CN1223383C - Angiosupport made of polyamide and polyhydroxy fatty acid ester comixture and its preparation method - Google Patents

Angiosupport made of polyamide and polyhydroxy fatty acid ester comixture and its preparation method Download PDF

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CN1223383C
CN1223383C CNB021534829A CN02153482A CN1223383C CN 1223383 C CN1223383 C CN 1223383C CN B021534829 A CNB021534829 A CN B021534829A CN 02153482 A CN02153482 A CN 02153482A CN 1223383 C CN1223383 C CN 1223383C
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phb
preparation
polyurethane
chloroform
valerate
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CN1410132A (en
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胡平
郇春艳
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Tsinghua University
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Tsinghua University
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Abstract

The present invention relates to a vascular stent prepared from polyurethane and ploy-hydroxy alkanoate blending objects and a preparation method of the vascular stent, which belongs to the field of biomedical engineering. The vascular stent of the present invention is prepared from polyurethane and ploy-hydroxy alkanoate blending objects; the vascular stent is composed of a porous inner membrane, a solid outer membrane and a reinforcing rib, wherein the reinforcing rib is wound at the surface layer of the outer membrane in a strip shape. The vascular stent of the present invention not only has favorable biocompatibility, anticoagulant property, cell adhesion performance and proper degradation speed but also mainly and substantially increase the mechanical strength and the stitching strength of the vascular stent.

Description

Polyurethane and polyhydroxyalkanoate blend are made intravascular stent and preparation method
Technical field
The present invention relates to the intravascular stent that polyurethane and polyhydroxyalkanoate blend are made, belong to biomedical engineering field.
Background technology
1. materials used
At present diameter is no more than that the main therapy of 6mm diseased vessel is useful does circuitous bypass from the body blood vessel, replace lesion vessels, but there are not suitable and enough blood vessels in many patient bodies as circuitous bypass, so produced the idea for preparing intravascular stent with synthetic material.Is that histiocyte is adsorbed on that biocompatibility is good, on the timbering material that can progressively be degraded and absorbed in human body, and provides nutrition to make it amplification to cell with the blood vessel of synthetic material preparation as the basic idea of circuitous bypass.When timbering material was progressively by the human body degraded and absorbed, cell was constantly bred justacrine substrate, finally form new, have and original function and the corresponding blood vessel of form, reach the purpose of repair and reconstruction function.At present, the vascular stent material of use mainly is a macromolecule polymer material, is divided into biological non-degraded polymeric material and biodegradation polymeric material.The early stage material of making blood vessel adopts the Nondegradable polymeric material usually, as politef (polytetrafluoroethylene, PTFE), polrvinyl chloride (polyvinylchliride, PVC), polyethylene (polyethylene, PE), polyester fiber (Dacron) etc., after the artificial blood vessel that these materials are made directly implants, can produce a series of untoward reaction, form thrombosis, artery-clogging.The biodegradation polymeric material is to grow up gradually along with the development of this frontier of organizational project.The biodegradation polymeric material has polyglycolic acid usually, and (polyglycolic acid PGA), gathers hydroxyl monooctyl ester (polyhydroxyoctanoate, PHO), and polylactic acid (polylactic acid, PLA), or the copolymer of PLA and PGA (polylactic-glycolic acid, PLGA).The blood vessel of such material construction and the affinity of cell are not good enough, moreover are exactly that degradation speed can not be complementary with the reproduction speed of tissue.Novel biodegradation material polyhydroxyalkanoate (PHA) awaits to improve in mechanical properties though all there has been tangible improvement the aspects such as intravascular stent biocompatibility, cell adhesion and degradation speed of preparation with respect to traditional material.
2. preparation method
Best at present engineering blood vessel makes up pattern and does not establish as yet, and as non-degraded polymeric material above-mentioned, traditional method is that material is woven into lamellar earlier, is cut into suitable dimensions then as required.When implanting, flaky material is stitched into tubulose with stitching thread.Since the development of organizational project, the Nondegradable polymeric material has the displaced trend of being degraded property polymeric material gradually, so whether this method for preparing blood vessel is fit to the further check that awaits of novel polymeric material.As for how with the degradability polymeric material earlier for outside be prepared into tubulose, and then implant and carry out cell adhesion, also do not have bibliographical information at present.
