Self-decomposing biocide protection nanotextile, method for preparing same and remote real-time human motion detection system

Abstract

The present application relates to a kind of self-kill biological protection nanometer textile and its preparation method and remote real-time human motion detection system.The polyimide nanofiber textile of the present application has excellent biological protection function, antibacterial and antiviral performance, self-kill function and excellent triboelectric performance, and the remote real-time human motion detection system integrated with bluetooth micro data acquisition card and micro battery can effectively perceive human fine motion such as swallowing, coughing, breathing, finger movement, etc., and can effectively identify the subtle differences between different motions, and has high sensitivity, effectively solves the problems of poor protective performance, poor wearing comfort and non-reusable of medical safety protection textiles.

Description

TECHNICAL FIELD

[0001] The present application belongs to the field of nanofiber textiles, and particularly relates to a self-sterilizing and killing biological protection nanotextile, a preparation method thereof and a remote real-time human motion detection system. BACKGROUND

[0002] At present, the existing biological protection textiles have the following problems: poor nanomicrobial barrier performance; poor resistance to high temperature or oxidative sterilizing agents, or lack of active sterilization function and reusability; complex donning and doffing process, and easy spread of pathogens after disposal.

[0003] Individual protection fabrics are generally composed of an isolation layer and a load-bearing layer. The isolation layer plays a physical barrier role, and the material is mostly electret polarized non-woven fabric material, which can adsorb bacteria and viruses through static electricity, and the pore diameter is mostly microns, which has strong barrier ability to bacteria but weak barrier ability to viruses. Therefore, in recent years, researchers have used nanofiber non-woven fabric material for the barrier layer, which can reduce the gap diameter to sub-micron or even nanometer, while ensuring thermal and moisture comfort, greatly improving the barrier ability. However, there are still many problems with individual protection fabrics in dealing with sudden epidemics: (1) individual protection materials only have passive barrier effect and lack active sterilization function; (2) lack of self-sterilization function, and individual protection materials need to be sterilized by high temperature before reuse; (3) individual protection materials lack anti-bioadhesion function, resulting in serious bio-deposition on the surface after multiple uses, greatly reducing the moisture and air permeability, and urgently needing super-hydrophobic self-cleaning function; (4) complex transportation process and the need for direct contact, lack of non-contact transfer methods such as magnetic adsorption; (5) lack of remote intelligent monitoring system for individual protection clothing, making it difficult to respond to sudden situations and seriously lagging in response.

[0004] With the rapid development of electronic information technology and nanotechnology, frictional nanosensing fabric has become a hot research direction. Compared with traditional semiconductor integrated sensing materials, fiber-based frictional nanogenerators have the characteristics of flexibility and miniaturization. However, the current fiber-based frictional electric fabric, especially the nanofiber-based frictional electric fabric, has poor mechanical properties, poor resistance to high temperature or sterilizing agents, or lacks self-sterilization function, making it difficult to be reused, and unable to meet the requirements of medical personnel for sensing materials. Integrating antibacterial materials into protective materials can achieve active sterilization, but conventional antibacterial materials are mostly metal nanoparticles, antibiotics, etc. However, antibacterial materials act slowly and are difficult to achieve rapid sterilization.

[0005] Chinese patent document CN104818461A discloses a preparation method of a nano-silver coated copper particle film composite material, specifically discloses that: first, a copper-chromium alloy film is prepared on the surface of a polyimide matrix, and the matrix is kept at a certain temperature to make copper atoms grow into copper particles on the surface of the alloy film, then a nano-silver film is deposited on the surface of the prepared copper-chromium alloy film to obtain the product. However, the method is to deposit a copper-chromium coating on the surface of the polyimide by magnetron sputtering, and then deposit nano-silver, and the prepared nano-copper-chromium alloy and nano-silver are layered coatings, which are not silver-copper alloys, and the particles are not protected by polymers, have poor chemical stability, the magnetron sputtering preparation process is complex, the price is high, and the application cannot be planned. In addition, the alloy particles are mainly on the surface of the polyimide, and due to the lack of chemical bonding between the metal material and the polyimide, the alloy particles are easy to fall off or oxidize. Finally, after the polyimide is covered with conductive material, the polyimide cannot contact the outside world, the triboelectric effect disappears, and the triboelectric sensor cannot be applied. SUMMARY

[0006] The first technical problem to be solved by the present application is that the existing biological protection textiles have poor nano-microorganism barrier performance, are not resistant to high temperature or oxidizing biocidal agents, lack active biocidal function, lack reusability, have a complex dressing and undressing process, and are easy to spread pathogens after being discarded. The second technical problem to be solved by the present application is that the existing flexible fiber-based triboelectric power generation fabric has poor bacterial barrier performance, poor biological protection performance, poor comfort, poor physical and chemical stability, or lacks self-biocidal function, and is difficult to reuse. The third technical problem to be solved by the present application is that the existing antibacterial material acts slowly and is difficult to achieve rapid sterilization. The fourth technical problem to be solved by the present application is that the existing biological protection fabric lacks biological micro-motion sensing function and cannot realize remote real-time health function.

[0007] To this end, the present application provides a gradient micro-nanopore structure antibacterial and antiviral polyimide nanofiber biological protection intelligent textile with passive barrier, active nano-silver copper / biocidal function and micro-motion intelligent sensing function, and further provides a remote real-time human motion detection system prepared therefrom.

[0008] The present application is realized by the following technical solutions:

[0009] In a first aspect, the present application provides a preparation method of the above-mentioned polyimide nanofiber textile, i.e., a self-biocidal biological protection nanofiber, which comprises the following steps:

[0010] (1) adding a hyperbranched polymer into an organic solvent, then adding a soluble silver salt and a soluble copper salt, and reacting under stirring to obtain a nano-silver copper alloy colloidal dispersion liquid;

[0011] (2) adding 4,4'-diamino diphenyl ether and pyromellitic dianhydride into an organic solvent, stirring to carry out polyamic acid (PAA) reaction, then adding nano silver copper alloy colloidal dispersion liquid, stirring to carry out hyperbranched polymer grafting polyamic acid (PAA) reaction, to obtain a hyperbranched polymer cross-linked polyamic acid (PAA) solution containing nano silver copper;

[0012] (3) obtaining a polyamic acid (PAA) nanofiber membrane by a spinning process such as an electrospinning process from the hyperbranched polymer cross-linked polyamic acid (PAA) solution containing nano silver copper, and then obtaining a polyimide nanofiber membrane by thermal imidization reaction;

[0013] (4) dissolving a soluble iron salt (such as FeCl3) and a soluble copper salt (such as CuSO4) in water to obtain a polymer complex solution, padding polyacrylonitrile (PAN) fabric into the polymer complex solution to obtain PAN fabric containing Fe 3+ ,Cu 2+ , and then carrying out high-temperature carbonization to obtain carbon fiber fabric containing nano Fe3O4, CuO;

[0014] (5) preparing a solution of polydimethylsiloxane (PDMS) and anhydrous ethanol (for example, in a ratio of 20 g / L) or water or a mixture of anhydrous ethanol and water, preferably a solution of PDMS and anhydrous ethanol, adding the carbon fiber fabric containing nano Fe3O4, CuO after ultrasonic treatment, mixing (for example, ultrasonic treatment), and then spraying water-based glue on the surface of the semi-dry carbon fiber fabric to obtain carbon fiber fabric sprayed with water-based glue, and finally attaching the polyimide nanofiber membrane to the surface of the carbon fiber fabric sprayed with water-based glue to obtain polyimide nanofiber textile.

