CN1283855C - Shape memory fiber and its prepn process - Google Patents
Shape memory fiber and its prepn process Download PDFInfo
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- CN1283855C CN1283855C CN 200410049347 CN200410049347A CN1283855C CN 1283855 C CN1283855 C CN 1283855C CN 200410049347 CN200410049347 CN 200410049347 CN 200410049347 A CN200410049347 A CN 200410049347A CN 1283855 C CN1283855 C CN 1283855C
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- shape memory
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- 238000002360 preparation method Methods 0.000 claims abstract description 23
- 230000002441 reversible effect Effects 0.000 claims abstract description 9
- 238000002166 wet spinning Methods 0.000 claims abstract description 9
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- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 36
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- 238000011084 recovery Methods 0.000 claims description 26
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- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 6
- WFKAJVHLWXSISD-UHFFFAOYSA-N isobutyramide Chemical compound CC(C)C(N)=O WFKAJVHLWXSISD-UHFFFAOYSA-N 0.000 claims description 6
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- 229920001451 polypropylene glycol Polymers 0.000 claims description 6
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- NIHJEJFQQFQLTK-UHFFFAOYSA-N butanedioic acid;hexanedioic acid Chemical compound OC(=O)CCC(O)=O.OC(=O)CCCCC(O)=O NIHJEJFQQFQLTK-UHFFFAOYSA-N 0.000 claims description 5
- 229920000909 polytetrahydrofuran Polymers 0.000 claims description 5
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 5
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 4
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 4
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 4
- 235000019260 propionic acid Nutrition 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims description 4
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims description 3
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 3
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 3
- 239000004359 castor oil Substances 0.000 claims description 3
- 235000019438 castor oil Nutrition 0.000 claims description 3
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 claims description 3
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 claims description 3
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 3
- 235000002906 tartaric acid Nutrition 0.000 claims description 3
- 239000011975 tartaric acid Substances 0.000 claims description 3
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims description 3
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 claims description 2
- UXFQFBNBSPQBJW-UHFFFAOYSA-N 2-amino-2-methylpropane-1,3-diol Chemical compound OCC(N)(C)CO UXFQFBNBSPQBJW-UHFFFAOYSA-N 0.000 claims description 2
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 2
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 claims description 2
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 2
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- 229920002334 Spandex Polymers 0.000 description 3
- 238000003475 lamination Methods 0.000 description 3
- 229920006306 polyurethane fiber Polymers 0.000 description 3
- 239000004759 spandex Substances 0.000 description 3
- BJZYYSAMLOBSDY-QMMMGPOBSA-N (2s)-2-butoxybutan-1-ol Chemical compound CCCCO[C@@H](CC)CO BJZYYSAMLOBSDY-QMMMGPOBSA-N 0.000 description 2
- 230000003187 abdominal effect Effects 0.000 description 2
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- 230000005489 elastic deformation Effects 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
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- 150000004672 propanoic acids Chemical class 0.000 description 2
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- 239000012209 synthetic fiber Substances 0.000 description 2
- 239000004753 textile Substances 0.000 description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N toluene Substances CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 2
- 230000037303 wrinkles Effects 0.000 description 2
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
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- 238000002474 experimental method Methods 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N ferric oxide Chemical compound O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- KHYBPSFKEHXSLX-UHFFFAOYSA-N iminotitanium Chemical compound [Ti]=N KHYBPSFKEHXSLX-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 239000004922 lacquer Substances 0.000 description 1
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- Polyurethanes Or Polyureas (AREA)
- Artificial Filaments (AREA)
Abstract
The present invention relates to a shape memorizing fiber and a preparation method thereof. The shape memorizing fiber is prepared from shape memorizing polyurethane, wherein the polyurethane is prepared from component (A) and component (B); the component (A) forms a reversible phase, and the component (B) forms a fixed phase. The preparation method for the shape memorizing fiber comprises: procedure (1): component (A) and component (B) are used for preparing polyurethane; procedure (2): polyurethane prepared in procedure (1) is prepared into a shape memorizing fiber by adopting a wet spinning preparation method. The shape memorizing fiber provided by the present invention has the following characteristics: the fiber number is higher than 300 tax; the breaking strength is from 1 to 1.5 CN/tax; the breaking elongation is from 100% to 400%; the deformation fixing rate is>=90%; the deformation reversion temperature range of a reversible phase is-10 DEG C <=T<s><=60 DEG C; the phase transition temperature of a fixed phase is higher than 100 DEG C; the deformation reversion rate also reaches higher than 90%.
Description
Technical field
The present invention relates to a kind of shape memory fiber and preparation method thereof, relate in particular to by the prepared shape memory fiber of shape memory polyurethane and this fiber preparation method.
Background technology
Shape-memory material is in the starting conceptual phase at present, has delivered a small amount of basic research and survey article both at home and abroad, proposes the various uses in fields such as weaving, biomedical material, packaging material, industrial encapsulants.The field of textiles main application comprise (1) as the functional coat of fabric and functional treatment to obtain waterproof, airy fabric, as sportswear, military fighting uniform, anorak, tent etc.(2) utilize the shape memory function of polyurethane, adjust suitable memory triggering temperature and be used for PADDING CLOTH (cuff, neckline etc.), make it have good performance such as crease-resistant and wear-resisting, when its fine wrinkle that in use produces can return to the original form it by elevated temperature.(3) utilize the shape memory function of polyurethane, can make orthopedic, conformal articles for use such as coating bandage, brassiere, abdominal belt etc.
