CN100344696C - Biological degradable shape memory polymer and its preparation process - Google Patents
Biological degradable shape memory polymer and its preparation process Download PDFInfo
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- CN100344696C CN100344696C CNB2004100433860A CN200410043386A CN100344696C CN 100344696 C CN100344696 C CN 100344696C CN B2004100433860 A CNB2004100433860 A CN B2004100433860A CN 200410043386 A CN200410043386 A CN 200410043386A CN 100344696 C CN100344696 C CN 100344696C
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Abstract
The present invention relates to a multicomponent biological degradable shape memory polymer. A poly-L-lactide-poly-(glycolide/caprolactone) segmented copolymer is synthesized by using poly-L-lactide low polymer as a hard phase and using poly-(glycolide/caprolactone) copolymerized low polymer as a soft phase by a coupling method. The preparation method of the segmented copolymer comprises the following steps: firstly, respectively synthesizing the poly-L-lactide low polymer and the poly-(glycolide/caprolactone) copolymerized low polymer; then, coupling the segmented copolymer from the two low polymers with diisocyanate. The biological degradable shape memory polymer of the present invention has the characteristics that the deformation holding capacity is high after the shape memory polymer is deformed by heating, the deformation recovery rate is high when the original shape of the shape memory polymer recovers after deforms by heating again and the repetitiveness of shape memory functions is high. In addition, the shape memory polymer has biodegradability, capability of disinfecting and machinability, and the performance of the shape memory polymer can be adjusted by adjusting the proportion and molecular weight of each component (prepolymer), so the biological degradable shape memory polymer easily satisfies different application requirements.
Description
Technical field
The present invention relates to a kind of biodegradable shape memory polymers.
The invention still further relates to the preparation method of above-mentioned polymkeric substance.
Background technology
(Shape memory alloy) is different with common metal and alloy for shape memory alloy, is a kind of alloy with shape memory effect, and this class material is at strain-induced martensitic transformation critical temperature (M
d) following distortion and significantly surpass yield-point after, in case be heated to martensite reverse transformation termination temperature (A
f) more than, the shape in the time of just can spontaneously returning to its parent phase martensitic state.Shape memory alloy has purposes widely, the shape memory alloy that has the one way memory function on engineering has been applied to the connection of pipe fitting etc., can make through precision machined tube stub to be fastenedly connected, and have advantages such as pipe fitting airtight, that assemble rapidly, connect reliably, can connect differing materials.The shape memory alloy that has the two-way shape memory function in addition also has been applied to electric connector, electric actuator and thermal actuator etc.The medical metal material that has shape memory function at medical field also has crucial purposes.Niti-shaped memorial alloy, the copper-based shape memory alloy of handling through unique shape memory for example, and the Ti-based shape memory alloy etc. that does not have nickel has the alloy of shape memory function, can revert to the shape of original design under human body temperature (about 37).Because the solidity to corrosion of niti-shaped memorial alloy is good, comprehensive mechanical property is better than medical stainless steel, and high fatigue resistance and wear resistance are arranged, surrounding tissue is not had bad influence substantially in the back that implants, therefore the niti-shaped memorial alloy that has super-elasticity and a memory characteristic not only in orthopedics's (as orthodontics, mouth cavity orthodontic, backbone correcting etc.), body the aspects such as diagnosis and treatment of tube chamber shape tissue and organ disease obtained clinical application widely (Shi Changxu edits, the material voluminous dictionary).But niti-shaped memorial alloy is except having nickel and may separating out and the toxicity problem that causes, also have: (1) deformation is less, the deformation temperature controllability is less; (2) be can not degradation in vivo bio-inert material, so behind patients ' recovery, must take out by operation once more, can increase patient's health misery and medical expense thus; (3) differ very big as the mechanical property of metallic substance and the mechanical property of people's human body, can therefore cause the necrosis of when injected organism tissue pressurized; (4) cause the danger of bad physiological response because of the biocompatibility of alloy material; (5) after the patient body is implanted into the metal medical device, will be affected and limit accepting medical examinations such as nucleus magnetic resonance, X-light, CT; Etc. a series of shortcoming, thereby limited the widespread use of niti-shaped memorial alloy at medical field.