Summary of the invention
It is good to the purpose of this invention is to provide a kind of biocompatibility, anticoagulant property, cell adhesion, has proper degradation speed, the intravascular stent that mechanical strength and suture strength are high.Intravascular stent of the present invention is made by polyurethane (PU) and polyhydroxyalkanoate (PHA) blend.This intravascular stent is made of porous inner membrance, solid adventitia and reinforcement, and reinforcement twines with band shape
On the adventitia top layer.
The preparation process that intravascular stent of the present invention is described is as follows:
Preparation method: the present invention is a matrix with poly butyric-valerate (PHB-HV), with polyurethane (PU) blend, introduces the preparation method of blend solid membrane, perforated membrane and reinforcement in detail, and the preparation technology of intravascular stent, and particular content is as follows:
1.PHB-HV/PU the preparation of blend solid membrane
1., with PHB-HV, chloroform mixed (proportion: 1gPHB-HV adds 10~30ml chloroform), heating in water bath, condensation, backflow are mixed with the solution of homogeneous in flask.With PU, oxolane mixed (proportion: 1gPU adds 10~30ml oxolane), heating in water bath, condensation, backflow are mixed with the solution of homogeneous in another flask.
2., pipette PU solution (the quality percentage composition that makes PU is 5%~50%) in proportion, slowly be added drop-wise in the PHB-HV solution, and stir condensing reflux while dripping with pipet.
3., adopt the method for casting film-forming, will pour in the secondary evaporating dish after the solution cooling that prepare in 2., evaporating dish is up and down fastened, and slowly volatilize chloroform and oxolane are inserted whole evaporating dish in the vacuum drying oven afterwards, vacuum drying places in the exsiccator stand-by.
2.PHB-HV/PU the preparation of blend perforated membrane
1., the Sal of buying is crossed standard screen, choose the NaCl particle (particle size range: 50~300 μ m), place in the exsiccator and preserve of diameter between different range.
2., with PHB-HV, chloroform mixed (proportion: 1gPHB-HV adds 10~30ml chloroform), heating in water bath, condensation, backflow are mixed with the solution of homogeneous in flask.With PU, oxolane mixed (proportion: 1gPU adds 10~30ml oxolane), heating in water bath, condensation, backflow are mixed with the solution of homogeneous in another flask.
3., proportionally pipette PU solution (the quality percentage composition that makes PU is 5%~50%), slowly be added drop-wise in the PHB-HV solution, and stir while dripping with pipet.
4., in the solution that obtains in pouring into the NaCl particle that obtains in 1. 3. according to a certain percentage (proportion: 1gPHB-HV adds 10g~30gNaCl particle), continue condensing reflux.
5., adopt the method for casting film-forming, will pour in the secondary evaporating dish after the solution cooling that prepare in 4., evaporating dish fastening up and down, chloroform and oxolane slowly volatilize.
6., take out 5. middle sample, it is immersed deionized water, regularly change water, take out porous chips after a period of time, earlier in indoor seasoning, vacuum drying places in the exsiccator stand-by then.
3.PHB-HV/PU the preparation of blend reinforcement
1., the solid membrane that makes in 1 is cut into the strip (width range: 1~3mm) of certain width with double blade.
2., with rectangular being placed on the hot platform that is heated to uniform temperature that obtains in 1., even heating, then with these rectangular stacking (2~3 layers of the numbers of plies), in adhesion process available chloroform as binding agent to strengthen bonding effect.Place in the exsiccator reinforcement that obtains stand-by.
4. the preparation of intravascular stent
1., according to actual needs the perforated membrane, solid membrane and the reinforcement that make in 1,2,3 being cut out becomes suitable dimensions, places in the exsiccator stand-by.
2., the perforated membrane with suitable dimension lies on the hot platform that is heated to uniform temperature, behind the even heating, with the round paper tube of drafting the intravascular stent diameter perforated membrane is rolled, after rotating a circle, seam crossing is done the binding agent heat bonding with chloroform, obtain the inner membrance of blood vessel.
3., in 2., obtain to such an extent that antipriming pipe is taped against on the solid membrane of same size, solid membrane is rolled, after rotating a circle, seam crossing is done the binding agent heat bonding with chloroform, obtain the complex of adventitia in the blood vessel.
4., on the tubular material that obtains in being wrapped in reinforcement 3., so obtain complete intravascular stent.Can drip a small amount of chloroform on the reinforcement, help bonding.
