CN101623516B - In-situ fiber-forming strengthened degradable medical elastic composite material and preparation method thereof - Google Patents
In-situ fiber-forming strengthened degradable medical elastic composite material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses an in-situ fiber-forming strengthened degradable medical elastic composite material and a preparation method thereof. The composite material is prepared by premixing polyglycolic acid or poly-(L-lactic acid) and poly-(L-lactide-tao-caprolactone) by a weight ratio of 20:80 to 5:95 in an inert gas atmosphere; extruding the mixture in a plastic extruder with a screw rotation speed of 10-80 r/min; hauling the extruded mixture by a hauling machine at a hauling speed of 1-30 m/min; controlling a die diameter/a spline diameter to be 1-6; and quenching with water in a hauling process. The composite material can be fully biologically degraded, has obviously improved tensile strength, enables fused mass to have little abrasion on the inner wall of an equipment cavity in the processing process and can be used in medical fields, such as degradable catheters, elastic fascia, artificial skin, and the like.
Description
Technical field
The invention belongs to the high-molecular biologic field of medical materials.Specifically; The present invention relates to a kind of by polyglycolic acid [poly (glycolic acid); PGA] or gather (L-lactic acid) [poly (L-lactic acid); PLLA] strengthen the method for preparing gather (L-lactide-epsilon-coprolactone) [poly (L-lactide-co-ε-caprolactone), PLLCA] in-situ fibrillation degradable medical elastic composite material.
Background technology
Along with clinical medical continuous development, the bio-medical elastomeric material has obtained application more and more widely.At present, the medical elastomer of having reported mainly is divided into degradable medical elastic body and non-degradable elastomer two big classes.Wherein, The non-degradable elastomer mainly has silicone rubber medical elastomer, polyurethane medical elastomer etc., and there are many deficiencies in the non-degradable medical elastomer in clinical practice, needs second operation to take out like elastomer; Increased operation risk when bringing very big misery to patient; Because the biocompatibility of most of non-degradable material is relatively poor, foreign body reaction after implanting, usually occurs, thereby cause a series of complication in addition.Degradable elastomers mainly is divided into the polyether ester bioelastomer, gathers the peptide bioelastomer, hydrogel and polyesters bioelastomer etc.; Though the degradable medical elastic body has better biocompatibility at present; But production cost is high; Processing conditions is complicated, bad mechanical property, thus limited application clinically.
In view of the defective that exists in the prior art, it is low to the invention provides a kind of production cost, easy and simple to handle, the degradable medical elastic composite material of good biocompatibility.
Summary of the invention
The invention provides by polyglycolic acid or gather (L-lactic acid) in-situ fibrillation and strengthen and to gather (L-lactide-epsilon-coprolactone) degradable medical elastic composite material and preparation method thereof.
A kind of in-situ fiber-forming strengthened degradable medical elastic composite material adopts polyglycolic acid or gathers (L-lactic acid) and, gather (L-lactide-epsilon-coprolactone) as filler as matrix, through following method preparation:
With polyglycolic acid or gather (L-lactic acid) and to gather (L-lactide-epsilon-coprolactone) be 20/80～5/95 premix by mass ratio, in atmosphere of inert gases, utilize extruding machine to extrude, the screw speed of extruding machine is 10～80r/min; Extrude the back with the hauling speed traction of traction machine with 1～30m/min, the value of control port mould diameter/batten diameter (draw ratio) is 1～6, uses water quench cooling in the distraction procedure.
Wherein, the weight average molecular weight (M that gathers (L-lactide-epsilon-coprolactone)
w) be 10-60 ten thousand, gathering (L-lactide-epsilon-coprolactone) middle 6-caprolactone unit molar percentage is 15%～30%.The intrinsic viscosity of polyglycolic acid [η] is 1～5g/dl; Weight average molecular weight (the M that gathers (L-lactic acid)
w) be 10～1,000,000.
