CN1706997A - Shape memory fiber prepared with shape memory polyurethane and its prepn process - Google Patents
Shape memory fiber prepared with shape memory polyurethane and its prepn process Download PDFInfo
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- CN1706997A CN1706997A CN 200410049303 CN200410049303A CN1706997A CN 1706997 A CN1706997 A CN 1706997A CN 200410049303 CN200410049303 CN 200410049303 CN 200410049303 A CN200410049303 A CN 200410049303A CN 1706997 A CN1706997 A CN 1706997A
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Abstract
The present invention relates to one kind of shape memory fiber prepared with shape memory polyurethane and its preparation process. The shape memory polyurethane is prepared with material including one hydroxyl containing polymer, chain expander, diisocyanate and blocking agent in the molar ratio of 1 to 1-3 to 2.4-4.8 to 0.8-1.6. The preparation process of the shape memory fiber includes the following steps: preparing shape memory polyurethane with excessive isocyanate; adding blocking agent to obtain blocked shape memory polyurethane; and melt spinning to obtain shape memory fiber. The shape memory fiber of the present invention has very wide temperature regulating range, practical elasticity, strength and shape memory performance and comfortable hand feeling, is easy to spin alone or together with synthetic fiber and natural fiber, and may find wide application in clothing, biomedical material and other fields.
Description
Technical field
The present invention relates to a kind of shape memory fiber by shape memory polyurethane preparation and preparation method thereof, this shape memory fiber has good shape-memory properties, promptly this fiber can change shape being higher than under the shape memory transition temperature, and when this fiber is cooled to be lower than the shape memory transition temperature, finalize the design, this fiber can recover original-shape when being heated to above the shape memory transition temperature.
Background technology
Shape-memory polymer is meant to have original shape, after deformation is fixing, can change external condition by methods such as heating, makes it recover the macromolecular material of original shape.The method of utilizing of shape memory is thereby that the shape that will change is heated to above shape memory transition temperature recovery reset condition.That is to say that shape-memory polymer finalizes the design in certain model deformation in certain variations in temperature.Shape memory polyurethane has the big and thermal insulation of deformation amount of recovery, and these characteristics are widely applied in the extensive stock.Has foamed material that the polyurethane of shape memory makes be widely used (day flat 2-113016 of disclosure special permission communique, 1990, Mitsubishi Heavy Industry Ltd.).These foaming bodies can under certain shape need and under certain model by post forming.The shape-memory polymer of moulding changes shape being higher than under its shape memory transition temperature but being lower than under the rheology temperature, when polymer is cooled to be lower than the shape memory transition temperature with the state after changing, and the shape of change just fixing.
The open WO01/07499 of PCT international application, the preparation method that CN1361799A discloses shape memory polyurethane or polyurethane-urea polymers is disclosed with Chinese patent application, its glass transition temperature is 20～100 ℃ of scopes, flexible polyurethane section monomer adopts the polysiloxanes macromolecule dihydric alcohol, the monomer cost is higher, is mainly used in medical equipment.The shape-memory material that also has some patents and bibliographical information polyurethane-base in addition.In addition, international patent publication WO99/03863 and U.S. Patent No. 5393858 have disclosed the scope of Biostatic based polyurethane, and they are in field extensive application such as bio-medical material, encapsulant, thermal control materials.
Fibrous material (spandex) based on polyurethane is widely known by the people, and Lycra industrial products such as (Lycra) occurred, and this fibrid has very excellent elasticity and brute force, in field extensive application such as clothes, medical health care products.But up to the present, still have only one piece of patent to mention shape memory fiber (U.S. Patent No. 5128197), in this piece patent, the inventor has introduced via shape memory fiber or the shape memory fabrics that obtains with other fiber blend, the shape memory fiber of being invented is that glassy state temperature with fiber is as the shape memory transition temperature, usually its shape memory transition temperature is lower than 40 ℃, and does not relate to for the preparation method of concrete shape memory fiber.