Description of drawings
Fig. 1. be the structure chart of intravascular stent:
Wherein:
1, outer Lycoperdon polymorphum Vitt is outer solid section
2, internal layer black is the internal layer porous part
3, Dark grey is a reinforcement
The specific embodiment
Embodiment one: diameter is that 8mm, length are the preparation of 50mmPHB-HV/PU intravascular stent
1.PHB-HV/PU the preparation of solid membrane
1., in flask PHB-HV, chloroform are mixed, mixed proportion: 1gPHB-HV adds the 20ml chloroform, and heating in water bath refluxed 15 minutes, was mixed with the solution of homogeneous.In another flask PU, oxolane are mixed, mixed proportion: 1gPU adds the 20ml oxolane, under the heating in water bath, refluxes 15 minutes, is mixed with uniform solution.
2., with pipet proportionally (PU quality percentage composition is 5%) pipette PU solution, slowly be added drop-wise in the PHB-HV solution, and stir condensing reflux 15 minutes while dripping.
3., adopt the method for casting film-forming, with pouring a secondary diameter into after the solution cooling for preparing in 2. is in the 10cm evaporating dish, evaporating dish is up and down fastened, chloroform and oxolane slowly volatilized in 2 day time, afterwards whole evaporating dish is inserted in the vacuum drying oven, vacuum drying 6 hours places in the exsiccator stand-by.
2.PHB-HV/PU the preparation of perforated membrane
1., the Sal of buying is crossed standard screen, choose the NaCl particle of diameter between 150~250 μ m, place in the exsiccator and preserve.
2., in flask PHB-HV, chloroform are mixed, mixed proportion: 1gPHB-HV adds the 20ml chloroform, under the heating in water bath, refluxes 15 minutes, is mixed with the solution of homogeneous.In another flask PU, oxolane are mixed, mixed proportion: 1gPU adds the 20ml oxolane, and heating in water bath refluxed 15 minutes, was mixed with the solution of homogeneous.
3., proportionally pipette PU solution (quality percentage composition 5%), slowly be added drop-wise in the PHB-HV solution, stir while dripping with pipet.
4., with the NaCl particle that obtains in 1. with 1gPHB-HV and PU mixture: the 20ml chloroform: the ratio of 9gNaCl particle is poured in the solution that 3. obtains, and continues condensing reflux.
5., adopting the method for casting film-forming, is in the 10cm evaporating dish with pouring a secondary diameter into after the solution cooling for preparing in 4., and evaporating dish fastening up and down, chloroform and oxolane slowly volatilized in 2 day time.
6., take out 5. in sample, it is immersed deionized water, changed water one time in per 8 hours, soaked 3 days, take out porous chips then, earlier in indoor seasoning, allow dry 1 day of final vacuum, temperature is 37 ℃, places exsiccator interior stand-by.
3.PHB-HV/PU the preparation of reinforcement
1., the solid membrane that makes in 1 is cut into the strip of the wide 1mm of being about with double blade.
2., with rectangular being placed on 115~120 ℃ the hot platform that obtains in 1., even heating, with these rectangular overlapping 3 layers, available chloroform is as binding agent in adhesion process then.Place in the exsiccator reinforcement that obtains stand-by.
4. diameter is 8mm, and length is the preparation of the PHB-HV/PU intravascular stent of 50mm
1., solid membrane standby in 1,2 and perforated membrane are cut into wide for 25mm, longly be the strip of 50mm.
2., the perforated membrane that obtains in 1. being lain on 115~120 ℃ the hot platform, behind the even heating, is that the round paper tube of 8mm is rolled perforated membrane with diameter, after rotating a circle, seam crossing is done the binding agent heat bonding with chloroform, obtains the inner membrance of blood vessel.
3., in 2., obtain to such an extent that antipriming pipe is put on the solid membrane of same size, solid membrane is rolled, after rotating a circle, seam crossing is done the binding agent heat bonding with chloroform, obtain the complex of adventitia in the blood vessel.
4., on the tubular material that obtains in being wrapped in the reinforcement in 3 3., so obtain complete PHB-HV/PU intravascular stent.
Embodiment two: diameter is that 3mm, length are the preparation of 10mmPHB/PU intravascular stent
1.PHB/PU the preparation of solid membrane
The method for preparing the PHB-HV/PU solid membrane among preparation method and the embodiment one is identical, just changes PHB-HV/PU into PHB/PU, and the percentage composition of PU is adjusted to 10%, and the diameter of evaporating dish is adjusted into 6cm.
