An MXene / TPU nanofiber and its preparation method and application

Abstract

The present invention belongs to the field of textile technology, and discloses an MXene / TPU nanofiber yarn and its preparation method and application. The MXene / TPU nanofiber yarn is mainly composed of a TPU nanofiber yarn and MXene flakes. The MXene flakes are attached to the surface of the TPU nanofibers and enriched on the surface layer of the MXene / TPU nanofiber yarn, and are evenly distributed on the surface layer. The preparation method is as follows: First, after the TPU solution is extruded from the needle head, a polymer jet is formed under the action of an electrostatic field force, and then the polymer jet is sent into a coagulation bath containing MXene flakes to form a nanofiber bundle, and then the nanofiber bundle is guided to move linearly, while controlling the coagulation bath to rotate spirally around the nanofiber bundle and winding it up. Its application is: using the MXene / TPU nanofiber yarn as the outer wrap yarn of the core-spun yarn to prepare the core-spun yarn, and then weaving the core-spun yarn and the hydrophilic Coolmax yarn into a two warp and two weft double-layer fabric.

Description

Technical Field

[0001] The present invention belongs to the technical field of textiles, and relates to an MXene / TPU nanofiber yarn, a preparation method thereof, and an application thereof. Background Art

[0002] With people's yearning for a high-quality life, the clothing fabric industry has received increasing attention. As the basic material of clothing, fabrics have gradually changed from the initial traditional production methods mainly based on cotton, linen, silk, and wool to the current intelligent textiles dominated by man-made fibers and diversified production, making their applications more extensive. In terms of sports and fitness, intelligent textiles can monitor exercise parameters such as heart rate, blood pressure, and pulse, enabling users to timely understand their physical conditions such as exercise intensity and energy consumption. Intelligent wearable textiles have functions such as sensing, human-computer interaction, unidirectional moisture conduction, and anti-aging, which are the new-generation user needs that traditional textiles cannot meet. Therefore, it is extremely urgent to develop intelligent wearable technologies.

[0003] MXene is a transition metal carbide or nitride material with excellent electrical conductivity and mechanical properties, having excellent electron conduction ability. The abundant functional groups on the surface of this material provide a large number of active sites and exhibit good processability in a variety of solvents. Electrospinning technology is a method of spinning polymer solutions or melts into fibers through electrostatic action. The micro-nano fibers prepared by this technology have advantages such as a high specific surface area, high porosity, and strong process controllability, and are thus widely used in scientific fields such as textiles, medicine, filtration, and energy.

[0004] In view of the excellent properties of MXene and the advantages of electrospinning technology, researchers at home and abroad have combined the two and are actively carrying out related research.

[0005] In the literature (Supercapacitor Performance of MXene-Coated Carbon Nanofiber Electrodes[J].C, 2024, 10(2).DOI:10.3390 / c10020032.), electrospinning technology was used to prepare polyacrylonitrile / MXene nanosheet blended nanofibers, and a highly sensitive sensor was successfully developed. However, the loading amount of MXene in the polyacrylonitrile / MXene nanosheet blended nanofibers prepared by this method is relatively low, only about 1 wt%.

[0006] Therefore, it is of great significance to provide an MXene / TPU nanofiber yarn, a preparation method thereof, and an application thereof to solve the above problems. Summary of the Invention

[0007] The object of the present invention is to solve the problems existing in the prior art and provide an MXene / TPU nanofiber yarn and its preparation method and application.

[0008] To achieve the above object, the technical solution adopted by the present invention is as follows:

[0009] An MXene / TPU nanofiber yarn mainly consists of TPU (thermoplastic polyurethane) nanofiber yarns and MXene sheets. The TPU nanofiber yarns are composed of multiple TPU nanofibers. The MXene sheets are attached to the surface of the TPU nanofibers and enriched on the surface layer of the MXene / TPU nanofiber yarn, and the MXene sheets are evenly distributed on the surface layer of the MXene / TPU nanofiber yarn.

[0010] As a preferred technical solution:

[0011] For the MXene / TPU nanofiber yarn as described above, the diameter of the MXene / TPU nanofiber yarn is 20 - 35 μm, the ratio of the thickness of the surface layer of the MXene / TPU nanofiber yarn to the diameter of the MXene / TPU nanofiber yarn is 1:1.5 - 2.5, and the diameter of the TPU nanofibers is 200 - 400 nm; the content of MXene sheets in the MXene / TPU nanofiber yarn is 15 - 30 wt%, and the loading amount of MXene can reach a level far higher than that of the prior art.

[0012] For the MXene / TPU nanofiber yarn as described above, the conductivity of the MXene / TPU nanofiber yarn is 30 - 100 S / cm, the sensing coefficient is 8 - 15, and the elongation at break is 400 - 500%. It can be seen that the MXene / TPU nanofiber yarn has high conductivity and stretchability, mainly because the MXene sheets are evenly distributed on the surface layer of the MXene / TPU nanofiber yarn.

[0013] The present invention also provides a method for preparing an MXene / TPU nanofiber yarn as described in any one of the above. First, the TPU solution is extruded from a needle head and forms a polymer jet under the action of an electrostatic field force. Then, the polymer jet is sent into a coagulation bath containing MXene sheets to form a nanofiber bundle. Then, the nanofiber bundle is guided to move linearly, and at the same time, the coagulation bath is controlled to rotate spirally around the nanofiber bundle, and the MXene / TPU nanofiber yarn is obtained by winding. Among them, controlling the coagulation bath to rotate spirally around the nanofiber bundle can improve the uniformity of the distribution of MXene sheets in the coagulation bath, which is beneficial to the enrichment of MXene sheets on the surface layer of the nanofiber yarn and also beneficial to the uniform distribution of MXene sheets on the surface layer of the nanofiber yarn.