Thereby biodegradable polymer is meant the molecular energy of constituent material under physiological environment and ruptures automatically, becomes small molecules from macromole and material is never dissolved become and can dissolve, yet gradually by the macromolecular material of organism metabolism or absorption.Since biodegradable polymer have than the better biocompatibility of metallic substance, automatically degradation in vivo, by metabolism or absorption, therefore behind patients ' recovery, can not need the taking-up of performing the operation again, have easy to use, side effect is little, can reduce the advantage of patient's misery and medical expense.Because the mechanical strength of macromolecular material is significantly less than metallic substance and more approaching with the mechanical strength of human body, so can avoid when injected organism tissue is caused damage; Exert an adverse impact in the time of also can avoiding medical examinations such as nucleus magnetic resonance, X-light, CT after using the polymeric medical device in addition in the implant patient body, so the biodegradable shape memory polymers medical device has very important and urgent application at medical field.
Shape-memory polymer mainly can be divided into (1) responsive to temperature type at present; (2) ion-sensitive type; (3) three major types such as photaesthesia type, wherein most species, most widely used be the responsive to temperature type polymkeric substance.Biodegradable shape memory polymers mainly adopts the biological degradation polyalcohol preparation that has obtained the clinical application permission and be used widely at present.The shape memory mechanism of shape-memory polymer is different with memorial alloy, its shape memory function is that the segment that depends on different components forms the microcell phase-splitting in polymkeric substance, and wherein the higher phase (being called hard phase) of deformation temperature play the maintenance effect of original-shape and the lower phase (being called soft phase) of deformation temperature play deformation is provided and keep deformation be used for realizing.The deformation temperature of shape-memory polymer is generally melt temperature (T
m) or second-order transition temperature (T
g).Polymkeric substance is being heated (temperature is higher than the transition temperature of soft phase and is lower than the transition temperature of hard phase) and is being applied under the situation of external force, make polymkeric substance become the shape of anticipation owing to the polymer molecular chain of soft phase can move, cooling under the situation that keeps external force then, the molecular chain that freezes soft phase make it keep the anticipation shape that deformation became; When heating (temperature be higher than the transition temperature of soft phase and be lower than the transition temperature of hard phase) once more, under the deforming stress that provides mutually firmly and soft self stress relaxation mutually, polymkeric substance can be returned to original-shape, and can keep original-shape after cooling.This process can repeatedly repeat.The obvious advantage of biodegradable shape memory polymers is: (1) can biological degradation, can not need the taking-up of performing the operation again after using in vivo; (2) mechanical property of polymkeric substance mechanical property and human body is close, biocompatibility is also better; (3) adjustability of transfer of shapes temperature is good, and deformation also big (＞200%); (4) degradation time of shape-memory polymer can be regulated as required.Therefore biodegradable shape memory polymers compare with shape memory alloy not only easy to use, can reduce medical expense, and performance better, have a wider range of application.
The common synthetic method of shape-memory polymer has: (1) carries out copolymerization with different monomers; (2) earlier synthetic low molecular weight prepolymer then becomes polymer with the coupling agent coupling again; (3) it is crosslinked to adopt method of radiating that polymer is carried out.Nowadays, people have developed multiple Biodegradable shape memory polymkeric substance, as: people such as langer with poly-1,4-dioxane-2-ketone oligopolymer is that hard phase, polycaprolactone oligopolymer or polylactide glycolide copolymer are the segmented copolymer of soft phase and the methacrylic ester cross-linked polymer (US Patent 6160084) that the polycaprolactone oligopolymer is soft phase; Have shape memory characteristic, biodegradable and absorbable poly(lactic acid) (US Patent 6281262) etc. in the time of people such as YasuoShikinami.But the needs of the repeatability of their shape-memory properties, performance and mechanical property, degradation speed and practical application also have bigger gap.
Summary of the invention
The object of the present invention is to provide a kind of new, polycomponent, with poly-L-rac-Lactide oligopolymer serve as hard mutually be soft biodegradable shape memory polymers mutually, that have the clinical medicine practical value to gather (glycollide/caprolactone) copolymerized oligomer.
Another purpose of the present invention is to provide the preparation method of above-mentioned polymkeric substance.
For achieving the above object, biodegradable shape memory polymers provided by the invention is the responsive to temperature type shape-memory polymer, and this polymkeric substance is soft phase with the poly-hard phase of L-rac-Lactide oligopolymer with poly-(glycollide/caprolactone) copolymerized oligomer; Wherein the molecular weight of poly-L-rac-Lactide oligopolymer is 2000～10000, and the molecular weight of poly-(glycollide/caprolactone) copolymerized oligomer is 2000～10000.