2.PHB/PU the preparation of perforated membrane
The method for preparing the PHB-HV/PU solid membrane among preparation method and the embodiment one is identical, just changes PHB-HV/PU into PHB/PU, and the percentage composition of PU is adjusted to 10%, and the diameter of evaporating dish is adjusted into 6cm, and the particle diameter of NaCl is adjusted to 200~300 μ m.
3.PHB/PU the preparation of reinforcement
The method for preparing the PHB-HV/PU reinforcement among preparation method and the embodiment one is identical, just changes PHB-HV/PU into PHB/PU.
4. diameter is that 3mm, length are the preparation of 10mm PHB/PU intravascular stent
The method for preparing the PHB-HV/PU intravascular stent among preparation method and the embodiment one is identical, just changes PHB-HV/PU into PHB/PU, and film is cut into the strip of wide 10mm, long 10mm, is that the round paper tube of 3mm is rolled porous chips with diameter.
Embodiment three: diameter is that 12mm, length are the preparation of 100mmPHB-HH/PU intravascular stent
1.PHB-HH/PU the preparation of solid membrane
The method for preparing the PHB-HV/PU solid membrane among preparation method and the embodiment one is identical, just changes PHB-HV/PU into PHB-HH/PU, and the percentage composition of PU is adjusted to 20%, and the diameter of evaporating dish is adjusted into 19cm.
2.PHB-HH/PU the preparation of perforated membrane
The method for preparing the PHB-HV/PU perforated membrane among preparation method and the embodiment one is identical, just change PHB-HV/PU into PHB-HH/PU, the percentage composition of PU is adjusted to 20%, the diameter of evaporating dish is adjusted into 19cm, the particle diameter of NaCl is adjusted to 200~300 μ m.
3.PHB-HH/PU the preparation of reinforcement
The method for preparing the PHB-HV/PU reinforcement among preparation method and the embodiment one is identical, just changes PHB-HV/PU into PHB-HH/PU.
4. diameter is that 12mm, length are the preparation of 100mm PHB-HH/PU intravascular stent
The method for preparing the PHB-HV/PU intravascular stent among preparation method and the embodiment one is identical, just changes PHB-HV/PU into PHB-HH/PU, with film be cut into wide for 38mm, longly be the strip of 100mm, be that the round paper tube of 12mm is rolled porous chips with diameter.
Embodiment four: diameter is that 3mm, length are the preparation of 10mmPHB/PHB-HV/PU intravascular stent
1.PHB/PHB-HV/PU the preparation of solid membrane
The method for preparing the PHB-HV/PU solid membrane among preparation method and the embodiment one is identical, just changes PHB-HV/PU into PHB/PHB-HV/PU, and the percentage composition of PU is adjusted to 30%, and the diameter of evaporating dish is adjusted into 6cm.
2.PHB/PHB-HV/PU the preparation of perforated membrane
The method for preparing the PHB-HV/PU perforated membrane among preparation method and the embodiment one is identical, just changes PHB-HV/PU into PHB/PHB-HV/PU, and the percentage composition of PU is adjusted to 30%, and the diameter of evaporating dish is adjusted into 6cm.
3.PHB/PHB-HV/PU the preparation of reinforcement
The method for preparing the PHB-HV/PU reinforcement among preparation method and the embodiment one is identical, just changes PHB-HV/PU into PHB/PHB-HV/PU.
4. diameter is that 3mm, length are the preparation of 10mmPHB/PHB-HV/PU intravascular stent
The method for preparing the PHB-HV/PU intravascular stent among preparation method and the embodiment one is identical, just changes PHB-HV/PU into PHB/PHB-HV/PU, and film is cut into the strip of wide 10mm, long 10mm, with the round paper tube of diameter 3mm porous chips is rolled.
Embodiment five: diameter is that 8mm, length are the preparation of 50mmPHB/PHB-HH/PU intravascular stent
1.PHB/PHB-HH/PU the preparation of solid membrane
The method for preparing the PHB-HV/PU solid membrane among preparation method and the embodiment one is identical, just changes PHB-HV/PU into PHB/PHB-HH/PU, and the percentage composition of PU is adjusted to 40%, and the diameter of evaporating dish is adjusted into 10cm.
