CN117141069B - High-strength nanofiber waterproof and moisture-permeable membrane and preparation method thereof - Google Patents
High-strength nanofiber waterproof and moisture-permeable membrane and preparation method thereof Download PDFInfo
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- CN117141069B CN117141069B CN202311393840.4A CN202311393840A CN117141069B CN 117141069 B CN117141069 B CN 117141069B CN 202311393840 A CN202311393840 A CN 202311393840A CN 117141069 B CN117141069 B CN 117141069B
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- 239000002121 nanofiber Substances 0.000 title claims abstract description 71
- 239000012528 membrane Substances 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 238000009987 spinning Methods 0.000 claims abstract description 65
- 239000000835 fiber Substances 0.000 claims abstract description 58
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000000758 substrate Substances 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 20
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000010041 electrostatic spinning Methods 0.000 claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 239000004814 polyurethane Substances 0.000 claims description 13
- 239000004744 fabric Substances 0.000 claims description 11
- 239000004626 polylactic acid Substances 0.000 claims description 11
- 229920002635 polyurethane Polymers 0.000 claims description 11
- 229920000747 poly(lactic acid) Polymers 0.000 claims description 10
- 230000035699 permeability Effects 0.000 claims description 9
- 230000002706 hydrostatic effect Effects 0.000 claims description 7
- 239000012046 mixed solvent Substances 0.000 claims description 7
- 239000004745 nonwoven fabric Substances 0.000 claims description 5
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- 238000004078 waterproofing Methods 0.000 claims 1
- 239000002904 solvent Substances 0.000 abstract description 43
- 238000004132 cross linking Methods 0.000 abstract description 41
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- 229910010293 ceramic material Inorganic materials 0.000 description 2
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- 238000012360 testing method Methods 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- SUAYFRHPQLERMW-UHFFFAOYSA-N 2-methyl-1,2-diphenylpropan-1-one Chemical compound C=1C=CC=CC=1C(C)(C)C(=O)C1=CC=CC=C1 SUAYFRHPQLERMW-UHFFFAOYSA-N 0.000 description 1
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- QJAOYSPHSNGHNC-UHFFFAOYSA-N octadecane-1-thiol Chemical compound CCCCCCCCCCCCCCCCCCS QJAOYSPHSNGHNC-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
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- D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
- D01F8/14—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyester as constituent
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- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
- B32B37/15—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer being manufactured and immediately laminated before reaching its stable state, e.g. in which a layer is extruded and laminated while in semi-molten state
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- B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
- B32B5/24—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
- B32B5/26—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer another layer next to it also being fibrous or filamentary
- B32B5/265—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer another layer next to it also being fibrous or filamentary characterised by one fibrous or filamentary layer being a non-woven fabric layer
- B32B5/271—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer another layer next to it also being fibrous or filamentary characterised by one fibrous or filamentary layer being a non-woven fabric layer characterised by separate non-woven fabric layers that comprise chemically different strands or fibre material
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- D01D5/00—Formation of filaments, threads, or the like
- D01D5/0007—Electro-spinning
- D01D5/0015—Electro-spinning characterised by the initial state of the material
- D01D5/003—Electro-spinning characterised by the initial state of the material the material being a polymer solution or dispersion
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
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- D01D5/00—Formation of filaments, threads, or the like
- D01D5/0007—Electro-spinning
- D01D5/0061—Electro-spinning characterised by the electro-spinning apparatus
- D01D5/0076—Electro-spinning characterised by the electro-spinning apparatus characterised by the collecting device, e.g. drum, wheel, endless belt, plate or grid
- D01D5/0084—Coating by electro-spinning, i.e. the electro-spun fibres are not removed from the collecting device but remain integral with it, e.g. coating of prostheses
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- 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
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- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
- D01F8/16—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one other macromolecular compound obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds as constituent
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- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
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- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Dispersion Chemistry (AREA)
- Nonwoven Fabrics (AREA)
- Artificial Filaments (AREA)
Abstract
Aiming at the problem of poor mechanical properties caused by lack of crosslinking among fibers of a nanofiber membrane prepared by a traditional electrostatic spinning method, the invention provides a high-strength nanofiber waterproof and moisture-permeable membrane and a preparation method thereof, wherein N, N-dimethylacetamide is selected to compound a low-volatility solvent N-methylpyrrolidone (the volume ratio of N, N-dimethylacetamide to N-methylpyrrolidone is 6:4), the temperature (the low temperature is 15 ℃) in the electrostatic spinning process is controlled, the solvent volatilization speed in the spinning process is slowed down, so that the fibers still have partial solvents which are not volatilized after receiving the fibers on a substrate, and the contacted parts among nanofibers can automatically generate crosslinking in a semi-dissolution state, so that the crosslinking effect can enhance the mechanical properties of the waterproof and moisture-permeable membrane, and the waterproof and moisture-permeable membrane has higher strength and durability.
