High-conductivity carbon nanotube modified polyurethane fiber membrane and preparation method thereof

Abstract

The invention relates to the technical field of polyurethane, and discloses a high-conductivity carbon nanotube modified polyurethane fiber membrane, which is characterized in that carbon nanotubes react with 1, 4-butanediamine to obtain aminated carbon nanotubes, 2, 4-toluene diisocynate reacts with polytetrahydrofuran ether glycol to form a polyurethane precursor, and the polyurethane precursor further reacts with 2, 2-dimethylolpropionic acid, 2, 2-dimethylolpropionic acid, 2, 2, 2-trimethyl-1, 3-pentanediol, 2, 2, 4-trimethyl-1, 3-pentanediol, 2, 2, 4-trimethyl-1, 3-pentanediol, 2, 2, 4-trimethyl-1, 3-pentanediol, 2 4-dihydroxyanisole reacts with N-methyldiethanolamine to obtain aldehyde polyurethane, the aldehyde polyurethane reacts with the aminated carbon nanotubes to finally obtain the composite fiber membrane, the interface bonding force of the carbon nanotubes and the polyurethane is enhanced through connection of chemical bonds, and when the composite fiber membrane is subjected to external force, stress passes through chemical cross-linking points, so that the composite fiber membrane is formed. The stress is transferred to the carbon nano tube from the polyurethane matrix, the carbon nano tube can absorb and transfer the stress, and the carbon nano tube can form a conductive network, so that the conductivity of the polyurethane is improved.

Description

Technical Field

[0001] The invention relates to the technical field of polyurethane, in particular to a highly conductive carbon nanotube-modified polyurethane fiber membrane and a preparation method thereof. Background Art

[0002] Carbon nanotubes have excellent mechanical properties, electrical properties, thermodynamic properties, etc., and are widely used in all aspects of daily production and life. In recent years, they have received more and more attention. At present, the main research direction is to use carbon nanotubes as functional reinforcing fillers and fill them into organic polymer materials such as epoxy resins and polyurethanes. By integrating their own excellent mechanical, electrical, thermodynamic and other properties into organic polymer materials such as epoxy resins and polyurethanes, the purpose of polymer modification is achieved. However, ordinary carbon nanotubes have very large specific surface area and aspect ratio, and the van der Waals interaction between them is strong. They are very easy to agglomerate and cannot be stably dispersed in the organic polymer matrix. Therefore, it is necessary to modify the carbon nanotubes and improve their interfacial compatibility with the organic polymer matrix, so as to achieve the purpose of modifying the polymer.

[0003] Polyurethane is a polymer material synthesized by the reaction of diisocyanate and polyol compounds with carbamate groups as structural units. It is widely used in electrode materials, sensors and antistatic fabrics. However, the mechanical properties and electrical conductivity of traditional polyurethane are poor, and have gradually failed to meet the needs of rapid technological development. Therefore, some improvements to traditional polyurethane are needed. The most scientific and effective modification method at present is filling modification, that is, inorganic nanomaterials such as graphene and carbon nanotubes with excellent mechanical, electrical and thermodynamic properties are filled into the polyurethane matrix through physical mixing or chemical grafting. By combining the excellent properties of inorganic nanomaterials such as graphene and carbon nanotubes, the mechanical properties and conductivity of polyurethane are improved, further expanding the application range of polyurethane. Summary of the invention

[0004] In view of the deficiencies in the prior art, the present invention provides a highly conductive carbon nanotube-modified polyurethane fiber membrane and a preparation method thereof, which solves the problem of poor dispersion of carbon nanotubes and the problem of poor mechanical properties and conductivity of polyurethane.

