CN104592453A - Polymer with bidirectional reversible shape memory effect and preparation method thereof - Google Patents
Polymer with bidirectional reversible shape memory effect and preparation method thereof Download PDFInfo
- Publication number
- CN104592453A CN104592453A CN201510016304.1A CN201510016304A CN104592453A CN 104592453 A CN104592453 A CN 104592453A CN 201510016304 A CN201510016304 A CN 201510016304A CN 104592453 A CN104592453 A CN 104592453A
- Authority
- CN
- China
- Prior art keywords
- shape memory
- polymkeric substance
- transition temperature
- polymer
- memory effect
- 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
Abstract
The invention discloses a polymer with a bidirectional reversible shape memory effect. The polymer comprises at least one amorphous phase and a crystal phase, wherein the glass-transition temperature of the amorphous phase is higher than the melting temperature of the crystal phase and the difference is at least 20 DEG C. The preparation method of the polymer comprises the step of preparing a single-crystal thermosetting bidirectional reversible shape memory molecule by taking the high-temperature amorphous phase as a stress phase to replace the high-temperature crystal phase in a bi-crystal thermosetting reversible shape memory molecule. The glass-transition temperature of the amorphous phase of the polymer can be continuously controlled through different comonomers; the control of the proportion of the two phases, the crosslinking densities and the transition temperature of the crystal phase can be realized under the premise of ensuring that the glass-transition temperature of the amorphous phase is higher than the transition temperature of the crystal phase. The polymer is light in material weight, easy to process and low in cost, has excellent insulation property and thermal insulation effect and has wide potential application value in the fields of biomedicine, cable industry and packaging industry.
Description
Technical field
The invention belongs to new function material field, relate to a kind of intelligent material and preparation method thereof, particularly relate to and a kind of there is polymer materials of bidirectional reversible shape memory effect and preparation method thereof.
Background technology
Traditional shapememory polymer is being heated to may be deformed to a temporary shapes on its thermal transition temperature and under the acting in conjunction of external force, this temporary shapes after the cooling period (to its thermal transition temperature) can be fixed, temporary shapes after fixing (such as reheating) under certain ambient conditions stimulates can return to its original-shape again, and the thermal transition temperature (such as second-order transition temperature or Tc) of its correspondence is commonly called shape memory transition temperature.Shapememory polymer known since half a century can only change at every turn between a temporary shapes and its permanent shape, namely present said dual-shaped memory effect, and its essence is exactly utilize a heat deflection to remember a temporary shapes.This Shape memory behavior, although simply, it is commercially successfully applied, such as, for red shortness's conduit of cable industry and the heat shrink label of packaging industry.Among the biomedical applications of other high added values is also in and tries to explore, and show its great potential gradually.
Research in recent years finds that in same macromolecular structure, two distinct heat deflection regions can realize the fixing triple shape memory effect systems of two temporary shapes, and the heat deflection of the single wide region of same polymeric inner can be used for fixing plural temporary shapes, namely adjustable multiple shape memory effect.Variation and the application prospect thereof of polymer shape memory behavior have been expanded in the discovery of these novel shape memory effect greatly.No matter be dual, triple, or multiple shape memory effect, without under External Force Acting, polymkeric substance all can be made to return to original-shape from temporary shapes by heating.But, same without under the condition of External Force Acting, but do not make polymkeric substance return to the temporary shapes under its low temperature by original-shape by cooling.These shape memories are all irreversible above, are referred to as one-way shape memory.