Description
Technical Field
The invention belongs to the technical field of nanofibers, and particularly relates to a high-strength nanofiber waterproof and moisture-permeable membrane and a preparation method thereof.
Background
With the improvement of the living standard of people and the development of economy and the adjustment of industrial structures, fabrics with waterproof and moisture permeable functions are widely applied to various industries. However, the waterproof moisture-permeable materials in the market at present have poor moisture permeability and lack flexibility, so that the application of the waterproof moisture-permeable materials in the wider field is limited. As an emerging preparation technology, the electrostatic spinning nanofiber technology provides a potential solution for solving the defects of the traditional waterproof moisture permeable material. Through the electrostatic spinning technology, the nanofiber film or textile with excellent waterproof and moisture permeability can be prepared.
First, electrospinning techniques can produce ultrafine diameters of fibers, typically on the nanometer scale, which give fibers with higher specific surface areas. Such a high specific surface area can increase the contact area between the fibers and air, thereby improving the moisture permeability of the material. Meanwhile, the nano-scale fiber diameter can also effectively prevent the penetration of moisture, so that excellent waterproof performance is realized. Secondly, the electrostatic spinning nanofiber material has excellent softness and flexibility, and can adapt to various complex shapes and surface structures. The material can be widely applied to various industries, such as outdoor sports products, medical dressing in the medicine industry, wading industry in the military industry, sanitary towel paper diapers in the daily chemical industry, building industry, fire-fighting industry, packaging industry and the like.
However, the nanofiber membranes prepared by conventional electrospinning methods have some limitations, such as: because of lack of crosslinking among the fibers, the mechanical properties of the whole nanofiber membrane are poor, and although the mechanical properties of the nanofiber membrane can be enhanced by thermal crosslinking, solvent crosslinking and other methods, the methods can increase additional energy consumption, damage the morphology and structure of the fibers, and influence the properties of waterproofness, breathability and the like.
Currently, there are also crosslinking agents to improve the mechanical properties of nanofiber membranes, for example as follows.
CN114134702a discloses a preparation method of fluorine-free electrostatic spinning waterproof wet film based on thio-ene photochemical reaction, N-dimethylacetamide (DMAc) and acetone are used as solvents to prepare silicon-based polyurethane/polymethyl methacrylate (Si-PU/PMMA) spinning solution, 2, 4, 6, 8-tetramethyl-2, 4, 6, 8-tetracyclosiloxane (TMTVSi) and N-octadecanethiol are added as hydrophobic agent and cross-linking agent, 2, 2-dimethyl-2-phenyl acetophenone (DMPA) is used as photocatalyst, the hydrophobic fiber film is prepared through electrostatic spinning process, after ultraviolet irradiation treatment, chemical cross-linking structure is formed between fibers, thus reducing the maximum aperture of the waterproof wet film and improving the water resistance of the waterproof wet film, meanwhile, the chemical cross-linking structure can obviously increase friction between fibers and improve the mechanical property of the waterproof wet film, and meet the application requirements of the waterproof wet film in the field of protective clothing.
