CN114028621A - Polymer pipe with controllable degradation speed and preparation method and application thereof - Google Patents
Polymer pipe with controllable degradation speed and preparation method and application thereof Download PDFInfo
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- CN114028621A CN114028621A CN202111333342.1A CN202111333342A CN114028621A CN 114028621 A CN114028621 A CN 114028621A CN 202111333342 A CN202111333342 A CN 202111333342A CN 114028621 A CN114028621 A CN 114028621A
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- 238000006731 degradation reaction Methods 0.000 title claims abstract description 101
- 230000015556 catabolic process Effects 0.000 title claims abstract description 100
- 229920000642 polymer Polymers 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000000463 material Substances 0.000 claims abstract description 31
- 229920006237 degradable polymer Polymers 0.000 claims abstract description 20
- JJTUDXZGHPGLLC-IMJSIDKUSA-N 4511-42-6 Chemical compound C[C@@H]1OC(=O)[C@H](C)OC1=O JJTUDXZGHPGLLC-IMJSIDKUSA-N 0.000 claims abstract description 11
- 229920000747 poly(lactic acid) Polymers 0.000 claims abstract description 11
- 239000004626 polylactic acid Substances 0.000 claims abstract description 11
- 229920000954 Polyglycolide Polymers 0.000 claims abstract description 8
- 239000004633 polyglycolic acid Substances 0.000 claims abstract description 8
- 229920001577 copolymer Polymers 0.000 claims abstract description 5
- 239000000835 fiber Substances 0.000 claims abstract description 5
- 229920000117 poly(dioxanone) Polymers 0.000 claims abstract description 5
- 229920001610 polycaprolactone Polymers 0.000 claims abstract description 5
- 239000004632 polycaprolactone Substances 0.000 claims abstract description 5
- 230000009477 glass transition Effects 0.000 claims description 14
- JVTAAEKCZFNVCJ-REOHCLBHSA-N L-lactic acid Chemical compound C[C@H](O)C(O)=O JVTAAEKCZFNVCJ-REOHCLBHSA-N 0.000 claims description 8
- 229920001432 poly(L-lactide) Polymers 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 3
- -1 poly D Chemical compound 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000012360 testing method Methods 0.000 description 24
- 238000001125 extrusion Methods 0.000 description 12
- 238000011056 performance test Methods 0.000 description 7
- 210000004204 blood vessel Anatomy 0.000 description 6
- 239000000126 substance Substances 0.000 description 5
- 230000006835 compression Effects 0.000 description 3
- 238000007906 compression Methods 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- 208000037803 restenosis Diseases 0.000 description 3
- 208000007536 Thrombosis Diseases 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 201000010099 disease Diseases 0.000 description 2
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 206010061218 Inflammation Diseases 0.000 description 1
- WAIPAZQMEIHHTJ-UHFFFAOYSA-N [Cr].[Co] Chemical class [Cr].[Co] WAIPAZQMEIHHTJ-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 210000003445 biliary tract Anatomy 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 210000004351 coronary vessel Anatomy 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 206010020718 hyperplasia Diseases 0.000 description 1
- 238000001727 in vivo Methods 0.000 description 1
- 230000004054 inflammatory process Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 210000005036 nerve Anatomy 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000013268 sustained release Methods 0.000 description 1
- 239000012730 sustained-release form Substances 0.000 description 1
- 210000003437 trachea Anatomy 0.000 description 1
- 208000019553 vascular disease Diseases 0.000 description 1
- 230000001457 vasomotor Effects 0.000 description 1
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/14—Macromolecular materials
- A61L27/18—Macromolecular materials obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
-
- 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
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
- A61L27/58—Materials at least partially resorbable by the body
-
- 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
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- Health & Medical Sciences (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- General Health & Medical Sciences (AREA)
- Oral & Maxillofacial Surgery (AREA)
- Transplantation (AREA)
- Life Sciences & Earth Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- Chemical & Material Sciences (AREA)
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- Medicinal Chemistry (AREA)
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- Chemical Kinetics & Catalysis (AREA)
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- Materials For Medical Uses (AREA)
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Abstract
The invention relates to the technical field of degradable polymer pipes, in particular to a polymer pipe with controllable degradation speed and a preparation method and application thereof. The polymer pipe with controllable degradation speed provided by the invention comprises a mechanical supporting layer and a speed-controlling degradation layer which are stacked from inside to outside; the mechanical support layer and the speed-control degradation layer are made of degradable polymers; the molecular weight of the material of the mechanical support layer is larger than that of the material of the speed control degradation layer; the degradable polymer is one or more of polylactic acid, poly D, L-lactide, polyglycolic acid, polylactic acid-glycolic acid copolymer, polycaprolactone and poly-p-dioxanone fiber. The polymer tubing can achieve the purpose of controlled degradation.