[0014] As a preferred technical solution:

[0015] For the method described above, the way to form a polymer jet under the action of electrostatic field force is as follows: connect the needle to a high-voltage power supply and ground the conductive container containing the coagulation bath; the voltage of the high-voltage power supply is 15 - 20 kV;

[0016] For the way to control the coagulation bath to spiral around the nanofiber bundle: after installing a paddle stirrer at the rear end of the starting point of the nanofiber bundle running path in the coagulation bath, start the paddle stirrer, and the central axis of the paddle stirrer is parallel to the nanofiber bundle running path in the coagulation bath.

[0017] For the method described above, the content of TPU in the TPU solution is 10 - 20 wt%, and the solvent is a mixture of DMF and acetone with a volume ratio of 1:1; the content of MXene flakes in the coagulation bath containing MXene flakes is 5 - 15 mg / ml, and the coagulation bath containing MXene flakes is composed of MXene flakes, water and DMF; the temperature of the coagulation bath containing MXene flakes is 25 - 35 °C; the paddle stirrer is a three-blade paddle stirrer with a rotation speed of 100 - 1000 rpm, and the paddle blades are flat paddle blades.

[0018] The present invention also provides a core-spun yarn, the core yarn is a polyester yarn, and the outer wrapping yarn is an MXene / TPU nanofiber yarn as described in any one of the above. The core-spun yarn of the present invention has both sensitivity and spinnability.

[0019] As a preferred technical solution:

[0020] For a core-spun yarn as described above, the diameter of the core yarn is 0.3 mm, the twist angle is 40°, and the internal and external twist ratio is 10 - 35.

[0021] The present invention also provides a unidirectional moisture-conductive conductive fabric, which is a double-layer fabric of a two warp and two weft structure woven from hydrophilic Coolmax yarns and a core-spun yarn as described in any one of the above. The hydrophilic Coolmax yarns are mainly located on the surface layer and enter the inner layer through a surface and inner layer changing weaving process at the same time. The core-spun yarn is located in the inner layer; the hydrophilic Coolmax fiber is a profiled-section polyester fiber with a cross-section of a four-groove type. These grooves enable the fiber to have a capillary core absorption effect, which is beneficial for the fiber to quickly absorb the sweat on the skin surface and promote the evaporation of sweat from the fabric surface layer. In the present invention, "the hydrophilic Coolmax yarns are mainly located on the surface layer and enter the inner layer through a surface and inner layer changing weaving process at the same time" can utilize the siphon effect of the hydrophilic Coolmax yarns, which can quickly export liquids such as sweat to the surface layer.

[0022] As a preferred technical solution:

[0023] A unidirectional moisture-conductive conductive fabric as described above, the wetting time of the unidirectional moisture-conductive conductive fabric is 10 - 20 s, the maximum wetting radius is 5 - 15 mm, the diffusion speed comprehensive moisture-conducting and quick-drying ability (OMMC) is 0.2 - 0.6, and the conductivity is 10 - 60 S / m.

[0024] Beneficial effects:

[0025] (1) By utilizing the advantage of the large specific surface area of electrospun fibers in the present invention, more MXene nanosheets can be loaded into the cross-section of the nanofiber yarn. Under the action of the electrostatic field force and by controlling the coagulation bath to rotate helically around the nanofiber bundle, the MXene sheets can be attached to the surface of the TPU nanofibers and enriched on the surface layer of the MXene / TPU nanofabric. The MXene sheets are evenly distributed on the surface layer of the MXene / TPU nanofabric, making the prepared MXene / TPU nanofabric have high conductivity and stretchability.

[0026] (2) By using a coaxial winding device in the present invention, polyester yarn is used as the core yarn, and MXene / TPU nanofiber yarn is used as the outer wrapping yarn, making the prepared core-spun yarn have high conductivity and the spinnability of traditional fibers.

[0027] (3) By designing the structure of the double-layer fabric in the present invention, it is ensured that the inner and outer layers have a synergistic effect, which also endows the fabric with unique unidirectional moisture-conductive performance, realizing the efficient transmission of liquid in a specific direction. At the same time, this characteristic also makes the unidirectional moisture-conductive conductive fabric prepared by the present invention more suitable for making clothing that can quickly sweat and keep dry.

[0028] (4) In the present invention, the MXene / TPU nanofiber yarn can be directly collected through the MXene coagulation bath, without the need to collect the suspension, wash, and dry to obtain the nanofiber yarn, saving many preparation steps, optimizing the working process, and improving the production efficiency.

[0029] (5) The molecular structure of TPU is unique, consisting of rigid segments formed by the reaction of diisocyanates and chain extenders, and flexible segments formed by the reaction of diisocyanates and macromolecular polyols arranged alternately. This special structure endows TPU with excellent anti-aging characteristics. By utilizing this characteristic of TPU in the present invention, MXene / TPU nanofabric and conductive fabric have been successfully prepared, and both materials exhibit excellent anti-aging performance. Description of the drawings

[0030] Figure 1 It is a schematic diagram of the rotation of the nanofiber bundle of the present invention in the coagulation bath containing MXene sheets;

[0031] Figure 2 It is a cross-sectional schematic diagram of the MXene / TPU nanofabric of the present invention;

[0032] Figure 3 Schematic diagram for preparing MXene / TPU nanofibers and core-spun yarns according to the present invention; in the figure, θ is the twist angle.

[0033] Among them, 1 is MXene flakes, 2 is TPU nanofibers, 3 is a high-voltage power supply, 4 is a TPU solution, 5 is a coagulation bath, 6 is MXene / TPU nanofibers, 7 is core-spun yarns, and 8 is a paddle stirrer. Specific embodiments

[0034] The present invention will be further described below in conjunction with specific embodiments. It should be understood that these embodiments are only used to illustrate the present invention and not to limit the scope of the present invention. In addition, it should be understood that after reading the content taught by the present invention, those skilled in the art can make various changes or modifications to the present invention, and these equivalent forms also fall within the scope defined by the appended claims of this application.

[0035] The test methods for relevant performance indicators in the following examples and comparative examples are as follows:

[0036] Conductivity: The unidirectional moisture-conductive and conductive fabrics prepared in each example and each comparative example were used as specimens, and the specimens were tested with reference to the standard of GB / T 12703-1991. The specific process was as follows: First, the specimens were processed by the methods in 4.1-4.4 of the standard of GB / T 12703-1991, and then the volume resistivity of the processed specimens was tested with reference to the standard of GB / T 12703.4-2010 (the test environmental conditions were: temperature 23°C; relative humidity 35%), and the conductivity was calculated based on the obtained resistivity.

[0037] Sensing coefficient: The MXene / TPU nanofibers prepared in each example and each comparative example were used as specimens. First, both ends of the specimens were fixed on an EUT2203 type electronic universal testing machine, and then the initial resistance value R 0 was measured using a 34456A type digital multimeter. Then, the specimens were stretched by an electronic tensile testing machine (the clamping length of the specimens was 20 mm, the stretching speed was 20 mm / min, and the initial tension was 0.2 cN). The stretching ended when the strain on the MXene / TPU nanofibers reached 80%. Then, the resistance value R 1 of the specimens after stretching was measured using a digital multimeter. Finally, the sensing coefficient (GF) was calculated based on the measured data through a calculation formula. The calculation formula was: , where is the resistance change amount (i.e., the resistance R 1 after stretching minus the initial resistance R 0 ), R 0 is the initial resistance, is the strain (i.e., the change in the length of the nanoyarn divided by its original length).

[0038] Elongation at break: The MXene / TPU nanoyarns prepared in each embodiment and each comparative example were used as samples, respectively, and the samples were placed in an environment of 25°C and 55% relative humidity for 4 hours, and then the elongation at break of the samples was tested with reference to GB / T 3923.1-2013 standard (the test environment conditions were: temperature 23°C; relative humidity 35%). A constant rate of elongation (CRE) tester was used during the test, and the constant rate of stretching was 100 mm / min.

[0039] Wetting time: The unidirectional moisture-conducting conductive fabrics prepared in each embodiment and each comparative example were respectively used as samples, and then the samples were tested using a liquid moisture management tester (MMT) in accordance with GB / T 21655.2-2009 standard. The wetting time is the time required from the liquid contacting the surface of the inner layer (hydrophobic layer) of the fabric to the fabric starting to absorb moisture.

[0040] Maximum wetting radius: The unidirectional moisture-conducting conductive fabrics prepared in each embodiment and each comparative example were respectively used as samples, and then the inner layer (hydrophobic layer) of the sample was tested with reference to GB / T 21655.1-2008 "Evaluation of Moisture Absorption and Quick-drying Properties of Textiles Part 1: Single Item Combined Test Method", and the standard atmosphere specified in GB6529 was used during the test.

[0041] Diffusion rate comprehensive moisture conduction and quick-drying ability: The unidirectional moisture conduction conductive fabrics prepared in each embodiment and each comparative example were respectively used as samples, and then the liquid moisture management tester (manufacturer: Wenzhou Fangyuan Instrument Co., Ltd., model: FFZ381-II) with its own data system was used to conduct a comprehensive evaluation of various indicators on both sides of the sample with reference to GB / T 21655.1-2008 "Evaluation of moisture absorption and quick-drying performance of textiles Part 1: Single combination test method" standard.

[0042] Example 1

[0043] A method for preparing MXene / TPU nano yarn, the steps are as follows:

[0044] (1) Preparation of raw materials and installation and connection of equipment;

[0045] TPU solution: TPU (thermoplastic polyurethane, manufactured by BASF Chemical (Shanghai) Co., Ltd., brand 1180A) was added to a mixed solvent of acetone and DMF (volume ratio 1:1), heated in a water bath at 60°C, and magnetically stirred until completely dissolved to obtain a TPU solution; wherein the content of TPU in the TPU solution was 10wt%;

[0046] Coagulation bath containing MXene flakes: It consists of MXene flakes (manufactured by Beijing Beike New Materials Technology Co., Ltd., grade BK2020040305, CAS 12363-89-2), water and DMF. The volume ratio of water to DMF is 7:3, and the content of MXene flakes is 5 mg / ml;

[0047] As Figure 3 shown, connect the needle to the high-voltage power supply 3 with a voltage of 15 kV, and ground the conductive container containing the coagulation bath 5;

[0048] The paddle stirrer 8 is a three-blade paddle stirrer, the blade is a flat blade, the paddle stirrer is installed at the rear end of the starting point of the running path of the nanofiber bundle in the coagulation bath, and the central axis of the paddle stirrer is parallel to the running path of the nanofiber bundle in the coagulation bath;

[0049] (2) As Figure 1 、 Figure 3 shown, first extrude the TPU solution 4 from the needle at a flow rate of 0.5 ml / h, form a polymer jet under the action of electrostatic field force, then send the polymer jet into the coagulation bath containing MXene flakes at 25 °C to form a nanofiber bundle, and then guide the nanofiber bundle to move linearly. At the same time, start the paddle stirrer 8 to control the coagulation bath 5 to rotate helically around the nanofiber bundle, and wind it to obtain the MXene / TPU nanofiber yarn 6; among them, the rotation speed of the paddle stirrer is 100 rpm.