Preparation method of the present invention is to be that poly-L-rac-Lactide-poly-(glycollide/caprolactone) segmented copolymer type multicomponent biodegradable shape-memory polymer that hard phase, poly-(glycollide/caprolactone) copolymerized oligomer are soft phase prepares with coupling method with poly-L-rac-Lactide oligopolymer.Because the poly-L-rac-Lactide of the component that is adopted, polycaprolactone and poly-glycollide all are the biodegradable polymers of generally acknowledging, therefore shape-memory polymer of the present invention can rupture automatically in vivo, from macromole become small molecules, never dissolving becomes and can dissolve, and finally by organism metabolism and absorption.Biodegradable shape memory polymers of the present invention have deformation hold facility after under the condition of heating deformation takes place strong, when heating again, be returned to deformation before the repeatability of deformation-recovery rate height, shape memory function of shape high, polymkeric substance has biological degradability, sterilizability and workability, and performance can be regulated by ratio and the molecular weight of regulating each component (performed polymer), thereby the characteristics of the different application demand that is content with very little.
Specifically, biodegradable shape memory polymers of the present invention is synthetic by following method:
1) molecular weight is the synthetic of 2000～10000 poly-L-rac-Lactide oligopolymer: in the presence of a certain amount of initiator (ethylene glycol) and catalyzer (stannous iso caprylate), carry out the vacuum sealing tube polymerization of L-rac-Lactide, polymkeric substance precipitates in ethanol after dissolving with chloroform again, throw out filtration and vacuum are drained, obtain the poly-L-rac-Lactide performed polymer of product.The weight of material of polyreaction (gram) is than being the L-rac-Lactide: ethylene glycol: stannous iso caprylate=100: (0.61～3.1): 0.073, and polymerization temperature is 100～160 ℃, polymerization time is 10～48 hours.
2) molecular weight is the synthetic of poly-(glycollide/caprolactone) copolymerized oligomer of 2000～10000: in the presence of a certain amount of initiator (ethylene glycol) and catalyzer (stannous iso caprylate), carry out the vacuum sealing tube polymerization of glycollide and caprolactone, polymkeric substance precipitates in ethanol after dissolving with chloroform again, throw out filtration and vacuum are drained, obtain poly-(glycollide/caprolactone) copolymerized oligomer of product.The weight of material of polyreaction (gram) ratio is glycollide: caprolactone: ethylene glycol=(30～100): (100～60): (0.6～3), polymerization temperature are 120～180 ℃, and polymerization time is 24～120 hours.
3) poly-L-rac-Lactide-poly-(glycollide/caprolactone) segmented copolymer is synthetic: will gather L-rac-Lactide oligopolymer and the synthetic poly-L-rac-Lactide of poly-(glycollide/caprolactone) copolymerized oligomer-poly-(glycollide/caprolactone) segmented copolymer with coupling method.To add in the reactor in certain proportion by above-mentioned (1) the poly-L-rac-Lactide oligopolymer that obtains and poly-two kinds of performed polymers of (glycollide/caprolactone) copolymerized oligomer that (2) obtain, with 1,2-ethylene dichloride solubilizing reaction thing adds coupling agent at 40～100 ℃ and carries out linked reaction.Reaction product is by the ethanol sedimentation, and vacuum is drained again, obtains the poly-L-rac-Lactide of end product-poly-(glycollide/caprolactone) segmented copolymer.The weight of material (gram) of reaction is than being poly-L-rac-Lactide oligopolymer: poly-(glycollide/caprolactone) copolymerized oligomer: coupling agent=(10～100): (100～10): (1.7～8.4), polymerization temperature are 120～180 ℃, and polymerization time is 8～48 hours.
Coupling agent of the present invention is 4,4 '-methylene radical-two (phenyl isocyanate) (MDI), 1,6-hexamethylene diisocyanate (HDI), 2,4 toluene diisocyanate (TDI), 1,4-phenylene diisocyanate (BDI) or the mixture between them.
Embodiment
Embodiment 1:(1) synthetic earlier gathering synthesizing of L-rac-Lactide oligopolymer: add 40 gram L-rac-Lactides, 1.2 gram ethylene glycol and 0.7mg stannous iso caprylates in polymerizing pipe respectively, tube sealing under the vacuum was in 130 ℃ of reactions 16 hours.Polymkeric substance refilters and vacuum-drying with chloroform dissolving, ethanol sedimentation, and obtaining molecular weight is 2000, pulverous poly-L-rac-Lactide oligopolymer (PLA (2000)) is white in color.