Satisfy the polyglycolic acid of above-mentioned molecular weight or viscosities or gather (L-lactic acid) and gather (L-lactide-epsilon-coprolactone) when cooperating, polyglycolic acid or the melt viscosity ratio range that gathers (L-lactic acid) and gather (L-lactide-epsilon-coprolactone) help better becoming fibre.If this ratio is too small, then become not fiber; This ratio is excessive, and then the draw ratio of fiber can be very little.Therefore, through to the molecular weight control that gathers (L-lactide-epsilon-coprolactone) with to polyglycolic acid or gather (L-lactic acid) and carry out viscosity or molecular weight control, control the ratio of viscosities of the two melt, thereby be controlled to fibrid.
Control the intensity of composite among the present invention through the usage ratio of regulating polyglycolic acid or gather (L-lactic acid) and gather (L-lactide-epsilon-coprolactone).The increase of fiber content in the composite, the hot strength of material present elder generation and increase the trend that afterwards reduces, and an amount of fiberfill fibers can play potentiation to material; If but fiber content is excessive, can make to form between fiber and reunite, in material, form defective, cause the mechanical property of materials to descend.Polyglycolic acid or gather (L-lactic acid) and be controlled to be 20/80～5/95 with the mass ratio that gathers (L-lactide-epsilon-coprolactone) among the present invention was compared with single gathering (L-lactide-epsilon-coprolactone), and the intensity of composite elastic body has had obvious enhancing.
Among the present invention through control port mould diameter/batten diameter (draw ratio) 1～6 control the composite elastic body that makes performance.Specifically, can regulate port mould diameter/batten diameter (draw ratio) through the screw speed of adjusting extruding machine and the hauling speed of traction machine.The screw speed of extruding machine has direct influence to fibre diameter size in the composite.Along with screw speed increases, the probability that dispersed phase drop collides each other reduces, and the fibre diameter that forms after dispersed phase drop is stretched like this can be very little; But then, excessive rotating speed can be given the bigger shearing force of polymer melt, is prone to cause depolymerization.The screw speed of extruding machine is 10～80r/min among the present invention.The hauling speed of traction machine is also influential to fibre diameter size in the composite.Hauling speed is big more, and the diameter of rod of then extruding is more little, and fiber is stretched obvious more in the composite.But then, if the fiber draw ratio is excessive in the composite, in secondary operations or material use, fiber ruptures easily, produces defective at material internal.The hauling speed of traction machine is 1～30m/min among the present invention.The diameter of the composite that makes is 100nm～500nm, and fiber has partial fusion mutually and between matrix, and the boundary effect is stronger.
Fiber in the In-situ Composite of the present invention mainly forms extrude and extrude two processes of rear haulage from the mouth mould.Therefore, also important influence of the temperature of extrusion process.The present invention adopts general many temperature provinces that material is heated, and to the mouth mould, is divided into four humidity provinces of I-IV from the terminal charging aperture of screw rod, and IV district temperature is a die temperature.The temperature set-up mode in four zones is undertaken by mode common in the prior art.Take to increase earlier the mode that afterwards reduces; The first material premix that under lower slightly temperature (I district temperature), makes; Make that then material melt extrudes; Usually guaranteeing that filler can get lower temperature under the complete fused prerequisite, the temperature that promptly melt extrudes process behind the premix is not less than the fusing point of filler, is preferably the fusing point of filler or a little more than the fusing point of filler.When filler is polyglycolic acid, complete 230 ℃ of left and right sides fusions; Filler is when gathering (L-lactic acid), and is complete 180 ℃ of left and right sides fusions.Different according to molecular weight, the filler fusing point can be slightly different.
Wherein noble gas can be various noble gases commonly used, nitrogen.
Because the melt viscosity of In-situ Composite is lower, the processing characteristics of composite is improved, and processing temperature is lower, and melt is littler to the wearing and tearing of equipment inwall in the course of processing.Carry out secondary operations after will making the In-situ Composite shear granulation, processing temperature is about 140 ℃, can be processed into material requested arbitrarily such as tubing, bar, sheet material and profile shapes.