Summary of the invention
One object of the present invention is to provide a kind of shape memory fiber, and this shape memory fiber is to be made by shape memory polyurethane.Shape memory polyurethane of the present invention can be got by following feedstock production: organic hydroxyl polymer-containing, chain extender, vulcabond, end-capping reagent, its mol ratio are 1: 1-3: 2.4-4.8: 0.8-1.6.
Another object of the present invention is to provide a kind of method for preparing above-mentioned shape memory fiber, said method comprising the steps of:
(1) the excessive shape memory polyurethane of preparation isocyanates;
(2) in the polyurethane that step (1) obtains, add end-capping reagent, obtain the shape memory polyurethane of end-blocking, prepare shape memory fiber through melt spinning.
The method for preparing shape memory fiber provided by the invention can adopt organic hydroxyl polymer-containing, chain extender, vulcabond, in molar ratio 1: 1-3: 2.4-4.8 mixes, the excessive shape memory polyurethane of preparation isocyanates, again with the end-capping reagent end-blocking, obtain the shape memory polyurethane of end-blocking, prepare the polyurethane shape memory fiber through melt spinning.In spinning process, end-blocking two isocyanic acid decomposes, the isocyanate group activation generates the shape memory polyurethane that contains part allophanate group, biuret crosslink body, prepares shape memory fiber.
Comprise polyester diol, polyether Glycols or its mixture in order to the organic hydroxyl polymer-containing in the raw material of preparation shape memory polyurethane, wherein polyester diol is preferably polycaprolactone glycol.Have the soft chain segment crystallization of better regularity and Geng Gao by polycaprolactone glycol as the polyurethane that organic hydroxyl polymer-containing reaction obtains, so also show better shape-memory properties.
End-capping reagent in the raw material comprises small molecular alcohol, phenol, oxime or Ester, is preferably diacetylmonoxime, phenmethylol, septichen or ethyl acetoacetate.
Vulcabond in the raw material comprises aliphatic isocyanates, aromatic isocyanate, alicyclic isocyanate or its mixture.
Chain extender in the raw material comprises 1,4-butanediol, 1, at least a in ammediol, ethylenediamine, hexamethylene diamine, ethylene glycol, bisphenol-A or the dihydromethyl propionic acid.
When the introducing dihydromethyl propionic acid is chain extender in the building-up process of shape memory polyurethane of the present invention, preferably adopt in the tertiary amine and the carrying out of dihydromethyl propionic acid and suitable catalysis entire reaction, because in dihydromethyl propionic acid and the tertiary amine and after, form strong chemical bond, improved the brute force and the elasticity of fiber.The tertiary amine that the present invention adopts is preferably triethylamine or triethanolamine.
Shape memory fiber provided by the invention is that the fusing point with the polymer soft chain segment is the shape memory transition temperature, has extremely wide temperature regulating range, and this fiber has good shape restore funcitons, i.e. shape memory function on the shape memory transition temperature.Promptly recover its original-shape and keep its elasticity simultaneously being higher than the various distortion that can recover to produce on the shape memory temperature.
The shape memory transition temperature of described shape memory fiber makes this fiber can change shape when being higher than the shape memory transition temperature, and when fiber is cooled to be lower than the shape memory transition temperature, making its typing, described then fiber can recover its original-shape when being heated to above the shape memory transition temperature.The shape memory transition temperature of shape memory fiber is in 10 ℃～80 ℃ scopes.
The characteristics that shape memory fiber provided by the invention has are as follows: this shape memory fiber comprises the rigid polyurethane segment of 30～50% weight, its shape memory transition temperature is between 10 ℃～80 ℃, and the fiber number of shape memory fiber is that 20～80dtex, fracture strength 1.0～1.5CN/dtex, elongation at break are 100～400%; Fiber typing rate is 90～100%.It is 90～100% that shape memory keeps recovery rate.
The method for preparing shape memory fiber provided by the invention is to adopt the melt spinning method that above-mentioned shape memory polyurethane is prepared into shape memory fiber, this melt spinning is compared with other spinning process, has advantages such as process route is short, equipment is simple, spin the speed height, cost is lower.For polymerization process, can adopt two kinds of methods of polymerisation in solution and melt polymerization to prepare the shape memory polyurethane of end-blocking, then in spinning process, the isocyano of end-blocking can deblocking, generation is crosslinked based on allophanate group, biuret, with heat resistance that improves fiber and the ordinary elasticity recoverability that improves fiber.