(2) poly-(glycollide/caprolactone) copolymerized oligomer of resynthesis: in polymerizing pipe, add 23 gram glycollide, 46 restrain oneself lactone and 2.1 gram ethylene glycol respectively, tube sealing under the vacuum, reaction is 4 days in 160 ℃ oil bath.Polymkeric substance refilters and vacuum-drying with chloroform dissolving, ethanol sedimentation, and obtaining molecular weight is 2000, pulverous poly-(glycollide/caprolactone) block copolymerization oligopolymer (PGC (33/67) 2000) is white in color.
(3) will gather L-rac-Lactide oligopolymer and the synthetic poly-L-rac-Lactide of poly-(glycollide/caprolactone) copolymerized oligomer-poly-(glycollide/caprolactone) segmented copolymer with coupling method.Poly-L-rac-Lactide (2000)-poly-(glycollide/caprolactone) (2000) segmented copolymer synthetic: in polymerization bottle, add 2.4 gram molecular weights respectively and be 2000 poly-L-rac-Lactide oligopolymer and 0.6 gram molecular weight and be poly-(glycollide/caprolactone) copolymerized oligomer of 2000, add 1,2-ethylene dichloride 30ml dissolving, and adding 0.54g coupling agent 4,4 '-methylene radical-two (phenyl isocyanate) (MDI) back reacted 24 hours at 70 ℃.Polymkeric substance is with chloroform dissolving, ethanol sedimentation, refilter and vacuum-drying, obtain white solid, ratio of components and be (poly-L-rac-Lactide oligopolymer): poly-L-rac-Lactide-poly-(glycollide/caprolactone) segmented copolymer (PLAGC (80/20-2000)) of (poly-(glycollide/caprolactone) copolymerized oligomer)=80: 20.
Embodiment 2: with the synthetic method of embodiment 1, be 4000 poly-L-rac-Lactide oligopolymer and with 1 but adopt molecular weight, 6-hexamethylene diisocyanate (HDI) is a coupling agent.Molecular weight is that 4000 poly-L-rac-Lactide oligopolymer synthetic method is: add 80 gram L-rac-Lactides, 1.2 gram ethylene glycol and 1.4mg stannous iso caprylates in polymerizing pipe respectively, tube sealing under the vacuum was in 120 ℃ of reactions 24 hours.Polymkeric substance refilters and vacuum-drying with chloroform dissolving, ethanol sedimentation, and obtaining molecular weight is 4000, pulverous poly-L-rac-Lactide oligopolymer (PLA (4000)) is white in color.
Embodiment 3: with the synthetic method of embodiment 1, but to adopt molecular weight be 6000 poly-L-rac-Lactide oligopolymer and be coupling agent with 2,4 toluene diisocyanate (TDI).Molecular weight is that 6000 poly-L-rac-Lactide oligopolymer synthetic method is: add 20 gram L-rac-Lactides, 0.2 gram ethylene glycol and 0.3mg stannous iso caprylate in polymerizing pipe respectively, tube sealing under the vacuum was in 110 ℃ of reactions 36 hours.Polymkeric substance refilters and vacuum-drying with chloroform dissolving, ethanol sedimentation, and obtaining molecular weight is 6000, pulverous poly-L-rac-Lactide oligopolymer (PLA (6000)) is white in color.
Embodiment 4: with the synthetic method of embodiment 1, but adopt molecular weight be 8000 poly-L-rac-Lactide oligopolymer and with volume ratio be 50: 50 4,4 '-methylene radical-two (phenyl isocyanate) and 1,6-hexamethylene diisocyanate (HDI) mixture coupling agent.Molecular weight is that 8000 poly-L-rac-Lactide oligopolymer synthetic method is: add 40 gram L-rac-Lactides, 0.3 gram ethylene glycol and 0.3mg stannous iso caprylate in polymerizing pipe respectively, tube sealing under the vacuum was in 150 ℃ of reactions 12 hours.Polymkeric substance refilters and vacuum-drying with chloroform dissolving, ethanol sedimentation, and obtaining molecular weight is 8000, pulverous poly-L-rac-Lactide oligopolymer (PLA (8000)) is white in color.