[0015] In this application, semi-dry refers to that only part of the surface of the fabric is wet, and the fabric is not completely covered with liquid or contains a small amount of water (for example, 5-20 wt% water). For example, a completely wet fabric can be semi-dried under the following conditions: drying temperature 80℃, drying time 30 min.

[0016] The molecular weight of polydimethylsiloxane is generally in the range of 500-100,000. For example, liquid silicone rubber produced by Dow Corning Company can be used, such as Dow Corning 184.

[0017] The present application uses in-situ synthesis to prepare nano silver copper alloy, and embeds the nano silver copper into the high-strength polyimide nanofiber by polymerization reaction and composite electrospinning method, thereby endowing the polyimide barrier layer nanofiber material with active antibacterial and antiviral functions, and improving the triboelectric performance and mechanical strength of the polyimide fiber non-woven fabric. Meanwhile, Fe 3+ ,Cu 2+The present application is a kind of conductive nanometer Fe3O4 / CuO loaded carbon fiber fabric bearing layer material with magnetic and anti-virus function, which is prepared by complexing with hyperbranched polymer and adsorbing to the surface of PAN fiber fabric, and then carbonizing. After the material is treated by PDMS, it has self-cleaning function. When the two ends of the bearing layer are electrified, Joule heat will be generated. By applying high voltage to the two ends, extremely high temperature can be generated in a short time, which can instantly kill bacteria and viruses. Since the polyimide nanofiber can withstand high temperature above 400 DEG C, the Joule heat disinfection will not damage the barrier layer. In summary, the prepared material has the following functions: (1) the polyimide nanofiber barrier layer has excellent physical barrier effect; (2) the barrier layer and the bearing layer material contain nano-silver copper or nano-copper, both of which have active antibacterial and anti-virus functions; (3) the carbon fiber fabric bearing layer has magnetism, which can be disposed by a magnet in a non-contact manner; (4) the carbon fiber fabric bearing layer has Joule heat disinfection effect, which can realize rapid disinfection and greatly shorten the disinfection process and time; (5) the carbon fiber fabric bearing layer has super-hydrophobic property, which can realize the function of preventing biological adhesion when placed in the outer layer, and the air permeability and moisture permeability decrease less after multiple uses; (6) the carbon fiber fabric bearing layer has conductivity, which can act on the conductive functional layer, and the polyimide nanofiber has strong triboelectric effect, the carbon fiber can collect and transmit the electric charge generated by the polyimide to the data acquisition card, so as to realize the triboelectric sensing function.

[0018] Firstly, the reducibility of hyperbranched polymer is used to reduce the soluble silver salt and soluble copper salt of metal precursors in an organic solvent to prepare a nanometer silver-copper alloy colloidal dispersion liquid. Then the nanometer silver-copper alloy colloidal dispersion liquid is added to a reaction monomer solution of polyimide. The hyperbranched polymer plays a role in grafting and cross-linking, improves the dispersibility of nanometer AgCu and the stability of the polymer, and then a PAA nanofiber membrane is obtained by an electrospinning process. Then, a polyimide nanofiber membrane is obtained through thermal imidization. Then, Fe 3+ , Cu 2+ is blended with the hyperbranched polymer to obtain a polymer complex solution. Then, the PAN fabric is immersed in the above-mentioned solution (Fe 3+ , Cu 2+ content is more than 2%), and then high-temperature carbonization is carried out to obtain a magnetic anti-virus carbon fiber fabric. Then, the carbon fiber fabric is treated by PDMS. When the fabric is semi-dry, water-based glue is sprayed on the surface of the fabric. Finally, the polyimide nanofiber membrane is attached to the surface of the fabric, and a polyimide nanofiber textile is finally prepared.

[0019] The reaction mechanism of steps (2) and (3) is shown as follows: first, 4,4'-diamino diphenyl ether is ring-opening polymerized with pyromellitic dianhydride to generate PAA polymer, then the PAA polymer is reacted with the added hyperbranched polymer to generate hyperbranched polymer-branching PAA polymer, and then through thermal imidization, the PAA segment is converted into a polyimide segment. The hyperbranched polymer has very high reactivity, and in the reaction process, not only acts as a protective agent for the nano silver-copper alloy, but also acts as a crosslinking agent to crosslink different PAA segments together, and finally through thermal imidization, it is converted into a crosslinked polyimide polymer, thereby improving the toughening performance of the nanofiber.

[0020]

[0021] Further, in step (1), the hyperbranched polymer is an amino-terminated hyperbranched polymer, and the molecular weight can be 500-10000; preferably, the hyperbranched polymer has the structure shown as follows:

[0022]

[0023] Further, in step (1), the hyperbranched polymer can be purchased from Xi'an Qiyue Biological Technology Co., Ltd., and the trade name is HBP-NH2, and the molecular weight is 800-10000; or it can be prepared according to the preparation method: a mixture solution of diethylenetriamine, methyl acrylate and methanol is reacted at 10-30°C for 2-5 hours to obtain a light yellow transparent substance, then methanol is removed under reduced pressure at 60-80°C, and then the temperature is immediately raised to 130-145°C, and the reaction is continued under reduced pressure for 2-3 hours, and the reaction is stopped; preferably, the volume ratio of diethylenetriamine to methyl acrylate is, for example, (0.9-1.5):1, further for example (1.08-1.2):1, and the volume ratio of methanol to the blending liquid of diethylenetriamine and methyl acrylate is, for example, (0.9-2):1, further for example (1.05-1.5):1.

[0024] Further, in step (1), the organic solvent is an amide solvent, preferably N,N-dimethylformamide and / or N,N-dimethylacetamide.

[0025] Further, in step (1), the mass ratio of the hyperbranched polymer and the organic solvent is (1-10):100, preferably (2-4):100.

[0026] Further, in step (1), the amount of the added soluble silver salt is 3-45% of the mass of the hyperbranched polymer, preferably 3-16%.

[0027] Further, in step (1), the soluble copper salt is added in an amount of 1-50%, preferably 1-40%, preferably 1-30%, more preferably 1-15%, such as 5%, 6%, 8%, 10% of the mass of the hyperbranched polymer.

[0028] Further, in step (1), the total content of copper and silver in the nano silver-copper alloy colloidal dispersion is 0.001%-2%, preferably 0.05%-0.8%, and the mass ratio of silver to copper is 2:1-1:3, preferably 1:1-1:1.5.

[0029] Further, in step (1), the soluble silver salt is silver nitrate, and the soluble copper salt is copper nitrate.

[0030] Further, in step (1), the ratio of the mass of the hyperbranched polymer to the sum of the masses of copper and silver is 1:1-4:1 to achieve good coating effect.

[0031] Further, in step (1), the reaction kettle is a hydrothermal reaction kettle, the filling degree is 70-80%, the reaction temperature is 80-120°C, and the reaction time is 1-8 hours. In order to ensure that silver nitrate and copper nitrate are completely reduced by the hyperbranched polymer and the organic solvent, the reaction is carried out in a sealed reaction kettle, and the reaction conditions are controlled within the above range.

[0032] Further, in step (2), the organic solvent is an amide solvent, preferably N,N-dimethylformamide and / or N,N-dimethylacetamide.

[0033] Further, in step (2), the molar ratio of 4,4'-diamino diphenyl ether to pyromellitic dianhydride is (1:0.8)-(1:1.2), preferably 1:1.

[0034] Further, in step (2), the sum of the masses of 4,4'-diamino diphenyl ether and pyromellitic dianhydride is 20-50wt%, preferably 30-40wt%, relative to the mass of the organic solvent.

[0035] Further, in step (2), the mass ratio of nano silver-copper alloy (silver and copper elements) to the sum of the masses of 4,4'-diamino diphenyl ether and pyromellitic dianhydride is 1:10000-7:1000, preferably 0.2:1000-5:1000, or preferably 0.5:1000-3:1000, or preferably 0.8:1000-1:1000.

