CN103876869A - Production method of biodegradable polymer support - Google Patents
Production method of biodegradable polymer support Download PDFInfo
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- CN103876869A CN103876869A CN201210563632.XA CN201210563632A CN103876869A CN 103876869 A CN103876869 A CN 103876869A CN 201210563632 A CN201210563632 A CN 201210563632A CN 103876869 A CN103876869 A CN 103876869A
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- tubing
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- biodegradable polymer
- original tube
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
- A61F2/00—Filters implantable into blood vessels; Prostheses, i.e. artificial substitutes or replacements for parts of the body; Appliances for connecting them with the body; Devices providing patency to, or preventing collapsing of, tubular structures of the body, e.g. stents
- A61F2/82—Devices providing patency to, or preventing collapsing of, tubular structures of the body, e.g. stents
- A61F2/86—Stents in a form characterised by the wire-like elements; Stents in the form characterised by a net-like or mesh-like structure
- A61F2/90—Stents in a form characterised by the wire-like elements; Stents in the form characterised by a net-like or mesh-like structure characterised by a net-like or mesh-like structure
- A61F2/91—Stents in a form characterised by the wire-like elements; Stents in the form characterised by a net-like or mesh-like structure characterised by a net-like or mesh-like structure made from perforated sheet material or tubes, e.g. perforated by laser cuts or etched holes
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
- A61F2/00—Filters implantable into blood vessels; Prostheses, i.e. artificial substitutes or replacements for parts of the body; Appliances for connecting them with the body; Devices providing patency to, or preventing collapsing of, tubular structures of the body, e.g. stents
- A61F2/82—Devices providing patency to, or preventing collapsing of, tubular structures of the body, e.g. stents
- A61F2/86—Stents in a form characterised by the wire-like elements; Stents in the form characterised by a net-like or mesh-like structure
- A61F2/90—Stents in a form characterised by the wire-like elements; Stents in the form characterised by a net-like or mesh-like structure characterised by a net-like or mesh-like structure
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C71/00—After-treatment of articles without altering their shape; Apparatus therefor
- B29C71/0063—After-treatment of articles without altering their shape; Apparatus therefor for changing crystallisation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C71/00—After-treatment of articles without altering their shape; Apparatus therefor
- B29C71/0072—After-treatment of articles without altering their shape; Apparatus therefor for changing orientation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C71/00—After-treatment of articles without altering their shape; Apparatus therefor
- B29C71/02—Thermal after-treatment
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
- A61F2210/00—Particular material properties of prostheses classified in groups A61F2/00 - A61F2/26 or A61F2/82 or A61F9/00 or A61F11/00 or subgroups thereof
- A61F2210/0004—Particular material properties of prostheses classified in groups A61F2/00 - A61F2/26 or A61F2/82 or A61F9/00 or A61F11/00 or subgroups thereof bioabsorbable
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
- A61F2240/00—Manufacturing or designing of prostheses classified in groups A61F2/00 - A61F2/26 or A61F2/82 or A61F9/00 or A61F11/00 or subgroups thereof
- A61F2240/001—Designing or manufacturing processes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C71/00—After-treatment of articles without altering their shape; Apparatus therefor
- B29C71/02—Thermal after-treatment
- B29C2071/022—Annealing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C49/00—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor
- B29C49/0005—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor characterised by the material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C49/00—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor
- B29C49/02—Combined blow-moulding and manufacture of the preform or the parison
- B29C49/04—Extrusion blow-moulding
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
- B29K2995/0037—Other properties
- B29K2995/0059—Degradable
- B29K2995/006—Bio-degradable, e.g. bioabsorbable, bioresorbable or bioerodible
Abstract
The invention provides a production method of a biodegradable polymer support. The method includes 1, producing a biodegradable polymer original pipe through biodegradable polymer material; 2, placing the original pipe into a tubular die and heating, injecting high-pressure gas into the original pipe, allowing the original pipe to realize height orientation radially, and axially drawing the original pipe along the axial direction of the original pipe to realize simultaneously radial and axial orientation of the original pipe; 3, annealing the pipe, expanded by blowing, at the annealing temperature to obtain a formed pipe; 4, producing the biodegradable polymer support through the formed pipe. The annealing temperature is higher than the glass transition temperature of the polymer material and is lower than the melting temperature of the polymer material. The immediate support capacity of the support is high, breakage occurs rarely, the inner stress of the pipe can be released effectively, and accordingly service lives of the support and shelves can be prolonged.