Irreversible shape memory, although the practical prospect also having it, its unidirectional deformational behavior hinders applying more widely of this kind of material.In calendar year 2001, Terentjev group finds that crosslinked liquid crystal elastic body is under the condition hanging constant weight (i.e. constant external force >0), the thermal contraction of completely reversibility and the phenomenon of cold elongation can be shown up and down at its liquid crystal transition temperature, the orientation of forced direction outside when its cold elongation originates from Formation of liquid crystals, this elimination when being oriented in heating then causes thermal contraction (TajbakhshAR, Terentjev EM.Eur.Phys.J.Ser.E.2001,6,181.).Based on similar mechanism, in 2008, Mather group has found that cross-linking crystal macromolecule network also shows same behavior, just corresponding heat deflection is that heat of crystallization changes (Chung T, Rorno-Uribe A, Mather P.Two-wayreversible shape memory in a semicrystalline network.Macromolecules 2008,41,184.).Thereafter, multiple research group (comprising applicant) also reports the high molecular reversible deformation behavior of different cross-linking crystal in succession.The advantage of this kind of reversible deformation is that deformation quantity can regulate and control along with the size of constant external force, and so its shortcoming is also very remarkable: can not realize when external force is zero, and need the condition of constant External Force Acting to greatly limit the possibility of its device application; Hang this constant external force the most easily realized of constant weight and mean that deformation can only be linear elongation and contraction.
Within 2010, Hu group achieves the reversible bending change without Polymer Systems under External Force Acting.The change completely reversibility of this material bending degree, and without the need to effect (the Chen S of external force, Hu J, Zhao H.Properties and mechanism of two-way shape memory polyurethane composites.Composites Sci.Technology 2010,70,1437.).Although this progress is functionally very important, the shortcoming of this type of material is still remarkable: macroscopical laminate structure means that material can only be applied to macroscopic devices; This composite system after the preparation its internal stress also just secures, that is, and the change that it can only be reversible between constant two shapes, and the sequencing that can not realize deformed shape changes.
CN103992631A provides a kind of polymer materials with bidirectional shape memory, comprises the interspersed two kinds of interpenetrating net polymers arranged mutually; Wherein network polymer is a shape-memory polymer for crystal class cross-linked polymer, and another kind of network polymer is cross-linked elastic material.Crystal class cross-linked polymer is one or more of the shape-memory polymer of urethane, polyethylene, polynorbornene, using trans-polyisoprene or styrene-butadiene copolymer; Cross-linked elastic material is one or more in polyurethane elastomer resins, SBS resin, propene-1-butene copolymer, vulcanite or silicon rubber.
CN101560302 discloses a kind of liquid crystal elastic body and fiber and preparation method thereof with bidirectional shape memory effect, and this liquid crystal elastic body or fibrous molecular structure are the mixture of a class in following two class general formula polymkeric substance or two base polymers.
CN101164770B relates to a kind of polymer composites with bidirectional shape memory effect and preparation method thereof, this polymer composites comprises the polymkeric substance that at least two superimposed is bonded together, wherein at least one one polymer is the shape memory polymer material being selected from urethane, crosslinked polyethylene, polynorbornene, using trans-polyisoprene or styrene-butadiene copolymer, and also comprising one deck resilient material and/or one deck in the polymkeric substance that described at least two superimposed is bonded together can flexural deformation the plastic tab that can initiatively reply.
The research of bidirectional reversible shapememory polymer achieved breakthrough progress in 2013.Lendlein group report a kind of there is microphase-separated and the reversible shape memory function of the different twin crystal thermoset polyurethane system of two-phase thermal transition temperature (BehlM, Kratz K, ZotzmannJ,
lendlein A.Reversible bidirectional shape-memory polymers.Adv.Mater.2013,25,4466.).But it has following shortcoming:
1. the adjustability of phase transition temperature is poor, the phase transition temperature of polymer crystallization usually can by introducing the adjustment that a small amount of comonomer comes among a small circle, but comonomer thoroughly will destroy crystallization too much, therefore the practical application of basis needs likely will come to regulate on a large scale two crystallization phases transition temperatures to be almost impossible simultaneously;
2. due to the impossible crystallization completely of polymer, and the degree of crystallinity of two-phase is also probably with the thermomechanical condition change of reversible shape memory, and the quantitative study mechanism that twin crystal thermoset system is remembered reversible shape is very unsuitable.By contrast, the second-order transition temperature of amorphous macromolecule can realize on a large scale regulation and control continuously by the introducing of comonomer, and its vitrifying is more complete, and second-order transition temperature is relatively more insensitive to thermomechanical condition.
