CN102634865B - Medical tube material with adjustable degradation time and preparation method thereof - Google Patents
Medical tube material with adjustable degradation time and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a medical tube material with adjustable degradation time and a preparation method thereof. The medical tube material comprises poly butylene glycol ester (PBC) and polycaprolactone (PCL), wherein the number-average molecular weight of the PBC ranges from 40,000 to 250,000, and the number-average molecular weight of the PCL ranges from 40,000 to 250,000; and the outer diameter of the tube material ranges from 0.1mm to 50mm, the inner diameter of the tube material ranges from 0.1mm to 50mm, and the length of the tube material ranges from 0.01m to 1m. The preparation method of the medical tube material comprises the following steps of: mixing the PBC and the PCL in proportion, performing grain-sized dicing on the PBC and the PCL, and then mixing the PCL and the PBC uniformly, dissolving or fusing the mixed ingredients, and adding a certain quantity of porogen in the ingredients according to needs; and performing processes of melt spinning, dry-wet spinning or wet spinning, thermally induced phase separation and the like on the solution to obtain a hollow tube. According to the tube material disclosed by the invention, the mechanical strength is good, the surface flatness is excellent, the internal porosity and the pore diameter are adjustable, and the degradation time is controllable; and the preparation method disclosed by the invention is simple to operate, low in cost and wide in application.
Description
Technical field
The invention belongs to artificial field of medical materials, particularly adjustable medical tube material of a kind of degradation time and preparation method thereof.
Background technology
Polycaprolactone (PCL) be a kind of biodegradable aliphatic polyester, by caprolactone ring-opening polymerization, made, this material is nontoxic to body, has good biocompatibility, is a kind of desirable bio-medical material.After implanting animal body, absorb gradually, be finally degraded to CO
2and H
2o excretes.It has good mechanical performance and good medicine trafficability characteristic simultaneously, and these character make it at field of medicaments, have certain application potential, as can be used as material implanted and drug release material.This material has obtained the approval of U.S. FDA at present.Yet PCL, owing to there being long continuous carbochain in strand, therefore its hydrophily is poor, be unfavorable for the generation of hydrolysis, so degradation rate is slower, general degradable 2～4 years, has therefore limited it and studied widely and apply in medical field.
Polytetramethylene carbonate diol (PBC) is a kind of in synthetic new polyester material in 20 end of the centurys, but does not cause at that time enough attention.Until day by day emphasize today of environmental protection consciousness, domestic existing company starts to produce this material.PBC material has the advantages such as melt strength is high, processing forming good, the strength of materials is good, degradation cycle is moderate.From Figure of abstract, this material backbone structure and polycaprolactone have very high similitude, and difference is that an other methylene of this material carbonyl is replaced by oxygen atom.According to macromolecule relevant knowledge and early-stage Study, find, the existence of this oxygen atom makes itself and polycaprolactone phase specific degradation rate obtain improving largely.
Summary of the invention
Technical problem to be solved by this invention is to provide adjustable medical tube material of a kind of degradation time and preparation method thereof, this medical tubing material feed tube mechanical strength is good, surface flatness is good, interior porosity is controlled, aperture is adjustable, degradation time can be empty, and the method is simple to operate, and cost is low.
The medical tube material that a kind of degradation time of the present invention is adjustable, this medical tube material comprises: polytetramethylene carbonate diol (PBC) and polycaprolactone (PCL), wherein the number-average molecular weight of polytetramethylene carbonate diol is 40,000～250,000, and the number-average molecular weight of polycaprolactone is 40,000～250,000; The external diameter of described tube material is 0.1～50mm, and internal diameter is 0.1～50mm, and length is 0.01～1m
Described polytetramethylene carbonate diol and the mass ratio of polycaprolactone are 1-99: 99-1.
In described medical tube material, contain water-soluble pore-foaming agent, described water-soluble organic pore-foaming agent is polyethylene glycol (PEG), polyvinyl alcohol (PVA), polyvinylpyrrolidone (PVP), gelatin or alginate.
Described medical tube material has micropore, and micropore size is 0.01um～1mm, and porosity is 1～95%.
The preparation method of the medical tube material that a kind of degradation time of the present invention is adjustable, comprises three kinds of technique approach, is respectively melt spinning, thermally induced phase separation, the preparation of dry-wet spinning/wet spinning.
