CN1563132A - Shape memory material based on poly(e-caprolactone), preparation and metod of application - Google Patents
Shape memory material based on poly(e-caprolactone), preparation and metod of application Download PDFInfo
- Publication number
- CN1563132A CN1563132A CN 200410010734 CN200410010734A CN1563132A CN 1563132 A CN1563132 A CN 1563132A CN 200410010734 CN200410010734 CN 200410010734 CN 200410010734 A CN200410010734 A CN 200410010734A CN 1563132 A CN1563132 A CN 1563132A
- Authority
- CN
- China
- Prior art keywords
- temperature
- shape
- pcl
- caprolactone
- distortion
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Abstract
The invention relates to a polyurethane which uses poly(exsilon-caprolactone) as soft block and has shape memory function. It is made up by using poly(epsilon-caprolactone) (PCL) of double hydroxyl and diisocyanate and small moleculeg glycol (EO) through process of reaction. Its melting point is in the range of 40 deg.C-60 deg.C, and is dependent on the molecular weight of PCL and the mole ratio of PCL and EO, and its restorable deformation temperature is room temperature to 60 deg.C and the deformation restorable temperature is room temperature to 60 deg.C and the deformation restorable temperature is room temperature to 50 deg.C, and also is dependent on the molecular weight of PCL and mole ratio of PCL and EO. Under the condition of that the extension is 300% and compresses is three times its deformation restoration rate can be up to 100%. Its deformation restorable temperature can be controlled near by human body temperature by utilizing regulation of polymer composition, so that it has biodegradation function and can obtain important application in medicine field.
Description
Technical field
The invention belongs to a kind of shape-memory material and preparation and using method, belong to the medical macromolecular materials field based on poly-(6-caprolactone).
Background technology
Shape-memory material has widely in industry and medical treatment and uses, and is implanted into element etc. as transmitter, transverter, protecting component, power element, human body.Various conduits and the support of making by the Ni-Ti alloy wherein, clinical use in surgical operation and interventional therapy.They have many good qualities, and are little, in light weight as volume, distortion is big, anchorage force is big etc., but tangible deficiency is also arranged, and as incompatible with tissue, the Ni element in the alloy is toxic, is implanted in the human body for a long time or all the life, and the Ni element oozes out and impairs one's health.Up to now, it is found that the macromolecular material that much has shape memory function, the industrialization that has, as thermal contraction casing tube etc., their materials are easy to get, handling ease, with low cost, but their distortion recovery temperature is generally than higher, again can not biological degradation, thereby can not medically use.In recent years, biodegradated polymer materal has had significant progress, and is also more and more in application medically, particularly lactide acid polymer, as poly(lactic acid), polyglycolic acid, poly-(6-caprolactone), and the multipolymer of lactic acid, oxyacetic acid and 6-caprolactone.Their physiologically acceptable do not have toxicity, can degrade and absorb in human body, but they do not have shape memory function basically.
Summary of the invention
The purpose of this invention is to provide a kind of shape-memory material based on poly-(6-caprolactone), this material advantage of all biodegradable polymers and shape memory alloy of holding concurrently, the distortion recovery temperature is convenient to obtain to use in surgical operation near human body temperature;
Another object of the present invention provides a kind of preparation method based on the shape-memory material that gathers (6-caprolactone);
The shape memory effect of macromolecular material is decided by its chemical constitution and structure, is decided by its state of aggregation, thereby has only under certain conditions and just show.On the basis of disclosing the synthetic shape-memory material constitutional features of institute, define the condition of generation shape memory effect, provide corresponding using method, be the 3rd purpose of the present invention.
Based on poly-(6-caprolactone) shape-memory polymer (PCL), it is formed by two ends hydroxyl PCL and vulcabond, the reaction of small molecules glycol, thereby be to be soft section with PCL, with vulcabond-small molecules glycol reaction product the multi-block polyurethane of hard section.Wherein soft section of PCL can biological degradation, and segmented polyurethane may hydrolysis in human body, finally excretes.