CN113123128A discloses a waterproof moisture-permeable film, a preparation method and application thereof. The fiber membrane is used as a base material, and the sealing solvent isocyanate cross-linking agent is used for carrying out cross-linking reaction with active groups in the waterproof agent after deblocking, so that the hydrophobic chain segment is stably coated on the surface of the fiber, and the durability of the waterproof agent coating is improved. The contact angle of the wear-resistant water-permeable ceramic material is not obviously changed after 50 wear cycles, the water pressure resistance and the moisture permeability flux are basically unchanged after 30 times of water washing, and the wear-resistant water-permeable ceramic material has wide application prospect in the fields of outdoor wear, field military uniform and medical and health.
The above patents all require crosslinking by adding a crosslinking agent to improve the mechanical properties of the nanofiber membrane, and the use of the crosslinking agent increases the production cost. Therefore, a simpler and practical method for preparing the high-strength nanofiber waterproof and moisture-permeable membrane is urgently needed, so that the wide application of the membrane in various fields is promoted.
Disclosure of Invention
Aiming at the problems, the invention provides a high-strength nanofiber waterproof and moisture-permeable membrane and a preparation method thereof. According to the invention, N-dimethylacetamide is selected to compound the low-volatility solvent N-methylpyrrolidone, the temperature during electrostatic spinning is controlled, and the solvent volatilization speed in the spinning process is slowed down, so that part of the solvent is still not volatilized after the fiber is received on a substrate, and the contacted part between the nanofibers can automatically generate crosslinking in a semi-dissolved state. The crosslinking effect can enhance the mechanical property of the nanofiber membrane, so that the nanofiber membrane has higher strength and durability, and can better cope with various mechanical stresses in practical application.
The technical scheme of the invention is as follows: the preparation method of the high-strength nanofiber waterproof and moisture-permeable membrane is characterized by comprising the following steps of:
1) Preparation of spinning solution
Adding fluorinated Polyurethane (PU) and polylactic acid (PLA) into a mixed solvent of N, N-Dimethylacetamide (DMAC) and N-methylpyrrolidone (NMP) (v: v=6:4), and stirring for 4-6 hours at 75-85 ℃ to obtain a transparent spinning solution; wherein the mass ratio of PU/PLA is 7:3, and the total mass percentage of the PU/PLA and the spinning solution in the spinning solution is 10-16%;
2) Electrostatic spinning process
Adding the spinning solution into an electrostatic spinning machine, wherein the spinning voltage is 35-60 kV, the spinning temperature is 15 ℃, the spinning humidity is 30-60%, antistatic non-woven fabrics, silk fabrics, nylon fabrics or chemical fiber fabrics are used as spinning substrates, the distance from a spinning nozzle to the substrates is 18-24 cm, a control switch is turned on, the spinning solution is spun on the spinning substrates to form hydrophobic nano fibers with the diameter of 200-400 nm, and cross-linking is formed at the contact place between the nano fibers, so that the high-strength nano fiber waterproof and moisture-permeable film is obtained.
The gram weight of the film layer of the waterproof moisture-permeable film obtained by the method is 5-6 g/m 2 Through detection, the tensile strength is more than or equal to 25 MPa, the elongation at break is more than or equal to 250%, the diameter of the nanofiber is between 200 and 400nm, and the nanofiber has high porosity, so that the film has excellent moisture permeability, and the water vapor permeability is more than or equal to 8500 g/m 2 And/day. Meanwhile, the prepared waterproof and moisture-permeable membrane still has excellent waterproof performance, and the hydrostatic pressure is more than or equal to 40Kpa.