Summary of the invention
The deficiency that the present invention exists according to shape-memory material in prior art, develops a kind of polymer materials with bidirectional reversible shape memory effect with monocrystalline thermoset system, and this material realizes reversible shape memory mutually using high-temperature amorphous as stress; Namely vary with temperature mutually by low temperature crystallization in crosslinked rear system and realize the reversible deformation of shape, there is the bidirectional memory function of repetitive memory two states shape.
The polymkeric substance with bidirectional reversible shape memory effect provided by the invention, comprises at least one amorphous phase and a crystallization phases, and wherein the second-order transition temperature of amorphous phase is higher than the melt temperature of crystallization phases, and both at least differ 20 DEG C.
Described polymer materials is prepared by the following method:
(1) a kind of material that high glass-transition temperature is provided is selected;
(2) a kind of crystal material is selected;
(3) by above-mentioned two kinds of material crosslinking curings.
Preferably, high-temperature amorphous phase material is provided to be the acrylate with high glass-transition temperature, as methyl methacrylate, cyclohexyl methacrylate, Tricyclodecane Dimethanol diacrylate or its mixture described in; Its glass transition temperature Tg need at about 100 DEG C or more, preferred glass transition temperature Tg>95 DEG C.
Preferably, described crystallization phases material is selected from polyethyleneglycol diacrylate, polyethylene glycol dimethacrylate or polycaprolactone diacrylate; Described polyethyleneglycol diacrylate or the molecular weight ranges of polyethylene glycol dimethacrylate are 3000 ~ 12000; The molecular weight of described polycaprolactone diacrylate is 3000 ~ 14000; Tm scope is at 45 ~ 65 DEG C.After crosslinked, the fusing point of bidirectional reversible shape memory effect polymkeric substance is at 35 ~ 55 DEG C.
Described polymkeric substance is the thermosetting polymer obtained by chemically crosslinked,
The second-order transition temperature of the high-temperature amorphous phase of described polymkeric substance and the melt temperature of low temperature crystallization phase are defined as T respectively
1, T
2(T
1> T
2), definition of T
high>T
1>T
middle>T
2>T
low, by this heating materials to T
high, make it be out of shape by applying certain external force, and be cooled to T
middlerear removing external force, is now labeled as Shape A (first time deformation) by the solid shape of material.Under the effect not having external force, material continues cooling (T
middlebe down to T
low) cause Shape A to become Shape B (second time deformation).After this, when temperature is at T
middlewith T
lowbetween repeatedly change (without external force), the change that material shape can be reversible between A and B accordingly.
Described polymkeric substance bidirectional reversible shape function can ensure, under the prerequisite of the second-order transition temperature of amorphous phase higher than crystallization phases crystalline melt temperature, can realize the regulation and control of two-phase proportion, cross-linking density, crystallization phases melt temperature and amorphous phase second-order transition temperature.
Preferably, the bidirectional reversible shape memory function of described polymer materials is realized by the change of ambient conditions, described ambient conditions, as transition temperature, mainly determined by the melt temperature of low temperature crystallization phase in polymkeric substance.
Principle of the present invention is more than the second-order transition temperature by polymkeric substance being heated to high-temperature amorphous phase, by applying the primary deformation process that certain external force causes, not only can determine first Shape A of polymkeric substance, additionally provide and impel the reversible required internal stress of second time deformation.The reversible motivating force of second time deformation is then the mutually temperature variant reversible orientation of low temperature crystallization under this internal stress effect.Although first time deformation is irreversible, the change that shape A can be programmed by this process, its change also correspondingly causes the change of shape B.
Innovation of the present invention is: propose to replace high temperature crystallization to realize reversible shape memory mutually as stress mutually using high-temperature amorphous, prepare monocrystalline thermoset reversible shape memory polymer with this; Achieve the adjustability of phase transition temperature.