But owing to also there is not the shape memory fiber weaving to process the fabric with shape memory function at present, its application mainly is by lamination polyurethane film on fabric/non-woven fabric or covers with paint, lacquer, colour wash, etc. polyurethane coating and give fabric with shape memory characteristics.The method that is prepared shape memory fabrics by shape memory resin, shape memory adhesive and nonwoven fabric by lamination is disclosed as Japan Patent (publication number 252353/1986).United States Patent (USP) (US5,5098,776/1992; US5,128,197/1992)) a kind of preparation method of shape memory fabrics is also disclosed, this fabric is made up of the polymer powder that natural fabric/synthetic fiber and one deck have shape memory, bonding between the two by bonding agent, polymer powder and adhesive also can be earlier with suitable dissolution with solvents, be depressed between the fiber of fabric by Kun then or the surface forms the thin and level and smooth film of one deck, this fabric has suitable shape memory and triggers temperature, be used for PADDING CLOTH (cuff, neckline etc.), band has good performance such as crease-resistant and wear-resisting, and in use the fine wrinkle of Chan Shenging can return to the original form it by elevated temperature.Reporting its shape memory polyurethane coated fabric " Azekura " according to another Mitsubishi heavy industry company not only can waterproof and breathable, and its moisture vapor permeability can be controlled by body temperature, reach effect [the Moisturepermeation controllable fabric by temperature.JTN.International of regulate body temperature, 1992,455:44].
Situation from present research, the way that shape memory fabrics is only put in order by the back, its complex process, also be difficult to solve bad [the Sundaram Krishnan of shape memory fabrics bonding interface, Stoneham Mass.Water-proof breathable fabric laminates andmethods for producing same.USA Pat.5,283,112.Feb.1,1994], accurate inadequately [the Wu Jiamin of shape memory temperature, Jiang Zhiguo, Wang Dechun etc. shape memory polyurethane, New Chemical Materials .2002,30 (11): 31 ~ 34], deformation restoring force weak [Abrahamson, Erik R; Lake, Mark S.Shape memory mechanics of an elastic memorycomposition resin.J.Intellgent material systems and structure.Vol 14 (10), Oct.2003: 623 ~ 632] etc. defective.The best method that addresses these problems is that fiber itself has shape memory characteristic.
Also find from the documents and materials of finding at present, the shape memory polyurethane of research is more as the research of sheet material and finishing agent, and this material is most promising, most important applications is mainly in fields such as biomedical, weaving dress ornament, toy, packing, defence and militaries.As necktie, abdominal belt, dress ornament lining, brassiere etc., dentistry orthopedic instrument, Osteological device, bandage, sportswear, military fighting uniform, anorak, tent, artificial hair etc., these materials mostly use with the form of fiber or fabric.And at present except that the Ni-Ti alloy fiber has research report, other shape memory fiber comprises that the shape memory polyurethane fiber there is no the research report is arranged both at home and abroad.Because traditional spandex does not have shape memory characteristic, and present shape memory polyurethane does not have good spinnability.In order to overcome the shortcoming of prior art, the inventor is at the shape memory polyurethane that has carried out having developed on deep research and a large amount of experimental basis a kind of block structure, and prepared shape memory fiber by the wet spinning technology that this area is known altogether.The acquisition of this this shape memory fiber fundamentally overcomes the complex process of bringing because of back arrangement ways such as laminations, and bonding interface is bad, and shape memory temperature is defective such as accurately and a little less than the deformation restoring force inadequately.
Summary of the invention
One object of the present invention is to provide a kind of shape memory fiber, this shape memory fiber is prepared by shape memory polyurethane, but described polyurethane can by the component that forms anti-phase (A) with form fixing component (B) mutually and be prepared into, component (A) and (B) be wherein:
(A)：
Catalyst 0.01-0.20 weight portion
Polyethers or polyester diol 30-100 weight portion
Aromatic series or aliphatic diisocyanate 5-30 weight portion
Solvent 0-500 weight portion
(B)：
Aromatic diisocyanate 5-100 weight portion
Crosslinking agent trihydroxy polyalcohol 0.10-2.00 weight portion
The dihydroxylic alcohols 2-30 of chain extender short-chain fat family weight portion
The carboxylic short-chain fat dihydroxylic alcohols 0-10 of family weight portion
Solvent 0-200 weight portion
Another object of the present invention is to provide a kind of preparation method of above-mentioned shape memory fiber, it comprises the following steps:
(1) by said components (A) and component (B) preparation shape memory polyurethane;
(2) polyurethane that obtains in the step (1) is prepared shape memory fiber by wet spinning process.
Above-mentioned preparation method is specially:
(1) by component (A) and component (B) preparation shape memory polyurethane:
(1) a, the reversible phase component that comprises 0.01-0.20 weight portion catalyst, 30-100 weight portion polyethers or polyester diol, 5-30 weight portion aromatic series or aliphatic diisocyanate, 0-500 parts by weight solvent is reacted in reactor, obtain containing the polyurethane prepolymer of reversible phase structure;
(1) b, add and comprise 5-70 weight portion aromatic diisocyanate, 2-30 weight portion chain extender short-chain fat family dihydroxylic alcohols, the carboxylic short-chain fat of 0-10 weight portion family's dihydroxylic alcohols and 0.10-2.00 weight portion crosslinking agent trihydroxy polyalcohol, continue reaction, add the 0-200 parts by weight solvent and adjust viscosity and concentration, but obtain to comprise anti-phase and fixing polyurethane mutually with shape memory characteristic.
(2) polyurethane that obtains in the step (1) is prepared shape memory fiber by wet spinning process.
