WO2022156149A1 - 一种具有可逆三形状记忆效应的氨纶纤维及其制备方法与应用 - Google Patents

一种具有可逆三形状记忆效应的氨纶纤维及其制备方法与应用 Download PDF

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WO2022156149A1
WO2022156149A1 PCT/CN2021/102662 CN2021102662W WO2022156149A1 WO 2022156149 A1 WO2022156149 A1 WO 2022156149A1 CN 2021102662 W CN2021102662 W CN 2021102662W WO 2022156149 A1 WO2022156149 A1 WO 2022156149A1
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spandex fiber
reversible
shape memory
memory effect
spandex
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English (en)
French (fr)
Inventor
范龙飞
闵磊
于晖
吴玉潇
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Wuyi University Fujian
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Wuyi University Fujian
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    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
    • D01F6/70—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C08G18/22—Catalysts containing metal compounds
    • C08G18/24—Catalysts containing metal compounds of tin
    • C08G18/244—Catalysts containing metal compounds of tin tin salts of carboxylic acids
    • C08G18/246—Catalysts containing metal compounds of tin tin salts of carboxylic acids containing also tin-carbon bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
    • C08G18/4269—Lactones
    • C08G18/4277—Caprolactone and/or substituted caprolactone
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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    • C08G18/48—Polyethers
    • C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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    • C08G18/6603—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6607—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
    • C08G18/6611—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203 having at least three hydroxy groups
    • C—CHEMISTRY; METALLURGY
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    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
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    • C08G18/6644—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203 having at least three hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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    • C08G18/72—Polyisocyanates or polyisothiocyanates
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
    • C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
    • Y02P70/62—Manufacturing or production processes characterised by the final manufactured product related technologies for production or treatment of textile or flexible materials or products thereof, including footwear

Definitions

  • the invention belongs to the technical field of intelligent polymer materials, and in particular relates to a spandex fiber with reversible three-shape memory effect and a preparation method and application thereof.
  • Shape memory fibers can be divided into shape memory alloy fibers and shape memory polymer fibers according to the raw materials used. Shape memory alloy fibers can realize the reversible deformation process under thermal stimulation using the principle of martensitic transformation. So far, the most commonly studied and applied shape memory fibers are Nitinol fibers.
  • the matrix material of shape memory polymer fiber is shape memory polymer, and shape memory polymer (SMP for short) can produce recoverable deformation when stimulated by the outside world.
  • shape memory polymers have both a "temporary shape” and a "permanent shape”. Shape memory polymers can fix a temporary shape under certain external force and environmental conditions, and return to a permanent shape through external stimuli such as light stimulation, thermal stimulation, and electrical stimulation.
  • the polymer network of the shape memory polymer has potential activity. Under the external stimulus, the "transition" of the shape memory polymer is triggered, and the strain energy stored in the temporary shape is released, which eventually leads to the recovery of the deformation. .
  • the shape memory effect mechanism of shape memory polymers is not based on the martensitic transformation principle of shape memory alloys. Shape memory polymers fix permanent shapes through cross-linking and temporary shapes through phase transformation.
  • the shape memory polymer fibers that are widely used and studied at present are all one-way shape memory polymer fibers, and the common thermotropic shape memory polymer fibers are triggered by thermal stimulation (heating or cooling) to trigger the fixation and recovery of the shape. Since the deformation process of the one-way shape memory polymer is not reversible, the shape recovery process of the shape memory polymer fiber prepared based on the shape memory polymer is also not reversible, and can only change from a temporary shape to a permanent shape, making the Shape memory polymer fibers can only be used as disposable products.
  • the above shortcomings greatly limit the development prospects and application fields of shape memory polymer fibers, and at the same time do not conform to the development concept of green environmental protection in today's world.
  • the purpose of the present invention is to provide a spandex fiber with reversible three-shape memory effect and a preparation method and application thereof.
  • a spandex fiber with reversible three shape memory effects comprising the following raw materials by weight:
  • the number average molecular weight of the crystalline polyester diol or the crystalline polyether diol is 1000-10000.
  • the crystalline polyester diol or crystalline polyether diol is at least two of the compounds of the following structural formula:
  • the diisocyanate is at least one of the following structural formula compounds:
  • the polyurethane chain extender is at least one of small molecule chain extenders such as diols, diamines, diacids, and dithiols, including but not limited to 1,3- Butanediol, 1,4-butanediol, 1,6-hexanediol, 1,2-propanediol, diethylene glycol ether, neopentyl glycol, 1,2-heptanediol, 1,7-heptanediol Diol, 1,2-octanediol, 1,8-octanediol, 1,2-nonanediol, 1,9-nonanediol, 1,10-decanediol, 1,2-cyclohexanediol Alcohol, estradiol, dipropylene glycol, dodecanol, 1,2-tetradecanediol, 2,8-quinolinediol, 1,2-hexaned
  • the polyurethane crosslinking agent is at least one of polyols, polyamines, polyacids, and polythiols, including but not limited to trimethylolpropane tris(3-mercaptopropionate) ), pentaerythritol mercaptopropionate, glycerol, 1-(p-nitrophenyl)glycerol, 1,2,4-butanetriol, swainsonine, 1,2,4-phloroglucinol, phytan three Alcohol, 1,8,9-trihydroxyanthracene, gallocatechin, catechin, 1-deoxynojirimycin, estriol, tris(hydroxymethyl)aminomethane, 1-thioglycerol, calcitriol , cyanuric acid, pentaerythritol, dipentaerythritol, threitol, erythritol, quinizarin, voglibose, dithioerythr
  • step (3) lowering the polyurethane prepolymer A obtained in step (1) and the polyurethane prepolymer B obtained in step (2) to room temperature and mixing uniformly, then adding a polyurethane crosslinking agent, stirring uniformly, and preparing a spinning dope;
  • step (3) completely defoaming the spinning stock solution obtained in step (3), then forming spandex fibers through a spinning process, and then heating the spandex fibers to make polyurethane prepolymer A and polyurethane prepolymer B and polyurethane crosslinking agent complete reaction;
  • step (4) heating the spandex fiber processed in step (4) to melt its internal crystal region and dissociate its hydrogen bonds, then further stretch it by drawing and fix the deformation with a clamp, then drop to room temperature, and remove the clamp , the spandex fiber is shrunk, then the temperature is raised to the upper melting limit temperature, the spandex fiber is further shrunk, and after the shrinkage is completed, the spandex fiber is lowered to room temperature to obtain the spandex fiber with reversible three-shape memory effect.
  • the synthesis reaction of the step (1) and the step (2) is carried out under the protection of an inert gas, and the reaction temperature is 25-100°C.
  • an organotin catalyst is also added during the synthesis reaction of the step (1) and the step (2).
  • the conditions for heating the spandex fiber are heating at 25-50° C. for 2-24 hours.
  • the temperature range for heating the spandex fiber is between the dissociation temperature of the hydrogen bond and the thermo-oxidative degradation temperature of the spandex.
  • the reversible three-shape memory effect mechanism of the spandex fiber is as follows: the spandex fiber prepared by the present invention has two different crystalline soft segments inside, and can memorize two temporary shapes. When in use, it is only necessary to increase the temperature of the spandex fiber to completely melt one of the crystalline soft segments, and the crystalline soft segment will be melted from oriented crystals with a smaller entropy value and transformed into random wires with a larger entropy value.
  • the spandex fiber shows a shortened length macroscopically; when the temperature of the spandex fiber continues to rise to the point where the other crystalline soft segment is completely melted, the spandex fiber will continue to shrink macroscopically; One of the crystalline soft segments begins to crystallize, and the molecular chain of the soft segment in the molten state is oriented and crystallized under the action of the tensile stress provided by the hydrogen bond network, so that the spandex fiber macroscopically shows an increase in length; when the temperature is further reduced, the spandex fiber Another crystalline soft segment inside the fiber begins to undergo oriented crystallization, and the spandex fiber will be further elongated macroscopically. Therefore, the reversible deformation process of the spandex fiber of the present invention between the three shapes is cyclic and reciprocal with the change of temperature, and the reversible three shape memory effect is realized.
  • the present invention also provides applications of the spandex fiber with reversible three-shape memory effect in the fields of smart polymer materials, smart textiles, actuators, soft robots and 4D printing.
  • the beneficial effects of the present invention are: compared with the existing single-pass shape-memory polymer fiber, the spandex fiber with reversible three-shape memory effect provided by the present invention has the following outstanding advantages:
  • the physical fiber can only achieve a one-time shape change under the external stimulus, while the deformation process of the spandex fiber of the present invention is reversible, and has the ability to transform between the "elongation" and "shortening" states infinitely under the action of the temperature field. , and can memorize two temporary shapes.
  • the raw materials used for preparing the spandex fiber in the present invention are easy to obtain, and the preparation method is simple, and is suitable for industrialized large-scale production.
  • FIG. 1 is a schematic diagram of the mechanism of the spandex fiber with reversible three shape memory effect according to the present invention to realize the reversible three shape memory effect.
  • the present invention provides a kind of spandex fiber with reversible three shape memory effects, which comprises the following raw materials in parts by weight:
  • the number average molecular weight of the crystalline polyester diol or crystalline polyether diol is 1000-10000.