Description
Technical field
The present invention relates to a kind of preparation method of the biodegradable polymer support for medical application.
Background technology
Support has obtained more and more wide application as the important apparatus for the treatment of angiostenosis in cardiovascular disease field.For being widely used at present clinical metal rack, because it will forever retain in human body after completed treatment task, weaken MRI coronarius or CT image, disturb surgery myocardial revascularization, hinder the formation of collateral circulation, the defect such as suppress that blood vessel positivity is reinvented so exist.Based on these problems, Biodegradable scaffold has caused people's extensive concern as possible a kind of alternative solution.
Biodegradable scaffold is made up of degradable polymer material or metal material.Implanting after diseased region, the effect that Biodegradable scaffold can play support blood vessels in a short time, realizes myocardial revascularization.After treatment completes, Biodegradable scaffold can be degraded into and can be absorbed by the body in human body environment, the Organic substance of metabolism, and finally this support can disappear.
Common can be used for degradable polymer material prepared by support and have polylactic acid, polyglycolic acid, polycaprolactone etc.; Common can be used for degradable metal material prepared by support and have magnesium alloy, ferrous alloy etc.But, in application process, to find, degradable metal material, because degradation time is too fast, is difficult to guarantee effective supporting time of support.And biodegradable polymer material (as polylactide and its copolymer etc.) is approved as by the FDA of FDA the biological engineering material that can be applicable to human body.Research take biodegradable polymer material as raw-material Biodegradable scaffold is current study hotspot.
A little less than the mechanical performance compare of common biodegradable polymer material (as polylactic acid, polyglycolic acid, polycaprolactone etc.), its Young's modulus only has 0.1-4GPa left and right, and intensity only has 40-80MPa.Because the mechanical strength of material is low, so the radial support power of the support of being made up of these materials is less, be difficult to play the effect of support blood vessels.And the elastic range of these materials is greater than traditional metallic stent material, make the support that the is prepared into rebound degree after expansion higher, this is also a very large problem.In addition, the plastically deforming area of these materials is little, and poor toughness makes support in process of expansion, easily occur the adverse events such as fracture.
In addition, because support must experience the storage of regular period, the short application that also can affect support of support shelf life after preparation completes.
In order to solve the support force of support and the problem of toughness, american documentation literature US8012402 carries out inflation to the original polymer tubing of preparing support more than glass transition temperature, to obtain the tubing of high-crystallinity, the support that the cutting of this tubing obtains is owing to having realized orientation radially, so support force is greatly improved.But, because tubing can not form perfect crystallizing system in the process of this short period of inflation, and tubing is inner when quenching after inflation completes can residual more internal stress, so cause support easily to rupture.
In addition, american documentation literature US20110260352 proposes in the time solving the physically aged of support, to after the support cooling of tubing cutting after the tubing after inflation or inflation, be elevated to again one higher than room temperature, lower than the temperature of the glass transition temperature of material, to improve the degree of crystallinity of tubing, slow down the physically aged of tubing in storing process.But, to find after deliberation, the technological merit of above-mentioned treatment effect not obvious, cannot slow down the physically aged of material, still easily ruptures with the method support after treatment.
Summary of the invention
In view of the above-mentioned technical problem of prior art, the object of the invention is to develop a kind of preparation method of biodegradable polymer support, make the support force at once of the biodegradable polymer support of preparing high, difficult fracture, and the internal stress of tubing can effectively be discharged, thereby can improve the shelf life of support.
According to the present invention, a kind of preparation method of biodegradable polymer support is provided, comprise the steps:
Step 1): prepare biodegradable polymer original tube by biodegradable polymer material;
Step 2): the original tube of preparing in described step 1) is put into tubular die, described original tube is heated, and inject gases at high pressure in described original tube, with original tube described in the radial direction inflation along described original tube, to make the external diameter of tubing after inflation equal the internal diameter of described tubular die, make tubing can realize height-oriented in radial direction; And, before described radial direction inflation tubing, in described radial direction inflation tubing or after described radial direction inflation tubing, axial direction along tubing carries out axial tension to tubing, is orientated in described radial direction and described axial direction to realize tubing;
Step 3): tubing after inflation is annealed under annealing temperature, and to obtain shaping pipe, wherein said annealing temperature is higher than the glass transition temperature of polymeric material and lower than the melt temperature of polymeric material;
Step 4): the shaping pipe obtaining in described step 3) is prepared into described biodegradable polymer support.