[0005] To achieve the above object, the present invention provides the following technical solution: a highly conductive carbon nanotube-modified polyurethane fiber membrane, wherein the method for preparing the highly conductive carbon nanotube-modified polyurethane fiber membrane comprises the following steps: (1) Add N-methylformamide solvent and carbon nanotubes treated with concentrated nitric acid into a three-necked flask, add N,N-dicyclohexylcarbodiimide and 1,4-butanediamine after ultrasonic dispersion, transfer to an oil bath for reaction, centrifuge, wash and dry the product to obtain amino carbon nanotubes; (2) Add 2,4-toluene diisocyanate, polytetramethylene glycol and dibutyltin dilaurate into a three-necked flask, react at 60-80° C. for 1-3 hours in a nitrogen atmosphere to obtain a polyurethane precursor, and then continue to add 2,2-dihydroxymethylpropionic acid, 2,4-dihydroxyanisole and N-methyldiethanolamine to react. After the product is cooled, it is washed and dried to obtain a formaldehyde polyurethane; (3) adding ethanol solvent, aldehyde-modified polyurethane and amino-modified carbon nanotubes into a three-necked flask, transferring the mixture into a water bath for Schiff base reaction, centrifuging, washing and drying the product to obtain a carbon nanotube-modified polyurethane emulsion; (4) Add N,N-dimethylacetamide solvent and carbon nanotube-modified polyurethane emulsion into a three-necked flask, mix well and perform vacuum degassing, pour the mixture into an electrospinning device for spinning, set the injection rate to 1-2 mL / h, the spinning voltage to 18-25 kV, and the receiving distance to 14-18 cm, and place the spinning product in a vacuum drying oven for drying to obtain a highly conductive carbon nanotube-modified polyurethane fiber membrane.

[0006] Preferably, in step (1), the mass ratio of carbon nanotubes, N,N-dicyclohexylcarbodiimide and 1,4-butanediamine is 100:280-320:190-210.

[0007] Preferably, the reaction temperature in step (1) is 110-130° C., and the reaction is carried out under reflux in a nitrogen atmosphere for 40-50 hours.

[0008] Preferably, in step (2), the mass ratio of 2,4-toluene diisocyanate, polytetramethylene glycol, dibutyltin dilaurate, 2,2-dihydroxymethylpropionic acid, 2,4-dihydroxyanisole and N-methyldiethanolamine is 30-60:100:0.6-1.2:3.5-7.5:3-6:4-8.

[0009] Preferably, the reaction temperature in step (2) is 70-90° C., and the chain extension reaction is carried out in a nitrogen atmosphere for 2-6 hours.

[0010] Preferably, in step (3), the mass ratio of the aldehyde-modified polyurethane to the amino-modified carbon nanotubes is 100:0.5-6.

[0011] Preferably, the temperature of the Schiff base reaction in step (3) is 20-35° C., and the reaction is carried out in a nitrogen atmosphere for 20-30 hours.

[0012] Compared with the prior art, the present invention has the following beneficial technical effects: The highly conductive carbon nanotube modified polyurethane fiber membrane comprises a carbon nanotube treated with concentrated nitric acid, the surface of which contains a large number of oxygen-containing functional groups such as hydroxyl and carboxyl groups. Under the catalytic action of N,N-dicyclohexylcarbodiimide, the carbon nanotube undergoes an amidation reaction with 1,4-butanediamine to obtain an amidated carbon nanotube. The amino group is introduced into the surface of the carbon nanotube through chemical bond connection, thereby achieving the amination modification of the carbon nanotube and effectively improving the application range of the carbon nanotube. 2,4-toluene diisocyanate and polytetrahydrofuran ether diol are reacted under the catalytic action of dibutyltin dilaurate. , forming a polyurethane precursor, the polyurethane precursor further reacts with 2,2-dihydroxymethylpropionic acid, 2,4-dihydroxyanisole and N-methyldiethanolamine, and finally obtains formaldehyde polyurethane, the aldehyde group of the formaldehyde polyurethane can react with the amino group of the amino carbon nanotube by Schiff base reaction, and further through the electrospinning method, finally obtains a highly conductive carbon nanotube-modified polyurethane fiber membrane, through the connection of chemical bonds, the carbon nanotubes are firmly grafted into the polyurethane matrix, which effectively enhances the interfacial bonding force between the carbon nanotubes and the polyurethane, and makes the carbon nanotubes evenly dispersed in the polyurethane matrix.