Microphase-separated can take place in the urethane of this many blocks.Between each hard segment molecule chain owing to there are a large amount of hydrogen bonds, form hard section phase region, the effect of in whole system, serving as physical crosslinking point, the fusing point that PCL is soft section is about 60 ℃, second-order transition temperature is below-20 ℃, thereby work as this polymkeric substance from the process of melt cooling, successively pass through the stages such as melt, thermoplastic elastomer, hypocrystalline solid.Transformation between thermoplastic elastomer and the hypocrystalline solid might produce shape memory effect.
The molecular weight of the PCL that the present invention uses is in 2000～20000 scopes, and fusing point is at 50～65 ℃.Generate after the urethane, because the restriction of hard section phase region, their fusing point descends to some extent, drops on the scope of room temperature～60 ℃, the characteristic temperature that causes this system shape memory is just in time in room temperature and body temperature, and this medical use to this material has decisive significance.
The present invention is used for the raw material of synthesis of polyurethane, is the hydroxyl PCL in two ends, vulcabond and small molecules glycol.Wherein the mole number of vulcabond equal PCL and small molecules glycol and, so that obtain high as far as possible polymericular weight.
The hydroxyl PCL in two ends is that spent glycol or butyleneglycol are initiator, in the presence of stannous octoate or other catalyzer, is obtained by the 6-caprolactone ring-opening polymerization.Regulate the feed ratio of 6-caprolactone and ethylene glycol, can satisfy needs of the present invention with the molecular weight control of PCL in 2000～20000 scope.
More than the vulcabond of Shi Yonging can be a 2,4 toluene diisocyanate, 2,6-tolylene diisocyanate or their mixture, '-diphenylmethane diisocyanate, isophorone diisocyanate etc.Their reactive behavior is difference slightly, suitably adjusts reaction conditions, can both synthesize needed urethane.
The chainextender that the present invention uses is ethylene glycol and butyleneglycol, and wherein the segmented polyurethane that is generated by ethylene glycol has higher second-order transition temperature, is more suitable for purpose of the present invention.
The fusing point of the PCL phase of poly-(6-caprolactone) urethane (PCL-PU is made in following letter) of the present invention's preparation 25～60 ℃ of scopes, is decided by the molecular weight size of used PCL prepolymer, and the PCL molecular weight is big more, and fusing point is high more; Fusing point also depends on the mol ratio between PCL and the hard section, and concerning the PCL of same length, hard section is long more, and fusing point is low more.
For the PCL-PU material that fusing point is arranged, more than fusing point, PCL-PU shows as thermoplastic elastomer, and below Tc, PCL-PU shows as the hypocrystalline solid.So, can adopt two kinds of methods to realize being out of shape and distortion being fixed up: (1) stretches, compresses or other deformation in fusing point or the above temperature of fusing point of PCL-PU, temperature with sample drops to below the Tc then, because crystallization takes place, the deformation of sample is preserved; (2) sample directly is out of shape below fusing point, is preferably in and implements distortion near the Tc, be out of shape and fix a step and finish.The latter is of practical significance to some medical uses, and the doctor can at room temperature implement distortion at operative site.
Through the PCL-PU after the above-mentioned distortion, be elevated to the fusing point of PCL phase when temperature after, sample reverts to thermoplastic elastomer, under the effect of the internal stress that is fixed up at low temperatures, inverse metamorphism takes place, sample recovers original shape.To the sample (seeing accompanying drawing 1) of 3 times of a series of stretchings 300% and compressions, measured before the distortion and shape is recovered later length or thickness, find to be out of shape recovery rate ((L3-L1)/L1 or (H1-H3)/H1) in 94～100% scopes in the accompanying drawing 1.And recovery rate is less than 100% situation, often because in above-mentioned first kind of deformation method, cooling rate is fast inadequately, takes place that stress relaxation causes.So, improve operational condition shape is recovered fully.