Note that " orientation " here refers to a technical term in materialogy field, it is to instigate the strand in certain material preferentially to be arranged along some directions.Thereby above-mentioned " making tubing can realize height-oriented in radial direction " refers to that the strand in the material that makes described tubing preferentially roughly arranges along radial direction; Above-mentioned " realize tubing is orientated in described radial direction and described axial direction " refers to that strand in the material that makes described tubing preferentially roughly arranges along described radial direction and this both direction of described axial direction.In actual processed, conventionally can be by making tubing expand the strand in material is roughly radially arranged along the expansion of its radial direction, and can the strand in material roughly radially be arranged with this both direction of axial direction by making tubing expand and stretch along its radial direction and this both direction expansion of axial direction.
At once the support force of the biodegradable stent obtaining by said method of the present invention is high, difficult fracture, and owing to having formed more perfect crystallizing system, the internal stress of tubing is also effectively discharged, so also have positive effect for the shelf life that improves support.
Preferably, the biodegradable polymer material in described step 1) is polylactic acid, polyglycolic acid, polycaprolactone, polydioxanone, poly-anhydride, tyrosine Merlon or its copolymer or blend.According to the difference of the material of selecting, the degradation cycle of described support in human body can be one month to 3 years, and user can select arbitrarily according to demand separately.
Preferably, the original tube obtaining in described step 1) is amorphous tubing, and the degree of crystallinity of this amorphous tubing is lower than 20%.
Preferably, described step 2) comprise the steps:
Step is a): described original tube is put into the good and on-deformable described tubular die of heat conductivity;
Step b): described original tube and described tubular die are heated to orientation temperature, this orientation temperature is higher than the glass transition temperature of polymeric material and lower than the melt temperature of polymeric material, thereby and apply expansion pressure to the inside injection gases at high pressure of described original tube to described original tube, with original tube described in the radial direction inflation along described original tube; And, before described radial direction inflation tubing, in described radial direction inflation tubing or after described radial direction inflation tubing, along the axial direction of tubing, tubing is carried out to axial tension;
Step c): tubing is kept to the expansion pressure in step b), the mode by water-cooled or air cooling to inflation after tubing and described tubular die lower the temperature rapidly so that it is cooled to below the glass transition temperature of polymeric material; Then, remove described expansion pressure, take out tubing after described inflation.
Preferably, the annealing in described step 3) refers to places one period of scheduled time by tubing after described inflation under described annealing temperature, and this scheduled time is 5 minutes ~ 24 hours.
Preferably, in described step 3), after to described inflation tubing anneal before after described inflation the inside of tubing place lining core, then after annealing completes, the inside of described lining core tubing from described inflation is taken out.The use of lining core can prevent tubing size generation atrophy in annealing process.
Preferably, in described step 4), described shaping pipe is prepared into described biodegradable polymer support by cut; Or after being cut into strip material, described shaping pipe is woven into described biodegradable polymer support.
Preferably, in described step b), before described original tube and described tubular die are heated to described orientation temperature, under preheat temperature, described original tube is carried out to preheating, described preheat temperature is higher than the glass transition temperature of polymeric material.Preferably, described preheat temperature is lower than glass transition temperature and 20 ℃ of sums of polymeric material.The growth of nucleus be conducive to polymer under this temperature range in, and be unfavorable for that the size of crystal increases, be conducive to like this form a large amount of small size crystal, when contributing to tubing intensity and toughness, improve.
Preferably, described step b) in, the resistance wire that utilization is wrapped on described tubular die heats, or utilizes the gases at high pressure of the inside of injecting described original tube to heat, thereby described original tube and described tubular die are heated to described orientation temperature.
Preferably, described step b) in, after described original tube and described inflation, the external diameter of tubing is than between 1:1.5 and 1:5; After described original tube and described inflation, the wall ratio of tubing is between 1.5:1 and 5:1; And after described original tube and described inflation, the Length Ratio of tubing is between 1:1 and 1:2.
Preferably, in described step b), in keeping described orientation temperature, make described expansion pressure keep one period of scheduled time, this scheduled time is between 2 seconds and 10 minutes.Can make like this tubing fully be orientated under said temperature and pressure, to improve the mechanical property of final support.
Preferably, in described step c), tubing after described inflation and described tubular die are cooled to rapidly lower than at least 20 ℃ of the glass transition temperatures of polymeric material.