The technical principle of the invention is as follows: during electrospinning, the key to fiber formation is the volatilization of the solvent. Conventional electrospinning processes typically accelerate the solvent evaporation rate, allowing the fibers to dry almost completely before contacting the substrate. Such fibers are susceptible to breakage by external forces without crosslinking, resulting in poor mechanical properties of the nanofiber membrane. According to the invention, the proper low-volatility solvent system is selected by controlling the temperature and the N, N-dimethylacetamide compounding during electrostatic spinning, so that the solvent volatilization speed in the spinning process is slowed down, and the fibers in the electrostatic spinning process still have partial solvent which is not volatilized after receiving the fibers on the substrate, and the contacted parts among the nanofibers can automatically generate crosslinking in a semi-dissolution state. So as to improve the strength of the nanofiber waterproof and moisture permeable membrane.
From the experimental results of tables 1 and 2 of the examples of the present invention, DMAC in the mixed solvent used: NMP=6:4, when the temperature during electrostatic spinning is controlled to 15 ℃, the effect of the product is optimal, and compared with other solvent proportions and temperatures, the tensile strength, elongation at break and hydrostatic pressure of the waterproof moisture-permeable membrane are remarkably improved on the premise that the water vapor transmittance meets the requirements, namely the prepared waterproof moisture-permeable membrane has higher strength and durability, so that various mechanical stresses in practical application are better dealt with.
In a word, the preparation method of the invention not only can reduce the production cost, but also can improve the mechanical properties (strength and durability) of the membrane. Therefore, the invention has wide application prospect and important application value in various industries such as outdoor sports goods, medical dressing in medicine industry, military industry wading industry, sanitary towel paper diaper in daily chemical industry, building industry, fire-fighting industry, packaging industry and the like.
Drawings
Fig. 1 nanofiber scanning electron microscopy (DMAC: nmp=7:3, 25 ℃);
fig. 2 nanofiber scanning electron microscopy (DMAC: nmp=6:4, 25 ℃);
fig. 3 nanofiber scanning electron microscopy (DMAC: nmp=5:5, 25 ℃);
fig. 4 nanofiber scanning electron microscopy (DMAC: nmp=6:4, 20 ℃);
fig. 5 nanofiber scanning electron microscopy (DMAC: nmp=6:4, 15 ℃);
fig. 6 nanofiber scanning electron microscopy (DMAC: nmp=6:4, 10 ℃);
FIG. 7 is an electron microscopic view of the high-strength nanofiber waterproof and moisture-permeable membrane prepared in example 2 of the present invention.
Detailed Description
In order to further describe the technical means and effects adopted by the invention for achieving the preset aim, the following detailed description of the specific implementation, the characteristics and the effects according to the invention is shown in the following with reference to the accompanying drawings and the preferred embodiments.
The spinning equipment of the invention consists of three mechanisms: the system control mechanism, the spinning mechanism and the winding and unwinding can take antistatic non-woven fabrics, silk fabrics, nylon fabrics or chemical fiber fabrics as spinning substrates, and the gram weight of the spinning substrates comprises 23 g/m 2 、25 g /m 2 、35 g /m 2 Etc.
In the embodiment of the invention, a universal tensile testing machine is adopted to characterize the mechanical properties of the prepared waterproof moisture-permeable film. The water vapor permeability of the prepared waterproof and moisture-permeable membrane is characterized by adopting a method in GB/T1037-2021 method for measuring cup weight gain and weight loss of water vapor permeability of plastic films and sheets. And testing the waterproof performance of the prepared waterproof and moisture-permeable membrane by adopting a fabric hydrostatic pressure tester. And observing the microstructure of the prepared waterproof and moisture-permeable film by adopting a scanning tunnel microscope.
Example 1
The present invention slows down the solvent evaporation rate by lowering the spinning temperature, selecting a suitable low-volatile solvent system, in which a certain amount of solvent is still present when the fiber contacts the substrate. At this time, the contact points between the fibers are crosslinked in a semi-dissolved state to form a connected lattice structure, and when a tensile force is applied, the lattice is elongated first and out-of-plane bending deformation occurs. Along with the increase of external force, cracks are gradually formed, partial grids with smaller sizes are broken and fused with surrounding grids, so that larger grids are formed, and the structure enhances the mechanical property of the nanofiber membrane.
The solvent used in the present invention is preferably a mixed solvent of N, N-Dimethylacetamide (DMAC) and N-methylpyrrolidone (NMP). The saturated vapor pressure of DMAC was 1.8.+ -. 0.3 mmHg (25 ℃ C.) and the saturated vapor pressure of NMP was 0.29 mmHg (20 ℃ C.). NMP has lower volatility than DMAC, and the volatilization speed of the solvent can be accurately controlled by adjusting the proportion of NMP and DMAC, so that part of the solvent is still not volatilized after the fiber is received on the substrate in the electrostatic spinning process, and the contact part between the nanofibers can be automatically crosslinked in a semi-dissolved state. At present, no study is made on the influence of the proportion on the crosslinking degree of the electrospun nanofibers.
In order to prove the influence of different solvent volatilities on spinning states, the invention prepares a mixed spinning solution with the total mass percent of PU/PLA of 10% (the mass ratio of PU to PLA is 7:3), the solvents are DMAC and NMP (7:3, 6:4 and 5:5) with different volume ratios (v/v), and the PU/PLA is added into the mixed solvent and stirred for 5 h at 80 ℃ to obtain the transparent spinning solution. The spinning solution is added into an electrostatic spinning machine to obtain antistatic non-woven fabric (gram weight: 25g/m 2 ) As a spinning substrate, spinning is carried out on PU/PLA mixed solutions with different solvent ratios for 10 min at the temperature of 25 ℃ and the humidity of 50%, the spinning voltage of 60 kV and the distance from a spinning nozzle to the substrate of 18 cm, so as to obtain the nanofiber waterproof and moisture-permeable film.
When the volume ratio DMAC: nmp=7:3, there are substantially no crosslinking sites between the nanofibers (as shown in fig. 1), and because the DMAC content is high and the solvent volatility is good, the nanofibers are substantially completely volatilized before they receive the substrate, and no crosslinking can occur between the fibers. When DMAC: nmp=6:4, the volatility of the solvent was further reduced, and cross-linking was partially generated between fibers (as shown in fig. 2). When DMAC: nmp=5:5, the non-volatile NMP content is higher, the solvent volatility is further reduced, the solvent is still not evaporated after the fibers receive the substrate, and most of the fiber contact portions are crosslinked. However, the fiber splitting was poor during spinning due to the change in the properties of the spinning fluid caused by the increase in NMP, and a case where a plurality of fibers were gathered into strands was occurred as shown in fig. 3.
The mechanical property test of the nanofiber waterproof and moisture permeable films prepared by different solvent ratios is shown in table 1, and when the fibers are not crosslinked, the tensile strength is 10.2+/-0.8 MPa, and the tensile strength is general. With increasing crosslinking sites, when the solvent ratio is DMAC: nmp=6:4, the tensile strength reaches 17.8±0.9 MPa. This is because the cross-linking points can enhance the interaction between the fibers, ensuring that when the nanofiber membrane is stretched, the stress is effectively transferred between the fibers first, avoiding the occurrence of tearing. The fiber is in a net structure by an in-situ crosslinking method, and when a stretching force is applied, the net is firstly elongated and out-of-plane bending deformation occurs. As the external force increases, cracks gradually form, and part of the grids with smaller sizes are broken and fused with surrounding grids, so that larger grids are formed. Accordingly, as the number of crosslinking sites increases, the elongation at break of the nanofiber membrane also increases, and the results are shown in table 1. This multi-stage network imparts excellent stretchability to the material. Therefore, as the number of crosslinking points increases, the elongation at break of the nanofiber membrane increases at the same time. When the solvent ratio is DMAC: nmp=5:5, the fiber splitting becomes worse during the spinning process due to the change of the spinning fluid performance caused by the increase of NMP, and the condition that a plurality of fibers are gathered into strands occurs, so that the number of effective cross-linking points among the fibers is reduced, and the tensile strength is also reduced.
It can also be seen from the data in table 1 that the hydrostatic pressure of the nanofiber membrane increases with increasing cross-linking sites. This is because a lattice structure is formed between the fibers, the pores between the fibers are reduced, the hydrophobic capillary force is increased, and the nanofiber membrane exhibits a better water repellent effect. But at the same time, as the number of crosslinking sites increases, the water vapor transmission rate is attenuated because crosslinking reduces the porosity of the nanofibers and the water vapor transmission pathways are reduced. But thanks to the excellent porosity of the nanofibers themselves, the water vapor transmission rate can still reach 16261±563 g/m even in the case of a large amount of crosslinking of the fibers with a solvent ratio DMAC: nmp=6:4 2 /day。
Finally, the solvent system used in the present invention is preferably DMAC to NMP ratio of 6:4 to ensure a moderate reduction in volatility, and the fibers still have some solvent residue after they have received the substrate during spinning, ensuring that cross-linking between the fibers can occur. By increasing the proportion of the non-volatile components in the solvent and changing the solvent proportion, the fibers can generate partial cross-linking and the mechanical properties of the film are partially improved. However, further changes in the solvent tend to change the conditions such as viscosity, hydrodynamic properties, chargeability, etc. of the spinning solution, which adversely affects spinning. How to further improve the crosslinking degree between fibers under the condition of not influencing the appearance of the electrostatic spinning nanofiber is a key difficulty in preparing the high-strength nanofiber waterproof breathable film.
The invention adopts a method for further reducing the spinning temperature to reduce the volatility of the solvent, thereby realizing the further crosslinking of the nanofiber. The invention explores the influence of different spinning temperatures on the morphology and other physical properties of the fiber membrane. As a result, as shown in fig. 4 to 6, the solvent ratio was still DMAC: nmp=6:4 with a decrease in temperature, the degree of crosslinking of the fibers was further increased, and the crosslinking nodes were further thickened. This is because the reduced temperature further reduces the rate of solvent evaporation, and after the fibers have received the substrate during spinning, there is still much solvent that has not evaporated, and the fiber contact portions are significantly crosslinked. As shown in Table 2, the tensile strength of the film prepared under the spinning condition of 20℃was improved over that at 25℃at ordinary temperature, because the temperature decrease affected the volatilization of the solvent and the degree of crosslinking of the fiber diameter was further increased. When the temperature is reduced to 15 ℃, the crosslinking degree is further increased, the breaking strength of the fiber can reach 26.5+/-1.3 MPa, and the breaking elongation is 257+/-19%. When the temperature is reduced to 10 ℃, the breaking strength is further increased, the stress strength of the cross-linking points is further increased because the cross-linking is more thorough, and the increase of the breaking elongation is limited, because the fiber diameter is mostly cross-linked at 15 ℃, and an effective grid structure is formed. In other words, where the fibers have been crosslinked where they are contacted, the crosslinking points are already near saturation, and thus further reduction in the volatility of the solvent is limited to increase the number of crosslinking points. Therefore, the spinning fiber membrane at 10 ℃ and 15 ℃ has a similar grid structure, and the elongation at break of the nanofiber is not obviously improved under the spinning condition at 10 ℃. In addition, it can be seen that as the degree of crosslinking increases further, the porosity of the nanofiber membrane decreases further, which also causes a further increase in the hydrostatic pressure of the fiber membrane and a further decrease in the water vapor transmission rate.
Thus, the final spinning temperature of the present invention was controlled at 15 ℃. Too low a temperature not only increases energy consumption at higher room temperature, but also may cause excessive solvent accumulation in the substrate causing dissolution of the nanofibers, failing to form an effective nanofiber lattice structure. And the solvent volatilizes too quickly due to the too high temperature, so that the solvent volatilizes after the fiber receives the substrate, and the fiber cannot crosslink by itself.