Embodiment 5: with the synthetic method of embodiment 1, but adopt molecular weight be 10000 poly-L-rac-Lactide oligopolymer and with volume ratio be 50: 50 4,4 '-methylene radical-two (phenyl isocyanate) (MDI) and 1,6-hexamethylene diisocyanate (HDI) mixture coupling agent.Molecular weight is that 10000 poly-L-rac-Lactide oligopolymer synthetic method is: add 20 gram L-rac-Lactides, 0.13 gram ethylene glycol and 0.15mg stannous iso caprylate in polymerizing pipe respectively, tube sealing under the vacuum was in 160 ℃ of reactions 10 hours.Polymkeric substance refilters and vacuum-drying with chloroform dissolving, ethanol sedimentation, and obtaining molecular weight is 10000, pulverous poly-L-rac-Lactide oligopolymer (PLA (10000)) is white in color.
Embodiment 6: with the synthetic method of embodiment 1, be poly-(glycollide/caprolactone) copolymerized oligomer of 4000 but adopt molecular weight.Molecular weight is that the synthetic method of poly-(glycollide/caprolactone) copolymerized oligomer of 4000 is: in polymerizing pipe, add 23 gram glycollide, 46 restrain oneself lactone and 1.6 gram ethylene glycol respectively, and tube sealing under the vacuum, reaction is 6 days in 150 ℃ oil bath.Polymkeric substance refilters and vacuum-drying with chloroform dissolving, ethanol sedimentation, and obtaining molecular weight is 4000, pulverous poly-(glycollide/caprolactone) copolymerized oligomer (PGC (33/67) 4000) is white in color.
Embodiment 7: with the synthetic method of embodiment 1, be 6000 poly-(glycollide/caprolactone) copolymerized oligomer and with 1 but adopt molecular weight, 6-hexamethylene diisocyanate (HDI) is a coupling agent.Molecular weight is that the synthetic method of poly-(glycollide/caprolactone) copolymerized oligomer of 6000 is: in polymerizing pipe, add 46 gram glycollide, 92 restrain oneself lactone and 1.4 gram ethylene glycol respectively, and tube sealing under the vacuum, reaction is 8 days in 140 ℃ oil bath.Polymkeric substance refilters and vacuum-drying with chloroform dissolving, ethanol sedimentation, and obtaining molecular weight is 6000, pulverous poly-(glycollide/caprolactone) copolymerized oligomer (PGC (33/67) 6000) is white in color.
Embodiment 8: with the synthetic method of embodiment 1, but to adopt molecular weight be 8000 poly-(glycollide/caprolactone) copolymerized oligomer and be coupling agent with 2,4 toluene diisocyanate (TDI).Molecular weight is that the synthetic method of poly-(glycollide/caprolactone) copolymerized oligomer of 8000 is: in polymerizing pipe, add 12 gram glycollide, 23 restrain oneself lactone and 0.27 gram ethylene glycol respectively, and tube sealing under the vacuum, reaction is 4 days in 160 ℃ oil bath.Polymkeric substance refilters and vacuum-drying with chloroform dissolving, ethanol sedimentation, and obtaining molecular weight is 8000, pulverous poly-(glycollide/caprolactone) copolymerized oligomer (PGC (33/67) 8000) is white in color.
Embodiment 9: with the synthetic method of embodiment 1, but adopt molecular weight be 10000 poly-(glycollide/caprolactone) copolymerized oligomer and with volume ratio be 50: 50 4,4 '-methylene radical-two (phenyl isocyanate) (MDI) and 1,6-hexamethylene diisocyanate (HDI) mixture coupling agent.Molecular weight is that the synthetic method of poly-(glycollide/caprolactone) copolymerized oligomer of 10000 is: in polymerizing pipe, add 18.6 gram glycollide, 37 restrain oneself lactone and 0.34 gram ethylene glycol respectively, and tube sealing under the vacuum, reaction is 6 days in 150 ℃ oil bath.Polymkeric substance refilters and vacuum-drying with chloroform dissolving, ethanol sedimentation, and obtaining molecular weight is 10000, pulverous poly-(glycollide/caprolactone) copolymerized oligomer (PGC (33/67) 10000) is white in color.