The shape memory effect of the PCL-PU material of the present invention preparation not only shows in simple stretching and the compression set, shows that also accompanying drawing 2 and 3 has provided two such examples in the more complicated distortion.In the accompanying drawing 2, PCL-PU garden tube is pressed into the plum blossom shape under 50 ℃, and its cross-sectional area is reduced, and in the room temperature setting, heats in 40 ℃ of water then, and in seconds sample changes back to round shape, and diameter also returns to original size.In the accompanying drawing 3, PCL-PU garden tube is enlarged diameter at first at room temperature, becomes thin-walled garden tube, flattens then, is rolled into the garden cylindricality again.When sample was put in 40 ℃ of water, in several seconds, sample returned to initial garden tubular.Be not difficult to find out that by Fig. 1 to Fig. 3 under certain conditions, the PCL-PU goods can show as " thermal contraction ", also can show as " thermal expansion ", and the recovery temperature of distortion can satisfy the needs of a lot of clinical applications fully about 40 ℃.
Hot recovery temperature that it is generally acknowledged the crystal class shapememory polymer should be more than fusing point, and lay special stress on of the present invention, the hot recovery temperature of PCL-PU is more much lower than fusing point, with the PCL2000-PU132 in the subordinate list 1 is example, its fusing point is 43 ℃, minimum distortion recovery temperature but has only 23 ℃, and both differ 20 ℃ more than.To other sample, these two temperature differ at least also 10 ℃.Minimum distortion recovery temperature is lower than the reason of fusing point, is to have stronger internal stress in the deformed sample.Under the driving of this internal stress, molecular chain is under lower temperature, and is promptly movable, changes elastomeric state into.
So concerning the PCL-PU shape-memory material, minimum distortion recovery temperature has more practical significance than fusing point.Under this temperature, sample can recover original shape and size.Because temperature is lower, the stress relaxation that the molecular chain thermal motion causes is less, so the distortion recovery extent is on the contrary than higher.
The present invention realizes that the method for " shape recovery " has two kinds: (1) constant temperature method: the sample after the distortion is put in the water of assigned temperature (above-mentioned minimum distortion recovery temperature or high slightly, for example 40 ℃ or 37 ℃), and this is easy to accomplish; (2) temperature-raising method: the sample heat temperature raising after will being out of shape, when arriving minimum distortion recovery temperature, sample generation inverse metamorphism returns to original shape and size.Use a kind of method in back to carry out dynamics research to the shape memory effect of sample, but and the lowest shape recovery temperature of working sample." minimum distortion recovery temperature " (LRT in the table 2) in the embodiment of the invention is exactly to measure in this way.
On the other hand, minimum distortion recovery temperature is compared with Tc, and is much higher.Obviously, more than the temperature, the distortion of the first step can not keep getting off at this.So the temperature of fixed deformation must be at this below temperature.By table 1 column data as seen, the synthetic PCL-PU of institute material of the present invention, minimum distortion recovery temperature near room temperature or a little higher than room temperature, is setting temperature (mode 1) or distortion/setting temperature (mode 2) so can select room temperature all, and this is the most convenient in actual applications.
In sum, the present invention realizes and utilizes the method for the shape memory effect of PCL-PU to be: (1) is extruded polymkeric substance, inject or other moulding under 120～150 ℃, obtains needed article shape and size.(2) goods are stretched, compress or other complex deformation, and should be out of shape and keep; Its method has two kinds: (40～50 ℃) distortion back formalizes again in the room temperature setting or at deformation at room temperature near fusing point.(3) goods after will being out of shape carry out heat treated, eliminate the distortion that is applied, and recover the original shape and the size of goods; Persevering gentle the intensification two kinds of heat treated only needs a little higher than minimum distortion recovery temperature to get final product.Concerning shape memory effect, minimum distortion recovery temperature more is of practical significance than fusing point, and its available heat sizing (TMA) method is measured, generally than low 10～20 ℃ of fusing point.Suitably adjust synthesis condition, minimum distortion recovery temperature can be adjusted near the human body temperature, satisfy the needs that clinical medicine is used.
Description of drawings
Fig. 1. the shape memory effect under stretching and the compression set.(a) stretch; (b) compression.
Fig. 2. one of shape memory effect example under the complex deformation: round shape-quincunx-round shape.