Prepared shape-memory polymer has the following advantages:
1) shape-memory polymer has bidirectional reversible memory effect, good stability, changes back and forth between two kinds of shapes by external stimulus;
2) selectable starting material are sufficient, can be designed to multiple different system according to the starting material selected simultaneously;
3) adjustability of shape-memory polymer phase transition temperature is larger;
4) shape-memory polymer light weight;
5) preparation method of shape-memory polymer is simple, can be designed to different shapes according to actual needs simultaneously;
6) shape-memory polymer low price;
7) shape-memory polymer has good electrical insulation capability and heat insulation effect.
Bidirectional reversible shape memory polymer material prepared by the present invention has important application prospect, and it all exists larger potential using value in fields such as biomedicine, textile materials, machinofacture, electronics, cable industry, packaging industries.
Accompanying drawing explanation
Fig. 1 is the DMA test pattern of the polymkeric substance that embodiment 1 obtains.
Fig. 2 is the dual shape memory characterization result figure after embodiment 1 sequencing sizing.
Fig. 3 is the DMA test pattern of the polymkeric substance obtained of embodiment 2.
Fig. 4 is the dual shape memory characterization result figure after embodiment 2 sequencing sizing.
Fig. 5 is the DMA test pattern of the polymkeric substance obtained of embodiment 3.
Fig. 6 is the dual shape memory characterization result figure after embodiment 3 sequencing sizing.
Fig. 7 is the DMA test pattern of the polymkeric substance obtained of embodiment 4.
Fig. 8 is the dual shape memory characterization result figure after embodiment 4 sequencing sizing.
Fig. 9 is repeatability and the stability test result figure of the dual shape memory of the polymkeric substance that embodiment 4 obtains.
Embodiment
Below in conjunction with embodiment, the present invention will be further described, but the scope of protection of present invention is not limited to the scope that embodiment is expressed.
Embodiment 1
Raw material:
A) polyethyleneglycol diacrylate (PEGDA): Mw=8000, Alfa Aesar company;
B) cyclohexyl methacrylate (CMA): Sigma-Aldrich company;
C) benzoyl peroxide (BPO): Aladdin reagent (Shanghai) Co., Ltd.;
Preparation method:
Prepared by employing mass polymerization: take a certain amount of polyethyleneglycol diacrylate and cyclohexyl methacrylate (wherein the mass ratio of PEGDA and CMA is 3:1), add benzoyl peroxide (its add-on is 3% of system total mass), by it 70 DEG C of dissolvings, pour in sealing glass groove after stirring, at 100 DEG C of solidification 2 ~ 3h.The crystalline melt temperature of the polymkeric substance obtained and the DMA test result of second-order transition temperature are as Fig. 1.
Dual shape memory characterizes: polymkeric substance is heated to 156 DEG C, and the power applying 1N stretches, and is cooled to 56 DEG C under this pulling force, and removing pulling force, this process is sequencing deformation process.Then continue to be cooled to 0 DEG C, be warming up to 56, this polymkeric substance can repeat cold elongation and thermal contraction dual shape memory phenomenon at 0 DEG C ~ 56 DEG C, and result is as Fig. 2.
Embodiment 2
Raw material:
D) polyethyleneglycol diacrylate (PEGDA): Mw=8000, Alfa Aesar company;
E) cyclohexyl methacrylate (CMA): Sigma-Aldrich company;
F) Tricyclodecane Dimethanol diacrylate (TDD): Sigma-Aldrich company;
G) benzoyl peroxide (BPO): Aladdin reagent (Shanghai) Co., Ltd.;
Preparation method:
Prepared by employing mass polymerization: take a certain amount of polyethyleneglycol diacrylate, cyclohexyl methacrylate and Tricyclodecane Dimethanol diacrylate (wherein the mass ratio of PEGDA and CMA and TDD is 6:1:2), add benzoyl peroxide (its add-on is 3% of system total mass), by it 70 DEG C of dissolvings, pour in sealing glass groove after stirring, at 100 DEG C of solidification 2 ~ 3h.The crystalline melt temperature of the polymkeric substance obtained and the DMA test result of second-order transition temperature are as Fig. 3.
Dual shape memory characterizes: polymkeric substance is heated to 170 DEG C, and the power applying 2N stretches, and is cooled to 56 DEG C under this pulling force, and removing pulling force, this process is sequencing deformation process.Then continue to be cooled to 0 DEG C, be warming up to 56, this polymkeric substance can repeat cold elongation and thermal contraction dual shape memory phenomenon at 0 DEG C ~ 56 DEG C, and result as shown in Figure 4.
Embodiment 3
Raw material:
H) polyethyleneglycol diacrylate (PEGDA): Mw=8000, Alfa Aesar company;
I) cyclohexyl methacrylate (CMA): Sigma-Aldrich company;
J) benzoyl peroxide (BPO): Aladdin reagent (Shanghai) Co., Ltd.;
Preparation method:
Prepared by employing mass polymerization: take a certain amount of polyethyleneglycol diacrylate, cyclohexyl methacrylate (wherein PEGDA and CMA mass ratio is 2:1), add benzoyl peroxide (its add-on is 3% of system total mass), by it 70 DEG C of dissolvings, pour in sealing glass groove after stirring, at 100 DEG C of solidification 2 ~ 3h.The crystalline melt temperature of the polymkeric substance obtained and the DMA test result of second-order transition temperature are as Fig. 5.
Dual shape memory characterizes: polymkeric substance is heated to 170 DEG C, and the power applying 2N stretches, and is cooled to 56 DEG C under this pulling force, and removing pulling force, this process is sequencing deformation process.Then continue to be cooled to 0 DEG C, be warming up to 56, this polymkeric substance can repeat cold elongation and thermal contraction dual shape memory phenomenon at 0 DEG C ~ 56 DEG C, and result as shown in Figure 6.
Embodiment 4
Raw material:
K) polyethyleneglycol diacrylate (PEGDA): Mw=8000, Alfa Aesar company;
L) cyclohexyl methacrylate (CMA): Sigma-Aldrich company;
M) Tricyclodecane Dimethanol diacrylate (TDD): Sigma-Aldrich company;
N) benzoyl peroxide (BPO): Aladdin reagent (Shanghai) Co., Ltd.;
Preparation method:
Prepared by employing mass polymerization: take a certain amount of polyethyleneglycol diacrylate, cyclohexyl methacrylate and Tricyclodecane Dimethanol diacrylate (wherein the mass ratio of PEGDA and CMA and TDD is 12:1:2), add benzoyl peroxide (its add-on is 3% of system total mass), by it 70 DEG C of dissolvings, pour in sealing glass groove after stirring, at 100 DEG C of solidification 2 ~ 3h.The crystalline melt temperature of the polymkeric substance obtained and the DMA test result of second-order transition temperature are as Fig. 7.
Dual shape memory characterizes: polymkeric substance is heated to 170 DEG C, and the power applying 2N stretches, and is cooled to 56 DEG C under this pulling force, and removing pulling force, this process is sequencing deformation process.Then continue to be cooled to 0 DEG C, be warming up to 56, this polymkeric substance can repeat cold elongation and thermal contraction dual shape memory phenomenon at 0 DEG C ~ 56 DEG C, and result as shown in Figure 8.Above-mentionedly repeatedly repeat, characterize repeatability and the stability of dual shape memory, result as shown in Figure 9.
Claims (7)
1. have a polymkeric substance for bidirectional reversible shape memory effect, it is characterized in that: this polymkeric substance comprises at least one amorphous phase and a crystallization phases, wherein the second-order transition temperature of amorphous phase is higher than the melt temperature of crystallization phases, and both at least differ 20 DEG C.
2. the polymkeric substance with bidirectional reversible shape memory effect according to claim 1, is characterized in that: the described material of high glass-transition temperature that provides is acrylate.
3. the polymkeric substance with bidirectional reversible shape memory effect according to claim 2, is characterized in that: described acrylate is methyl methacrylate, cyclohexyl methacrylate, Tricyclodecane Dimethanol diacrylate or its mixture.