Description
Technical Field
The invention relates to the technical field of degradable polymer pipes, in particular to a polymer pipe with controllable degradation speed and a preparation method and application thereof.
Background
At present, as a main medical apparatus for treating vascular diseases including thin blood vessels and the like, a drug-coated stent body is always made of inert metal materials, mainly 316L medical stainless steel and cobalt-chromium alloy, and the metal stent is implanted into the blood vessels as a heterologous substance and is consistently remained in a human body, so that the treatment is more troublesome when restenosis occurs. The biodegradable medical polymer tube has good biodegradability and excellent biocompatibility, can be degraded into small molecular compounds in vivo and metabolized, absorbed or excreted by a substrate, does not need secondary operation when being used for clinical applications such as implanted medical devices, drug sustained-release systems, tissue engineering stents and the like, can relieve the pain of patients, simplify operation procedures, and has the effects of improving treatment effect, prolonging the illness of patients, improving the life quality of patients and the like. Therefore, the biodegradable medical polymer tubing is increasingly widely applied in the field of biomedicine, and the development of biomedicine and clinical medicine is favorably promoted.
However, for the treatment of different diseases and the conditions of patients, the required treatment time is different, and the mechanical property requirements are also different, so that different requirements are imposed on the degradation time of the pipe. For example, coronary stents require at least 6 months of mechanical properties and then a short degradation time, but pure PLLA tubing degrades for more than 24 months and for too long. But some other cavities have low requirements on mechanical properties, and can be kept for 3 months, and different ratios of the speed control layer and the mechanical layer are selected according to different diseases to be treated and different conditions of patients.
Disclosure of Invention
The invention aims to provide a polymer pipe with controllable degradation speed, a preparation method and application thereof, and the polymer pipe can realize the purpose of controllable degradation.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a polymer pipe with controllable degradation speed, which comprises a mechanical supporting layer and a speed-controlling degradation layer which are stacked from inside to outside;
the mechanical support layer and the speed-control degradation layer are made of degradable polymers;
the molecular weight of the material of the mechanical support layer is larger than that of the material of the speed control degradation layer;
the degradable polymer is one or more of polylactic acid, poly D, L-lactide, polyglycolic acid, polylactic acid-glycolic acid copolymer, polycaprolactone and poly-p-dioxanone fiber.
Preferably, the number average molecular weight of the material of the speed-control degradation layer is 8-15 ten thousand;
the number average molecular weight of the material of the mechanical support layer is 20-50 ten thousand.
Preferably, the polylactic-co-glycolic acid comprises PLGA50:50, PLGA40:60, PLGA70:30 or PLGA80: 20;
the polylactic acid comprises PLLA or PLA.
Preferably, the material of the speed-control degradation layer is one or more of poly D, L-lactide, PLGA50:50, PLGA40:60 and polyglycolic acid;
the mechanical support layer is made of one or more of PLLA, poly D, L-lactide, PLGA70:30 and PLGA80: 20.
Preferably, the thickness of the speed-control degradation layer is 20-60 mu m;
the thickness of the mechanical support layer is 50-100 mu m.
Preferably, the speed-control degradation layer comprises more than or equal to 1 degradable polymer layer;
the mechanical support layer comprises more than or equal to 1 degradable polymer layer.
The invention also provides a preparation method of the polymer pipe material in the technical scheme, which comprises the following steps:
preparing a mechanical support layer pipe and a speed-control degradation layer pipe;
and after carrying out first thermal expansion on the speed-control degradation layer pipe in a mould, placing the mechanical support layer pipe in the mould containing the thermally expanded speed-control degradation layer pipe for second thermal expansion, and then sequentially carrying out third thermal expansion to obtain the polymer pipe.