Fig. 3. two of the shape memory effect example under the complex deformation: round shape-reel shape-round shape.(a) original-shape; (b) after the enlarged diameter; (c) curl after; (d～i) puts into 40 ℃ of water; (j) final form.
Fig. 4. the hot mechanical paths of sample P CL3500-PU176.
Fig. 5. the hot mechanical paths of typical sample.From left to right be respectively PCL2000-PU132, PCL2500-PU132, PCL3000-PU132, PCL3500-PU176, PCL5000-PU176, PCL8000-PU176 and PCL10000-PU176.Their minimum distortion recovery temperature data rows is in table 1.
Embodiment
Embodiment 1:
With 114g 6-caprolactone, 1.4g ethylene glycol and 5ml concentration is 0.1molL
-1Sn (Oct)
2/ toluene solution successively joins a process thorough drying and is furnished with in the vial of magnetic stirring bar, adding isopyknic toluene with syringe, stir, put into 120 ℃ constant temperature oil bath, reacting by heating 24 hours, cooling is room temperature, obtains poly-(6-caprolactone) toluene solution (PCL) with the both-end hydroxyl.
The 2,4 toluene diisocyanate (TDI) that adds calculated amount in this solution 65 ℃ of heated and stirred 15 minutes, adds the ethylene glycol (EG) of calculated amount then, makes the mole number of TDI equal the mole number sum of PCL and EO just.Continuation is dissolved in reaction product in the chloroform then, and uses the hexane precipitation process, 40 ℃ of vacuum-dryings 24 hours 65 ℃ of following stirring reactions 3 hours.
Change the ratio of above-mentioned 6-caprolactone and ethylene glycol, other reaction conditions is constant, then obtains the different PCL prepolymer of molecular weight.Correspondingly adjust the consumption of TDI and EO, obtain the polymerisate of soft section of difference and hard section ratio.
The molecular weight of centre and final product and fusing point, Tc obtain table 1 more than measuring.The molecular weight of the PCL prepolymer of the band both-end hydroxyl that records with magnetic nuclear resonance method of the numeral of PCL back wherein, the mol ratio of the numeral PCL of PU back, TDI, EO is represented PCL as PU132: TDI: EO=1: 3: 2.Corresponding weight composition provides in secondary series, and " hard section " refers to the consumption sum of TDI and EO, supposes that here the transformation efficiency of two-stage polymerization is 100%.Fusing point and Tc are measured with the DSC method, the minimum recovery temperature of deformation with thermomechanical analyzer (TMA) with (5 ℃/min) obtain of constant heatingrate's methods.
Composition and the characteristic temperature of table 1.PCL-PU
| ????PCL-PU | Hard section (wt%) | Fusing point Tm (℃) | Tc Tc (℃) | Minimum recovery temperature LRT (℃) |
| ????PCL-500 | ????- | ????19.0 | ?????-2.9 | |
| ????PCL-1000 | ????- | ????45.8 | ?????11.2 | |
| ????PCL1000-PU132 | ????39.3 | ????- | ||
| ????PCL1000-PU154 | ????52.8 | ????- | ||
| ????PCL1000-PU176 | ????61.4 | ????- | ||
| ????PCL-2000 | ????- | ????54.3 | ?????20.8 | |
| ????PCL2000-PU132 | ????24.4 | ????43.0 | ????23 | |
| ????PCL2000-PU154 | ????35.9 | ????- | ||
| ????PCL2000-PU176 | ????44.3 | ????- | ||
| ????PCL-2500 | ????- | ????55.6 | ||
| ????PCL2500-PU132 | ????20.5 | ????44.0 | ????27 | |
| ????PCL-3000 | ????- | ????56.9 | ||
| ????PCL3000-PU132 | ????17.7 | ????46.5 | ????30 | |
| ????PCL-3500 | ????- | ????60.3 | ?????27.1 | |
| ????PCL3500-PU132 | ????15.6 | ????52.3 | ||
| ????PCL3500-PU154 | ????24.2 | ????51.1 | ||
| ????PCL3500-PU176 | ????31.2 | ????49.4 | ????37 | |
| ????PCL-5000 | ????- | ????62.0 | ?????27.9 | |
| ????PCL5000-PU132 | ????11.4 | ????55.5 | ?????-1.1 | |
| ????PCL5000-PU154 | ????18.3 | ????54.5 | ?????- | |