4. the polymkeric substance with bidirectional reversible shape memory effect according to claim 1, is characterized in that: the fusing point of described crystal material is at 45 ~ 65 DEG C, and the fusing point of crosslinked post-consumer polymer is at 35 ~ 55 DEG C.
5. the polymkeric substance with bidirectional reversible shape memory effect according to claim 4, is characterized in that: described crystal material is selected from polyethyleneglycol diacrylate, polyethylene glycol dimethacrylate or polycaprolactone diacrylate.
6. the polymkeric substance with bidirectional reversible shape memory effect according to claim 5, is characterized in that: described polyethyleneglycol diacrylate or the molecular weight ranges of polyethylene glycol dimethacrylate are 3000 ~ 12000; The molecular weight of described polycaprolactone diacrylate is 3000 ~ 14000.
7., according to the arbitrary described preparation method with the polymkeric substance of bidirectional reversible shape memory effect of claim 1-6, it is characterized in that, described polymkeric substance is prepared by the following method:
(1) a kind of material that high glass-transition temperature is provided is selected; Its glass transition temperature Tg >95 DEG C;
(2) select a kind of crystal material, its fusing point is at 45 ~ 65 DEG C;
(3) by above-mentioned two kinds of material crosslinking curings.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510016304.1A CN104592453B (en) | 2015-01-13 | 2015-01-13 | Polymer with bidirectional reversible shape memory effect and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510016304.1A CN104592453B (en) | 2015-01-13 | 2015-01-13 | Polymer with bidirectional reversible shape memory effect and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104592453A true CN104592453A (en) | 2015-05-06 |
| CN104592453B CN104592453B (en) | 2017-04-12 |
Family
ID=53118540
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510016304.1A Active CN104592453B (en) | 2015-01-13 | 2015-01-13 | Polymer with bidirectional reversible shape memory effect and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104592453B (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105199052A (en) * | 2015-09-16 | 2015-12-30 | 江苏锐康新材料科技有限公司 | Preparation method, product and application of thermosetting unsaturated polyester resin capable of being formed through hot working and recycled |
| WO2017143620A1 (en) * | 2016-02-24 | 2017-08-31 | 香港纺织及成衣研发中心有限公司 | Orthosis, and method for preparing shape memory high-polymer material used on orthosis |
| CN107118313A (en) * | 2017-05-12 | 2017-09-01 | 浙江工业大学之江学院 | One kind has triple SME polymer and preparation method thereof |
| CN110003395A (en) * | 2019-04-23 | 2019-07-12 | 深圳大学 | Shape-memory material and its preparation method and application |
| CN110372922A (en) * | 2019-07-22 | 2019-10-25 | 北京化工大学 | A kind of polymer material and its preparation and application with triple shape memory effect |
| CN110527036A (en) * | 2019-09-12 | 2019-12-03 | 临沂大学 | High molecular material and preparation method thereof with water-responsive bidirectional reversible shape memory function |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1771294A (en) * | 2003-04-10 | 2006-05-10 | 尼莫科学有限公司 | Blends with shape memory characteristics |
| US20140099848A1 (en) * | 2012-10-05 | 2014-04-10 | Syracuse University | Waterborne Shape Memory Polymer Coatings |
-
2015
- 2015-01-13 CN CN201510016304.1A patent/CN104592453B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1771294A (en) * | 2003-04-10 | 2006-05-10 | 尼莫科学有限公司 | Blends with shape memory characteristics |
| US20140099848A1 (en) * | 2012-10-05 | 2014-04-10 | Syracuse University | Waterborne Shape Memory Polymer Coatings |
Non-Patent Citations (3)
| Title |
|---|
| DEBDATTA RATNA等: "Shape memory polymer system of semi-interpenetrating network structure composed of crosslinked poly (methyl methacrylate) and poly (ethylene oxide)", 《POLYMER》 * |
