Irradiation modified waterproof high-insulation rubber cable material and preparation method thereof

Abstract

The invention discloses an irradiation modified waterproof high-insulation rubber cable material which comprises the following components in parts by mass: 40-60 parts of natural rubber; 20 to 30 parts of nitrile rubber; 10 to 20 parts of irradiation modified polyvinylidene fluoride; 5 to 10 parts of a nitrogen-doped graphene composite material; 1 to 3 parts of polydopamine modified graphene; 2 to 5 parts of nano silicon dioxide; 3-8 parts of graphite powder; 5-10 parts of calcium carbonate; 2-5 parts of an anti-aging agent; 3-6 parts of a plasticizer; 1-3 parts of a cross-linking agent; the irradiation modified polyvinylidene fluoride has good hydrophobicity and can effectively prevent water from permeating into a cable, meanwhile, due to the addition of the nano silicon dioxide, tiny pores in a rubber matrix can be filled, the compactness of rubber is enhanced, the waterproof performance of the cable material is further improved, the cable material has excellent waterproof performance, and meanwhile, the cable material has a good application prospect. And the compound can also physically or chemically act with a rubber molecular chain, so that the mechanical property and the wear resistance of the rubber are improved.

Description

Technical Field

[0001] The invention belongs to the technical field of cable materials, and in particular relates to a radiation-modified waterproof high-insulation rubber cable material. Background Art

[0002] Traditional rubber cable materials have deficiencies in waterproofing and insulation performance, making them difficult to meet the requirements of use in some special environments (such as humid environments and high voltages). Although there have been attempts to modify rubber cable materials in the prior art, there is still considerable room for improvement in terms of introducing innovative ingredients and enhancing overall performance. Therefore, the development of an irradiation-modified rubber cable material with excellent waterproofing and high insulation properties is of great practical significance.

[0003] Based on this, a radiation-modified waterproof high-insulation rubber cable material was designed. Summary of the Invention

[0004] In view of the above situation, in order to overcome the defects of the prior art, the present invention provides an irradiation-modified waterproof high-insulation rubber cable material and a preparation method thereof, which effectively solves the problems raised in the above background.

[0005] To achieve the above object, the present invention provides the following technical solution: an irradiation-modified waterproof high-insulation rubber cable material, comprising the following components in parts by mass:

[0006] Natural rubber: 40-60 parts;

[0007] Nitrile rubber: 20-30 parts;

[0008] Radiation-modified polyvinylidene fluoride: 10-20 parts;

[0009] Nitrogen-doped graphene composite material: 5-10 parts;

[0010] Polydopamine modified graphene: 1-3 parts;

[0011] Nano silicon dioxide: 2-5 parts;

[0012] Graphite powder: 3-8 parts;

[0013] Calcium carbonate: 5-10 parts;

[0014] Antiaging agent: 2-5 parts;

[0015] Plasticizer: 3-6 parts;

[0016] Cross-linking agent: 1-3 parts.

[0017] Preferably, the preparation method of the radiation-modified polyvinylidene fluoride is as follows:

[0018] S1. Raw material preparation: Dry the polyvinylidene fluoride particles in a vacuum drying oven at 80-100°C for 4-6 hours to remove moisture and set aside;

[0019] S2. Irradiation treatment: evenly spread the dried polyvinylidene fluoride particles on an irradiation tray, place the irradiation tray in an electron accelerator irradiation device, and irradiate the PVDF particles with an electron beam at room temperature. The irradiation dose is 100-300 kGy and the irradiation time is 10-30 minutes. During the irradiation process, the electron beam energy is 1-2 MeV.

[0020] S3. Post-treatment: The irradiated polyvinylidene fluoride particles are taken out from the irradiation device and placed in a forced air drying oven at 50-70° C. for 2-4 hours to stabilize the free radical active substances generated during the irradiation process, thereby obtaining irradiation-modified polyvinylidene fluoride.

[0021] Preferably, the preparation method of the nitrogen-doped graphene composite material is as follows:

[0022] S1. Preparation of graphene oxide: Graphene oxide was prepared by Hummers method;

[0023] S2. Preparation of a mixed solution: Weigh a certain amount of graphite oxide, dissolve it in deionized water, and then add urea to obtain a mixed solution of graphite oxide and urea; the mass concentration of graphite oxide in the mixed solution is 1-5 mg / mL, and the mass ratio of urea to graphite oxide is 1:1-1:3;

[0024] S3, ultrasound and stirring: ultrasonically treat the mixed solution at an ultrasonic power of 200-400 W for 1-2 hours to fully disperse the graphite oxide and urea, and then stir and mix at a stirring speed of 200-400 r / min for 2-4 hours;

[0025] S4. Freeze drying: freeze drying the stirred mixed solution to obtain a mixed powder of graphite oxide and urea, the freeze drying temperature is -50°C to 30°C, the vacuum degree is 10-30 Pa, and the drying time is 24-48 hours;

[0026] S5. High temperature treatment: Place the mixed powder in a vacuum furnace, evacuate and introduce nitrogen. The temperature of the vacuum furnace is 850-1000°C and the insulation time is 3 hours. The urea is decomposed to produce nitrogen, thereby achieving nitrogen doping and obtaining a nitrogen-doped graphene composite material.

[0027] Preferably, the preparation method of the polydopamine-modified graphene is as follows:

[0028] S1. Preparation of graphene oxide: Disperse the dried graphite oxide filter disc prepared by the Hummers method in deionized water and perform ultrasonic treatment at an ultrasonic power of 200-400 W for 1-2 hours to obtain a graphene oxide dispersion;

[0029] S2. Polydopamine modification: The graphene oxide dispersion was mixed with a dopamine hydrochloride solution, and a Tris-HCl buffer solution was added to adjust the pH to 8.5. The mixture was stirred at room temperature for 12-24 hours to allow dopamine to self-polymerize on the graphene oxide surface to form polydopamine-coated graphene;

[0030] S3. Separation and drying: After the reaction is completed, the product is separated by centrifugation or filtration, washed with deionized water for multiple times, and then dried in a vacuum drying oven to obtain polydopamine-modified graphene.

