidone, in nitrogen or inert gas atmosphere
Be stirred to react at 70-80 DEG C and be stirred to react 4-6 hours under enclosing, after settle out in acetone, the polymer to settle out is placed in vacuum and is done
It dries to constant weight at 70-80 DEG C of dry case, obtains copolymer；
III chitosan-modified copolymer: it is 5- that the copolymer, the chitosan that are prepared by step II, which are added to mass fraction,
It in 10% acetic acid solution, is stirred to react at 50-60 DEG C 8-10 hours, ammonium hydroxide is added afterwards, adjust solution to neutrality, rear revolving
Solvent is removed, then washes crude product 3-5 times with ethyl alcohol, 90-100 DEG C of drying of vacuum oven is finally placed in constant weight, it is poly- to obtain shell
Sugar-modified copolymer；
The synthesis of IV furyl polyesters condensation polymer: by 2,5-furandicarboxylic acid, ethylene glycol be added dimethyl sulfoxide in after, then to its
In plus dicyclohexylcarbodiimide, 4-dimethylaminopyridine, stirred 1-2 hours under the conditions of ice-water bath under nitrogen atmosphere, then
It is stirred to react at 150-170 DEG C 18-22 hours, after reaction, settles out in acetone, the polymer to settle out is placed in vacuum and is done
It is dried 15-20 hours at 70-80 DEG C in dry case, obtains furyl polyesters condensation polymer；
The molding of V bracket: it is prepared by the chitosan-modified copolymer being prepared by step III, by step IV
Furyl polyesters condensation polymer is dissolved in the mixed solvent, is heated to 150-180 DEG C, is stirred at reflux 20-30 minutes, after be cooled to room
Temperature obtains mixed solution, then mixed solution is carried out electrostatic spinning, obtains vascular stent material.
3. the preparation method of vascular stent material according to claim 2, which is characterized in that maleic acid described in step I
Imines end group polycaprolactone, the chloro- 1,3- butadiene of (E, Z) -1,4- two, high boiling solvent mass ratio be 20:1:(40-50)；
The high boiling solvent is selected from one or more of dimethyl sulfoxide, N,N-dimethylformamide, N-Methyl pyrrolidone.
4. the preparation method of vascular stent material according to claim 2, which is characterized in that chloro horse described in step II
Come acid imide end group polycaprolactone, D- glucose saccharic acid 2- propylene -1- ester, 2- methyllactic acid allyl ester, initiator, N- methylpyrrole
The mass ratio of alkanone is 2:1:1:(0.02-0.04): (20-25).
5. the preparation method of vascular stent material according to claim 2, which is characterized in that the initiator is selected from azo
At least one of bis-isobutyronitrile, azobisisoheptonitrile；The inert gas is selected from one of helium, neon, argon gas.
6. the preparation method of vascular stent material according to claim 2, which is characterized in that be copolymerized described in step III
Object, chitosan, acetic acid solution mass ratio be 1:(0.5-0.8): (8-12).
7. the preparation method of vascular stent material according to claim 2, which is characterized in that 2,5- furan described in step IV
Mutter dioctyl phthalate, ethylene glycol, dimethyl sulfoxide, dicyclohexylcarbodiimide, 4-dimethylaminopyridine mass ratio be 2.5:1:(15-
20):(0.4-0.6):0.3。
8. the preparation method of vascular stent material according to claim 2, which is characterized in that chitosan described in step V
Modify copolymer, furyl polyesters condensation polymer, organic solvent mass ratio be 1:2:(10-15)；The mixed solvent is four
Hydrogen furans, water, acetic acid 5:5:1 in mass ratio are mixed.
9. the preparation method of vascular stent material according to claim 2, which is characterized in that the parameter of the electrostatic spinning
As follows: spinning voltage 5-15KV, fltting speed 0.5-2mL/h, receiving distance is 15-35cm.
10. a kind of intravascular stent that the preparation method using any one of the claim 1-9 vascular stent material is prepared
Material.
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| CN202011219729.XA CN112336917A (en) | 2018-09-25 | 2018-09-25 | Degradable implantation type blood vessel support |
| CN202011218812.5A CN112274706A (en) | 2018-09-25 | 2018-09-25 | Intravascular stent material |
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| CN111820886A (en) * | 2020-06-24 | 2020-10-27 | 浙江大学 | Vasospasm monitoring devices based on friction electricity generation technique |
| CN114163696A (en) * | 2021-12-08 | 2022-03-11 | 大连海川科技有限公司 | Preparation method of degradable bio-based film material with phase change function |
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| CN112336917A (en) | 2021-02-09 |
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