By preparation method of the present invention, can make tubing before cutting into support, in radial and axial direction, realize height-orientedly, material is greatly improved in radial and axial intensity and toughness.And, by the annealing of certain hour, form perfect crystallizing system, and discharged the internal stress of tubing, effectively improve support in support force and toughness at once and after storage, reduce the phenomenon of rupture in retraction and the process of expansion of support.
At once and more than the support radial support power of storage after 3 months all can reach 120KPa of the support that technical method according to the present invention is prepared into, the relaxation shrinkage after support expansion can be controlled in 5%, and support is not easy to occur fracture in process of expansion.In addition, this method of the present invention only relates to the preparation for processing of support to innovate, and does not change the raw material of support, thus on the biological safety of support without any impact.
Accompanying drawing explanation
In order to be illustrated more clearly in the technical scheme of the embodiment of the present invention, below the accompanying drawing of required use during embodiment is described is briefly described.It is evident that, the accompanying drawing in the following describes is only some specific embodiments of recording in the application, and it is not the restriction to protection scope of the present invention.For those of ordinary skills, do not paying under the prerequisite of creative work, certainly can also obtain some other embodiment and accompanying drawing according to these embodiment of the present invention and accompanying drawing thereof.
Fig. 1 is the schematic diagram of cutting open along the longitudinal axis of tubular die and original tube, and it shows the original tube of putting into tubular die.
Fig. 2 is the schematic diagram of cutting open along the longitudinal axis of tubing after tubular die and inflation, and it shows the situation of original tube after by inflation, and wherein the arrow in figure represents respectively the power that tubing is subject at radial direction and axial direction.
Fig. 3 shows the structure chart of the support that the present invention finally obtains.
Description of reference numerals:
1 represents tubular die, and 2 represent original tube, and 3 represent tubing after inflation, and 4 represent final biodegradable polymer support.
The specific embodiment
In order to make those skilled in the art understand better the technical scheme in the application, below in conjunction with the accompanying drawing in the embodiment of the present invention, the technical scheme in the embodiment of the present invention is clearly and completely described.Obviously, described embodiment is only the application's part embodiment, rather than whole embodiment.Based on the specific embodiment described in the application, all other embodiment that those of ordinary skills obtain under the prerequisite of not making creative work, within should dropping on design scope of the present invention.
The present invention provides a kind of preparation method of the biodegradable polymer support for medical application generally.
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 long than metal material.So support of the present invention mainly considers to use Biodegradable polymeric material to form.
Describe the preferred embodiments of the present invention in detail below with reference to Fig. 1～Fig. 3.
The present invention provides a kind of preparation method of biodegradable polymer support generally, comprises the steps:
Step 1): prepare biodegradable polymer original tube 2 by biodegradable polymer material;
Step 2): the original tube of preparing in described step 1) 2 is put into tubular die 1 (as shown in Figure 1, original tube 2 is inserted in the endoporus of tubular die 1), described original tube 2 is heated, and to the interior injection gases at high pressure of described original tube 2, with original tube 2 described in the radial direction inflation along described original tube 2, to make the external diameter of tubing 3 after inflation equal the internal diameter (as shown in Figure 2) of described tubular die 1, make tubing can realize height-oriented in radial direction; And, can before described radial direction inflation tubing, carry out axial tension along the axial direction of tubing to tubing, or can be tubing being carried out to axial tension along the axial direction of tubing in described radial direction inflation tubing, or can after described radial direction inflation tubing, carry out axial tension along the axial direction of tubing to tubing, be orientated in described radial direction and described axial direction to realize tubing;
Step 3): tubing after inflation 3 is annealed under annealing temperature, and to obtain shaping pipe, wherein said annealing temperature is higher than the glass transition temperature Tg of polymeric material and lower than the melt temperature Tm of polymeric material;
Step 4): the shaping pipe obtaining in described step 3) is prepared into described biodegradable polymer support.Final biodegradable polymer support 4 has been shown in Fig. 3.
The biodegradable stent obtaining by said method of the present invention not only support force is at once high, difficult fracture, and owing to having formed more perfect crystallizing system, the internal stress of tubing is also effectively discharged, so have positive effect for the shelf life that improves support.