| ????PCL5000-PU176 | ????24.1 | ????52.2 | ?????- | |
| ????PCL-8000 | ????- | ????62.8 | ?????36.7 | |
| ????PCL8000-PU132 | ????7.5 | ????56.9 | ?????16.8 | |
| ????PCL8000-PU154 | ????12.3 | ????57.9 | ?????11.7 | |
| ????PCL8000-PU176 | ????16.6 | ????56.4 | ?????-0.4 | ????45 |
| ????PCL-10000 | ????- | ????61.7 | ?????26.3 | |
| ????PCL10000-PU132 | ????6.1 | ????57.9 | ?????20.7 | |
| ????PCL10000-PU154 | ????10.1 | ????58.8 | ?????19.6 | |
| ????PCL10000-PU176 | ????13.7 | ????58.1 | ?????19.4 | ????48 |
As shown in Table 1, the molecular weight of PCL prepolymer is only greater than 2000, and polymer PC L-PU just has fusing point, and material just can show shape memory function.Otherwise they at room temperature only show as thermoplastic elastomer.
Wherein, the typical hot recovery curve that records with the TMA method is seen attached Figure 4 and 5.Fig. 4 uses the PCL3500-PU176 sample in the table 1, and as seen its minimum distortion recovery temperature is 37 ℃, just in time is the temperature of human body.Fig. 5 has provided the TMA curve of a series of samples, and sample from left to right is respectively PCL2000-PU132, PCL2500-PU132, PCL3000-PU132, PCL3500-PU176, PCL5000-PU176, PCL8000-PU176 and PCL10000-PU176.As seen, the minimum distortion recovery temperature of PCL-PU is decided by the molecular weight of PCL prepolymer and soft, hard section relative proportion, by regulating molecular weight and the two-phase proportion of PCL, the distortion recovery temperature can be controlled near the human body temperature, promptly 37～42 ℃, so that realize medical use.Obviously, the minimum distortion recovery temperature (seeing Table 1) that records of test is more much lower than corresponding fusing point.As in specification sheets, point out, this temperature has more practical significance than fusing point and Tc, it has determined the service performance and the working conditions of PCL-PU material.
Embodiment 2:
Adopt the reaction conditions among the embodiment 1, but synthetic at the first step PCL, obtain PCL toluene solution with the both-end hydroxyl after, be not directly to carry out next step reaction, but PCL be precipitated out that washing, vacuum-drying obtain purified PCL prepolymer with normal hexane.Then with the PCL prepolymer in being dissolved into toluene, add 0.1molL
-1The Sn of concentration (Oct)
2/ toluene carries out next step reaction.This response procedures is accurately to measure the molecular weight and the functionality of PCL prepolymer with respect to the advantage of embodiment 1, so that accurate equivalent control is carried out in the reaction of second step, obtains higher molecular weight.But the fusing point of product, Tc and minimum distortion recovery temperature do not have to change substantially.
Embodiment 3:
Adopt the response procedures of embodiment 1, but change 2,4 toluene diisocyanate into 2, the 6-tolylene diisocyanate.The fusing point of products therefrom, Tc and minimum distortion recovery temperature are with in embodiment 1 is in identical temperature range.
Embodiment 4:
Adopt the response procedures of embodiment 1, but change 2,4 toluene diisocyanate into '-diphenylmethane diisocyanate.The fusing point of products therefrom, Tc and minimum distortion recovery temperature are with in embodiment 1 is in identical temperature range.
Embodiment 5:
Adopt the response procedures of embodiment 1, but change 2,4 toluene diisocyanate into isophorone diisocyanate.The fusing point of products therefrom, Tc and minimum distortion recovery temperature are with in embodiment 1 is in identical temperature range.