[0031] Preferably, the preparation method of the nano-silicon dioxide is as follows:

[0032] S1. Raw material preparation: prepare ethyl orthosilicate, ethanol, deionized water, and ammonia water as raw materials;

[0033] S2. Sol-gel reaction: dissolving tetraethyl orthosilicate in a mixed solution of ethanol and deionized water, stirring evenly, slowly adding ammonia water dropwise, adjusting the pH value of the solution to alkaline, and stirring the reaction at 40-60° C. for 2-4 hours to allow the tetraethyl orthosilicate to undergo hydrolysis and polycondensation reaction to form a nano-silica sol;

[0034] S3, aging: aging the reacted sol at room temperature for 12-24 hours to allow the nanoparticles to further grow and stabilize;

[0035] S4. Drying: Drying the aged sol by spray drying or vacuum drying to obtain nano-silicon dioxide powder.

[0036] Preferably, the preparation method of the cable material is as follows:

[0037] S1. Raw material mixing: weigh natural rubber, nitrile rubber, irradiated modified polyvinylidene fluoride, nitrogen-doped graphene composite material, polydopamine-modified graphene, nano-silica, graphite powder, calcium carbonate, antioxidant, plasticizer, and cross-linking agent according to the above-mentioned mass parts, add them to an internal mixer, and mix the mixer at a temperature of 80-100°C, a speed of 40-60 r / min, and a mixing time of 10-15 minutes to fully mix the raw materials;

[0038] S2, plasticizing: the mixed material is transferred to the open mill for plasticizing. The roller temperature of the open mill is 60-80 ° C, the roller distance is 1-2 mm, and the plasticizing time is 5-10 minutes to further plasticize the material;

[0039] S3, cross-linking: the plasticized material is placed in a flat vulcanizing machine for cross-linking. The temperature of the flat vulcanizing machine is 180-200 ° C, the pressure is 20 MPa, and the cross-linking time is 10-15 minutes. After the cross-linking is completed, the material is cooled to room temperature;

[0040] S4. Degassing: Place the cooled material in a vacuum oven for degassing. The temperature of the vacuum oven is 100-120°C, the vacuum degree is 0.08-0.1 MPa, and the degassing time is 2-4 hours to remove bubbles and volatiles in the material.

[0041] Compared with the prior art, the present invention has the following beneficial effects:

[0042] The irradiated modified polyvinylidene fluoride of the present invention has good hydrophobicity and can effectively prevent moisture from penetrating into the interior of the cable. At the same time, the addition of nano-silica can fill the tiny pores in the rubber matrix, enhance the density of the rubber, and further improve the waterproof performance of the cable material, making it have excellent waterproof performance. At the same time, it can also physically or chemically react with the rubber molecular chain to improve the mechanical properties and wear resistance of the rubber.

[0043] Nitrogen-doped graphene composites and polydopamine-modified graphene have excellent electrical conductivity, but after special treatment, they can form a conductive network in the rubber matrix, effectively increasing the volume resistivity of the cable material, thereby giving the cable material high insulation performance;

[0044] Polydopamine-modified graphene is evenly dispersed in the rubber matrix, further improving the mechanical properties, thermal stability and electromagnetic shielding performance of the cable material;

[0045] The blending of natural rubber and nitrile rubber gives the cable material good elasticity and strength. At the same time, the addition of various fillers can further enhance the mechanical properties of the cable material, improve the cable's tensile and compression resistance, and have good mechanical properties.

[0046] The addition of antioxidants can effectively inhibit the aging reaction of rubber under the influence of environmental factors such as light, heat, and oxygen, extend the service life of cable materials, and improve their aging resistance. DETAILED DESCRIPTION

[0047] The technical solutions of the present invention will be clearly and completely described below in conjunction with specific embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, rather than all the embodiments; based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative work are within the scope of protection of the present invention.

[0048] The present invention provides an irradiation-modified waterproof high-insulation rubber cable material, comprising the following components in parts by mass:

[0049] Natural rubber: 40-60 parts;

[0050] Nitrile rubber: 20-30 parts;

[0051] Radiation-modified polyvinylidene fluoride: 10-20 parts;

[0052] Irradiation modification changes the molecular structure of polyvinylidene fluoride, improving its high temperature resistance and enabling the cable material to be used in a wider temperature range, generally maintaining good performance between -40°C and 150°C, thus improving its high temperature resistance.

[0053] Polyvinylidene fluoride itself has excellent electrical insulation properties. After irradiation modification, its insulation properties are further improved, which helps to improve the overall insulation stability of cable materials and enhance the insulation performance.

[0054] Irradiation modification enhances the compatibility of polyvinylidene fluoride with the rubber matrix, helps to form a more uniform and stable composite material, improves the overall performance of the cable material, and improves compatibility;

[0055] Nitrogen-doped graphene composite material: 5-10 parts;

[0056] Nitrogen-doped graphene has excellent electrical properties. After compounding with the rubber matrix, it can form a good conductive network, improve the conductivity of the cable material, and enhance the electrical conductivity;

[0057] Nitrogen-doped graphene has high strength and toughness, which can enhance the mechanical properties of the rubber matrix, such as tensile strength, tear strength and wear resistance, thereby improving the mechanical properties;

[0058] The introduction of nitrogen-doped graphene helps to improve the thermal stability of cable materials, enabling them to maintain good performance in high-temperature environments and improve thermal stability;

[0059] Polydopamine modified graphene: 1-3 parts;

[0060] Polydopamine-modified graphene combines the excellent properties of graphene and the good adhesion of polydopamine. It can be better dispersed in rubber cable materials to form a uniform composite material and improve dispersibility.