[0036] Further, in step (2), in the polyamide acid PAA reaction, the reaction temperature is 10-30°C, preferably 24°C, and the reaction time is 5-120min, preferably 30min.

[0037] Further, in step (2), the reaction temperature in the reaction of grafting the hyperbranched polymer onto the polyamic acid PAA is 10-30°C, preferably 24°C, and the reaction time is 5-120 min, preferably 20 min.

[0038] Further, in step (3), the process parameters of the electrospinning process are as follows: the electrospinning voltage is 15-19 kV, preferably 16 kV or 17 kV; the injection speed is 0.1-1.0 mL / h, preferably 0.5 mL / h; and the drum rotation speed is 200-400 r / min, preferably 260 r / min or 350 r / min.

[0039] Further, in step (3), the reaction temperature of the thermal imidization reaction is 100-350°C, preferably 100-300°C, and the reaction time is 1-5 hours, preferably 2-4 hours; more preferably, the thermal imidization reaction is carried out in the following way of gradually increasing the temperature: 100°C for 2 h, increasing the temperature to 150°C for 0.5 h, increasing the temperature to 250°C for 0.5 h, and increasing the temperature to 300°C for 0.5 h. The thermal imidization must be carried out by gradually increasing the temperature, so that the polymer gradually polymerizes, and thus the polyimide has excellent thermal stability and mechanical properties, otherwise the thermal shock will cause the polymer to decompose.

[0040] Further, in step (3), the thickness of the polyamic acid PAA nanofiber membrane is 0.020-0.045 cm.

[0041] Further, in step (3), the thickness of the polyimide nanofiber membrane is 0.020-0.050 cm.

[0042] Further, in step (4), the soluble iron salt is FeCl3, and the soluble copper salt is CuSO4.

[0043] Further, the hyperbranched polymer in step (4) is an amino-terminated hyperbranched polymer with a molecular weight of 2000-8000, which protects the metal ions and prevents excessive growth of the particle size. The molecular weight of the amino-terminated hyperbranched polymer in step (1) is smaller, otherwise the size is too large to affect the crystallization performance and mechanical strength of the polyimide nanofiber. Preferably, the hyperbranched polymer in step (4) has the following structure:

[0044]

[0045] Further, in step (4), the mass ratio of FeCl3, CuSO4, the hyperbranched polymer to water is 1:0.5-2:1-6:50-200, preferably 1:0.8-1.5:2-5:80-150, and preferably 1:1:4:100-1:1:5:100.

[0046] Further, in step (4), the impregnation rate of the PAN fabric is 50% to 200%, preferably 100%.

[0047] Further, in step (4), the high-temperature carbonization is pre-oxidation at 200 to 280°C for 1 to 3 hours and heat preservation at 800 to 900°C for 1 to 3 hours in a nitrogen atmosphere, preferably pre-oxidation at 240°C for 1 hour and heat preservation at 850°C for 2 hours in a nitrogen atmosphere.

[0048] Further, in step (5), the mass ratio of PDMS to anhydrous ethanol is 1:(30 to 70), preferably 1:(40 to 60), more preferably 1:50.

[0049] Further, in step (5), the ultrasonic time is 1 to 30 minutes, preferably 5 to 20 minutes, more preferably 10 to 15 minutes.

[0050] Further, in step (5), the drying time is 1 to 60 minutes, preferably 20 to 40 minutes.

[0051] Further, in step (5), the drying temperature is 23 to 150°C, preferably 60 to 80°C.

[0052] In a second aspect, the present application also provides a polyimide nanofiber textile prepared by the above preparation method.

[0053] The application concept of the present application is as follows: polyimide is a high molecular material obtained by polymerization reaction, and the repeat unit structure is composed of a central amide group and a side imine group. This structure makes polyimide have good mechanical strength, chemical resistance, flame resistance, high temperature resistance, high energy radiation resistance and other properties. In addition, polyimide has high negative charge and is widely used as a negative friction layer material for a friction nanogenerator. The micro-nano nanofiber membrane prepared by the electrospinning process has a large specific surface area and porosity, and can generate more charges, thus having excellent triboelectric performance. The material can generate nanoscale sterilization ions in situ, and can realize super strong electrostatic adsorption and high pressure electrostatic sterilization (electrostatic breakdown) of microorganisms, physical barrier, and nanosilver copper self-sterilization function through triboelectric charging. The formed pores can block most bacteria and viruses. In order to further improve its performance, the polyimide nanofiber membrane is compounded with a super-hydrophobic magnetic carbon fiber fabric conductive layer on the surface. This layer can effectively filter smaller nanoparticles, while maintaining good moisture and air permeability, and can act as a charge collection layer for triboelectric materials to realize self-power supply and sensing functions. More importantly, the material can kill pathogens in a short time through Joule heating by reverse power supply, thereby realizing rapid sterilization function. In cold winter, it can also serve as a heating layer. In addition, the super-hydrophobic magnetic carbon fiber fabric has self-cleaning and anti-bioadhesion functions, which can effectively prevent pathogenic organisms from adhering, thereby realizing certain biological protection function. The magnetic Fe3O4 can be used to adsorb protective clothing, thereby realizing no-contact sterilization and other operations, and avoiding the risk of pathogen contact caused by direct operation of protective clothing by human hands. Finally, the composite material has good waterproof and moisture permeability and flexibility, and can be closely attached to the surface of the skin or clothing through electrostatic adsorption, can sense small human movements, and can distinguish the subtle differences between different fine movements, such as the difference between swallowing and drinking actions.

[0054] The polyimide nanofiber textile has the functions of personal biological protection such as ultra-light, ultra-soft, highly hydrophobic, waterproof and moisture permeable, nanometer microbial barrier, nanosilver copper / self-sterilization, human kinetic energy collection, and intelligent sensing.

[0055] In a third aspect, the present application also provides an application of the above-mentioned polyimide nanofiber textile in preparing a remote real-time human motion detection system.

[0056] In a fourth aspect, the present application also provides a remote real-time human motion detection system, which comprises the above-mentioned polyimide nanofiber textile.

[0057] Further, the above-mentioned remote real-time human motion detection system further comprises a Bluetooth micro data acquisition card and a micro battery. The Bluetooth micro data acquisition card and the micro battery are attached to the surface of the above-mentioned polyimide nanofiber textile fabric through a watchband or adhesion. Figure 1 As shown in the figure.

[0058] The remote real-time human motion detection system can be used for health monitoring of respiratory system, throat movement, limb movement, finger movement, etc., and the specific principle is that when the prepared polyimide nanofiber textile fabric contacts with the outside world, a strong voltage is generated through triboelectric effect, and after the Bluetooth micro data acquisition card detects the voltage change, the signal is transmitted to the mobile phone in real time through Bluetooth.

[0059] The wearable remote intelligent sensing system prepared from the polyimide nanofiber textile, i.e., the remote real-time human motion detection system, has a total mass of only 18g, a continuous time of more than 30 hours, can realize real-time sensing of breathing, throat, limbs, gestures and other movements, and has potential application value in the field of personal biological protection and epidemic prevention.

[0060] The technical scheme of the present application has the following advantages:

[0061] (1) The polyimide nanofiber textile of the present application has excellent biological protection function, antibacterial and antiviral performance, self-sterilization function and excellent triboelectric performance, and the remote real-time human motion detection system integrated with the Bluetooth micro data acquisition card and the micro battery can effectively sense the fine human movements such as swallowing, coughing, breathing, finger movement, etc., can effectively identify the subtle differences between different movements, and has high sensitivity, effectively solving the problems of poor protection performance, poor wearing comfort and non-reusable of medical safety protection textiles;

[0062] (2) The polyimide nanofiber textile of the present application uses electrospinning process, encapsulates nano silver copper alloy into the fiber by in-situ polymerization reaction in polyimide solution, and prepares flexible nanoscale hyperbranched polymer copolymer polyimide fiber membrane with excellent antibacterial performance, which has large specific surface area, excellent electrostatic adsorption and microbial barrier properties, excellent mechanical properties, good wearing comfort and air permeability, moisture permeability, hydrophobicity, excellent triboelectric performance, after adding nano silver copper alloy, a large number of nano capacitors are formed in the fiber, thereby greatly improving the charge storage efficiency of charge separation, and the triboelectric output power can reach 1.2W / m 2 ; The conductive carbon fiber contains nano copper oxide, also has antiviral effect, and the conductive carbon fiber treated by PDMS has super-hydrophobic self-cleaning function, thereby having certain anti-pathogen adhesion function, and the fabric can remove surface impurities after simple washing, thus having certain repeatability and biological protection; The carbon fiber fabric in the composite fabric has instantaneous joule heat sterilization capacity, and 100% of pathogens can be killed after heating for 15 minutes under 5-volt voltage, and the prepared composite fabric can be reused after simple joule heat sterilization treatment;

[0063] (3) The polyimide nanofiber textile of the present application has extremely light weight (total weight about 18g), excellent friction piezoelectric performance and sensing sensitivity, can wirelessly sense breathing, throat movement, limb movement, etc., has extremely strong sensitivity to micro-movement and small differences, and can identify different micro-movement states, such as normal breathing and deep breathing, normal speaking and shouting, drinking and swallowing, etc.; in general, the composite fabric has excellent biological protection performance, wearing comfort and wearable performance, reusability, and high-sensitivity remote intelligent biological monitoring function, and has potential application value in the field of medical biological protection intelligent wearable. BRIEF DESCRIPTION OF DRAWINGS

[0064] In order to make the content of the present application more easily understood, the present application will be further described in detail below according to specific embodiments of the present application and in conjunction with the drawings, in which:

[0065] Figure 1 The wearable remote real-time human motion detection system prepared, wherein (a) represents the hardware composition of the wearable remote real-time human motion detection system; (b) represents assembling the hardware into a watch to realize the wearable function;

[0066] Figure 2 TEM image of the hyperbranched polymer crosslinked polyamic acid PAA solution containing nano silver copper prepared in Example 1;

[0067] Figure 3 In the figure, (a) and (b) are respectively TEM images of pure polyimide nanofiber and polyimide nanofiber film in Example 1;

[0068] Figure 4 In the figure, (a) is a pure carbon fiber fabric FEEM image obtained after carbonization of the PNA fabric without adsorbing Fe 3+ ,Cu 2+ ; (b) is a carbon fiber fabric FEEM image containing nano Fe3O4 and CuO obtained after carbonization of the PNA fabric adsorbing Fe 3+ ,Cu 2+ ; (c) is an electron microscope image of super-hydrophobic carbon fiber fabric containing nano Fe3O4 and CuO obtained after PDMS treatment of the carbon fiber fabric;

[0069] Figure 5 The composite fabric prepared in Example 1 is pasted on the back of the hand and connected with a single-channel Bluetooth data acquisition card, and the wireless signal received by the mobile phone by patting the back of the hand; the test results show that patting the back of the hand can produce obvious signal, the sensing voltage is between 1-3 volts, and has good responsiveness;

[0070] Figure 6UPF value of the cotton fabric and the composite fabric prepared in Example 2; the test results show that the UPF value of the cotton fabric is less than 20, while the UPF value of the composite fabric can reach more than 6000, indicating that it has super strong ultraviolet shielding performance;

[0071] Figure 7 Friction voltage (a), friction current (b) and friction induced charge (c) of the composite fabric prepared in Example 3 under different contact pressures; the test shows that the triboelectric performance of the composite fabric is related to the contact pressure, when the contact pressure increases, the triboelectric voltage, current and charge all increase, so the material has a certain pressure sensitivity;

[0072] Figure 8 Signal diagram generated by tapping the composite fabric of Example 4; the composite fabric of Example 4 is pasted on the thumb, index finger, middle finger and ring finger, and then the four fabrics are connected with a four-channel miniature Bluetooth data acquisition card for collecting the coordinated motion signals of the four fingers, Figure 8 Signal generated by tapping the keyboard with the index finger; the test results show that the composite fabric can generate strong induced signals, in which the signal generated by the index finger can reach up to 4V. DETAILED DESCRIPTION

[0073] The technical solutions in the embodiments of the present application will be described clearly and completely in combination with the drawings in the embodiments of the present application. Obviously, the described embodiments are only part of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor fall within the scope of protection of the present application.

[0074] In the following examples, the hyperbranched polymer is purchased from Xi'an Qiyue Biological Technology Co., Ltd., with the trade name HBP-NH2, and the molecular weight is 800-10000;

[0075] The PAN fabric is a commercially available product;

[0076] The water-based glue, i.e. water-based polyurethane, is purchased from Shenzhen Jitian Chemical Co., Ltd., with the trade name F0401, the viscosity is >300 mPa·s, and the pH value is 5-6;

[0077] The PDMS is purchased from Dow Corning, with the model number 184;

[0078] The Bluetooth miniature data acquisition card is purchased from Jiyuan, with the voltage measurement range of 0.5-10V;

[0079] The miniature battery has a rated voltage of 3.7V.

[0080] Example 1

[0081] The preparation method of the polyimide nanofiber textile of the embodiment includes the following steps:

[0082] S1, 8g of hyperbranched polymer is dissolved in 100g of N,N-dimethylformamide, then 0.3148g of silver nitrate and 0.7868g of copper nitrate are added to the above solvent, after sufficient stirring, the above solution is transferred to a hydrothermal reactor, and the reaction is carried out at 100℃ for 2h, the filling degree is 80%, and a nano silver copper alloy colloidal dispersion liquid is obtained (wherein the total content of copper element and silver element is 2000mg / kg (0.2%));

[0083] S2, 1.35g of 4,4'-diamino diphenyl ether and 1.35g of pyromellitic dianhydride are dissolved in 7.3g of N,N-dimethylformamide, and the solution is stirred and dissolved, and the polyamic acid PAA reaction is carried out at 24℃ for 30min to obtain a PAA polymer, then 1g of the nano silver copper alloy colloidal dispersion liquid is added, and the hyperbranched polymer grafted polyamic acid PAA reaction is carried out by stirring at 24℃ for 20min to obtain a hyperbranched polymer cross-linked polyamic acid PAA solution containing nano silver copper, and the TEM diagram thereof is as shown in Figure 2 It can be seen from Figure 2 that the prepared nano silver copper particles are round, uniform in size, indicating the successful synthesis of nano silver copper;

[0084] S3, 1mL of the hyperbranched polymer cross-linked polyamic acid PAA solution containing nano silver copper is obtained by an electrospinning process (the electrospinning voltage is 17kV, the injection speed is 0.5mL / h, and the drum rotation speed is 350r / min) to obtain a PAA nanofiber membrane, and then a thermal imidization reaction (the gradual heating conditions are as follows: 100℃ for 2h, 150℃ for 0.5h, 250℃ for 0.5h, and 300℃ for 0.5h) is carried out to obtain a polyimide nanofiber membrane (thickness 0.036cm), and the TEM diagram thereof is as shown in Figure 3 It can be seen from Figure 3 that compared with the uniform interior of pure polyimide nanofiber, the silver copper alloy loaded polyimide nanofiber is uniformly distributed with nano silver copper particles with a particle size range of 5-20nm, which is consistent with the TEM observation result;

[0085] S4, 2g of FeCl3, 2g of CuSO4 and 10g of hyperbranched polymer are dissolved in 100g of water to obtain a polymer complex solution, and the PAN fabric is padded (the padding rate is 100%) into the polymer complex solution to obtain a PAN fabric containing Fe 3+ ,Cu 2+ , and then high-temperature carbonization (high-temperature carbonization is 240℃ pre-oxidation in a nitrogen atmosphere for 1h, and 850℃ for 2h) is carried out to obtain a carbon fiber fabric containing nano Fe3O4 and CuO;

[0086] S5, polydimethylsiloxane PDMS and anhydrous ethanol were mixed into a solution at a ratio of 1:50 (mass ratio), after ultrasonic treatment for 20 min, carbon fiber fabric containing nano Fe3O4 and CuO was added, and ultrasonic treatment was performed for 20 min. When the surface was semi-dry (drying temperature 80℃, drying time 30 min), water-based glue was sprayed, and finally the polyimide nanofiber membrane was pasted on the surface of the fabric. The final polyimide nanofiber textile was obtained, as shown in Figure 4 .

[0087] The polyimide nanofiber textile prepared in Example 1 was integrated with a Bluetooth micro data acquisition card (measurement range 0.5-10V) and a micro battery to prepare a remote real-time human motion detection system through a watchband or by pasting the fabric. The system can be used for elbow motion health monitoring.

[0088] Example 2

[0089] The preparation method of the polyimide nanofiber textile of the present embodiment comprises the following steps:

[0090] S1, 4g of hyperbranched polymer was dissolved in 100g of N,N-dimethylformamide, then 0.1573g of silver nitrate and 0.3934g of copper nitrate were added to the above solvent, and after stirring, the above solution was transferred to a hydrothermal reactor, and reacted at 100℃ for 2h, with a filling degree of 80%, to obtain a nano silver-copper alloy colloidal dispersion (wherein the total content of copper and silver elements is 1000mg / kg (0.1%));

[0091] S2, 1.35g of 4,4'-diamino diphenyl ether and 1.35g of pyromellitic dianhydride were dissolved in 7.3g of N,N-dimethylformamide, and stirred to dissolve, and reacted at 24℃ for 30min to carry out polyamic acid PAA reaction, to obtain PAA polymer, then 1.5g of nano silver-copper alloy colloidal dispersion was added, and stirred to react at 24℃ for 20min to carry out hyperbranched polymer grafting polyamic acid PAA reaction, to obtain a hyperbranched polymer cross-linked polyamic acid PAA solution containing nano silver-copper;

[0092] S3, 1mL of the hyperbranched polymer cross-linked polyamic acid PAA solution containing nano silver-copper was obtained by electrospinning process (electrospinning voltage 17kV, injection speed 0.5mL / h, drum rotation speed 350r / min) to obtain a PAA nanofiber membrane, and then a thermal imidization reaction (gradual heating conditions as follows: 100℃ for 2h, 150℃ for 0.5h, 250℃ for 0.5h, 300℃ for 0.5h) was carried out to obtain a polyimide nanofiber membrane (thickness 0.038cm);

[0093] S4, 2g FeCl3, 2g CuSO4 and 10g hyperbranched polymer were dissolved in 100g water to obtain a polymer complex solution, and PAN fabric was padded (padding rate was 100%) into the polymer complex solution to obtain PAN fabric containing Fe 3+ ,Cu 2+ , and then high-temperature carbonization (high-temperature carbonization was 240℃ pre-oxidation for 1h in nitrogen atmosphere, and 850℃ for 2h) was performed to obtain carbon fiber fabric containing nano Fe3O4, CuO;

[0094] S5, PDMS and anhydrous ethanol were mixed into a solution at a ratio (mass ratio) of 1:50, and after ultrasonic treatment for 20min, the carbon fiber fabric containing nano Fe3O4, CuO was added, and then ultrasonic treatment was performed for another 20min. When the surface was semi-dry (drying temperature was 80℃, and drying time was 30min), water-based glue was sprayed, and the polyimide nanofiber membrane was pasted on the surface of the fabric to obtain polyimide nanofiber textile.

[0095] The polyimide nanofiber textile prepared in Example 2 was integrated with a Bluetooth micro data acquisition card and a micro battery through a watchband or by pasting the fabric to obtain a remote real-time human motion detection system, which can be used for sports health monitoring. Figure 6 The UPF values of (a) cotton fabric and (b) composite fabric are shown. The test results show that the UPF value of cotton fabric is less than 20, while the UPF value of composite fabric can reach more than 6000, indicating that it has super strong ultraviolet shielding performance.

[0096] Example 3

[0097] The preparation method of the polyimide nanofiber textile of the present embodiment comprises the following steps:

[0098] S1, 1g hyperbranched polymer was dissolved in 100g N,N-dimethylformamide, and then 0.1573g silver nitrate and 0.3934g copper nitrate were added to the above solvent. After stirring, the above solution was transferred to a hydrothermal reaction kettle and reacted at 100℃ for 2h with a filling degree of 80% to obtain a nano silver-copper alloy colloidal dispersion (wherein the total content of copper element and silver element was 1000mg / kg (0.1%));

[0099] S2, 1.35g 4,4'-diamino diphenyl ether and 1.35g pyromellitic dianhydride were dissolved in 7.3g N,N-dimethylformamide, and stirred to dissolve. The reaction was carried out at 24℃ for 30min to carry out polyamic acid PAA reaction to obtain PAA polymer, and then 1g nano silver-copper alloy colloidal dispersion was added and stirred to react at 24℃ for 20min to carry out hyperbranched polymer grafting polyamic acid PAA reaction to obtain hyperbranched polymer crosslinked polyamic acid PAA solution containing nano silver-copper.

[0100] S3, 1 mL of hyperbranched polymer cross-linked polyamic acid (PAA) solution containing nano silver copper was obtained by electrospinning process (electrospinning voltage was 17 kV, injection speed was 0.5 mL / h, and drum rotation speed was 350 r / min), and then polyimide nanofiber membrane (thickness was 0.042 cm) was obtained by thermal imidization reaction (gradual heating conditions were as follows: 100 ℃ for 2 h, 150 ℃ for 0.5 h, 250 ℃ for 0.5 h, and 300 ℃ for 0.5 h);

[0101] S4, 2 g of FeCl3, 2 g of CuSO4 and 10 g of hyperbranched polymer were dissolved in 100 g of water to obtain a polymer complex solution, PAN fabric was padded (padding rate was 100%) into the polymer complex solution to obtain PAN fabric containing Fe 3+ ,Cu 2+ , and then high-temperature carbonization (high-temperature carbonization was 240 ℃ pre-oxidation for 1 h in nitrogen atmosphere, and 850 ℃ for 2 h) was performed to obtain carbon fiber fabric containing nano Fe3O4 and CuO;

[0102] S5, PDMS and anhydrous ethanol were mixed into a solution at a ratio (mass ratio) of 1:50, and then the carbon fiber fabric containing nano Fe3O4 and CuO was added after ultrasonic treatment for 20 min, and then ultrasonic treatment was performed for another 20 min. When the surface was semi-dried (drying temperature was 80 ℃, and drying time was 30 min), water-based glue was sprayed on the surface, and then the polyimide nanofiber membrane was attached to the surface of the fabric to finally obtain polyimide nanofiber textile.

[0103] The polyimide nanofiber textile prepared in Example 3 was integrated with a Bluetooth micro data acquisition card (measurement range was 0.5-10 V) and a micro battery to prepare a remote real-time human motion detection system by means of a watchband or by pasting the fabric, which can be used to detect "SOS" radio voltage signals.