2.PHB/PHB-HH/PU the preparation of perforated membrane
The method for preparing the PHB-HV/PU perforated membrane among preparation method and the embodiment one is identical, just changes PHB-HV/PU into PHB/PHB-HH/PU, and the percentage composition of PU is adjusted to 40%, and the diameter of evaporating dish is adjusted into 10cm.
3.PHB/PHB-HH/PU the preparation of reinforcement
The method for preparing the PHB-HV/PU reinforcement among preparation method and the embodiment one is identical, just changes PHB-HV/PU into PHB/PHB-HH/PU.
4. diameter is that 8mm, length are the preparation of 50mmPHB/PHB-HH/PU intravascular stent
The method for preparing the PHB-HV/PU intravascular stent among preparation method and the embodiment one is identical, just changes PHB-HV/PU into PHB/PHB-HH/PU, and film is cut into the strip of wide 25mm, long 50mm, is that the round paper tube of 8mm is rolled porous chips with diameter.
Embodiment six: diameter is that 10mm, length are the preparation of 50mmPHB-HV/PHB-HH/PU intravascular stent
1.PHB-HV/PHB-HH/PU the preparation of solid membrane
The method for preparing the PHB-HV/PU solid membrane among preparation method and the embodiment one is identical, just changes PHB-HV/PU into PHB-HV/PHB-HH/PU, and the percentage composition of PU is adjusted to 40%, and the diameter of evaporating dish is adjusted into 12cm.
2.PHB-HV/PHB-HH/PU the preparation of perforated membrane
The method for preparing the PHB-HV/PU perforated membrane among preparation method and the embodiment one is identical, just changes PHB-HV/PU into PHB-HV/PHB-HH/PU, and the percentage composition of PU is adjusted to 40%, and the diameter of evaporating dish is adjusted into 12cm.
3.PHB-HV/PHB-HH/PU the preparation of reinforcement
The method for preparing the PHB-HV/PU reinforcement among preparation method and the embodiment one is identical, just changes PHB-HV/PU into PHB-HV/PHB-HH/PU.
4. diameter is that 10mm, length are the preparation of 50mmPHB-HV/PHB-HH/PU intravascular stent
The method for preparing the PHB-HV/PU intravascular stent among preparation method and the embodiment one is identical, just changes PHB-HV/PU into PHB-HV/PHB-HH/PU, and film is cut into the strip of wide 32mm, long 50mm, is that the round paper tube of 10mm is rolled porous chips with diameter.
Embodiment seven: diameter is that 10mm, length are the preparation of 80mmPHB/PHB-HV/PHB-HH/PU intravascular stent
1.PHB/PHB-HV/PU the preparation of solid membrane
The method for preparing the PHB-HV/PU solid membrane among preparation method and the embodiment one is identical, just changes PHB-HV/PU into PHB/PHB-HV/PU, and the percentage composition of PU is adjusted to 50%, and the diameter of evaporating dish is adjusted into 12cm.
2.PHB/PHB-HV/PU the preparation of perforated membrane
The method for preparing the PHB-HV/PU perforated membrane among preparation method and the embodiment one is identical, just changes PHB-HV/PU into PPHB/PHB-HV/PU, and the percentage composition of PU is adjusted to 50%, and the diameter of evaporating dish is adjusted into 12cm.
3.PHB/PHB-HV/PU the preparation of reinforcement
The method for preparing the PHB-HV/PU reinforcement among preparation method and the embodiment one is identical, just changes PHB-HV/PU into PHB/PHB-HV/PU.
4. diameter is that 10mm, length are the preparation of 10mmPHB/PHB-HV/PU intravascular stent
The method for preparing the PHB-HV/PU intravascular stent among preparation method and the embodiment one is identical, just changes PHB-HV/PU into PHB/PHB-HV/PU, and film is cut into the strip of wide 32mm, long 80mm, is that the round paper tube of 10mm is rolled porous chips with diameter.

Claims (2)

1, the intravascular stent that a kind of polyurethane and polyhydroxyalkanoate blend are made, it is characterized in that being made by polyurethane and polyhydroxyalkanoate blend, this intravascular stent is made of porous inner membrance, solid adventitia and reinforcement, and reinforcement is wrapped in the adventitia top layer with band shape.