Preferably, the temperature of the first thermal expansion is 10-30 ℃ higher than the glass transition temperature of the speed-control degradation layer pipe, the time is 20-60 s, and the pressure is 3-10 bar;
the temperature of the second thermal expansion is 25-52 ℃ higher than the glass transition temperature of the mechanical support layer pipe, the time is 80-200 s, and the pressure is 12-20 bar.
Preferably, the expansion ratio of the first thermal expansion, the second thermal expansion and the third thermal expansion is independently 100 to 500%.
The invention also provides the application of the polymer pipe in the technical scheme or the polymer pipe prepared by the preparation method in the technical scheme in the field of medical instruments.
The invention provides a polymer pipe with controllable degradation speed, which comprises a mechanical supporting layer and a speed-controlling degradation layer which are stacked from inside to outside; the mechanical support layer and the speed-control degradation layer are made of degradable polymers; the molecular weight of the material of the mechanical support layer is larger than that of the material of the speed control degradation layer; the degradable polymer is one or more of polylactic acid, poly D, L-lactide, polyglycolic acid, polylactic acid-glycolic acid copolymer, polycaprolactone and poly-p-dioxanone fiber. According to the invention, the speed-control degradation layer is arranged on the outer layer of the polymer pipe, and the molecular weight of the speed-control degradation layer is controlled to be smaller than that of the mechanical support layer, so that the speed-control degradation layer is slowly degraded in a human body firstly, and then micromolecular organic acid is generated in the degradation process, and the micromolecular organic acid provides an acidic environment for the subsequent degradation of the mechanical support layer, so that the degradation time of the mechanical support layer can be shortened, and the purpose of controllable degradation is realized.
Detailed Description
The invention provides a polymer pipe with controllable degradation speed, which comprises a mechanical supporting layer and a speed-controlling degradation layer which are stacked from inside to outside;
the mechanical support layer and the speed-control degradation layer are made of degradable polymers;
the molecular weight of the material of the mechanical support layer is larger than that of the material of the speed control degradation layer;
the degradable polymer is one or more of polylactic acid, poly D, L-lactide (PDLLA), polyglycolic acid, polylactic acid-glycolic acid copolymer, polycaprolactone and poly-p-dioxanone fiber.
In the present invention, the polylactic-co-glycolic acid preferably comprises PLGA50:50, PLGA40:60, PLGA70:30 or PLGA80: 20; the polylactic acid preferably comprises PLLA, PDLLA or PLA.
In the invention, the thickness of the speed-control degradation layer is preferably 20-60 μm, and more preferably 40-50 μm. In the present invention, the rate-controlling degradable layer preferably comprises 1 or more degradable polymer layers, more preferably 1 degradable polymer layer.
In the present invention, the thickness of the rate-controlling degradation layer is controlled within the above range to prevent incomplete endothelialization of blood vessels and restenosis of blood vessels due to too high a degradation rate. Prevent the intimal hyperplasia caused by too slow degradation time and increase the possibility of thrombus.
In the present invention, the number average molecular weight of the material of the rate-controlling degradation layer is preferably 8 to 15 ten thousand, more preferably 9 to 13 ten thousand, and most preferably 10 to 12 ten thousand.
In the invention, the material of the speed-control degradation layer is preferably one or more of poly D, L-lactide, PLGA50:50, PLGA40:60 and polyglycolic acid; when the materials of the speed-control degradation layer are more than two of the specific choices, the proportion of the specific substances is not limited in any way, and the specific substances can be mixed according to any proportion.
In the invention, the thickness of the mechanical support layer is preferably 50-100 μm, and more preferably 60-80 μm; the mechanical support layer preferably comprises 1 or more degradable polymer layers, more preferably 1 degradable polymer layer.
In the invention, the function of controlling the thickness of the mechanical support layer in the range can achieve the purposes of maintaining the smoothness of the blood vessel by the expected radial support force strength and achieving the rapid degradation, thereby reducing the long-term inflammatory reaction, restenosis and thrombus, and recovering the integrity of the blood vessel and the vasomotor function.
In the present invention, the number average molecular weight of the material of the mechanical support layer is preferably 20 to 50 ten thousand, and more preferably 30 to 40 ten thousand.