  • the crystalline polyester diol or crystalline polyether diol is at least one of the compounds of the following structural formula:
  • the diisocyanate is at least one of the following structural formula compounds:
  • the polyurethane chain extender is at least one of small molecule chain extenders such as diols, diamines, diacids, and dithiols, including but not limited to 1,3- Butanediol, 1,4-butanediol, 1,6-hexanediol, 1,2-propanediol, diethylene glycol ether, neopentyl glycol, 1,2-heptanediol, 1,7-heptanediol Diol, 1,2-octanediol, 1,8-octanediol, 1,2-nonanediol, 1,9-nonanediol, 1,10-decanediol, 1,2-cyclohexanediol Alcohol, estradiol, dipropylene glycol, dodecanol, 1,2-tetradecanediol, 2,8-quinolinediol, 1,2-hexaned
  • the polyurethane crosslinking agent is at least one of polyols, polyamines, polyacids, and polythiols, including but not limited to trimethylolpropane tris(3-mercaptopropionate) ), pentaerythritol mercaptopropionate, glycerol, 1-(p-nitrophenyl)glycerol, 1,2,4-butanetriol, swainsonine, 1,2,4-phloroglucinol, phytan three Alcohol, 1,8,9-trihydroxyanthracene, gallocatechin, catechin, 1-deoxynojirimycin, estriol, tris(hydroxymethyl)aminomethane, 1-thioglycerol, calcitriol , cyanuric acid, pentaerythritol, dipentaerythritol, threitol, erythritol, quinizarin, voglibose, dithioerythr
  • step (3) lowering the polyurethane prepolymer A obtained in step (1) and the polyurethane prepolymer B obtained in step (2) to room temperature and mixing uniformly, then adding a polyurethane crosslinking agent, stirring uniformly, and preparing a spinning dope;
  • step (3) defoaming the spinning dope solution obtained in step (3) under vacuum conditions and room temperature conditions to ensure that no air bubbles exist in the spinning dope solution, and then press the spinning dope solution into the pipeline through a metering pump, and pass the spinneret.
  • the spinneret on the top extrudes a thin stream of spinning stock solution. After the spinning stock solution ejected from the spinneret enters the hot tunnel, the solvent in the spinning stock solution is rapidly evaporated by the high-temperature airflow and recovered from the lower outlet of the tunnel.
  • the thin stream of the raw liquid is solidified into long filaments and thinned, and finally spandex fibers are formed; the spandex fibers are heated at 25 to 50 ° C for 2 to 24 hours, so that the polyurethane prepolymer A and the polyurethane prepolymer B are combined with the polyurethane crosslinking agent. complete reaction;
  • step (4) heating the spandex fiber processed in step (4) to melt its internal crystal region and dissociate its hydrogen bonds, then further stretch it by drawing and fix the deformation with a clamp, then drop to room temperature, and remove the clamp , the spandex fiber is shrunk, then the temperature is raised to the upper melting limit temperature, the spandex fiber is further shrunk, and after the shrinkage is completed, the spandex fiber is lowered to room temperature to obtain the spandex fiber with reversible three-shape memory effect.
  • the working principle of the reversible three-shape memory effect of the spandex fiber prepared by the present invention is as follows: as shown in FIG. 1 , the spandex fiber has a phase-separated structure, and the crystal region inside the spandex fiber without training is arbitrarily oriented; The heating makes the two crystal regions completely melt and the hydrogen bonds dissociate; in this state, the spandex fiber whose inner crystal region is completely melted is stretched, and the molecular chains inside the spandex fiber are oriented under the action of stress; the deformation The two ends of the spandex fiber are fixed and lowered to room temperature.
  • the two crystalline soft segments inside the spandex fiber will be oriented and crystallized under the action of external force, and the hydrogen bond network inside will be regenerated.
  • the regenerated hydrogen bond network is in a stressed state; after the temperature is lowered to room temperature, the crystalline soft segment inside it It will crystallize under the stress provided by the hydrogen bond network and grow along this stress direction, so that the macroscopic length of the spandex fiber becomes longer.
  • the spandex fiber has a reversible shape memory effect. Since the spandex fiber has two different crystalline soft segments inside, it can memorize two temporary shapes. When in use, it is only necessary to increase the temperature of the spandex fiber to completely melt one of the crystalline soft segments, and the crystalline soft segment will be melted from oriented crystals with a smaller entropy value and transformed into random wires with a larger entropy value.
  • the spandex fiber shows a shortened length macroscopically; when the temperature of the spandex fiber continues to rise until the other crystalline soft segment is completely melted, the spandex fiber will continue to shrink macroscopically; A crystalline soft segment begins to crystallize, and the molecular chain of the soft segment in the molten state is oriented and crystallized under the action of the tensile stress provided by the hydrogen bond network, so that the spandex fiber macroscopically shows an increase in length; when the temperature is further reduced, the spandex fiber Another crystalline soft segment in the interior begins to crystallize in orientation, and the spandex fiber will be further elongated macroscopically at this time. It can be seen that the reversible deformation process of the spandex fiber of the present invention between the above three shapes is cyclic and reciprocal with the change of temperature, and the reversible three shape memory effect is realized.
  • the ester diol was dissolved in an appropriate amount of dichloromethane, then added to a three-necked flask and stirred for 1 h, and then added with 0.13 parts of chain extender 1,4-butanediol (BDO) and stirred for 1 h to obtain polyurethane prepolymer A; 2.59 parts of 1,6-hexamethylene diisocyanate (HDI) and two drops of dibutyltin dilaurate (DBTDL) were dissolved in an appropriate amount of dichloromethane, placed in a three-necked flask protected by argon at 60 °C, and 20.3 parts of polytetrahydrofuran binary The alcohol is dissolved in an appropriate amount of dichloromethane, then added to a three-necked flask and stirred for 1 hour, and then 0.3 parts of chain extender 1,4-butanediol (BDO) is added to stir for 1 hour to obtain polyurethane prepolymer B;
  • the spinning dope was deaerated for 30 min under vacuum conditions and room temperature to ensure that no air bubbles existed in the spinning dope.
  • the spinning dope is pressed into the pipeline by the metering pump, and the thin stream of the spinning dope is extruded through the spinneret on the spinneret.
  • the solvent is quickly evaporated by the high-temperature air flow and recovered from the outlet at the bottom of the tunnel.
  • the spandex fiber was heated at 50°C for 2 hours, so that the reaction between the polyurethane prepolymer and the polyurethane crosslinking agent was completed.
  • the spandex fiber is heated to melt the inner crystal region and dissociate the hydrogen bond, and then stretch it further and fix the deformation with a clamp. After that, it is lowered to room temperature, and the clamp for fixing the spandex fiber is removed, and the spandex fiber will shrink slightly. Then the temperature is raised to the upper melting limit temperature. At this time, the spandex fiber will further shrink. After the shrinkage is completed, the spandex fiber with the reversible three-shape memory effect is obtained.
  • the spinning dope was deaerated for 30 min under vacuum conditions and room temperature to ensure that no air bubbles existed in the spinning dope.
  • the spinning dope is pressed into the pipeline by the metering pump, and the thin stream of the spinning dope is extruded through the spinneret on the spinneret.
  • the solvent is quickly evaporated by the high-temperature air flow and recovered from the outlet at the bottom of the tunnel.
  • the spandex fiber was heated at 50°C for 2 hours, so that the reaction between the polyurethane prepolymer and the polyurethane crosslinking agent was completed.
  • the spandex fiber is heated to melt the inner crystal region and dissociate the hydrogen bond, and then stretch it further and fix the deformation with a clamp. After that, it is lowered to room temperature, and the clamp for fixing the spandex fiber is removed, and the spandex fiber will shrink slightly. Then the temperature is raised to its melting limit upper limit temperature, and the spandex fiber will further shrink at this time, and the spandex fiber with reversible three-shape memory effect is obtained after the shrinkage is completed.
  • polyurethane prepolymer B After cooling to room temperature, polyurethane prepolymer A and polyurethane prepolymer B are mixed and stirred for 30 minutes, and 1.91 Parts of cross-linking agent trihydroxypropane tris(3-mercaptoacrylate) were stirred evenly, and by adjusting the amount of dichloromethane used, a spinning stock solution with a mass fraction of 35% was prepared.
  • the spinning dope was deaerated for 30 min under vacuum conditions and room temperature to ensure that no air bubbles existed in the spinning dope.
  • the spinning dope is pressed into the pipeline by the metering pump, and the thin stream of the spinning dope is extruded through the spinneret on the spinneret.
  • the solvent is quickly evaporated by the high-temperature air flow and recovered from the outlet at the bottom of the tunnel.
  • the spandex fiber was heated at 50°C for 2 hours, so that the reaction between the polyurethane prepolymer and the polyurethane crosslinking agent was completed.
  • the spandex fiber is heated to melt the inner crystal region and dissociate the hydrogen bond, and then stretch it further and fix the deformation with a clamp. After that, it is lowered to room temperature, and the clamp for fixing the spandex fiber is removed, and the spandex fiber will shrink slightly. Then the temperature is raised to the upper melting limit temperature. At this time, the spandex fiber will further shrink. After the shrinkage is completed, the spandex fiber with the reversible three-shape memory effect is obtained.
  • the spinning dope was deaerated for 30 min under vacuum conditions and room temperature to ensure that no air bubbles existed in the spinning dope.
  • the spinning dope is pressed into the pipeline by the metering pump, and the thin stream of the spinning dope is extruded through the spinneret on the spinneret.
  • the solvent is quickly evaporated by the high-temperature air flow and recovered from the outlet at the bottom of the tunnel.