Embodiment 10: with the synthetic method of embodiment 1, but the employing molecular weight is all the poly-L-rac-Lactide oligopolymer of 6 grams and poly-(glycollide/caprolactone) copolymerized oligomer of 2.6 grams of 4000, with 0.30g 2,4 toluene diisocyanate (TDI) is coupling agent, reacts 30 hours down in 60 ℃.Polymkeric substance refilters and vacuum-drying with chloroform dissolving, ethanol sedimentation, obtains ratio of components and is (poly-L-rac-Lactide): poly-L-rac-Lactide-poly-(glycollide/caprolactone) segmented copolymer of (poly-(glycollide/caprolactone) multipolymer)=70: 30.
Embodiment 11: with the synthetic method of embodiment 1, but the employing molecular weight is all the poly-L-rac-Lactide oligopolymer of 7 grams and poly-(glycollide/caprolactone) copolymerized oligomer of 4.7 grams of 6000, with 0.32ml 1,6-hexamethylene diisocyanate (HDI) is a coupling agent, reacts 20 hours down in 80 ℃.Polymkeric substance refilters and vacuum-drying with chloroform dissolving, ethanol sedimentation, obtains ratio of components and is (poly-L-rac-Lactide): poly-L-rac-Lactide-poly-(glycollide/caprolactone) segmented copolymer of (poly-(glycollide/caprolactone) multipolymer)=60: 40.
Embodiment 12: with the synthetic method of embodiment 1, but the employing molecular weight is all the poly-L-rac-Lactide oligopolymer of 6 grams and poly-(glycollide/caprolactone) copolymerized oligomer of 6 grams of 8000, with 0.23g 1,4-phenylene diisocyanate (BDI) is a coupling agent, reacts 50 hours down in 50 ℃.Polymkeric substance refilters and vacuum-drying with chloroform dissolving, ethanol sedimentation, obtains ratio of components and is (poly-L-rac-Lactide): poly-L-rac-Lactide-poly-(glycollide/caprolactone) segmented copolymer of (poly-(glycollide/caprolactone) multipolymer)=50: 50.
Embodiment 13: embodiment 12: with the synthetic method of embodiment 1, but the employing molecular weight is all the poly-L-rac-Lactide oligopolymer of 7 grams and poly-(glycollide/caprolactone) copolymerized oligomer of 10.5 grams of 10000, with 0.28ml 1,6-hexamethylene diisocyanate (HDI) is a coupling agent, reacts 24 hours down in 70 ℃.Polymkeric substance refilters and vacuum-drying with chloroform dissolving, ethanol sedimentation, obtains ratio of components and is (poly-L-rac-Lactide): poly-L-rac-Lactide-poly-(glycollide/caprolactone) segmented copolymer of (poly-(glycollide/caprolactone) multipolymer)=40: 60.
Embodiment 14: the performance of the poly-L-rac-Lactide oligopolymer of part, poly-(glycollide/caprolactone) copolymerized oligomer and poly-L-rac-Lactide-poly-(glycollide/caprolactone) segmented copolymer is as shown in table 1.
Table 1 part is gathered the performance of L-rac-Lactide oligopolymer, poly-(glycollide/caprolactone) copolymerized oligomer and poly-L-rac-Lactide-poly-(glycollide/caprolactone) segmented copolymer
| Oligopolymer | Molecular weight M n(×10 -4) | T m() | T g() | Tensile modulus (Mpa) | Extension at break (%) |
| PLA(2000) | 0.24 | 113 | 54 | ||
| PLA(4000) | 0.39 | 137 | 56 | ||
| PLA(6000) | 0.65 | 145 | 60 | ||
| PLA(8000) | 0.87 | 153 | 63 | ||
| PLA(10000) | 1.09 | 157 | 64 | ||
| PGC(2000) | 0.24 | 37 | |||
| PGC(4000) | 0.45 | 39 | |||
| PGC(6000) | 0.63 | 43 | |||
| PGC(8000) | 0.79 | 43 | |||
| PGC(10000) | 1.06 | 44 | |||
| PLAGC(40/60-2000) | 7.29 | 95 | 36 | ||
| PLAGC(50/50-2000) | 7.97 | 95 | 37 | 12.0 | 776 |
| PLAGC(80/20-2000) | 9.35 | 105 | 40 | 30.2 | 543 |
| PLAGC(60/40-4000) | 6.88 | 104 | 38 | 26.4 | 587 |
| PLAGC(70/30-4000) | 6.61 | 136 | 36 | 31.3 | 756 |
| PLAGC(40/60-6000) | 11.1 | 140 | 40 | 31.4 | 524 |
| PLAGC(60/40-6000) | 10.7 | 147 | 43 | 41.3 | 532 |
| PLAGC(60/40-8000) | 4.50 | 157 | 46 | 33.1 | 536 |
| PLAGC(70/30-8000) | 10.0 | 156 | 46 | 35.7 | 407 |
| PLAGC(80/20-8000) | 13.4 | 152 | 46 | 46.8 | 395 |
| PLAGC(90/10-8000) | 11.4 | 155 | 48 | 44.6 | 301 |
| PLAGC(50/50-10000) | 5.32 | 159 | 49 | 25.9 | 451 |
| PLAGC(80/20-10000) | 10.9 | 156 | 49 | 43.6 | 318 |
Embodiment 15: the shape-memory properties of the various poly-L-rac-Lactide of gained of the present invention-poly-(glycollide/caprolactone) segmented copolymer is recorded by following method.Be cast into the tetrafluoroethylene mould after polymkeric substance being made into 8% dichloromethane solution, treat solvent evaporates and further after the vacuum-drying film forming, being cut into stretches use batten, carries out the shape memory mensuration of tensile deformation again.Because the second-order transition temperature (T of polymkeric substance
g) about 40 ℃, promptly the shape memory transition temperature of polymkeric substance is about 40 ℃, so adopt 45 ℃ of probe temperatures as shape recovery ratio.