In the invention, the material of the mechanical support layer is preferably one or more of PLLA, poly D, L-lactide, PLGA70:30 and PLGA80: 20; when the materials of the mechanical support layer are more than two of the specific choices, the specific proportion of the specific substances is not limited in any way, and the specific substances can be mixed according to any proportion.
The invention also provides a preparation method of the polymer pipe material in the technical scheme, which comprises the following steps:
preparing a mechanical support layer pipe and a speed-control degradation layer pipe;
and after carrying out first thermal expansion on the speed-controlled degradation layer pipe in a mould, placing the mechanical support layer pipe in the mould containing the thermally expanded speed-controlled degradation layer pipe for second thermal expansion, and then sequentially carrying out co-extrusion and third thermal expansion to obtain the polymer pipe.
In the present invention, all the starting materials for the preparation are commercially available products known to those skilled in the art unless otherwise specified.
The invention prepares a mechanical supporting layer pipe and a speed-control degradation layer pipe. In the invention, the mode for preparing the mechanical support layer pipe and the speed-control degradation layer pipe is preferably extrusion; the extrusion is not subject to any particular limitation in the present invention, and may be carried out by a process well known to those skilled in the art.
In the invention, the wall thickness of the speed-control degradation layer pipe is preferably 70-300 μm, more preferably 150-250 μm, and most preferably 180-220 μm. In the invention, the wall thickness of the mechanical support layer is preferably 200-400 μm, more preferably 250-350 μm, and most preferably 280-320 μm.
After obtaining the mechanical support layer pipe and the speed-control degradation layer pipe, the invention carries out first thermal expansion on the speed-control degradation layer pipe in a mould, then places the mechanical support layer pipe in the mould containing the thermally expanded speed-control degradation layer pipe for second thermal expansion, and then carries out co-extrusion and third thermal expansion in sequence to obtain the polymer pipe.
In the invention, the temperature of the first thermal expansion is 10-30 ℃ higher than the glass transition temperature of the speed-control degradation layer pipe, more preferably 13-27 ℃ higher, and most preferably 15-25 ℃ higher; the time is preferably 20 to 60s, and more preferably 30 to 50 s; the pressure is preferably 3 to 10bar, more preferably 6 to 8 bar. In the present invention, the expansion ratio of the first thermal expansion is preferably 100 to 500%, more preferably 200 to 400%, and most preferably 250 to 350%.
In the invention, the first thermal expansion is used for pre-expanding and forming the speed-controlled degradation layer pipe with smaller diameter outwards along the radial direction under the action of pressure by means of stretching of materials to obtain the speed-controlled degradation layer pipe with the optimal wall thickness.
In the invention, the temperature of the second thermal expansion is preferably 25-52 ℃ higher than the glass transition temperature of the mechanical support layer pipe, more preferably 27-50 ℃ higher, and most preferably 30-45 ℃ higher; the time is preferably 80 to 200s, more preferably 100 to 180s, and most preferably 120 to 150 s; the pressure is preferably 12 to 20bar, more preferably 14 to 18bar, and most preferably 15 to 16 bar. In the present invention, the expansion ratio of the second thermal expansion is preferably 100 to 500%, more preferably 200 to 400%, and most preferably 250 to 350%.
In the invention, the second thermal expansion is used for pre-expanding and forming the mechanical support layer pipe with a smaller diameter outwards along the radial direction under the action of pressure by means of stretching of materials, so that the mechanical support layer with the optimal wall thickness is obtained under the condition of ensuring that the outer wall of the mechanical support layer is completely attached to the inner wall of the speed-control degradation pipe.
In the invention, the temperature of the third thermal expansion is preferably 92-140 ℃, more preferably 95-135 ℃, and most preferably 100-120 ℃; the time is preferably 180 to 300s, more preferably 200 to 280s, and most preferably 235 to 245 s; the pressure is preferably 17 to 26bar, more preferably 19 to 24bar, most preferably 22 to 23 bar. In the present invention, the expansion ratio of the third thermal expansion is preferably 100 to 500%, more preferably 200 to 400%, and most preferably 300 to 390%.