Shape memory fiber through the present invention's preparation shows the good practicability energy at aspects such as elasticity, brute force and shape-memory properties, and comfortable feel, spin separately easily or with other synthetic fiber, natural fibre blended, in field extensive application such as textile garment, bio-medical materials.
It is more stiffening when the fabric that shape memory fiber is made into just is lower than the shape memory transition temperature of fiber under normal room temperature.No matter fabric produces fold or distortion when placing or wearing for a long time, this fabric is heated in air or hot water more than the shape memory transition temperature, and fabric can be relatively easy to return to the reset condition that it remembers and eliminate the distortion of generation.
The specific embodiment
By the following examples shape memory fiber of the present invention and preparation method thereof is elaborated, these embodiment only are used for that the invention will be further described, and have no intention protection domain of the present invention is limited.Protection scope of the present invention should be as the criterion with the content that limits in the claim.Those skilled in the art can do various changes with enforcement the present invention to instantiation of the present invention or parameter etc., and needn't pay performing creative labour according to of the present invention open.Therefore, protection scope of the present invention should be understood to comprise the variation and the change of these routines.
Used test instrument of the present invention: carry out thermography with Pyris Diamond DSC differential scanning calorimeter and measure, sample size is about 5mg, and intensification and rate of temperature fall are 10 ℃/min.The shape-memory properties test is adopted and is had thermoregulator Instron4466 test.
Embodiment 1:
Polycaprolactone glycol (the PLACCEL240 that adds 800g, Daciel ChemicalIndustries, LTD.) (molecular weight 4000, dry), the methyl diphenylene diisocyanate of 1000 milliliters of dimethyl formamides (solvent) and 240g in 3000 milliliters, be with mechanical agitation, be connected in the four-hole glass flask of nitrogen port.Feed drying nitrogen, mechanical agitation remains under 80 ℃～90 ℃ temperature and reacted 4 hours.Add 1 of 13.5g dihydromethyl propionic acid and 45g then successively, the 4-butanediol continues reaction 2 hours as under the condition of chain extender between keeping 80 ℃～90 ℃.Can add a spot of dimethyl formamide in this course of reaction.Add the 34.5g phenmethylol then, continue reaction one hour, then reduce the temperature to 50 ℃ of reactant, the triethylamine that adds 11g continues reaction one hour with the carboxyl in the neutralization reactant.
The shape memory polyurethane that is obtained by embodiment 1 polymerization obtains the polyurethane pellet except that the back granulation of desolvating.This pellet adopts dry 24 hours (45 ℃ of baking temperatures, the vacuum 0.05MPa) of vacuum drying oven, removes moisture, with the spinning of screw rod extrusion method.Screw rod is respectively distinguished temperature: a district 160-170 ℃, two district 160-170 ℃, three district 165-175 ℃, spinneret assembly 170-180 ℃.Orifice diameter 0.4mm, winding speed 350M/min, undrawn yarn stretches 1.45 times down at 45 ℃, and anxiety was handled 1 hour under this temperature, obtained shape memory fiber thus.Shape memory fiber fiber number 50dtex/1F, fracture strength 1.5CN/dtex, extension at break 100% that this method obtains.Fiber shape memory performance test (the Instron4466 tester test of adopting reload temperature to regulate): fiber shape memory transition temperature is 62 ℃, the fiber that 30mm is long is stretched to 60mm, typing 10min at 77 ℃, be cooled to loose after 47 ℃ of coolings, to measure its length be 54.0mm, the typing rate is 90.0%.Be warming up to 77 ℃, this moment, fiber was retracted to 30mm rapidly, and recovery rate is 100%.
