CN101003181A - Process method for polymer in poly lactic acid series to obtain shape memory effect in cold deformation molding - Google Patents
Process method for polymer in poly lactic acid series to obtain shape memory effect in cold deformation molding Download PDFInfo
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Abstract
聚乳酸系聚合物获得冷变形成型形状记忆效应的处理方法，本发明属于一种使医用可降解材料获得冷变形成型形状记忆效应的方法，它是为了解决聚乳酸系聚合物实施变形时必须在玻璃化转变温度以上15～20℃进行及形变固定后成品恢复力低的问题。该方法通过以下步骤实现：(一)模压成型；(二)退火处理，聚乳酸系聚合物获得冷变形成型形状记忆效应。经本发明处理后的聚乳酸系聚合物获得冷变形成型形状记忆效应，即材料在常温下即可实施形变处理，形变固定后将材料加热，形变发生恢复；处理过后的聚乳酸系聚合物的结晶度在10～25％之间，形变恢复率为85～96％，形变固定后成品恢复力在6.0～7.5Mpa之间；尤其适用于对恢复力要求较高的医学制品的使用需求。A treatment method for polylactic acid polymers to obtain cold deformation forming shape memory effects. The invention belongs to a method for obtaining medical degradable materials with cold deformation forming shape memory effects. The problem of low recovery force of the finished product after the glass transition temperature is 15-20°C and the deformation is fixed. The method is realized through the following steps: (1) compression molding; (2) annealing treatment, and the polylactic acid polymer obtains the shape memory effect of cold deformation molding. The polylactic acid polymer treated by the present invention obtains the shape memory effect of cold deformation forming, that is, the material can be deformed at room temperature, and the material is heated after the deformation is fixed, and the deformation recovers; the polylactic acid polymer after treatment The crystallinity is between 10-25%, the deformation recovery rate is 85-96%, and the recovery force of the finished product after deformation is fixed is between 6.0-7.5Mpa; it is especially suitable for the use of medical products that require high recovery force.
Description
Technical field
The present invention relates to a kind of method that makes the medical degradable material obtain cold deformation forming shape memory effect.
Background technology
Polymer in poly lactic acid series is important biological medical polymer material, obtains excellent biological compatibility and biodegradability, fixes in fracture, aspects such as tissue engineering bracket, surgical sutures, medicine controlled releasing system have obtained extensive use.Degradable poly lactic acid polymer medically commonly used is poly-L-lactide, poly-L-lactide copolymer, poly-L-lactide blend or poly-L-lactide composite.Polymer in poly lactic acid series has thermal deformation forming shape memory effect, that is: material is heated to more than the glass transition temperature 15～20 ℃, after it is out of shape with material cooled to below the glass transition temperature 15～20 ℃, deformation is fixed, when once more material being heated to glass transition temperature when above, deformation recovers.Polymer in poly lactic acid series must be implemented distortion in 15～20 ℃ more than glass transition temperature, the fixing back of deformation finished product restoring force is very low, have only 1～3Mpa, be difficult to satisfy the user demand of the medical articles (fracture fixation material, vascular stent material and intracanal scaffold) that restoring force is had relatively high expectations.
Summary of the invention
The present invention be must be more than glass transition temperature in order to solve polymer in poly lactic acid series and to implement distortion 15～20 ℃ carry out and be out of shape the fixing very low problem of finished product restoring force afterwards.The processing method that polymer in poly lactic acid series obtains cold deformation forming shape memory effect realizes by following steps: (one) compression molding: with relative molecular weight is that 100000～400000 polymer in poly lactic acid series is heated to more than the fusing point 20～30 ℃, after polymer in poly lactic acid series melts fully, at pressure be under the condition of 2～5Mpa with the polymer in poly lactic acid series compression molding of fusing, with the cooling velocity of 10～50 ℃/min the polymer in poly lactic acid series of compression molding is cooled to room temperature; (2) annealing in process: the polymer in poly lactic acid series of compression molding is put into annealing furnace, and annealing in process 15～60min in 80～120 ℃ is cooled to room temperature then, makes polymer in poly lactic acid series obtain cold deformation forming shape memory effect.Polymer in poly lactic acid series after the present invention handles obtains cold deformation forming shape memory effect, be the present invention handle later polymer in poly lactic acid series need be more than glass transition temperature 15～20 ℃ be out of shape fixing, material at normal temperatures can be by stretching, compression, crooked, reversing any or several modes implements deformation and fixes, after deformation is fixing material is heated to it more than glass transition temperature, deformation promptly recovers, the present invention handles polymer in poly lactic acid series degree of crystallinity later between 10～25%, the deformation recovery rate is 85～96%, and the fixing back of deformation finished product restoring force is between 6.0～7.5Mpa; Be particularly useful for the user demand of medical articles (fracture fixation material, vascular stent material and intracanal scaffold) that restoring force is had relatively high expectations.
The specific embodiment
The specific embodiment one: the processing method that polymer in poly lactic acid series in the present embodiment obtains cold deformation forming shape memory effect realizes by following steps: (one) compression molding: with relative molecular weight is that 100000～400000 polymer in poly lactic acid series is heated to more than the fusing point 20～30 ℃, after polymer in poly lactic acid series melts fully, at pressure be under the condition of 2～5Mpa with the polymer in poly lactic acid series compression molding of fusing, with the cooling velocity of 10～50 ℃/min the polymer in poly lactic acid series of compression molding is cooled to room temperature; (2) annealing in process: the polymer in poly lactic acid series of compression molding is put into annealing furnace, and annealing in process 15～60min in 80～120 ℃ is cooled to room temperature then, makes polymer in poly lactic acid series obtain cold deformation forming shape memory effect.
The polymer in poly lactic acid series of handling through present embodiment obtains cold deformation forming shape memory effect, the degree of crystallinity of handling polymer in poly lactic acid series later is between 10～25%, the deformation recovery rate is 85～96%, and the fixing back of deformation finished product elastic restoring force is between 6.0～7.5Mpa; Be particularly useful for the user demand of medical articles (fracture fixation material, vascular stent material and intracanal scaffold) that restoring force is had relatively high expectations.
The specific embodiment two: the difference of the present embodiment and the specific embodiment one is that step () polymer in poly lactic acid series is the poly-L-lactide in the medical degradable polylactic acid polymer, poly-L-lactide biodegradable block copolymer, poly-L-lactide blend or poly-L-lactide composite.Other step is identical with the specific embodiment one.
The specific embodiment three: the difference of the present embodiment and the specific embodiment two is that poly-L-lactide biodegradable block copolymer is poly-L-lactide/epsilon-caprolactone copolymer, poly-L/DL-lactide copolymer or poly-L-poly (lactide-co-glycolide) in the step (); Poly-L-lactide accounts for 80～95% of copolymer molar percentage in the copolymer.Other step is identical with the specific embodiment two.
The specific embodiment four: the difference of the present embodiment and the specific embodiment two is that poly-L-lactide biodegradable block copolymer is poly-L-lactide/epsilon-caprolactone copolymer, poly-L/DL-lactide copolymer or poly-L-poly (lactide-co-glycolide) in the step (); Poly-L-lactide accounts for 85～95% of copolymer molar percentage in the copolymer.Other step is identical with the specific embodiment two.
The specific embodiment five: the difference of the present embodiment and the specific embodiment two is that poly-L-lactide biodegradable block copolymer is poly-L-lactide/epsilon-caprolactone copolymer, poly-L/DL-lactide copolymer or poly-L-poly (lactide-co-glycolide) in the step (); Poly-L-lactide accounts for 82% of copolymer molar percentage in the copolymer.Other step is identical with the specific embodiment two.
The specific embodiment six: the difference of the present embodiment and the specific embodiment two is that poly-L-lactide degradable blend is poly-L-lactide/poly DL-lactide blend, poly-L-lactide/poly-glycolide blend or poly-L-lactide/poly-epsilon-caprolactone blend in the step (); Poly-L-lactide accounts for 80～95% of blend molar percentage in the blend.Other step is identical with the specific embodiment two.
The specific embodiment seven: the difference of the present embodiment and the specific embodiment two is that poly-L-lactide degradable blend is poly-L-lactide/poly DL-lactide blend, poly-L-lactide/poly-glycolide blend or poly-L-lactide/poly-epsilon-caprolactone blend in the step (); Poly-L-lactide accounts for 85～95% of blend molar percentage in the blend.Other step is identical with the specific embodiment two.
The specific embodiment eight: the difference of the present embodiment and the specific embodiment two is that poly-L-lactide degradable blend is poly-L-lactide/poly DL-lactide blend, poly-L-lactide/poly-glycolide blend or poly-L-lactide/poly-epsilon-caprolactone blend in the step (); Poly-L-lactide accounts for 88% of blend molar percentage in the blend.Other step is identical with the specific embodiment two.
The specific embodiment nine: the difference of the present embodiment and the specific embodiment two is that the poly-L-lactide composite of step () is poly-L-lactide/epsilon-caprolactone copolymer/bioactive particles composite, wherein bioactive particles is hydroxyapatite particle, Dicalcium Phosphate, tricalcium phosphate or bio-vitric, bioactive particles accounts for 5～30% of composite molar percentage in the composite, poly-L-lactide/epsilon-caprolactone copolymer accounts for 70～95% of composite molar percentage, and other step is identical with the specific embodiment two.
The specific embodiment ten: the difference of the present embodiment and the specific embodiment two is that poly-L-lactide composite is poly-L-lactide/epsilon-caprolactone copolymer/bioactive particles composite in the step (), wherein bioactive particles is the hydroxyapatite particle, Dicalcium Phosphate, tricalcium phosphate or bio-vitric, bioactive particles accounts for 10～25% of composite molar percentage in the composite, poly-L-lactide and poly-epsilon-caprolactone account for 75～90% of composite molar percentage, and the molar percentage between poly-L-lactide and the poly-epsilon-caprolactone is an arbitrary proportion.Other step is identical with the specific embodiment two.
The specific embodiment 11: the difference of the present embodiment and the specific embodiment two is that poly-L-lactide composite is poly-L-lactide/epsilon-caprolactone copolymer/bioactive particles composite in the step (), wherein bioactive particles is the hydroxyapatite particle, Dicalcium Phosphate, tricalcium phosphate or bio-vitric, bioactive particles accounts for 20% of composite molar percentage in the composite, poly-L-lactide and poly-epsilon-caprolactone account for 80% of composite molar percentage, and the molar percentage between poly-L-lactide and the poly-epsilon-caprolactone is an arbitrary proportion.Other step is identical with the specific embodiment two.
The specific embodiment 12: the difference of the present embodiment and the specific embodiment one is compression molding in the step (): with relative molecular weight is that 120000～380000 polymer in poly lactic acid series is heated to more than the fusing point 22～29 ℃, after PLA series melts fully, at pressure be under the condition of 3.5～4.5Mpa with the PLA series compression molding of fusing, with the cooling velocity of 15～45 ℃/min the PLA series of compression molding is cooled to room temperature.Other step is identical with the specific embodiment one.
The specific embodiment 13: the difference of the present embodiment and the specific embodiment one is compression molding in the step (): with relative molecular weight is that 140000～350000 polymer in poly lactic acid series is heated to more than the fusing point 24～28 ℃, after polymer in poly lactic acid series melts fully, at pressure be under the condition of 3～4Mpa with the polymer in poly lactic acid series compression molding of fusing, with the cooling velocity of 20～40 ℃/min the polymer in poly lactic acid series of compression molding is cooled to room temperature.Other step is identical with the specific embodiment one.
The specific embodiment 14: the difference of the present embodiment and the specific embodiment one is compression molding in the step (): with relative molecular weight is that 150000～200000 polymer in poly lactic acid series is heated to more than the fusing point 26 ℃, after polymer in poly lactic acid series melts fully, at pressure be under the condition of 4Mpa with the polymer in poly lactic acid series compression molding of fusing, with the cooling velocity of 35 ℃/min the polymer in poly lactic acid series of compression molding is cooled to room temperature.Other step is identical with the specific embodiment one.
The specific embodiment 15: the difference of the present embodiment and the specific embodiment one is in the step (two) polymer in poly lactic acid series of compression molding to be put into annealing furnace, handle 20～55min with 90～110 ℃ annealing temperatures, be cooled to room temperature, polymer in poly lactic acid series obtains cold deformation forming shape memory effect.Other step is identical with the specific embodiment one.
The specific embodiment 16: the difference of the present embodiment and the specific embodiment one is in the step (two) polymer in poly lactic acid series of compression molding to be put into annealing furnace, handle 30～50min with 95～105 ℃ annealing temperatures, be cooled to room temperature, polymer in poly lactic acid series obtains cold deformation forming shape memory effect.Other step is identical with the specific embodiment one.
The specific embodiment 17: the difference of the present embodiment and the specific embodiment one is in the step (two) polymer in poly lactic acid series of compression molding to be put into annealing furnace, handle 45min with 100 ℃ annealing temperatures, be cooled to room temperature, polymer in poly lactic acid series obtains cold deformation forming shape memory effect.Other step is identical with the specific embodiment one.
The specific embodiment 18: the processing method that polymer in poly lactic acid series in the present embodiment obtains cold deformation forming shape memory effect realizes by following steps: (one) compression molding: with relative molecular weight is that 200000 poly-L-lactide is heated to more than the fusing point 30 ℃, after poly-L-lactide melts fully, at pressure is the poly-L-lactide compression molding that will melt under the condition of 5Mpa, with the cooling velocity of 30 ℃/min the poly-L-lactide of compression molding is cooled to room temperature; (2) annealing in process: the poly-L-lactide of compression molding is put into annealing furnace, handle 50min with 100 ℃ annealing temperatures, be cooled to room temperature then, poly-L-lactide obtains cold deformation forming shape memory effect.
The poly-L-lactide that present embodiment is handled later obtains cold deformation forming shape memory effect, and the degree of crystallinity of handling poly-L-lactide later is 15.5%, and the deformation recovery rate is 85%, and the fixing back of deformation finished product restoring force is 6.0Mpa; Be particularly useful for the user demand of medical articles (fracture fixation material, vascular stent material and intracanal scaffold) that restoring force is had relatively high expectations.
The specific embodiment 19: the processing method that polymer in poly lactic acid series in the present embodiment obtains cold deformation forming shape memory effect realizes by following steps: (one) compression molding: with relative molecular weight is that poly-L-lactide/6-caprolactone random copolymer of 310000 is heated to more than the fusing point 30 ℃, when poly-after the L-lactide/the 6-caprolactone random copolymer melts fully, at pressure is the poly-L-lactide/6-caprolactone random copolymer compression molding that will melt under the condition of 5Mpa, with the cooling velocity of 30 ℃/min the poly-L-lactide/6-caprolactone random copolymer of compression molding is cooled to room temperature; (2) annealing in process: the poly-L-lactide/6-caprolactone random copolymer of compression molding is put into annealing furnace, handle 50min with 100 ℃ annealing temperatures, be cooled to room temperature then, poly-L-lactide/6-caprolactone random copolymer obtains cold deformation forming shape memory effect.
Present embodiment is handled poly-L-lactide later/6-caprolactone and is obtained cold deformation forming shape memory effect, the degree of crystallinity of handling poly-L-lactide/6-caprolactone later is 13.2%, the deformation recovery rate is 91.3%, and the fixing back of deformation finished product restoring force is 6.3Mpa; Be particularly useful for the user demand of medical articles (fracture fixation material, vascular stent material and intracanal scaffold) that restoring force is had relatively high expectations.
The specific embodiment 20: the processing method that polymer in poly lactic acid series in the present embodiment obtains cold deformation forming shape memory effect realizes by following steps: (one) compression molding: with relative molecular weight is that 120000 poly-L/DL-lactide copolymer is heated to more than the fusing point 25 ℃, after poly-L/DL-lactide copolymer melts fully, at pressure is the poly-L/DL-lactide copolymer compression molding that will melt under the condition of 4.5Mpa, with the cooling velocity of 35 ℃/min the poly-L/DL-lactide copolymer of compression molding is cooled to room temperature; (2) annealing in process: the poly-L/DL-lactide copolymer of compression molding is put into annealing furnace, handle 50min with 90 ℃ annealing temperatures, be cooled to room temperature then, poly-L/DL-lactide copolymer obtains cold deformation forming shape memory effect.
The poly-L/DL-lactide copolymer that present embodiment is handled later obtains cold deformation forming shape memory effect, the degree of crystallinity of handling poly-L/DL-lactide copolymer later is 14.3%, the deformation recovery rate is 93.5%, and the fixing back of deformation finished product restoring force is 7.0Mpa; Be particularly useful for the user demand of medical articles (fracture fixation material, vascular stent material and intracanal scaffold) that restoring force is had relatively high expectations.
The specific embodiment 21: the processing method that polymer in poly lactic acid series in the present embodiment obtains cold deformation forming shape memory effect realizes by following steps: (one) compression molding: with relative molecular weight is that 120000 poly-L-poly (lactide-co-glycolide) is heated to more than the fusing point 25 ℃, after poly-L-poly (lactide-co-glycolide) melts fully, at pressure is the poly-L-poly (lactide-co-glycolide) compression molding that will melt under the condition of 4.5Mpa, with the cooling velocity of 35 ℃/min the poly-L-poly (lactide-co-glycolide) of compression molding is cooled to room temperature; (2) annealing in process: the poly-L-poly (lactide-co-glycolide) of compression molding is put into annealing furnace, handle 40min with 90 ℃ annealing temperatures, be cooled to room temperature then, poly-L-poly (lactide-co-glycolide) obtains cold deformation forming shape memory effect.
The poly-L-poly (lactide-co-glycolide) that present embodiment is handled later obtains cold deformation forming shape memory effect, the degree of crystallinity of handling poly-L-poly (lactide-co-glycolide) later is 11.3%, the deformation recovery rate is 91.5%, and the fixing back of deformation finished product restoring force is 6.6Mpa; Be particularly useful for the user demand of medical articles (fracture fixation material, vascular stent material and intracanal scaffold) that restoring force is had relatively high expectations.
The specific embodiment 22: the processing method that polymer in poly lactic acid series in the present embodiment obtains cold deformation forming shape memory effect realizes by following steps: (one) compression molding: with relative molecular weight is that poly-L-lactide/poly DL-lactide blend of 100000～400000 is heated to more than the fusing point 28 ℃, when poly-after the L-lactide/the poly DL-lactide blend melts fully, at pressure is the poly-L-lactide/poly DL-lactide blend compression molding that will melt under the condition of 5.0Mpa, with the cooling velocity of 45 ℃/min the poly-L-lactide/poly DL-lactide blend of compression molding is cooled to room temperature; (2) annealing in process: the poly-L-lactide/poly DL-lactide blend of compression molding is put into annealing furnace, handle 55min with 90 ℃ annealing temperatures, be cooled to room temperature then, poly-L-lactide/poly DL-lactide blend obtains cold deformation forming shape memory effect.
Present embodiment is handled poly-L-lactide later/poly DL-lactide blend and is obtained cold deformation forming shape memory effect, the degree of crystallinity of handling poly-L-lactide/poly DL-lactide blend later is 17.5～18.5%, the deformation recovery rate is 85～91.0%, and the fixing back of deformation finished product restoring force is between 6.1～6.9Mpa; Be particularly useful for the user demand of medical articles (fracture fixation material, vascular stent material and intracanal scaffold) that restoring force is had relatively high expectations.