In the invention, the third thermal expansion is used for expanding and forming two kinds of pipes which are completely jointed outwards in a radial direction under the action of pressure by means of stretching of materials, and polymer pipes with more preferable wall thickness are obtained.
The invention also provides the application of the polymer pipe in the technical scheme or the polymer pipe prepared by the preparation method in the technical scheme in the field of medical instruments. In the invention, the application is preferably the application of the polymer pipe in the preparation of stents for coronary vessels, peripheral vessels, nerve vessels, trachea, biliary tracts and other natural body cavities.
The polymer pipe and the preparation method and application thereof provided by the present invention will be described in detail with reference to the following examples, but they should not be construed as limiting the scope of the present invention.
Example 1
The structure is as follows: a mechanical supporting layer: layer number: 1 layer; materials: PDLLA (number average molecular weight 31 ten thousand, glass transition temperature 58 ℃); the thickness is 100 mu m;
a speed-controlled degradation layer: layer number: 1 layer of PLGA50:50 (number average molecular weight 11.5 ten thousand, glass transition temperature 55 deg.C); the thickness is 30 μm;
the preparation process comprises the following steps:
respectively preparing a mechanical support layer pipe and a speed-control degradation layer pipe in an extrusion mode, wherein the wall thickness of the mechanical support layer pipe is 300 micrometers; the wall thickness of the speed-control degradation layer pipe is 90 micrometers;
and (2) carrying out first thermal expansion (thermal expansion ratio is 200%) on the speed-control degradation layer pipe in a mould, wherein the temperature of the first thermal expansion is 74 ℃, the pressure is 10bar, after 60s, placing the mechanical support layer pipe in the mould containing the speed-control degradation layer pipe subjected to thermal expansion for second thermal expansion (thermal expansion ratio is 200%), wherein the temperature of the second thermal expansion is 92 ℃, the pressure is 20bar, after 200s, carrying out third thermal expansion (thermal expansion ratio is 150%), the temperature of the third thermal expansion is 105 ℃, the pressure is 20bar, and the time is 240s, thus obtaining the polymer pipe.
The polymer pipe is subjected to mechanical property test, and the test standard is YY/T0663.2-2016 anti-parallel plate extrusion performance; the test result shows that the average radial strength is 0.88N/mm when the diameter of the pipe is reduced by 50 percent, and the average force value is 10.61N;
carrying out degradation performance test on the polymer pipe, wherein the test standard is GB/T16886.13-2017 midbody external accelerated degradation test; the test results were 0% loss in average mass, 3% loss in 1-balance homogeneity, 20% loss in 7-balance homogeneity, 50% loss in 14-balance homogeneity and 70% loss in 28-balance homogeneity when sampled and weighed on day 0.
Example 2
The structure is as follows: a mechanical supporting layer: layer number: 1 layer; materials: PLLA (number average molecular weight 39 ten thousand, glass transition temperature 60 ℃ C.); the thickness is 100 mu m;
a speed-controlled degradation layer: layer number: 1 layer of PLGA50:50 (number average molecular weight 11 ten thousand, glass transition temperature 55 deg.C); the thickness is 30 μm;
the preparation process comprises the following steps:
respectively preparing a mechanical support layer pipe and a speed-control degradation layer pipe in an extrusion mode, wherein the wall thickness of the mechanical support layer pipe is 350 micrometers; the wall thickness of the speed-control degradation layer pipe is 70 mu m;
and (2) carrying out first thermal expansion (thermal expansion ratio is 200%) on the speed-control degradation layer pipe in a mould, wherein the temperature of the first thermal expansion is 75 ℃, the pressure is 10bar, after 60s, placing the mechanical support layer pipe in the mould containing the speed-control degradation layer pipe subjected to thermal expansion for second thermal expansion (thermal expansion ratio is 250%), the temperature of the second thermal expansion is 93 ℃, the pressure is 20bar, after 200s, carrying out third thermal expansion (thermal expansion ratio is 135%), the temperature of the third thermal expansion is 120 ℃, the pressure is 20bar, and the time is 245s, thus obtaining the polymer pipe.