Claims (7)
1. shape-memory material based on poly-(6-caprolactone), it is be soft section with poly-(6-caprolactone), serve as firmly section multi-block polyurethane with vulcabond-small molecules glycol reaction product; Wherein the molecular weight of soft section of PCL is 2000～20000, and fusing point is in room temperature to 60 ℃, and Tc is in room temperature to 0 ℃; It has biological degradation and shape memory dual-use function, and the setting temperature of recoverable deformation is at 0～30 ℃, and recovery temperature is at 20～60 ℃, but recovery extent is 90～100%.
2. the synthetic method of the described shape-memory material based on poly-(6-caprolactone) of claim 1, it is formed with vulcabond, the reaction of small molecules glycol by two ends hydroxyl poly-(6-caprolactone), the mole number of vulcabond equals the mole number sum of PCL and small molecules glycol, uses stannous octoate to be catalysts; Wherein the hydroxyl PCL in two ends is that spent glycol or butyleneglycol are initiator, in the presence of stannous octoate or other catalyzer, is obtained by the 6-caprolactone ring-opening polymerization; Vulcabond is a 2,4 toluene diisocyanate, 2,6-tolylene diisocyanate or their mixture, '-diphenylmethane diisocyanate, isophorone diisocyanate; The small molecules diol chain-extension agent is ethylene glycol and butyleneglycol.
3. the using method of the described shape-memory material based on poly-(6-caprolactone) of claim 1: (1) is extruded polymkeric substance, inject or other moulding under 120～150 ℃, obtains needed article shape and size; (2) goods are stretched, compress or other complex deformation, and should be out of shape and keep; (3) goods after will being out of shape carry out heat treated, eliminate the distortion that is applied, and recover the original shape and the size of goods.
4. the using method of the described shape-memory material based on poly-(6-caprolactone) of claim 3, it is characterized in that, adopt following two kinds of methods to realize distortion and distortion be fixed up: (1) the fusing point of material or than fusing point slightly high-temperature implement distortion, keep distortion near then the temperature of sample being dropped to Tc; (2) goods are directly implemented distortion under a temperature between minimum distortion recovery temperature and the Tc, be out of shape and fix a step and finish.
5. the described using method based on the shape-memory material that gathers (6-caprolactone) of claim 3 is characterized in that temperature is implemented distortion near the fusing point of material, and the temperature with sample drops to room temperature maintenance distortion then.
6. the using method of the described shape-memory material based on poly-(6-caprolactone) of claim 3 is characterized in that, goods are directly at room temperature implemented distortion, is out of shape and fixes a step and finish.
7. the using method of the described shape-memory material based on poly-(6-caprolactone) of claim 3, it is characterized in that, adopt following two kinds of methods to eliminate distortion, recover article shape: (1) constant temperature method: the sample after will being out of shape put into minimum distortion recovery temperature than this sample high slightly water, sample generation inverse metamorphism returns to original shape and size; (2) temperature-raising method: the sample heat temperature raising after will being out of shape, when arriving minimum distortion recovery temperature, sample generation inverse metamorphism returns to original shape and size.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410010734 CN1279077C (en) | 2004-03-19 | 2004-03-19 | Shape memory material based on poly(e-caprolactone), preparation and metod of application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410010734 CN1279077C (en) | 2004-03-19 | 2004-03-19 | Shape memory material based on poly(e-caprolactone), preparation and metod of application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1563132A true CN1563132A (en) | 2005-01-12 |
| CN1279077C CN1279077C (en) | 2006-10-11 |
Family
ID=34477870