2, the preparation method of the intravascular stent that a kind of poly butyric-valerate/polyurethane blends is made is characterized in that preparation process is as follows:
1). the preparation of poly butyric-valerate/polyurethane blends solid membrane
1., in flask poly butyric-valerate, chloroform are mixed, proportion: 1g poly butyric-valerate adds 10~30ml chloroform, and heating in water bath, condensation, backflow are mixed with uniform solution; In another flask polyurethane, oxolane are mixed, proportion: 1g polyurethane adds 10~30ml oxolane, and heating in water bath, condensation, backflow are mixed with uniform solution;
2., pipette polyurethane solutions in proportion with pipet, the quality percentage composition that makes polyurethane slowly is added drop-wise in poly butyric-valerate solution 5%~50%, and stirs condensing reflux while dripping;
3., adopt the method for casting film-forming, will pour in the secondary evaporating dish after the solution cooling that prepare in 2., evaporating dish is up and down fastened, and slowly volatilize chloroform and oxolane are inserted whole evaporating dish in the vacuum drying oven afterwards, vacuum drying places in the exsiccator stand-by;
2). the preparation of poly butyric-valerate/polyurethane blends perforated membrane
1., the Sal of buying is crossed standard screen, choose the NaCl particle of diameter between different range, particle size range: 50~300 μ m place in the exsiccator and preserve;
2., in flask poly butyric-valerate, chloroform are mixed, proportion: 1g poly butyric-valerate adds 10~30ml chloroform, and heating in water bath, condensation, backflow are mixed with uniform solution; In another flask polyurethane, oxolane are mixed, proportion: 1g polyurethane adds 10~30ml oxolane, and heating in water bath, condensation, backflow are mixed with uniform solution;
3., proportionally pipette polyurethane solutions with pipet, the quality percentage composition that makes polyurethane slowly is added drop-wise in poly butyric-valerate solution 5%~50%, and stirs while dripping;
4., in the solution that obtains in pouring into the NaCl particle that obtains in 1. 3. according to a certain percentage, proportion: 1g poly butyric-valerate adds 10g~30gNaCl particle, continues condensing reflux;
5., adopt the method for casting film-forming, will pour in the secondary evaporating dish after the solution cooling that prepare in 4., evaporating dish fastening up and down, chloroform and oxolane slowly volatilize;
6., take out 5. middle sample, it is immersed deionized water, regularly change water, take out porous chips after a period of time, earlier in indoor seasoning, vacuum drying places in the exsiccator stand-by then;
3). the preparation of poly butyric-valerate/polyurethane blends reinforcement
1., with 1) in the solid membrane that makes be cut into the strip of certain width, width range: 1~3mm with double blade; 2., rectangularly be placed on the hot platform that is heated to uniform temperature even heating with what obtain in 1., then with these rectangular stacking, 2~3 layers of the numbers of plies, the usefulness chloroform to strengthen bonding effect, places in the exsiccator reinforcement that obtains stand-by as binding agent in adhesion process;
4). the preparation of poly butyric-valerate/polyurethane intravascular stent
1., according to actual needs with 1), 2), 3) in the perforated membrane, solid membrane and the reinforcement that make cut out and become suitable dimensions, place in the exsiccator stand-by;
2., the perforated membrane with suitable dimension lies on the hot platform that is heated to uniform temperature, behind the even heating, with the round paper tube of drafting the intravascular stent diameter perforated membrane is rolled, after rotating a week, seam crossing is done the binding agent heat bonding with chloroform, obtain the inner membrance of blood vessel;
3., the antipriming pipe that obtains in 2. is taped against on the solid membrane of same size, solid membrane is rolled, after rotating a circle, seam crossing is done the binding agent heat bonding with chloroform, obtain the complex of adventitia in the blood vessel;
4., on the tubular material that obtains in being wrapped in reinforcement 3.,, drip a small amount of chloroform on the reinforcement, help bonding so obtain complete intravascular stent.
CNB021534829A 2002-11-29 2002-11-29 Angiosupport made of polyamide and polyhydroxy fatty acid ester comixture and its preparation method Expired - Fee Related CN1223383C (en)

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CN100357343C (en) * 2004-05-19 2007-12-26 清华大学 Method for preparing porous polymer film
CN103933609B (en) * 2014-02-28 2016-06-08 武汉杨森生物技术有限公司 One-time formed polyurethane artificial blood vessel and preparation method thereof
CN115418091B (en) * 2022-09-29 2023-12-08 浙江首康生物科技有限公司 Liquid-transferring gun head material, preparation method thereof and liquid-transferring gun head

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