Described melt spinning method, comprising:
(1), by PBC and PCL pelletizing and pulverize, after mixing, heating and melting stirring at 100～140 ℃, extrudes to obtain doughnut with the spinning head that spins doughnut at 70～90 ℃, cooling;
(2) first cooled doughnut step (1) being obtained carries out cold stretch at 0-20 ℃, cold stretch ratio is 10%～30%, then at 40～50 ℃, carry out hot-stretch, hot-stretch ratio is 30%～100%, product after stretching is carried out to HEAT SETTING under tensile stress effect, setting temperature is 47～52 ℃, and shaping time 1-10h, obtains.
Described in step (1) by after PBC and PCL pelletizing pulverizing, add water-soluble pore-foaming agent; The cooled doughnut that step (1) is obtained is put into water and is soaked, thereby extract water-soluble pore-foaming agent, obtains intermediate products, and then carries out the described operation of step (2).
The rate of extension sum of the cold stretch described in step (2) and hot-stretch is 10mm/min-500mm/min.
Described thermally induced phase separation, comprising:
(1) by PBC and PCL pelletizing pulverizing, after mixing, join in solvent (as chloroform, carrene, formic acid etc.), in temperature, be that at 65～70 ℃, (this temperature is higher than the fusing point of PBC and PCL, therefore for thermally induced phase separation) stirring and dissolving makes solution, filtering solution then, vacuum defoamation, to without naked eyes visible bubble in bubble, obtains spinning solution;
(2) at 50～65 ℃, above-mentioned spinning solution is extruded with the spinning head of spinning doughnut, adopt the technique curing molding similar to dry-wet method or wet spinning, parameter is: air layer height 0～20cm, 0～40 ℃ of coagulation bath temperature; It is stretched as 1～3 grade, and tepidarium is as drawing medium, and tepidarium temperature is 10～40 ℃, and draw ratio is 1～10 times;
(3) product step (2) being obtained is dried under inert gas shielding, and last sterilization treatment, obtains.
Described in step (1) by after PBC and PCL pelletizing pulverizing, add water-soluble pore-foaming agent; The product that step (2) is obtained is immersed in warm water (10-35 ℃) except desolventizing and water-soluble pore-foaming agent, and then carries out the described operation of step (3).
Described in step (1) by after PBC and PCL pelletizing pulverizing, add water-soluble pore-foaming agent; The product that step (2) is obtained is removed after solvent by volatilization, then impregnated in and in water, remove water-soluble pore-foaming agent and residual solvent, and then carries out the described operation of step (3).
Described dry-wet spinning/wet spinning, comprising:
(1) by PBC and PCL pelletizing pulverizing, after mixing, join in solvent (as chloroform, carrene, formic acid etc.), at 50～70 ℃, stirring and dissolving is made solution, then filtering solution, vacuum defoamation, to without naked eyes visible bubble in bubble, obtains spinning solution;
(2) then above-mentioned spinning solution is carried out to dry-wet spinning, its technological parameter is: air layer height 0.5～20cm, 0～40 ℃ of coagulation bath temperature; It is stretched as 1～3 grade, and tepidarium is as drawing medium, and tepidarium temperature is 10～40 ℃, and draw ratio is 1～10 times;
Or above-mentioned spinning solution is carried out to wet spinning, its technological parameter is: 0～40 ℃ of coagulation bath temperature; It is stretched as 1～3 grade, and tepidarium is as drawing medium, and tepidarium temperature is 10～40 ℃, and draw ratio is 1～10 times;
(3) spinning is dried after completing under inert gas shielding, and last sterilization treatment, obtains.
Described in step (1) by after PBC and PCL pelletizing pulverizing, add water-soluble pore-foaming agent; The product that step (2) is obtained is immersed in warm water (10-35 ℃) except desolventizing and water-soluble pore-foaming agent, and then carries out the described operation of step (3).
Described in step (1) by after PBC and PCL pelletizing pulverizing, add water-soluble pore-foaming agent; The product that step (2) is obtained is removed after solvent by volatilization, then impregnated in and in water, remove water-soluble pore-foaming agent and residual solvent, and then carries out the described operation of step (3).
