CN102429749A - Novel processing method for biodegradable stent - Google Patents
Novel processing method for biodegradable stent Download PDFInfo
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- CN102429749A CN102429749A CN2011102191476A CN201110219147A CN102429749A CN 102429749 A CN102429749 A CN 102429749A CN 2011102191476 A CN2011102191476 A CN 2011102191476A CN 201110219147 A CN201110219147 A CN 201110219147A CN 102429749 A CN102429749 A CN 102429749A
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Abstract
The invention provides a novel processing method for a biodegradable stent. The method comprises the following steps of: (1) providing an original tube blank made of a biodegradable raw material, wherein the original tube blank is provided with a preset outer diameter and a preset wall thickness; (2) applying pressure to the original tube blank to prepare a molding tube, wherein blow molding is performed on the original tube blank, so that the material of the original tube blank is highly oriented along the radial direction of the tube blank, or the material of the original tube blank is oriented along the radial direction and the axial direction of the tube blank; and (3) preparing the molding tube into a biodegradable stent. According to the processing method disclosed by the invention, the radial support force of the stent can be enhanced effectively; and moreover, the toughness of the material which is subjected to radial orientation treatment is increased greatly, so that the resilience of the stent can be reduced effectively, and the phenomenon of fracture in the expanding process is avoided.
Description
Technical field
The present invention relates to a kind of processing method that is used for the Biodegradable scaffold of medical application.
Background technology
As the important means of treatment angiostenosis, support has obtained application more and more widely.Present widely used support is metal material, and this support will forever remain in the human body after treatment is accomplished, and this can weaken the MRI or the CT image of blood vessel.In addition, also there are some other shortcomings in metal rack, and for example, it may disturb the formation of surgery myocardial revascularization, obstruction collateral circulation, inhibition blood vessel positivity to reinvent or the like.Based on such problem, Biodegradable scaffold has caused people's extensive concern as possible a kind of alternative solution.Biodegradable scaffold can play the effect of support blood vessels in a short time after implanting lesion locations.After treatment was accomplished, Biodegradable scaffold can be degraded in the human body environment and can be absorbed by the body, metabolic Organic substance, and finally this support can disappear.
The raw material of common Biodegradable scaffold has polymeric material (like polylactic acid, polyglycolic acid, polycaprolactone etc.) and degradable metal material (like magnesium alloy, ferrous alloy etc.).The degradable metal material is difficult to guarantee effective supporting time of support because degradation time is too fast.And biodegradable polymer material (like polylactic acid and copolymer thereof etc.) has been the biological engineering material that can be applicable to human body by the FDA of FDA approval.With the biodegradable polymer material is that the research of raw-material Biodegradable scaffold is present research focus.
The mechanical property of common biodegradable polymer material (like polylactic acid, polyglycolic acid, polycaprolactone etc.) is more weak, and its Young's modulus has only about 0.1-4GPa, and intensity has only 40-80MPa.Because the mechanical strength of material is low, after processing support by these materials, the radial support power of support is less, generally all under 100KPa, thereby is difficult to play the effect of support blood vessels.And the elastic range of these materials makes that greater than traditional metallic stent material the support that is prepared into is higher at the later rebound degree of expansion, and this also is a very big problem.In addition, the plastically deforming area of these materials is little, and poor toughness makes support in process of expansion, occur fracture easily and waits adverse events.
Problem for the support force that solves support; Chinese patent document CN 101925370A (denomination of invention is " support and a manufacturing approach thereof ") has proposed a kind of support manufacturing method; Wherein: earlier Biodegradable material is constituted fiber; The bonding each other or friendship network formation non-woven fabrics with fiber is made support cylindraceous with non-woven fabrics more then.Because fiber has rule or irregular orientation, the support of this method preparation has required rigidity (radial support power) and flexible (compliance).Yet, the support of the method preparation solve the rack elasticity retraction big with the expansion fracture aspect not significantly improvement.And the fiber in this patent documentation can only accomplish along circumferencial direction and axial direction orientation, and can not be orientated along radial direction, makes the radial support power of this support still can not be significantly improved like this.
Summary of the invention
Above-mentioned technical problem in view of prior art the objective of the invention is to develop a kind of processing method of Biodegradable scaffold, so that effectively improve the radial support power of this support.