Polyglycolic acid of the present invention or gather (L-lactic acid) in-situ fibrillation and strengthen and to gather (L-lactide-epsilon-coprolactone) composite and can be widely used in the medical elastomer field is used to prepare medical apparatus and instruments such as degradable medical conduit, degradable elasticity fascia, degradable artificial skin.Particularly when producing the degradable conduit; Because fento is in the conduit molding, to form on the spot; Therefore, fento can be height-oriented along the conduit axial direction, thereby make the hot strength increase of conduit more obvious; And other short fiber reinforcing materials are isotropic, can't compare with in-situ fibrillation reinforcing material of the present invention.
The present invention avoids adopting general thermotropic liquid crystal as fibre-forming material, thereby has broken through general fibre-forming material because expensive and non-degradable property are difficult to the restriction applied in the degradable medical field.The present invention will have preferably crystallizing power and hot strength degradable biological medical material polyglycolic acid and gather (L-lactic acid) as reinforcing material (fibre-forming material); With gather (L-lactide-epsilon-coprolactone) matrix blend processing; The reinforcing material and the matrix compatibility are suitable; Too poor system can't realize reinforced effects both to have avoided the compatibility, has avoided the two complete consolute in the very good system of the compatibility to cause forming the defective of fiber again, and reinforcing material fully disperses in matrix; It is about 180 ℃ that reinforcing material gathers (L-lactic acid) processing temperature; The processing temperature of polyglycolic acid is about 230 ℃; The processing temperature of matrix is about 140 ℃; Because the processing temperature that temperature will be equal to or higher than matrix during the composite secondary operations makes the matrix fusion, but the processing temperature that will be lower than fibre-forming material simultaneously is held in the fibre morphology of fiber material, so the composite fabricating temperature is between the processing temperature of matrix and fibre-forming material; And the processing temperature difference of reinforcing material and base material is enough big among the present invention, thereby has guaranteed the composite fabricating temperature scope of broad; In the course of processing; Wild phase is orientated the formation fento on the spot; In-situ fibrillation obtains fiber-reinforced polymer; The polyglycolic acid that obtains like this or gather (L-lactic acid) in-situ fibrillation to strengthen the fiber reinforcement phase diameter gather in (L-lactide-epsilon-coprolactone) composite littler combines better off with the interface of matrix, dispersion more easily in matrix material; The reinforcing material crystal property is good simultaneously, avoids fiber to form after-contraction, makes the loss of fiber draw ratio; Material coextrusion after-drawing helps the formation of fortifying fibre; The fento diameter is little of submicron order in the In-situ Composite that finally obtains, and is 100nm～500nm among the present invention, and melt viscosity obviously descends, and processability is better.
Strengthen polymer composite with traditional fibre and compare, polyglycolic acid of the present invention or gather (L-lactic acid) in-situ fibrillation and strengthen that to gather (L-lactide-epsilon-coprolactone) composite be a kind of medical material that can complete biodegradable; Directly add the fibre-reinforced high molecular composite with tradition and compare, polyglycolic acid of the present invention or gather (L-lactic acid) in-situ fibrillation to strengthen the fiber phase diameter gather (L-lactide-epsilon-coprolactone) composite thinner, diameter is 100nm～500nm; Fiber has partial fusion mutually and between matrix, and the boundary effect is stronger; Polyglycolic acid of the present invention or gather (L-lactic acid) in-situ fibrillation and strengthen and to gather (L-lactide-epsilon-coprolactone) composite and on mechanical performance, have clear improvement than gathering (L-lactide-epsilon-coprolactone) merely, the hot strength of composite can increase by 20～50%; In addition, polyglycolic acid of the present invention or gather (L-lactic acid) in-situ fibrillation to strengthen the melt viscosity gather (L-lactide-epsilon-coprolactone) composite lower can alleviate in the course of processing melt effectively to the wearing and tearing of equipment cavity inner wall.