PBC is at physical characteristics of materials, and particularly mechanical property, thermal property (as glass transition temperature and fusing point etc.), dissolution properties aspect and PCL are very approaching.By further research, find that both have extraordinary compatibility.
The present invention can add a certain amount of water-soluble organic pore-foaming agent as required to create pore space structure.
In PCL and this bi-material of PBC, the degradation time of PCL is longer, generally about 2～4 years, can reach substantially in vivo degradable, and the degradation time of PBC is relatively short.So bi-material, by different proportion blend, can be prepared to the transformable composite of degradation time.Wherein, the amount that increases PCL has extended degradation time relatively, makes material can keep in a long time mechanical property relatively preferably; The ratio that improves PBC can marginally improve the hydrophily of material, the more important thing is and has shortened degradation time, and material is more suitable in shorter purposes of restore cycle.
Meanwhile, by adding water miscible organic pore-foaming agent, not only can improve the hydrophily of material, meanwhile, because pore space structure has increased the specific area of material, material degradation speed be accelerated.On the other hand, give material and also make material can be expected to for some other special purposes with pore structure, as filtered tubular film etc.
The material degradation time of the present invention can be adjusted in one to four year, can be in organizational project as artificial blood vessel repair materials, catheter holder material, organize barrier material etc. to use, and can be prepared into target product by multiple different preparation methods' processing.
Beneficial effect:
(1) tube material mechanical strength of the present invention is good, surface flatness is good, interior porosity is controlled, aperture is adjustable; Tube material degradation time of the present invention can be according to the difference at purposes and position and relative variation matched with the human body restore cycle;
(2) preparation method of the present invention is common and the most general method and apparatus, simple to operate, and cost is low;
(3) hollow-fibre membrane of the present invention can, as artificial blood vessel repair materials, catheter holder materials'use in organizational project, also can be used for other aspects in the bio-medical field except organizational project and the other field outside medical science.
Accompanying drawing explanation
Fig. 1 is the chemical structural formula of PBC and PCL.
The specific embodiment
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment are only not used in and limit the scope of the invention for the present invention is described.In addition should be understood that those skilled in the art can make various changes or modifications the present invention after having read the content of the present invention's instruction, these equivalent form of values fall within the application's appended claims limited range equally.
Embodiment 1
The PBC that is 120,000 by molecular weight and molecular weight are 80,000 PCL pelletizing and pulverize, degradation time is controlled both mass fractions and is 50% by the expected, simultaneously because material applications is not added pore-foaming agent, after being mixed, above-mentioned two components pour in barrel, in temperature, it is heating and melting stirring at 110 ℃, with the spinning head (temperature control is at 75 ℃) of spinning doughnut, be extruded into doughnut, cooling by cooling pipe.Total rate of extension by intermediate product with 12mm/min stretches, minute cold stretch and a hot-stretch stretch, first at cold drawing temperature, be cold stretch below 20 ℃, cold stretch ratio is 10%, then in hot-stretch temperature, be hot-stretch at 50 ℃, hot-stretch ratio is 60%, and the polytetramethylene carbonate diol tube material after stretching carries out HEAT SETTING under tensile stress effect, setting temperature is 50 ℃, shaping time 3h.Prepare all good transparent hollow tube of intensity and pliability, the external diameter of described tube material is 4mm, and internal diameter is 3mm, and length is 15cm; This pipe can be used for vascular repair field, and its degradation time is about 2 years.
Embodiment 2
By molecular weight, be PCL pelletizing the pulverizing of 60,000 PBC and 50,000, to control both ratios be 8: 2 to degradation time by the expected, according to material applications, add the water-soluble pore-foaming agent PEG 20000 of PBC and PCL quality sum 15% simultaneously, and after being mixed, said components joins their high-temperature solvent N, in dinethylformamide, in temperature, be that at 70 ℃, stirring and dissolving is made solution, filtering solution then, vacuum defoamation is to without naked eyes visible bubble in bubble.
Spinning solution is encased in the barrel with heating and heat preserving function, maintains the temperature at 65 ℃, with the spinning head of spinning doughnut, extrude, adopt the technique curing molding similar to wet spinning, parameter is: 15 ℃ of coagulation bath temperatures; Adopt 3 grades of stretchings, tepidarium is as drawing medium, and tepidarium temperature is 20 ℃, and draw ratio is 2 times; Then in warm water, remove desolventizing and pore-foaming agent, under inert gas shielding, dry, through sterilization treatment, obtain PBC hollow tube.