Shape memory polyurethane by method for preparing be a kind of by fixing phase (also claiming hard section phase) but and the block polyurethane formed of anti-phase (also claiming soft section mutually), wherein fixing has good heat endurance mutually, but anti-phase has-10 ℃～60 ℃ deformation recovery temperature (T
s), fixing has the glass transition temperature (T that is higher than 100 ℃ mutually
Gh) or crystalline melt temperature (T
Mh), when environment temperature is higher than T
sThe time, but anti-phase produces high elastic deformation under external force, and, still be in glassy state or crystalline state at this moment because fixedly the phase transition temperature of phase is higher, play a part support, required elastic restoring force is provided in the deformation recovery process.When environment temperature is reduced to T again
sWhen following, but compare at this moment the fixedly elastic restoring force height of phase owing to be in the brute force of the anti-phase of glassy state, deformation still " is freezed " after the external force unloading and is fixed up; When environment temperature rises to T
sWhen above, the reversible flexible state that is in mutually resists fixedly that the factor of phase elastic restoring force is eliminated, and polymer is returned to original state owing to the fixing elastic recovery of phase.Therefore the polyurethane of this block structure reaches and has good shape memory characteristic by its fiber that makes.
Shape memory fiber of the present invention, except that the good characteristic that possesses general fiber such as elasticity, intensity, extensibility and mechanical property, also has good shape memory characteristic, both can singly knit also can be with other natural or synthetic fiber mix and knit the multiple textiles of preparation with shape memory function, have broad application prospects in fields such as biomedical, novel weaving dress ornament, toy, packing, defence and militaries, present significant social and economic benefit.
But the ratio between the anti-phase of the employed polyurethane of shape memory fiber provided by the invention and the fixing phase can change in the scope of broad, does not have specific restriction.But in order to realize purpose of the present invention better, be benchmark in the solids content, preferably fixedly the quality percentage composition of phase is 20%-80%, but the quality percentage composition of anti-phase is 80%-20%; More preferably fixedly the quality percentage composition of phase is 20%-50%, but the quality percentage composition of anti-phase is 80%-50%.In another preferred embodiment of the present invention, in the block shape memory polyurethane-NCO is 1.0～1.5 with the mole number ratio of-OH.
Preferably, the used water base block shape memory polyurethane of the present invention is colourless to faint yellow viscous liquid, and its mass percent concentration is 15%-25%, and has tangible two phase structure, preferably deformation recovery temperature (T wherein
s) between-10～60 ℃, the fixing glass transition temperature (T of phase
Gh) be higher than 100 ℃.The deformation fixed rate of film and deformation-recovery rate are all more than 90%.
Used catalyst can be to promote the isocyanate group of reversible phase component and any material of the reaction between the alcoholic extract hydroxyl group in reversible being combined to of shape memory polyurethane of the present invention, preferred organotin, organic germanium, organic zinc compound or polynary tertiary amine, preferred especially dibutyl tin laurate, stannous octoate or triethylenediamine or its combination.
Polyethers or polyester diol are preferably the crystalline melt point temperature range at 10-60 ℃ glycol, as polyethylene glycol adipate glycol (PHEP), poly adipate succinic acid ester glycol (PHB), polycaprolactone glycol (PCL), at least a in polyethylene glycol (PEG) and/or the polytetrahydrofuran diol (PTMG), preferred especially number average relative molecular mass are 1000～4000 polyethylene glycol adipate glycol (PHEP), the number average relative molecular mass is 1000～6000 poly adipate succinic acid ester glycol (PHB), the number average relative molecular mass is 1250～8000 polycaprolactone glycol (PCL), the number average relative molecular mass is 200～6000 polyethylene glycol (PEG), the number average relative molecular mass is 200～4000 polytetrahydrofuran diol (PTMG), or its combination.
Aromatic series or aliphatic diisocyanate are preferably 2,4 toluene diisocyanate (TDI), 4, at least a in 4 '-'-diphenylmethane diisocyanate (MDI), hexamethylene diisocyanate (HDI) or the isophorone diisocyanate (IPDI).
Crosslinking agent trihydroxy polyalcohol is preferably at least a in glycerol, castor oil, trimethylolpropane or the polypropylene glycol (PPG-303, PPG-330, its number average relative molecular mass is respectively 300 and 3000).
Chain extender is preferably short-chain fat family dihydroxylic alcohols, for example 1,4-butanediol, 1,5-pentanediol, 1,6-hexylene glycol, 1,2-ethylene glycol, 1, at least a in ammediol or the diglycol, more preferably 1,4-butanediol, 1,6-hexylene glycol, ethylene glycol or diglycol or its combination.
Carboxylic short-chain fat family dihydroxylic alcohols is preferably at least a in dihydromethyl propionic acid, dimethylolpropionic acid or the tartaric acid.
Organic solvent is preferably at least a in dimethyl formamide, dimethylacetylamide, dimethyl sulfoxide (DMSO), acetone or the MEK.
The preparation method of block shape memory fiber of the present invention comprises that step (1) preparation shape memory polyurethane and step (2) prepare shape memory fiber by wet spinning, when wherein preparing polyurethane, but be generally earlier synthetic anti-phase, synthetic more fixedly phase, step (1) can by said components (A) and (B) preparation polyurethane, it comprises following two steps:
(1) a, make and comprise that 0～500 parts by weight solvent, 0.01～0.20 weight portion catalyst, 30～100 weight portion polyethers or polyester diol, 5～30 weight portion aromatic series or aliphatic diisocyanate react, and obtain containing the polyurethane prepolymer of reversible phase structure in reactor;
(1) b, add the fixing component mutually that comprises 5-70 weight portion aromatic diisocyanate, 2-30 weight portion chain extender short-chain fat family dihydroxylic alcohols, the carboxylic short-chain fat of 0-10 weight portion family dihydroxylic alcohols and 0.10-2.00 weight portion crosslinking agent trihydroxy polyalcohol, continue reaction, but acquisition comprises anti-phase and the fixing polyurethane with block structure mutually, adds the mass percent concentration of the solvent adjustment of 0-200 weight portion to 15-25%.