[0061] The introduction of polydopamine-modified graphene helps to improve the mechanical properties and thermal stability of cable materials, enabling them to maintain good performance in various environments and enhance mechanical properties and thermal stability;

[0062] The high specific surface area of graphene sheets can absorb electromagnetic waves. After modification with polydopamine, it helps to further improve the electromagnetic shielding performance of cable materials and enhance the electromagnetic shielding performance;

[0063] Nano silicon dioxide: 2-5 parts;

[0064] Nano-silica has a large specific surface area and surface activity, which can fill the gaps between rubber molecular chains and enhance the density of rubber, thereby improving the waterproof performance of cable materials and enhancing density;

[0065] Nano-silica reacts physically or chemically with rubber molecular chains, which can improve the mechanical properties of rubber, such as toughness, tear strength and wear resistance, and improve mechanical properties;

[0066] The introduction of nano-silica also helps to improve the electrical insulation properties of cable materials, making them more suitable for use as cable insulation materials and improving electrical properties;

[0067] Graphite powder: 3-8 parts;

[0068] Calcium carbonate: 5-10 parts;

[0069] Antiaging agent: 2-5 parts;

[0070] Plasticizer: 3-6 parts;

[0071] Cross-linking agent: 1-3 parts.

[0072] The preparation method of the radiation-modified polyvinylidene fluoride of this embodiment is as follows:

[0073] S1. Raw material preparation: Dry the polyvinylidene fluoride particles in a vacuum drying oven at 80-100°C for 4-6 hours to remove moisture and set aside;

[0074] S2. Irradiation treatment: evenly spread the dried polyvinylidene fluoride particles on an irradiation tray, place the irradiation tray in an electron accelerator irradiation device, and irradiate the PVDF particles with an electron beam at room temperature. The irradiation dose is 100-300 kGy and the irradiation time is 10-30 minutes. During the irradiation process, the electron beam energy is 1-2 MeV.

[0075] S3. Post-treatment: The irradiated polyvinylidene fluoride particles are taken out from the irradiation device and placed in a forced air drying oven at 50-70° C. for 2-4 hours to stabilize the free radical active substances generated during the irradiation process, thereby obtaining irradiation-modified polyvinylidene fluoride.

[0076] The preparation method of the nitrogen-doped graphene composite material of this embodiment is as follows:

[0077] S1. Preparation of graphene oxide: Graphene oxide was prepared by Hummers method;

[0078] S2. Preparation of a mixed solution: Weigh a certain amount of graphite oxide, dissolve it in deionized water, and then add urea to obtain a mixed solution of graphite oxide and urea; the mass concentration of graphite oxide in the mixed solution is 1-5 mg / mL, and the mass ratio of urea to graphite oxide is 1:1-1:3;

[0079] S3, ultrasound and stirring: ultrasonically treat the mixed solution at an ultrasonic power of 200-400 W for 1-2 hours to fully disperse the graphite oxide and urea, and then stir and mix at a stirring speed of 200-400 r / min for 2-4 hours;

[0080] S4. Freeze drying: freeze drying the stirred mixed solution to obtain a mixed powder of graphite oxide and urea, the freeze drying temperature is -50°C to 30°C, the vacuum degree is 10-30 Pa, and the drying time is 24-48 hours;

[0081] S5. High temperature treatment: Place the mixed powder in a vacuum furnace, evacuate and introduce nitrogen. The temperature of the vacuum furnace is 850-1000°C and the insulation time is 3 hours. The urea is decomposed to produce nitrogen, thereby achieving nitrogen doping and obtaining a nitrogen-doped graphene composite material.

[0082] The preparation method of the polydopamine-modified graphene of this embodiment is as follows:

[0083] S1. Preparation of graphene oxide: Disperse the dried graphite oxide filter disc prepared by the Hummers method in deionized water and perform ultrasonic treatment at an ultrasonic power of 200-400 W for 1-2 hours to obtain a graphene oxide dispersion;

[0084] S2. Polydopamine modification: The graphene oxide dispersion was mixed with a dopamine hydrochloride solution, and a Tris-HCl buffer solution was added to adjust the pH to 8.5. The mixture was stirred at room temperature for 12-24 hours to allow dopamine to self-polymerize on the graphene oxide surface to form polydopamine-coated graphene;

[0085] S3. Separation and drying: After the reaction is completed, the product is separated by centrifugation or filtration, washed with deionized water for multiple times, and then dried in a vacuum drying oven to obtain polydopamine-modified graphene.

[0086] The preparation method of the nano silicon dioxide of the present embodiment is as follows:

[0087] S1. Raw material preparation: prepare ethyl orthosilicate, ethanol, deionized water, and ammonia water as raw materials;

[0088] S2. Sol-gel reaction: dissolving tetraethyl orthosilicate in a mixed solution of ethanol and deionized water, stirring evenly, slowly adding ammonia water dropwise, adjusting the pH value of the solution to alkaline, and stirring the reaction at 40-60° C. for 2-4 hours to allow the tetraethyl orthosilicate to undergo hydrolysis and polycondensation reaction to form a nano-silica sol;

[0089] S3, aging: aging the reacted sol at room temperature for 12-24 hours to allow the nanoparticles to further grow and stabilize;

[0090] S4. Drying: Drying the aged sol by spray drying or vacuum drying to obtain nano-silicon dioxide powder.

[0091] The preparation method of the cable material of this embodiment is as follows:

[0092] S1. Raw material mixing: weigh natural rubber, nitrile rubber, irradiated modified polyvinylidene fluoride, nitrogen-doped graphene composite material, polydopamine-modified graphene, nano-silica, graphite powder, calcium carbonate, antioxidant, plasticizer, and cross-linking agent according to the above-mentioned mass parts, add them to an internal mixer, and mix the mixer at a temperature of 80-100°C, a speed of 40-60 r / min, and a mixing time of 10-15 minutes to fully mix the raw materials;

[0093] S2, plasticizing: the mixed material is transferred to the open mill for plasticizing. The roller temperature of the open mill is 60-80 ° C, the roller distance is 1-2 mm, and the plasticizing time is 5-10 minutes to further plasticize the material;

[0094] S3, cross-linking: the plasticized material is placed in a flat vulcanizing machine for cross-linking. The temperature of the flat vulcanizing machine is 180-200 ° C, the pressure is 20 MPa, and the cross-linking time is 10-15 minutes. After the cross-linking is completed, the material is cooled to room temperature;

[0095] S4. Degassing: Place the cooled material in a vacuum oven for degassing. The temperature of the vacuum oven is 100-120°C, the vacuum degree is 0.08-0.1 MPa, and the degassing time is 2-4 hours to remove bubbles and volatiles in the material.