  • the spandex fiber was heated at 50°C for 2 hours, so that the reaction between the polyurethane prepolymer and the polyurethane crosslinking agent was completed.
  • the spandex fiber is heated to melt the inner crystal region and dissociate the hydrogen bond, and then stretch it further and fix the deformation with a clamp. After that, it is lowered to room temperature, and the clamp for fixing the spandex fiber is removed, and the spandex fiber will shrink slightly. Then the temperature is raised to the upper melting limit temperature. At this time, the spandex fiber will further shrink. After the shrinkage is completed, the spandex fiber with the reversible three-shape memory effect is obtained.
  • the spinning dope was deaerated for 30 min under vacuum conditions and room temperature to ensure that no air bubbles existed in the spinning dope.
  • the spinning dope is pressed into the pipeline by the metering pump, and the thin stream of the spinning dope is extruded through the spinneret on the spinneret.
  • the solvent is quickly evaporated by the high-temperature air flow and recovered from the outlet at the bottom of the tunnel.
  • the spandex fiber was heated at 50°C for 2 hours, so that the reaction between the polyurethane prepolymer and the polyurethane crosslinking agent was completed.
  • the spandex fiber is heated to melt the inner crystal region and dissociate the hydrogen bond, and then stretch it further and fix the deformation with a clamp. After that, it is lowered to room temperature, and the clamp for fixing the spandex fiber is removed, and the spandex fiber will shrink slightly. Then the temperature is raised to the upper melting limit temperature. At this time, the spandex fiber will further shrink. After the shrinkage is completed, the spandex fiber with the reversible three-shape memory effect is obtained.
  • the spinning dope was deaerated for 30 min under vacuum conditions and room temperature to ensure that no air bubbles existed in the spinning dope.
  • the spinning dope is pressed into the pipeline by the metering pump, and the thin stream of the spinning dope is extruded through the spinneret on the spinneret.
  • the solvent is quickly evaporated by the high-temperature air flow and recovered from the outlet at the bottom of the tunnel.
  • the spandex fiber was heated at 50°C for 2 hours, so that the reaction between the polyurethane prepolymer and the polyurethane crosslinking agent was completed.
  • the spandex fiber is heated to melt the inner crystal region and dissociate the hydrogen bond, and then stretch it further and fix the deformation with a clamp. After that, it is lowered to room temperature, and the clamp for fixing the spandex fiber is removed, and the spandex fiber will shrink slightly. Then the temperature is raised to its upper melting limit temperature, and the spandex fiber will further shrink at this time. After the shrinkage is completed, the spandex fiber with reversible shape memory effect is obtained.
  • the spinning dope was deaerated for 30 min under vacuum conditions and room temperature to ensure that no air bubbles existed in the spinning dope.
  • the spinning dope is pressed into the pipeline by the metering pump, and the thin stream of the spinning dope is extruded through the spinneret on the spinneret.
  • the solvent is quickly evaporated by the high-temperature air flow and recovered from the outlet at the bottom of the tunnel.
  • the reversible shape memory effect of the obtained materials was evaluated by dynamic thermomechanical analyzer (DMA).
  • DMA dynamic thermomechanical analyzer
  • the spandex fibers obtained in Examples 1 to 5 and Comparative Examples 1 to 2 were cut into fiber samples that met the DMA test requirements for DMA test.
  • the test conditions are: tensile mode, without applying any stress, from -20 °C as a starting point with a heating rate of 1 °C/min to 60 °C, constant temperature for 2 minutes, and then cooling at a cooling rate of 1 °C/min to 60 °C. -20°C, constant temperature for 2min, test the change of strain of the tested spline with temperature during the above temperature change process. Repeat the above temperature change process 5 times, and calculate the average strain of the tested sample in 5 cycles.
  • Table 1 The test results are shown in Table 1.

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Abstract

本发明公开了一种具有可逆三形状记忆效应的氨纶纤维及其制备方法与应用，该氨纶纤维包括如下重量份的原料：结晶性聚酯二醇或结晶性聚醚二醇3-100份、二异氰酸酯1-30份、聚氨酯扩链剂0.1-15份和聚氨酯交联剂0.2-11份，所述结晶性聚酯二醇或结晶性聚醚二醇的数均分子量为1000～10000。本发明的氨纶材料的形变过程具有可逆性，在温度场作用下具有无限次在"伸长"和"缩短"状态相互转变的能力，且能够记忆两种临时形状，制备所用的原料易得，制备方法简单，适合工业化大规模生产。

Description

一种具有可逆三形状记忆效应的氨纶纤维及其制备方法与应用 技术领域
本发明属于智能聚合物材料技术领域，具体涉及一种具有可逆三形状记忆效应的氨纶纤维及其制备方法与应用。
背景技术
形状记忆纤维根据使用的原材料可分为形状记忆合金纤维和形状记忆聚合物纤维。形状记忆合金纤维利用马氏体相变原理能够实现在热刺激下的可逆变形过程。迄今为止，研究、应用最普遍的形状记忆纤维是镍钛合金纤维。形状记忆聚合物纤维的基体材料为形状记忆聚合物，形状记忆聚合物(shape memory polymer，简称SMP)受到外界的刺激，能够产生可恢复的形变。形状记忆聚合物具有“临时形状”和“永久形状”两种形状。形状记忆聚合物在一定的外力和环境条件下，能够固定临时形状，通过光刺激、热刺激、电刺激等外界刺激回复到永久形状。形状记忆聚合物的聚合物网络具有潜在的活动能力，在外界的刺激之下，形状记忆聚合物的“转变”被触发，储存在临时形状的应变能被释放出来，从而最终导致了形变的恢复。形状记忆聚合物的形状记忆效应机理并非采用形状记忆合金的马氏体相变原理，形状记忆聚合物通过交联固定永久形状，通过相转变固定临时形状。
目前广泛使用、研究的形状记忆聚合物纤维均为单程形状记忆聚合物纤维，常见的热致型形状记忆聚合物纤维是通过热刺激(升温或降温)来触发形状的固定和回复。由于单程形状记忆聚合物的变形过程不具有可逆性，因此基于形状记忆聚合物制备得到的形状记忆聚合物纤维的形状回复过程也不具备可逆性，仅能从临时形状转变为永久形状，使得该形状记忆聚合物纤维仅能作为一次性产品使用。上述缺点极大地限制了形状记忆聚合物纤维的发展前景和应用领域，同时也不符合当今世界绿色环保的发展理念。
发明内容
为解决上述现有技术中存在的不足之处，本发明的目的在于提供一种具有可逆三形状记忆效应的氨纶纤维及其制备方法与应用。
为达到其目的，本发明所采用的技术方案为：
一种具有可逆三形状记忆效应的氨纶纤维，其包括如下重量份的原料：
Figure PCTCN2021102662-appb-000001
所述结晶性聚酯二醇或结晶性聚醚二醇的数均分子量为1000～10000。
优选地，所述的结晶性聚酯二醇或结晶性聚醚二醇为如下结构式化合物中的至少两种：
Figure PCTCN2021102662-appb-000002
优选地，所述的二异氰酸酯为如下结构式化合物中的至少一种：
Figure PCTCN2021102662-appb-000003
优选地，所述聚氨酯扩链剂为二元醇类、二元胺类、二元酸类、二元硫醇类等小分子扩链剂中的至少一种，包括但不限于1,3-丁二醇、1,4-丁二醇、1,6-己二醇、1,2-丙二醇、二乙二醇醚、新戊二醇、1,2-庚二醇、1,7-庚二醇、1,2-辛二醇、1,8-辛二醇、1,2-壬二醇、1,9-壬二醇、1,10-癸二醇、1,2-环己二醇、雌二醇、一缩二丙二醇、十二醇、1,2-十四碳二醇、2,8-喹啉二醇、1,2-十六烷二醇、1,4-环己二醇、2,3-樟脑二醇、1,12-十二烷二醇、三乙二醇、2-乙基-1,2-己二醇、1-苯基-1,2-乙二醇、3-甲基-1,3-丁二醇、1，4-丁炔二醇、3-氯-1,2-丙二醇、骨化二醇、2,5-二溴-1,4-苯二醇、2-乙基-1,3-己二醇、2-丁基-1,3-丙二醇、1,4-二溴-2,3-丁二醇、2,3-二溴-1,4-丁二醇、2-甲基-2,4-戊二醇、2,5-二甲基-3-己炔-2,5-二醇、2,5-二甲基-2,5-己二醇，2,2,4-三甲基-1,3-戊二醇、2,3-蒎烷二醇、2-氨基-1-苯基-1,3-丙二醇、2-甲基-1,3-丙二醇、2-甲基-2-丙基-1,3-丙二醇、1-苯基-1,2-乙二醇、2,3-二羟基吡啶、1,4-双(二苯基膦基)-2,3-O-异亚丙基-2,3-丁二醇、十二甘醇、2,5-二羟基-1,4-二噻烷、N-苯基二乙醇胺、1H,2H，10H,10H-全氟-1,10-癸二醇、2-对甲苯磺酸-1-苯基-1,2-乙二醇、3-叔丁基氨基-1,2-丙二醇、临氯苯基乙二醇、3,6-二硫杂-1,8-辛二醇、3,7-二硫杂-1,9-壬二醇，1,3-金刚烷二醇、3-苄氧基-1,2-丙二醇、1,1-二苯基-1,2-丙二醇、三缩四乙二醇、丙二酸、癸二酸、己二酸、戊二酸、α-酮戊二酸、顺丁烯二酸、十四烷二 酸、十一烷二酸、十五烷二酸、丁二酸、十二烷二酸、辛二酸、山俞酸、反丁烯二酸、戊二酸、庚二酸、丁二酸、3-(4-氯苯基)戊二酸、2,3-二溴丁二酸、2,2-二甲基丙二酸、顺式-已二烯二酸、反式-1,2-环丁二酸、苯基丁二酸、3-噻吩丙二酸、癸二酸、3-苯基戊二酸、苯丙二酸、壬二酸、丁炔二酸、2-氨基己二酸、金刚烷丙二酸、溴代丁二酸、2-甲基戊二酸、5-甲基间苯二酸、苯基丁二酸、3,3-二甲基戊二酸、2-氨基辛二酸、2,2-二甲基戊二酸、3,6,9-三噁十一烷二酸、2,3-二巯基丁二酸、1,2-环己烷二甲酸、1,3-丙酮二羧酸、2,6-吡啶二羧酸、2,2'-联苯二羧酸、4,4'-二苯乙烯二羧酸、DL-2-氨基己二酸、乙二胺、草酰二胺、对苯二胺、1,6-己二胺、间苯二胺、二氰二胺、4-溴-1,2-苯二胺、N-Boc-间苯二胺、N-苄基乙二胺、萘乙二胺、4-硝基邻苯二胺、1,2-二苯基乙二胺、(1,1'-联萘)-2,2'-二胺、N-Boc-乙二胺、4-氯邻苯二胺、N-Boc-对苯二胺、N,N-二乙基乙二胺、4,5-二氯邻苯二胺、N,N′-二苯基乙二胺、1,8-辛二胺、4-氟-1,2-苯二胺、N-(2-羟乙基)乙二胺、间苯二胺、N-苯基对苯二胺、1,2-丙二胺、1,3-丙二胺、1,2-环己二胺、1,4-丁二胺、N,N-二甲基乙二胺、1,10-二氨基癸烷、N,N-二异丙基乙二胺、2-氯-5-甲基-1,4-苯二胺、N,N-二甲基对苯二胺、N-苯基邻苯二胺、N-(叔丁氧羰基)-1,4-丁二胺、N,N'-双(3-氨丙基)乙二胺、N,N′-双(2-羟乙基)乙二胺、N,N'-二苯基对苯二胺、1,2-环己二胺、4,5-二氟-1,2-苯二胺、N，N，N`-三苯基联苯二胺、2-(三氟甲基)-1,4-亚苯基二胺、N,N'-双(亚水杨基)-1,4-丁烷二胺、2-硝基-1,4-苯二胺、N,N′-二(2-氨乙基)-1,3-丙二胺、2,5-二氯-1,4-苯二胺、N,N,N',N'-四甲基-1,3-丙二胺、二(4-甲氧基苯)-1,2-乙二胺、9,10-二氢-9,10-乙撑蒽-11,12-二胺、四(4-甲氧基苯基)-[1,1'-联苯]-4,4'-二胺、二甲基-1,2-二苯基-1,2-乙二胺、N,N,N,N-四甲基-1,6-己二胺、N,N'-二甲基环己烷-1,2-二胺、1,2-二苯基-1,2-乙二胺、1,2-环己二胺、N,N-二乙基-1,3-丙二胺、3,6,9-三氧杂十一烷-1,11-二胺、N,N′-二甲基-1,3-丙二胺、4-(羟乙氧基)-1,3-苯二胺盐酸盐、N-甲基-1,2-苯二胺、三甲基己二胺、异佛尔酮二胺、2,7-二氨基芴、1,8-二氨基萘、1,12-二氨基十二烷、2,6-二氨基蒽醌、9,10-二氨基菲、2,4-二氨基苯甲醚、1,4-二氨基环己烷、1,5-二氨基戊烷、2,3-二氨基萘、2,3-二氨基甲苯、尿素、N,N′-乙烯基双丙烯酰胺、N-Boc-2,2′-(亚乙二氧基)二乙胺、联苯胺、三亚乙基四胺、1,4-苯二甲胺、N,N'-二甲基乙二胺、N-(2-羟乙基)乙二胺、N,N'-二甲基环己烷-1,2-二胺、N-(对甲苯磺酰基)-1,2-二苯基乙二胺、4,6-嘧啶二胺、 4-乙酰氨基苯胺、乙二胺、草酰二胺、对苯二胺、1,6-己二胺、间苯二胺、二氰二胺、4-溴-1,2-苯二胺、N-Boc-间苯二胺、N-苄基乙二胺、萘乙二胺、4-硝基邻苯二胺、1,2-二苯基乙二胺、(1,1'-联萘)-2,2'-二胺、N-Boc-乙二胺、4-氯邻苯二胺、N-Boc-对苯二胺、N,N-二乙基乙二胺、4,5-二氯邻苯二胺、N,N′-二苯基乙二胺、1,8-辛二胺、4-氟-1,2-苯二胺、N-(2-羟乙基)乙二胺、间苯二胺、N-苯基对苯二胺、1,2-丙二胺、1,3-丙二胺、1,2-环己二胺、1,4-丁二胺、N,N-二甲基乙二胺、1,10-二氨基癸烷、N,N-二异丙基乙二胺、2-氯-5-甲基-1,4-苯二胺、N,N-二甲基对苯二胺、N-苯基邻苯二胺、N-(叔丁氧羰基)-1,4-丁二胺、N,N'-双(3-氨丙基)乙二胺、N,N′-双(2-羟乙基)乙二胺、N,N'-二苯基对苯二胺、1,2-环己二胺、4,5-二氟-1,2-苯二胺、N，N，N`-三苯基联苯二胺、2-(三氟甲基)-1,4-亚苯基二胺、N,N'-双(亚水杨基)-1,4-丁烷二胺、2-硝基-1,4-苯二胺、N,N′-二(2-氨乙基)-1,3-丙二胺、2,5-二氯-1,4-苯二胺、N,N,N',N'-四甲基-1,3-丙二胺、二(4-甲氧基苯)-1,2-乙二胺、9,10-二氢-9,10-乙撑蒽-11,12-二胺、四(4-甲氧基苯基)-[1,1'-联苯]-4,4'-二胺、二甲基-1,2-二苯基-1,2-乙二胺、N,N,N,N-四甲基-1,6-己二胺、N,N'-二甲基环己烷-1,2-二胺、1,2-二苯基-1,2-乙二胺、1,2-环己二胺、N,N-二乙基-1,3-丙二胺、3,6,9-三氧杂十一烷-1,11-二胺、N,N′-二甲基-1,3-丙二胺、4-(羟乙氧基)-1,3-苯二胺盐酸盐、N-甲基-1,2-苯二胺、三甲基己二胺、异佛尔酮二胺、2,7-二氨基芴、1,8-二氨基萘、1,12-二氨基十二烷、2,6-二氨基蒽醌、9,10-二氨基菲、2,4-二氨基苯甲醚、1,4-二氨基环己烷、1,5-二氨基戊烷、2,3-二氨基萘、2,3-二氨基甲苯、尿素、N,N′-乙烯基双丙烯酰胺、N-Boc-2,2′-(亚乙二氧基)二乙胺、联苯胺、三亚乙基四胺、1,4-苯二甲胺、N,N'-二甲基乙二胺、N-(2-羟乙基)乙二胺、N,N'-二甲基环己烷-1,2-二胺、N-(对甲苯磺酰基)-1,2-二苯基乙二胺、4,6-嘧啶二胺、4-乙酰氨基苯胺、二巯基丙醇、2，4-二巯基嘧啶、2,6-二巯基嘌呤、1,6-己二硫醇、甲苯-3,4-二硫酚、1,3-丙二硫醇、1,2-乙二硫醇中的一种或几种的混合物。
优选地，所述聚氨酯交联剂为多元醇类、多元胺类、多元酸类、多元硫醇类化合物中的至少一种，包括但不限于三羟甲基丙烷三(3-巯基丙酸酯)、巯基丙酸季戊四醇酯、丙三醇、1-(对硝基苯)甘油、1,2,4-丁三醇、苦马豆素、1,2,4-苯三酚、植烷三醇、1,8,9-三羟基蒽、棓儿茶酸、儿茶素、1-脱氧野尻霉素、雌 三醇、三(羟甲基)氨基甲烷、1-硫代甘油、钙三醇、三聚氰酸、季戊四醇、双季戊四醇、苏糖醇、赤藓醇、醌茜隐色体、伏格列波糖、二硫赤藓醇、木糖醇、甜醇、肌醇、山梨醇、碘海醇、N-丁基硫代磷酸三胺、1,4,7-三氮杂环壬烷、3,3'-二氨基二丙胺、三聚氰胺、三亚乙基四胺、3,3'-二氨基联苯胺中的一种或几种的混合物。
本发明所述的具有可逆三形状记忆效应的氨纶纤维的制备方法，包括如下步骤：
(1)通过二异氰酸酯、单体A、以及聚氨酯扩链剂合成聚氨酯预聚物A，所述单体A为所述结晶性聚酯二醇或结晶性聚醚二醇；
(2)通过二异氰酸酯、单体B、以及聚氨酯扩链剂合成聚氨酯预聚物B，所述单体B为所述结晶性聚酯二醇或结晶性聚醚二醇、且与所述单体A为不同的物质；
(3)将步骤(1)得到的聚氨酯预聚物A与步骤(2)得到的聚氨酯预聚物B降至室温并混合均匀，然后加入聚氨酯交联剂，搅拌均匀，配制成纺丝原液；
(4)将步骤(3)得到的纺丝原液完全脱泡，然后通过纺丝工艺形成氨纶纤维，然后将氨纶纤维进行加热，使聚氨酯预聚物A和聚氨酯预聚物B与聚氨酯交联剂反应完全；
(5)将经步骤(4)处理的氨纶纤维进行加热，使其内部晶区熔融及氢键解离，然后通过牵伸使其进一步伸长并用夹具固定形变，然后降至室温，卸除夹具，使氨纶纤维收缩，然后升温至其熔限上限温度，使氨纶纤维进一步收缩，收缩结束后降至室温，即得所述具有可逆三形状记忆效应的氨纶纤维。
优选地，所述步骤(1)和所述步骤(2)的合成反应在惰性气体保护下进行，反应温度为25～100℃。优选地，所述步骤(1)和所述步骤(2)的合成反应过程中还加入了有机锡催化剂。
优选地，所述步骤(4)中，对氨纶纤维进行加热的条件为25～50℃下加热2～24h。
所述步骤(5)中，对氨纶纤维进行加热的温度区间为氢键的解离温度至氨纶的热氧降解温度之间。
所述氨纶纤维的可逆三形状记忆效应机理为：本发明制备的氨纶纤维内部具有两种不同的结晶性软段，能够记忆两种临时形状。在使用时，只需将氨纶纤维的温度升高至使其中一种结晶性软段完全熔融，该结晶性软段将由熵值较小的取向结晶融化并转变为熵值较大的无规线团状态，氨纶纤维在宏观上表现为长度缩短；当氨纶纤维的温度继续升高至使另一种结晶性软段完全熔融，氨纶纤维在宏观上将继续收缩；当温度降低至使氨纶纤维的其中一种结晶性软段开始结晶，该处于熔融状态的软段分子链又在氢键网络提供的张应力作用下取向结晶，从而氨纶纤维宏观上表现为长度增加；当温度进一步降低，使氨纶纤维内部的另外一种结晶性软段开始发生取向结晶，此时氨纶纤维在宏观上将进一步伸长。因此，本发明的氨纶纤维在三种形状之间可逆的形变过程是随温度变化而循环往复的，实现了可逆三形状记忆效应。
另一方面，本发明还提供了所述具有可逆三形状记忆效应的氨纶纤维在智能聚合物材料、智能纺织品、驱动器、软机器人和4D打印领域中的应用。
与现有技术相比，本发明的有益效果为：本发明提供的具有可逆三形状记忆效应的氨纶纤维与现有的单程形状记忆聚合物纤维相比，具有如下突出的优势：单程形状记忆聚合物纤维在外界刺激下仅能实现一次性的形状转变，而本发明的氨纶纤维的形变过程具有可逆性，在温度场作用下具有无限次在“伸长”和“缩短”状态相互转变的能力，且能够记忆两种临时形状。另外，本发明制备所述氨纶纤维所用的原料易得，制备方法简单，适合工业化大规模生产。
附图说明
图1为本发明所述具有可逆三形状记忆效应的氨纶纤维实现可逆三形状记忆效应的机理示意图。
具体实施方式
本发明提供了一种具有可逆三形状记忆效应的氨纶纤维，其包括如下重量份的原料：
Figure PCTCN2021102662-appb-000004
Figure PCTCN2021102662-appb-000005
所述的结晶性聚酯二醇或结晶性聚醚二醇的数均分子量为1000～10000。
优选地，所述的结晶性聚酯二醇或结晶性聚醚二醇为如下结构式化合物中的至少一种：
Figure PCTCN2021102662-appb-000006
优选地，所述的二异氰酸酯为如下结构式化合物中的至少一种：
Figure PCTCN2021102662-appb-000007
优选地，所述聚氨酯扩链剂为二元醇类、二元胺类、二元酸类、二元硫醇类等小分子扩链剂中的至少一种，包括但不限于1,3-丁二醇、1,4-丁二醇、1,6-己二醇、1,2-丙二醇、二乙二醇醚、新戊二醇、1,2-庚二醇、1,7-庚二醇、1,2-辛二醇、1,8-辛二醇、1,2-壬二醇、1,9-壬二醇、1,10-癸二醇、1,2-环己二醇、雌二醇、一缩二丙二醇、十二醇、1,2-十四碳二醇、2,8-喹啉二醇、1,2-十六烷二醇、1,4-环己二醇、2,3-樟脑二醇、1,12-十二烷二醇、三乙二醇、2-乙基-1,2-己二醇、1-苯基-1,2-乙二醇、3-甲基-1,3-丁二醇、1，4-丁炔二醇、3-氯-1,2-丙二醇、骨化二醇、2,5-二溴-1,4-苯二醇、2-乙基-1,3-己二醇、2-丁基-1,3-丙二醇、1,4-二溴-2,3-丁二醇、2,3-二溴-1,4-丁二醇、2-甲基-2,4-戊二醇、2,5-二甲基-3-己炔-2,5-二醇、2,5-二甲基-2,5-己二醇，2,2,4-三甲基-1,3-戊二醇、2,3-蒎烷二醇、2-氨基-1-苯基-1,3-丙二醇、2-甲基-1,3-丙二醇、2-甲基-2-丙基-1,3-丙二醇、1-苯基-1,2-乙二醇、2,3-二羟基吡啶、1,4-双(二苯基膦基)-2,3-O-异亚丙基-2,3-丁二醇、十二甘醇、2,5-二羟基-1,4-二噻烷、N-苯基二乙醇胺、1H,2H，10H,10H-全氟-1,10-癸二醇、2-对甲苯磺酸-1-苯基-1,2-乙二醇、3-叔丁基氨基-1,2-丙二醇、临氯苯基乙二醇、3,6-二硫杂-1,8-辛二醇、3,7-二硫杂-1,9-壬二醇，1,3-金刚烷二醇、3-苄氧基-1,2-丙二醇、1,1-二苯基-1,2-丙二醇、三缩四乙二醇、丙二酸、癸二酸、己二酸、戊二酸、α-酮戊二酸、顺丁烯二酸、十四烷二酸、十一烷二酸、十五烷二酸、丁二酸、十二烷二酸、辛二酸、山俞酸、反丁烯二酸、戊二酸、庚二酸、丁二酸、3-(4-氯苯基)戊二酸、2,3-二溴丁二酸、2,2-二甲基丙二酸、顺式-已二烯二酸、反式-1,2-环丁二酸、苯基丁二酸、3-噻吩丙二酸、癸二酸、3-苯基戊二酸、苯丙二酸、壬二酸、丁炔二酸、2-氨基己二酸、金刚烷丙二酸、溴代丁二酸、2-甲基戊二酸、5-甲基间苯二酸、苯基丁二酸、3,3-二甲基戊二酸、2-氨基辛二酸、2,2-二甲基戊二酸、3,6,9-三噁十一烷二酸、2,3-二巯基丁二酸、1,2-环己烷二甲酸、1,3-丙酮二羧酸、2,6-吡啶二羧酸、2,2'-联苯二羧酸、4,4'-二苯乙烯二羧酸、DL-2-氨基己二酸、乙二胺、草酰二胺、对苯二胺、1,6-己二胺、间苯二胺、二氰二胺、4-溴-1,2-苯二胺、N-Boc-间苯二胺、N-苄基乙二胺、萘乙二胺、4-硝基邻苯二胺、1,2-二苯基乙二胺、(1,1'-联萘)-2,2'-二胺、N-Boc-乙二胺、4-氯邻苯二胺、N-Boc-对苯二胺、N,N-二乙基乙二胺、4,5-二氯邻苯二胺、N,N′-二苯基乙二胺、1,8-辛二胺、4-氟-1,2-苯二胺、N-(2-羟乙基)乙二胺、间苯二胺、N-苯基对苯二胺、1,2-丙二胺、1,3-丙二胺、1,2- 环己二胺、1,4-丁二胺、N,N-二甲基乙二胺、1,10-二氨基癸烷、N,N-二异丙基乙二胺、2-氯-5-甲基-1,4-苯二胺、N,N-二甲基对苯二胺、N-苯基邻苯二胺、N-(叔丁氧羰基)-1,4-丁二胺、N,N'-双(3-氨丙基)乙二胺、N,N′-双(2-羟乙基)乙二胺、N,N'-二苯基对苯二胺、1,2-环己二胺、4,5-二氟-1,2-苯二胺、N，N，N`-三苯基联苯二胺、2-(三氟甲基)-1,4-亚苯基二胺、N,N'-双(亚水杨基)-1,4-丁烷二胺、2-硝基-1,4-苯二胺、N,N′-二(2-氨乙基)-1,3-丙二胺、2,5-二氯-1,4-苯二胺、N,N,N',N'-四甲基-1,3-丙二胺、二(4-甲氧基苯)-1,2-乙二胺、9,10-二氢-9,10-乙撑蒽-11,12-二胺、四(4-甲氧基苯基)-[1,1'-联苯]-4,4'-二胺、二甲基-1,2-二苯基-1,2-乙二胺、N,N,N,N-四甲基-1,6-己二胺、N,N'-二甲基环己烷-1,2-二胺、1,2-二苯基-1,2-乙二胺、1,2-环己二胺、N,N-二乙基-1,3-丙二胺、3,6,9-三氧杂十一烷-1,11-二胺、N,N′-二甲基-1,3-丙二胺、4-(羟乙氧基)-1,3-苯二胺盐酸盐、N-甲基-1,2-苯二胺、三甲基己二胺、异佛尔酮二胺、2,7-二氨基芴、1,8-二氨基萘、1,12-二氨基十二烷、2,6-二氨基蒽醌、9,10-二氨基菲、2,4-二氨基苯甲醚、1,4-二氨基环己烷、1,5-二氨基戊烷、2,3-二氨基萘、2,3-二氨基甲苯、尿素、N,N′-乙烯基双丙烯酰胺、N-Boc-2,2′-(亚乙二氧基)二乙胺、联苯胺、三亚乙基四胺、1,4-苯二甲胺、N,N'-二甲基乙二胺、N-(2-羟乙基)乙二胺、N,N'-二甲基环己烷-1,2-二胺、N-(对甲苯磺酰基)-1,2-二苯基乙二胺、4,6-嘧啶二胺、4-乙酰氨基苯胺、乙二胺、草酰二胺、对苯二胺、1,6-己二胺、间苯二胺、二氰二胺、4-溴-1,2-苯二胺、N-Boc-间苯二胺、N-苄基乙二胺、萘乙二胺、4-硝基邻苯二胺、1,2-二苯基乙二胺、(1,1'-联萘)-2,2'-二胺、N-Boc-乙二胺、4-氯邻苯二胺、N-Boc-对苯二胺、N,N-二乙基乙二胺、4,5-二氯邻苯二胺、N,N′-二苯基乙二胺、1,8-辛二胺、4-氟-1,2-苯二胺、N-(2-羟乙基)乙二胺、间苯二胺、N-苯基对苯二胺、1,2-丙二胺、1,3-丙二胺、1,2-环己二胺、1,4-丁二胺、N,N-二甲基乙二胺、1,10-二氨基癸烷、N,N-二异丙基乙二胺、2-氯-5-甲基-1,4-苯二胺、N,N-二甲基对苯二胺、N-苯基邻苯二胺、N-(叔丁氧羰基)-1,4-丁二胺、N,N'-双(3-氨丙基)乙二胺、N,N′-双(2-羟乙基)乙二胺、N,N'-二苯基对苯二胺、1,2-环己二胺、4,5-二氟-1,2-苯二胺、N，N，N`-三苯基联苯二胺、2-(三氟甲基)-1,4-亚苯基二胺、N,N'-双(亚水杨基)-1,4-丁烷二胺、2-硝基-1,4-苯二胺、N,N′-二(2-氨乙基)-1,3-丙二胺、2,5-二氯-1,4-苯二胺、N,N,N',N'-四甲基-1,3-丙二胺、二(4-甲氧基苯)-1,2-乙二胺、9,10-二氢-9,10-乙撑蒽-11,12-二胺、四(4-甲氧基 苯基)-[1,1'-联苯]-4,4'-二胺、二甲基-1,2-二苯基-1,2-乙二胺、N,N,N,N-四甲基-1,6-己二胺、N,N'-二甲基环己烷-1,2-二胺、1,2-二苯基-1,2-乙二胺、1,2-环己二胺、N,N-二乙基-1,3-丙二胺、3,6,9-三氧杂十一烷-1,11-二胺、N,N′-二甲基-1,3-丙二胺、4-(羟乙氧基)-1,3-苯二胺盐酸盐、N-甲基-1,2-苯二胺、三甲基己二胺、异佛尔酮二胺、2,7-二氨基芴、1,8-二氨基萘、1,12-二氨基十二烷、2,6-二氨基蒽醌、9,10-二氨基菲、2,4-二氨基苯甲醚、1,4-二氨基环己烷、1,5-二氨基戊烷、2,3-二氨基萘、2,3-二氨基甲苯、尿素、N,N′-乙烯基双丙烯酰胺、N-Boc-2,2′-(亚乙二氧基)二乙胺、联苯胺、三亚乙基四胺、1,4-苯二甲胺、N,N'-二甲基乙二胺、N-(2-羟乙基)乙二胺、N,N'-二甲基环己烷-1,2-二胺、N-(对甲苯磺酰基)-1,2-二苯基乙二胺、4,6-嘧啶二胺、4-乙酰氨基苯胺、二巯基丙醇、2，4-二巯基嘧啶、2,6-二巯基嘌呤、1,6-己二硫醇、甲苯-3,4-二硫酚、1,3-丙二硫醇、1,2-乙二硫醇中的一种或几种的混合物。
优选地，所述聚氨酯交联剂为多元醇类、多元胺类、多元酸类、多元硫醇类化合物中的至少一种，包括但不限于三羟甲基丙烷三(3-巯基丙酸酯)、巯基丙酸季戊四醇酯、丙三醇、1-(对硝基苯)甘油、1,2,4-丁三醇、苦马豆素、1,2,4-苯三酚、植烷三醇、1,8,9-三羟基蒽、棓儿茶酸、儿茶素、1-脱氧野尻霉素、雌三醇、三(羟甲基)氨基甲烷、1-硫代甘油、钙三醇、三聚氰酸、季戊四醇、双季戊四醇、苏糖醇、赤藓醇、醌茜隐色体、伏格列波糖、二硫赤藓醇、木糖醇、甜醇、肌醇、山梨醇、碘海醇、N-丁基硫代磷酸三胺、1,4,7-三氮杂环壬烷、3,3'-二氨基二丙胺、三聚氰胺、三亚乙基四胺、3,3'-二氨基联苯胺中的一种或几种的混合物。
所述具有可逆三形状记忆效应的氨纶纤维的制备方法，包括如下步骤：
(1)将二异氰酸酯和有机锡催化剂溶于溶剂中，然后置于惰性气体保护的反应容器中，将单体A用溶剂溶解后加入上述反应容器中，25～100℃搅拌反应1～3h，然后加入适量聚氨酯扩链剂，搅拌反应1～3h，得到聚氨酯预聚物A；所述单体A为所述结晶性聚酯二醇或结晶性聚醚二醇；
(2)将二异氰酸酯和有机锡催化剂溶于溶剂中，然后置于惰性气体保护的反应容器中，将单体B用溶剂溶解后加入上述反应容器中，25～100℃搅拌反应1～3h，然后加入余量聚氨酯扩链剂，搅拌反应1～3h，得到聚氨酯预聚物B；所 述单体B为所述结晶性聚酯二醇或结晶性聚醚二醇、且与所述单体A为不同的物质；
(3)将步骤(1)得到的聚氨酯预聚物A与步骤(2)得到的聚氨酯预聚物B降至室温并混合均匀，然后加入聚氨酯交联剂，搅拌均匀，配制成纺丝原液；
(4)将步骤(3)得到的纺丝原液在真空条件及室温条件下进行脱泡，以确保纺丝原液中无气泡存在，然后将纺丝原液经过计量泵压入管道，经喷丝板上的喷丝口挤出纺丝原液细流，从喷丝口中喷出的纺丝原液细流进入热甬道后，纺丝原液中的溶剂被高温气流迅速蒸发并从甬道下出口回收，纺丝原液细流则凝固成长条丝状并细化，最后形成氨纶纤维；将氨纶纤维置于25～50℃下加热2～24h，使聚氨酯预聚物A和聚氨酯预聚物B与聚氨酯交联剂反应完全；
(5)将经步骤(4)处理的氨纶纤维进行加热，使其内部晶区熔融及氢键解离，然后通过牵伸使其进一步伸长并用夹具固定形变，然后降至室温，卸除夹具，使氨纶纤维收缩，然后升温至其熔限上限温度，使氨纶纤维进一步收缩，收缩结束后降至室温，即得所述具有可逆三形状记忆效应的氨纶纤维。
本发明所制备的氨纶纤维可逆三形状记忆效应的工作原理是：如图1所示，所述的氨纶纤维具有相分离结构，未经训练的氨纶纤维其内部的晶区是任意取向的；对其加热使其两种晶区完全融化且氢键解离；在此状态下将内部晶区完全融化的氨纶纤维进行拉伸，此时氨纶纤维内部的分子链在应力的作用下取向；将形变后的氨纶纤维两端固定并降至室温，此时氨纶纤维内部的两种结晶性软段将在外力作用下取向结晶，且其内部的氢键网络将重新生成，此时氢键网络处于不受力的状态；将氨纶纤维两端的固定去除并加热至其熔限上限温度，氨纶纤维内部的分子链将会熔融回缩从而使处于伸长状态的氨纶纤维回缩，但由于内部重新生成的氢键限制了氨纶纤维分子链的回缩程度，使其并不能完全回复到原始状态，此时重新生成的氢键网络处于受力状态；将温度降至室温后，其内部的结晶性软段将在氢键网络提供的应力作用下结晶并沿着此应力方向生长，从而氨纶纤维的宏观长度变长。经过以上训练过程后，氨纶纤维即具备了可逆形状记忆效应。由于氨纶纤维内部具有两种不同的结晶性软段，因此能够记忆两种临时形状。在使用时，只需将氨纶纤维的温度升高至使其中一种结晶性软段完全熔融，该结晶性软段将由熵值较小的取向结晶融化并转变为熵值较 大的无规线团状态，氨纶纤维在宏观上表现为长度缩短；当氨纶纤维温度继续升高至使另一种结晶性软段完全熔融，氨纶纤维在宏观上将继续收缩；当温度降低至使氨纶纤维的其中一种结晶性软段开始结晶，该处于熔融状态的软段分子链又在氢键网络提供的张应力作用下取向结晶，从而氨纶纤维宏观上表现为长度增加；当温度进一步降低，使氨纶纤维内部另外一种结晶性软段开始发生取向结晶，此时氨纶纤维在宏观上将进一步伸长。可见，本发明的氨纶纤维在上述三种形状之间可逆的形变过程是随温度变化循环往复的，实现了可逆三形状记忆效应。
下面将结合实施例对本发明的技术方案作进一步描述，显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。实施例中所使用的原料、溶剂和试剂均可通过市售购买获得。如无特别说明，实施例中提及的“份”均指重量份数。
实施例1
取1.11份1,6-己二异氰酸酯(HDI)和两滴二月桂酸二丁基锡(DBTDL)溶于适量二氯甲烷中，置于60℃氩气保护的三口烧瓶中，将9份聚己内酯二元醇溶于适量二氯甲烷中，然后加入三口烧瓶中搅拌反应1h，然后加入0.13份扩链剂1,4-丁二醇(BDO)搅拌反应1h，得到聚氨酯预聚物A；取2.59份1,6-己二异氰酸酯(HDI)和两滴二月桂酸二丁基锡(DBTDL)溶于适量二氯甲烷中，置于60℃氩气保护的三口烧瓶中，将20.3份聚四氢呋喃二元醇溶于适量二氯甲烷中，然后加入三口烧瓶中搅拌反应1h，然后加入0.3份扩链剂1,4-丁二醇(BDO)搅拌反应1h，得到聚氨酯预聚物B；将冷却至室温后的聚氨酯预聚物A和聚氨酯预聚物B混合搅拌30min后，加入1.91份交联剂三羟基丙烷三(3-巯基丙烯酸酯)(TMPMP)搅拌均匀，然后通过调控所用二氯甲烷的用量，配制成质量分数为35％的纺丝原液。
将纺丝原液在真空条件及室温条件下进行脱泡30min，确保纺丝原液中无气泡存在。纺丝原液经过计量泵压入管道，经喷丝板上的喷丝口挤出纺丝原液细流，从喷丝口中喷出的纺丝原液细流进入120℃热甬道后，纺丝原液中的溶剂被 高温气流迅速蒸发并从甬道下出口回收，纺丝原液细流则凝固成长条丝状并细化，最后形成氨纶纤维。将氨纶纤维置于50℃下加热2h，使聚氨酯预聚物与聚氨酯交联剂反应完全。
将氨纶纤维加热使其内部晶区熔融及氢键解离，后通过牵伸使其进一步伸长并用夹具固定形变，后降至室温，去除固定氨纶纤维的夹具，氨纶纤维将轻微收缩。后升温至其熔限上限温度，此时氨纶纤维将发生进一步收缩，收缩结束后即得到具有可逆三形状记忆效应的氨纶纤维。
实施例2
取1.85份1,6-己二异氰酸酯(HDI)和两滴二月桂酸二丁基锡溶于适量二氯甲烷中，置于60℃氩气保护的三口烧瓶中，将15份聚己内酯二元醇溶于适量二氯甲烷中，然后加入三口烧瓶中搅拌反应1h，然后加入0.22份扩链剂1,4-丁二醇搅拌反应1h，得到聚氨酯预聚物A；取1.85份1,6-己二异氰酸酯和两滴二月桂酸二丁基锡溶于适量二氯甲烷中，置于60℃氩气保护的三口烧瓶中，将14.5份聚四氢呋喃二元醇溶于适量二氯甲烷中，然后加入三口烧瓶中搅拌反应1h，然后加入0.3份扩链剂1,4-丁二醇搅拌反应1h，得到聚氨酯预聚物B；将冷却至室温后的聚氨酯预聚物A和聚氨酯预聚物B混合搅拌30min后，加入1.91份交联剂三羟基丙烷三(3-巯基丙烯酸酯)搅拌均匀，通过调控所用二氯甲烷的用量，配制成质量分数为35％的纺丝原液。
将纺丝原液在真空条件及室温条件下进行脱泡30min，确保纺丝原液中无气泡存在。纺丝原液经过计量泵压入管道，经喷丝板上的喷丝口挤出纺丝原液细流，从喷丝口中喷出的纺丝原液细流进入120℃热甬道后，纺丝原液中的溶剂被高温气流迅速蒸发并从甬道下出口回收，纺丝原液细流则凝固成长条丝状并细化，最后形成氨纶纤维。将氨纶纤维置于50℃下加热2h，使聚氨酯预聚物与聚氨酯交联剂反应完全。
将氨纶纤维加热使其内部晶区熔融及氢键解离，后通过牵伸使其进一步伸长并用夹具固定形变，后降至室温，去除固定氨纶纤维的夹具，氨纶纤维将轻微收缩。后升温至其熔限上限温度，此时氨纶纤维将发生进一步收缩，收缩结束 后即得到具有可逆三形状记忆效应的氨纶纤维。
实施例3
取2.75份二苯基甲烷二异氰酸酯和两滴二月桂酸二丁基锡溶于适量二氯甲烷中，置于60℃氩气保护的三口烧瓶中，将15份聚己内酯二元醇溶于适量二氯甲烷中，然后加入三口烧瓶中搅拌反应1h，然后加入0.22份扩链剂1,4-丁二醇搅拌反应1h，得到聚氨酯预聚物A；取2.75份二苯基甲烷二异氰酸酯和两滴二月桂酸二丁基锡溶于适量二氯甲烷中，置于60℃氩气保护的三口烧瓶中，将14.5份聚四氢呋喃二元醇溶于适量二氯甲烷中，然后加入三口烧瓶中搅拌反应1h，然后加入0.3份扩链剂1,4-丁二醇搅拌反应1h，得到聚氨酯预聚物B；将冷却至室温后的聚氨酯预聚物A和聚氨酯预聚物B混合搅拌30min后，加入1.91份交联剂三羟基丙烷三(3-巯基丙烯酸酯)搅拌均匀，通过调控所用二氯甲烷的用量，配制成质量分数为35％的纺丝原液。
将纺丝原液在真空条件及室温条件下进行脱泡30min，确保纺丝原液中无气泡存在。纺丝原液经过计量泵压入管道，经喷丝板上的喷丝口挤出纺丝原液细流，从喷丝口中喷出的纺丝原液细流进入120℃热甬道后，纺丝原液中的溶剂被高温气流迅速蒸发并从甬道下出口回收，纺丝原液细流则凝固成长条丝状并细化，最后形成氨纶纤维。将氨纶纤维置于50℃下加热2h，使聚氨酯预聚物与聚氨酯交联剂反应完全。
将氨纶纤维加热使其内部晶区熔融及氢键解离，后通过牵伸使其进一步伸长并用夹具固定形变，后降至室温，去除固定氨纶纤维的夹具，氨纶纤维将轻微收缩。后升温至其熔限上限温度，此时氨纶纤维将发生进一步收缩，收缩结束后即得到具有可逆三形状记忆效应的氨纶纤维。
实施例4
取1.11份1,6-己二异氰酸酯和两滴二月桂酸二丁基锡溶于适量二氯甲烷中，置于60℃氩气保护的三口烧瓶中，将9份聚己内酯二元醇溶于适量二氯甲烷中，然后加入三口烧瓶中搅拌反应1h，然后加入0.13份扩链剂1,4-丁二醇搅拌反应1h，得到聚氨酯预聚物A；取2.59份1,6-己二异氰酸酯和两滴二月桂酸二丁基 锡溶于适量二氯甲烷中，置于60℃氩气保护的三口烧瓶中，将20.3份聚四氢呋喃二元醇溶于适量二氯甲烷中，然后加入三口烧瓶中搅拌反应1h，然后加入0.3份扩链剂1,4-丁二醇(BDO)搅拌反应1h，得到聚氨酯预聚物B；将冷却至室温后的聚氨酯预聚物A和聚氨酯预聚物B混合搅拌30min后，加入0.6份交联剂丙三醇搅拌均匀，通过调控所用二氯甲烷的用量，配制成质量分数为35％的纺丝原液。
将纺丝原液在真空条件及室温条件下进行脱泡30min，确保纺丝原液中无气泡存在。纺丝原液经过计量泵压入管道，经喷丝板上的喷丝口挤出纺丝原液细流，从喷丝口中喷出的纺丝原液细流进入120℃热甬道后，纺丝原液中的溶剂被高温气流迅速蒸发并从甬道下出口回收，纺丝原液细流则凝固成长条丝状并细化，最后形成氨纶纤维。将氨纶纤维置于50℃下加热2h，使聚氨酯预聚物与聚氨酯交联剂反应完全。
将氨纶纤维加热使其内部晶区熔融及氢键解离，后通过牵伸使其进一步伸长并用夹具固定形变，后降至室温，去除固定氨纶纤维的夹具，氨纶纤维将轻微收缩。后升温至其熔限上限温度，此时氨纶纤维将发生进一步收缩，收缩结束后即得到具有可逆三形状记忆效应的氨纶纤维。
实施例5
取1.85份1,6-己二异氰酸酯和两滴二月桂酸二丁基锡溶于适量二氯甲烷中，置于60℃氩气保护的三口烧瓶中，将15份聚己内酯二元醇溶于适量二氯甲烷中，然后加入三口烧瓶中搅拌反应1h，然后加入0.15份扩链剂乙二醇搅拌反应1h，得到聚氨酯预聚物A；取1.85份1,6-己二异氰酸酯和两滴二月桂酸二丁基锡溶于适量二氯甲烷中，置于60℃氩气保护的三口烧瓶中，将14.5份聚四氢呋喃二元醇溶于适量二氯甲烷中，然后加入三口烧瓶中搅拌反应1h，然后加入0.15份扩链剂乙二醇搅拌反应1h，得到聚氨酯预聚物B；将冷却至室温后的聚氨酯预聚物A和聚氨酯预聚物B混合搅拌30min后，加入1.91份交联剂三羟基丙烷三(3-巯基丙烯酸酯)搅拌均匀，通过调控所用二氯甲烷的用量，配制成质量分数为35％的纺丝原液。
将纺丝原液在真空条件及室温条件下进行脱泡30min，确保纺丝原液中无气泡存在。纺丝原液经过计量泵压入管道，经喷丝板上的喷丝口挤出纺丝原液细流，从喷丝口中喷出的纺丝原液细流进入120℃热甬道后，纺丝原液中的溶剂被高温气流迅速蒸发并从甬道下出口回收，纺丝原液细流则凝固成长条丝状并细化，最后形成氨纶纤维。将氨纶纤维置于50℃下加热2h，使聚氨酯预聚物与聚氨酯交联剂反应完全。
将氨纶纤维加热使其内部晶区熔融及氢键解离，后通过牵伸使其进一步伸长并用夹具固定形变，后降至室温，去除固定氨纶纤维的夹具，氨纶纤维将轻微收缩。后升温至其熔限上限温度，此时氨纶纤维将发生进一步收缩，收缩结束后即得到具有可逆三形状记忆效应的氨纶纤维。
对比例1
取1.85份1,6-己二异氰酸酯和两滴二月桂酸二丁基锡溶于适量二氯甲烷中，置于60℃氩气保护的三口烧瓶中，将15份聚己内酯二元醇溶于适量二氯甲烷中，然后加入三口烧瓶中搅拌反应1h，然后加入0.22份扩链剂1,4-丁二醇搅拌反应1h，得到聚氨酯预聚物；将得到的聚氨酯预聚物冷却至室温后，加入0.96份交联剂三羟基丙烷三(3-巯基丙烯酸酯)搅拌均匀，通过调控所用二氯甲烷的用量，配制成质量分数为35％的纺丝原液。
将纺丝原液在真空条件及室温条件下进行脱泡30min，确保纺丝原液中无气泡存在。纺丝原液经过计量泵压入管道，经喷丝板上的喷丝口挤出纺丝原液细流，从喷丝口中喷出的纺丝原液细流进入120℃热甬道后，纺丝原液中的溶剂被高温气流迅速蒸发并从甬道下出口回收，纺丝原液细流则凝固成长条丝状并细化，最后形成氨纶纤维。将氨纶纤维置于50℃下加热2h，使聚氨酯预聚物与聚氨酯交联剂反应完全。
将氨纶纤维加热使其内部晶区熔融及氢键解离，后通过牵伸使其进一步伸长并用夹具固定形变，后降至室温，去除固定氨纶纤维的夹具，氨纶纤维将轻微收缩。后升温至其熔限上限温度，此时氨纶纤维将发生进一步收缩，收缩结束后即得到具有可逆形状记忆效应的氨纶纤维。
对比例2
取1.11份1,6-己二异氰酸酯和两滴二月桂酸二丁基锡溶于适量二氯甲烷中，置于60℃氩气保护的三口烧瓶中，将9份聚己内酯二元醇溶于适量二氯甲烷中，然后加入三口烧瓶中搅拌反应1h，然后加入0.13份扩链剂1,4-丁二醇搅拌反应1h，得到聚氨酯预聚物A；取2.59份1,6-己二异氰酸酯和两滴二月桂酸二丁基锡溶于适量二氯甲烷中，置于60℃氩气保护的三口烧瓶中，将20.3份聚四氢呋喃二元醇溶于适量二氯甲烷中，然后加入三口烧瓶中搅拌反应1h，然后加入0.3份扩链剂1,4-丁二醇(BDO)搅拌反应1h，得到聚氨酯预聚物B；将冷却至室温后的聚氨酯预聚物A和聚氨酯预聚物B混合搅拌30min后，加入1.91份交联剂三羟基丙烷三(3-巯基丙烯酸酯)搅拌均匀，通过调控所用溶剂的用量，配制成质量分数为35％的纺丝原液。
将纺丝原液在真空条件及室温条件下进行脱泡30min，确保纺丝原液中无气泡存在。纺丝原液经过计量泵压入管道，经喷丝板上的喷丝口挤出纺丝原液细流，从喷丝口中喷出的纺丝原液细流进入120℃热甬道后，纺丝原液中的溶剂被高温气流迅速蒸发并从甬道下出口回收，纺丝原液细流则凝固成长条丝状并细化，最后形成氨纶纤维。
性能测试：
通过动态热机械分析仪(DMA)评价所得材料的可逆形状记忆效应，将实施例1～5和对比例1～2所得的氨纶纤维裁切成符合DMA测试要求的纤维试样，进行DMA测试。测试条件为：拉伸模式，在不施加任何应力的条件下，从-20℃为起点以1℃/min的升温速率升温至60℃，恒温2min，后以1℃/min的降温速率降温至-20℃，恒温2min，测试在上述温度变化过程中，被测样条的应变随温度的变化。重复5次上述变温过程，并计算5个循环中被测试样应变平均值，测试结果见表1。
表1氨纶纤维的可逆应变测试结果
Figure PCTCN2021102662-appb-000008
Figure PCTCN2021102662-appb-000009
最后所应当说明的是，以上实施例仅用以说明本发明的技术方案而非对本发明保护范围的限制，尽管参照较佳实施例对本发明作了详细说明，本领域技术人员应当理解，可以对本发明的技术方案进行修改或者等同替换，而不脱离本发明技术方案的实质和范围。

Claims (10)

  1. 一种具有可逆三形状记忆效应的氨纶纤维，其特征在于，包括如下重量份的原料：
    Figure PCTCN2021102662-appb-100001
    所述结晶性聚酯二醇或结晶性聚醚二醇的数均分子量为1000～10000。
  2. 如权利要求1所述的具有可逆三形状记忆效应的氨纶纤维，其特征在于，所述的结晶性聚酯二醇或结晶性聚醚二醇为如下结构式化合物中的至少两种：
    Figure PCTCN2021102662-appb-100002
  3. 如权利要求1所述的具有可逆三形状记忆效应的氨纶纤维，其特征在于，所述的二异氰酸酯为如下结构式化合物中的至少一种：
    Figure PCTCN2021102662-appb-100003
  4. 如权利要求1所述的具有可逆三形状记忆效应的氨纶纤维，其特征在于，所述聚氨酯扩链剂为二元醇类、二元胺类、二元酸类、二元硫醇类化合物中的至少一种。
  5. 如权利要求1所述的具有可逆三形状记忆效应的氨纶纤维，其特征在于，所述聚氨酯交联剂为多元醇类、多元胺类、多元酸类、多元硫醇类化合物中的至少一种。
  6. 如权利要求1～5任一项所述的具有可逆三形状记忆效应的氨纶纤维的制备方法，其特征在于，包括如下步骤：
    (1)通过二异氰酸酯、单体A、以及聚氨酯扩链剂合成聚氨酯预聚物A，所述单体A为所述结晶性聚酯二醇或结晶性聚醚二醇；
    (2)通过二异氰酸酯、单体B、以及聚氨酯扩链剂合成聚氨酯预聚物B，所述单体B为所述结晶性聚酯二醇或结晶性聚醚二醇、且与所述单体A为不同的物质；
    (3)将步骤(1)得到的聚氨酯预聚物A与步骤(2)得到的聚氨酯预聚物B降至室温并混合均匀，然后加入聚氨酯交联剂，搅拌均匀，配制成纺丝原液；
    (4)将步骤(3)得到的纺丝原液完全脱泡，然后通过纺丝工艺形成氨纶纤维，然后将氨纶纤维进行加热，使聚氨酯预聚物A和聚氨酯预聚物B与聚氨酯交联剂反应完全；
    (5)将经步骤(4)处理的氨纶纤维进行加热，使其内部晶区熔融及氢键解离，然后通过牵伸使其进一步伸长并用夹具固定形变，然后降至室温，卸除夹具，使氨纶纤维收缩，然后升温至其熔限上限温度，使氨纶纤维进一步收缩，收缩结束后降至室温，即得所述具有可逆三形状记忆效应的氨纶纤维。
  7. 如权利要求6所述的具有可逆三形状记忆效应的氨纶纤维的制备方法，其特征在于，所述步骤(1)和所述步骤(2)的合成反应在惰性气体保护下进行，反应温度为25～100℃。
  8. 如权利要求6所述的具有可逆三形状记忆效应的氨纶纤维的制备方法，其特征在于，所述步骤(1)和所述步骤(2)的合成反应过程中还加入了有机锡催化剂。
  9. 如权利要求6所述的具有可逆三形状记忆效应的氨纶纤维的制备方法，其特征在于，所述步骤(4)中，对氨纶纤维进行加热的条件为25～50℃下加热2～24h。
  10. 如权利要求1～5任一项所述的具有可逆三形状记忆效应的氨纶纤维在智能聚合物材料、智能纺织品、驱动器、软机器人和4D打印领域中的应用。
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CN114031742B (zh) * 2021-12-15 2023-03-21 河北邦泰氨纶科技有限公司 一种生物可降解熔纺氨纶切片及其制备方法和应用
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