Preferably, the biodegradable polymer material in described step 1) is polylactic acid, polyglycolic acid, polycaprolactone, polydioxanone, poly-anhydride, tyrosine Merlon or its copolymer or blend.According to the difference of the material of selecting, the degradation cycle of final biodegradable polymer support 4 in human body can be one month to 3 years, and user can select arbitrarily according to demand separately.
Preferably, the original tube 2 obtaining in described step 1) is amorphous tubing, and the degree of crystallinity of this amorphous tubing is lower than 20%.
Preferably, described step 2) comprise the steps:
Step is a): original tube 2 is put into the good and on-deformable described tubular die 1 of heat conductivity;
Step b): described original tube 2 and described tubular die 1 are heated to orientation temperature T, this orientation temperature T is higher than the glass transition temperature Tg of polymeric material and lower than the melt temperature Tm of polymeric material, thereby and apply expansion pressure to the inside injection gases at high pressure of described original tube 2 to described original tube 2, with original tube 2 described in the radial direction inflation along described original tube 2; And, before described radial direction inflation tubing, in described radial direction inflation tubing or after described radial direction inflation tubing, along the axial direction of tubing, tubing is carried out to axial tension;
Step c): tubing is kept to the expansion pressure in step b), the mode by water-cooled or air cooling to inflation after tubing 3 and described tubular die 1 lower the temperature rapidly so that it is cooled to below the glass transition temperature Tg of polymeric material; Then, remove described expansion pressure, take out tubing 3 after described inflation.
Preferably, the annealing in described step 3) refers to places one period of scheduled time by tubing 3 after described inflation under described annealing temperature, and this scheduled time is 5 minutes ~ 24 hours.Preferably, in described step 3), after to described inflation tubing 3 anneal before after described inflation the inside of tubing 3 place the suitable lining core of size, then after annealing completes, the inside of described lining core tubing 3 from described inflation is taken out.The use of lining core can prevent tubing size generation atrophy in annealing process.
Preferably, in described step 4), described shaping pipe is prepared into described biodegradable polymer support 4 by cut; Or after being cut into strip material, described shaping pipe is woven into described biodegradable polymer support 4.
Preferably, in described step b), before described original tube 2 and described tubular die 1 are heated to described orientation temperature T, under preheat temperature T1, described original tube 2 is carried out to preheating, described preheat temperature T1 is higher than the glass transition temperature Tg of polymeric material.Preferably, described preheat temperature T1 is lower than glass transition temperature Tg and 20 ℃ of sums of polymeric material.That is, described preheat temperature T1>Tg, and the concrete scope of described preheat temperature T1 can be: Tg ~ Tg+20 ℃, wherein Tg is the glass transition temperature of polymeric material.The growth of nucleus be conducive to polymer under this temperature range in, and be unfavorable for that the size of crystal increases, be conducive to like this form a large amount of small size crystal, when contributing to tubing intensity and toughness, improve.
Preferably, described step b) in, in the periphery of described tubular die 1, be wound with resistance wire to form heater, utilize the resistance wire that is wrapped on described tubular die 1 to heat; Or make the gases at high pressure of the inside of injecting described original tube 2 there is high temperature, utilize the gases at high pressure of the inside of injecting described original tube 2 to heat, thereby described original tube 2 and described tubular die 1 are heated to described orientation temperature.Certainly, mode of heating of the present invention is unrestricted, only illustrates above.
Preferably, described step b) in, original tube 2 has predetermined external diameter, predetermined wall thickness and predetermined length, and after inflation, tubing 3 has corresponding external diameter, wall thickness and the length after inflation, and after described original tube 2 and described inflation, the external diameter of tubing 3 is than between 1:1.5 and 1:5; After described original tube 2 and described inflation, the wall ratio of tubing 3 is between 1.5:1 and 5:1; And after described original tube 2 and described inflation, the Length Ratio of tubing 3 is between 1:1 and 1:2.
Preferably, in described step b), in keeping described orientation temperature T, make described expansion pressure keep one period of scheduled time, this scheduled time is between 2 seconds and 10 minutes.Can make like this tubing fully be orientated under said temperature and pressure, to improve the mechanical property of final support.
Preferably, in described step c), tubing 3 after described inflation and described tubular die 1 are cooled to rapidly lower than at least 20 ℃ of the glass transition temperature Tg of polymeric material.
Below adopt design parameter to describe two examples of preparation method of the present invention.
Example one:
The polymeric material of the original tube 2 of choosing in this example is Biodegradable polymer material polylactic acid.By this polylactic acid particle, by extruding, to obtain external diameter be the original tube 2 that 1.5mm, wall thickness are 0.5mm.This original tube 2 is put into the rustless steel tubulose mould 1 that internal diameter is 2.5mm, as shown in fig. 1.One end sealing of polylactic acid original tube 2, the other end is connected with high-pressure gas circuit.First, original tube 2 and tubular die 1 being heated, make its temperature be raised to 120 ℃, is 200psi(pound/square inch to being filled with pressure in original tube 2 then) high pressure nitrogen, original tube 2 is carried out to axial tension simultaneously, stretching distance is 40mm.Original tube 2 has been prepared into the tubing of external diameter 2.5mm, wall thickness 0.15mm under the condition of high temperature, high pressure and stretching, i.e. tubing 3 after inflation, as shown in Figure 2.Afterwards by rapid whole system cool to room temperature, then pressure release, takes out tubing 3 after inflation.Finally tubing after inflation 3 is enclosed within on the metal liner core that external diameter is 2.2mm, the baking oven that is placed in 90 ℃ is annealed 5 minutes, then shaping pipe annealing being completed carries out cut, finally obtains final biodegradable polymer support 4 as shown in Figure 3.
The support pressure that preparation is completed is held on suitable sacculus, and the external diameter that pressure is held after-poppet is 1.0mm.Then, in the normal saline of 37 ℃, support is expanded to external diameter 3.0mm, process of expansion medium-height trestle ruptures.After sacculus withdraws, the support force of measuring expansion after-poppet is greater than 100kpa.
, the support pressure preparing with same method is held on suitable sacculus meanwhile, then, with aluminium foil bag vacuum nitrogen filling gas bag dress, placed at ambient temperature 3 months.Then support is taken out, in the normal saline of 37 ℃, support is expanded to external diameter 3.0mm, process of expansion medium-height trestle ruptures.After sacculus withdraws, measure the support force of expansion after-poppet, result support force is greater than 100kpa.
First the support of preparing with same method is pressed and held suitable sacculus, then will not store and the support of storage at room temperature after 3 months is transported to the narrow positions of blood vessel respectively, Filled Balloon is with expandable stent, thereby struts narrow blood vessel, strut in process, do not observe the fracture of support.After sacculus pumpback, angiography is observed, and blood vessel is still strutted by support, and the adverse events that support subsides does not occur in whole operation process.After 2 years, can't see support by intravascular ultrasound while carrying out Clinical Follow-up, this explanation rack body material is degradable, and restenosis phenomenon and inflammatory reaction do not appear in the diseased region of implant frame.
Example two:
The polymeric material of the original tube 2 of choosing in this example is Biodegradable polymer material PLGA (PLGA), and copolymerization ratio is 85:15.It is the original tube 2 that 1.2mm, wall thickness are 0.3mm that this copolymerization particle is obtained to external diameter by injection moulding.This original tube 2 is put into the rustless steel tubulose mould 1 that internal diameter is 2.5mm.One end sealing of PLGA original tube 2, the other end is connected with high-pressure gas circuit.First, original tube 2 and tubular die 1 are heated and make it be warming up to 80 ℃, then in original tube 2, be filled with the high-pressure helium that pressure is 400psi.Original tube 2 has been prepared into the tubing of external diameter 2.5mm, wall thickness 0.15mm under the condition of high temperature, high pressure.Afterwards whole system is cooled to rapidly to 20 ℃, then pressure release, tubing 3 after taking-up inflation.Finally tubing after inflation 3 is enclosed within on the metal liner core that external diameter is 2.2mm, the baking oven that is placed in 80 ℃ is annealed 30 minutes, then shaping pipe annealing being completed is the thin slice of width 0.2mm by cut, and this thin slice is woven, and is finally met the support of demand.
The support pressure that preparation is completed is held on suitable sacculus, and the external diameter that pressure is held after-poppet is 1.1mm.Then, in the normal saline of 37 ℃, support is expanded to external diameter 2.5mm, process of expansion medium-height trestle ruptures.Measure the support force of expansion after-poppet, result support force is 140kpa left and right.
, the support pressure preparing with same method is held on suitable sacculus meanwhile, then, with aluminium foil bag vacuum nitrogen filling gas bag dress, placed at ambient temperature 3 months.Then, support is taken out, in the normal saline of 37 ℃, support is expanded to external diameter 2.5mm, in process of expansion, support ruptures.After sacculus withdraws, measure the support force of expansion after-poppet, result support force is 145kpa left and right.