[0096] Example 1:

[0097] An irradiation-modified waterproof high-insulation rubber cable material comprises the following components in parts by mass:

[0098] Natural rubber: 40 parts;

[0099] Nitrile rubber: 20 parts;

[0100] Radiation-modified polyvinylidene fluoride: 10 parts;

[0101] Nitrogen-doped graphene composite material: 5 parts;

[0102] Polydopamine modified graphene: 1 part;

[0103] Nano silicon dioxide: 2 parts;

[0104] Graphite powder: 3 parts;

[0105] Calcium carbonate: 5 parts;

[0106] Anti-aging agent: 2 parts;

[0107] Plasticizer: 3 parts;

[0108] Cross-linking agent: 1 part.

[0109] The preparation method of the radiation-modified polyvinylidene fluoride of this embodiment is as follows:

[0110] S1. Raw material preparation: Dry the polyvinylidene fluoride particles in a vacuum drying oven at 80°C for 4 hours to remove moisture and set aside;

[0111] S2. Irradiation treatment: The dried polyvinylidene fluoride particles are evenly spread on an irradiation tray, placed in an electron accelerator irradiation device, and irradiated with an electron beam at room temperature. The irradiation dose is 100 kGy and the irradiation time is 10 minutes. During the irradiation process, the electron beam energy is 1 MeV.

[0112] S3. Post-treatment: The irradiated polyvinylidene fluoride particles are taken out from the irradiation device and placed in a forced air drying oven at 50° C. for 2 hours to stabilize the free radical active substances generated during the irradiation process, thereby obtaining irradiation-modified polyvinylidene fluoride.

[0113] The preparation method of the nitrogen-doped graphene composite material of this embodiment is as follows:

[0114] S1. Preparation of graphene oxide: Graphene oxide was prepared by Hummers method;

[0115] S2. Preparation of a mixed solution: Weigh a certain amount of graphite oxide, dissolve it in deionized water, and then add urea to obtain a mixed solution of graphite oxide and urea; the mass concentration of graphite oxide in the mixed solution is 1 mg / mL, and the mass ratio of urea to graphite oxide is 1:1;

[0116] S3, ultrasound and stirring: The mixed solution was ultrasonically treated at an ultrasonic power of 200 W for 1 hour to fully disperse the graphite oxide and urea, and then stirred and mixed at a stirring speed of 200 r / min for 2 hours;

[0117] S4. Freeze drying: freeze drying the stirred mixed solution to obtain a mixed powder of graphite oxide and urea, the freeze drying temperature is -50°C, the vacuum degree is 10 Pa, and the drying time is 24 hours;

[0118] S5. High temperature treatment: Place the mixed powder in a vacuum furnace, evacuate and introduce nitrogen. The temperature of the vacuum furnace is 850°C and the insulation time is 3 hours to decompose the urea to produce nitrogen, thereby achieving nitrogen doping and obtaining a nitrogen-doped graphene composite material.

[0119] The preparation method of the polydopamine-modified graphene of this embodiment is as follows:

[0120] S1. Preparation of graphene oxide: A dried graphite oxide filter disc prepared by the Hummers method was dispersed in deionized water and subjected to ultrasonic treatment at an ultrasonic power of 200 W for 1 hour to obtain a graphene oxide dispersion.

[0121] S2. Polydopamine modification: The graphene oxide dispersion was mixed with a dopamine hydrochloride solution, and a Tris-HCl buffer solution was added to adjust the pH to 8.5. The mixture was stirred at room temperature for 12 hours to allow dopamine to self-polymerize on the graphene oxide surface to form polydopamine-coated graphene;

[0122] S3. Separation and drying: After the reaction is completed, the product is separated by centrifugation or filtration, washed with deionized water for multiple times, and then dried in a vacuum drying oven to obtain polydopamine-modified graphene.

[0123] The preparation method of the nano silicon dioxide of the present embodiment is as follows:

[0124] S1. Raw material preparation: prepare ethyl orthosilicate, ethanol, deionized water, and ammonia water as raw materials;

[0125] S2. Sol-gel reaction: dissolving tetraethyl orthosilicate in a mixed solution of ethanol and deionized water, stirring evenly, slowly adding ammonia water dropwise to adjust the pH value of the solution to alkaline, and stirring the mixture at 40°C for 2 hours to allow the tetraethyl orthosilicate to undergo hydrolysis and polycondensation to form a nano-silica sol;

[0126] S3, aging: aging the reacted sol at room temperature for 12 hours to allow the nanoparticles to further grow and stabilize;

[0127] S4. Drying: Drying the aged sol by spray drying or vacuum drying to obtain nano-silicon dioxide powder.

[0128] The preparation method of the cable material of this embodiment is as follows:

[0129] S1. Raw material mixing: weigh natural rubber, nitrile rubber, irradiated modified polyvinylidene fluoride, nitrogen-doped graphene composite material, polydopamine-modified graphene, nano-silica, graphite powder, calcium carbonate, antioxidant, plasticizer, and cross-linking agent according to the above-mentioned mass parts, add them to an internal mixer, and mix the mixer at a temperature of 80° C., a speed of 40 r / min, and a mixing time of 10 minutes to fully mix the raw materials;

[0130] S2, plasticizing: the mixed material is transferred to the open mill for plasticizing. The roller temperature of the open mill is 60 ° C, the roller distance is 1 mm, and the plasticizing time is 5 minutes to further plasticize the material;

[0131] S3, cross-linking: the plasticized material is placed in a flat vulcanizing machine for cross-linking. The temperature of the flat vulcanizing machine is 180°C, the pressure is 20 MPa, and the cross-linking time is 10 minutes. After the cross-linking is completed, the material is cooled to room temperature.

[0132] S4. Degassing: Place the cooled material in a vacuum oven for degassing. The temperature of the vacuum oven is 100°C, the vacuum degree is 0.08 MPa, and the degassing time is 2 hours to remove bubbles and volatiles in the material.