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200410010734 Expired - Fee Related CN1279077C (en) | 2004-03-19 | 2004-03-19 | Shape memory material based on poly(e-caprolactone), preparation and metod of application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1279077C (en) |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1324174C (en) * | 2004-06-09 | 2007-07-04 | 香港理工大学 | Shape memory fiber prepared with shape memory polyurethane and its prepn process |
| CN101443383B (en) * | 2006-05-15 | 2011-04-20 | Gkss研究中心盖斯特哈赫特有限公司 | Multiblock copolymers with shape-memory properties |
| CN101496758B (en) * | 2008-12-08 | 2011-04-27 | 中国人民解放军第三军医大学 | Shape memory contraceptive device on oviduct for realizing contraception |
| CN105820301A (en) * | 2016-04-22 | 2016-08-03 | 哈尔滨工业大学 | Production method of shape memory polymer plastic coin substrate |
| WO2017012560A1 (en) * | 2015-07-23 | 2017-01-26 | 浙江大学 | Application method of plastic shape memory polymer based on ester exchange |
| CN107033304A (en) * | 2017-05-09 | 2017-08-11 | 东南大学 | With can self-repair function shape memory inlay section thermal plastic high polymer material |
| CN108264623A (en) * | 2018-01-23 | 2018-07-10 | 中国科学院长春应用化学研究所 | A kind of polyester polyurethane shape-memory material and preparation method thereof |
| CN108976383A (en) * | 2018-06-27 | 2018-12-11 | 西北民族大学 | A kind of Medical macromolecular splint |
| CN109880054A (en) * | 2019-03-29 | 2019-06-14 | 中国科学院宁波材料技术与工程研究所 | Polyurethane and preparation method thereof with shape memory function |
| CN110041503A (en) * | 2019-04-02 | 2019-07-23 | 镇江利德尔复合材料有限公司 | A kind of novel shape memory polyurethane material can be used for bionical 4D printing |
| CN110982037A (en) * | 2019-12-26 | 2020-04-10 | 郑州大学 | Body temperature response shape memory polyurethane material and preparation method thereof |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101906472B1 (en) | 2017-04-04 | 2018-10-10 | 연세대학교 산학협력단 | A photo-crosslinkable shape memory polymer and manufacturing method thereof |
-
2004
- 2004-03-19 CN CN 200410010734 patent/CN1279077C/en not_active Expired - Fee Related
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1324174C (en) * | 2004-06-09 | 2007-07-04 | 香港理工大学 | Shape memory fiber prepared with shape memory polyurethane and its prepn process |
| CN101443383B (en) * | 2006-05-15 | 2011-04-20 | Gkss研究中心盖斯特哈赫特有限公司 | Multiblock copolymers with shape-memory properties |
| CN101496758B (en) * | 2008-12-08 | 2011-04-27 | 中国人民解放军第三军医大学 | Shape memory contraceptive device on oviduct for realizing contraception |
| WO2017012560A1 (en) * | 2015-07-23 | 2017-01-26 | 浙江大学 | Application method of plastic shape memory polymer based on ester exchange |
| US10449709B2 (en) | 2015-07-23 | 2019-10-22 | Zhejiang University | Fabrication and application of shape memory polymer possessing transesterification induced permanent reshaping property |
| CN105820301A (en) * | 2016-04-22 | 2016-08-03 | 哈尔滨工业大学 | Production method of shape memory polymer plastic coin substrate |
| CN107033304A (en) * | 2017-05-09 | 2017-08-11 | 东南大学 | With can self-repair function shape memory inlay section thermal plastic high polymer material |
| CN108264623A (en) * | 2018-01-23 | 2018-07-10 | 中国科学院长春应用化学研究所 | A kind of polyester polyurethane shape-memory material and preparation method thereof |
| CN108976383A (en) * | 2018-06-27 | 2018-12-11 | 西北民族大学 | A kind of Medical macromolecular splint |
| CN109880054A (en) * | 2019-03-29 | 2019-06-14 | 中国科学院宁波材料技术与工程研究所 | Polyurethane and preparation method thereof with shape memory function |
| CN110041503A (en) * | 2019-04-02 | 2019-07-23 | 镇江利德尔复合材料有限公司 | A kind of novel shape memory polyurethane material can be used for bionical 4D printing |
| CN110982037A (en) * | 2019-12-26 | 2020-04-10 | 郑州大学 | Body temperature response shape memory polyurethane material and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1279077C (en) | 2006-10-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Xue et al. | Biodegradable shape-memory block co-polymers for fast self-expandable stents | |
| AU2008307139B2 (en) | High modulus polyurethane and polyurethane/urea compositions | |
| Hu | Shape memory polymers and textiles | |