Polymer sample rods is carried out with following four steps the shape memory test of tensile deformation.(1) with batten 40 ℃ of following constant temperature 5 minutes; (2) then under 40 ℃ constant temperature with at the uniform velocity tensile elongation 200% of batten; (3) under the state that keeps tensile deformation, make batten slowly cool to room temperature; (4) remove external force, sample is placed under 45 ℃ of envrionment temperatures carry out recovery of shape.
In rate of extension is the 6mm/ branch, and tensile elongation is that the shape memory result of three tensile deformations of 200% o'clock part batten is as shown in the table.
Deformation conservation rate (R wherein
f) hold facility to deformation: R takes place under the condition of heating after the deformation for material
f(%)=(deformation that is kept under the room temperature/under heating total deformation) * 100; Deformation-recovery rate (R
r) can reply ability for material into shape before the deformation, be measuring of material shape recovery capacity; R
r(%)=(in the total deformation of back regressive deformation/under heating of heating again) * 100.The recovery of shape performance data of the poly-L-rac-Lactide of part-poly-(glycollide/caprolactone) segmented copolymer is as shown in table 2.
Table 2 part is gathered the recovery of shape performance of L-rac-Lactide-poly-(glycollide/caprolactone) segmented copolymer
| Stretch for the first time | Stretch for the second time | Stretch for the third time | ||||
| R f (％) | R f (％) | R f (％) | R r (％) | R f (％) | R r (％) | |
| PLAGC90/10-2000 | 95.7 | 93.8 | 96.5 | 92.5 | 94.6 | 99.7 |
| PLAGC70/30-4000 | 97.6 | 96.0 | 97.7 | 93.4 | 96.5 | 95.8 |
| PLAGC80/20-4000 | 99.3 | 98.4 | 98.5 | 98.5 | 98.2 | 98.5 |
| PLAGC90/10-4000 | 97.7 | 99.2 | 94.2 | 99.3 | 98.1 | 96.5 |
| PLAGC70/30-6000 | 98.1 | 99.2 | 98.3 | 99.5 | 98.6 | 99.4 |
| PLAGC80/20-6000 | 96.8 | 99.5 | 98.7 | 99.6 | 98.9 | 99.4 |
| PLAGC90/10-6000 | 97.5 | 99.3 | 98.2 | 100 | 97.7 | 99.8 |
| PLAGC50/50-8000 | 90.3 | 90.2 | 94.4 | 95.2 | 92.6 | 94.8 |
| PLAGC60/40-8000 | 97.3 | 90.7 | 96.2 | 90.7 | 96.0 | 93.9 |
| PLAGC70/30-8000 | 96.7 | 97.9 | 96.9 | 97.6 | 97.4 | 96.7 |
| PLAGC80/20-8000 | 96.9 | 99.5 | 96.6 | 99.4 | 98.1 | 99.4 |
| PLAGC60/40-10000 | 96.3 | 83.7 | 97.2 | 92.7 | 95.2 | 93.5 |
| PLAGC70/30-10000 | 98.0 | 90.0 | 97.2 | 94.7 | 96.1 | 99.1 |
| PLAGC80/20-10000 | 98.4 | 94.9 | 97.3 | 97.4 | 97.0 | 97.8 |
Reference examples: the deformation recall tests result of single polymer-crosslinked polycaprolactone (crosslinked PCL) and two single polymer-copolymerization (D-rac-Lactide/L-rac-Lactide) (P (DLA/LLA) (25/75)) and copolymerization (L-rac-Lactide/caprolactone) (PLC (90/10)) batten is as shown in table 3.Compare deformation conservation rate (R with biodegradable shape memory polymers of the present invention
f), deformation-recovery rate (R
r) and the memory characteristic repeatability all have a long way to go.