The specific embodiment
Embodiment 1
Is 5/95 premix with gathering (L-lactide-epsilon-coprolactone) by mass ratio with polyglycolic acid, in nitrogen atmosphere, utilizes single multiple screw extruder to extrude, and the extruding machine temperature is set to: (I) district is 220 ℃, and (II) district is 240 ℃, and (III) district is 230 ℃, and (IV) district is 230 ℃; The extruder screw rotating speed is 10r/min; Extrude the back with the hauling speed traction of traction machine with 1.8m/min, control draw ratio (port mould diameter/batten diameter) is 3, uses water quench cooling in the distraction procedure, obtains the enhancing of polyglycolic acid in-situ fibrillation and gathers (L-lactide-epsilon-coprolactone) composite.Gather (L-lactide-epsilon-coprolactone) weight average molecular weight (M
w) be 15.5 ten thousand, wherein 6-caprolactone unit mole percent is 15%; The intrinsic viscosity of polyglycolic acid [η] is 1.5g/dl.Test result shows: gathering (L-lactide-epsilon-coprolactone) hot strength is 28.2MPa; The hot strength of the polyglycolic acid of gained/gather (L-lactide-epsilon-coprolactone) is 33.2MPa, and elongation at break is 590%.
Embodiment 2
Is 10/90 premix with gathering (L-lactide-epsilon-coprolactone) by mass ratio with polyglycolic acid, in nitrogen atmosphere, utilizes single multiple screw extruder to extrude, and the extruding machine temperature is set to: (I) district is 220 ℃, and (II) district is 240 ℃, and (III) district is 230 ℃, and (IV) district is 230 ℃; The extruder screw rotating speed is 20r/min; Extrude the back with the hauling speed traction of traction machine with 3.7m/min, control draw ratio (port mould diameter/batten diameter) is 3, uses water quench cooling in the distraction procedure, obtains the enhancing of polyglycolic acid in-situ fibrillation and gathers (L-lactide-epsilon-coprolactone) composite.Wherein, gather (L-lactide-epsilon-coprolactone) weight average molecular weight (M
w) be 28.4 ten thousand, 6-caprolactone unit mole percent is 18%; The intrinsic viscosity of polyglycolic acid [η] is 2.1g/dl.Test result shows: gathering (L-lactide-epsilon-coprolactone) hot strength is 25.1MPa; The hot strength of gathering (L-lactide-epsilon-coprolactone)/polyglycolic acid of gained is 33.4MPa, and elongation at break is 568%.
Embodiment 3
Is 10/90 premix with gathering (L-lactide-epsilon-coprolactone) by mass ratio with polyglycolic acid, in nitrogen atmosphere, utilizes single multiple screw extruder to extrude, and the extruding machine temperature is set to: (I) district is 220 ℃, and (II) district is 240 ℃, and (III) district is 230 ℃, and (IV) district is 230 ℃; The extruder screw rotating speed is 25r/min; Extrude the back with the hauling speed traction of traction machine with 8.3m/min, control draw ratio (port mould diameter/batten diameter) is 4, uses water quench cooling in the distraction procedure, obtains the enhancing of polyglycolic acid in-situ fibrillation and gathers (L-lactide-epsilon-coprolactone) composite.Wherein, gather (L-lactide-epsilon-coprolactone) weight average molecular weight (M
w) be 40.3 ten thousand, 6-caprolactone unit mole percent is 22%; The intrinsic viscosity of polyglycolic acid [η] is 2.6g/dl.Test result shows: gathering (L-lactide-epsilon-coprolactone) hot strength is 26.1MPa; The hot strength of gathering (L-lactide-epsilon-coprolactone)/polyglycolic acid of gained is 36.4MPa, and elongation at break is 572%.
Embodiment 4
Is 15/85 premix with gathering (L-lactide-epsilon-coprolactone) by mass ratio with polyglycolic acid, in nitrogen atmosphere, utilizes single multiple screw extruder to extrude, and the extruding machine temperature is set to: (I) district is 220 ℃, and (II) district is 240 ℃, and (III) district is 230 ℃, and (IV) district is 230 ℃; The extruder screw rotating speed is 30r/min; Extrude the back with the hauling speed traction of traction machine with 14.8m/min, control draw ratio (port mould diameter/batten diameter) is 5, uses water quench cooling in the distraction procedure, obtains the enhancing of polyglycolic acid in-situ fibrillation and gathers (L-lactide-epsilon-coprolactone) composite.Wherein, gather (L-lactide-epsilon-coprolactone) weight average molecular weight (M
w) be 48.1 ten thousand, 6-caprolactone unit mole percent is 25%, the intrinsic viscosity of polyglycolic acid [η] is 3.5g/dl.Test result shows: gathering (L-lactide-epsilon-coprolactone) hot strength is 22.4MPa; The hot strength of gathering (L-lactide-epsilon-coprolactone)/polyglycolic acid of gained is 38.4MPa, and elongation at break is 536%.
Embodiment 5
Is 20/80 premix with gathering (L-lactide-epsilon-coprolactone) by mass ratio with polyglycolic acid, in nitrogen atmosphere, utilizes single multiple screw extruder to extrude, and the extruding machine temperature is set to: (I) district is 220 ℃, and (II) district is 240 ℃, and (III) district is 230 ℃, and (IV) district is 230 ℃; The extruder screw rotating speed is 35r/min; Extrude the back with the hauling speed traction of traction machine with 12.2m/min, control draw ratio (port mould diameter/batten diameter) is 4, uses water quench cooling in the distraction procedure, obtains the enhancing of polyglycolic acid in-situ fibrillation and gathers (L-lactide-epsilon-coprolactone) composite.Wherein, gather (L-lactide-epsilon-coprolactone) weight average molecular weight (M
w) be 30.3 ten thousand, 6-caprolactone unit mole percent is 20%; The intrinsic viscosity of polyglycolic acid [η] is 4.1g/dl.Test result shows: gathering (L-lactide-epsilon-coprolactone) hot strength is 25.4MPa; The hot strength of gathering (L-lactide-epsilon-coprolactone)/polyglycolic acid of gained is 31.1MPa, and elongation at break is 472%.
Embodiment 6
To gather (L-lactic acid) is 5/95 premix with gathering (L-lactide-epsilon-coprolactone) by mass ratio, in nitrogen atmosphere, utilizes single multiple screw extruder to extrude, and the extruding machine temperature is set to: (I) district is 170 ℃, and (II) district is 190 ℃, and (III) district is 180 ℃, and (IV) district is 180 ℃; The extruder screw rotating speed is 10r/min; Extrude the back with the hauling speed traction of traction machine with 2.1m/min, control draw ratio (port mould diameter/batten diameter) is 3, uses water quench cooling in the distraction procedure, is gathered the enhancing of (L-lactic acid) in-situ fibrillation and gathers (L-lactide-epsilon-coprolactone) composite.Wherein, gather (L-lactide-epsilon-coprolactone) weight average molecular weight (M
w) be 15.5 ten thousand, 6-caprolactone unit mole percent is 15%; Weight average molecular weight (the M that gathers (L-lactic acid)
w) be 20.4 ten thousand.Test result shows: gathering (L-lactide-epsilon-coprolactone) hot strength is 28.2MPa; The hot strength of the gathering of gained (L-lactide-epsilon-coprolactone)/gather (L-lactic acid) is 21.4MPa, and elongation at break is 694%.
Embodiment 7
To gather (L-lactic acid) is 10/90 premix with gathering (L-lactide-epsilon-coprolactone) by mass ratio, in nitrogen atmosphere, utilizes single multiple screw extruder to extrude, and the extruding machine temperature is set to: (I) district is 170 ℃, and (II) district is 190 ℃, and (III) district is 180 ℃, and (IV) district is 180 ℃; The extruder screw rotating speed is 20r/min; Extrude the back with the hauling speed traction of traction machine with 4.1m/min, control draw ratio (port mould diameter/batten diameter) is 3, uses water quench cooling in the distraction procedure, is gathered the enhancing of (L-lactic acid) in-situ fibrillation and gathers (L-lactide-epsilon-coprolactone) composite.Wherein, gather (L-lactide-epsilon-coprolactone) weight average molecular weight (M
w) be 28.4 ten thousand, 6-caprolactone unit mole percent is 18%; Weight average molecular weight (the M that gathers (L-lactic acid)
w) be 45.3 ten thousand.Test result shows: gathering (L-lactide-epsilon-coprolactone) hot strength is 25.1MPa; The hot strength of the gathering of gained (L-lactide-epsilon-coprolactone)/gather (L-lactic acid) is 32.3MPa, and elongation at break is 582%.
Embodiment 8
To gather (L-lactic acid) is 10/90 premix with gathering (L-lactide-epsilon-coprolactone) by mass ratio, in nitrogen atmosphere, utilizes single multiple screw extruder to extrude, and the extruding machine temperature is set to: (I) district is 170 ℃, and (II) district is 190 ℃, and (III) district is 180 ℃, and (IV) district is 180 ℃; The extruder screw rotating speed is 25r/min; Extrude the back with the hauling speed traction of traction machine with 8.5m/min, control draw ratio (port mould diameter/batten diameter) is 4, uses water quench cooling in the distraction procedure, is gathered the enhancing of (L-lactic acid) in-situ fibrillation and gathers (L-lactide-epsilon-coprolactone) composite.Wherein, gather (L-lactide-epsilon-coprolactone) weight average molecular weight (M
w) be 40.3 ten thousand, 6-caprolactone unit mole percent is 22%; Weight average molecular weight (the M that gathers (L-lactic acid)
w) be 58.6 ten thousand.Test result shows: gathering (L-lactide-epsilon-coprolactone) hot strength is 26.1MPa; The hot strength of the gathering of gained (L-lactide-epsilon-coprolactone)/gather (L-lactic acid) is 35.1MPa, and elongation at break is 583%.
Embodiment 9
To gather (L-lactic acid) is 15/85 premix with gathering (L-lactide-epsilon-coprolactone) by mass ratio, in nitrogen atmosphere, utilizes single multiple screw extruder to extrude, and the extruding machine temperature is set to: (I) district is 170 ℃, and (II) district is 190 ℃, and (III) district is 180 ℃, and (IV) district is 180 ℃; The extruder screw rotating speed is 30r/min; Extrude the back with the hauling speed traction of traction machine with 15.5m/min, control draw ratio (port mould diameter/batten diameter) is 5, uses water quench cooling in the distraction procedure, is gathered the enhancing of (L-lactic acid) in-situ fibrillation and gathers (L-lactide-epsilon-coprolactone) composite.Wherein, gather (L-lactide-epsilon-coprolactone) weight average molecular weight (M
w) be 48.1 ten thousand, 6-caprolactone unit mole percent is 25%; Weight average molecular weight (the M that gathers (L-lactic acid)
w) be 77.5 ten thousand.Test result shows: gathering (L-lactide-epsilon-coprolactone) hot strength is 22.4MPa; The hot strength of the gathering of gained (L-lactide-epsilon-coprolactone)/gather (L-lactic acid) is 46.3MPa, and elongation at break is 557%.