[0013] The invention discloses a highly conductive carbon nanotube-modified polyurethane fiber membrane. Stably dispersed carbon nanotubes form chemical crosslinking points in a polyurethane matrix, thereby improving the mutual force of polyurethane molecular chains. When the composite fiber membrane is subjected to external force, the stress is transferred from the polyurethane matrix to the carbon nanotubes through the chemical crosslinking points. The carbon nanotubes absorb part of the stress through their own excellent mechanical properties. Meanwhile, the ultra-high specific surface area of ​​the carbon nanotubes can play a role in load transfer and stress concentration elimination, thereby effectively improving the mechanical properties of the polyurethane. In addition, when the doping amount of the carbon nanotubes reaches a certain range, the electrons of the carbon nanotubes in the polyurethane matrix transition, and the electrons pass through the polyurethane interface to form current tunnels between the carbon nanotubes at the polyurethane interface. Meanwhile, the uniformly dispersed carbon nanotubes contact and entangle with each other to form a conductive network, thereby effectively improving the conductivity of the polyurethane. DETAILED DESCRIPTION

[0014] To achieve the above object, the present invention provides the following specific implementation methods and examples: A highly conductive carbon nanotube-modified polyurethane fiber membrane, the preparation method of which comprises the following steps: (1) Add N-methylformamide solvent and carbon nanotubes treated with concentrated nitric acid to a three-necked flask, add N,N-dicyclohexylcarbodiimide and 1,4-butanediamine after ultrasonic dispersion, wherein the mass ratio of carbon nanotubes, N,N-dicyclohexylcarbodiimide and 1,4-butanediamine is 100:280-320:190-210, transfer to an oil bath, reflux at 110-130° C. in a nitrogen atmosphere for 40-50 hours, centrifuge, wash and dry the product to obtain amino carbon nanotubes; (2) Add 2,4-toluene diisocyanate, polytetramethylene glycol and dibutyltin dilaurate to a three-necked flask, react at 60-80°C in a nitrogen atmosphere for 1-3 hours to obtain a polyurethane precursor, continue to add 2,2-dihydroxymethylpropionic acid, 2,4-dihydroxyanisole and N-methyldiethanolamine, wherein the mass ratio of 2,4-toluene diisocyanate, polytetramethylene glycol, dibutyltin dilaurate, 2,2-dihydroxymethylpropionic acid, 2,4-dihydroxyanisole and N-methyldiethanolamine is 30-60:100:0.6-1.2:3.5-7.5:3-6:4-8, carry out chain extension reaction at 70-90°C in a nitrogen atmosphere for 2-6 hours, wash and dry the product after cooling to obtain a formaldehyde polyurethane; (3) adding ethanol solvent, formaldehyde-modified polyurethane and amino-modified carbon nanotubes into a three-necked flask, wherein the mass ratio of formaldehyde-modified polyurethane to amino-modified carbon nanotubes is 100:0.5-6, transferring the flask into a water bath, reacting at 20-35° C. for 20-30 h in a nitrogen atmosphere, centrifuging, washing and drying the product to obtain a carbon nanotube-modified polyurethane emulsion; (4) Add N,N-dimethylacetamide solvent and carbon nanotube-modified polyurethane emulsion into a three-necked flask, mix well and perform vacuum degassing, pour the mixture into an electrospinning device for spinning, set the injection rate to 1-2 mL / h, the spinning voltage to 18-25 kV, and the receiving distance to 14-18 cm, and place the spinning product in a vacuum drying oven for drying to obtain a highly conductive carbon nanotube-modified polyurethane fiber membrane. Example 1

[0015] (1) Add N-methylformamide solvent and carbon nanotubes treated with concentrated nitric acid to a three-necked flask, add N,N-dicyclohexylcarbodiimide and 1,4-butanediamine after ultrasonic dispersion, wherein the mass ratio of carbon nanotubes, N,N-dicyclohexylcarbodiimide and 1,4-butanediamine is 100:280:190, transfer to an oil bath, reflux at 110°C in a nitrogen atmosphere for 40 hours, centrifuge, wash and dry the product to obtain amino carbon nanotubes; (2) Add 2,4-toluene diisocyanate, polytetramethylene glycol and dibutyltin dilaurate to a three-necked flask, react at 60°C for 1 hour in a nitrogen atmosphere to obtain a polyurethane precursor, continue to add 2,2-dihydroxymethylpropionic acid, 2,4-dihydroxyanisole and N-methyldiethanolamine, wherein the mass ratio of 2,4-toluene diisocyanate, polytetramethylene glycol, dibutyltin dilaurate, 2,2-dihydroxymethylpropionic acid, 2,4-dihydroxyanisole and N-methyldiethanolamine is 30:100:0.6:3.5:3:4, carry out chain extension reaction at 70°C for 2 hours in a nitrogen atmosphere, wash and dry the product after cooling to obtain a formaldehyde polyurethane; (3) Adding ethanol solvent, formaldehyde-modified polyurethane and amino-modified carbon nanotubes into a three-necked flask, wherein the mass ratio of formaldehyde-modified polyurethane to amino-modified carbon nanotubes is 100:0.5, transferring the flask into a water bath, reacting at 20° C. for 20 h in a nitrogen atmosphere, centrifuging, washing and drying the product to obtain a carbon nanotube-modified polyurethane emulsion; (4) Add N,N-dimethylacetamide solvent and carbon nanotube-modified polyurethane emulsion into a three-necked flask, mix well and then perform vacuum degassing. Pour the mixture into an electrospinning device for spinning. Set the injection rate to 1 mL / h, the spinning voltage to 18 kV, and the receiving distance to 14 cm. Place the spinning product in a vacuum drying oven for drying to obtain a highly conductive carbon nanotube-modified polyurethane fiber membrane. Example 2

[0016] (1) Add N-methylformamide solvent and carbon nanotubes treated with concentrated nitric acid to a three-necked flask, add N,N-dicyclohexylcarbodiimide and 1,4-butanediamine after ultrasonic dispersion, wherein the mass ratio of carbon nanotubes, N,N-dicyclohexylcarbodiimide and 1,4-butanediamine is 100:290:195, transfer to an oil bath, reflux at 115°C in a nitrogen atmosphere for 42 hours, centrifuge, wash and dry the product to obtain amino carbon nanotubes; (2) Add 2,4-toluene diisocyanate, polytetramethylene glycol and dibutyltin dilaurate to a three-necked flask, react at 65°C for 1.5 hours in a nitrogen atmosphere to obtain a polyurethane precursor, continue to add 2,2-dihydroxymethylpropionic acid, 2,4-dihydroxyanisole and N-methyldiethanolamine, wherein the mass ratio of 2,4-toluene diisocyanate, polytetramethylene glycol, dibutyltin dilaurate, 2,2-dihydroxymethylpropionic acid, 2,4-dihydroxyanisole and N-methyldiethanolamine is 38:100:0.75:4.5:3.8:5, carry out chain extension reaction at 75°C for 3 hours in a nitrogen atmosphere, wash and dry the product after cooling to obtain a formaldehyde-modified polyurethane; (3) Adding ethanol solvent, formaldehyde-modified polyurethane and amino-modified carbon nanotubes into a three-necked flask, wherein the mass ratio of formaldehyde-modified polyurethane to amino-modified carbon nanotubes is 100:1.9, transferring the flask into a water bath, reacting at 25°C for 22 hours in a nitrogen atmosphere, centrifuging, washing and drying the product to obtain a carbon nanotube-modified polyurethane emulsion; (4) Add N,N-dimethylacetamide solvent and carbon nanotube-modified polyurethane emulsion into a three-necked flask, mix well and then perform vacuum degassing. Pour the mixture into an electrospinning device for spinning. Set the injection rate to 1 mL / h, the spinning voltage to 20 kV, and the receiving distance to 15 cm. Place the spinning product in a vacuum drying oven for drying to obtain a highly conductive carbon nanotube-modified polyurethane fiber membrane. Example 3