The polymer pipe is subjected to mechanical property test, and the test standard is YY/T0663.2-2016 anti-parallel plate extrusion performance test; the test result shows that the average radial strength is 1.18N/mm when the diameter of the pipe is reduced by 50% in compression, and the average force value is 14.10N;
carrying out degradation performance test on the polymer pipe, wherein the test standard is GB/T16886.13-2017 midbody external accelerated degradation test; the test results were 0% loss of average mass, 1% loss of homogeneity on balance 1, less than 10% loss of homogeneity on balance 7, 19% loss of homogeneity on balance 14, and 43% loss of homogeneity on balance 28, sampled and weighed on day 0.
Example 3
The structure is as follows: a mechanical supporting layer: layer number: 1 layer; materials: PLGA70:30 (number average molecular weight 35 ten thousand, glass transition temperature 57 ℃ C.); the thickness is 100 mu m;
a speed-controlled degradation layer: layer number: 1 layer of PLGA50:50 (number average molecular weight 11.8 ten thousand, glass transition temperature 55 deg.C); the thickness is 30 μm;
the preparation process comprises the following steps:
respectively preparing a mechanical support layer pipe and a speed-control degradation layer pipe in an extrusion mode, wherein the wall thickness of the mechanical support layer pipe is 250 micrometers; the wall thickness of the speed-control degradation layer pipe is 75 micrometers;
and (2) carrying out first thermal expansion (thermal expansion ratio is 200%) on the speed-control degradation layer pipe in a mould, wherein the temperature of the first thermal expansion is 80 ℃, the pressure is 10bar, after 60s, placing the mechanical support layer pipe in the mould containing the speed-control degradation layer pipe subjected to thermal expansion for second thermal expansion (thermal expansion ratio is 200%), wherein the temperature of the second thermal expansion is 95 ℃, the pressure is 20bar, after 200s, carrying out third thermal expansion (thermal expansion ratio is 125%), the temperature of the third thermal expansion is 115 ℃, the pressure is 20bar, and the time is 240s, thus obtaining the polymer pipe.
The polymer pipe is subjected to mechanical property test, and the test standard is YY/T0663.2-2016 anti-parallel plate extrusion performance test; the test result shows that the average radial strength is 1.03N/mm when the diameter of the pipe is reduced by 50% in compression, and the average force value is 12.35N;
carrying out degradation performance test on the polymer pipe, wherein the test standard is GB/T16886.13-2017 midbody external accelerated degradation test; the test results were 0% loss of average mass, 3% loss of 1-balance homogeneity, less than 16% loss of 7-balance homogeneity, 30% loss of 14-balance homogeneity and 61% loss of 28-balance homogeneity.
Example 4
The structure is as follows: a mechanical supporting layer: layer number: 1 layer; materials: PLGA80:20 (number average molecular weight 37 ten thousand, glass transition temperature 58 ℃ C.); the thickness is 100 mu m;
a speed-controlled degradation layer: layer number: 1 layer of PLGA50:50 (number average molecular weight 11.9 ten thousand, glass transition temperature 55 deg.C); the thickness is 30 μm;
the preparation process comprises the following steps:
respectively preparing a mechanical support layer pipe and a speed-control degradation layer pipe in an extrusion mode, wherein the wall thickness of the mechanical support layer pipe is 270 mu m; the wall thickness of the speed-control degradation layer pipe is 80 mu m;
and (2) carrying out first thermal expansion (thermal expansion ratio is 200%) on the speed-control degradation layer pipe in a mould, wherein the temperature of the first thermal expansion is 78 ℃, the pressure is 10bar, after 60s, placing the mechanical support layer pipe in the mould containing the speed-control degradation layer pipe subjected to thermal expansion for second thermal expansion (thermal expansion ratio is 200%), wherein the temperature of the second thermal expansion is 95 ℃, the pressure is 20bar, after 200s, carrying out third thermal expansion (thermal expansion ratio is 135%), the temperature of the third thermal expansion is 120 ℃, the pressure is 20bar, and the time is 240s, thus obtaining the polymer pipe.