Example 2:
the preparation method of the high-strength nanofiber waterproof and moisture-permeable membrane specifically comprises the following steps:
1) Preparation of spinning solution
Adding PU and PLA (mass ratio 7:3) into a mixed solvent of N, N-dimethylacetamide and N-methylpyrrolidone (v: v=6:4), wherein the total mass percent of PU/PLA is 12%, and stirring at 80+/-5 ℃ for 5+/-1+/-h to obtain a transparent spinning solution;
2) The above spinning solution was fed into an electrostatic spinning machine, the spinning voltage was 40 kV, the spinning temperature was 15 ℃ and the spinning humidity was 50%, and the antistatic nonwoven fabric (gram weight: 25g/m 2 ) As a spinning substrate, the distance from a spinning nozzle to the substrate is 18 cm, a control switch is turned on, spinning solution is spun on the substrate, the spinning time is 10 min, the nanofiber waterproof and moisture-permeable film is obtained, and the gram weight of the film layer of the obtained waterproof and moisture-permeable film is 5.49 g/m 2 。
The obtained waterproof moisture-permeable film is detected, and the tensile strength is 28.1+/-1.2 MPa and the elongation at break is 263+/-21%; the water vapor transmittance is 8936+/-431 g/m 2 Day; the hydrostatic pressure resistance value was 43 KPa.
The microstructure of the waterproof and moisture-permeable film prepared by observation with a scanning electron microscope is shown in fig. 7, and it can be seen from fig. 7: the high-strength nanofiber waterproof and moisture-permeable membrane prepared by the embodiment has good particle size uniformity, the diameter of the nanofiber is 200-400 nm, and obvious crosslinking is realized among the fibers, so that the feasibility of the theory and the practice of the invention is proved.
Claims (6)
1. The preparation method of the high-strength nanofiber waterproof and moisture-permeable membrane is characterized by comprising the following steps of:
1) Preparing a spinning solution:
adding fluorinated polyurethane and polylactic acid into a mixed solvent of N, N-dimethylacetamide and N-methylpyrrolidone, heating and stirring to obtain transparent spinning solution;
the mass ratio of the fluorinated polyurethane to the polylactic acid is 7:3, and the total mass percentage of the fluorinated polyurethane to the polylactic acid in the spinning solution is 10-16%; the volume ratio of the N, N-dimethylacetamide to the N-methylpyrrolidone in the mixed solvent is 6:4;
2) And (3) electrostatic spinning:
adding the spinning solution into an electrostatic spinning machine, wherein the spinning voltage is 35-60 kV, the spinning temperature is 15 ℃, the spinning humidity is 30-60%, the distance from a spinning nozzle to a spinning substrate is 18-24 cm, and the spinning solution is spun on the spinning substrate by opening a control switch to obtain the high-strength nanofiber waterproof and moisture-permeable membrane.
2. The method for preparing the high-strength nanofiber waterproof and moisture-permeable membrane according to claim 1, wherein the heating and stirring in the step 1) are carried out at 75-85 ℃ for 4-6 hours.
3. The method for preparing a high-strength nanofiber waterproof and moisture-permeable membrane according to claim 1, wherein the spinning substrate in the step 2) is antistatic, and is one of antistatic non-woven fabrics, silk fabrics, nylon fabrics or chemical fiber fabrics.
4. A high strength nanofiber waterproofing moisture permeable membrane prepared by the method of any one of claims 1-3.
5. The high-strength nanofiber waterproof and moisture-permeable membrane according to claim 4, wherein the diameter of the nanofibers is 200-400 nm, and cross-links are formed at the contact points between the nanofibers.
6. The high-strength nanofiber waterproof and moisture-permeable membrane according to claim 4, wherein the tensile strength is not less than 25 MPa, the elongation at break is not less than 250%, and the water vapor permeability is not less than 8500 g/m 2 And/day, the hydrostatic pressure is more than or equal to 40Kpa.
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