Embodiment 2:
Polycaprolactone glycol (the PLACCEL240 that adds 120g, Daciel ChemicalIndustries, LTD.) (molecular weight 4000, dry), 12g gathers ethanol (molecular weight 200, dry), the toluene di-isocyanate(TDI) of 300 milliliters of dimethyl formamides and 38g in 500 milliliters, band mechanical agitation, be connected in the four-hole glass flask of nitrogen port.Feed drying nitrogen, mechanical agitation remains under 80 ℃～90 ℃ temperature and reacted 5 hours.Add 1 of 8.1g then, the 4-butanediol continues reaction 2 hours as under the condition of chain extender between keeping 80 ℃～90 ℃.Can add a spot of dimethyl formamide in this course of reaction.Add the 6.3g diacetylmonoxime then, continue reaction one hour.The shape memory polyurethane that is obtained by example 2 polymerizations obtains the polyurethane pellet except that the back granulation of desolvating.
This pellet adopts dry 22 hours (48 ℃ of baking temperatures, the vacuum 0.05MPa) of vacuum drying oven, removes moisture, with the spinning of screw rod extrusion method.Screw rod is respectively distinguished temperature: a district 165-175 ℃, two district 165-175 ℃, three district 170-185 ℃, spinneret assembly 170-185 ℃.Orifice diameter 0.3mm, winding speed 300M/min, undrawn yarn stretches 1.5 times down at 48 ℃, and anxiety was handled 1 hour under this temperature, obtained shape memory fiber thus.Shape fibre number 25dtex/F, fracture strength 1.22CN/dtex, extension at break 176% that this method obtains.The fiber shape Memorability: fiber shape memory transition temperature is 50 ℃, and the fiber that 30mm is long is stretched to 60mm, typing 10min at 65 ℃, be cooled to loose after 35 ℃ of coolings, to measure its length be 59.5mm, the typing rate is 99.2%.Again this fiber is warming up to 65 ℃, this moment, fiber was retracted to 30.5mm rapidly, and recovery rate is 98%.
Embodiment 3:
Polycaprolactone glycol (the PLACCEL240 that adds 300g, Daciel ChemicalIndustries, LTD.) (molecular weight 3000, dry), 40g gathers propyl alcohol (molecular weight 200, oneself is dry), 27g 1, the two isocyanic acid isophorones of 4-butanediol and 300g in 1000 milliliters, band mechanical agitation, be connected in the reactor of nitrogen port.In 130 ℃ of reactions 1 hour, add the unreacted isocyanates of 100g phenmethylol end-blocking then, continue to react half an hour at 130 ℃, obtain the shape memory polyurethane of the end-blocking of melt polymerization, use the spinning of screw rod extrusion method then.Screw rod is respectively distinguished temperature: a district 175-180 ℃, two district 175-185 ℃, three district 180-195 ℃, spinneret assembly 180-195 ℃.Orifice diameter 0.3mm, winding speed 300M/min, undrawn yarn stretches 1.6 times down at 48 ℃, and anxiety was handled 1 hour under this temperature, obtained shape memory fiber thus.Shape fibre number 75dtex, fracture strength 1.45CN/dtex, extension at break 400% that this method obtains.The fiber shape Memorability: fiber shape memory transition temperature is 30 ℃, and the fiber that 30mm is long is stretched to 60mm, typing 10min at 45 ℃, be cooled to loose after 15 ℃ of coolings, to measure its length be 57.0mm, the typing rate is 90.0%.Again this fiber is warming up to 55 ℃, this moment, fiber was retracted to 30.3mm rapidly, and recovery rate is 99%.