The specific embodiment 23: the processing method that polymer in poly lactic acid series in the present embodiment obtains cold deformation forming shape memory effect realizes by following steps: (one) compression molding: with relative molecular weight is that 100000～400000 poly-L-lactide composite is heated to more than the fusing point 25 ℃, after poly-L-lactide composite melts fully, at pressure is the composite material moulded moulding of poly-L-lactide that will melt under the condition of 4.5Mpa, with the cooling velocity of 35 ℃/min with the poly-L-lactide composite cools down of compression molding to room temperature; (2) annealing in process: the poly-L-lactide composite of compression molding is put into annealing furnace, handle 40min with 90 ℃ annealing temperatures, be cooled to room temperature then, poly-L-lactide composite obtains cold deformation forming shape memory effect.
The poly-L-lactide composite that present embodiment is handled later obtains cold deformation forming shape memory effect, the degree of crystallinity of handling poly-L-lactide composite later is 15.3～16.4%, the deformation recovery rate is 91.5～95.1%, and the fixing back of deformation finished product restoring force is between 7.2～7.5Mpa; Be particularly useful for the user demand of medical articles (fracture fixation material, vascular stent material and intracanal scaffold) that restoring force is had relatively high expectations.
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Cited By (6)
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| CN102772831A (en) * | 2012-08-20 | 2012-11-14 | 道淼科技(北京)有限公司 | Degradable drug loading stent |
| CN103998208A (en) * | 2011-12-14 | 2014-08-20 | 帝斯曼知识产权资产管理有限公司 | Process for medical components and uses thereof |
| CN105813662A (en) * | 2013-12-11 | 2016-07-27 | 伊西康公司 | Absorbable bimodal polymeric blend compositions, processing methods, and medical devices therefrom |
| CN105992571A (en) * | 2014-07-07 | 2016-10-05 | 美利奴生命科学有限公司 | Thin strut stent from bioabsorbable polymer with high fatigue and radial strength and method to manufacture thereof |
| CN110093021A (en) * | 2019-05-22 | 2019-08-06 | 吉林大学 | A kind of polylactic acid modified shape memory intelligent deformation material and preparation method thereof |
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| AU2003300377B2 (en) * | 2002-10-11 | 2009-04-02 | University Of Connecticut | Blends of amorphous and semicrystalline polymers having shape memory properties |
| CN1253217C (en) * | 2004-05-13 | 2006-04-26 | 哈尔滨工业大学 | Novel use of ploy-L-lactic acid as medical shape memory material |
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- 2007-01-22 CN CNB2007100716789A patent/CN100463795C/en not_active Expired - Fee Related
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103998208A (en) * | 2011-12-14 | 2014-08-20 | 帝斯曼知识产权资产管理有限公司 | Process for medical components and uses thereof |
| CN103998208B (en) * | 2011-12-14 | 2016-10-19 | 帝斯曼知识产权资产管理有限公司 | Prepare the method for medical assembly with and application thereof |
| CN102772831A (en) * | 2012-08-20 | 2012-11-14 | 道淼科技(北京)有限公司 | Degradable drug loading stent |
| CN105813662A (en) * | 2013-12-11 | 2016-07-27 | 伊西康公司 | Absorbable bimodal polymeric blend compositions, processing methods, and medical devices therefrom |
| CN105992571A (en) * | 2014-07-07 | 2016-10-05 | 美利奴生命科学有限公司 | Thin strut stent from bioabsorbable polymer with high fatigue and radial strength and method to manufacture thereof |
| CN110093021A (en) * | 2019-05-22 | 2019-08-06 | 吉林大学 | A kind of polylactic acid modified shape memory intelligent deformation material and preparation method thereof |
| CN110093021B (en) * | 2019-05-22 | 2021-03-02 | 吉林大学 | A kind of polylactic acid modified shape memory intelligent deformation material and preparation method thereof |
| CN110346548A (en) * | 2019-08-13 | 2019-10-18 | 南京林业大学 | The evaluation method of gutta-percha modified pitch shape-memory properties |
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