The external diameter of described tube material is 2mm, and internal diameter is 1mm, and length is 25cm; Described medical tube material has micropore, and micropore average pore size is 3 μ m, and porosity is 70%.This material can be used as nerve conduit stent materials'use, is degraded into little molecule and discharges in nerve growth reparation, and its degradation time is about 1.5 years.
Embodiment 3
The PBC that is 150,000 by molecular weight and 150,000 PCL pelletizing are also pulverized, to control both ratios be 2: 8 to degradation time by the expected, according to material applications, add the water-soluble pore-foaming agent polyvinyl alcohol (PVA1788) of PBC and PCL quality sum 30% simultaneously, and after said components is mixed, join in their common solvent chloroform, in temperature, be that at 50 ℃, stirring and dissolving is made solution, filtering solution then, vacuum defoamation is to without naked eyes visible bubble in bubble.By dry-wet spinning, prepare tube material, its technological parameter is: air layer height 3cm, 20 ℃ of coagulation bath temperatures; Employing single-stage stretches, and tepidarium is as drawing medium, and tepidarium temperature is 25 ℃, and draw ratio is 4 times; Then in warm water, remove desolventizing and pore-foaming agent, under inert gas shielding, dry, through sterilization treatment, obtain PBC hollow tube.
The external diameter of described tube material is 5mm, and internal diameter is 3.5mm, and length is 7cm; Described medical tube material has micropore, and micropore size is 10 μ m, and porosity is 90%.This tube material porosity is high, and aperture is larger, can be used as tissue carrier material and uses, and its degradation time is about 2.5 years.
Claims (5)
1. a preparation method for the adjustable medical tube material of degradation time, is characterized in that: this preparation method is melt spinning, comprising:
(1), by PBC and PCL pelletizing and pulverize, after mixing, heating and melting stirring at 100～140 ℃, extrudes to obtain doughnut with the spinning head that spins doughnut at 70～90 ℃, cooling;
(2) first cooled doughnut step (1) being obtained carries out cold stretch at 0-20 ℃, cold stretch ratio is 10%～30%, then at 40～50 ℃, carry out hot-stretch, hot-stretch ratio is 30%～100%, and the rate of extension sum of described cold stretch and hot-stretch is 10mm/min-500mm/min; Product after stretching is carried out to HEAT SETTING under tensile stress effect, and setting temperature is 47～52 ℃, and shaping time 1-10h, obtains;
Described medical tube material comprises: polytetramethylene carbonate diol and polycaprolactone, and wherein the number-average molecular weight of polytetramethylene carbonate diol is 40,000～250,000, the number-average molecular weight of polycaprolactone is 40,000～250,000; The external diameter of described tube material is 0.1～50mm, and internal diameter is 0.1～50mm, and length is 0.01～1m;
Described polytetramethylene carbonate diol and the mass ratio of polycaprolactone are 1-99:99-1;
Described medical tube material has micropore, and micropore size is 0.01um～1mm, and porosity is 1～95%.
2. the preparation method of the adjustable medical tube material of a kind of degradation time according to claim 1, is characterized in that: described in step (1) by after PBC and PCL pelletizing pulverizing, add water-soluble pore-foaming agent; The cooled doughnut that step (1) is obtained is put into water and is soaked, thereby extract water-soluble pore-foaming agent, obtains intermediate products, and then carries out the described operation of step (2).
3. a preparation method for the adjustable medical tube material of degradation time, is characterized in that: this preparation method is thermally induced phase separation spinning, comprising:
(1) by PBC and PCL pelletizing and pulverize, after mixing, join in solvent, in temperature, be that at 65～70 ℃, stirring and dissolving is made solution, filtering solution then, vacuum defoamation, to without naked eyes visible bubble in bubble, obtains spinning solution;
(2) at 50～65 ℃, above-mentioned spinning solution is extruded with the spinning head of spinning doughnut, adopt the technique curing molding similar to dry-wet method or wet spinning, parameter is: air layer height 0～20cm, 0～40 ℃ of coagulation bath temperature; It is stretched as 1～3 grade, and tepidarium is as drawing medium, and tepidarium temperature is 10～40 ℃, and draw ratio is 1～10 times;
(3) product step (2) being obtained is dried under inert gas shielding, and last sterilization treatment, obtains;
Described medical tube material comprises: polytetramethylene carbonate diol and polycaprolactone, and wherein the number-average molecular weight of polytetramethylene carbonate diol is 40,000～250,000, the number-average molecular weight of polycaprolactone is 40,000～250,000; The external diameter of described tube material is 0.1～50mm, and internal diameter is 0.1～50mm, and length is 0.01～1m;
Described polytetramethylene carbonate diol and the mass ratio of polycaprolactone are 1-99:99-1;
Described medical tube material has micropore, and micropore size is 0.01um～1mm, and porosity is 1～95%.
4. a preparation method for the adjustable medical tube material of degradation time, is characterized in that: this preparation method is dry-wet spinning/wet spinning, comprising:
(1) by PBC and PCL pelletizing and pulverize, after mixing, join in solvent, at 50～70 ℃, stirring and dissolving is made solution, filtering solution then, vacuum defoamation, to without naked eyes visible bubble in bubble, obtains spinning solution;
(2) then above-mentioned spinning solution is carried out to dry-wet spinning, its technological parameter is: air layer height 0.5～20cm, 0～40 ℃ of coagulation bath temperature; It is stretched as 1～3 grade, and tepidarium is as drawing medium, and tepidarium temperature is 10～40 ℃, and draw ratio is 1～10 times;
Or above-mentioned spinning solution is carried out to wet spinning, its technological parameter is: 0～40 ℃ of coagulation bath temperature; It is stretched as 1～3 grade, and tepidarium is as drawing medium, and tepidarium temperature is 10～40 ℃, and draw ratio is 1～10 times;
(3) spinning is dried after completing under inert gas shielding, and last sterilization treatment, obtains;
Described medical tube material comprises: polytetramethylene carbonate diol and polycaprolactone, and wherein the number-average molecular weight of polytetramethylene carbonate diol is 40,000～250,000, the number-average molecular weight of polycaprolactone is 40,000～250,000; The external diameter of described tube material is 0.1～50mm, and internal diameter is 0.1～50mm, and length is 0.01～1m;
Described polytetramethylene carbonate diol and the mass ratio of polycaprolactone are 1-99:99-1;
Described medical tube material has micropore, and micropore size is 0.01um～1mm, and porosity is 1～95%.
5. according to the preparation method of the adjustable medical tube material of a kind of degradation time described in claim 3 or 4, it is characterized in that, described in step (1) by after PBC and PCL pelletizing pulverizing, add water-soluble pore-foaming agent; The product that step (2) is obtained is immersed in the water of 10-35 ℃ except desolventizing and water-soluble pore-foaming agent, and then carries out the described operation of step (3).
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| CN104213211B (en) * | 2014-09-18 | 2016-06-08 | 东华大学 | A kind of method preparing doughnut artificial blood vessel for raw material with polycaprolactone |
| KR101897218B1 (en) * | 2015-05-11 | 2018-09-10 | 주식회사 아모라이프사이언스 | Cell culture scaffold using water soluble polymer |
| EP3393537B1 (en) * | 2015-12-22 | 2024-05-22 | Access Vascular, Inc. | High strength biomedical materials |
| CN106913393B (en) * | 2015-12-28 | 2020-10-30 | 烟台蓝创生物技术有限公司 | Artificial nerve scaffold and preparation method and application thereof |
| EP3641842A4 (en) | 2017-06-21 | 2021-03-17 | Access Vascular, Inc. | High strength porous materials incorporating water soluble polymers |
| CA3183979A1 (en) | 2020-06-30 | 2022-01-06 | Michael Bassett | Articles comprising markings and related methods |
| CN112472877B (en) * | 2020-12-18 | 2022-03-08 | 南京鼓楼医院 | Method for preparing lubricating oil-infused ultra-smooth porous surface for medical catheter |
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| CN102085393A (en) * | 2011-01-26 | 2011-06-08 | 东华大学 | Biodegradable nerve conduit with bilayer structure and preparation method thereof |
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