The recovery of shape performance of table 3 part single polymer and two single polymers
| Stretch for the first time | Stretch for the third time | |||
| R f (％) | R r (％) | R f (％) | R r (％) | |
| Crosslinked PCL | 93.9 | 93.3 | ||
| P(DLA/LLA)(25/75) | 98.2 | 94.5 | ||
| PLC(90/10) | 97.8 | 98.0 | 97.1 | 92.3 |
Claims (3)
1, a kind of biodegradable shape memory polymers is hard phase with poly-L-rac-Lactide oligopolymer, is soft phase with poly-(glycollide/caprolactone) copolymerized oligomer; Wherein the molecular weight of poly-L-rac-Lactide oligopolymer is 2000～10000, and the molecular weight of poly-(glycollide/caprolactone) copolymerized oligomer is 2000～10000, and hard is 10～100: 100～10 with soft weight ratio mutually mutually.
2, shape-memory polymer according to claim 1 is characterized in that, this polymkeric substance is the responsive to temperature type shape-memory polymer.
3, shape-memory polymer according to claim 1, it is characterized in that, when preparing this polymkeric substance, used the diisocyanate type coupling agent, refer to 4,4 '-methylene radical-two (phenyl isocyanate), 1,6-hexamethylene diisocyanate, 2,4-tolylene diisocyanate or 1, the 4-phenylene diisocyanate.
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| CN101554488B (en) * | 2009-05-22 | 2012-10-03 | 西南交通大学 | Preparation method and use method of biologically degradable shape memory tubular support stent |
| NL1039667C2 (en) * | 2012-06-11 | 2013-12-12 | Purac Biochem Bv | Quantification of lactide amounts in a polymeric matrix. |
| CN103445884B (en) * | 2013-07-17 | 2018-07-31 | 绍兴易比纺织科技有限公司 | A kind of intelligent tendon repair device with bidirectional shape memory function |
| CN103601903B (en) * | 2013-11-15 | 2016-02-10 | 无锡中科光远生物材料有限公司 | A kind of can the preparation method of shape-memory material that excites of body heat |
| CN104667356A (en) * | 2013-11-27 | 2015-06-03 | 山东瑞安泰医疗技术有限公司 | In-vivo biodegradable shape memory macromolecule coronary stent system and manufacturing method thereof |
| CN111685861A (en) * | 2019-03-13 | 2020-09-22 | 田大为 | Degradable shape memory femoral internal fixation body |
| US20210017329A1 (en) * | 2019-07-19 | 2021-01-21 | Evonik Operations Gmbh | Multi-block shape memory bioresorbable polymers |
| CN110499008A (en) * | 2019-08-20 | 2019-11-26 | 湖北工业大学 | A kind of polylactic acid and caprolactone based elastomeric blend and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPH11209595A (en) * | 1998-01-20 | 1999-08-03 | Agency Of Ind Science & Technol | Method of shape-memorizing biodegradable shape-memory polymer molding product and its shape restoration |
| US6281262B1 (en) * | 1998-11-12 | 2001-08-28 | Takiron Co., Ltd. | Shape-memory, biodegradable and absorbable material |
| CN1361799A (en) * | 1999-07-20 | 2002-07-31 | 阿奥技术生物材料控股有限公司 | Shape memory polyurethane or polyurethane-urea polymers |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11209595A (en) * | 1998-01-20 | 1999-08-03 | Agency Of Ind Science & Technol | Method of shape-memorizing biodegradable shape-memory polymer molding product and its shape restoration |
| US6281262B1 (en) * | 1998-11-12 | 2001-08-28 | Takiron Co., Ltd. | Shape-memory, biodegradable and absorbable material |
| CN1361799A (en) * | 1999-07-20 | 2002-07-31 | 阿奥技术生物材料控股有限公司 | Shape memory polyurethane or polyurethane-urea polymers |
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