Embodiment 10
To gather (L-lactic acid) is 20/80 premix with gathering (L-lactide-epsilon-coprolactone) by mass ratio, in nitrogen atmosphere, utilizes single multiple screw extruder to extrude, and the extruding machine temperature is set to: (I) district is 170 ℃, and (II) district is 190 ℃, and (III) district is 180 ℃, and (IV) district is 180 ℃; The extruder screw rotating speed is 35r/min; Extrude the back with the hauling speed traction of traction machine with 15.1m/min, control draw ratio (port mould diameter/batten diameter) is 4, uses water quench cooling in the distraction procedure, is gathered the enhancing of (L-lactic acid) in-situ fibrillation and gathers (L-lactide-epsilon-coprolactone) composite.Wherein, gather (L-lactide-epsilon-coprolactone) weight average molecular weight (M
w) be 30.3 ten thousand, 6-caprolactone unit mole percent is 20%; Weight average molecular weight (the M that gathers (L-lactic acid)
w) be 94.5 ten thousand.Test result shows: gathering (L-lactide-epsilon-coprolactone) hot strength is 25.4MPa; The hot strength of the gathering of gained (L-lactide-epsilon-coprolactone)/gather (L-lactic acid) is 31.3MPa, and elongation at break is 496%.
Claims (4)
1. the method for preparing of an in-situ fiber-forming strengthened degradable medical elastic composite material comprises:
With polyglycolic acid or to gather (L-lactic acid) be 20/80～5/95 premix at normal temperatures with gathering (L-lactide-epsilon-coprolactone) by mass ratio, in atmosphere of inert gases, utilize extruding machine to melt extrude, the screw speed of extruding machine is 10～80r/min; Extrude the back with the hauling speed traction of traction machine with 1～30m/min, the value of control port mould diameter/batten diameter is 1～6, uses water quench cooling in the distraction procedure;
Wherein, the weight average molecular weight of gathering (L-lactide-epsilon-coprolactone) is 10-60 ten thousand, and gathering (L-lactide-epsilon-coprolactone) middle 6-caprolactone unit molar percentage is 15%～30%; The intrinsic viscosity of polyglycolic acid is 1～5g/dl; The weight average molecular weight of gathering (L-lactic acid) is 10～1,000,000.
2. method for preparing as claimed in claim 1 is characterized in that: described noble gas is a nitrogen.
3. the polyglycolic acid that obtains of according to claim 1 or claim 2 method for preparing or gather (L-lactic acid) in-situ fibrillation and strengthen and gather (L-lactide-epsilon-coprolactone) degradable medical elastic composite material.
4. polyglycolic acid as claimed in claim 3 or gather (L-lactic acid) in-situ fibrillation and strengthen and to gather of the application of (L-lactide-epsilon-coprolactone) degradable medical elastic composite material in degradable conduit, degradable elasticity fascia and degradable artificial skin medical field.
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| CN101947353B (en) * | 2010-09-26 | 2012-10-31 | 苏州同科生物材料有限公司 | Degradable medical composite conduit containing functional nano coating and preparation method thereof |
| CN102920528A (en) * | 2012-10-19 | 2013-02-13 | 东华大学 | Hollowed-out membrane used as hernia patch and preparation method thereof |
| CN106237396B (en) * | 2016-07-27 | 2019-11-19 | 沈阳百奥医疗器械有限公司 | A kind of degradable macromolecule intermingling material and its preparation method and application based on in-situ fibrillation technology |
| CN109777059B (en) * | 2019-02-26 | 2021-03-16 | 中国医学科学院生物医学工程研究所 | Poly-L-lactide-caprolactone (PLCL) composite material capable of being printed in 3D mode and preparation method thereof |
| CN110028770A (en) * | 2019-04-28 | 2019-07-19 | 广州知旺科技有限公司 | It is a kind of can degradable composite membrane and preparation method thereof |
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| CN1159456A (en) * | 1995-09-07 | 1997-09-17 | 三井东压化学株式会社 | Bios absorbable polymer and preparation process thereof |
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| CN1159456A (en) * | 1995-09-07 | 1997-09-17 | 三井东压化学株式会社 | Bios absorbable polymer and preparation process thereof |
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