According to the present invention, a kind of processing method of Biodegradable scaffold is provided, comprise the steps:
Step 1): the original pipe by the biodegradable raw material preparing is provided, and this original pipe has predetermined outer diameter and predetermined wall thickness;
Step 2): said original pipe is exerted pressure; With the preparation shaping pipe; Wherein, Said original pipe is carried out blowing, height-oriented so that the material of said original pipe carries out along the pipe radial direction, perhaps make the material of said original pipe carry out biaxial orientation along pipe radial direction and pipe axial direction; And
Step 3): said shaping pipe is prepared into said Biodegradable scaffold.
Note that here " orientation " is meant a technical term in the materialogy field, it is to instigate the strand in certain material preferential along some direction arrangements.Thereby above-mentioned " making the material of said original pipe carry out height-oriented along the pipe radial direction " is meant and makes the interior strand of material of said original pipe preferentially roughly arrange along radial direction; Above-mentioned " making the material of said original pipe carry out biaxial orientation along pipe radial direction and pipe axial direction " is meant and makes the interior strand of material of said original pipe preferentially roughly arrange along radial direction and this both direction of axial direction.In actual processed; Usually can make the strand in the material roughly radially arrange through making original pipe expand along the expansion of its radial direction, and can through make original pipe along this both direction expansion of its radial direction and axial direction expand make in the material strand roughly radially with axially this both direction arrangement.
Preferably, in the present invention, said step 2) comprise the steps:
Step a): said original pipe is put into the good and on-deformable tubular die of heat conductivity, and the internal diameter of this tubular die is greater than the said predetermined outer diameter of said original pipe;
Step b): said original pipe and said tubular die are heated to system's heating-up temperature; And the inside of said original pipe applied expansion external force; So that said original pipe is being expanded expansion under the said system heating-up temperature and under the effect of said expansion external force, and the tube outer diameter after the said original pipe expansion equals the internal diameter of said tubular die; And
Step c): under the situation that keeps said expansion external force; Make said original pipe and said tubular die be cooled to a system cools temperature rapidly; Remove said expansion external force then, will pass through cooling processing pipe afterwards and from said tubular die, take out, thereby obtain said shaping pipe.
In the present invention, owing to be positioned at the existence of outside tubular die, be in the inner original pipe of tubular die and can not break because of overdistension.And, can be greatly improved through radially modulus, intensity and the toughness of the resulting shaping pipe of above-mentioned steps of the present invention.
Preferably, to above-mentioned procedure of processing 1) in the physical dimension of the original pipe mentioned carry out strictness control can satisfy requirements such as external diameter, wall thickness so that guarantee the physical dimension of last support.Preferably, in the present invention, the ratio of the external diameter of said original pipe and the external diameter of said shaping pipe is between 1: 1.5 to 1: 5, and the ratio of the wall thickness of the wall thickness of said original pipe and said shaping pipe is between 1.5: 1 to 5: 1.
Preferably, in said step b), said system heating-up temperature is higher than the glass transition temperature of the material of said original pipe, and is lower than the melt temperature or the flow temperature of the material of said original pipe.
Preferably, in said step b), when keeping said system heating-up temperature, make said expansion external force keep one period scheduled time.Like this, it is longer to make that tubing carries out time of orientation process, and the degree of orientation of material can be improved, and this helps to obtain the better support of final mechanical property.
Preferably; In said step b); Apply in the process of said expansion external force in inside said original pipe; Said original pipe is being applied in the external force of pipe radial direction, also said original pipe is being applied along the tensile force of pipe axial direction, so that the material of said original pipe carries out biaxial orientation along pipe radial direction and pipe axial direction.
Preferably, in said step c), said system cools temperature is hanged down 20 ℃ or more than the glass transition temperature of the material of said original pipe.
Preferably, in said step b), be blown into gases at high pressure, apply said expansion external force through inside to said original pipe.
Preferably, in said step 1), prepare said original pipe through extrusion method or injection moulding process.
Preferably, in said step 3), said shaping pipe is prepared into said Biodegradable scaffold through laser cutting method.
In a word, through processing method of the present invention, can be so that before tubing be cut into support, it is height-oriented that pipe material is radially carried out, and material is in the radial direction the height-oriented radial support power that can improve support effectively.And the toughness of the material after the radial oriented processing of process also can increase greatly, thereby also can effectively reduce the resilience of support and the phenomenon of rupture in the process of expansion.