Preferably, the reaction of step (1) a under agitation, have in the reactor of reflux condenser, under temperature 40-100 ℃, carry out under preferred 60-85 ℃.Reaction time is depended on reaction temperature and concrete reaction process, is generally 30 minutes to 6 hours, most preferably is 2-3 hour
Preferably, under being temperature in room temperature to 85 ℃, the continuation of step (1) b reaction carries out.More preferably, continuing reaction is what to carry out under 50-70 ℃ temperature.A kind of preferred embodiment in, wherein in step (1) b, fixedly the phase component is that gradation adds, and identical or different in the identical or different following reaction time of temperature.More preferably, in step (1) b, add 5-70 weight portion aromatic diisocyanate, 5-30 weight portion chain extender short-chain fat family's dihydroxylic alcohols and the carboxylic short-chain fat of 0-10 weight portion family dihydroxylic alcohols, 0.10-2.00 weight portion crosslinking agent trihydroxy polyalcohol down at 50-60 ℃, temperature control 55-70 ℃ then, reacted 3-4 hour.
Preferably, the solvent in the step (1) is a polar organic solvent, as dimethyl formamide, dimethylacetylamide, dimethyl sulfoxide (DMSO), acetone or MEK etc.
Shape memory fiber of the present invention has following characteristics: fiber number is higher than 300dtex, fracture strength 1～1.5CN/dtex, extension at break 100%～400%, its deformation fixed rate 〉=90%, deformation-recovery rate 〉=90%.
Compare with the polyurethane fiber or the shape memory fabrics of prior art, block structure polyurethane shape memory fiber of the present invention all has outstanding feature on structure and performance:
(1) design feature:
Introduced tangible two phase structure (block structure), but wherein the deformation recovery temperature range of anti-phase is-10 ℃≤T
s≤ 60 ℃, fixedly the phase transition temperature of phase is higher than 100 ℃.
(2) performance characteristics:
The polyurethane of block structure and fiber thereof also have the intelligent characteristic of shape memory except that the general characteristic that possesses fiber.
When environment temperature is higher than Ts, but anti-phase produces high elastic deformation under external force, reduces to Ts again when following when environment temperature, and deformation is in external force unloading back " being freezed " and be fixed up, and its deformation fixed rate is greater than 90%; When environment temperature rises to Ts when above again, polymer is returned to original state again; Its deformation-recovery rate also reaches and reaches more than 90%.
Innovation part of the present invention is: 1) invented first and utilized shape-memory polymer to make the method for fiber; (2) prepared fiber has tangible shape memory intelligent characteristic, has increased the kind of intelligent fiber, has widened the Application Areas of shape-memory polymer.
Below by specific embodiment the present invention is carried out more concrete description.Be necessary to be pointed out that at this; the embodiment here only is used for that the invention will be further described; at all can not be interpreted as limiting the scope of the invention; those skilled in the art can make some nonessential and improvement and adjustment others to content of the present invention according to content of the present invention under the situation that does not exceed protection scope of the present invention.
But have some to illustrate:
(1) raw material involved in the present invention is industrialization raw material, needs through processed before using; Employed synthesis device also is the synthesis device of industrial polyurethane commonly used, and employed wet spinning technology and equipment also adopt traditional wet spinning technology and equipment.
(2) compare with the polyurethane that common being used to prepares spandex, block polyurethane provided by the present invention, structurally the difference of Cun Zaiing is to have designed tangible two phase structure (block structure), but its anti-phase has a tangible deformation recovery temperature in-10～60 ℃ of scopes, make polyurethane and fiber have tangible shape memory characteristics.
(3) because structural particularity so the synthesis technique that this experiment provides adopts step synthesis, but is generally synthesized the anti-phase block earlier, synthetic more fixedly phase block.Synthetic method is mainly solution polymerization process, and solvent is the organic solvent of polarity, as dimethyl formamide, and dimethylacetylamide, dimethyl sulfoxide (DMSO), acetone and MEK etc.
(4) but the phase state analysis of polyurethane blocks structure and anti-phase, fixing phase transition temperature mutually adopt thermal analyzer DSC or DMA (PE company) to test; The shape memory characteristic of polyurethane film and fiber adopts the test of INSTRON 4466 (Instron company) universal testing machine, and method is as follows: will grow sample strip for L earlier in constant speed and temperature T
1(T
1=T
s+ 15 ℃) be pulled down to regulation deformation ε
m(ε
m=100%, 200%), keeps external force, keep deformation, sample is cooled to temperature T
u(T
u=T
s-15 ℃), remove external force, deformation is fixed as (ε
m-ε
u); Again sample is heated to T again
u, kept 10 minutes, obtain deformation recovery ε
r, its work schematic diagram is seen accompanying drawing.
Deformation fixed rate and deformation-recovery rate can calculate with following formula:
Deformation fixed rate=ε
u/ ε
m* 100%; Deformation-recovery rate=ε
r/ ε
m* 100%
Description of drawings
Fig. 1 is the work schematic diagram of test polyurethane shape memory characteristic.
The specific embodiment
Below shape memory fiber of the present invention and preparation method thereof is done more concrete description, by these descriptions, characteristics of the present invention and advantage will more clearly show.Wherein said raw material is industrialization product, and equipment is general production of polyurethane equipment and spandex wet spinning equipment, and described raw material umber is parts by weight except that specifying.