The polymer pipe is subjected to mechanical property test, and the test standard is YY/T0663.2-2016 anti-parallel plate extrusion performance test; the test result shows that the average radial strength is 1.14N/mm when the diameter of the pipe is reduced by 50% in compression, and the average force value is 13.67N;
carrying out degradation performance test on the polymer pipe, wherein the test standard is GB/T16886.13-2017 midbody external accelerated degradation test; the test results were 0% loss of average mass, 2% loss of 1-balance homogeneity, less than 13% loss of 7-balance homogeneity, 22% loss of 14-balance homogeneity and 50% loss of 28-balance homogeneity.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. A polymer pipe with controllable degradation speed is characterized by comprising a mechanical support layer and a speed-control degradation layer which are stacked from inside to outside;
the mechanical support layer and the speed-control degradation layer are made of degradable polymers;
the molecular weight of the material of the mechanical support layer is larger than that of the material of the speed control degradation layer;
the degradable polymer is one or more of polylactic acid, poly D, L-lactide, polyglycolic acid, polylactic acid-glycolic acid copolymer, polycaprolactone and poly-p-dioxanone fiber.
2. The polymer tubing of claim 1, wherein the number average molecular weight of the material of the rate controlling degradation layer is from 8 to 15 ten thousand;
the number average molecular weight of the material of the mechanical support layer is 20-50 ten thousand.
3. The polymer tubing of claim 1, wherein the polylactic-co-glycolic acid comprises PLGA50:50, PLGA40:60, PLGA70:30, or PLGA80: 20;
the polylactic acid comprises PLLA or PLA.
4. The polymer tubing of claim 3, wherein the material of the rate controlling degradation layer is one or more of poly D, L-lactide, PLGA50:50, PLGA40:60, and polyglycolic acid;
the mechanical support layer is made of one or more of PLLA, poly D, L-lactide, PLGA70:30 and PLGA80: 20.
5. The polymer tubing of any one of claims 1-4, wherein the thickness of the rate-controlling degradation layer is 20-60 μm;
the thickness of the mechanical support layer is 50-100 mu m.
6. The polymer tubing of claim 5, wherein the rate-controlling degradation layer comprises ≥ 1 degradable polymer layer;
the mechanical support layer comprises more than or equal to 1 degradable polymer layer.
7. A method for producing a polymer pipe according to any one of claims 1 to 6, comprising the steps of:
preparing a mechanical support layer pipe and a speed-control degradation layer pipe;
and after carrying out first thermal expansion on the speed-control degradation layer pipe in a mould, placing the mechanical support layer pipe in the mould containing the thermally expanded speed-control degradation layer pipe for second thermal expansion, and then sequentially carrying out third thermal expansion to obtain the polymer pipe.
8. The preparation method according to claim 7, wherein the temperature of the first thermal expansion is 10-30 ℃ higher than the glass transition temperature of the speed-control degradation layer pipe, the time is 20-60 s, and the pressure is 3-10 bar;
the temperature of the second thermal expansion is 25-52 ℃ higher than the glass transition temperature of the mechanical support layer pipe, the time is 80-200 s, and the pressure is 12-20 bar.
9. The method of claim 7, wherein the expansion ratio of the first thermal expansion, the second thermal expansion, and the third thermal expansion is independently 100 to 500%.
10. Use of the polymer tube according to any one of claims 1 to 6 or the polymer tube prepared by the preparation method according to any one of claims 7 to 9 in the field of medical devices.
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| CN202111333342.1A CN114028621A (en) | 2021-11-11 | 2021-11-11 | Polymer pipe with controllable degradation speed and preparation method and application thereof |
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| CN107693854A (en) * | 2016-08-04 | 2018-02-16 | 上海微创医疗器械（集团）有限公司 | Tubing for preparing support and preparation method thereof, support and preparation method thereof |
| CN109350770A (en) * | 2018-12-11 | 2019-02-19 | 上海七木医疗器械有限公司 | A kind of preparation method being layered degradation polymer bracket |
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| US20090216316A1 (en) * | 2008-02-25 | 2009-08-27 | Yunbing Wang | Bioabsorbable Stent With Layers Having Different Degradation Rates |
| US20130261736A1 (en) * | 2012-04-02 | 2013-10-03 | Abbott Cardiovascular Systems Inc. | Multilayer bioabsorbable scaffolds and methods of fabricating |
| CN105477690A (en) * | 2014-09-17 | 2016-04-13 | 上海微创医疗器械（集团）有限公司 | Multilayer degradable tube and stent and preparation method thereof |
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