First the support of preparing with same method is pressed and held suitable sacculus, then will not store and the support of storage at room temperature after 3 months is transported to the narrow positions of blood vessel respectively, Filled Balloon is with expandable stent, thereby struts narrow blood vessel, struts the fracture of not observing support in process.After sacculus pumpback, angiography is observed, and blood vessel is still strutted by support, and the adverse events that support subsides does not occur in whole operation process.After 1.5 years, can't see support by intravascular ultrasound while carrying out Clinical Follow-up, this explanation rack body material is degradable, and restenosis phenomenon and inflammatory reaction do not appear in the diseased region of implant frame.
By preparation method of the present invention, can make tubing before cutting into support, in radial and axial direction, realize height-orientedly, material is greatly improved in radial and axial intensity and toughness.And, by the annealing of certain hour, form perfect crystallizing system, and discharged the internal stress of tubing, effectively improve support in support force and toughness at once and after storage, reduce the phenomenon of rupture in retraction and the process of expansion of support.
At once and more than the support radial support power of storage after 3 months all can reach 120KPa of the support that technical method according to the present invention is prepared into, the relaxation shrinkage after support expansion can be controlled in 5%, and support is not easy to occur fracture in process of expansion.In addition, this method of the present invention only relates to the preparation for processing of support to innovate, and does not change the raw material of support, thus on the biological safety of support without any impact.
The above is only some specific embodiments of the application.Should be understood that; for those skilled in the art; do not departing under the prerequisite of the present application principle and inventive concept; can also carry out various combinations or make some improvement and modification above-described embodiment, within these combinations, improvement and modification also should be considered as dropping on the application's protection domain and inventive concept.
Claims (13)
1. a preparation method for biodegradable polymer support, comprises the steps:
Step 1): prepare biodegradable polymer original tube (2) by biodegradable polymer material;
Step 2): the original tube of preparing in described step 1) (2) is put into tubular die (1), described original tube (2) is heated, and inject gases at high pressure in described original tube (2), with original tube (2) described in the radial direction inflation along described original tube (2), to make the external diameter of tubing (3) after inflation equal the internal diameter of described tubular die (1), make tubing can realize height-oriented in radial direction; And, before described radial direction inflation tubing, in described radial direction inflation tubing or after described radial direction inflation tubing, axial direction along tubing carries out axial tension to tubing, is orientated in described radial direction and described axial direction to realize tubing;
Step 3): tubing (3) after described inflation is annealed under annealing temperature, and to obtain shaping pipe, wherein said annealing temperature is higher than the glass transition temperature of polymeric material and lower than the melt temperature of polymeric material;
Step 4): the shaping pipe obtaining in described step 3) is prepared into described biodegradable polymer support (4).
2. the preparation method of biodegradable polymer support according to claim 1, is characterized in that:
Biodegradable polymer material in described step 1) is polylactic acid, polyglycolic acid, polycaprolactone, polydioxanone, poly-anhydride, tyrosine Merlon or its copolymer or blend.
3. the preparation method of biodegradable polymer support according to claim 1, is characterized in that:
The original tube (2) obtaining in described step 1) is amorphous tubing, and the degree of crystallinity of this amorphous tubing is lower than 20%.
4. the preparation method of biodegradable polymer support according to claim 1, is characterized in that:
Described step 2) comprise the steps:
Step is a): described original tube (2) is put into the good and on-deformable described tubular die (1) of heat conductivity;
Step b): described original tube (2) and described tubular die (1) are heated to orientation temperature, this orientation temperature is higher than the glass transition temperature of polymeric material and lower than the melt temperature of polymeric material, and to described original tube (2) thus inside inject gases at high pressure apply expansion pressure to described original tube (2), with original tube described in the radial direction inflation along described original tube (2); And, before described radial direction inflation tubing, in described radial direction inflation tubing or after described radial direction inflation tubing, along the axial direction of tubing, tubing is carried out to axial tension;
Step c): tubing is kept to the expansion pressure in described step b), the mode by water-cooled or air cooling to inflation after tubing (3) and described tubular die (1) lower the temperature rapidly so that it is cooled to below the glass transition temperature of polymeric material; Then, remove described expansion pressure, take out tubing (3) after described inflation.