Embodiment
Embodiment 1
But with 60 kilograms of 0.02 kilogram of anti-phase component dibutyl tin laurates, polycaprolactone glycol (number average relative molecular mass 3000), 2,6.96 kilograms of 4-toluene di-isocyanate(TDI)s, dimethyl formamide add 1000L for 400 kilograms and have in the reactor of agitator, thermometer and reflux condenser, react 2 hours down in temperature 70-80 ℃.Be cooled to 50～55 ℃ then, add fixedly phase component 1,0.1 kilogram of 5.4 kilograms of 4-butanediol, trimethylolpropane, 4,1.34 kilograms of 20 kilograms of 4 '-'-diphenylmethane diisocyanates and dihydroxymethyl third carboxylics, temperature control 55-60 ℃, react after 3-4 hour, add 131 kilograms in acetone, regulate viscosity, obtain colourless to faint yellow, thick polyurethane.
Calculate through theoretical, in the present embodiment gained polyurethane-NCO :-OH=1: 1.27; Fixedly the quality percentage composition of phase is 37.1%, but the quality percentage composition of anti-phase is 62.9%; Its quality percentage composition is 15%; But the crystalline melt point temperature of anti-phase adopts the DSC thermal analyzer test of PE company to be respectively 48 ℃ and 147 ℃ with fixing glass transition temperature mutually; The shape memory characteristic of film adopts the test of INSTRON 4466 (Instron company) universal testing machine, and its deformation fixed rate is 96.4%, and deformation-recovery rate is 94.1%.
The as-spun fibre of gained polyurethane solutions preparation is at room temperature dried, but do not carry out after-drawing and typing processing, the fiber number 360dtex of gained fiber, intensity 1.36CN/dtex, extension at break 235%.The deformation fixed rate of fiber is 95.1%, and deformation-recovery rate is 95.4%.
Embodiment 2
With stannous octoate 0.01 gram, polycaprolactone glycol (number average relative molecular mass 4000) 24 grams, polyethylene glycol adipate glycol (number average relative molecular mass 1000) 6 grams, hexamethylene diisocyanate 5.0 grams, dimethylacetylamide 100 grams add 250mL and have in the reaction bulb of agitator, thermometer and reflux condenser, react 2 hours down for 65～70 ℃ in temperature.Be cooled to 55-60 ℃ then, add 1,4-butanediol 1.0 grams, diglycol 1.0 grams, castor oil 2.0 grams, 4,4 '-'-diphenylmethane diisocyanate, 11.96 grams and dihydroxymethyl fourth carboxylic 1.48 grams, 60～65 ℃ of temperature controls, react after 3 hours, add MEK 57 grams and regulate viscosity, obtain faint yellow, thick polyurethane.
Calculate through theoretical, in the present embodiment gained polyurethane-NCO :-OH=1.5: 1.0; Fixedly the quality percentage composition of phase is 50.0%, but the quality percentage composition of anti-phase is 50.0%; Its quality percentage composition is 25%; But the crystalline melt point temperature of anti-phase adopts the DSC thermal analyzer test of PE company to be respectively 44 ℃ and 139 ℃ with fixing glass transition temperature mutually; The shape memory characteristic of film adopts the test of INSTRON 4466 (Instron company) universal testing machine, and its deformation fixed rate is 95.2%, and deformation-recovery rate is 94.3%.
With the polyurethane solutions that obtains, adjusting polymer content with dimethylacetylamide is 15%.Spinning condition is orifice diameter 0.15mm, hole count 40, measuring pump 0.6cc/r.40-55 ℃ of spinning solution temperature, setting medium be water, coagulation bath temperature 30-40 ℃, spinning speed 10-15M/min, stretch 2.0 times in bathing.The gained fiber is removed in the fiber behind the contained solvent through extraction, dries under 20-25 ℃, and in 65-70 ℃ of 1.5 times of typings 6-8 minute that stretch down, obtains the polyurethane shape memory fiber.
The mechanical property of this fiber and extensibility etc. adopt the test of INSTRON 4466 (Instron company) universal testing machine, this fibre number of its fiber 369dtex, intensity 1.0CN/dtex, extension at break 228.3%.The shape memory characteristic of fiber adopts the method test of embodiment 1-4, and its deformation fixed rate is 95.2%, and deformation-recovery rate is 96.9%.
Embodiment 3
With 0.02 kilogram of trimethylene diamines, 85 kilograms of poly adipate succinic acid ester glycol (number average relative molecular mass 4000), 15 kilograms of polyethylene glycol (number average relative molecular mass 600), 10.45 kilograms of isophorone diisocyanate, dimethyl sulfoxide (DMSO) adds 1000L for 375 kilograms and has in the reactor of agitator, thermometer and reflux condenser, reacts 2～3 hours down in temperature 78-80 ℃.Be cooled to 55-60 ℃ then, add 1,1.125 kilograms of 6-hexylene glycol 2.36 grams, glycerol, 4,1.5 kilograms in 10.21 kilograms of 4 '-'-diphenylmethane diisocyanates and tartaric acid, 60～65 ℃ of temperature controls react after 3 hours, be cooled to 30-40 ℃, obtain colourless, thick polyurethane.
Calculate through theoretical, in the present embodiment gained polyurethane-NCO :-OH=1.0: 1.0; Fixedly the quality percentage composition of phase is 20.0%, but the quality percentage composition of anti-phase is 80.0%; Its quality percentage composition is 25%; But the crystalline melt point temperature of anti-phase adopts the DSC thermal analyzer test of PE company to be respectively 52 ℃ and 144 ℃ with fixing glass transition temperature mutually; The shape memory characteristic of film adopts the test of INSTRON 4466 (Instron company) universal testing machine, and its deformation fixed rate is 92.2%, and deformation-recovery rate is 94.3%.