[0050] The finally prepared MXene / TPU nanofiber yarn (whose cross-section is as Figure 2 shown) consists of TPU nanofiber yarns and MXene flakes 1. The TPU nanofiber yarns are composed of multiple TPU nanofibers 2. The MXene flakes are attached to the surface of the TPU nanofibers 2 and enriched on the surface layer of the MXene / TPU nanofiber yarn, and the MXene flakes are evenly distributed on the surface layer of the MXene / TPU nanofiber yarn;

[0051] The diameter of the MXene / TPU nanofiber yarn is 35 μm. The ratio of the thickness of the surface layer of the MXene / TPU nanofiber yarn to the diameter of the MXene / TPU nanofiber yarn is 1:2.5. The diameter of the TPU nanofiber is 200 nm; the content of MXene flakes in the MXene / TPU nanofiber yarn is 15 wt%; the conductivity of the MXene / TPU nanofiber yarn is 30 S / cm, the sensing coefficient is 8, and the elongation at break is 400%.

[0052] A core-spun yarn is prepared by a coaxial winding device. As Figure 3 shown, use a polyester yarn (manufactured by Dongguan Jinxin New Materials Wire & Tape Co., Ltd., grade JXA009, yarn count 40s, diameter 0.3 mm) as the core yarn, and use the above-prepared MXene / TPU nanofiber yarn 6 as the outer wrap yarn to obtain the core-spun yarn 7.

[0053] The twist angle of the finally obtained core-spun yarn is 40°, and the internal and external twist ratio is 35.

[0054] A unidirectional moisture-conductive conductive fabric is a two-warp and two-weft double-layer fabric woven from hydrophilic Coolmax yarn (manufactured by Haiyan Jinyi Spinning Co., Ltd., product number 67671, yarn count 40s) and the above-mentioned core-spun yarn. The hydrophilic Coolmax yarn is mainly located on the surface layer and enters the inner layer through the inside-out layer weaving process, while the core-spun yarn is located in the inner layer.

[0055] The wetting time of the finally obtained unidirectional moisture-conductive conductive fabric is 20 s, the maximum wetting radius is 5 mm, the diffusion speed comprehensive moisture-conduction and quick-drying ability is 0.2, and the conductivity is 10 S / m.

[0056] Comparative Example 1

[0057] A preparation method of MXene / TPU nanofibers is basically the same as that of Example 1, except that: in step (2), the paddle stirrer is not started to control the coagulation bath to spiral around the nanofiber bundle.

[0058] The structure of the finally obtained MXene / TPU nanofibers is basically the same as that of Example 1, except that: MXene flakes are evenly distributed on the surface layer of the MXene / TPU nanofibers; the diameter of the MXene / TPU nanofibers is 40 μm, and the ratio of the thickness of the surface layer of the MXene / TPU nanofibers to the diameter of the MXene / TPU nanofibers is 1:2.6; the content of MXene flakes in the MXene / TPU nanofibers is 7.5 wt%; the conductivity of the MXene / TPU nanofibers is 20 S / cm, the sensing coefficient is 5, and the elongation at break is 240%.

[0059] A core-spun yarn is basically the same as that of Example 1, except that: the outer wrap yarn is the MXene / TPU nanofibers prepared in this comparative example.

[0060] A unidirectional moisture-conductive conductive fabric is basically the same as that of Example 1, except that: the core-spun yarn used is the core-spun yarn prepared in this comparative example;

[0061] The conductivity of the finally obtained unidirectional moisture-conductive conductive fabric is 8 S / m.

[0062] Comparing Comparative Example 1 with Example 1, it can be seen that the conductivity, sensing coefficient, and elongation at break of the MXene / TPU nanofibers prepared in Comparative Example 1 decrease, and the conductivity of the unidirectional moisture-conductive conductive fabric prepared also decreases. This is because the conductivity depends to a large extent on the integrity of the continuous network structure composed of MXene flakes. In Comparative Example 1, the nanofiber bundles lack the uniform mixing effect of the paddle stirrer, and the distribution of MXene flakes in the coagulation bath becomes uneven. This not only reduces the enrichment of MXene flakes on the surface layer of the nanofibers but also makes the distribution of MXene flakes enriched on the surface layer of the MXene / TPU nanofibers uneven, resulting in a decrease in the conductivity of the MXene / TPU nanofibers. Moreover, since MXene flakes provide mechanical reinforcement, the uneven distribution of MXene flakes on the surface layer of the MXene / TPU nanofibers also leads to a decrease in the mechanical properties of the MXene / TPU nanofibers. Therefore, the conductivity of the unidirectional moisture-conductive conductive fabric prepared in this comparative example also decreases.

[0063] Comparative Example 2

[0064] A method for preparing MXene / TPU nanofibers is the same as that in Example 1.

[0065] A core-spun yarn is the same as that in Example 1.

[0066] A unidirectional moisture-conductive conductive fabric is basically the same as that in Example 1, except that: in this comparative example, the hydrophilic Coolmax yarn does not enter the inner layer through the surface and inner layer changing weaving process;

[0067] The wetting time of the finally prepared unidirectional moisture-conductive conductive fabric is 55 s, the maximum wetting radius is 4 mm, and the comprehensive moisture-conducting and quick-drying ability of the diffusion rate is 0.15.

[0068] Comparing Comparative Example 2 with Example 1, it can be seen that the comprehensive moisture-conducting and quick-drying ability of the diffusion rate of the unidirectional moisture-conductive conductive fabric in Comparative Example 2 decreases. This is because the unidirectional moisture-conductive conductive fabric prepared in Comparative Example 2 does not adopt the surface and inner layer changing weaving process, which will cause the hydrophilic yarn to not enter the hydrophobic layer, unable to form uniformly distributed hydrophilic moisture-conducting points, and may also hinder the rapid conduction of liquid to the outer layer and effective evaporation due to the inner layer of the conductive fabric being completely composed of hydrophobic yarns, thereby weakening the unidirectional moisture-conducting ability of the fabric and making the liquid unable to spread and evaporate quickly.

[0069] Example 2

[0070] A method for preparing MXene / TPU nanofibers is as follows:

[0071] (1) Preparation of raw materials and installation and connection of equipment;

[0072] TPU solution: TPU (thermoplastic polyurethane, manufactured by BASF Chemical Industry (Shanghai) Co., Ltd., grade 1180A) was added to a mixed solvent of acetone and DMF (volume ratio 1:1), and heated in a water bath at 60 °C with magnetic stirring until completely dissolved to obtain a TPU solution; among them, the content of TPU in the TPU solution was 12 wt%;

[0073] Coagulation bath containing MXene flakes: It consists of MXene flakes (manufactured by Beijing Beike New Materials Technology Co., Ltd., grade BK2020040305, CAS 12363-89-2), water and DMF. The volume ratio of water to DMF is 7:3, and the content of MXene flakes is 8 mg / ml;

[0074] Connect the needle to a power supply with a voltage of 16 kV, and ground the conductive container containing the coagulation bath;

[0075] The paddle stirrer is a three-blade paddle stirrer, the blades are flat blades, the paddle stirrer is installed at the rear end of the starting point of the running path of the nanofiber bundle in the coagulation bath, and the central axis of the paddle stirrer is parallel to the running path of the nanofiber bundle in the coagulation bath;

[0076] (2) First, the TPU solution was extruded from the needle at a flow rate of 0.5 ml / h, and then a polymer jet was formed under the action of electrostatic field force. Then, the polymer jet was sent into a coagulation bath containing MXene flakes at 28 °C to form a nanofiber bundle. Then, the nanofiber bundle was guided to move linearly, and at the same time, the paddle stirrer was started to control the coagulation bath to rotate spirally around the nanofiber bundle, and the MXene / TPU nanofabric was obtained by winding; among them, the rotation speed of the paddle stirrer was 300 rpm.

[0077] The finally prepared MXene / TPU nanofabric consists of TPU nanofabric yarns and MXene flakes. The TPU nanofabric yarns are composed of multiple TPU nanofibers. The MXene flakes are attached to the surface of the TPU nanofibers and enriched on the surface layer of the MXene / TPU nanofabric. The MXene flakes are evenly distributed on the surface layer of the MXene / TPU nanofabric;

[0078] The diameter of the MXene / TPU nanofabric is 32 μm. The ratio of the thickness of the surface layer of the MXene / TPU nanofabric to the diameter of the MXene / TPU nanofabric is 1:2.3. The diameter of the TPU nanofibers is 250 nm. The content of MXene flakes in the MXene / TPU nanofabric is 17 wt%. The conductivity of the MXene / TPU nanofabric is 40 S / cm, the sensing coefficient is 10, and the elongation at break is 420%.

[0079] A core-spun yarn is prepared by a coaxial winding device. The polyester yarn (manufactured by Dongguan Jinxin New Material Thread Co., Ltd., grade JXA009, yarn count: 40s, diameter 0.3mm) is used as the core yarn, and the prepared MXene / TPU nanofiber yarn is used as the outer wrapping yarn.

[0080] The twist angle of the finally prepared core-spun yarn is 40°, and the internal and external twist ratio is 23.

[0081] A unidirectional moisture-conductive conductive fabric is a two-over-two-under double-layer fabric woven from hydrophilic Coolmax yarn (manufactured by Haiyan Jinyi Spinning Co., Ltd., item number 67671, yarn count: 40s) and the above-prepared core-spun yarn. The hydrophilic Coolmax yarn is mainly located on the surface layer and enters the inner layer through the inside-out layer weaving process, while the core-spun yarn is located in the inner layer.

[0082] The wetting time of the finally prepared unidirectional moisture-conductive conductive fabric is 18s, the maximum wetting radius is 7mm, the diffusion speed comprehensive moisture-conducting and quick-drying ability is 0.3, and the conductivity is 20S / m.

[0083] Example 3

[0084] A preparation method of MXene / TPU nanofiber yarn is as follows:

[0085] (1) Preparation of raw materials and installation and connection of equipment;

[0086] TPU solution: Add TPU (thermoplastic polyurethane, manufactured by BASF Chemical Industry (Shanghai) Co., Ltd., grade 1180A) to a mixed solvent of acetone and DMF (volume ratio 1:1), heat in a water bath at 60°C, and stir magnetically until completely dissolved to obtain a TPU solution; among them, the content of TPU in the TPU solution is 14wt%.

[0087] Coagulation bath containing MXene flakes: It is composed of MXene flakes (manufactured by Beijing Beike New Material Technology Co., Ltd., grade BK2020040305, CAS 12363-89-2), water and DMF. The volume ratio of water to DMF is 7:3, and the content of MXene flakes is 10mg / ml.

[0088] Connect the needle to a power supply with a voltage of 17kV, and ground the conductive container containing the coagulation bath.

[0089] The paddle stirrer is a three-blade paddle stirrer, the paddle blade is a flat paddle blade, the paddle stirrer is installed at the rear end of the starting point of the running path of the nanofiber bundle in the coagulation bath, and the central axis of the paddle stirrer is parallel to the running path of the nanofiber bundle in the coagulation bath.

[0090] (2)First, extrude the TPU solution from the needle at a flow rate of 0.5 ml / h. Under the action of the electrostatic field force, a polymer jet is formed. Then, the polymer jet is sent into a coagulation bath at 29 °C containing MXene sheets to form nanofiber bundles. Next, guide the nanofiber bundles to move linearly. At the same time, start the paddle stirrer to control the coagulation bath to rotate helically around the nanofiber bundles. After winding, MXene / TPU nanofibers are obtained; among them, the rotation speed of the paddle stirrer is 500 rpm.

[0091] The finally prepared MXene / TPU nanofibers are composed of TPU nanofiber yarns and MXene sheets. The TPU nanofiber yarns are composed of multiple TPU nanofibers. The MXene sheets are attached to the surface of the TPU nanofibers and enriched on the surface layer of the MXene / TPU nanofibers. The MXene sheets are evenly distributed on the surface layer of the MXene / TPU nanofibers;

[0092] The diameter of the MXene / TPU nanofibers is 29 μm. The ratio of the thickness of the surface layer of the MXene / TPU nanofibers to the diameter of the MXene / TPU nanofibers is 1:2.1. The diameter of the TPU nanofibers is 300 nm; the content of MXene sheets in the MXene / TPU nanofibers is 20 wt%; the conductivity of the MXene / TPU nanofibers is 55 S / cm, the sensing coefficient is 11, and the elongation at break is 450%.

[0093] A core-spun yarn is prepared by a coaxial winding device. Using a polyester yarn (manufacturer: Dongguan Jinxin New Material Thread Co., Ltd., brand: JXA009, yarn count: 40s, diameter: 0.3 mm) as the core yarn, and the above-prepared MXene / TPU nanofibers as the outer wrapping yarn.

[0094] The finally prepared core-spun yarn has a twist angle of 40° and an internal and external twist ratio of 17.5.

[0095] A unidirectional moisture-conducting conductive fabric is a two-warp and two-weft double-layer fabric woven from hydrophilic Coolmax yarns (manufacturer: Haiyan Jinyi Silk Spinning Co., Ltd., product number: 67671, yarn count: 40s) and the above-prepared core-spun yarns. The hydrophilic Coolmax yarns are mainly located on the surface layer and enter the inner layer through the inside-out layer weaving process. The core-spun yarns are located in the inner layer.

[0096] The finally prepared unidirectional moisture-conducting conductive fabric has a wetting time of 16 s, a maximum wetting radius of 8 mm, a diffusion speed and a comprehensive moisture-conducting and quick-drying ability of 0.35, and a conductivity of 30 S / m.

[0097] Example 4

[0098] A preparation method of MXene / TPU nanofibers is as follows:

[0099] (1) Preparation of raw materials and installation and connection of the device;

[0100] TPU solution: TPU (thermoplastic polyurethane, manufactured by BASF Chemical Industry (Shanghai) Co., Ltd., grade 1180A) was added to a mixed solvent of acetone and DMF (volume ratio 1:1), heated in a water bath at 60 °C, and magnetically stirred until completely dissolved to obtain a TPU solution; among them, the content of TPU in the TPU solution was 15 wt%.

[0101] Coagulation bath containing MXene flakes: It consists of MXene flakes (manufactured by Beijing Beike New Materials Technology Co., Ltd., grade BK2020040305, CAS 12363-89-2), water and DMF. The volume ratio of water to DMF is 7:3, and the content of MXene flakes is 12 mg / ml;

[0102] Connect the needle to a power supply with a voltage of 18 kV, and ground the conductive container containing the coagulation bath;

[0103] The paddle stirrer is a three-blade paddle stirrer, the paddle blades are flat paddle blades, the paddle stirrer is installed at the rear end of the starting point of the running path of the nanofiber bundle in the coagulation bath, and the central axis of the paddle stirrer is parallel to the running path of the nanofiber bundle in the coagulation bath;

[0104] (2) First, the TPU solution was extruded from the needle at a flow rate of 0.5 ml / h, and then a polymer jet was formed under the action of an electrostatic field force. Then the polymer jet was sent into a coagulation bath containing MXene flakes at 30 °C to form a nanofiber bundle. Then the nanofiber bundle was guided to move linearly, and at the same time, the paddle stirrer was started to control the coagulation bath to rotate spirally around the nanofiber bundle, and the MXene / TPU nanoyarn was obtained by winding; among them, the rotation speed of the paddle stirrer was 700 rpm.

[0105] The finally prepared MXene / TPU nanoyarn consists of TPU nanoyarns and MXene flakes. The TPU nanoyarns are composed of multiple TPU nanofibers. The MXene flakes are attached to the surface of the TPU nanofibers and enriched on the surface layer of the MXene / TPU nanoyarn. The MXene flakes are evenly distributed on the surface layer of the MXene / TPU nanoyarn;

[0106] The diameter of the MXene / TPU nanoyarn is 26 μm. The ratio of the thickness of the surface layer of the MXene / TPU nanoyarn to the diameter of the MXene / TPU nanoyarn is 1:1.9. The diameter of the TPU nanofiber is 350 nm; the content of MXene flakes in the MXene / TPU nanoyarn is 25 wt%; the conductivity of the MXene / TPU nanoyarn is 65 S / cm, the sensing coefficient is 12, and the elongation at break is 460%.

[0107] A core-spun yarn is prepared by a coaxial winding device. The core yarn is a polyester yarn (manufactured by Dongguan Jinxin New Material Wire & Tape Co., Ltd., grade JXA009, yarn count: 40s, diameter: 0.3 mm), and the prepared MXene / TPU nanofiber yarn is the sheath yarn.

[0108] The twist angle of the finally prepared core-spun yarn is 40°, and the internal and external twist ratio is 14.

[0109] A unidirectional moisture-conductive conductive fabric is a two-layer fabric of a two warp and two weft structure woven from hydrophilic Coolmax yarn (manufactured by Haiyan Jinyi Silk Spinning Co., Ltd., product number 67671, yarn count: 40s) and the prepared core-spun yarn. The hydrophilic Coolmax yarn is mainly located on the surface layer and enters the inner layer through the surface and inner layer changing weaving process, while the core-spun yarn is located in the inner layer.

[0110] The wetting time of the finally prepared unidirectional moisture-conductive conductive fabric is 14 s, the maximum wetting radius is 10 mm, the diffusion speed comprehensive moisture-conducting and quick-drying ability is 0.4, and the conductivity is 40 S / m.

[0111] Example 5

[0112] A preparation method of MXene / TPU nanofiber yarn is as follows:

[0113] (1) Preparation of raw materials and installation and connection of the device;

[0114] TPU solution: Add TPU (thermoplastic polyurethane, manufactured by BASF Chemical Industry (Shanghai) Co., Ltd., grade 1180A) to a mixed solvent of acetone and DMF (volume ratio 1:1), heat in a water bath at 60 °C, and stir magnetically until completely dissolved to obtain a TPU solution; among them, the content of TPU in the TPU solution is 18 wt%;

[0115] Coagulation bath containing MXene flakes: It consists of MXene flakes (manufactured by Beijing Beike New Material Technology Co., Ltd., grade BK2020040305, CAS: 12363-89-2), water and DMF. The volume ratio of water to DMF is 7:3, and the content of MXene flakes is 13 mg / ml;

[0116] Connect the needle to a power supply with a voltage of 19 kV, and ground the conductive container containing the coagulation bath;

[0117] The paddle stirrer is a three-blade paddle stirrer, the paddle blade is a flat paddle blade, the paddle stirrer is installed at the rear end of the starting point of the running path of the nanofiber bundle in the coagulation bath, and the central axis of the paddle stirrer is parallel to the running path of the nanofiber bundle in the coagulation bath;

[0118] (2)First, extrude the TPU solution from the needle at a flow rate of 0.5 ml / h. Under the action of the electrostatic field force, a polymer jet is formed. Then, the polymer jet is fed into a coagulation bath containing MXene flakes at 32 °C to form nanofiber bundles. Next, guide the nanofiber bundles to perform linear motion. At the same time, start the paddle stirrer to control the coagulation bath to rotate spirally around the nanofiber bundles. After winding, the MXene / TPU nanofabric is obtained. Among them, the rotation speed of the paddle stirrer is 900 rpm.

[0119] The finally prepared MXene / TPU nanofabric is composed of TPU nanofabric yarns and MXene flakes. The TPU nanofabric yarns are composed of multiple TPU nanofibers. The MXene flakes are attached to the surface of the TPU nanofibers and enriched on the surface layer of the MXene / TPU nanofabric. The MXene flakes are evenly distributed on the surface layer of the MXene / TPU nanofabric.

[0120] The diameter of the MXene / TPU nanofabric is 23 μm. The ratio of the thickness of the surface layer of the MXene / TPU nanofabric to the diameter of the MXene / TPU nanofabric is 1:1.7. The diameter of the TPU nanofibers is 380 nm. The content of MXene flakes in the MXene / TPU nanofabric is 28 wt%. The conductivity of the MXene / TPU nanofabric is 80 S / cm, the sensing coefficient is 13, and the elongation at break is 480%.

[0121] A core-spun yarn is prepared by a coaxial winding device. Using a polyester yarn (manufacturer: Dongguan Jinxin New Material Thread Co., Ltd., brand: JXA009, yarn count: 40s, diameter: 0.3 mm) as the core yarn, and the above-prepared MXene / TPU nanofabric as the outer wrapping yarn.

[0122] The finally prepared core-spun yarn has a twist angle of 40° and an internal and external twist ratio of 12.

[0123] A unidirectional moisture-conducting conductive fabric is a two-warp and two-weft double-layer fabric woven from hydrophilic Coolmax yarns (manufacturer: Haiyan Jinyi Silk Spinning Co., Ltd., product number: 67671, yarn count: 40s) and the above-prepared core-spun yarn. The hydrophilic Coolmax yarns are mainly located on the surface layer and enter the inner layer through the inside-out layer weaving process. The core-spun yarn is located in the inner layer.

[0124] The finally prepared unidirectional moisture-conducting conductive fabric has a wetting time of 12 s, a maximum wetting radius of 12 mm, a diffusion speed and a comprehensive moisture-conducting and quick-drying ability of 0.5, and a conductivity of 50 S / m.

[0125] Example 6

[0126] A preparation method of MXene / TPU nanofabric is as follows:

[0127] (1) Preparation of raw materials and installation and connection of the device;

[0128] TPU solution: TPU (thermoplastic polyurethane, manufactured by BASF Chemical Industry (Shanghai) Co., Ltd., grade 1180A) was added to a mixed solvent of acetone and DMF (volume ratio 1:1), and heated in a water bath at 60 °C, and magnetically stirred until completely dissolved to obtain a TPU solution; among them, the content of TPU in the TPU solution was 20 wt%;

[0129] Coagulation bath containing MXene flakes: composed of MXene flakes (manufactured by Beijing Beike New Materials Technology Co., Ltd., grade BK2020040305, CAS 12363-89-2), water and DMF, the volume ratio of water to DMF was 7:3, and the content of MXene flakes was 15 mg / ml;

[0130] Connect the needle to a power supply with a voltage of 20 kV, and ground the conductive container containing the coagulation bath;

[0131] The paddle stirrer is a three-blade paddle stirrer, the blades are flat blades, the paddle stirrer is installed at the rear end of the starting point of the running path of the nanofiber bundle in the coagulation bath, and the central axis of the paddle stirrer is parallel to the running path of the nanofiber bundle in the coagulation bath;

[0132] (2) First, the TPU solution was extruded from the needle at a flow rate of 0.5 ml / h, and then a polymer jet was formed under the action of an electrostatic field force. Then, the polymer jet was sent into a coagulation bath containing MXene flakes at 35 °C to form a nanofiber bundle. Then, the nanofiber bundle was guided to move linearly. At the same time, the paddle stirrer was started to control the coagulation bath to rotate spirally around the nanofiber bundle, and the MXene / TPU nanofiber yarn was obtained by winding; among them, the rotation speed of the paddle stirrer was 1000 rpm.

[0133] The finally prepared MXene / TPU nanofiber yarn is composed of TPU nanofiber yarns and MXene flakes. The TPU nanofiber yarns are composed of multiple TPU nanofibers. The MXene flakes are attached to the surface of the TPU nanofibers and enriched on the surface layer of the MXene / TPU nanofiber yarn. The MXene flakes are evenly distributed on the surface layer of the MXene / TPU nanofiber yarn;

[0134] The diameter of the MXene / TPU nanofiber yarn is 20 μm. The ratio of the thickness of the surface layer of the MXene / TPU nanofiber yarn to the diameter of the MXene / TPU nanofiber yarn is 1:1.5. The diameter of the TPU nanofiber is 400 nm; the content of MXene flakes in the MXene / TPU nanofiber yarn is 30 wt%; the conductivity of the MXene / TPU nanofiber yarn is 100 S / cm, the sensing coefficient is 15, and the elongation at break is 500%.

[0135] A core-spun yarn is prepared by a coaxial winding device, using a polyester yarn (manufactured by Dongguan Jinxin New Material Wire & Tape Co., Ltd., grade JXA009, yarn count: 40s, diameter: 0.3 mm) as the core yarn, and the above-prepared MXene / TPU nanofiber yarn as the outer wrapping yarn.

[0136] The twist angle of the finally prepared core-spun yarn is 40°, and the internal and external twist ratio is 10.

[0137] A unidirectional moisture-conducting conductive fabric is a two-over-two-under double-layer fabric woven from hydrophilic Coolmax yarn (manufactured by Haiyan Jinyi Silk Spinning Co., Ltd., product number 67671, yarn count: 40s) and the above-prepared core-spun yarn. The hydrophilic Coolmax yarn is mainly located on the surface layer and enters the inner layer through the surface-to-inner layer weaving process, while the core-spun yarn is located in the inner layer.

[0138] The wetting time of the finally prepared unidirectional moisture-conducting conductive fabric is 10 s, the maximum wetting radius is 15 mm, the diffusion speed and the comprehensive moisture-conducting and quick-drying ability is 0.6, and the conductivity is 60 S / m.

Claims

1. A method for preparing MXene / TPU nano yarn, characterized in that: After the TPU solution is squeezed out of the needle, a polymer jet is formed under the action of the electrostatic field force, and then the polymer jet is sent into a coagulation bath containing MXene sheets to form a nanofiber bundle. The nanofiber bundle is then guided to move linearly, and the coagulation bath is controlled to rotate spirally around the nanofiber bundle, and the MXene / TPU nano yarn is obtained by winding. The method of controlling the spiral rotation of the coagulation bath around the nanofiber bundle is as follows: after installing a paddle stirrer at the rear end of the starting point of the running path of the nanofiber bundle in the coagulation bath, the paddle stirrer is started, and the central axis of the paddle stirrer is parallel to the running path of the nanofiber bundle in the coagulation bath; MXene / TPU nanoyarn is mainly composed of TPU nanoyarn and MXene sheets. TPU nanoyarn is composed of multiple TPU nanofibers. MXene sheets are attached to the surface of TPU nanofibers and enriched in the surface layer of MXene / TPU nanoyarn. MXene sheets are evenly distributed on the surface layer of MXene / TPU nanoyarn.

2. The method for preparing a MXene / TPU nano yarn according to claim 1, characterized in that: The diameter of the MXene / TPU nano yarn is 20-35 μm, the ratio of the thickness of the surface layer of the MXene / TPU nano yarn to the diameter of the MXene / TPU nano yarn is 1:1.5-2.5, the diameter of the TPU nanofiber is 200-400 nm; the content of MXene sheets in the MXene / TPU nano yarn is 15-30 wt%.

3. The method for preparing a MXene / TPU nano yarn according to claim 2, characterized in that: The conductivity of MXene / TPU nanoyarn is 30-100S / cm, the sensing coefficient is 8-15, and the elongation at break is 400-500%.

4. The method for preparing a MXene / TPU nano yarn according to claim 1, characterized in that: The formation of the polymer jet under the action of the electrostatic field force is achieved by connecting the needle to a high-voltage power supply and grounding the conductive container containing the coagulation bath; the voltage of the high-voltage power supply is 15-20 kV.

5. The method for preparing a MXene / TPU nano yarn according to claim 4, characterized in that: The content of TPU in the TPU solution is 10-20wt%; the content of MXene sheets in the coagulation bath containing MXene sheets is 5-15mg / ml; the temperature of the coagulation bath containing MXene sheets is 25-35°C; the paddle agitator is a three-blade paddle agitator, the rotation speed is 100-1000rpm, and the paddles are flat blades.

6. A core-spun yarn, characterized in that: The core yarn is polyester yarn, and the outer covering yarn is MXene / TPU nano yarn prepared by the preparation method of MXene / TPU nano yarn according to any one of claims 1 to 5.

7. A core-spun yarn according to claim 6, characterized in that: The diameter of the core yarn is 0.3mm, the twist angle is 40°, and the internal and external twist ratio is 10-35.

8. A one-way moisture-conducting conductive fabric, characterized in that: The invention is a double-layer fabric with two warps and two wefts woven from hydrophilic Coolmax yarn and a core-spun yarn as claimed in claim 6 or 7, wherein the hydrophilic Coolmax yarn is mainly located in the surface layer and enters the inner layer through the surface-inside layer changing weaving process, and the core-spun yarn is located in the inner layer.

9. The one-way moisture-conducting conductive fabric according to claim 8, characterized in that: The wetting time of the unidirectional moisture-conducting conductive fabric is 10-20s, the maximum wetting radius is 5-15mm, the diffusion rate and comprehensive moisture-conducting and quick-drying ability are 0.2-0.6, and the conductivity is 10-60S / m.

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