Description of drawings
In order to be illustrated more clearly in the technical scheme of the embodiment of the invention, the accompanying drawing of required use is done to introduce simply in will describing embodiment below.It is obvious that, and the accompanying drawing in describing below only is some specific embodiments of putting down in writing among the application, and it is not the restriction to protection scope of the present invention.For those of ordinary skills, under the prerequisite of not paying creative work, can also obtain some other embodiment and accompanying drawing according to these embodiment of the present invention and accompanying drawing thereof certainly.
Fig. 1 shows the perspective view of original according to an embodiment of the invention pipe and outer tubular mould.
Fig. 2 shows the cross sectional representation of original pipe and the outer tubular mould of Fig. 1.
Fig. 3 show according to the present invention the physical dimension of the original pipe before handling and handle according to the present invention after the comparison sketch map of physical dimension of shaping pipe.
Fig. 4 shows the structural representation of the support that is cut out by shaping pipe.
The specific embodiment
In order to make those skilled in the art understand the technical scheme among the application better, will combine the accompanying drawing in the embodiment of the invention below, the technical scheme in the embodiment of the invention is carried out clear, intactly description.Obviously, described embodiment only is the application's part embodiment, rather than whole embodiment.Based on the described specific embodiment of the application, all other embodiment that those of ordinary skills are obtained under the prerequisite of not making creative work should drop within the concept of the present invention.
The present invention provides a kind of processing method that is used for the Biodegradable scaffold of medical application generally, through this processing method, can effectively improve the radial support power of this support.
As previously mentioned, the raw material of common Biodegradable scaffold has polymeric material and degradable metal material.The degradation time of degradable metal material is too fast, is difficult to guarantee effective supporting time of support.The degradation time of biodegradable polymer material is then long than metal material.So support of the present invention mainly considers to use the Biodegradable polymeric material to constitute.
Describe the preferred embodiments of the present invention in detail below with reference to Fig. 1～Fig. 4.
Fig. 1 shows the perspective view of original according to an embodiment of the invention pipe and outer tubular mould, and wherein 1 representes original pipe, 2 expression tubular dies.Fig. 2 is the cross sectional representation of original pipe and the outer tubular mould of Fig. 1, and wherein 1 representes original pipe, 2 expression tubular dies, and A representes the expansion external force that pipe receives.Fig. 3 show according to the present invention the physical dimension of the original pipe before handling and handle according to the present invention after the comparison sketch map of physical dimension of shaping pipe; The external diameter of the original pipe before wherein handling according to the present invention is that the wall thickness of R1, original pipe is T1, and the external diameter of the shaping pipe after handling according to the present invention be the wall thickness of R2, shaping pipe is T2.As can beappreciated from fig. 3, R2＞R1, T2＜T1.Fig. 4 then shows the structural representation of the support that is cut out by shaping pipe.
The core idea of the processing method of Biodegradable scaffold of the present invention is: before biodegradable polymer tubing is cut into support; Earlier tubing is carried out blowing; So that pipe material is height-oriented along radially carrying out, perhaps along the radial and axial double-shaft radial that carries out.
The concrete steps of method of the present invention comprise:
1. at first the biodegradable raw material is prepared into the original pipe 1 that external diameter is less, wall thickness is bigger through the method for extruding perhaps injection moulding.Original pipe 1 has been shown among Fig. 1～Fig. 2.
2. original pipe 1 is put into the good and on-deformable tubular die 2 of heat conductivity, the internal diameter of tubular die 2 equals the aimed dia of tubing.Also show tubular die 2 among Fig. 1～Fig. 2.
3. the processing system that has comprised original pipe 1 and tubular die 2 is heated, and, make original pipe 1 that expanse take place under the effect of high temperature and external force being blown into gases at high pressure in the original pipe 1 or applying external force with additive method.Fig. 3 shows this expanse.Because the existence of outside tubular die 2, original pipe can not break because of overdistension.The external diameter of the shaping pipe 3 after the expansion equals the internal diameter of tubular die 2.
4. keep under the situation of external force the entire process system being cooled off rapidly, remove external force then, cooled tubing is taken out from tubular die 2, promptly obtain the shaping pipe 3 that radially modulus, intensity and toughness increase substantially.
5. shaping pipe 3 perhaps is prepared into support with other method through cut.Fig. 4 shows the support that cuts out.
For the original pipe 1 that above-mentioned procedure of processing is mentioned in 1., its physical dimension is preferably carried out strictness control, can satisfy requirements such as external diameter, wall thickness with the physical dimension that guarantees last support.The ratio of the external diameter of general original pipe 1 and shaping pipe 3 can be chosen as between 1: 1.5 to 1: 5, and the ratio of the wall thickness of the wall thickness of original pipe 1 and shaping pipe 3 can be chosen as between 1.5: 1 to 5: 1.