[0133] Example 2:

[0134] An irradiation-modified waterproof high-insulation rubber cable material comprises the following components in parts by mass:

[0135] Natural rubber: 60 parts;

[0136] Nitrile rubber: 30 parts;

[0137] Radiation-modified polyvinylidene fluoride: 20 parts;

[0138] Nitrogen-doped graphene composite material: 10 parts;

[0139] Polydopamine modified graphene: 3 parts;

[0140] Nano silicon dioxide: 5 parts;

[0141] Graphite powder: 8 parts;

[0142] Calcium carbonate: 10 parts;

[0143] Anti-aging agent: 5 parts;

[0144] Plasticizer: 6 parts;

[0145] Cross-linking agent: 3 parts.

[0146] The preparation method of the radiation-modified polyvinylidene fluoride of this embodiment is as follows:

[0147] S1. Raw material preparation: Dry the polyvinylidene fluoride particles in a vacuum drying oven at 100° C. for 6 hours to remove moisture and set aside;

[0148] S2. Irradiation treatment: The dried polyvinylidene fluoride particles are evenly spread on an irradiation tray, placed in an electron accelerator irradiation device, and irradiated with an electron beam at room temperature. The irradiation dose is 300 kGy and the irradiation time is 30 minutes. During the irradiation process, the electron beam energy is 2 MeV.

[0149] S3. Post-treatment: The irradiated polyvinylidene fluoride particles are taken out from the irradiation device and placed in a forced air drying oven at 70° C. for 4 hours to stabilize the free radical active substances generated during the irradiation process, thereby obtaining irradiation-modified polyvinylidene fluoride.

[0150] The preparation method of the nitrogen-doped graphene composite material of this embodiment is as follows:

[0151] S1. Preparation of graphene oxide: Graphene oxide was prepared by Hummers method;

[0152] S2. Preparation of a mixed solution: Weigh a certain amount of graphite oxide, dissolve it in deionized water, and then add urea to obtain a mixed solution of graphite oxide and urea; the mass concentration of graphite oxide in the mixed solution is 5 mg / mL, and the mass ratio of urea to graphite oxide is 1:3;

[0153] S3, ultrasound and stirring: The mixed solution was ultrasonically treated at an ultrasonic power of 400 W for 2 hours to fully disperse the graphite oxide and urea, and then stirred and mixed at a stirring speed of 400 r / min for 4 hours;

[0154] S4. Freeze drying: freeze drying the stirred mixed solution to obtain a mixed powder of graphite oxide and urea, the freeze drying temperature is -30°C, the vacuum degree is 30 Pa, and the drying time is 48 hours;

[0155] S5. High temperature treatment: Place the mixed powder in a vacuum furnace, evacuate and introduce nitrogen. The temperature of the vacuum furnace is 1000°C and the insulation time is 3 hours to decompose the urea to produce nitrogen, thereby achieving nitrogen doping and obtaining a nitrogen-doped graphene composite material.

[0156] The preparation method of the polydopamine-modified graphene of this embodiment is as follows:

[0157] S1. Preparation of graphene oxide: A dried graphite oxide filter disc prepared by the Hummers method was dispersed in deionized water and subjected to ultrasonic treatment at an ultrasonic power of 400 W for 2 hours to obtain a graphene oxide dispersion.

[0158] S2. Polydopamine modification: The graphene oxide dispersion was mixed with a dopamine hydrochloride solution, and a Tris-HCl buffer solution was added to adjust the pH to 8.5. The mixture was stirred at room temperature for 24 hours to allow dopamine to self-polymerize on the graphene oxide surface to form polydopamine-coated graphene;

[0159] S3. Separation and drying: After the reaction is completed, the product is separated by centrifugation or filtration, washed with deionized water for multiple times, and then dried in a vacuum drying oven to obtain polydopamine-modified graphene.

[0160] The preparation method of the nano silicon dioxide of the present embodiment is as follows:

[0161] S1. Raw material preparation: prepare ethyl orthosilicate, ethanol, deionized water, and ammonia water as raw materials;

[0162] S2, sol-gel reaction: dissolving tetraethyl orthosilicate in a mixed solution of ethanol and deionized water, stirring evenly, slowly adding ammonia water dropwise to adjust the pH value of the solution to alkaline, and stirring the mixture at 60°C for 4 hours to allow the tetraethyl orthosilicate to undergo hydrolysis and polycondensation to form a nano-silica sol;

[0163] S3, aging: aging the reacted sol at room temperature for 24 hours to allow the nanoparticles to further grow and stabilize;

[0164] S4. Drying: Drying the aged sol by spray drying or vacuum drying to obtain nano-silicon dioxide powder.

[0165] The preparation method of the cable material of this embodiment is as follows:

[0166] S1. Raw material mixing: weigh natural rubber, nitrile rubber, irradiated modified polyvinylidene fluoride, nitrogen-doped graphene composite material, polydopamine-modified graphene, nano-silica, graphite powder, calcium carbonate, antioxidant, plasticizer, and cross-linking agent according to the above-mentioned mass parts, add them to an internal mixer, and mix the mixer at a temperature of 100° C., a speed of 60 r / min, and a mixing time of 15 minutes to fully mix the raw materials;

[0167] S2, plasticizing: the mixed material is transferred to the open mill for plasticizing. The roller temperature of the open mill is 80 ° C, the roller distance is 2 mm, and the plasticizing time is 10 minutes to further plasticize the material.

[0168] S3, cross-linking: the plasticized material is placed in a flat vulcanizing machine for cross-linking. The temperature of the flat vulcanizing machine is 200 ° C, the pressure is 20 MPa, and the cross-linking time is 15 minutes. After the cross-linking is completed, the material is cooled to room temperature;

[0169] S4. Degassing: Place the cooled material in a vacuum oven for degassing. The temperature of the vacuum oven is 120°C, the vacuum degree is 0.1 MPa, and the degassing time is 4 hours to remove bubbles and volatiles in the material.

[0170] Example 3:

[0171] An irradiation-modified waterproof high-insulation rubber cable material comprises the following components in parts by mass:

[0172] Natural rubber: 50 parts;

[0173] Nitrile rubber: 25 parts;

[0174] Radiation-modified polyvinylidene fluoride: 15 parts;

[0175] Nitrogen-doped graphene composite material: 7.5 parts;

[0176] Polydopamine modified graphene: 2 parts;

[0177] Nano silicon dioxide: 3.5 parts;

[0178] Graphite powder: 5.5 parts;

[0179] Calcium carbonate: 7.5 parts;

[0180] Antiaging agent: 3.5 parts;

[0181] Plasticizer: 4.5 parts;

[0182] Cross-linking agent: 2 parts.

[0183] The preparation method of the radiation-modified polyvinylidene fluoride of this embodiment is as follows:

[0184] S1. Raw material preparation: Dry the polyvinylidene fluoride particles in a vacuum drying oven at 90° C. for 5 hours to remove moisture and set aside;

[0185] S2. Irradiation treatment: The dried polyvinylidene fluoride particles are evenly spread on an irradiation tray, placed in an electron accelerator irradiation device, and irradiated with an electron beam at room temperature. The irradiation dose is 200 kGy and the irradiation time is 20 minutes. During the irradiation process, the electron beam energy is 1.5 MeV.

[0186] S3. Post-treatment: The irradiated polyvinylidene fluoride particles are taken out from the irradiation device and placed in a forced air drying oven at 60° C. for 3 hours to stabilize the free radical active substances generated during the irradiation process, thereby obtaining irradiation-modified polyvinylidene fluoride.

[0187] The preparation method of the nitrogen-doped graphene composite material of this embodiment is as follows:

[0188] S1. Preparation of graphene oxide: Graphene oxide was prepared by Hummers method;

[0189] S2. Preparation of a mixed solution: Weigh a certain amount of graphite oxide, dissolve it in deionized water, and then add urea to obtain a mixed solution of graphite oxide and urea; the mass concentration of graphite oxide in the mixed solution is 3 mg / mL, and the mass ratio of urea to graphite oxide is 1:2;

[0190] S3, ultrasound and stirring: The mixed solution was ultrasonically treated at an ultrasonic power of 300 W for 1.5 hours to fully disperse the graphite oxide and urea, and then stirred and mixed at a stirring speed of 300 r / min for 3 hours;

[0191] S4. Freeze drying: freeze drying the stirred mixed solution to obtain a mixed powder of graphite oxide and urea, the freeze drying temperature is -40°C, the vacuum degree is 20 Pa, and the drying time is 36 hours;

[0192] S5. High temperature treatment: Place the mixed powder in a vacuum furnace, evacuate and introduce nitrogen. The temperature of the vacuum furnace is 925.5°C and the holding time is 3 hours. The urea is decomposed to produce nitrogen, thereby achieving nitrogen doping and obtaining a nitrogen-doped graphene composite material.

[0193] The preparation method of the polydopamine-modified graphene of this embodiment is as follows:

[0194] S1. Preparation of graphene oxide: A dried graphite oxide filter disc prepared by the Hummers method was dispersed in deionized water and subjected to ultrasonic treatment at an ultrasonic power of 300 W for 1.5 hours to obtain a graphene oxide dispersion.

[0195] S2. Polydopamine modification: The graphene oxide dispersion was mixed with a dopamine hydrochloride solution, and a Tris-HCl buffer solution was added to adjust the pH to 8.5. The mixture was stirred at room temperature for 18 hours to allow dopamine to self-polymerize on the graphene oxide surface to form polydopamine-coated graphene;

[0196] S3. Separation and drying: After the reaction is completed, the product is separated by centrifugation or filtration, washed with deionized water for multiple times, and then dried in a vacuum drying oven to obtain polydopamine-modified graphene.

[0197] The preparation method of the nano silicon dioxide of the present embodiment is as follows:

[0198] S1. Raw material preparation: prepare ethyl orthosilicate, ethanol, deionized water, and ammonia water as raw materials;

[0199] S2, sol-gel reaction: dissolving tetraethyl orthosilicate in a mixed solution of ethanol and deionized water, stirring evenly, slowly adding ammonia water dropwise, adjusting the pH value of the solution to alkaline, and stirring the mixture at 50°C for 3 hours to allow the tetraethyl orthosilicate to undergo hydrolysis and polycondensation to form a nano-silica sol;

[0200] S3, aging: aging the reacted sol at room temperature for 18 hours to allow the nanoparticles to further grow and stabilize;

[0201] S4. Drying: Drying the aged sol by spray drying or vacuum drying to obtain nano-silicon dioxide powder.

[0202] The preparation method of the cable material of this embodiment is as follows:

[0203] S1. Raw material mixing: weigh natural rubber, nitrile rubber, irradiated modified polyvinylidene fluoride, nitrogen-doped graphene composite material, polydopamine-modified graphene, nano-silica, graphite powder, calcium carbonate, antioxidant, plasticizer, and cross-linking agent according to the above-mentioned mass parts, add them to an internal mixer, and mix the mixer at a temperature of 90° C., a speed of 50 r / min, and a mixing time of 12.5 minutes to fully mix the raw materials;

[0204] S2, plasticizing: the mixed material is transferred to an open mill for plasticizing. The roll temperature of the open mill is 70°C, the roll distance is 1.5mm, and the plasticizing time is 7.5 minutes to further plasticize the material.

[0205] S3, cross-linking: the plasticized material is placed in a flat vulcanizing press for cross-linking. The temperature of the flat vulcanizing press is 190°C, the pressure is 20 MPa, and the cross-linking time is 12.5 minutes. After the cross-linking is completed, the material is cooled to room temperature.

[0206] S4. Degassing: The cooled material is placed in a vacuum oven for degassing. The temperature of the vacuum oven is 110°C, the vacuum degree is 0.09 MPa, and the degassing time is 3 hours to remove bubbles and volatiles in the material.

[0207] Example 4:

[0208] An irradiation-modified waterproof high-insulation rubber cable material comprises the following components in parts by mass:

[0209] Natural rubber: 45 parts;

[0210] Nitrile rubber: 22 parts;

[0211] Radiation-modified polyvinylidene fluoride: 12 parts;

[0212] Nitrogen-doped graphene composite material: 6 parts;

[0213] Polydopamine modified graphene: 2 parts;

[0214] Nano silicon dioxide: 3 parts;

[0215] Graphite powder: 4 parts;

[0216] Calcium carbonate: 6 parts;

[0217] Anti-aging agent: 3 parts;

[0218] Plasticizer: 4 parts;

[0219] Cross-linking agent: 2 parts.