[0104] Example 4

[0105] The preparation method of the polyimide nanofiber textile in this example includes the following steps:

[0106] S1, 2 g of hyperbranched polymer was dissolved in 100 g of N,N-dimethylformamide, and then 0.3148 g of silver nitrate and 0.7868 g of copper nitrate were added to the above solvent. After being stirred thoroughly, the above solution was transferred to an autoclave, and then reaction was performed at 100 ℃ for 2 h with a filling degree of 80% to obtain a nano silver copper alloy colloidal dispersion (in which the total content of copper element and silver element was 2000 mg / kg (0.2%));

[0107] S2, 1.35 g of 4,4'-diamino diphenyl ether and 1.35 g of pyromellitic dianhydride were dissolved in 7.3 g of N,N-dimethylformamide, and stirred to dissolve, and reacted at 24°C for 30 min to perform polyamic acid PAA reaction to obtain a PAA polymer, and then 0.5 g of a nano silver copper alloy colloidal dispersion liquid was added, and stirred to react at 24°C for 20 min to perform hyperbranched polymer grafting polyamic acid PAA reaction to obtain a hyperbranched polymer cross-linked polyamic acid PAA solution containing nano silver copper;

[0108] S3, 1 mL of the hyperbranched polymer cross-linked polyamic acid PAA solution containing nano silver copper was obtained by an electrospinning process (an electrospinning voltage of 17 kV, an injection speed of 0.5 mL / h, and a drum rotation speed of 350 r / min) to obtain a PAA nanofiber membrane, and then a thermal imidization reaction (gradual heating conditions as follows: 100°C for 2 h, 150°C for 0.5 h, 250°C for 0.5 h, and 300°C for 0.5 h) was performed to obtain a polyimide nanofiber membrane (a thickness of 0.030 cm);

[0109] S4, 2 g of FeCl3, 2 g of CuSO4, and 10 g of a hyperbranched polymer were dissolved in 100 g of water to obtain a polymer complex solution, and a PAN fabric was padded (a padding rate of 100%) into the polymer complex solution to obtain a PAN fabric containing Fe 3+ ,Cu 2+ , and then high-temperature carbonization (high-temperature carbonization was 240°C pre-oxidation for 1 h and 850°C for 2 h in a nitrogen atmosphere) was performed to obtain a carbon fiber fabric containing nano Fe3O4 and CuO;

[0110] S5, PDMS and anhydrous ethanol were mixed into a solution at a ratio (mass ratio) of 1:50, and then the carbon fiber fabric containing nano Fe3O4 and CuO was added after ultrasonic treatment for 20 min, and then ultrasonic treatment was performed for another 20 min, and then the surface was sprayed with water-based glue when it was semi-dried (drying temperature: 80°C, drying time: 30 min), and then the polyimide nanofiber membrane was attached to the surface of the fabric, and finally a polyimide nanofiber textile was obtained.

[0111] The polyimide nanofiber textile prepared in Example 4 was integrated with a Bluetooth micro data acquisition card (a measurement range of 0.5-10V) and a micro battery to obtain a remote real-time human motion detection system which can be used for sports health monitoring.

[0112] Example 5

[0113] The preparation method of the polyimide nanofiber textile of the present embodiment comprises the following steps:

[0114] S1, 4g of hyperbranched polymer was dissolved in 100g of N,N-dimethylformamide, then 0.1573g of silver nitrate and 0.3934g of copper nitrate were added to the above solvent, after stirring, the above solution was transferred to a hydrothermal reactor, reacted at 100℃ for 2h, the filling degree was 80%, and a nano silver-copper alloy colloidal dispersion was obtained (wherein the content of copper element and silver element was 1000mg / kg (0.1%));

[0115] S2, 1.35g of 4,4'-diamino diphenyl ether and 1.35g of pyromellitic dianhydride were dissolved in 7.3g of N,N-dimethylformamide, stirred and dissolved, reacted at 24℃ for 30min, and a polyamic acid PAA reaction was carried out to obtain a PAA polymer, then 1.5g of nano silver-copper alloy colloidal dispersion was added, stirred, reacted at 24℃ for 20min, and a hyperbranched polymer grafted polyamic acid PAA reaction was carried out to obtain a hyperbranched polymer cross-linked polyamic acid PAA solution containing nano silver-copper;

[0116] S3, 1mL of the hyperbranched polymer cross-linked polyamic acid PAA solution containing nano silver-copper was obtained by electrospinning process (electrospinning voltage was 17kV, injection speed was 0.5mL / h, and drum rotation speed was 350r / min) to obtain a PAA nanofiber membrane, and then a thermal imidization reaction (gradual heating conditions were as follows: 100℃ for 2h, 150℃ for 0.5h, 250℃ for 0.5h, and 300℃ for 0.5h) was carried out to obtain a polyimide nanofiber membrane (thickness was 0.036cm);

[0117] S4, 2g of FeCl3, 2g of CuSO4 and 10g of hyperbranched polymer were dissolved in 100g of water to obtain a polymer complex solution, and a PAN fabric was padded (padding rate was 100%) into the polymer complex solution to obtain a PAN fabric containing Fe 3+ ,Cu 2+ , and then high-temperature carbonization (high-temperature carbonization was 240℃ pre-oxidation in nitrogen atmosphere for 1h and 850℃ for 2h) was carried out to obtain a carbon fiber fabric containing nano Fe3O4 and CuO;

[0118] S5, PDMS and anhydrous ethanol were mixed into a solution at a ratio of 1:50 (mass ratio), then the carbon fiber fabric containing nano Fe3O4 and CuO was added after ultrasonic treatment for 20min, and then ultrasonic treatment was carried out for another 20min, and then the surface was sprayed with water-based glue when it was semi-dried (drying temperature was 80℃ and drying time was 30min), and then the polyimide nanofiber membrane was attached to the surface of the fabric, and finally a polyimide nanofiber textile was obtained.

[0119] The polyimide nanofiber textile prepared in Example 5 is integrated with a Bluetooth micro data acquisition card (measurement range 0.5-10V) and a micro battery to prepare a remote real-time human motion detection system through a watchband or by pasting the fabric, which can be used for monitoring sports health.

[0120] The killing rate test of E. coli and S. aureus is performed according to "Evaluation of Antimicrobial Finished Textiles - Part 3: Shake Flask Method":

[0121] Table 1 Killing rate of composite fabric with different nano-silver-copper content on E. coli and S. aureus

[0122]

[0123] As shown in Table 1, when the nano-silver-copper content exceeds 70 parts per million, the antibacterial rate on E. coli and S. aureus exceeds 100%, which proves the super strong bactericidal effect.

[0124] Table 2 Killing rate of composite fabric (composite fabric of Example 5) on E. coli and S. aureus under different voltages (heating for 15 min)

[0125] Voltage (V) Escherichia coli Staphylococcus aureus 3 58.25 82.22 4 78.18 99.32 5 100 100 6 100 100

[0126] As shown in Table 2, when a voltage of 5V or more is applied to the two ends of the composite fabric, E. coli and S. aureus can be completely killed in 15 minutes, so the microorganisms on the surface of the material can be simply killed by applying a voltage, greatly simplifying the disinfection procedure.

[0127] Comparative Example 1

[0128] The difference between this comparative example and Example 1 is that only copper nitrate is added in step S1, which specifically includes the following steps:

[0129] S1, 8g of hyperbranched polymer is dissolved in 100g of N,N-dimethylformamide, then 0.7868g of copper nitrate is added to the above solvent, after sufficient stirring, the above solution is transferred to a hydrothermal reaction kettle, and the reaction is carried out at 100℃ for 2h, the filling degree is 80%, and a nano-cuprous oxide alloy colloidal dispersion liquid is obtained;

[0130] S2, 1.35g of 4,4'-diamino diphenyl ether and 1.35g of pyromellitic dianhydride are dissolved in 7.3g of N,N-dimethylformamide, and stirred to dissolve, and a polyamide acid PAA reaction is carried out at 24℃ for 30min to obtain a PAA polymer, then 1g of the nano-cuprous oxide alloy colloidal dispersion liquid is added, and stirred to react at 24℃ for 20min to carry out a hyperbranched polymer grafting polyamide acid PAA reaction, to obtain a hyperbranched polymer crosslinked polyamide acid PAA solution containing nano-copper;

[0131] S3, 1 mL of hyperbranched polymer cross-linked polyamide acid (PAA) solution containing nano-cuprous oxide was obtained by electrospinning process (the electrospinning voltage was 17 kV, the injection speed was 0.5 mL / h, and the drum rotation speed was 350 r / min), and then polyimide nanofiber membrane (thickness 0.036 cm) was obtained by thermal imidization reaction (the gradual heating conditions were as follows: 100°C for 2 h, 150°C for 0.5 h, 250°C for 0.5 h, and 300°C for 0.5 h);

[0132] S4, 2 g of FeCl3, 2 g of CuSO4, and 10 g of hyperbranched polymer were dissolved in 100 g of water to obtain a polymer complex solution, and PAN fabric was immersed (the immersion rate was 100%) in the polymer complex solution to obtain PAN fabric containing Fe 3+ ,Cu 2+ , and then high-temperature carbonization (high-temperature carbonization was 240°C pre-oxidation for 1 h in a nitrogen atmosphere, and 850°C for 2 h) was performed to obtain carbon fiber fabric containing nano-Fe3O4 and CuO;

[0133] S5, PDMS and anhydrous ethanol were mixed according to a mass ratio of 1:50 to form a solution, and then the solution was ultrasonically treated for 20 min. The carbon fiber fabric containing nano-Fe3O4 and CuO was added, and then ultrasonic treatment was performed for another 20 min. When the surface was semi-dried (drying temperature 80°C, drying time 30 min), water-based glue was sprayed on the surface. Finally, the polyimide nanofiber membrane was attached to the surface of the fabric, and a polyimide nanofiber textile was finally obtained.

[0134] The polyimide nanofiber textile prepared in the comparative example had poor antibacterial performance. Since nano-copper obtained by reduction of copper nitrate is unstable and quickly converts into nano-cuprous oxide, the antibacterial performance of nano-cuprous oxide is one order of magnitude lower than that of nano-silver copper.

[0135] Table 3 Killing rates of composite fabrics containing nano-silver copper and composite fabrics containing only nano-cuprous oxide on Escherichia coli and Staphylococcus aureus

[0136]

[0137] Comparative Example 2

[0138] The difference between the comparative example and Example 1 is that the PAN fabric is not immersed in CuSO4 and FeCl3 in step S4, but is directly carbonized. The specific steps include the following steps:

[0139] S1, 8 g of hyperbranched polymer was dissolved in 100 g of N,N-dimethylformamide, then 0.3148 g of silver nitrate and 0.7868 g of copper nitrate were added to the above solvent, after stirring, the above solution was transferred to a hydrothermal reactor, reacted at 100℃ for 2h, the filling degree was 80%, and a nano silver copper alloy colloidal dispersion was obtained, wherein the content of copper element and silver element was 0.2%, and the content of nano silver copper alloy was 0.4%;

[0140] S2, 1.35 g of 4,4'-diamino diphenyl ether and 1.35 g of pyromellitic dianhydride were dissolved in 7.3 g of N,N-dimethylformamide, and stirred to dissolve, reacted at 24℃ for 30 min to carry out polyamic acid PAA reaction, and then 1 g of nano silver copper alloy colloidal dispersion was added, stirred, and reacted at 24℃ for 20 min to carry out hyperbranched polymer grafting polyamic acid PAA reaction, and a hyperbranched polymer cross-linked polyamic acid PAA solution containing nano silver copper was obtained;

[0141] S3, 1 mL of the hyperbranched polymer cross-linked polyamic acid PAA solution containing nano silver copper was obtained by electrospinning process (electrospinning voltage was 17 kV, injection speed was 0.5 mL / h, and drum rotation speed was 350 r / min) to obtain PAA nanofiber membrane, and then heat imidization reaction (gradual heating conditions were as follows: 100℃ for 2h, 150℃ for 0.5h, 250℃ for 0.5h, and 300℃ for 0.5h) to obtain polyimide nanofiber membrane (thickness was 0.036 cm);

[0142] S4, 2 g of CuSO4 and 10 g of hyperbranched polymer were dissolved in 100 g of water to obtain a polymer complex solution, and the PAN fabric was padded (padding rate was 100%) into the polymer complex solution, and then high-temperature carbonization (high-temperature carbonization was 240℃ pre-oxidation in nitrogen atmosphere for 1h, and 850℃ for 2h) was carried out to obtain a high-temperature carbonized carbon fiber fabric;

[0143] S5, PDMS and anhydrous ethanol were mixed into a solution at a mass ratio of 1:50, and after ultrasonic treatment for 20 min, the high-temperature carbonized carbon fiber fabric was added and ultrasonic treatment was carried out for another 20 min, and then the surface was sprayed with water-based glue when it was semi-dried (drying temperature was 80℃, and drying time was 30 min), and finally the polyimide nanofiber membrane was attached to the surface of the fabric, and a polyimide nanofiber textile was obtained.

[0144] The PAN fabric in step S4 of the present comparative example was not impregnated with CuSO4 and FeCl3, and was directly carbonized. After carbonization, the fiber surface was too smooth, and after PDMS treatment, the contact angle was only 142°, which was lower than that of the PAN fabric impregnated with CuSO4 and FeCl3 and carbonized (see Table 4). The rolling angle of the composite fabric of Comparative Example 2 was greater than that of the composite fabric of Example 1, indicating that the composite fabric of Comparative Example 2 did not meet the super-hydrophobic requirement.

[0145] The contact angle was tested according to the standard GB_T 42694-2023 Textiles - Determination of the resistance to wetting - Contact angle and rolling angle method.

[0146] The rolling angle was tested according to the standard GB_T 42694-2023 Textiles - Determination of the resistance to wetting - Contact angle and rolling angle method.

[0147] Table 4 Contact angle and rolling angle of the composite fabric of Example 1 and Comparative Example 2

[0148]

[0149] In addition, the carbon fibers in the composite fabric prepared in Comparative Example 2 lack magnetism, and in actual use, due to the inability to use a magnet or the like for contactless disposal, the risk of contact with pathogens is increased.

[0150] Obviously, the above examples are merely examples for the sake of clarity, and are not limitations on the embodiments. Based on the above description, other different forms of changes or variations can also be made by those of ordinary skill in the art. It is not necessary or possible to exhaust all embodiments, and obvious changes or variations derived therefrom are still within the protection scope of the present application.

Claims

1. A method of preparing a self-decontaminating bioprotective nanotextile, characterized in that, The method comprises the following steps: (1) adding hyperbranched polymer into organic solvent, then adding soluble silver salt and soluble copper salt, and stirring to react, to obtain nanosilver-copper alloy colloidal dispersion liquid; (2) adding 4,4'-diamino diphenyl ether and pyromellitic dianhydride into organic solvent, stirring to carry out polyamide acid reaction, then adding nanosilver-copper alloy colloidal dispersion liquid, and stirring to carry out hyperbranched polymer grafting polyamide acid reaction, to obtain hyperbranched polymer cross-linked polyamide acid solution containing nanosilver-copper; (3) obtaining polyamide acid nanofiber membrane through electrospinning process of the hyperbranched polymer cross-linked polyamide acid solution containing nanosilver-copper, and obtaining polyimide nanofiber membrane through thermal imidization reaction; (4) dissolving the soluble iron salt, the soluble copper salt and the hyperbranched polymer in water to obtain a polymer complex solution, and immersing and padding polyacrylonitrile fabric into the polymer complex solution to obtain polyacrylonitrile fabric containing Fe 3+ , Cu 2+ , and then performing high-temperature carbonization to obtain carbon fiber fabric containing nano Fe3O4, CuO; (5) preparing a solution of polydimethylsiloxane and anhydrous ethanol, water or mixture of the two, adding carbon fiber fabric containing nanoscale Fe3O4 and CuO after ultrasonic treatment, mixing, spraying water-based glue on the surface when semi-drying, to obtain carbon fiber fabric sprayed with water-based glue, and finally pasting polyimide nanofiber membrane on the surface of the carbon fiber fabric sprayed with water-based glue, to obtain polyimide nanofiber textile, In step (1), the hyperbranched polymer is an amino-terminated hyperbranched polymer, and the hyperbranched polymer has the following structure: 。 2. The production method according to claim 1, characterized by, In step (1), the molecular weight of the hyperbranched polymer is 500-10000.

3. The method of claim 1, wherein, In step (1), the preparation method of the hyperbranched polymer is as follows: reacting a mixed solution of diethylenetriamine, methyl acrylate and methanol at 10-30 DEG C for 2-5 hours to obtain a light yellow transparent substance, then removing methanol under reduced pressure at 60-80 DEG C, immediately heating to 130-145 DEG C, and continuing to react under reduced pressure for 2-3 hours to stop the reaction.

4. The production method according to claim 3, characterized by, The volume ratio of diethylenetriamine to methyl acrylate is (0.9-1.5):1, and the volume ratio of methanol to the blending liquid of diethylenetriamine and methyl acrylate is (0.9-2):

1.

5. The preparation method according to claim 4, characterized in that, The volume ratio of diethylenetriamine to methyl acrylate is (1.08-1.2):1, and the volume ratio of methanol to the blending liquid of diethylenetriamine and methyl acrylate is (1.05-1.5):

1.

6. The method of claim 1, wherein, In step (1), the organic solvent is an amide solvent.

7. The production method according to claim 6, wherein The amide solvent is N,N-dimethylformamide and / or N,N-dimethylacetamide.

8. The method of claim 1, wherein, In step (1), the mass ratio of the hyperbranched polymer to the organic solvent is (1-10):

100.

9. The production method according to claim 8, characterized by, In step (1), the mass ratio of the hyperbranched polymer to the organic solvent is (2-4):

100.

10. The method of claim 1, wherein, In step (1), the addition amount of the soluble silver salt is 3-45% of the mass of the hyperbranched polymer.

11. The method of claim 10, wherein, In step (1), the addition amount of the soluble silver salt is 3-16% of the mass of the hyperbranched polymer.

12. The method of claim 1, wherein, In step (1), the addition amount of the soluble copper salt is 1-50% of the mass of the hyperbranched polymer.

13. The method of claim 12, wherein, In step (1), the addition amount of the soluble copper salt is 5-40% of the mass of the hyperbranched polymer.

14. The method of claim 1, wherein, In step (1), the total content of copper element and silver element in the nano silver-copper alloy colloidal dispersion is 0.001% to 2%, and the mass ratio of silver to copper is 2:1 to 1:

3.

15. The preparation method according to claim 14, characterized in that, In step (1), the total content of copper element and silver element in the nano silver-copper alloy colloidal dispersion is 0.05% to 0.8%, and the mass ratio of silver to copper is 1:1 to 1:1.

5.

16. The method of claim 1, wherein, In step (1), the soluble silver salt is silver nitrate, and the soluble copper salt is copper nitrate.

17. The method of claim 1, wherein, In step (1), the reaction is carried out in a hydrothermal reaction kettle, the filling degree is 70-80%, the reaction temperature is 80-120℃, and the reaction time is 1-8 hours.

18. The method of claim 1, wherein, In step (2), the organic solvent is an amide solvent.

19. The method of claim 18, wherein, The amide solvent is N,N-dimethylformamide and / or N,N-dimethylacetamide.

20. The method of claim 1, wherein, In step (2), the molar ratio of 4,4'-diamino diphenyl ether and pyromellitic dianhydride is (1:0.8) to (1:1.2), In step (2), the sum of the mass of 4,4'-diamino diphenyl ether and pyromellitic dianhydride is 20-50wt% relative to the mass of the organic solvent, In step (2), the mass ratio of nano silver-copper alloy (silver element and copper element) to the sum of the mass of 4,4'-diamino diphenyl ether and pyromellitic dianhydride is 0.1:1000 to 7:1000, In step (2), in the polyamic acid reaction, the reaction temperature is 10-30℃, and the reaction time is 5-120min, In step (2), in the super-branched polymer grafted polyamic acid reaction, the reaction temperature is 10-30℃, and the reaction time is 5-120min.

21. The method of claim 1, wherein, In step (3), the process parameters of the electrospinning process are: electrospinning voltage is 15-19kV, injection speed is 0.1-1.0mL / h, and drum rotation speed is 200-400r / min.

22. The method of claim 1, wherein, In step (3), the reaction temperature of the thermal imidization reaction is 100-350℃, and the reaction time is 1-5 hours.

23. The method of claim 22, wherein, In step (3), the reaction temperature of the thermal imidization reaction is 100-300℃, and the reaction time is 2-4 hours.

24. The method of claim 1, wherein, The thermal imidization reaction is carried out in the following step-by-step heating manner: 100℃ for 2h, heating to 150℃ for 0.5h, heating to 250℃ for 0.5h, and heating to 300℃ for 0.5h.

25. The method of claim 1, wherein, In step (3), the thickness of the polyamic acid nanofiber membrane is 0.020-0.045cm, and the thickness of the polyimide nanofiber membrane is 0.020-0.050cm.

26. The method of claim 1, wherein, In step (4), the soluble iron salt is FeCl3, and the soluble copper salt is CuSO4.

27. The method of claim 1, wherein, In step (4), the mass ratio of the soluble iron salt, the soluble copper salt, and the super-branched polymer is 1:0.5 to 2:1 to 6.

28. The method of claim 1, wherein, In step (4), the padding rate of the polyacrylonitrile fabric is 50%-200%.

29. The method of claim 1, wherein, In step (4), the high-temperature carbonization is pre-oxidation at 200-280℃ for 1-3h in a nitrogen atmosphere, and heat preservation at 800-900℃ for 1-3h.

30. The method of claim 29, wherein, Pre-oxidation at 240℃ for 1h and heat preservation at 850℃ for 2h in a nitrogen atmosphere.

31. The method of claim 1, wherein, In step (5), the mass ratio of polydimethylsiloxane to anhydrous ethanol is 1: (30-70), In step (5), the ultrasonic treatment time is 1-30 min, In step (5), the drying time for semi-drying is 1-60 min, In step (5), the drying temperature for semi-drying is 23-150℃.

32. The self-disinfecting biodefense nanotextile prepared by the preparation method in any one of claims 1-31.

33. The use of the self-disinfecting biodefense nanotextile in claim 32 in the preparation of a remote real-time human motion detection system.

34. A remote real-time human motion detection system, comprising: It comprises: The self-disinfecting biodefense nanotextile in claim 32.

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