5. according to the preparation method of the biodegradable polymer support described in any one in claim 1 ~ 4, it is characterized in that:
Annealing in described step 3) refers to places one period of scheduled time by tubing (3) after described inflation under described annealing temperature, and this scheduled time is 5 minutes ~ 24 hours.
6. the preparation method of biodegradable polymer support according to claim 5, is characterized in that:
In described step 3), after to described inflation tubing (3) anneal before after described inflation the inside of tubing (3) place lining core, then after annealing completes, the inside of described lining core tubing (3) from described inflation is taken out.
7. according to the preparation method of the biodegradable polymer support described in any one in claim 1 ~ 4, it is characterized in that:
In described step 4), described shaping pipe is prepared into described biodegradable polymer support (4) by cut; Or after being cut into strip material, described shaping pipe is woven into described biodegradable polymer support (4).
8. the preparation method of biodegradable polymer support according to claim 4, is characterized in that:
In described step b), before described original tube (2) and described tubular die (1) are heated to described orientation temperature, under preheat temperature, described original tube (2) is carried out to preheating, described preheat temperature is higher than the glass transition temperature of polymeric material.
9. the preparation method of biodegradable polymer support according to claim 8, is characterized in that:
Described preheat temperature is lower than glass transition temperature and 20 ℃ of sums of polymeric material.
10. the preparation method of biodegradable polymer support according to claim 4, is characterized in that:
Described step b) in, the resistance wire that utilization is wrapped on described tubular die (1) heats, or utilize the gases at high pressure of the inside of injecting described original tube (2) to heat, thereby described original tube (2) and described tubular die (1) are heated to described orientation temperature.
The preparation method of 11. biodegradable polymer supports according to claim 4, is characterized in that:
Described step b) in, after described original tube (2) and described inflation, the external diameter of tubing (3) is than between 1:1.5 and 1:5; After described original tube (2) and described inflation, the wall ratio of tubing (3) is between 1.5:1 and 5:1; And after described original tube (2) and described inflation, the Length Ratio of tubing (3) is between 1:1 and 1:2.
The preparation method of 12. biodegradable polymer supports according to claim 4, is characterized in that:
In described step b), in keeping described orientation temperature, make described expansion pressure keep one period of scheduled time, this scheduled time is between 2 seconds and 10 minutes.
The preparation method of 13. biodegradable polymer supports according to claim 4, is characterized in that:
In described step c), tubing (3) after described inflation and described tubular die (1) are cooled to rapidly lower than at least 20 ℃ of the glass transition temperatures of polymeric material.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711213237.8A CN108016023A (en) | 2012-12-21 | 2012-12-21 | A kind of preparation method of polylactide and its copolymer stent |
| CN201210563632.XA CN103876869A (en) | 2012-12-21 | 2012-12-21 | Production method of biodegradable polymer support |
| CN201710109320.4A CN106618820A (en) | 2012-12-21 | 2012-12-21 | Method for preparing biodegradable polymer scaffold |
| PCT/CN2013/090097 WO2014094652A1 (en) | 2012-12-21 | 2013-12-20 | Method for preparing biodegradable polymer frame |
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| CN201210563632.XA CN103876869A (en) | 2012-12-21 | 2012-12-21 | Production method of biodegradable polymer support |
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| CN201710109320.4A Division CN106618820A (en) | 2012-12-21 | 2012-12-21 | Method for preparing biodegradable polymer scaffold |
| CN201711213237.8A Division CN108016023A (en) | 2012-12-21 | 2012-12-21 | A kind of preparation method of polylactide and its copolymer stent |
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| CN201710109320.4A Pending CN106618820A (en) | 2012-12-21 | 2012-12-21 | Method for preparing biodegradable polymer scaffold |
| CN201210563632.XA Pending CN103876869A (en) | 2012-12-21 | 2012-12-21 | Production method of biodegradable polymer support |
| CN201711213237.8A Pending CN108016023A (en) | 2012-12-21 | 2012-12-21 | A kind of preparation method of polylactide and its copolymer stent |
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| WO (1) | WO2014094652A1 (en) |
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| 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 |
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| CN108289747A (en) * | 2015-11-26 | 2018-07-17 | 株式会社日本医疗机器技研 | Bioabsorbable holder |
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Also Published As
| Publication number | Publication date |
|---|---|
| CN108016023A (en) | 2018-05-11 |
| WO2014094652A1 (en) | 2014-06-26 |
| CN106618820A (en) | 2017-05-10 |
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