[0220] The preparation method of the radiation-modified polyvinylidene fluoride of this embodiment is as follows:

[0221] S1. Raw material preparation: Dry the polyvinylidene fluoride particles in a vacuum drying oven at 85°C for 4.5 hours to remove moisture and set aside;

[0222] S2. Irradiation treatment: The dried polyvinylidene fluoride particles are evenly spread on an irradiation tray, placed in an electron accelerator irradiation device, and irradiated with an electron beam at room temperature. The irradiation dose is 150 kGy and the irradiation time is 15 minutes. During the irradiation process, the electron beam energy is 2 MeV.

[0223] S3. Post-treatment: The irradiated polyvinylidene fluoride particles are taken out from the irradiation device and placed in a forced air drying oven at 55° C. for 2.5 hours to stabilize the free radical active substances generated during the irradiation process, thereby obtaining irradiation-modified polyvinylidene fluoride.

[0224] The preparation method of the nitrogen-doped graphene composite material of this embodiment is as follows:

[0225] S1. Preparation of graphene oxide: Graphene oxide was prepared by Hummers method;

[0226] S2. Preparation of a mixed solution: Weigh a certain amount of graphite oxide, dissolve it in deionized water, and then add urea to obtain a mixed solution of graphite oxide and urea; the mass concentration of graphite oxide in the mixed solution is 2 mg / mL, and the mass ratio of urea to graphite oxide is 1:1;

[0227] S3, ultrasound and stirring: the mixed solution was ultrasonically treated at an ultrasonic power of 250 W for 1.2 hours to fully disperse the graphite oxide and urea, and then stirred and mixed at a stirring speed of 250 r / min for 2.5 hours;

[0228] S4. Freeze drying: freeze drying the stirred mixed solution to obtain a mixed powder of graphite oxide and urea, the freeze drying temperature is -35°C, the vacuum degree is 15 Pa, and the drying time is 30 hours;

[0229] S5. High temperature treatment: Place the mixed powder in a vacuum furnace, evacuate and introduce nitrogen. The temperature of the vacuum furnace is 900°C and the holding time is 3 hours to decompose the urea to produce nitrogen, thereby achieving nitrogen doping and obtaining a nitrogen-doped graphene composite material.

[0230] The preparation method of the polydopamine-modified graphene of this embodiment is as follows:

[0231] S1. Preparation of graphene oxide: A dried graphite oxide filter disc prepared by the Hummers method was dispersed in deionized water and subjected to ultrasonic treatment at an ultrasonic power of 250 W for 1.2 hours to obtain a graphene oxide dispersion.

[0232] S2. Polydopamine modification: The graphene oxide dispersion was mixed with a dopamine hydrochloride solution, and a Tris-HCl buffer solution was added to adjust the pH to 8.5. The mixture was stirred at room temperature for 15 hours to allow dopamine to self-polymerize on the graphene oxide surface to form polydopamine-coated graphene;

[0233] S3. Separation and drying: After the reaction is completed, the product is separated by centrifugation or filtration, washed with deionized water for multiple times, and then dried in a vacuum drying oven to obtain polydopamine-modified graphene.

[0234] The preparation method of the nano silicon dioxide of the present embodiment is as follows:

[0235] S1. Raw material preparation: prepare ethyl orthosilicate, ethanol, deionized water, and ammonia water as raw materials;

[0236] S2. Sol-gel reaction: dissolving tetraethyl orthosilicate in a mixed solution of ethanol and deionized water, stirring evenly, slowly adding ammonia water dropwise to adjust the pH value of the solution to alkaline, and stirring the mixture at 45°C for 2.5 hours to allow the tetraethyl orthosilicate to undergo hydrolysis and polycondensation to form a nano-silica sol;

[0237] S3, aging: aging the reacted sol at room temperature for 15 hours to allow the nanoparticles to further grow and stabilize;

[0238] S4. Drying: Drying the aged sol by spray drying or vacuum drying to obtain nano-silicon dioxide powder.

[0239] The preparation method of the cable material of this embodiment is as follows:

[0240] S1. Raw material mixing: weigh natural rubber, nitrile rubber, irradiated modified polyvinylidene fluoride, nitrogen-doped graphene composite material, polydopamine-modified graphene, nano-silica, graphite powder, calcium carbonate, antioxidant, plasticizer, and cross-linking agent according to the above-mentioned mass parts, add them to an internal mixer, and mix the mixer at a temperature of 85° C., a speed of 45 r / min, and a mixing time of 12 minutes to fully mix the raw materials;

[0241] S2, plasticizing: the mixed material is transferred to the open mill for plasticizing. The roller temperature of the open mill is 65 ° C, the roller distance is 2 mm, and the plasticizing time is 6 minutes to further plasticize the material;

[0242] S3, cross-linking: the plasticized material is placed in a flat vulcanizing press for cross-linking. The temperature of the flat vulcanizing press is 185°C, the pressure is 20 MPa, and the cross-linking time is 11 minutes. After the cross-linking is completed, the material is cooled to room temperature.

[0243] S4. Degassing: The cooled material is placed in a vacuum oven for degassing. The temperature of the vacuum oven is 105°C, the vacuum degree is 0.08 MPa, and the degassing time is 2.5 hours to remove bubbles and volatiles in the material.

[0244] It should be noted that, in this document, relational terms such as first and second, etc., are used only to distinguish one entity or operation from another entity or operation, and do not necessarily require or imply any actual relationship or order between these entities or operations. Moreover, the terms "comprises," "comprising," or any other variations thereof are intended to cover non-exclusive inclusion, such that a process, method, article, or apparatus that includes a list of elements includes not only those elements but also other elements not explicitly listed, or elements inherent to such process, method, article, or apparatus.

[0245] While embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that various changes, modifications, substitutions, and variations may be made to these embodiments without departing from the principles and spirit of the invention, and that the scope of the invention is defined by the appended claims and their equivalents.

Claims

1. An irradiation-modified waterproof high-insulation rubber cable material, characterized in that: It includes the following components by mass: Natural rubber: 40-60 parts; Nitrile rubber: 20-30 parts; Radiation-modified polyvinylidene fluoride: 10-20 parts; Nitrogen-doped graphene composite material: 5-10 parts; Polydopamine modified graphene: 1-3 parts; Nano silicon dioxide: 2-5 parts; Graphite powder: 3-8 parts; Calcium carbonate: 5-10 parts; Antiaging agent: 2-5 parts; Plasticizer: 3-6 parts; Cross-linking agent: 1-3 parts.

2. The irradiation-modified waterproof high-insulation rubber cable material according to claim 1, characterized in that: The preparation method of the irradiation-modified polyvinylidene fluoride is as follows: S1. Raw material preparation: Dry the polyvinylidene fluoride particles in a vacuum drying oven at 80-100°C for 4-6 hours to remove moisture and set aside; S2. Irradiation treatment: evenly spread the dried polyvinylidene fluoride particles on an irradiation tray, place the irradiation tray in an electron accelerator irradiation device, and irradiate the PVDF particles with an electron beam at room temperature. The irradiation dose is 100-300 kGy and the irradiation time is 10-30 minutes. During the irradiation process, the electron beam energy is 1-2 MeV. S3. Post-treatment: The irradiated polyvinylidene fluoride particles are taken out from the irradiation device and placed in a forced air drying oven at 50-70° C. for 2-4 hours to stabilize the free radical active substances generated during the irradiation process, thereby obtaining irradiation-modified polyvinylidene fluoride.

3. The irradiation-modified waterproof high-insulation rubber cable material according to claim 1, characterized in that: The preparation method of the nitrogen-doped graphene composite material is as follows: S1. Preparation of graphene oxide: Graphene oxide was prepared by Hummers method; S2. Preparation of a mixed solution: Weigh a certain amount of graphite oxide, dissolve it in deionized water, and then add urea to obtain a mixed solution of graphite oxide and urea; the mass concentration of graphite oxide in the mixed solution is 1-5 mg / mL, and the mass ratio of urea to graphite oxide is 1:1-1:3; S3, ultrasound and stirring: ultrasonically treat the mixed solution at an ultrasonic power of 200-400 W for 1-2 hours to fully disperse the graphite oxide and urea, and then stir and mix at a stirring speed of 200-400 r / min for 2-4 hours; S4. Freeze drying: freeze drying the stirred mixed solution to obtain a mixed powder of graphite oxide and urea, the freeze drying temperature is -50°C to 30°C, the vacuum degree is 10-30 Pa, and the drying time is 24-48 hours; S5. High temperature treatment: Place the mixed powder in a vacuum furnace, evacuate and introduce nitrogen. The temperature of the vacuum furnace is 850-1000°C and the insulation time is 3 hours. The urea is decomposed to produce nitrogen, thereby achieving nitrogen doping and obtaining a nitrogen-doped graphene composite material.

4. The irradiation-modified waterproof high-insulation rubber cable material according to claim 1, characterized in that: The preparation method of the polydopamine-modified graphene is as follows: S1. Preparation of graphene oxide: Disperse the dried graphite oxide filter disc prepared by the Hummers method in deionized water and perform ultrasonic treatment at an ultrasonic power of 200-400 W for 1-2 hours to obtain a graphene oxide dispersion; S2. Polydopamine modification: The graphene oxide dispersion was mixed with a dopamine hydrochloride solution, and a Tris-HCl buffer solution was added to adjust the pH to 8.

5. The mixture was stirred at room temperature for 12-24 hours to allow dopamine to self-polymerize on the graphene oxide surface to form polydopamine-coated graphene; S3. Separation and drying: After the reaction is completed, the product is separated by centrifugation or filtration, washed with deionized water for multiple times, and then dried in a vacuum drying oven to obtain polydopamine-modified graphene.

5. The irradiation-modified waterproof high-insulation rubber cable material according to claim 1, characterized in that: The preparation method of the nano silicon dioxide is as follows: S1. Raw material preparation: prepare ethyl orthosilicate, ethanol, deionized water, and ammonia water as raw materials; S2. Sol-gel reaction: dissolving tetraethyl orthosilicate in a mixed solution of ethanol and deionized water, stirring evenly, slowly adding ammonia water dropwise, adjusting the pH value of the solution to alkaline, and stirring the reaction at 40-60° C. for 2-4 hours to allow the tetraethyl orthosilicate to undergo hydrolysis and polycondensation reaction to form a nano-silica sol; S3, aging: aging the reacted sol at room temperature for 12-24 hours to allow the nanoparticles to further grow and stabilize; S4. Drying: Drying the aged sol by spray drying or vacuum drying to obtain nano-silicon dioxide powder.

6. The irradiation-modified waterproof high-insulation rubber cable material according to any one of claims 1 to 5, characterized in that: The preparation method of the cable material is as follows: S1. Raw material mixing: weigh natural rubber, nitrile rubber, irradiated modified polyvinylidene fluoride, nitrogen-doped graphene composite material, polydopamine-modified graphene, nano-silica, graphite powder, calcium carbonate, antioxidant, plasticizer, and cross-linking agent according to the above-mentioned mass parts, add them to an internal mixer, and mix the mixer at a temperature of 80-100°C, a speed of 40-60 r / min, and a mixing time of 10-15 minutes to fully mix the raw materials; S2, plasticizing: the mixed material is transferred to the open mill for plasticizing. The roller temperature of the open mill is 60-80 ° C, the roller distance is 1-2 mm, and the plasticizing time is 5-10 minutes to further plasticize the material; S3, cross-linking: the plasticized material is placed in a flat vulcanizing machine for cross-linking. The temperature of the flat vulcanizing machine is 180-200 ° C, the pressure is 20 MPa, and the cross-linking time is 10-15 minutes. After the cross-linking is completed, the material is cooled to room temperature; S4. Degassing: Place the cooled material in a vacuum oven for degassing. The temperature of the vacuum oven is 100-120°C, the vacuum degree is 0.08-0.1 MPa, and the degassing time is 2-4 hours to remove bubbles and volatiles in the material.