Embodiment 4:
Polycaprolactone glycol (the PLACCEL240 that adds 600g, Daciel ChemicalIndustries, LTD.) (molecular weight 2000, oneself is dry), 300g polytetrahydrofuran diol (molecular weight 1000, dry), 139g 1, the hexamethylene diisocyanate of 6-hexamethylene diamine and 308g in 2000 milliliters, the band mechanical agitation, be connected in the reactor of nitrogen port.In 140 ℃ of reactions 2 hours, add 110g then and face the unreacted isocyanates of hydroxybenzoic acid end-blocking, continue to react half an hour at 140 ℃, obtain the shape memory polyurethane of the end-blocking of melt polymerization, use the spinning of screw rod extrusion method then.Screw rod is respectively distinguished temperature: a district 175-180 ℃, two district 175-185 ℃, three district 180-195 ℃, spinneret assembly 180-195 ℃.Orifice diameter 0.3mm, winding speed 300M/min, undrawn yarn stretches 1.55 times down at 48 ℃, and anxiety was handled 1 hour under this temperature, obtained shape memory fiber thus.Shape fibre number 70dtex, fracture strength 1.48CN/dtex, extension at break 400% that this method obtains.The fiber shape Memorability: fiber shape memory transition temperature is 18 ℃, and the fiber that 30mm is long is stretched to 60mm, typing 10min at 33 ℃, be cooled to loose after 3 ℃ of coolings, to measure its length be 59.5mm, the typing rate is 99.1%.Again this fiber is warming up to 33 ℃, this moment, fiber was retracted to 30.0mm rapidly, and recovery rate is 100%.
Embodiment 5:
Polycaprolactone glycol (the PLACCEL240 that adds 300g, Daciel ChemicalIndustries, LTD.) (molecular weight 3000, dry), 80g gathers propyl alcohol (molecular weight 400, oneself is dry), 18g 1, the two isocyanic acid isophorones of 2-ethylenediamine and 178g in 2000 milliliters, band mechanical agitation, be connected in the reactor of nitrogen port.In 130 ℃ of reactions 1 hour, add the unreacted isocyanates of 43g phenmethylol end-blocking then, continue to react half an hour at 130 ℃, obtain the shape memory polyurethane of the end-blocking of melt polymerization, use the spinning of screw rod extrusion method then.Screw rod is respectively distinguished temperature: a district 175-180 ℃, two district 175-185 ℃, three district 180-195 ℃, spinneret assembly 180-195 ℃.Orifice diameter 0.3mm, winding speed 300M/min, undrawn yarn stretches 1.6 times down at 48 ℃, and anxiety was handled 1 hour under this temperature, obtained shape memory fiber thus.Shape fibre number 60dtex, fracture strength 1.42CN/dtex, extension at break 360% that this method obtains.The fiber shape Memorability: fiber shape memory transition temperature is 10 ℃, and the fiber that 30mm is long is stretched to 60mm, typing 10min at 25 ℃, be cooled to loose after-5 ℃ of coolings, to measure its length be 60.0mm, the typing rate is 100.0%.Again this fiber is warming up to 25 ℃, this moment, fiber was retracted to 30.3mm rapidly, and recovery rate is 99%.
Embodiment 6:
Polycaprolactone glycol (the PLACCEL240 that adds 800g, Daciel ChemicalIndustries, LTD.) (molecular weight 2000, dry), 200g polytetrahydrofuran diol (molecular weight 1000, dry), 66g 1, the 2,4 toluene diisocyanate of 4-hydroquinones and 261g in 2000 milliliters, the band mechanical agitation, be connected in the reactor of nitrogen port.In 140 ℃ of reactions 2 hours, add the unreacted isocyanates of 65g phenmethylol end-blocking then, continue to react half an hour at 140 ℃, obtain the shape memory polyurethane of the end-blocking of melt polymerization, use the spinning of screw rod extrusion method then.Screw rod is respectively distinguished temperature: a district 175-180 ℃, two district 175-185 ℃, three district 180-195 ℃, spinneret assembly 180-195 ℃.Orifice diameter 0.3mm, winding speed 300M/min, undrawn yarn stretches 1.55 times down at 48 ℃, and anxiety was handled 1 hour under this temperature, obtained shape memory fiber thus.Shape fibre number 50dtex, fracture strength 1.28CN/dtex, extension at break 300% that this method obtains.The fiber shape Memorability: fiber shape memory transition temperature is 40 ℃, and the fiber that 30mm is long is stretched to 60mm, typing 10min at 55 ℃, be cooled to loose after 25 ℃ of coolings, to measure its length be 58.5mm, the typing rate is 95.0%.Again this fiber is warming up to 55 ℃, this moment, fiber was retracted to 30.3mm rapidly, and recovery rate is 99%.