System's heating-up temperature about above-mentioned procedure of processing is mentioned in 3. is typically chosen in the glass transition temperature of the material that is higher than original pipe 1, and is lower than the melt temperature or the flow temperature of original pipe 1.
Above-mentioned procedure of processing 3. in, also can under the condition that keeps system's heating-up temperature, keep expansion one period scheduled time of external force.Like this, the orientation process time of tubing is longer, and the degree of orientation of material can be further enhanced, and helps to obtain the better support of final mechanical property.
Above-mentioned procedure of processing 3. in, when original pipe 1 is applied the external force of an expanded radially, can apply a tensile force vertically, thereby tubing is realized along radial and axial double orientation original pipe 1.
Above-mentioned procedure of processing 4. in, the temperature in processing system when cooling preferably is lower than 20 ℃ of the glass transition temperatures of material of original pipe 1 or more.
Useful technique effect of the present invention is described below:
The radial support power of the support that technical method according to the present invention is prepared into can reach more than the 100KPa, and the rebound degree after the support expansion can be controlled in 5%, and support is not easy to occur fracture in process of expansion.Like this, behind the support implant into body, support is support blood vessels effectively at the lesion locations place, and struts the back and be difficult for rupturing, bouncing back and be shifted.In addition, this method only relates to the preparation for processing of support is innovated, and does not change the raw material of support, thereby the biological safety of support is had no influence.
Below adopt two instances of concrete parametric description processing method of the present invention.
Instance one:
The material of the rack body of choosing in this instance one is biodegradable macromolecular material polylactic acid.Through the method for extruding, polylactic acid is extruded into the pipe of external diameter 1mm, wall thickness 0.35mm.This pipe is put into the rustless steel sleeve pipe that internal diameter is 3mm.The one end sealing of polylactic acid pipe, the other end and high-pressure gas circuit join.Then; To comprise that pipe and telescopic whole system all are heated to 80 ℃; In pipe, charging into pressure is the high pressure nitrogen of 200PSI (pound/square inch) (being 1.379MPa); With pipe axial tension 10mm, pipe expands, is drawn into the tubing of external diameter 3mm, wall thickness 0.15mm under high temperature, high pressure simultaneously.With the rapid cool to room temperature of system, lay down high pressure then, with tubing from outer mold, be that the medium and small heart of rustless steel sleeve pipe is taken out.Then, through cut, cut into support shown in Figure 4 to tubing.
The support pressure that preparation is accomplished is held on the suitable sacculus, and the diameter of holding after-poppet in pressure is 1.4mm.Then, in 37 ℃ normal saline, be expanded to 3.0mm to support with the mode of balloon expandable.The process of expansion medium-height trestle ruptures.After sacculus returned and removes, the rebound degree of measurement bracket was 4%.Measure the support force of the support after expanding, the power of being supported is 115-120KPa.
To hold on the suitable sacculus with pressing, be transported to the narrow positions of blood vessel then, and fill sacculus with expandable stent, thereby strut narrow blood vessel, strut the fracture of not observing support in the process with the support of quadrat method preparation.After the sacculus pumpback, angiography is observed blood vessel and is still strutted by support, and the adverse events that support subsides does not take place in the whole surgery process.Can't see support when carrying out Clinical Follow-up through intravascular ultrasound after 2 years, this explanation rack body material is degraded fully, and restenosis phenomenon and inflammatory reaction do not appear in the diseased region of implant frame.
Instance two:
The material of the rack body of choosing in this instance two is the copolymer of biodegradable macromolecular material polylactic acid-glycolic guanidine-acetic acid.Through the method for injection moulding, polylactic acid-glycolic guanidine-acetic acid copolymer is injection molded into the pipe of external diameter 1.5mm, wall thickness 0.4mm.This pipe is put into the rustless steel sleeve pipe that internal diameter is 2.5mm.Simultaneously, put into an elastic tube in pipe inside, the elastic tube that for example forms by polyamide pipe or polyether block amide tubing, wherein, and the sealing of an end of elastic tube, the other end and high-pressure gas circuit join.Then, will comprise that the whole system of sleeve pipe, pipe and elastic tube all is heated to 113 ℃, in elastic tube, feed the gases at high pressure of 480PSI (being 3.3096MPa), simultaneously the tensile elasticity pipe.Pipe is expanded, and pipe expand into the tubing of external diameter 2.5mm, wall thickness 0.2mm under the expansion pressure of high temperature and elastic tube.System is cooled to 15 ℃ rapidly, lays down high pressure, then the elastic tube of the inside is taken away, tubing carefully from outer mold, be to take out the rustless steel sleeve pipe.Through cut, cut into tubing on the support of screw type.