With the polyurethane/dimethyl formamide solution of gained, reconciling polymer content with dimethyl formamide is 15%.Spinning condition is orifice diameter 0.15mm, hole count 25, measuring pump 0.6cc/r.60 ℃ of spinning solution temperature, setting medium be water, coagulation bath temperature 30-40 ℃, spinning speed 8-12M/min, bathe in stretching 1.5-2.5 doubly.The gained fiber is removed in the fiber behind the contained solvent through extraction, at room temperature dries, and in 60 ℃ of 1.3 times of typings 8 minutes that stretch down, obtains the polyurethane shape memory fiber.
The mechanical property of this fiber and extensibility etc. adopt the test of INSTRON 4466 (Instron company) universal testing machine, and its fibre number is 315dtex, and intensity is 1.26CN/dtex, and extension at break is 190.1%.The shape memory characteristic of fiber adopts the method test of embodiment 1-3, and its deformation fixed rate is 94.2%, and deformation-recovery rate is 95.3%.
Embodiment 4
With 0.02 kilogram of dibutyl tin laurate, 15 kilograms of polyethylene glycol adipate glycol (number average relative molecular mass 6000), polytetrahydrofuran diol 20 kilograms (number average relative molecular mass 1000), 2,7.5 kilograms of 4-toluene di-isocyanate(TDI)s, dimethyl formamide adds 300L for 200 kilograms and has in the reactor of agitator, thermometer and reflux condenser, reacts 2 hours down for 75～80 ℃ in temperature.Be cooled to 50～55 ℃ then, add 1,4.0 kilograms of 4-butanediols, polypropylene glycol (PPG303, number average relative molecular mass 300) 0.6 kilogram of 3.0 kilogram, ethylene glycol, 4,2.5 kilograms of 19.1 kilograms of 4 '-'-diphenylmethane diisocyanates and dihydromethyl propionic acids, 65～70 ℃ of temperature controls, react 85 kilograms of adjustings of adding MEK viscosity after 2.5 hours, obtain faint yellow, thick polyurethane solutions.
Calculate through theoretical, in the present embodiment gained polyurethane-NCO :-OH=1: 1.15; Fixedly the quality percentage composition of phase is 40.7%, but the quality percentage composition of anti-phase is 59.3%; Its quality percentage composition is 20%; But the crystalline melt point temperature of anti-phase adopts the DSC thermal analyzer test of PE company to be respectively 47 ℃ and 154 ℃ with fixing glass transition temperature mutually; The shape memory characteristic of film adopts the test of INSTRON 4466 (Instron company) universal testing machine, and its deformation fixed rate is 96.2%, and deformation-recovery rate is 97.8%.
With the polyurethane solutions that obtains, adjusting polymer content with dimethyl formamide solution is 17-20%.Spinning condition is orifice diameter 0.15mm, hole count 40, measuring pump 0.6-0.8cc/r.55-60 ℃ of spinning solution temperature, setting medium be water, coagulation bath temperature 30-35 ℃, spinning speed 8-10m/min, bathe in stretching 1.5-2.0 doubly.The gained fiber is removed in the fiber behind the contained solvent through extraction, dries under 18-25 ℃, and in 65 ℃ of 1.5 times of typings 8-10 minute that stretch down, obtains the polyurethane shape memory fiber.
The mechanical property of this fiber and extensibility etc. adopt the test of INSTRON 4466 (Instron company) universal testing machine, this fibre number of its fiber 375dtex, intensity 1.29CN/dtex, extension at break 258.3%.The shape memory characteristic of fiber adopts the method test of embodiment 1-3, and its deformation fixed rate is 95.8%, and deformation-recovery rate is 96%.
Embodiment 5
But with 0.02 kilogram of anti-phase component dibutyl tin laurate, 60 kilograms of polycaprolactone glycols (number average relative molecular mass 3000), polytetrahydrofuran diol 20 kilograms (number average relative molecular mass 2000), 4,12.5 kilograms of 4 '-'-diphenylmethane diisocyanates, dimethyl sulfoxide (DMSO) add 1000L for 500 kilograms and have in the reactor of agitator, thermometer and reflux condenser, react 2 hours down in temperature 75-80 ℃.Be cooled to 50～55 ℃ then, add fixedly phase component 1,15 kilograms of 15.75 kilograms of 4-butanediols, polypropylene glycol PPG 330 (number average relative molecular mass 3000), 4,2.01 kilograms of 48.12 kilograms of 4 '-'-diphenylmethane diisocyanates and dihydroxymethyl third carboxylics, temperature control 55-60 ℃, react after 3-4 hour, add 200.0 kilograms in acetone, regulate viscosity, obtain colourless to faint yellow, thick polyurethane.
Calculate through theoretical, in the present embodiment gained polyurethane-NCO :-OH=1.1: 1.0; Fixedly the quality percentage composition of phase is 54.3%, but anti-phase quality percentage composition is 45.7%; Its quality percentage composition is 16.27%; But the crystalline melt point temperature of anti-phase adopts the DSC thermal analyzer test of PE company to be respectively 47.2 ℃ and 168 ℃ with fixing glass transition temperature mutually; The shape memory characteristic of film adopts the test of INSTRON 4466 (Instron company) universal testing machine, and its deformation fixed rate is 95.4%, and deformation-recovery rate is 94.8%.
With the polyurethane solutions that obtains, adjusting polymer content with dimethyl formamide solution is 17-20%.Spinning condition is orifice diameter 0.15mm, hole count 40, measuring pump 0.6-0.8cc/r.55-60 ℃ of spinning solution temperature, setting medium be water, coagulation bath temperature 30-35 ℃, spinning speed 8-10m/min, bathe in stretching 1.5-2.0 doubly.The gained fiber is removed in the fiber behind the contained solvent through extraction, dries under 18-25 ℃, and in 65 ℃ of 1.5 times of typings 8-10 minute that stretch down, obtains the polyurethane shape memory fiber.
The mechanical property of this fiber and extensibility etc. adopt the test of INSTRON 4466 (Instron company) universal testing machine, this fibre number of its fiber 323dtex, intensity 1.49CN/dtex, extension at break 128.1%.The shape memory characteristic of fiber adopts the method test of embodiment 1-4, and its deformation fixed rate is 94.6%, and deformation-recovery rate is 93.2%.
Embodiment 6
With 0.02 kilogram of dibutyl tin laurate, 10 kilograms of poly adipate succinic acid ester glycol (number average relative molecular mass 6000), polyethylene glycol 20 kilograms (number average relative molecular mass 600), 4,30 kilograms of 4 '-'-diphenylmethane diisocyanates, dimethyl formamide adds 1000L for 400 kilograms and has in the reactor of agitator, thermometer and reflux condenser, reacts 2 hours down for 75 ℃ in temperature.Be cooled to 50～55 ℃ then, add 1,30.0 kilograms of 4-butanediols, polypropylene glycol (PPG303, number average relative molecular mass 300) 10.0 kilograms, 4,10.0 kilograms of 4 '-'-diphenylmethane diisocyanate double centner and dihydromethyl propionic acids, 65～70 ℃ of temperature controls, react 200 kilograms of adjustings of adding MEK viscosity after 2.5 hours, obtain faint yellow, thick polyurethane solutions.
Calculate through theoretical, in the present embodiment gained polyurethane-NCO :-OH=1.03: 1.0; Fixedly the quality percentage composition of phase is 80%, but the quality percentage composition of anti-phase is 20%; Its quality percentage composition is 20%; But the crystalline melt point temperature of anti-phase adopts the DSC thermal analyzer test of PE company to be respectively 12 ℃ and 198 ℃ with fixing glass transition temperature mutually; The shape memory characteristic of film adopts the test of INSTRON 4466 (Instron company) universal testing machine, and its deformation fixed rate is 96.2%, and deformation-recovery rate is 90.0%.
With the polyurethane solutions that obtains, adjusting polymer content with dimethyl formamide solution is 17-20%.Spinning condition is orifice diameter 0.15mm, hole count 40, measuring pump 0.6-0.8cc/r.55-60 ℃ of spinning solution temperature, setting medium be water, coagulation bath temperature 30-35 ℃, spinning speed 8-10m/min, bathe in stretching 1.5-2.0 doubly.The gained fiber is removed in the fiber behind the contained solvent through extraction, dries under 18-25 ℃, and in 65 ℃ of 1.5 times of typings 8-10 minute that stretch down, obtains the polyurethane shape memory fiber.
The mechanical property of this fiber and extensibility etc. adopt the test of INSTRON 4466 (Instron company) universal testing machine, this fibre number of its fiber 335dtex, intensity 1.5CN/dtex, extension at break 100%.The shape memory characteristic of fiber adopts the method test of embodiment 1-3, and its deformation fixed rate is 95.8%, and deformation-recovery rate is 90.2%.
Claims (21)
1. a shape memory fiber is characterized in that, described shape memory fiber is to be prepared into by shape memory polyurethane, but this polyurethane be prepared into forming fixing component (B) mutually by the component that forms anti-phase (A) again, component (A) with (B) be:
(A)：
Catalyst 0.01-0.20 weight portion;
Polyethers or polyester diol 30-100 weight portion;
Aromatic series or aliphatic diisocyanate 5-30 weight portion;
Solvent 0-500 weight portion;
(B)：
Aromatic diisocyanate 5-100 weight portion;
Crosslinking agent trihydroxy polyalcohol 0.1-2.0 weight portion;
The dihydroxylic alcohols 2-30 of chain extender short-chain fat family weight portion;
The carboxylic short-chain fat dihydroxylic alcohols 0-10 of family weight portion;
Solvent 0-200 weight portion.
2. shape memory fiber according to claim 1 is characterized in that, the polyurethane fixedly quality percentage composition of phase is 20%-80%, but the quality percentage composition of anti-phase is 80%-20%.
3. shape memory fiber according to claim 2 is characterized in that, fixedly the quality percentage composition of phase is 20%-50%, but the quality percentage composition of anti-phase is 80%-50%.
4. shape memory fiber according to claim 1 is characterized in that, wherein in the polyurethane-and the mole number of NCO and-OH is than being 1.0-1.5.
5. shape memory fiber according to claim 1 is characterized in that, polyethers or polyester diol are the crystalline melt point temperature range at 10-60 ℃ glycol.
6. shape memory fiber according to claim 5, it is characterized in that described glycol is that 1000～4000 polyethylene glycol adipate glycol or PPA glycol, number average relative molecular mass are that 1000～6000 poly adipate succinic acid ester glycol, number average relative molecular mass are that 1250～8000 polycaprolactone glycol, number average relative molecular mass are that 200～6000 polyethylene glycol, number average relative molecular mass are 200～4000 polytetrahydrofuran diol or its combination for the number average relative molecular mass.
7. shape memory fiber according to claim 1, it is characterized in that, aromatic series or aliphatic diisocyanate are selected from 2,4 toluene diisocyanate, 4,4 '-'-diphenylmethane diisocyanate, hexamethylene diisocyanate or isophorone diisocyanate or its combination.
8. shape memory fiber according to claim 1 is characterized in that, it is at least a in 300 or 3000 the three-functionality-degree polypropylene glycol that crosslinking agent trihydroxy polyalcohol is selected from glycerol, castor oil, trimethylolpropane or number average relative molecular mass.
9. shape memory fiber according to claim 1 is characterized in that, chain extender is a short-chain fat family dihydroxylic alcohols, and it is selected from 1,4-butanediol, 1,5-pentanediol, 1,6-hexylene glycol, ethylene glycol, 1, at least a in ammediol or the diglycol.
10. shape memory fiber according to claim 1 is characterized in that, carboxylic short-chain fat family dihydroxylic alcohols is at least a in dihydromethyl propionic acid, dimethylolpropionic acid or the tartaric acid.
11. shape memory fiber according to claim 1 is characterized in that, solvent is at least a in dimethyl formamide, dimethylacetylamide, dimethyl sulfoxide (DMSO), acetone or the MEK.
12. shape memory fiber according to claim 1 is characterized in that, but the deformation recovery temperature of anti-phase between-10 ℃～60 ℃, or fixedly the glass transition temperature of phase is higher than 100 ℃.
13. shape memory fiber according to claim 1 is characterized in that, described polyurethane is colourless to light yellow thick solution, and its mass percent concentration is 15%～25% weight.
14. shape memory fiber according to claim 1 is characterized in that, catalyst is at least a in dibutyl tin laurate, stannous octoate or the triethylenediamine.
15. shape memory fiber according to claim 1 is characterized in that, the deformation fixed rate of this fiber and deformation-recovery rate are all greater than 90%.
16. shape memory fiber according to claim 1 is characterized in that, the fiber number of this fiber is greater than 300dtex, intensity 1.0-1.5CN/dtex, elongation at break 100-400%.
17. a method for preparing any shape memory fiber of claim 1 to 16, it comprises the following steps:
(1) by component (A) with (B) preparation polyurethane:
(1) a, make and comprise that 0-500 parts by weight solvent, 0.01-0.2 weight portion catalyst, 30-100 weight portion polyethers or polyester diol, 5-30 weight portion aromatic series or aliphatic diisocyanate react, and obtain containing the polyurethane prepolymer of reversible phase structure in reactor;
(1) b, add and comprise 5-70 weight portion aromatic diisocyanate, 2-30 weight portion short-chain fat family dihydroxylic alcohols, the carboxylic short-chain fat of 0-10 weight portion family's dihydroxylic alcohols and 0.1-2.0 weight portion crosslinking agent trihydroxy polyalcohol, continue reaction, add the 0-200 parts by weight solvent and adjust concentration and viscosity, but obtain to comprise anti-phase and fixing shape memory polyurethane solution mutually with block structure;
(2) polyurethane that step (1) is made adopts the wet spinning preparation method and makes shape memory fiber.
18. preparation method according to claim 17 is characterized in that, being reflected under 40-100 ℃ the temperature of step (1) a carried out, and the reaction time is 30 minutes to 6 hours.
19. preparation method according to claim 18 is characterized in that, being reflected under 60-85 ℃ the temperature of step (1) a carried out, and the reaction time is 2-3 hour.
20. preparation method according to claim 17 is characterized in that, the reaction of step (1) b is to carry out under 50-70 ℃ temperature.
21. preparation method according to claim 17, it is characterized in that, in step (1) b, add 5-70 weight portion aromatic diisocyanate, 2-30 weight portion chain extender short-chain fat family's dihydroxylic alcohols and the carboxylic short-chain fat of 0-10 weight portion family dihydroxylic alcohols, 0.1-2.0 weight portion crosslinking agent trihydroxy polyalcohol down at 50-60 ℃, temperature control 55-70 ℃ then, reacted 3-4 hour.
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| CN101173031B (en) * | 2006-11-01 | 2010-11-03 | 北京林氏精化新材料有限公司 | Polyurethane prepolymer, aquosity polyurethane binder and uses thereof |
| WO2009000128A1 (en) * | 2007-06-25 | 2008-12-31 | The Hong Kong Polytechnic University | A textile with shape memory function and treatment process thereof |
| CN102691118B (en) * | 2011-03-23 | 2015-02-25 | 香港理工大学 | Preparation method of shape memory hollow fiber |
| CN102501414A (en) * | 2011-09-30 | 2012-06-20 | 常熟市众望经纬编织造有限公司 | Anti-wrinkle thermal insulation fabric |
| CN102532464A (en) * | 2012-03-12 | 2012-07-04 | 烟台美瑞化学材料有限公司 | Low permanent compression deformation thermoplastic polyurethane elastomer |
| CN104695041B (en) * | 2013-12-09 | 2017-06-16 | 香港纺织及成衣研发中心有限公司 | A kind of shape memory fiber, its manufacture method and its textile being made |
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| CN105088799A (en) * | 2015-09-16 | 2015-11-25 | 太仓市国峰纺织印染有限责任公司 | Finishing method for textile with shape memorization function |
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| CN110067041B (en) * | 2019-01-28 | 2021-09-17 | 上海益弹新材料有限公司 | Wear-resistant elastic fiber and preparation method thereof |
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| CN112663168B (en) * | 2020-12-22 | 2022-07-19 | 五邑大学 | Spandex fiber with reversible shape memory effect and preparation method and application thereof |
| CN112962165B (en) * | 2021-01-21 | 2022-07-05 | 五邑大学 | Spandex fiber with reversible three-shape memory effect and preparation method and application thereof |
| CN113209386A (en) * | 2021-04-21 | 2021-08-06 | 成都理工大学 | Preparation method of polyurethane bone scaffold with body temperature shape memory effect |
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