| CN1279077C (en) | Shape memory material based on poly(e-caprolactone), preparation and metod of application | |
| Heijkants et al. | Uncatalyzed synthesis, thermal and mechanical properties of polyurethanes based on poly (ε-caprolactone) and 1, 4-butane diisocyanate with uniform hard segment | |
| Gunatillake et al. | Designing biostable polyurethane elastomers for biomedical implants | |
| Loh et al. | Synthesis and water-swelling of thermo-responsive poly (ester urethane) s containing poly (ε-caprolactone), poly (ethylene glycol) and poly (propylene glycol) | |
| Xue et al. | Synthesis and characterization of three-arm poly (ε-caprolactone)-based poly (ester− urethanes) with shape-memory effect at body temperature | |
| Calvo-Correas et al. | Thermally-responsive biopolyurethanes from a biobased diisocyanate | |
| CA2962665C (en) | Polymer network with triple-shape-memory effect and associated programming method | |
| CN108264623B (en) | Polyester type polyurethane shape memory material and preparation method thereof | |
| CN107137789B (en) | Preparation method and application of ureteral stent tube with shape memory effect | |
| EP1907434A1 (en) | Shape memory polymers based on semicrystalline thermoplastic polyurethanes bearing nanostructured hard segments | |
| CN111269373B (en) | Preparation method of remodelable shape memory elastomer based on eutectic | |
| Liu et al. | Effect of chain extender on hydrogen bond and microphase structure of biodegradable thermoplastic polyurethanes | |
| CN107474212A (en) | A kind of method for preparing polyurethane elastic body of the compound crystal containing polylactic acid stereoscopic | |
| WO2005007210A1 (en) | Degradable biocompatible block copolymer | |
| CN105504248B (en) | The preparation and application of the linear degradable poly ester elastomer of controllable elasticity and SME | |
| Yagci et al. | Development of metformin chain extended polyurethane elastomers as bone regenerative films | |
| CN114479120B (en) | Acrylic ester modified polyurethane adhesive hydrogel material and preparation method thereof | |
| CN110627996A (en) | Polyurethane urea, preparation method thereof and super-tough polyurethane urea based on polyurethane urea | |
| Candau et al. | Stiff, strong, tough, and highly stretchable hydrogels based on dual stimuli-responsive semicrystalline poly (urethane–urea) copolymers | |
| CN113817145B (en) | Polyester type biodegradable shape memory copolymer based on poly epsilon-caprolactone and preparation method thereof | |
| CN114524913A (en) | High-flexibility high-elasticity degradable-controllable absorbable polyurethane elastomer, and preparation method and application thereof | |
| Meng et al. | A low-temperature thermoplastic anti-bacterial medical orthotic material made of shape memory polyurethane ionomer: influence of ionic group |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| ASS | Succession or assignment of patent right |
Owner name: CHANGZHOU INSTITUTE OF ENERGY STORAGE MATERIALS + Free format text: FORMER OWNER: CHANGCHUN INSTITUTE OF APPLIED CHEMISTRY HINESE ACADEMY OF SCIENCES Effective date: 20121231 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| COR | Change of bibliographic data |
Free format text: CORRECT: ADDRESS; FROM: 130022 CHANGCHUN, JILIN PROVINCE TO: 213000 CHANGZHOU, JIANGSU PROVINCE |
|
| TR01 | Transfer of patent right |
Effective date of registration: 20121231 Address after: Changzhou City, Jiangsu province Hehai road 213000 No. 9 Patentee after: Changzhou Institute of Energy Storage Materials & Devices Address before: 130022 Changchun people's street, Jilin, No. 5625 Patentee before: Changchun Institue of Applied Chemistry, Chinese Academy of Sciences |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20170204 Address after: 130022 Changchun people's street, Jilin, No. 5625 Patentee after: Changchun Applied Chemistry Inst., Chinese Academy of Sciences Address before: Changzhou City, Jiangsu province Hehai road 213000 No. 9 Patentee before: Changzhou Institute of Energy Storage Materials & Devices |
|
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20061011 Termination date: 20180319 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |