High abrasion and corrosion resistant cable and method of making same

Abstract

The application discloses a kind of high wear-resistant corrosion-resistant cable and preparation method thereof, it is related to cable technical field.The application first selects hydroxylated carbon nanotube, and the terminal amino of 1,11-bismaleimide group-3,6,9-trioxo undecane is reacted, bismaleimide molecule is grafted to the outer surface of carbon nanotube, and DA click reaction is carried out, and is stably constructed on the outer surface of carbon nanotube.By the reaction of acyl chloride group and the hydroxyl of carbon nanotube inner wall, grafting photoresponsive cinnamate group, to form inside and outside double effect self-repairing carbon nanotube, form " hot-light " dual-response complementary mechanism.Self-repairing carbon nanotube is compounded with aminated fluorinated graphene, and multi-level labyrinth structure is constructed: three-dimensional network framework is combined with sheet structure, the penetration path of corrosive medium is extended, and the chemical corrosion resistance is enhanced.Simultaneously, surface segment can improve the compatibility of filler and cable matrix, and strong interface combination further ensures that filler is uniformly dispersed.The cable prepared by the application has the effects of high wear resistance and corrosion resistance.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of cables, in particular to a high-wear-resistant and corrosion-resistant cable and a preparation method thereof. BACKGROUND

[0002] As the core carrier of modern power transmission and signal transmission, the reliability of the cable directly affects the safe operation of the energy network and the communication system. The traditional cable structure is usually composed of a conductor, an insulation layer and a sheath, and the materials are mainly polymers such as polyethylene and polyvinyl chloride. Although it can meet the basic insulation requirements, it faces severe challenges in complex working conditions. For example, in the scenes of mine machinery, ocean platforms and rail transit, the cable is exposed to mechanical friction, chemical corrosion, ultraviolet radiation and alternating temperature and humidity environments for a long time. The sheath is easy to cause insulation failure due to wear or corrosion, which may cause short circuit, electric leakage and even fire. Therefore, developing high-wear-resistant and corrosion-resistant cable materials has become a key requirement to improve the service life and safety of the cable. The existing technology mainly enhances the wear resistance by adding inorganic fillers (such as silicon dioxide and silicon carbide) or surface coatings (such as polyurethane and fluororubber), but these methods often sacrifice the flexibility of the material, and cannot solve the problem of deep damage repair.

[0003] In recent years, self-repairing cable materials have become a research hotspot, which realizes self-repairing at the damaged place by introducing microcapsules and dynamic reversible bonds. For example, polyurethane microcapsules are used to encapsulate repair agents (such as silane coupling agents), and when the material cracks, the microcapsules break to release the repair agent to fill the defects; or a reversible covalent network based on Diels-Alder reaction is used to trigger the bond recombination by heating. However, the existing self-repairing technology still has significant defects: first, the repair efficiency is limited by environmental conditions, such as the need for precise breaking threshold of microcapsules and the failure after single repair; second, the introduction of self-repairing components often leads to a decrease in mechanical properties of the material, such as a decrease in elastic modulus and a loss of wear resistance. More importantly, the existing self-repairing materials mainly focus on a single damage mode (such as cracks), and it is difficult to consider multiple functions such as wear resistance, corrosion resistance and ultraviolet resistance, which cannot meet the long-term protection requirements of the cable in the extreme multi-factor coupled environment. Therefore, it is urgent to develop a new cable material system with high wear resistance and corrosion resistance and intelligent self-repairing ability. SUMMARY

[0004] The purpose of the present application is to provide a high-wear-resistant and corrosion-resistant cable and a preparation method thereof to solve the problems in the prior art.

[0005] In order to solve the above technical problems, the present application provides the following technical scheme: a high-wear-resistant and corrosion-resistant cable, comprising the following preparation steps:

[0006] (1) 1,11-bismaleimide-3,6,9-trioxoundecane is dissolved in N,N-dimethylformamide with a mass concentration of 5-15 mg / mL, modified carbon nanotubes are added, stirring at 80°C for 12 h, stirring speed is 120 rpm, centrifugation at 8000 rpm for 10 min, after removing unreacted reagents by washing with N,N-dimethylformamide for 3 times, washing with ethanol for 1 time, drying at 50°C for 3 h, to obtain outer-grafted carbon nanotubes; the outer-grafted carbon nanotubes and furan-terminated polyurethane prepolymer are dispersed in toluene at a mass ratio of 1:5, stirring at 60°C for 12 h, stirring speed is 60 rpm, then cooling to room temperature, centrifugation at 3000 rpm for 5 min, drying at 50°C for 5 h, to obtain outer-surface-grafted carbon nanotubes;

[0007] (2) 0.2 g of outer-surface-grafted carbon nanotubes are dispersed in 50 ml of anhydrous tetrahydrofuran, 1 ml of triethylamine is added as an acid-binding agent, ultrasonic treatment is performed at a power of 50 kHz for 60 min, 0.8-1.4 mmol of cinnamyl chloride is added dropwise, stirring at 25°C in the dark for 24 h, stirring speed is 240 rpm, after the reaction is completed, filtration is performed, the solid is washed with tetrahydrofuran and acetone in sequence, vacuum drying at 0.085 MPa and 50°C for 3 h, to obtain a self-repairing filler;

[0008] (3) the self-repairing filler and aminated fluorinated graphene are added into a thermoplastic polyurethane / dimethylacetamide solution at a mass ratio of 6:1-2, pulse mode ultrasonic dispersion is performed at 50°C; then melt blending is performed through a twin-screw extruder, temperature is 120-130°C, screw rotation speed is 80-100 rpm, extrusion granulation obtains a uniform cable material, which is directly coated on the surface of a cable conductor to form an insulation layer; after shaping in a cooling water tank, annealing at 80°C for 1 h, a high-wear-resistant and corrosion-resistant cable is prepared.

[0009] Further, in the step (1), the surface-modified carbon nanotube is prepared by the following method: carbon nanotubes with an inner diameter of 1-1.5 nm and an outer diameter of 4-8 nm are soaked in a sulfuric acid / nitric acid mixed solution, the concentration of sulfuric acid is 13.8 mol / L, the concentration of nitric acid is 3.625 mol / L, the solid-liquid ratio is 1:5-10, then ultrasonic treatment is performed at 40°C for 2 h, ultrasonic power is 300 W, then centrifugation is performed at 8000 rpm for 10 min, then washing with deionized water for 3 times, and vacuum drying at 0.085 MPa and 50°C for 5 h, to obtain the surface-modified carbon nanotube.

[0010] Further, in the step (1), the furan-terminated polyurethane prepolymer is prepared by the following method: polytetrahydrofuran diol and isophorone diisocyanate are used as raw materials, pre-polymerization is performed at 60°C for 2 h, then furan methanol is added for termination, termination time is 2 h, temperature is 60-80°C, to obtain the furan-terminated polyurethane prepolymer.

[0011] Further, the molar ratio of the polytetrahydrofuran diol, isophorone diisocyanate and furfuryl alcohol is 1:2:2.

[0012] Further, the mass ratio of the modified carbon nanotube and 1,11-bismaleimide-3,6,9-trioxoundecane in step (1) is 2-4:1.

[0013] Further, the mass ratio of the outer grafted carbon nanotube and toluene in step (1) is 1:15.

[0014] Further, the mass ratio of the self-repairing filler and the thermoplastic polyurethane in step (3) is 3:80-90.

[0015] Further, the solid content of the plastic polyurethane / dimethylacetamide solution in step (3) is 10%.

[0016] Further, the preparation method of the aminated fluorinated graphene in step (3) is as follows: 0.5g of the fluorinated graphene with C / F=2:1 is dispersed in 50mL of a 10wt% ethylenediamine aqueous solution, stirring is carried out at 60℃ for 6h, the stirring speed is 120rpm, 5000rpm centrifugation is carried out for 10min, then the aminated fluorinated graphene is prepared by washing with deionized water for 3 times, and freeze-drying at-40℃.

[0017] Further, the power of the pulse mode ultrasonic dispersion in step (3) is 300W, and the time is 2h.

[0018] Compared with the prior art, the application has the following beneficial effects:

[0019] The self-made double-response complementary mechanism self-repairing filler and the composite aminated fluorinated graphene are used to prepare the cable, so that the high wear resistance and corrosion resistance are achieved.

[0020] Firstly, the size-matched carbon nanotubes are selected, and carboxyl and hydroxyl active sites are introduced on the outer wall of the carbon nanotubes through surface modification; then, the terminal amino groups of 1,11-bismaleimide-3,6,9-trioxoundecane react with the carboxyl / hydroxyl groups, the bismaleimide molecules are grafted to the outer surface of the carbon nanotubes, and the Diels-Alder (DA) click reaction is carried out between the unreacted end of the bismaleimide and the furan-terminated polyurethane prepolymer. Since the size of the bismaleimide molecules and the polyurethane prepolymer is larger than the inner diameter of the carbon nanotube, the dynamic DA bond network can only be stably constructed on the outer surface of the carbon nanotube.

[0021] Further, by using a cinnamyl chloride with a small molecular size, the light-responsive cinnamate groups are grafted on the inner surface of the carbon nanotubes by the reaction between the acyl chloride group and the hydroxyl group on the inner wall of the carbon nanotubes, thereby forming the inner and outer double-effect self-repairing carbon nanotubes; the outer surface DA dynamic covalent bond can be triggered to reversibly break and recombine by the local heat generated by friction, thereby realizing heat-driven self-repairing and significantly improving the wear resistance; and if the carbon nanotubes are cracked due to mechanical damage, the cinnamate groups on the inner surface are exposed and can complete the crack repair through the light-reversible [2+2] cycloaddition reaction under ultraviolet irradiation, thereby forming a “heat-light” dual-response complementary mechanism.

[0022] Finally, the above self-repairing carbon nanotubes are combined with the aminated fluorinated graphene to construct a multi-level labyrinth structure: the three-dimensional network skeleton of the carbon nanotubes provides mechanical barrier and wear-resistant support at the macro level, and the lamellar structure of the aminated fluorinated graphene prolongs the penetration path of the corrosion medium and enhances the chemical corrosion resistance through the physical stacking and hydrogen bonding at the micro level. Meanwhile, the polyurethane prepolymer segments grafted on the surface of the carbon nanotubes can improve the compatibility of the filler and the cable matrix, and the strong interface bonding between the aminated fluorinated graphene and the polyurethane further ensures the uniform dispersion of the filler, thereby realizing the synergistic optimization of wear resistance and corrosion resistance. DETAILED DESCRIPTION

[0023] The technical solutions in the embodiments of the present application will be clearly and completely described below with reference to 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 of ordinary skill in the art without creative labor fall within the scope of the present application.

[0024] In order to more clearly illustrate the method provided by the present application, the following embodiments are described in detail. The test methods of various indexes of a high wear-resistant and corrosion-resistant cable prepared in the following embodiments are as follows:

[0025] Mechanical properties: the raw materials prepared in the embodiments and the comparative examples are molded into 5B dumbbell-shaped sample bars on a molding machine according to GB / T2951.11-2008, the cut sample bars are conditioned at 25°C and a relative humidity of 65% for 16h, and the mechanical properties are tested on a universal material testing machine, the tensile strength of the sample is detected, the test speed is 10mm / min, each group of samples is tested 5 times, and the average value is taken.

[0026] Wear resistance: the cable sheath prepared in the embodiments and the comparative examples is pressed into a circular sheet with a thickness of 30mm and a diameter of 30mm, and the circular sheet is dry rubbed under the conditions of a rotation speed of 200r / min and a load of 196N for 2h.

[0027] Self-repairing: the cable sheath prepared from the examples and comparative examples was made into a sample with a length of 120 mm, a width of 80 mm and a thickness of 1 mm, a 300 μm long and 300 μm deep scratch was drawn on the surface of the sample, the sample was kept at 50℃ for 12 h, the tensile strength was tested, and the ratio of the tensile strength after the scratch test to the initial tensile strength was used to represent the self-repairing rate;

[0028] Corrosion resistance: the cable sheath prepared from the examples and comparative examples was pressed into a disc with a thickness of 30 mm and a diameter of 30 mm, and the disc was immersed in acid solution (5 wt% H2SO4 solution) and alkali solution (20 wt% NaOH solution) for 500 h. Example 1

[0029] (1) carbon nanotubes with an inner diameter of 1 nm and an outer diameter of 4 nm were immersed in a sulfuric acid / nitric acid mixed solution, the concentration of sulfuric acid was 13.8 mol / L, the concentration of nitric acid was 3.625 mol / L, the solid-liquid ratio was 1:5, then ultrasonic treatment was carried out at 40℃ for 2 h, the ultrasonic power was 300 W, then centrifugation was carried out at 8000 rpm for 10 min, then the sample was washed with deionized water for 3 times, and vacuum drying was carried out at 0.085 MPa and 50℃ for 5 h, thus surface modified carbon nanotubes were prepared; 1,11-bismaleimide-3,6,9-trioxoundecane was dissolved in N,N-dimethylformamide, the mass concentration was 5 mg / mL, modified carbon nanotubes were added, the mass ratio of modified carbon nanotubes to 1,11-bismaleimide-3,6,9-trioxoundecane was 2:1, stirring was carried out at 80℃ for 12 h, the stirring speed was 120 rpm, centrifugation was carried out at 8000 rpm for 10 min, then the sample was washed with N,N-dimethylformamide for 3 times to remove unreacted reagents, then the sample was washed with ethanol for 1 time, and drying was carried out at 50℃ for 3 h, thus externally grafted carbon nanotubes were prepared; furan-terminated polyurethane prepolymer was prepared by using polytetrahydrofuran diol and isophorone diisocyanate as raw materials, pre-polymerization was carried out at 60℃ for 2 h, then furfuryl alcohol was used for end capping, the end capping time was 2 h, and the temperature was 60℃, the molar ratio of polytetrahydrofuran diol, isophorone diisocyanate and furfuryl alcohol was 1:2:2; the externally grafted carbon nanotubes and the furan-terminated polyurethane prepolymer were dispersed in toluene according to a mass ratio of 1:5, the mass ratio of externally grafted carbon nanotubes to toluene was 1:15, stirring was carried out at 60℃ for 12 h, the stirring speed was 60 rpm, then the sample was cooled to room temperature, centrifugation was carried out at 3000 rpm for 5 min, and drying was carried out at 50℃ for 5 h, thus externally grafted carbon nanotubes were prepared;

[0030] (2) 0.2 g of outer surface grafted carbon nanotubes were dispersed in 50 mL of anhydrous tetrahydrofuran, 1 mL of triethylamine was added as an acid binding agent, and the mixture was ultrasonically treated at a power of 50 kHz for 60 min. Then, 0.8 mmol of cinnamyl chloride was added dropwise, and the mixture was stirred at 25 °C in the dark for 24 h at a stirring speed of 240 rpm. After the reaction, the mixture was filtered, and the solid was washed with tetrahydrofuran and acetone, respectively. The solid was dried under vacuum at 50 °C for 3 h at a pressure of 0.085 MPa to obtain the self-repairing filler;

[0031] (3) 0.5 g of fluorinated graphene with a C / F ratio of 2:1 was dispersed in 50 mL of an ethylenediamine aqueous solution with a concentration of 10 wt%, and the mixture was stirred at 60 °C for 6 h at a stirring speed of 120 rpm. Then, the mixture was centrifuged at 5000 rpm for 10 min, and then washed with deionized water for 3 times. Finally, the mixture was freeze-dried at -40 °C to obtain amino-functionalized fluorinated graphene. The self-repairing filler and the amino-functionalized fluorinated graphene were mixed at a mass ratio of 6:1, and then added into a thermoplastic polyurethane / dimethylacetamide solution. The mass ratio of the self-repairing filler to the thermoplastic polyurethane was 3:80, and the solid content of the thermoplastic polyurethane / dimethylacetamide solution was 10%. The thermoplastic polyurethane was low-melting-point Estane 58887. The mixture was ultrasonically dispersed at a power of 300 W for 2 h at 50 °C in a pulse mode. Then, the mixture was melt-blended by a twin-screw extruder at a temperature of 120 °C and a screw rotation speed of 80 rpm to obtain a uniform cable material. The cable material was directly coated on the surface of a cable conductor to form an insulation layer. After shaping in a cooling water tank, the insulation layer was annealed at 80 °C for 1 h to obtain a high-wear-resistant and corrosion-resistant cable. Example 2

[0032] (1) carbon nanotubes with an inner diameter of 1.25 nm and an outer diameter of 6 nm are immersed in a sulfuric acid / nitric acid mixed solution, the concentration of sulfuric acid is 13.8 mol / L, the concentration of nitric acid is 3.625 mol / L, the solid-liquid ratio is 1:7.5, then ultrasonic treatment is carried out at 40℃ for 2h, the ultrasonic power is 300W, then centrifugation is carried out at 8000 rpm for 10 min, then washing is carried out with deionized water for 3 times, and vacuum drying is carried out at 0.085 MPa and 50℃ for 5h, to obtain surface modified carbon nanotubes; 1,11-bismaleimide-3,6,9-trioxoundecane is dissolved in N,N-dimethylformamide, the mass concentration is 10 mg / mL, the modified carbon nanotubes are added, the mass ratio of the modified carbon nanotubes to 1,11-bismaleimide-3,6,9-trioxoundecane is 3:1, stirring is carried out at 80℃ for 12h, the stirring speed is 120 rpm, centrifugation is carried out at 8000 rpm for 10 min, then washing is carried out with N,N-dimethylformamide for 3 times to remove unreacted reagents, then washing is carried out with ethanol once, and drying is carried out at 50℃ for 3h, to obtain outer-grafted carbon nanotubes; polytetrahydrofuran diol and isophorone diisocyanate are used as raw materials, pre-polymerization is carried out at 60℃ for 2h, then furfuryl alcohol is added for capping, the capping time is 2h, the temperature is 70℃, furan-terminated polyurethane pre-polymer is prepared, the molar ratio of polytetrahydrofuran diol, isophorone diisocyanate and furfuryl alcohol is 1:2:2; the outer-grafted carbon nanotubes and the furan-terminated polyurethane pre-polymer are dispersed in toluene according to a mass ratio of 1:5, the mass ratio of the outer-grafted carbon nanotubes to toluene is 1:15, stirring is carried out at 60℃ for 12h, the stirring speed is 60 rpm, then cooling is carried out to room temperature, centrifugation is carried out at 3000 rpm for 5 min, and drying is carried out at 50℃ for 5h, to obtain outer surface-grafted carbon nanotubes;

[0033] (2) 0.2g of outer surface-grafted carbon nanotubes are dispersed in 50ml of anhydrous tetrahydrofuran, 1ml of triethylamine is added as an acid-binding agent, ultrasonic treatment is carried out at a power of 50kHz for 60min, 1.1mmol of cinnamyl chloride is added dropwise, stirring is carried out at 25℃ in the dark for 24h, the stirring speed is 240 rpm, after the reaction is completed, filtration is carried out, the solid is washed with tetrahydrofuran and acetone in sequence, and vacuum drying is carried out at 0.085 MPa and 50℃ for 3h, to obtain a self-repairing filler;

[0034] (3) The fluorinated graphene with C / F=2:1 is weighed 0.5 g, dispersed in 50 mL of 10 wt% ethylenediamine aqueous solution, stirred at 60℃ for 6 h, the stirring speed is 120 rpm, centrifuged at 5000 rpm for 10 min, then washed with deionized water for 3 times, freeze-dried at -40℃ to obtain the aminated fluorinated graphene; the self-repairing filler and the aminated fluorinated graphene are added into the thermoplastic polyurethane / dimethylacetamide solution according to the mass ratio of 4:1, the mass ratio of the self-repairing filler and the thermoplastic polyurethane is 3:85, the solid content of the thermoplastic polyurethane / dimethylacetamide solution is 10%, the thermoplastic polyurethane is low-melting-point Estane 58887, ultrasonic dispersion is carried out at 50℃ in pulse mode, the power is 300 W, the time is 2 h; then melt blending is carried out through a twin-screw extruder, the temperature is 125℃, the screw speed is 90 rpm, the extruded granules are obtained, which are directly coated on the surface of the cable conductor to form an insulation layer; after shaping in a cooling water tank, annealing is carried out at 80℃ for 1 h, and the high wear-resistant and corrosion-resistant cable is prepared. Example 3

[0035] (1) The carbon nanotube with an inner diameter of 1.5 nm and an outer diameter of 8 nm is immersed in a sulfuric acid / nitric acid mixed solution, the concentration of sulfuric acid is 13.8 mol / L, the concentration of nitric acid is 3.625 mol / L, the solid-liquid ratio is 1:10, then ultrasonic treatment is carried out at 40℃ for 2 h, the ultrasonic power is 300 W, then centrifuged at 8000 rpm for 10 min, washed with deionized water for 3 times, and vacuum dried at 0.085 MPa and 50℃ for 5 h to obtain the surface-modified carbon nanotube; 1,11-bismaleimide-3,6,9-trioxoundecane is dissolved in N,N-dimethylformamide, the mass concentration is 15 mg / mL, the modified carbon nanotube is added, the mass ratio of the modified carbon nanotube and 1,11-bismaleimide-3,6,9-trioxoundecane is 4:1, stirring is carried out at 80℃ for 12 h, the stirring speed is 120 rpm, centrifuged at 8000 rpm for 10 min, then washed with N,N-dimethylformamide for 3 times to remove the unreacted reagent, washed with ethanol once, and dried at 50℃ for 3 h to obtain the outer-grafted carbon nanotube; polytetrahydrofuran diol and isophorone diisocyanate are used as raw materials, pre-polymerization is carried out at 60℃ for 2 h, then capped with furan methanol, the capping time is 2 h, the temperature is 80℃, the furan-based capped polyurethane prepolymer is prepared, the molar ratio of polytetrahydrofuran diol, isophorone diisocyanate and furan methanol is 1:2:2; the outer-grafted carbon nanotube and the furan-based capped polyurethane prepolymer are dispersed in toluene according to the mass ratio of 1:5, the mass ratio of the outer-grafted carbon nanotube and toluene is 1:15, stirring is carried out at 60℃ for 12 h, the stirring speed is 60 rpm, then cooled to room temperature, centrifuged at 3000 rpm for 5 min, and dried at 50℃ for 5 h to obtain the outer-grafted carbon nanotube;

[0036] (2) 0.2 g of the outer surface grafted carbon nanotubes were dispersed in 50 ml of anhydrous tetrahydrofuran, 1 ml of triethylamine was added as an acid binding agent, ultrasonic treatment was carried out at a power of 50 kHz for 60 min, 1.4 mmol of cinnamyl chloride was added dropwise, stirring was carried out at 25°C in the dark for 24 h at a stirring speed of 240 rpm, after the reaction was completed, filtration was carried out, the solid was washed with tetrahydrofuran and acetone in turn, and vacuum drying was carried out at 0.085 MPa and 50°C for 3 h to obtain the self-repairing filler;

[0037] (3) 0.5 g of the fluorinated graphene with C / F = 2:1 was dispersed in 50 ml of an ethylenediamine aqueous solution with a concentration of 10 wt%, stirring was carried out at 60°C for 6 h at a stirring speed of 120 rpm, centrifugation was carried out at 5000 rpm for 10 min, then washing was carried out with deionized water for 3 times, freeze drying was carried out at -40°C to obtain the aminated fluorinated graphene; the self-repairing filler and the aminated fluorinated graphene were added into a thermoplastic polyurethane / dimethylacetamide solution at a mass ratio of 6:2, the mass ratio of the self-repairing filler to the thermoplastic polyurethane was 3:90, the solid content of the thermoplastic polyurethane / dimethylacetamide solution was 10%, the thermoplastic polyurethane was low-melting-point Estane 58887, pulse mode ultrasonic dispersion was carried out at 50°C, the power was 300 W, and the time was 2 h; then melt blending was carried out through a twin-screw extruder at a temperature of 130°C and a screw rotating speed of 100 rpm to obtain uniform cable material, which was directly coated on the surface of a cable conductor to form an insulation layer; after shaping in a cooling water tank, annealing was carried out at 80°C for 1 h to obtain a high-wear-resistant and corrosion-resistant cable.

[0038] Comparative Example 1 (without DA)

[0039] Comparative Example 1 and Example 2 differ in step (1), which is changed to: (1) carbon nanotubes with an inner diameter of 1.25 nm and an outer diameter of 6 nm were immersed in a sulfuric acid / nitric acid mixed solution, the concentration of sulfuric acid was 13.8 mol / L, the concentration of nitric acid was 3.625 mol / L, the solid-liquid ratio was 1:7.5, then ultrasonic treatment was carried out at 40°C for 2 h at a power of 300 W, followed by centrifugation at 8000 rpm for 10 min, washing was carried out with deionized water for 3 times, and vacuum drying was carried out at 0.085 MPa and 50°C for 5 h to obtain surface-modified carbon nanotubes;

[0040] (2) 0.2 g of the surface-modified carbon nanotubes were dispersed in 50 ml of anhydrous tetrahydrofuran, 1 ml of triethylamine was added as an acid binding agent, ultrasonic treatment was carried out at a power of 50 kHz for 60 min, 1.1 mmol of cinnamyl chloride was added dropwise, stirring was carried out at 25°C in the dark for 24 h at a stirring speed of 240 rpm, after the reaction was completed, filtration was carried out, the solid was washed with tetrahydrofuran and acetone in turn, and vacuum drying was carried out at 0.085 MPa and 50°C for 3 h to obtain the self-repairing filler; the remaining steps were the same as those in Example 2.

[0041] Comparative Example 2 (no photoresponse)

[0042] Comparative Example 2 differs from Example 2 in that step (2) is not performed, and step (3) is changed to: using fluorinated graphene with C / F = 2:1, 0.5 g is weighed and dispersed in 50 mL of 10 wt% ethylenediamine aqueous solution, stirring at 60°C for 6 h at a stirring speed of 120 rpm, centrifuging at 5000 rpm for 10 min, then washing with deionized water 3 times, freeze-drying at -40°C to obtain aminated fluorinated graphene; the outer surface grafted carbon nanotubes and the aminated fluorinated graphene are added to a thermoplastic polyurethane / dimethylacetamide solution at a mass ratio of 4:1, the mass ratio of the outer surface grafted carbon nanotubes to the thermoplastic polyurethane is 3:85, the solid content of the thermoplastic polyurethane / dimethylacetamide solution is 10%, the thermoplastic polyurethane is low-melting-point Estane 58887, and the thermoplastic polyurethane / dimethylacetamide solution is subjected to pulsed mode ultrasonic dispersion at 50°C, with a power of 300 W and a time of 2 h; then melt blending is performed by a twin-screw extruder at a temperature of 125°C and a screw speed of 90 rpm to obtain a uniform cable material, which is directly coated on the surface of a cable conductor to form an insulating layer; after shaping in a cooling water tank, annealing at 80°C for 1 h, a high wear-resistant and corrosion-resistant cable is obtained; the remaining steps are the same as in Example 2.

[0043] Comparative Example 3 (non-standard inside and outside)

[0044] Comparative Example 3 differs from Example 2 in steps (1) and (2) which are changed to: (1) carbon nanotubes with inner diameter of 5 nm and outer diameter of 9 nm are immersed in a mixture of sulfuric acid / nitric acid, the concentration of sulfuric acid is 13.8 mol / L, the concentration of nitric acid is 3.625 mol / L, the solid-liquid ratio is 1:7.5, then ultrasonic treatment is carried out at 40℃ for 2h, the ultrasonic power is 300W, followed by centrifugation at 8000 rpm for 10 min, washing with deionized water for 3 times, and vacuum drying at 0.085 MPa and 50℃ for 5h, to obtain surface-modified carbon nanotubes; 1,11-bismaleimide-3,6,9-trioxoundecane is dissolved in N,N-dimethylformamide with a mass concentration of 10 mg / mL, the modified carbon nanotubes are added, the mass ratio of the modified carbon nanotubes to 1,11-bismaleimide-3,6,9-trioxoundecane is 3:1, stirring is carried out at 80℃ for 12h, the stirring speed is 120 rpm, centrifugation is carried out at 8000 rpm for 10 min, after removing the unreacted reagents by washing with N,N-dimethylformamide for 3 times, washing with ethanol once, and drying at 50℃ for 3h, grafted carbon nanotubes are obtained; furan-terminated polyurethane prepolymer is prepared by using polytetrahydrofuran diol and isophorone diisocyanate as raw materials, pre-polymerization is carried out at 60℃ for 2h, then end-capping is carried out by adding furfuryl alcohol, the end-capping time is 2h, the temperature is 70℃, the molar ratio of polytetrahydrofuran diol, isophorone diisocyanate and furfuryl alcohol is 1:2:2; the grafted carbon nanotubes and the furan-terminated polyurethane prepolymer are dispersed in toluene at a mass ratio of 1:5, the mass ratio of the grafted carbon nanotubes to toluene is 1:15, stirring is carried out at 60℃ for 12h, the stirring speed is 60 rpm, then cooling is carried out to room temperature, centrifugation is carried out at 3000 rpm for 5 min, and drying is carried out at 50℃ for 5h, to obtain DA grafted carbon nanotubes;

[0045] (2) 0.2g of DA grafted carbon nanotubes are dispersed in 50ml of anhydrous tetrahydrofuran, 1ml of triethylamine is added as an acid-binding agent, ultrasonic treatment is carried out at a power of 50kHz for 60min, 1.1mmol of cinnamyl chloride is added dropwise, stirring is carried out at 25℃ in the dark for 24h, the stirring speed is 240 rpm, after the reaction is completed, filtration is carried out, the solid is washed with tetrahydrofuran and acetone in sequence, and vacuum drying is carried out at 0.085 MPa and 50℃ for 3h, to obtain a self-repairing filler; the remaining steps are the same as in Example 2.

[0046] Comparative Example 4 (ordinary graphene)

[0047] The difference between Comparative Example 4 and Example 2 is that step (3) is different, step (3) is changed to: using fluorinated graphene with C / F = 2:1, adding the self-repairing filler and the fluorinated graphene into the thermoplastic polyurethane / dimethylacetamide solution at a mass ratio of 4:1, the mass ratio of the self-repairing filler and the thermoplastic polyurethane is 3:85, the solid content of the thermoplastic polyurethane / dimethylacetamide solution is 10%, the thermoplastic polyurethane is low-melting-point Estane 58887, and the ultrasonic dispersion is carried out at 50°C in a pulse mode, the power is 300W, and the time is 2h; then, the melt blending is carried out through a double-screw extruder, the temperature is 125°C, the screw rotation speed is 90rpm, the uniform cable material is obtained by extruding and granulating, and the cable material is directly coated on the surface of the cable conductor to form an insulation layer; after shaping in a cooling water tank, annealing is carried out at 80°C for 1h, and a high-wear-resistant and corrosion-resistant cable is prepared; the remaining steps are the same as those in Example 2.

[0048] Comparative Example 5 (without adding graphene composite)

[0049] The difference between Comparative Example 5 and Example 2 is that step (3) is different, step (3) is changed to: adding the self-repairing filler into the thermoplastic polyurethane / dimethylacetamide solution, the mass ratio of the self-repairing filler and the thermoplastic polyurethane is 3:85, the solid content of the thermoplastic polyurethane / dimethylacetamide solution is 10%, the thermoplastic polyurethane is low-melting-point Estane 58887, and the ultrasonic dispersion is carried out at 50°C in a pulse mode, the power is 300W, and the time is 2h; then, the melt blending is carried out through a double-screw extruder, the temperature is 125°C, the screw rotation speed is 90rpm, the uniform cable material is obtained by extruding and granulating, and the cable material is directly coated on the surface of the cable conductor to form an insulation layer; after shaping in a cooling water tank, annealing is carried out at 80°C for 1h, and a high-wear-resistant and corrosion-resistant cable is prepared; the remaining steps are the same as those in Example 2.

[0050] Effect Example

[0051] The performance analysis results of a high-wear-resistant and corrosion-resistant cable prepared by using Examples 1 to 3 and Comparative Examples 1 to 5 of the application are shown in Table 1 below.

[0052] Table 1

[0053]

[0054] From the comparison of the self-repairing experimental data of the examples and the comparative examples, it can be found that the size-matched carbon nanotubes are selected in the application, carboxyl and hydroxyl active sites are introduced on the outer wall of the carbon nanotubes through surface modification; then, the terminal amino group of 1,11-bismaleimide-3,6,9-trioxoundecane reacts with the carboxyl / hydroxyl to graft the bismaleimide molecules to the outer surface of the carbon nanotubes, and then the unreacted end of the maleimide reacts with the furan-terminated polyurethane prepolymer through Diels-Alder (DA) click reaction. Since the size of the bismaleimide molecules and the polyurethane prepolymer is larger than the inner diameter of the carbon nanotubes, the dynamic DA bond network can only be stably constructed on the outer surface of the carbon nanotubes. The molecular size of cinnamoyl chloride is smaller, and the cinnamoyl chloride group reacts with the hydroxyl group on the inner wall of the carbon nanotubes to graft the photoresponsive cinnamate group on the inner surface, thereby forming the inner and outer double-effect self-repairing carbon nanotubes; when the carbon nanotubes are added as fillers into the cable material, the outer surface DA dynamic covalent bond can be triggered to reversibly break and recombine through the local heat generated by friction, realizing heat-driven self-repairing and significantly improving the wear resistance; and if the carbon nanotubes are cracked due to mechanical damage, the cinnamate group on the inner surface is exposed, and under ultraviolet irradiation, the photo-reversible [2+2] cycloaddition reaction can complete the crack repair, forming a “heat-light” dual-response complementary mechanism. From the comparison of the wear resistance experimental data of the examples and the comparative examples, it can be found that the self-repairing carbon nanotubes and the aminated fluorinated graphene are compounded in the application to construct a multi-level labyrinth structure: the three-dimensional network skeleton of the carbon nanotubes provides mechanical barrier and wear-resistant support on the macroscopic level. From the comparison of the corrosion resistance experimental data of the examples and the comparative examples, it can be found that the sheet structure of the aminated fluorinated graphene prolongs the penetration path of the corrosion medium through the physical stacking and hydrogen bonding on the microscopic level, and enhances the chemical corrosion resistance. At the same time, the polyurethane prepolymer segments grafted on the surface of the carbon nanotubes can improve the compatibility of the filler and the cable matrix, and the strong interface between the aminated fluorinated graphene and the polyurethane further ensures the uniform dispersion of the filler, realizing the synergistic optimization of wear resistance and corrosion resistance.

[0055] It will be obvious to a person skilled in the art that the application is not limited to the details of the above-described exemplary embodiments, but that the application can be implemented in other concrete forms without departing from the spirit or essential characteristics of the application. The embodiments should, therefore, be considered in all respects as illustrative and not restrictive, the scope of the application being indicated by the appended claims rather than by the above description, and it is intended to encompass all changes and modifications that fall within the meaning and scope of the equivalent elements of the claims. Any reference signs in the claims should not be construed as limiting the claims concerned.

Claims

1. A high wear-resistant and corrosion-resistant cable, characterized in that, The preparation steps include the following: (1) Dissolve 1,11-bismaleimide-3,6,9-trioxoundecane in N,N-dimethylformamide at a mass concentration of 5-15 mg / mL, add modified carbon nanotubes, stir at 80°C for 12 h at a stirring speed of 120 rpm, centrifuge at 8000 rpm for 10 min, wash three times with N,N-dimethylformamide to remove unreacted reagents, wash once with ethanol, and dry at 50°C for 3 h to obtain externally grafted carbon nanotubes; disperse the externally grafted carbon nanotubes and furanyl-terminated polyurethane prepolymer in toluene at a mass ratio of 1:5, stir at 60°C for 12 h at a stirring speed of 60 rpm, then cool to room temperature, centrifuge at 3000 rpm for 5 min, and dry at 50°C for 5 h to obtain externally grafted carbon nanotubes; (2) 0.2 g of externally grafted carbon nanotubes were dispersed in 50 ml of anhydrous tetrahydrofuran, and 1 ml of triethylamine was added as an acid-binding agent. The mixture was sonicated at 50 kHz for 60 min. 0.8-1.4 mmol of cinnamyl chloride was added dropwise. The mixture was stirred at 25 ℃ in the dark for 24 h at a stirring speed of 240 rpm. After the reaction was completed, the mixture was filtered. The solid was washed with tetrahydrofuran and acetone in sequence and dried under vacuum at 0.085 MPa and 50 ℃ for 3 h to obtain the self-healing filler. (3) The self-healing filler and aminated fluorinated graphene were added to a thermoplastic polyurethane / dimethylacetamide solution at a mass ratio of 6:1-2. The thermoplastic polyurethane was Estane 58887. The mixture was ultrasonically dispersed in pulse mode at 50°C. Then, it was melt-blended by a twin-screw extruder at a temperature of 120-130°C and a screw speed of 80-100 rpm. The mixture was extruded and granulated to obtain a uniform cable material, which was directly coated on the surface of the cable conductor to form an insulation layer. After being shaped in a cooling water tank, the mixture was annealed at 80°C for 1 hour to obtain a high wear-resistant and corrosion-resistant cable.

2. The high wear-resistant and corrosion-resistant cable according to claim 1, characterized in that, The method for preparing surface-modified carbon nanotubes in step (1) is as follows: carbon nanotubes with an inner diameter of 1-1.5 nm and an outer diameter of 4-8 nm are immersed in a sulfuric acid / nitric acid mixture with a sulfuric acid concentration of 13.8 mol / L, a nitric acid concentration of 3.625 mol / L, and a solid-liquid ratio of 1:5-10. Then, they are ultrasonically treated at 40°C for 2 h with an ultrasonic power of 300 W. After that, they are centrifuged at 8000 rpm for 10 min, washed three times with deionized water, and vacuum dried at 0.085 MPa and 50°C for 5 h to obtain surface-modified carbon nanotubes.

3. The high wear-resistant and corrosion-resistant cable according to claim 1, characterized in that, The preparation method of furan-based capped polyurethane prepolymer in step (1) is as follows: using polytetrahydrofuran diol and isophorone diisocyanate as raw materials, prepolymerizing at 60°C for 2 hours, then adding furan methanol for capping, capping time for 2 hours, and temperature of 60-80°C, to obtain furan-based capped polyurethane prepolymer.

4. The high wear-resistant and corrosion-resistant cable according to claim 3, characterized in that, The molar ratio of polytetrahydrofuran diol, isophorone diisocyanate, and furanol methanol is 1:2:

2.

5. The high wear-resistant and corrosion-resistant cable according to claim 1, characterized in that, In step (1), the mass ratio of modified carbon nanotubes to 1,11-bismaleimide-3,6,9-trioxoundecane is 2-4:

1.

6. The high wear-resistant and corrosion-resistant cable according to claim 1, characterized in that, In step (1), the mass ratio of externally grafted carbon nanotubes to toluene is 1:

15.

7. The high wear-resistant and corrosion-resistant cable according to claim 1, characterized in that, In step (3), the mass ratio of self-healing filler to thermoplastic polyurethane is 3:80-90.

8. The high wear-resistant and corrosion-resistant cable according to claim 1, characterized in that, The solid content of the plastic polyurethane / dimethylacetamide solution in step (3) is 10%.

9. A high wear-resistant and corrosion-resistant cable according to claim 1, characterized in that, The preparation method of aminated fluorinated graphene in step (3) is as follows: 0.5g of fluorinated graphene with C / F=2:1 is weighed and dispersed in 50mL of 10wt% ethylenediamine aqueous solution, stirred at 60℃ for 6h at a stirring speed of 120rpm, centrifuged at 5000rpm for 10min, then washed 3 times with deionized water, and freeze-dried at -40℃ to obtain aminated fluorinated graphene.

10. A high wear-resistant and corrosion-resistant cable according to claim 1, characterized in that, In step (3), the power of the pulse mode ultrasonic dispersion is 300W and the time is 2h.

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