| GUOQIN LIU等: "Shape Memory of Hydrogen-Bonded Polymer Network/Poly(ethylene glycol) Complexes", 《MACROMOLECULES》 * |
| KATSUHIRO INOMATA等: "Shape memory behavior of poly(methyl methacrylate)-graft-poly(ethyleneglycol) copolymers", 《POLYMER》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105199052A (en) * | 2015-09-16 | 2015-12-30 | 江苏锐康新材料科技有限公司 | Preparation method, product and application of thermosetting unsaturated polyester resin capable of being formed through hot working and recycled |
| WO2017143620A1 (en) * | 2016-02-24 | 2017-08-31 | 香港纺织及成衣研发中心有限公司 | Orthosis, and method for preparing shape memory high-polymer material used on orthosis |
| CN107118313A (en) * | 2017-05-12 | 2017-09-01 | 浙江工业大学之江学院 | One kind has triple SME polymer and preparation method thereof |
| CN110003395A (en) * | 2019-04-23 | 2019-07-12 | 深圳大学 | Shape-memory material and its preparation method and application |
| CN110372922A (en) * | 2019-07-22 | 2019-10-25 | 北京化工大学 | A kind of polymer material and its preparation and application with triple shape memory effect |
| CN110527036A (en) * | 2019-09-12 | 2019-12-03 | 临沂大学 | High molecular material and preparation method thereof with water-responsive bidirectional reversible shape memory function |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104592453B (en) | 2017-04-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104592453A (en) | Polymer with bidirectional reversible shape memory effect and preparation method thereof | |
| Li et al. | A versatile approach to achieve quintuple-shape memory effect by semi-interpenetrating polymer networks containing broadened glass transition and crystalline segments | |
| Choong et al. | 4D printing of high performance shape memory polymer using stereolithography | |
| Ni et al. | A self-healing photoinduced-deformable material fabricated by liquid crystalline elastomers using multivalent hydrogen bonds as cross-linkers | |
| Qin et al. | Combined one-way and two-way shape memory in a glass-forming nematic network | |
| Meng et al. | Shape actuation via internal stress-induced crystallization of dual-cure networks | |
| Clarke et al. | Effect of crosslinker geometry on equilibrium thermal and mechanical properties of nematic elastomers | |
| US20210331374A1 (en) | Extrusion printing of liquid crystal elastomers | |
| CN102574992B (en) | Liquid-crystal polymer and molded articles | |
| WO2002095456A3 (en) | Multilayer optical films comprising polymers having low glass transition temperatures (tg) | |
| Zhang et al. | A facile strategy to fabricate multishape memory polymers with controllable mechanical properties | |
| DE602005025290D1 (en) | POLYMER COMPOSITION WITH HEAT-STORING PHASE RECHARGEABLE MATERIAL AND PRODUCT BASED ON IT | |
| US20110049768A1 (en) | Liquid crystal elastomers with two-way shape ;memory effect | |
| CN107118313A (en) | One kind has triple SME polymer and preparation method thereof | |
| Gao et al. | Thermoplastic polyolefin elastomer blends for multiple and reversible shape memory polymers | |
| CN102863597B (en) | V-shaped gradient copolymer and preparation process thereof | |
| Hao et al. | Triple one‐way and two‐way shape memory poly (ethylene‐co‐vinyl acetate)/poly (ε‐caprolactone) immiscible blends | |
| CN102399366A (en) | Preparation method for liquid cyanate resin | |
| CN101798370A (en) | Reactive side chain type liquid crystal copolymer | |
| CN101413151A (en) | Crust type liquid crystal polymer shape memory high polymer material and preparation thereof | |
| CN103497329A (en) | Nylon copolymer and preparation method thereof | |
| Zhang et al. | Synthesis and analysis of two-way-reversible shape-memory polymers | |
| Hui et al. | Two‐Way Reversible Shape Memory Properties of Benzoyl Peroxide Crosslinked Poly (ethylene‐co‐vinyl acetate) under Different Stress Conditions | |
| Hirai et al. | Elastocaloric effect of shape memory polymers in elastic response regime | |
| KR20180071310A (en) | Stimuli-reactive adhesive |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |