CN117488480A - Asymmetric functional fiber membrane and preparation method and application thereof - Google Patents

Asymmetric functional fiber membrane and preparation method and application thereof Download PDF

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Publication number
CN117488480A
CN117488480A CN202410005079.0A CN202410005079A CN117488480A CN 117488480 A CN117488480 A CN 117488480A CN 202410005079 A CN202410005079 A CN 202410005079A CN 117488480 A CN117488480 A CN 117488480A
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spinning
layer
functional
photo
metal organic
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CN117488480B (en
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熊佳庆
张雨凡
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Donghua University
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Donghua University
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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
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/10—Other agents for modifying properties
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
    • D04H1/4374—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece using different kinds of webs, e.g. by layering webs
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
    • D04H1/4382—Stretched reticular film fibres; Composite fibres; Mixed fibres; Ultrafine fibres; Fibres for artificial leather
    • D04H1/43835—Mixed fibres, e.g. at least two chemically different fibres or fibre blends
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/70—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres
    • D04H1/72—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged
    • D04H1/728—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged by electro-spinning

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Laminated Bodies (AREA)

Abstract

The invention relates to an asymmetric functional fiber membrane, a preparation method and application thereof, belonging to the field of functional materials. The functional layer material component comprises a hydrophobic polymer and a metal organic framework intercalation photo-thermal material; the transition layer has a structural gradient, the content of the integral metal organic framework intercalation photo-thermal material gradually decreases from the functional layer to the inert layer, and obvious wettability gradient change is formed in the thickness direction of the transition layer; the inert layer is a hydrophobic polymer. The asymmetric functional fiber membrane developed by the invention has the advantages of mild preparation process conditions, low requirements on materials and processing environments, strong adjustability of components and structural properties and large scale production potential. The designed asymmetric functional fiber membrane preparation strategy is widely suitable for diversified organic and inorganic functional materials, the fiber membrane can be customized and designed according to different functional requirements, and compared with the traditional sheet structure, the asymmetric functional fiber membrane preparation strategy has better integration compatibility with other functional components, and various advanced intelligent devices can be easily developed.

Description

Asymmetric functional fiber membrane and preparation method and application thereof
Technical Field
The invention belongs to the field of functional materials, and particularly relates to an asymmetric functional fiber membrane, and a preparation method and application thereof.
Background
The breathable and moisture-conducting property, the warmth retention/coolness property and the electric intelligent property of the clothes/fabrics are of great significance for meeting the wearing requirements of extreme dry-cold or wet-heat scenes such as outdoor activities, polar work, individual combat and the like. Intelligent electronic fibers/fabrics have shown good potential in the fields of human body intelligent thermal management and wearable electronic carriers, can convert specific infrared radiation in the human body/environment into controllable heat energy and realize active warm or cool effects. However, the current electronic fiber/fabric material has a single function, and cannot achieve both active moisture control and accurate thermal energy management. The traditional fiber/fabric cannot take the synergistic effect of the above functions together no matter in terms of material properties and structural functions, and has the main problems that the material with good wearing comfort needs excellent humidity (sweat and the like) leading-out performance, but the leading-out of the humidity in a dry and cold environment inevitably takes away the heat of a human body, so that the thermal insulation effect is reduced, and the material with good wearing comfort has the functions of directional dehumidification and dynamic heat compensation management which are particularly important for improving the wearing comfort of the human body. The integrated processing and forming are adopted to accurately regulate and control the hierarchical structure and the function of the fiber materials and to realize the cooperative-compensation control of the materials on the moisture and the heat energy, and the method has important significance in promoting the breakthrough development of the fiber material industry in the fields of multiple energy management and control and intelligent wearing in China.
The traditional technology is mainly selected from spin coating, deposition and pouring methods or adopts a mode of later adhesive bonding or tape bonding and the like to realize effective combination of different materials so as to meet the requirement of integrating multiple functions.
For the above research, although the conventional multifunctional film processing mode is relatively simple and has lower production cost, the defects of compact film structure, poor comfort, low space adjustability of functional particles and polymers, incapability of realizing accurate control of the film thickness and proportion of each layer and the like exist. The existing processing method cannot meet the requirements of accurate regulation and differentiation layout of the hierarchical structure and the functional effect of the fiber materials, meanwhile, the compact structure and the functional materials are limited by the membrane structural design, active moisture regulation and accurate thermal energy management of the fiber membranes are difficult to realize, and effective application of the intelligent wearable fabric is limited.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide an asymmetric functional fiber membrane as well as a preparation method and application thereof.
The asymmetric functional fiber membrane comprises a functional layer, a transition layer and an inert layer in sequence; wherein the functional layer material component comprises a hydrophobic polymer, a photo-thermal filler and a metal organic framework material; the transition layer material comprises hydrophobic polymer, photo-thermal filler and metal organic frame material, and the transition layer has a structural gradient, and the contents of the metal organic frame material and the photo-thermal material gradually decrease from the functional layer to the inert layer; the inert layer material component comprises a hydrophobic polymer.
The asymmetric functional fiber membrane has significant functional differential performance under different environmental conditions. The environment conditions triggered by the fiber membrane differentiation function are a dry-cold environment and a wet-hot environment respectively, and the environment conditions comprise sleeping, static state, movement and the like of a human body.
Further, the fiber membrane shows a warm-keeping effect when the body surface microenvironment is in a dry and cold (sleep, rest) state; exhibits a directional dehumidifying effect in a damp-heat (exercise) state.
Further, the functional layer is far away from the skin layer, and the inert layer is a skin-sticking layer.
Preferably, the thickness of the asymmetric functional fiber membrane is 60-100 μm.
Preferably, the transition layer has a structural gradient, the contents of the metal organic framework material and the photo-thermal material gradually decrease from the functional layer to the inert layer, and multistage continuous guiding and conveying of interlayer moisture under the difference of wettability are realized; the difference of photo-thermal management performance of the functional layer and the inert layer is enlarged, and the precise energy management (dry cooling, warm keeping, wet heating and heat dissipation) under multiple scenes is realized.
The inert layer material component comprises a hydrophobic polymer.
The fiber transition layer has a structural gradient, the spinning solution A and the spinning solution B in the spinning of the transition layer are controlled to spray at the same time so as to realize the function gradient design of the transition layer, the content of the integral metal organic framework intercalation photo-thermal material is gradually decreased from the functional layer to the inert layer, obvious wettability gradient change is formed in the thickness direction of the transition layer, the hygroscopicity difference is enlarged, and moisture can be spontaneously conducted from the hydrophobic surface to the hydrophilic surface through the transition layer; the gradient layer of the transition layer structure is optimized, so that the capillary effect of the hydrophilic-hydrophobic interface can be enhanced, the directional transmission of moisture can be realized, and the effects of mutual fusion of the interfaces and enhanced moisture regulation and control can be achieved.
Preferably, the hydrophobic polymer comprises one or more of polyvinylidene fluoride, polyurethane, p-styrene-isoprene, polystyrene, polypropylene and polylactic acid.
Preferably, the photo-thermal filler comprises one or more of a zero-dimensional material, a one-dimensional material and a two-dimensional material; wherein the zero-dimensional material comprises one or more of gold nanoparticles, silver nanoparticles and zinc oxide nanoparticles; the one-dimensional material comprises one or more of gold nanowires, silver nanowires, copper nanowires and carbon nanotubes; the two-dimensional material comprises one or more of graphene, graphene oxide and transition metal carbide MXene.
And the filler in the functional layer realizes a heat management and control effect.
Further preferably, the photo-thermal filler is a two-dimensional material.
Such as MXene. The filler material has the advantages of high flexibility, easy integration, low IR, high conductivity, excellent active heat management performance, high efficiency of passive Joule heating performance and the like, and can effectively improve the dynamic management and control of the fiber on the body surface heat radiation as a functional material in the wearable fabric.
The MXene is formed by etching and stripping titanium aluminum carbide serving as a raw material in a hydrochloric acid/lithium fluoride system, wherein the mass ratio of the titanium aluminum carbide to the lithium fluoride is 2:1-1:5, and the mass ratio of the lithium fluoride to the hydrochloric acid to the volume ratio is 1:1-1:20 (g: mL).
Preferably, in order to realize moisture regulation and control, hydrophilic-hydrophobic differential design and transition layer capillary effect are constructed on two sides of the fiber membrane.
Preferably, the metal organic framework material comprises MIL-100, MIL-47, MIL-53, MIL-88A, MIL-101, MIL-125-NH 2 、SHF-61、SHF-62、SHF-81、CAU-10-H、Co 2 Cl 2 One or more of (BTDD), Y-shp-MOF-5 and MIL-101 (Cr).
Further preferably, the metal organic framework material is a cavity structure and water stable metal organic framework material.
For example, the metal organic framework material is MIL-125-NH 2 MIL-88A. The metal organic frame has the advantages of high hygroscopicity, high geometric space form adjustability, nanoscale size, rich cavities and various compound modes with other functional components, and can be used as a moisture absorption material to expand the hydrophilic-hydrophobic difference at two sides of asymmetric fibers, thereby effectively improving the conveying efficiency and the somatosensory comfort of directional adjustment of moisture.
The MIL-125-NH 2 From titanium isopropoxide as Ti source, 2-amino-1, 4-phthalic acid (NH) 2 -BDC) as an organism linking agent; wherein titanium isopropoxide and NH 2 The molar ratio of BDC is 5:1-1:5, and the solvent comprises one or more of deionized water, ethanol, methanol, N-dimethylformamide, N-dimethylacetamide and chloroform.
Preferably, the mass ratio of the total amount of the metal organic framework material and the photo-thermal material in the functional layer to the hydrophobic polymer is 10:1-1:200; the mass ratio of the photo-thermal filler to the metal organic frame material is 10:1-1:5; the thickness ratio of the functional layer to the transition layer to the inert layer is 10:1:2-2:1:10.
Preferably, the metal organic framework material and the filler are combined in an inserting or compounding way; i.e. a metal organic framework intercalated with a photo-thermal material or a mixture of metal organic framework and photo-thermal material.
The metal organic framework material and/or the photo-thermal material are embedded, partially distributed or densely distributed in the hydrophobic polymer.
Further preferably, the metal organic framework is intercalated with the photo-thermal material in a manner of being embedded or partially arranged on the surface of the hydrophobic polymer fiber.
The metal organic framework intercalation photo-thermal material is prepared by mixing metal organic framework material raw materials with the photo-thermal material and performing hydrothermal reaction.
The preparation method of the asymmetric functional fiber membrane comprises the following steps:
mixing a metal organic frame material, a photo-thermal filler, a hydrophobic polymer and a solvent, and stirring to obtain a spinning solution A;
mixing a hydrophobic polymer and a solvent to obtain a spinning solution B;
spinning the spinning solution A to obtain a functional layer, continuously spinning the spinning solution A, and simultaneously spinning the solution B to prepare a transition layer; and finally, spinning the solution B independently to obtain the asymmetric functional fiber membrane.
The adding mode of the metal organic frame material and the photo-thermal filler in the spinning solution A comprises the step of adding or respectively adding the metal organic frame material and the photo-thermal filler in a mode of inserting the photo-thermal material into the metal organic frame.
Preferably, the solvent comprises one or more of deionized water, ethanol, methanol, isopropanol, N-dimethylformamide, N-dimethylacetamide, tetrahydrofuran, chloroform, acetone, toluene, pyridine and thionyl chloride.
Preferably, the spinning mode comprises one or more of dry spinning, wet spinning, microfluidic spinning, electrostatic spinning and melt-blown spinning.
The stirring temperature of the spinning solution is 20-80 ℃ and the stirring time is 1-24 h.
Further preferably, the spinning is electrostatic spinning.
Preferably, the concentration of the hydrophobic polymer in the spinning solution A and the spinning solution B is 1 wt% -50 wt%; the mass ratio of the total amount of the metal organic frame material and the photo-thermal material to the hydrophobic polymer is 10:1-1:200; the mass ratio of the photo-thermal filler to the metal organic frame material is 10:1-1:5; the thickness ratio of the functional layer to the transition layer to the inert layer is 10:1:2-2:1:10.
In the preparation method, the spinning solution A is subjected to spinning to obtain a functional layer, and the functional layer fiber is controlled to be partially solidified when reaching the substrate by adjusting the spinning advancing rate and the temperature in the latter half stage.
In the preparation process of the transition layer, the advancing rates of the spinning solution of the functional layer and the spinning solution of the inert layer at the same time are changed in a time-sharing manner, so that the contents of the metal organic framework material and the photo-thermal material in the transition layer gradually decrease from the functional layer to the inert layer.
Spinning the spinning solution A to obtain a functional layer, wherein the spinning process parameters are as follows: with 15-20kV voltage, 15-20 cm receiving distance, 600-1500 r rotating speed, 1-2 mL h -1 Spinning is carried out at the advancing speed, and a heating lamp is turned on in the whole process or the temperature is raised by 28-35 ℃ so as to accelerate the real-time solidification of the fibers on the receiver. Turning off the heating lamp or cooling to 20-25deg.C for 5-10min at the last 5-10min of spinning, and increasing the advancing speed to 2-3mL h -1 And controlling partial solidification when the functional layer fiber reaches the substrate, and realizing mutual adhesion with the inert layer fiber of the subsequent electrospinning so as to form transition layers with different gradient layers.
Spinning solution A continues spinning, and spinning solution B simultaneously, so as to prepare a transition layer; the method comprises the following steps: spinning is carried out in 2-3 time periods, the first 1/2 or 1/3 spinning time is used for respectively controlling the advancing rate ratio of the spinning solution A to the spinning solution B to be 3:1-2:1, the second 1/2 or 1/3 spinning time is used for adjusting the advancing rate ratio of the spinning solution A to the spinning solution B to be 1:1-1:2, and the advancing rate of the spinning solution A to the spinning solution B to be 1:3-1:5 is not carried out in the third time period or the last 1/3 spinning. The content of the metal organic framework intercalation photo-thermal material in the transition layer gradually decreases from the functional layer to the inert layer, obvious wettability gradient change is formed in the thickness direction of the transition layer, the capillary effect of the hydrophilic-hydrophobic interface is enhanced, and the directional transmission of moisture is accelerated.
And finally, spinning the solution B independently, wherein the spinning is carried out at a voltage of 15-20kV, a receiving distance of 15-20 cm and a rotating speed of 600-1500 r. The first 5-10min under the condition of no heating (20-25 ℃) with the temperature of 2-3mL h -1 Advancing to strengthen the connection of the transition layer fiber and the inert layer, and then adjusting the advancing speed to be 1-2 mL h -1 The heating lamp is turned on or the temperature is raised (28-35 ℃) to accelerate the real-time solidification of the fiber on the receiver, an asymmetric functional fiber film of a functional layer-a transition layer-an inert layer is formed, and active and efficient moisture (sweat) removal under the hot and humid environment is realized; meanwhile, the photo-thermal material and the polymer fiber can jointly construct a micro-nano multi-level structure fiber membrane with heat radiation management function and directional moisture transmission, so as to meet the requirements of heat dynamic compensation under dry and cold environment conditions, active heat dissipation under wet and hot conditions and rapidnessDirectional dehumidifying function.
The invention relates to a preparation method of an asymmetric functional fiber membrane, which comprises the following steps: firstly, mixing a metal organic frame, a photo-thermal filler, a hydrophobic polymer and a solvent, stirring to obtain a functional spinning solution for spinning, adjusting spinning parameters (improving the advancing rate and turning off a heating lamp) in the latter half stage, and controlling the functional layer fiber to be partially solidified when reaching a substrate; simultaneously, electro-spinning the inert layer fiber to realize the mutual bonding of two materials, accurately controlling the spinning quantity of two spinning solutions at the same time, developing a transition layer with a multistage gradual gradient structure (the content of the metal organic framework intercalation photo-thermal material gradually decreases from a functional layer to an inert layer), strengthening the capillary effect, and finally, independently using the inert layer to construct the wettability of two sides and the difference of the photo-thermal management performance of the two sides; a fiber membrane with asymmetric functionality is obtained.
The application of the asymmetric functional fiber membrane in the fields of information, energy, medical treatment or intelligent response.
Preferably, the application of the information field comprises a sensing or information interaction device.
Preferably, the application of the energy field comprises an energy harvesting or energy management device.
Preferably, the medical field of application comprises a flexible or wearable medical device.
Preferably, the application in the intelligent response field comprises an application in the field of artificial muscle, soft robot or human-computer interaction.
The invention prepares the octahedral structure metal organic framework MIL-125-NH by regulating and controlling a titanium source 2 Nano materials are introduced into the functional layer to enlarge the hydrophilic-hydrophobic difference of the two sides of the film, so that active and efficient moisture removal of moisture (sweat) in a hot-tidal environment is realized; on the basis, the material is effectively combined with a photo-thermal material (such as MIL-125-NH with rich cavity structure 2 In-situ combination of MXene materials on particles, intercalation treatment and the like), and can jointly construct a micro-nano multi-stage structure fiber membrane with heat radiation management function and directional moisture transmission with polymer fibers so as to meet the requirements of dynamic heat compensation under dry and cold environment conditions and active heat dissipation under wet and hot conditionsHeat and rapid directional moisture removal.
The invention adopts the integrated spinning technology of intermittent temperature control spinning-interface anchoring effect-structure gradient assembly, and can realize the development of an asymmetric functional fiber membrane. Specifically, in continuous electrospinning, the curing speed of the asymmetric functional fiber transition layer is regulated and controlled by intermittently changing the environmental temperature and humidity conditions. Selecting a hydrophobic polymer as an electrostatic spinning raw material, firstly spinning a functional layer, adjusting spinning parameters (improving the advancing rate and closing heating) in the next 10min, controlling partial solidification when the functional layer fiber reaches a substrate, realizing the mutual bonding with the fiber of a subsequent electrospinning transition layer and the self-anchoring effect between asymmetric functional fiber layers, and improving the interface stability of a fiber membrane; the micro-nano fiber membranes with different gradient layers can be processed by precisely controlling the spinning parameters of the transition layer stage (namely changing the advancing rate of the functional layer spinning solution and the inert layer spinning solution at the same time in a time-sharing manner), and the method can break the barriers of poor interfacial compatibility among different materials and realize precise design and customized assembly of different functional fiber layers.
The differentiation function of the invention is triggered by moisture and temperature factors, and the functional fiber layer is formed by photo-thermal materials (such as low IR value two-dimensional filler MXene and the like) and metal organic frame materials (such as MIL-125-NH with multiple cavities 2 Etc.), a thermal radiation capturing barrier and a graded hydrophilic pathway are created. Wherein the metal organic framework material (e.g. MIL-125-NH 2 ) The enhanced differential wettability and volume shrinkage after water absorption can induce capillary effect between gradient transition layers, so as to realize high-efficiency directional transportation of surface sweat (water vapor) in a damp-heat state (such as from a skin-sticking inner layer to a functional layer) and active heat dissipation. In a dry and cold state, the fiber film keeps dry and comfortable, is protected by the low emission performance of photo-thermal materials (such as MXene and the like) on heat radiation, saves the body surface heat to the greatest extent, effectively prevents the heat radiation from escaping from the fiber film, and improves the warm-keeping effect.
The asymmetric functional fiber membrane developed by the invention relates to environment conditions triggered by differentiated functions, namely a dry-cold environment and a wet-hot environment, and comprises states of sleeping, static state, movement and the like of a human body.
The composite fiber membrane comprises a functional layer, a transition layer and an inert layer, wherein the asymmetric function of the fiber membrane is represented by a warm-keeping effect when the body surface microenvironment is in a dry and cold (sleep and rest) state, and a directional dehumidifying effect when the fiber membrane is in a damp and hot (movement) state. The preparation method comprises the following steps: and respectively dissolving the hydrophobic polymer, the photo-thermal material and the metal organic framework and the single hydrophobic polymer in a solvent to obtain the spinning solution of the functional layer and the inert layer. The spinning parameters (the advancing speed is improved, the heating is turned off), the partial solidification of the functional layer fiber when reaching the substrate is controlled, and the interface stability between the asymmetric fiber films is improved; simultaneously, the electro-spinning inert layer fiber realizes the mutual bonding of two materials, precisely controls the spinning quantity of two spinning solutions at the same time, develops a transition layer with a multistage gradient structure (the content of the metal organic framework intercalation photo-thermal material gradually decreases from a functional layer to an inert layer), and strengthens the capillary effect; and finally, closing the spinning head of the functional layer, and independently spinning the inert layer to construct wettability at two sides and poor photo-thermal management performance of the functional layer, thereby obtaining the fiber membrane with asymmetric functionality.
The functional layer takes photo-thermal filler with low heat radiation emissivity as a thermal insulation source, so that the control of heat released by a human body can be realized to the greatest extent in a cold environment; the metal organic frame is selected as a moisture absorption material, so that the difference of the hydrophilicity and the hydrophobicity of two sides of the fiber is enlarged, and active heat dissipation and moisture removal under a humid condition are realized. And the micro-nano structure and the multi-stage cavity design among the polymer fiber, the low heat radiation emission material and the metal organic framework particles and the influence on a human body microenvironment dynamic control cooperative mechanism are researched, so that the wearing comfort of a human body is effectively improved. The preparation strategy of the asymmetric functional double-layer fiber membrane provided by the invention is widely suitable for various functional materials, and fiber membrane-based electronic devices can be custom designed according to different functional requirements.
Advantageous effects
The asymmetric functional fiber membrane developed by the invention has the advantages of mild preparation process conditions, low requirements on materials and processing environments, strong adjustability of components and structural properties and large scale production potential. In addition, the functional particle-fiber can provide more abundant multipleThe level structure effectively improves the differential functional performance of the fiber membrane under different triggering environments. According to the invention, a hydrophobic polymer is used as a substrate, a metal organic frame and a photo-thermal material are used as functional fillers (such as polyurethane/MXene intercalation MIL-125-NH 2 Metal organic frames, etc.), an asymmetric functional fiber membrane can be constructed with the inert layer, and the thermal insulation effect is shown when the body surface microenvironment is in a dry and cold (sleep and rest) state; exhibits a directional dehumidifying effect in a damp-heat (exercise) state. The designed asymmetric functional double-layer fiber membrane preparation strategy is widely suitable for various functional materials, the fiber membrane can be customized according to different functional requirements, compared with a traditional sheet structure, the compatibility of integration with other functional components is better, and various advanced intelligent devices can be developed.
Drawings
FIG. 1 is a diagram of two sides of an asymmetric functional fiber membrane according to the present invention (example 2); wherein the inert layer (a), the functional layer (b);
FIG. 2 is a scanning electron microscope image of MXene of the present invention;
FIG. 3 is a metal organic framework MIL-125-NH of the invention 2 Scanning electron microscope images of (2);
FIG. 4 is a scanning electron microscope image of a metal-organic framework MIL-88A of the present invention;
FIG. 5 is an MXene intercalated MIL-125-NH according to the invention 2 Scanning electron microscope images of (2);
FIG. 6 is a differential thermal management effect of an asymmetric functional film of an embodiment of the present invention in hot and humid (a-c) and cold (d-f) environments;
FIG. 7 is a graph of the moisture vapor transport effect (a) and the turned over water vapor attachment effect (b) of an asymmetric functional fibrous membrane according to an embodiment of the present invention and the time (c) required to achieve this effect for different asymmetric functional fibrous membranes; wherein the white inert layer of the sample I faces outwards when the sample II covers the steam port, and the black functional layer of the sample II faces outwards;
FIG. 8 is a flow chart of the preparation of an asymmetric functional fiber membrane.
Detailed Description
The invention will be further illustrated with reference to specific examples. It is to be understood that these examples are illustrative of the present invention and are not intended to limit the scope of the present invention. Further, it is understood that various changes and modifications may be made by those skilled in the art after reading the teachings of the present invention, and such equivalents are intended to fall within the scope of the claims appended hereto.
Polyurethane: hydrophobic, available from basf, germany, model 685A.
Examples selected MXene, metal organic frameworks MIL-125-NH 2 MIL-88A, MXene intercalated MIL-125-NH for metal organic frameworks 2 The preparation method of the metal organic framework functional particles comprises the following steps:
(a) The mass ratio of the materials is 20:1 and lithium fluoride, mixing the mixture at 400rpm for 30min, and slowly adding titanium aluminum carbide, wherein the mass of the titanium aluminum carbide and the lithium fluoride is respectively 2g and 3.2g. The whole system was reacted 48 h under 35℃water bath conditions. The reacted solution was subjected to multiple centrifugal washes to obtain a single layer/multi layer MXene composite solution having a pH of about 7. The single layer of MXene was subsequently obtained by ultrasound 1 h. The monolayer MXene was dissolved in N, N dimethylformamide solution, nitrogen was introduced and the refrigerator (1-10 ℃ C.) was set aside for later use (as shown in FIG. 2).
(b) Weighing titanium isopropoxide and 2-amino-1, 4-phthalic acid (NH) with the molar ratio of 3:2 2 -BDC), dissolved in a volume ratio of 9:1, wherein the mass ratio volume of the total solute to the solvent of the whole system in the N, N dimethylformamide/methanol mixed solution is 1:5 (g: mL). After the powder is completely dissolved, the powder is transferred into a polytetrafluoroethylene reaction kettle and placed in the autoclave for reaction at 150 ℃ for 24 h. After the reaction is finished, respectively washing with N, N dimethylformamide and methanol, drying overnight in a vacuum oven at 65 ℃ and calcining at 200 ℃ for 2 h to remove free solvent to obtain yellow crystals MIL-125-NH 2 A metal organic framework (as shown in fig. 3).
(c) Weighing ferric chloride hexahydrate and fumaric acid with the mass ratio of 5:2, dissolving in N, N dimethylformamide solution, adding the morphology regulator polyvinylpyrrolidone (the mass ratio of polyvinylpyrrolidone to ferric chloride hexahydrate is 1:1) after the powder is completely dissolved, carrying out ultrasonic treatment until the powder is completely dissolved, transferring the mixed solution into a polytetrafluoroethylene reaction kettle, and placing the polytetrafluoroethylene reaction kettle in an environment of 85 ℃ for reaction 6 h, wherein the mass ratio of the total solute of the whole system to the solvent is 1:3. After the reaction is finished, the mixture is respectively washed by absolute ethyl alcohol and deionized water, and is dried overnight in a vacuum oven at 65 ℃ to obtain a yellow crystal MIL-88A metal organic frame (shown in figure 4).
(d) Weighing titanium isopropoxide and 2-amino-1, 4-phthalic acid NH with the molar ratio of 5:4 2 BDC is dissolved in N, N dimethylformamide/methanol mixed solution with the volume ratio of 3:1, after ultrasonic treatment is carried out, the prepared MXene solution is added for mixing (the mass ratio of MXene to metal organic frame is 1:2, the mass ratio of total solute to solvent in the whole system is 1:10 (g: mL)), the mixture is stirred uniformly and then transferred into a polytetrafluoroethylene reaction kettle, the polytetrafluoroethylene reaction kettle is placed in the high-pressure kettle for reaction at 150 ℃ for 24 h, after the reaction is finished, the mixture is respectively washed clean by N, N dimethylformamide and methanol, after the reaction is finished, a vacuum oven at 65 ℃ is dried overnight, a nitrogen environment at 200 ℃ is calcined for 2 h to remove free solvent, and metal organic frame photo-thermal inserted particles MIL-125-NH are obtained 2 @MXene (FIG. 5 is MIL-125-NH 2 Scanning electron microscope image of intercalated MXene).
(e) Weighing ferric chloride hexahydrate and fumaric acid with the molar ratio of 5:2, dissolving in an N, N dimethylformamide/methanol mixed solution with the volume ratio of 3:1, adding polyvinylpyrrolidone (the mass ratio of polyvinylpyrrolidone to ferric chloride hexahydrate is 1:1), adding the prepared MXene solution for mixing after ultrasonic treatment to dissolve the powder (the mass ratio of MXene to metal organic frame is 1:2), and the mass ratio of the total solute to the solvent of the whole system is 1:10 (g: mL). After being stirred evenly, the mixture is transferred into a polytetrafluoroethylene reaction kettle and placed into the autoclave to react at 150 ℃ for 24 h. After the reaction is finished, respectively washing with N, N dimethylformamide and methanol, drying overnight in a vacuum oven at 65 ℃, and calcining 2 h in a nitrogen environment at 200 ℃ to remove the free solvent to obtain the metal organic framework intercalated photo-thermal particles MIL-88A@MXene.
Example 1
In this embodiment, an asymmetric functional fiber membrane is provided, and the preparation method is as follows:
dissolving polyurethane in N, N dimethylformamide to prepare 15wt% of inert layer spinning solution;
dissolving polyurethane into N, N-dimethylformamide to prepare spinning solution with 15wt%, weighing a metal organic framework (MIL-88A) as moisture absorption functional particles, adding MXene after the solution is uniform, wherein the mass ratio of MIL-88A to MXene is 2:1, the mass ratio of functional filler (metal organic framework and photo-thermal material) to polymer is 1:20, stirring uniformly to obtain the spinning solution for the functional layer, and stirring uniformly with ultrasonic and magnetic particles to obtain the spinning solution for the functional layer.
Receiving a distance of 15 cm at a voltage of 15 kV, a rotational speed of 600 r, 1.0 mL.h -1 The electrostatic spinning parameters are spun and a heating lamp is turned on or the temperature is raised (30+/-2 ℃) to accelerate the volatilization of the solvent, and the spinning parameters are adjusted 10min after spinning (the advancing speed is improved to 2 mL h) -1 And turning off the heating lamp or cooling to 23+/-2 ℃, and controlling the PU/MX-MOF fiber of the functional layer to be partially solidified when reaching the substrate so as to realize the mutual adhesion with the fiber of the transition layer of the subsequent electrospinning;
the pushing rate of the spinning solution of the functional layer and the spinning solution of the inert layer is regulated and controlled in a time-sharing manner to design the structural gradient of the transition layer, wherein the method comprises the following steps: the first 1/3 spinning time, the advancing rate of the spinning solution of the functional layer and the spinning solution of the inert layer is 1.5 mL h -1 And 0.5 mL h -1 The second 1/3 spinning time, the advancing rate of the two spinning times is adjusted to be 1.0 mL h -1 Finally, the propelling speed of the spinning solution of the 1/3 spinning control functional layer and the spinning solution of the inert layer is 0.5 mL h -1 And 1.5 mL.h -1 . The content of the metal organic framework composite photo-thermal material in the whole transition layer gradually decreases from the functional layer to the inert layer;
the final inert layer alone was spun, in particular at a voltage of 15 kV, a receiving distance of 15 cm, a rotational speed of 600 r. The first 10 minutes at 2 mL h without heating (23.+ -. 2 ℃ C.) -1 Advancing to strengthen the connection between the transition layer fiber and the inert layer, and then adjusting the advancing speed to be 1 mL.h -1 And turning on a heating lamp or raising the temperature (30+ -2deg.C) to accelerate solvent evaporation to form a functional layer-transition layer-inert layer pairThe functional fiber film (total thickness 70 μm) was called. The thickness ratio of the functional layer, the transition layer and the inert layer in the formed asymmetric functional composite fiber membrane is 2:1:4.
The heat dissipation effect of the fiber membrane in the embodiment under the damp-heat condition is shown in fig. 6b, which shows that the fiber membrane has warmth retention property under the dry-cold condition, the active heat dissipation effect under the damp-heat condition is weak, and the directional dehumidification needs 3 min from the hydrophobic surface to the hydrophilic surface (fig. 7 c).
Example 2
In this embodiment, an asymmetric functional fiber membrane is provided, and the preparation method is as follows:
dissolving polyurethane in N, N dimethylformamide to prepare 15wt% of inert layer spinning solution;
the polyurethane was dissolved in N, N dimethylformamide to prepare a spinning solution of 15wt%, and the prepared metal organic frame (MIL-125-NH was weighed 2 ) Intercalation of MXene as a functional particle (wherein MIL-125-NH 2 The mass ratio to MXene was 2:1, the functional filler (metal organic framework (MIL-125-NH) 2 ) Intercalation MXene) and the polymer in a mass ratio of 1:20, and uniformly stirring to obtain the functional layer spinning solution.
Receiving a distance of 15 cm at a voltage of 15 kV, a rotational speed of 600 r, 1.0 mL.h -1 The electrostatic spinning parameters are spun and a heating lamp is turned on or the temperature is raised to 30+/-2 ℃ to accelerate the volatilization of the solvent, and the spinning parameters are adjusted 10min after spinning (the advancing speed is increased to 2 mL h) -1 And turning off the heating lamp or cooling to 23+/-2 ℃, and controlling the PU/MX-MOF fiber of the functional layer to be partially solidified when reaching the substrate so as to realize the mutual adhesion with the fiber of the transition layer of the subsequent electrospinning;
the pushing rate of the spinning solution of the functional layer and the spinning solution of the inert layer is regulated and controlled in a time-sharing manner to design the structural gradient of the transition layer, wherein the method comprises the following steps: the first 1/3 spinning time, the advancing rate of the spinning solution of the functional layer and the spinning solution of the inert layer is 1.5 mL h -1 And 0.5 mL h -1 The second 1/3 spinning time, the advancing rate of the two spinning times is adjusted to be 1.0 mL h -1 Finally, the propelling speed of the spinning solution of the 1/3 spinning control functional layer and the spinning solution of the inert layer is 0.5 mL h -1 And 1.5 mL.h -1 . Metal organic frame in whole transition layerThe content of the intercalation photo-thermal material gradually decreases from the functional layer to the inert layer;
the final inert layer alone was spun, in particular at a voltage of 15 kV, a receiving distance of 15 cm, a rotational speed of 600 r. The first 10 minutes under unheated conditions (23.+ -. 2 ℃) were followed by 2 mL h -1 Advancing to strengthen the connection of the transition layer fiber and the inert layer, and then adjusting the advancing speed to be 1mL h -1 And turning on a heating lamp or raising the temperature (30.+ -. 2 ℃ C.) to accelerate the solvent evaporation, to form an asymmetric functional fiber film (total thickness: 70 μm) of the functional layer-transition layer-inert layer. The ratio of the functional layer, the transition layer and the inert layer thickness in the formed asymmetric functional composite fiber membrane is 2:1:4.
the heat dissipation effect of the fiber membrane in the embodiment under the damp-heat condition is shown in fig. 6c, which shows the warmth retention property under the dry-cold condition, the active heat dissipation effect under the damp-heat condition, and the directional moisture removal from the hydrophobic surface to the hydrophilic surface only needs 1 min (fig. 7 c).
Example 3
In this embodiment, an asymmetric functional fiber membrane is provided, and the preparation method is as follows:
dissolving polyurethane in N, N dimethylformamide to prepare 15wt% of inert layer spinning solution;
the polyurethane was dissolved in N, N dimethylformamide to prepare a spinning solution of 15wt%, and the prepared metal organic frame (MIL-125-NH was weighed 2 ) Intercalation of MXene as a functional particle (wherein MIL-125-NH 2 The mass ratio to MXene was 2:1, the functional filler (metal organic framework (MIL-125-NH) 2 ) Intercalation MXene) and the polymer in a mass ratio of 1:50, and uniformly stirring to obtain the functional layer spinning solution.
Receiving a distance of 15 cm at a voltage of 15 kV, a rotational speed of 600 r, 1.0 mL.h -1 The electrostatic spinning parameters are spun and a heating lamp is turned on or the temperature is raised to 30+/-2 ℃ to accelerate the volatilization of the solvent, and the spinning parameters are adjusted 10min after spinning (the advancing speed is increased to 2 mL h) -1 And turning off the heating lamp or cooling to 23+/-2 ℃, and controlling the PU/MX-MOF fiber of the functional layer to be partially solidified when reaching the substrate so as to realize the mutual adhesion with the fiber of the transition layer of the subsequent electrospinning;
the pushing rate of the spinning solution of the functional layer and the spinning solution of the inert layer is regulated and controlled in a time-sharing manner to design the structural gradient of the transition layer, wherein the method comprises the following steps: the first 1/3 spinning time, the advancing rate of the spinning solution of the functional layer and the spinning solution of the inert layer is 1.5 mL h -1 And 0.5 mL h -1 The second 1/3 spinning time, the advancing rate of the two spinning times is adjusted to be 1.0 mL h -1 Finally, the propelling speed of the spinning solution of the 1/3 spinning control functional layer and the spinning solution of the inert layer is 0.5 mL h -1 And 1.5 mL.h -1 . The content of the metal organic framework composite photo-thermal material in the whole transition layer gradually decreases from the functional layer to the inert layer; the final inert layer alone was spun, in particular at a voltage of 15 kV, a receiving distance of 15 cm, a rotational speed of 600 r. The first 10 minutes at 2 mL h without heating (23.+ -. 2 ℃ C.) -1 Advancing to strengthen the connection of the transition layer fiber and the inert layer, and then adjusting the advancing speed to be 1mL h -1 And turning on a heating lamp or raising the temperature (30.+ -. 2 ℃ C.) to form an asymmetric functional fiber film (total thickness: 70 μm) of the functional layer-transition layer-inert layer. The thickness ratio of the functional layer, the transition layer and the inert layer in the formed asymmetric functional composite fiber membrane is 2:1:4.
The thermal insulation effect of the fiber film in the dry and cold conditions is shown in fig. 6d, and the higher the temperature is, the more heat is dissipated, which means that the fiber exhibits poor heat compensation effect and the oriented dehumidification from the hydrophobic surface to the hydrophilic surface needs 6 min (fig. 7 c).
Example 4
In this embodiment, an asymmetric functional fiber membrane is provided, and the preparation method is as follows:
dissolving polyurethane in N, N dimethylformamide to prepare 15wt% of inert layer spinning solution;
the polyurethane is dissolved in N, N dimethylformamide to prepare spinning solution with 15wt%, the prepared metal organic framework (MIL-88A) intercalation MXene is weighed as functional particles (the mass ratio of MIL-88A to MXene is 2:1), the mass ratio of functional filler ((MIL-88A) intercalation MXene) to polymer is 1:20, and the spinning solution is used as the spinning solution of the functional layer after uniform stirring.
Turning on the heating lamp or raising the temperature to 30+ -2deg.C, and receiving at 15 kV voltage, 15 cmDistance, 600 r rpm, 1.0 mL.h -1 And spinning the functional layer and the inert layer sequentially by using the electrostatic spinning parameters to form the asymmetric functional composite fiber membrane (the total thickness is 70 mu m), wherein the thickness ratio of the functional layer to the inert layer is 1:2.
The warmth retention effect of the fiber film in the dry and cold condition of the embodiment is shown in fig. 6e, the fiber film has a certain warmth retention property in the dry and cold condition, and the oriented dehumidification is required to be 15 min from the hydrophobic surface to the hydrophilic surface (fig. 7 c).
Example 5
In this embodiment, an asymmetric functional fiber membrane is provided, and the preparation method is as follows:
dissolving polyurethane in N, N dimethylformamide to prepare 15wt% of inert layer spinning solution;
dissolving polyurethane into N, N-dimethylformamide to obtain 15wt% spinning solution, and weighing the prepared metal organic frame (MIL-125-NH) 2 ) Intercalation of MXene as a functional particle (wherein MIL-125-NH 2 The mass ratio of the functional filler ((MIL-125-NH 2) intercalation MXene) to the polymer is 1:20, and the functional filler and the polymer are uniformly stirred to form the functional layer spinning solution.
Turning on the heating lamp or raising the temperature (30+ -2deg.C), receiving the distance of 15 cm at 15 kV voltage, 600 r rotation speed of 1.0 mL.h -1 The electrostatic spinning parameters are spun and a heating lamp is turned on or the temperature is raised to 30+/-2 ℃ to accelerate the volatilization of the solvent, and the spinning parameters are adjusted 10min after spinning (the advancing speed is increased to 2 mL h) -1 And turning off the heating lamp or cooling to 23+/-2 ℃, and controlling the PU/MX-MOF fiber of the functional layer to be partially solidified when reaching the substrate so as to realize the mutual adhesion with the fiber of the transition layer of the subsequent electrospinning;
the pushing rate of the spinning solution of the functional layer and the spinning solution of the inert layer is regulated and controlled in a time-sharing manner to design the structural gradient of the transition layer, wherein the method comprises the following steps: the previous 1/2 spinning time, the advancing rate of the spinning solution of the functional layer and the spinning solution of the inert layer is 1.5 mL h -1 And 0.5 mL h -1 After 1/2 spinning time, the advancing rates of the two spinning materials are adjusted to be 1. mL.h -1 . The content of the metal organic framework intercalation photo-thermal material in the whole transition layer gradually decreases from the functional layer to the inert layer;
the final inert layer alone was spun, in particular at a voltage of 15 kV, a receiving distance of 15 cm, a rotational speed of 600 r. The first 10 minutes at 2 mL h without heating (23.+ -. 2 ℃ C.) -1 Advancing to strengthen the connection between the transition layer fiber and the inert layer, and then adjusting the advancing speed to be 1mL h -1 And turning on a heating lamp or raising the temperature (30.+ -. 2 ℃ C.) to form an asymmetric functional fiber film (total thickness: 70 μm) of the functional layer-transition layer-inert layer. The ratio of the functional layer, the transition layer and the inert layer thickness in the formed asymmetric functional composite fiber membrane is 2:1:4.
the heat dissipation effect of the fiber film in the embodiment under the damp-heat condition is shown in fig. 6f, which shows good heat preservation effect under the dry-cold condition, and the directional dehumidification requires 2 min from the hydrophobic surface to the hydrophilic surface (fig. 7 c).
Comparative example 1
In this embodiment, a Janus affinity/hydrophobicity composite membrane is provided, and the preparation method is as follows:
adding graphene sheets into an ethanol solution, and performing ultrasonic dispersion to obtain graphene oxide sheet dispersion liquid with the concentration of 10 g/ml; stirring 8 h the polyvinylidene fluoride high polymer and the mixed solvent (the mass ratio of N, N dimethylformamide to tetrahydrofuran is 1:1) by a magnetic stirrer at 80 ℃ until the mixture is uniformly mixed, and then mixing the mixture according to the mass ratio of 5:1, adding the graphene dispersion liquid to obtain a polyvinylidene fluoride composite spinning solution with the mass concentration of 15%; stirring a cellulose acetate high polymer and a mixed solvent (the mass ratio of dimethylacetamide to acetone is 1:2) for 3 h until the mixture is uniformly mixed, so as to obtain a cellulose acetate spinning solution with the mass concentration of 13%; the two solutions are spun successively, and the obtained Janus lyophobic composite film with the thickness of 300 mu m can realize the highest cooling temperature of 13 ℃.

Claims (10)

1. An asymmetric functional fiber membrane is characterized by comprising a functional layer, a transition layer and an inert layer in sequence; wherein the functional layer material component comprises a hydrophobic polymer, a photo-thermal filler and a metal organic framework material; the transition layer material comprises hydrophobic polymer, photo-thermal filler and metal organic frame material, and the transition layer has a structural gradient, and the contents of the metal organic frame material and the photo-thermal material gradually decrease from the functional layer to the inert layer; the inert layer material component comprises a hydrophobic polymer.
2. The fiber membrane of claim 1 wherein the hydrophobic polymer comprises one or more of polyvinylidene fluoride, polyurethane, p-styrene-isoprene, polystyrene, polypropylene, polylactic acid.
3. The fiber membrane according to claim 1, wherein the photo-thermal filler comprises one or more of a zero-dimensional material, a one-dimensional material, and a two-dimensional material; wherein the zero-dimensional material comprises one or more of gold nanoparticles, silver nanoparticles and zinc oxide nanoparticles; the one-dimensional material is one or more of gold nanowire, silver nanowire, copper nanowire and carbon nanotube; the two-dimensional material comprises one or more of graphene, graphene oxide and transition metal carbide MXene;
the metal organic frame material comprises MIL-100, MIL-47, MIL-53, MIL-88, MIL-101, MIL-125-NH 2 、SHF-61、SHF-62、SHF-81、CAU-10-H、Co 2 Cl 2 One or more of (BTDD), Y-shp-MOF-5 and MIL-101 (Cr).
4. The fiber membrane according to claim 1, wherein the mass ratio of the total amount of the photo-thermal filler and the metal organic framework material to the hydrophobic polymer in the functional layer is 10:1-1:200; the mass ratio of the photo-thermal filler to the metal organic frame material is 10:1-1:5; the thickness ratio of the functional layer to the transition layer to the inert layer is 10:1:2-2:1:10.
5. The fiber film of claim 1, wherein the metal organic framework material and photo-thermal filler are combined in an insertion or compounding manner; the metal organic framework material and/or the photo-thermal material are embedded, partially embedded or densely distributed in the hydrophobic polymer.
6. A method of making the asymmetric functional fiber membrane of claim 1, comprising:
mixing a metal organic frame material, a photo-thermal filler, a hydrophobic polymer and a solvent, and stirring to obtain a spinning solution A;
mixing a hydrophobic polymer and a solvent to obtain a spinning solution B;
spinning the spinning solution A to obtain a functional layer, continuously spinning the spinning solution A, and simultaneously spinning the solution B to prepare a transition layer; and finally, spinning the solution B independently to obtain the asymmetric functional fiber membrane.
7. The preparation method according to claim 6, wherein the solvent comprises one or more of deionized water, ethanol, methanol, isopropanol, N-dimethylformamide, N-dimethylacetamide, tetrahydrofuran, chloroform, acetone, toluene, pyridine, thionyl chloride; the spinning mode comprises one or more of dry spinning, wet spinning, microfluidic spinning, electrostatic spinning and melt-blown spinning;
the concentration of the hydrophobic polymer in the spinning solution A and the spinning solution B is 1 wt% -50 wt%; the mass ratio of the total amount of the photo-thermal filler and the metal organic frame material to the hydrophobic polymer is 10:1-1:200; the mass ratio of the photo-thermal filler to the metal organic frame material is 10:1-1:5; the thickness ratio of the functional layer to the inert layer is 10:1-1:10.
8. The preparation method according to claim 6, wherein the spinning solution A is subjected to spinning to obtain the functional layer, and the functional layer fiber is controlled to be partially solidified when reaching the substrate by adjusting the spinning advancing rate and the temperature in the latter half stage;
in the preparation process of the transition layer, the advancing rates of the spinning solution of the functional layer and the spinning solution of the inert layer at the same time are changed in a time-sharing manner, so that the contents of the metal organic framework material and the photo-thermal material in the transition layer gradually decrease from the functional layer to the inert layer.
9. The process of claim 8, wherein the spinning solution A is spun to give a functional layer, wherein the spinning processThe technological parameters are as follows: with 15-20kV voltage, 15-20 cm receiving distance, 600-1500 r rotating speed, 1-2 mL h -1 Spinning at the advancing speed, and turning on a heating lamp or raising the temperature to 28-35 ℃ in the whole process to accelerate the real-time solidification of the fibers on the receiver; turning off the heating lamp or cooling to 20-25deg.C for 5-10min at the end of spinning and increasing the advancing rate to 2-3mL hr -1 Controlling the partial solidification of the functional layer fiber when reaching the substrate, and realizing the mutual adhesion with the inert layer of the subsequent electrospinning;
spinning solution A continues spinning, and spinning solution B simultaneously, so as to prepare a transition layer; the method comprises the following steps: spinning in 2-3 time periods, wherein the first time is 1/2 or 1/3 of the spinning time, the advancing rate ratio of the spinning solution A to the spinning solution B is controlled to be 3:1-2:1 respectively, and the second time is 1/2 or 1/3 of the spinning time, and the advancing rate ratio of the spinning solution A to the spinning solution B is adjusted to be 1:1-1:2; the third period or the third 1/3 spinning is not carried out, and the advancing rate ratio of the spinning solution A to the spinning solution B is controlled to be 1:3-1:5; the contents of the metal organic framework material and the photo-thermal material in the transition layer gradually decrease from the functional layer to the inert layer;
and finally spinning the solution B independently, wherein the spinning is performed at a voltage of 15-20kV, a receiving distance of 15-20 cm and a rotating speed of 600-1500 r; heating at 20-25deg.C for 5-10min for 2-3mL hr -1 Advancing to strengthen the connection of the transition layer fiber and the inert layer, and then adjusting the advancing speed to be 1-2 mL h -1 The heating lamp is turned on or the temperature is raised by 28-35 ℃ to accelerate the fiber solidification, so that the functional fiber film with asymmetric wettability and photo-thermal management difference of the functional layer-transition layer-inert layer is formed.
10. Use of the asymmetric functional fiber membrane of claim 1 in the fields of information, energy, medical or smart response.
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Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110983483A (en) * 2019-11-27 2020-04-10 武汉纺织大学 Heat-moisture response fiber with photo-thermal conversion and antibacterial performance and preparation method thereof
CN111268639A (en) * 2020-02-19 2020-06-12 东华大学 Multi-stimulus response actuating film and preparation and application thereof
CN112981653A (en) * 2021-02-05 2021-06-18 武汉纺织大学 Asymmetric structure stimulus response yarn and preparation method and application thereof
CN112999885A (en) * 2021-02-18 2021-06-22 上海工程技术大学 MXene-GO composite membrane with humidity response and preparation method and application thereof
CN113230903A (en) * 2021-04-26 2021-08-10 浙江大学 Portable photo-thermal seawater desalination hollow fiber membrane, preparation method, device and application
CN114555203A (en) * 2019-10-17 2022-05-27 新加坡国立大学 Composite material for water capture and water release
CN116375471A (en) * 2023-03-01 2023-07-04 青岛科技大学 Preparation method of self-repairing thin film driver with multiple stimulus responses
CN116587318A (en) * 2023-04-27 2023-08-15 东华大学 Metal organic framework reinforced micro-nano fiber film-based actuator and preparation and application thereof
US20230256397A1 (en) * 2020-06-23 2023-08-17 Commonwealth Scientific And Industrial Research Organisation Dual-layer membrane
CN117005107A (en) * 2022-04-28 2023-11-07 北京服装学院 Preparation method of Janus fiber membrane for regulating and controlling heat and humidity comfort

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114555203A (en) * 2019-10-17 2022-05-27 新加坡国立大学 Composite material for water capture and water release
CN110983483A (en) * 2019-11-27 2020-04-10 武汉纺织大学 Heat-moisture response fiber with photo-thermal conversion and antibacterial performance and preparation method thereof
CN111268639A (en) * 2020-02-19 2020-06-12 东华大学 Multi-stimulus response actuating film and preparation and application thereof
US20230256397A1 (en) * 2020-06-23 2023-08-17 Commonwealth Scientific And Industrial Research Organisation Dual-layer membrane
CN112981653A (en) * 2021-02-05 2021-06-18 武汉纺织大学 Asymmetric structure stimulus response yarn and preparation method and application thereof
CN112999885A (en) * 2021-02-18 2021-06-22 上海工程技术大学 MXene-GO composite membrane with humidity response and preparation method and application thereof
CN113230903A (en) * 2021-04-26 2021-08-10 浙江大学 Portable photo-thermal seawater desalination hollow fiber membrane, preparation method, device and application
CN117005107A (en) * 2022-04-28 2023-11-07 北京服装学院 Preparation method of Janus fiber membrane for regulating and controlling heat and humidity comfort
CN116375471A (en) * 2023-03-01 2023-07-04 青岛科技大学 Preparation method of self-repairing thin film driver with multiple stimulus responses
CN116587318A (en) * 2023-04-27 2023-08-15 东华大学 Metal organic framework reinforced micro-nano fiber film-based actuator and preparation and application thereof

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
JAVIER TROYANO等: ""A Self-folding polymer film based on swelling metal-organic frameworks"", 《ANGEWANDTE CHEMIE》, no. 130, 31 December 2018 (2018-12-31), pages 15646 - 15620 *
JIAHUI ZHOU等: ""Breathable Metal−Organic Framework Enhanced Humidity-Responsive Nanofiber Actuator with Autonomous Triboelectric Perceptivity"", 《AMERICAN CHEMICAL SOCIETY》, no. 17, 5 September 2023 (2023-09-05), pages 17920 - 17930 *
许文静等: ""纤维素基湿度响应驱动器的研究进展"", 《纤维素科学与技术》, vol. 31, no. 3, 30 June 2023 (2023-06-30), pages 64 - 70 *
郑宗敏等: ""湿度响应致动器的研究进展和展望"", 《复合材料学报》, vol. 40, no. 3, 30 June 2023 (2023-06-30), pages 1354 - 1364 *

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