Embodiment 7:
Polycaprolactone glycol (the PLACCEL240 that adds 120g, Daciel ChemicalIndustries, LTD.) (molecular weight 4000, dry), 30g gathers ethanol (molecular weight 3000, dry), the toluene di-isocyanate(TDI) of 200 milliliters of dimethyl formamides and 25g in 500 milliliters, band mechanical agitation, be connected in the four-hole glass flask of nitrogen port.Feed drying nitrogen, mechanical agitation remains under 80 ℃～90 ℃ temperature and reacted 5 hours.The bisphenol-A (molecular weight 228) that adds 5.4g dihydromethyl propionic acid and 9.2g then successively continues reaction 2 hours as under the condition of chain extender between keeping 80 ℃～90 ℃.Can add a spot of dimethyl formamide in this course of reaction.Add the 6.2g ethyl acetoacetate then, continue reaction one hour.Then reduce the temperature to 50 ℃ of reactant, the triethanolamine that adds 6g continues reaction one hour with the carboxyl in the neutralization reactant.The shape memory polyurethane that is obtained by example 7 polymerizations obtains the polyurethane pellet except that the back granulation of desolvating.
This pellet adopts dry 22 hours (50 ℃ of baking temperatures, the vacuum 0.05MPa) of vacuum drying oven, removes moisture, with the spinning of screw rod extrusion method.Screw rod is respectively distinguished temperature: a district 170-175 ℃, two district 170-175 ℃, three district 175-185 ℃, spinneret assembly 175-190 ℃.Orifice diameter 0.3mm, winding speed 300M/min, undrawn yarn stretches 1.5 times down at 50 ℃, and anxiety was handled 1 hour under this temperature, obtained shape memory fiber thus.Shape fibre number 75dtex/F, fracture strength 1.48CN/dtex, extension at break 136% that this method obtains.The fiber shape Memorability: fiber shape memory transition temperature is 80 ℃, and the fiber that 30mm is long is stretched to 60mm, typing 10min at 95 ℃, be cooled to loose after 65 ℃ of coolings, to measure its length be 59.7mm, the typing rate is 99.5%.Again this fiber is warming up to 95 ℃, this moment, fiber was retracted to 30.5mm rapidly, and recovery rate is 98%.
Claims (15)
1. shape memory fiber by shape memory polyurethane preparation is characterized in that described shape memory polyurethane is to be got by following feedstock production:
Organic hydroxyl polymer-containing, chain extender, vulcabond, end-capping reagent, its mol ratio are 1: 1-3: 2.4-4.8: 0.8-1.6.
2. shape memory fiber according to claim 1 is characterized in that, organic hydroxyl polymer-containing comprises polyester diol, polyether Glycols or its mixture.
3. shape memory fiber according to claim 2 is characterized in that, polyester diol is the polycaprolactone dihydroxylic alcohols.
4. shape memory fiber according to claim 1 is characterized in that, described end-capping reagent is small molecular alcohol, phenol, oxime or Ester.
5. shape memory fiber according to claim 4 is characterized in that, described end-capping reagent is phenmethylol, septichen, diacetylmonoxime or ethyl acetoacetate.
6. shape memory fiber according to claim 1 is characterized in that, vulcabond comprises aliphatic isocyanates, aromatic isocyanate, alicyclic isocyanate or its mixture.
7. shape memory fiber according to claim 1 is characterized in that described chain extender comprises 1,4-butanediol, 1, at least a in ammediol, ethylenediamine, hexamethylene diamine, ethylene glycol, bisphenol-A or the dihydromethyl propionic acid.
8. shape memory fiber according to claim 7 is characterized in that, when chain extender is dihydromethyl propionic acid, also need comprise tertiary amine in the raw material.
9. shape memory fiber according to claim 8 is characterized in that described tertiary amine comprises triethylamine or triethanolamine.
10. shape memory fiber according to claim 1 is characterized in that, wherein this fiber comprises the rigid polyurethane segment of 30～50% weight.
11. shape memory fiber according to claim 1 is characterized in that, the shape memory transition temperature of described shape memory fiber is at 10 ℃～80 ℃.
12. shape memory fiber according to claim 1 is characterized in that, the fiber number of described shape memory fiber is that 20～80dtex, fracture strength 1.0～1.5CN/dtex, elongation at break are 100～400%.
13. shape memory fiber according to claim 1 is characterized in that, the fiber typing rate of this shape memory fiber is 90～100%, and it is 90～100% that shape memory keeps recovery rate.
14. a method for preparing any shape memory fiber of claim 1-13 is characterized in that, said method comprising the steps of:
(1) the excessive shape memory polyurethane of preparation isocyanates;
(2) in the polyurethane that step (1) obtains, add end-capping reagent, obtain the shape memory polyurethane of end-blocking, prepare shape memory fiber through melt spinning.
15. method according to claim 14 is characterized in that, preparation shape memory polyurethane method comprises solution polymerization process and melt phase polycondensation.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101775177A (en) * | 2010-02-11 | 2010-07-14 | 哈尔滨工业大学 | Polyurethane fiber-reinforced shape memory polymer composite material |
| CN101100500B (en) * | 2006-07-07 | 2011-06-08 | 西安工程大学 | Polyurethane shape memory macromolecule material and synthetic technique thereof |
| CN102845841A (en) * | 2010-06-30 | 2013-01-02 | 香港理工大学 | Items of clothing having shape memory |
| CN103160948A (en) * | 2013-04-07 | 2013-06-19 | 苏州聚复高分子材料有限公司 | Rapid prototyping shape memory high polymer material and preparation method and application thereof |
| CN104695041A (en) * | 2013-12-09 | 2015-06-10 | 香港纺织及成衣研发中心有限公司 | Shape memory fiber, manufacturing method thereof and textile product manufactured by shape memory fiber |
| CN106750127A (en) * | 2016-12-27 | 2017-05-31 | 宁波高新区敦和科技有限公司 | A kind of method by chain catalytic reaction preparation temperature shape memory high molecule material |
| CN109652993A (en) * | 2017-10-11 | 2019-04-19 | 台北科技大学 | Shape memory polyurethane composition and the laminate for using it |
| 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 |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1279077C (en) * | 2004-03-19 | 2006-10-11 | 中国科学院长春应用化学研究所 | Shape memory material based on poly(e-caprolactone), preparation and metod of application |
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- 2004-06-09 CN CNB2004100493039A patent/CN1324174C/en not_active Expired - Fee Related
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101100500B (en) * | 2006-07-07 | 2011-06-08 | 西安工程大学 | Polyurethane shape memory macromolecule material and synthetic technique thereof |
| CN101775177A (en) * | 2010-02-11 | 2010-07-14 | 哈尔滨工业大学 | Polyurethane fiber-reinforced shape memory polymer composite material |
| CN102845841A (en) * | 2010-06-30 | 2013-01-02 | 香港理工大学 | Items of clothing having shape memory |
| CN103160948A (en) * | 2013-04-07 | 2013-06-19 | 苏州聚复高分子材料有限公司 | Rapid prototyping shape memory high polymer material and preparation method and application thereof |
| CN103160948B (en) * | 2013-04-07 | 2015-11-25 | 苏州聚复高分子材料有限公司 | Rapid shaping shape memory high molecule material and its preparation method and application |
| CN104695041A (en) * | 2013-12-09 | 2015-06-10 | 香港纺织及成衣研发中心有限公司 | Shape memory fiber, manufacturing method thereof and textile product manufactured by shape memory fiber |
| WO2015085762A1 (en) * | 2013-12-09 | 2015-06-18 | 香港纺织及成衣研发中心有限公司 | Shape memory fiber, method for manufacture thereof and textile made therefrom |
| CN106750127A (en) * | 2016-12-27 | 2017-05-31 | 宁波高新区敦和科技有限公司 | A kind of method by chain catalytic reaction preparation temperature shape memory high molecule material |
| CN109652993A (en) * | 2017-10-11 | 2019-04-19 | 台北科技大学 | Shape memory polyurethane composition and the laminate for using it |
| 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 |
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| CN1324174C (en) | 2007-07-04 |
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