[0017] (1) Add N-methylformamide solvent and carbon nanotubes treated with concentrated nitric acid to a three-necked flask, add N,N-dicyclohexylcarbodiimide and 1,4-butanediamine after ultrasonic dispersion, wherein the mass ratio of carbon nanotubes, N,N-dicyclohexylcarbodiimide and 1,4-butanediamine is 100:300:200, transfer to an oil bath, reflux at 120°C in a nitrogen atmosphere for 45 hours, centrifuge, wash and dry the product to obtain amino carbon nanotubes; (2) Add 2,4-toluene diisocyanate, polytetramethylene glycol and dibutyltin dilaurate to a three-necked flask, react at 70°C for 2 hours in a nitrogen atmosphere to obtain a polyurethane precursor, continue to add 2,2-dihydroxymethylpropionic acid, 2,4-dihydroxyanisole and N-methyldiethanolamine, wherein the mass ratio of 2,4-toluene diisocyanate, polytetramethylene glycol, dibutyltin dilaurate, 2,2-dihydroxymethylpropionic acid, 2,4-dihydroxyanisole and N-methyldiethanolamine is 46:100:0.9:5.5:4.6:6, carry out chain extension reaction at 80°C for 4 hours in a nitrogen atmosphere, wash and dry the product after cooling to obtain a formaldehyde polyurethane; (3) Adding ethanol solvent, formaldehyde-modified polyurethane and amino-modified carbon nanotubes into a three-necked flask, wherein the mass ratio of formaldehyde-modified polyurethane to amino-modified carbon nanotubes is 100:3.3, transferring the flask into a water bath, reacting at 30°C for 25 h in a nitrogen atmosphere, centrifuging, washing and drying the product to obtain a carbon nanotube-modified polyurethane emulsion; (4) Add N,N-dimethylacetamide solvent and carbon nanotube-modified polyurethane emulsion into a three-necked flask, mix well and then perform vacuum degassing. Pour the mixture into an electrospinning device for spinning. Set the injection rate to 1 mL / h, the spinning voltage to 22 kV, and the receiving distance to 16 cm. Place the spinning product in a vacuum drying oven for drying to obtain a highly conductive carbon nanotube-modified polyurethane fiber membrane. Example 4

[0018] (1) Add N-methylformamide solvent and carbon nanotubes treated with concentrated nitric acid to a three-necked flask, add N,N-dicyclohexylcarbodiimide and 1,4-butanediamine after ultrasonic dispersion, wherein the mass ratio of carbon nanotubes, N,N-dicyclohexylcarbodiimide and 1,4-butanediamine is 100:310:205, transfer to an oil bath, reflux at 125°C in a nitrogen atmosphere for 48 hours, centrifuge, wash and dry the product to obtain amino carbon nanotubes; (2) Add 2,4-toluene diisocyanate, polytetramethylene glycol and dibutyltin dilaurate to a three-necked flask, react at 75°C for 2.5 hours in a nitrogen atmosphere to obtain a polyurethane precursor, continue to add 2,2-dihydroxymethylpropionic acid, 2,4-dihydroxyanisole and N-methyldiethanolamine, wherein the mass ratio of 2,4-toluene diisocyanate, polytetramethylene glycol, dibutyltin dilaurate, 2,2-dihydroxymethylpropionic acid, 2,4-dihydroxyanisole and N-methyldiethanolamine is 54:100:1.05:6.5:5.4:7, carry out chain extension reaction at 85°C for 5 hours in a nitrogen atmosphere, wash and dry the product after cooling to obtain a formaldehyde polyurethane; (3) Adding ethanol solvent, formaldehyde-modified polyurethane and amino-modified carbon nanotubes into a three-necked flask, wherein the mass ratio of formaldehyde-modified polyurethane to amino-modified carbon nanotubes is 100:4.7, transferring the flask into a water bath, reacting at 30°C for 28 hours in a nitrogen atmosphere, centrifuging, washing and drying the product to obtain a carbon nanotube-modified polyurethane emulsion; (4) Add N,N-dimethylacetamide solvent and carbon nanotube-modified polyurethane emulsion into a three-necked flask, mix well and then perform vacuum degassing. Pour the mixture into an electrospinning device for spinning. Set the injection rate to 2 mL / h, the spinning voltage to 24 kV, and the receiving distance to 16 cm. Place the spinning product in a vacuum drying oven for drying to obtain a highly conductive carbon nanotube-modified polyurethane fiber membrane. Example 5

[0019] (1) Add N-methylformamide solvent and carbon nanotubes treated with concentrated nitric acid to a three-necked flask, add N,N-dicyclohexylcarbodiimide and 1,4-butanediamine after ultrasonic dispersion, wherein the mass ratio of carbon nanotubes, N,N-dicyclohexylcarbodiimide and 1,4-butanediamine is 100:320:210, transfer to an oil bath, reflux at 130°C in a nitrogen atmosphere for 50 hours, centrifuge, wash and dry the product to obtain amino carbon nanotubes; (2) Add 2,4-toluene diisocyanate, polytetramethylene glycol and dibutyltin dilaurate to a three-necked flask, react at 80°C for 3 hours in a nitrogen atmosphere to obtain a polyurethane precursor, continue to add 2,2-dihydroxymethylpropionic acid, 2,4-dihydroxyanisole and N-methyldiethanolamine, wherein the mass ratio of 2,4-toluene diisocyanate, polytetramethylene glycol, dibutyltin dilaurate, 2,2-dihydroxymethylpropionic acid, 2,4-dihydroxyanisole and N-methyldiethanolamine is 60:100:1.2:7.5:6:8, carry out chain extension reaction at 90°C for 6 hours in a nitrogen atmosphere, wash and dry the product after cooling to obtain a formaldehyde polyurethane; (3) Adding ethanol solvent, formaldehyde-modified polyurethane and amino-modified carbon nanotubes into a three-necked flask, wherein the mass ratio of formaldehyde-modified polyurethane to amino-modified carbon nanotubes is 100:6, transferring the flask into a water bath, reacting at 35°C for 30 h in a nitrogen atmosphere, centrifuging, washing and drying the product to obtain a carbon nanotube-modified polyurethane emulsion; (4) Add N,N-dimethylacetamide solvent and carbon nanotube-modified polyurethane emulsion into a three-necked flask, mix well and then perform vacuum degassing. Pour the mixture into an electrospinning device for spinning. Set the injection rate to 2 mL / h, the spinning voltage to 25 kV, and the receiving distance to 18 cm. Place the spinning product in a vacuum drying oven for drying to obtain a highly conductive carbon nanotube-modified polyurethane fiber membrane.

[0020] Comparative Example 1 (1) Add N-methylformamide solvent and carbon nanotubes treated with concentrated nitric acid to a three-necked flask, add N,N-dicyclohexylcarbodiimide and 1,4-butanediamine after ultrasonic dispersion, wherein the mass ratio of carbon nanotubes, N,N-dicyclohexylcarbodiimide and 1,4-butanediamine is 100:330:215, transfer to an oil bath, reflux at 130°C in a nitrogen atmosphere for 60 hours, centrifuge, wash and dry the product to obtain amino carbon nanotubes; (2) Add 2,4-toluene diisocyanate, polytetramethylene glycol and dibutyltin dilaurate to a three-necked flask, react at 80°C for 5 hours in a nitrogen atmosphere to obtain a polyurethane precursor, continue to add 2,2-dihydroxymethylpropionic acid, 2,4-dihydroxyanisole and N-methyldiethanolamine, wherein the mass ratio of 2,4-toluene diisocyanate, polytetramethylene glycol, dibutyltin dilaurate, 2,2-dihydroxymethylpropionic acid, 2,4-dihydroxyanisole and N-methyldiethanolamine is 68:100:1.35:8.5:6.8:9, carry out chain extension reaction at 90°C for 8 hours in a nitrogen atmosphere, wash and dry the product after cooling to obtain a formaldehyde polyurethane; (3) Adding ethanol solvent, formaldehyde-modified polyurethane and amino-modified carbon nanotubes into a three-necked flask, wherein the mass ratio of formaldehyde-modified polyurethane to amino-modified carbon nanotubes is 100:7.4, transferring the flask into a water bath, reacting at 35°C for 40 h in a nitrogen atmosphere, centrifuging, washing and drying the product to obtain a carbon nanotube-modified polyurethane emulsion; (4) Add N,N-dimethylacetamide solvent and carbon nanotube-modified polyurethane emulsion into a three-necked flask, mix well and then perform vacuum degassing. Pour the mixture into an electrospinning device for spinning. Set the injection rate to 5 mL / h, the spinning voltage to 30 kV, and the receiving distance to 20 cm. Place the spinning product in a vacuum drying oven for drying to obtain a highly conductive carbon nanotube-modified polyurethane fiber membrane.

[0021] The tensile strength and elongation at break of the highly conductive carbon nanotube-modified polyurethane fiber membrane were tested using a DRK101 tensile strength testing machine.

[0022]

[0023] The conductivity of the highly conductive carbon nanotube-modified polyurethane fiber membrane was tested using an EC215 conductivity meter.

[0024]

Claims

1. A highly conductive carbon nanotube-modified polyurethane fiber membrane, characterized in that: The method for preparing the highly conductive carbon nanotube-modified polyurethane fiber membrane comprises the following steps: (1) Adding carbon nanotubes treated with concentrated nitric acid to N-methylformamide solvent, adding N,N-dicyclohexylcarbodiimide and 1,4-butanediamine after ultrasonic dispersion, transferring to an oil bath for reaction, centrifuging, washing and drying the product to obtain amino carbon nanotubes; (2) Add 2,4-toluene diisocyanate, polytetramethylene glycol and dibutyltin dilaurate into a three-necked flask, react at 60-80° C. for 1-3 hours in a nitrogen atmosphere to obtain a polyurethane precursor, and then continue to add 2,2-dihydroxymethylpropionic acid, 2,4-dihydroxyanisole and N-methyldiethanolamine to react. After the product is cooled, it is washed and dried to obtain a formaldehyde polyurethane; (3) adding aldehyde-modified polyurethane and amino-modified carbon nanotubes to an ethanol solvent, transferring the mixture to a water bath for Schiff base reaction, centrifuging, washing and drying the product to obtain a carbon nanotube-modified polyurethane emulsion; (4) Add carbon nanotube-modified polyurethane emulsion to N,N-dimethylacetamide solvent, mix well and then perform vacuum degassing, pour it into an electrospinning device for spinning, set the injection rate to 1-2 mL / h, the spinning voltage to 18-25 kV, and the receiving distance to 14-18 cm, and place the spinning product in a vacuum drying oven for drying to obtain a highly conductive carbon nanotube-modified polyurethane fiber membrane.

2. The highly conductive carbon nanotube-modified polyurethane fiber membrane according to claim 1, characterized in that: In the step (1), the mass ratio of carbon nanotubes, N,N-dicyclohexylcarbodiimide and 1,4-butanediamine is 100:280-320:190-210.

3. The highly conductive carbon nanotube-modified polyurethane fiber membrane according to claim 1, characterized in that: The reaction temperature in step (1) is 110-130° C., and the reaction is carried out under reflux in a nitrogen atmosphere for 40-50 hours.

4. The highly conductive carbon nanotube-modified polyurethane fiber membrane according to claim 1, characterized in that: In the step (2), the mass ratio of 2,4-toluene diisocyanate, polytetramethylene glycol, dibutyltin dilaurate, 2,2-dihydroxymethylpropionic acid, 2,4-dihydroxyanisole and N-methyldiethanolamine is 30-60:100:0.6-1.2:3.5-7.5:3-6:4-8.

5. The highly conductive carbon nanotube-modified polyurethane fiber membrane according to claim 1, characterized in that: The reaction temperature in step (2) is 70-90° C., and the chain extension reaction is carried out in a nitrogen atmosphere for 2-6 hours.

6. The highly conductive carbon nanotube-modified polyurethane fiber membrane according to claim 1, characterized in that: In the step (3), the mass ratio of the aldehyde-modified polyurethane to the amino-modified carbon nanotubes is 100:0.5-6.

7. The highly conductive carbon nanotube-modified polyurethane fiber membrane according to claim 1, characterized in that: The temperature of the Schiff base reaction in step (3) is 20-35° C., and the reaction is carried out in a nitrogen atmosphere for 20-30 hours.

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