The support pressure that preparation is accomplished is held on the suitable sacculus, and the diameter of holding after-poppet in pressure is 1.5mm.Then, in 37 ℃ normal saline, be expanded to 2.8mm to support with the mode of balloon expandable.The process of expansion medium-height trestle ruptures.After sacculus returned and removes, the rebound degree of measurement bracket was 3%.Measure the support force of the support after expanding, the power of being supported is about 120KPa.
Will be with being transported to the narrow positions of blood vessel through the sacculus induction system with the support of quadrat method preparation, the mode with balloon expandable struts support then, thereby supports narrow blood vessel.Do not observe the fracture of support in the operation process.After the sacculus pumpback, angiography is observed blood vessel and is still strutted by support.The adverse events that support subsides does not take place in the whole surgery process.Can't see support when carrying out Clinical Follow-up through intravascular ultrasound after 18 months, this explanation rack body material is degraded fully, and restenosis phenomenon and inflammatory reaction do not appear in the diseased region of implant frame.
The above only is some specific embodiments of the application.Should be understood that; For those skilled in the art; Under the prerequisite that does not break away from the application's inventive principle and inventive concept; Can also carry out various combinations or make some improvement and modification the foregoing description, these combinations, improvement and modification also should be regarded as dropping within the application's the protection domain and inventive concept.
Claims (10)
1. the processing method of a Biodegradable scaffold comprises the steps:
Step 1): the original pipe by the biodegradable raw material preparing is provided, and this original pipe has predetermined outer diameter and predetermined wall thickness;
Step 2): said original pipe is exerted pressure; With the preparation shaping pipe; Wherein, Said original pipe is carried out blowing, height-oriented so that the material of said original pipe carries out along the pipe radial direction, perhaps make the material of said original pipe carry out biaxial orientation along pipe radial direction and pipe axial direction; And
Step 3): said shaping pipe is prepared into said Biodegradable scaffold.
2. the processing method of Biodegradable scaffold according to claim 1 is characterized in that:
Said step 2) comprises the steps:
Step a): said original pipe is put into the good and on-deformable tubular die of heat conductivity, and the internal diameter of this tubular die is greater than the said predetermined outer diameter of said original pipe;
Step b): said original pipe and said tubular die are heated to system's heating-up temperature; And the inside of said original pipe applied expansion external force; So that said original pipe is being expanded expansion under the said system heating-up temperature and under the effect of said expansion external force, and the tube outer diameter after the said original pipe expansion equals the internal diameter of said tubular die; And
Step c): under the situation that keeps said expansion external force; Make said original pipe and said tubular die be cooled to a system cools temperature rapidly; Remove said expansion external force then, will pass through cooling processing pipe afterwards and from said tubular die, take out, thereby obtain said shaping pipe.
3. the processing method of Biodegradable scaffold according to claim 1 and 2 is characterized in that:
The ratio of the external diameter of said original pipe and the external diameter of said shaping pipe is between 1: 1.5 to 1: 5, and the ratio of the wall thickness of the wall thickness of said original pipe and said shaping pipe is between 1.5: 1 to 5: 1.
4. the processing method of Biodegradable scaffold according to claim 2 is characterized in that:
In said step b), said system heating-up temperature is higher than the glass transition temperature of the material of said original pipe, and is lower than the melt temperature or the flow temperature of the material of said original pipe.
5. the processing method of Biodegradable scaffold according to claim 2 is characterized in that:
In said step b), when keeping said system heating-up temperature, make said expansion external force keep one period scheduled time.
6. the processing method of Biodegradable scaffold according to claim 2 is characterized in that:
In said step b); Apply in the process of said expansion external force in inside said original pipe; Said original pipe is being applied in the external force of pipe radial direction; Also said original pipe is applied along the tensile force of pipe axial direction, so that the material of said original pipe carries out biaxial orientation along pipe radial direction and pipe axial direction.
7. the processing method of Biodegradable scaffold according to claim 2 is characterized in that:
In said step c), said system cools temperature is hanged down 20 ℃ or more than the glass transition temperature of the material of said original pipe.
8. the processing method of Biodegradable scaffold according to claim 2 is characterized in that:
In said step b), be blown into gases at high pressure through inside to said original pipe, apply said expansion external force.
9. the processing method of Biodegradable scaffold according to claim 1 and 2 is characterized in that:
In said step 1), prepare said original pipe through extrusion method or injection moulding process.
10. the processing method of Biodegradable scaffold according to claim 1 and 2 is characterized in that:
In said step 3), said shaping pipe is prepared into said Biodegradable scaffold through laser cutting method.
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| CN2011102191476A CN102429749A (en) | 2011-07-27 | 2011-07-27 | Novel processing method for biodegradable stent |
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| CN2011102191476A CN102429749A (en) | 2011-07-27 | 2011-07-27 | Novel processing method for biodegradable stent |
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| CN103876869A (en) * | 2012-12-21 | 2014-06-25 | 上海微创医疗器械（集团）有限公司 | Production method of biodegradable polymer support |
| CN105148331A (en) * | 2015-07-24 | 2015-12-16 | 山东华安生物科技有限公司 | Method for producing completely biodegradable intravascular stent and produced intravascular stent |
| CN106361465A (en) * | 2015-07-17 | 2017-02-01 | 上海微创医疗器械（集团）有限公司 | Manufacture method for degradable tube and degradable stent |
| CN106668959A (en) * | 2017-01-06 | 2017-05-17 | 上海君联医疗设备有限公司 | Method for preparing polymer PALL pipes applicable to human body implant brackets |
| CN108814781A (en) * | 2015-02-16 | 2018-11-16 | 上海微创医疗器械（集团）有限公司 | Biodegradable stent and preparation method thereof |
| CN111231383A (en) * | 2020-01-20 | 2020-06-05 | 东南大学泰州生物医药与医疗器械研究院 | Medical thin-walled tube continuous forming equipment and polylactic acid thin-walled tube forming method |
| WO2023160440A1 (en) * | 2022-02-25 | 2023-08-31 | 浙江脉通智造科技(集团)有限公司 | Preparation method for heat-shrinkable tube |
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| CN103876869A (en) * | 2012-12-21 | 2014-06-25 | 上海微创医疗器械（集团）有限公司 | Production method of biodegradable polymer support |
| WO2014094652A1 (en) * | 2012-12-21 | 2014-06-26 | 上海微创医疗器械（集团）有限公司 | Method for preparing biodegradable polymer frame |
| CN106618820A (en) * | 2012-12-21 | 2017-05-10 | 上海微创医疗器械（集团）有限公司 | Method for preparing biodegradable polymer scaffold |
| CN108016023A (en) * | 2012-12-21 | 2018-05-11 | 上海微创医疗器械（集团）有限公司 | A kind of preparation method of polylactide and its copolymer stent |
| CN108814781A (en) * | 2015-02-16 | 2018-11-16 | 上海微创医疗器械（集团）有限公司 | Biodegradable stent and preparation method thereof |
| CN106361465A (en) * | 2015-07-17 | 2017-02-01 | 上海微创医疗器械（集团）有限公司 | Manufacture method for degradable tube and degradable stent |
| CN106361465B (en) * | 2015-07-17 | 2018-11-13 | 上海微创医疗器械（集团）有限公司 | A kind of manufacturing method of degradable pipe and biodegradable stent |
| CN105148331A (en) * | 2015-07-24 | 2015-12-16 | 山东华安生物科技有限公司 | Method for producing completely biodegradable intravascular stent and produced intravascular stent |
| CN105148331B (en) * | 2015-07-24 | 2018-03-30 | 山东华安生物科技有限公司 | A kind of method for producing fully biodegradable intravascular stent and thus obtained intravascular stent |
| CN106668959A (en) * | 2017-01-06 | 2017-05-17 | 上海君联医疗设备有限公司 | Method for preparing polymer PALL pipes applicable to human body implant brackets |
| CN111231383A (en) * | 2020-01-20 | 2020-06-05 | 东南大学泰州生物医药与医疗器械研究院 | Medical thin-walled tube continuous forming equipment and polylactic acid thin-walled tube forming method |
| WO2023160440A1 (en) * | 2022-02-25 | 2023-08-31 | 浙江脉通智造科技(集团)有限公司 | Preparation method for heat-shrinkable tube |
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