Special wire based on electron accelerator irradiation crosslinking fluororubber and preparation method thereof

Abstract

The invention relates to the technical field of materials, and discloses a special electric wire based on electron accelerator irradiation crosslinking fluororubber and a preparation method thereof.The special electric wire is prepared by uniformly coating a conductor with a fluororubber coating material and then conducting irradiation crosslinking through an electron accelerator, a basalt fiber modified component and the like are used as auxiliary materials and are mixed, the basalt fiber modified component is formed by grafting a macromolecular modifier with a siloxane and flexible long aliphatic chain alternate connection structure on the surface of basalt fiber, and the macromolecular modifier can realize crosslinking with fluororubber in the subsequent irradiation crosslinking process, so that the crosslinking performance of the fluororubber is improved, and the service life of the fluororubber is prolonged. Therefore, a three-dimensional cross-linked network taking the basalt fiber as a cross-linking center is formed, and the temperature resistance of the fluororubber is improved while the mechanical property of the fluororubber is enhanced.

Description

Technical Field

[0001] The invention relates to the technical field of materials, and in particular to a special electric wire based on electron accelerator irradiation cross-linked fluororubber and a preparation method thereof. Background Art

[0002] Special wires refer to cable products used in extreme working conditions (high temperature, corrosion, high voltage, radiation, etc.), and their design needs to break through the performance limits of conventional materials. In the fields of oil extraction, aerospace, nuclear energy industry, etc., traditional wires, such as PVC, XLPE insulated cables, etc., are difficult to meet the needs due to insufficient temperature resistance, poor chemical stability or low mechanical strength. Fluororubber (FKM, fluorocarbon rubber), as a high-performance elastomer, has excellent high and low temperature resistance, corrosion resistance and mechanical properties due to its unique molecular structure, making it one of the core materials of special wires.

[0003] Although fluororubber has excellent comprehensive performance, its low temperature resistance is insufficient. It will harden, lose elasticity, and even crack at low temperatures, which will affect the service life of the cable. Therefore, the use of fluororubber special wires in cold environments will be limited. Moreover, as a special cable, the mechanical properties of fluororubber are also slightly insufficient. These defects greatly limit the further development of fluororubber in the field of wires and cables. Therefore, it is of great significance to improve fluororubber and improve its low temperature resistance and mechanical properties. Summary of the invention

[0004] In order to solve the problems mentioned in the background technology, the object of the present invention is to provide a special electric wire based on electron accelerator irradiation cross-linked fluororubber and a preparation method thereof.

[0005] The purpose of the present invention can be achieved through the following technical solutions: A method for preparing a special electric wire of cross-linked fluororubber based on electron accelerator irradiation comprises the following steps: The first step is to make fluororubber coating material: S1, adding fluororubber, basalt fiber modified component, crosslinking agent, antioxidant, carbon black and lubricant into a mixer, and mixing at room temperature for 1-2 hours to form a rubber mixture; S2, transferring the rubber mixture to an extruder for extrusion granulation, and then extruding the obtained granules into wires, and pre-treating the wires in a temperature environment of 160-180° C. for 30-60 minutes to form a fluororubber coating material; Step 2: Prepare special wires: The fluororubber coating material is evenly coated around the conductor, and then an electron accelerator is used for irradiation cross-linking. The irradiation energy is controlled to 50-100KGy to form a special wire.

[0006] As a further solution of the present invention, in the production process of the fluororubber coating material, the weight proportions of the raw materials are: 78-85 parts of fluororubber, 2-4.5 parts of basalt fiber modified component, 3-5 parts of cross-linking agent, 0.5-1 part of antioxidant, 5-10 parts of carbon black, and 1-2 parts of lubricant.

[0007] As a further solution of the present invention, the molecular weight of the fluororubber is 450-500, and the fluorine content is 38-45%.

[0008] As a further solution of the present invention, the basalt fiber modified component is prepared by the following method: Step 1: add basalt fiber to an ethanol aqueous solution medium with a volume fraction of 60-70%, disperse evenly, then add a silane coupling agent, stir and mix, then increase the temperature to 60-70°C, keep stirring for 3-6 hours, cool and discharge, collect the solid material, and obtain a fiber intermediate; Step 2: Disperse the fiber intermediate in toluene solvent to form a uniform dispersion, exhaust the air through nitrogen, and then add 1,1,3,3-tetramethyl-1,3-di[2-(5-norbornene-2-yl)ethyl]disiloxane and a photoinitiator to the dispersion. After the addition, stir mechanically to make it uniform. Irradiate with an ultraviolet lamp with a wavelength of 365nm for 20-40min, then add the chain extension monomer to the dispersion, continue irradiation for 2-6h, discharge the material, centrifuge the solid material, wash it, and vacuum dry it to obtain a basalt fiber modified component.

[0009] As a further embodiment of the present invention, in step 1, the silane coupling agent is 3-mercaptopropyltrimethoxysilane or 3-mercaptopropyltriethoxysilane.

[0010] As a further solution of the present invention, in step 2, the photoinitiator is any one of Irgacure 2959, Irgacure 184 or Irgacure 907.

[0011] As a further embodiment of the present invention, in step 2, the chain extension monomer is any one of 1,5-pentanedithiol, 1,8-octanedithiol, 1,9-nonanedithiol or 1,10-decanedithiol.

[0012] As a further embodiment of the present invention, in step 2, the mass ratio of the fiber intermediate, 1,1,3,3-tetramethyl-1,3-di[2-(5-norbornene-2-yl)ethyl]disiloxane and the chain extension monomer is 1:2.5-4:0.3-0.6.

[0013] In the above technical scheme, the surface of basalt fiber is firstly modified by a mercapto-containing silane coupling agent to obtain a basalt fiber intermediate material. Then, the mercapto groups on the surface of the basalt fiber are used as active initiation sites. Under the conditions of photoinitiator and light, the unsaturated olefinic functional groups in the structure of 1,1,3,3-tetramethyl-1,3-di[2-(5-norbornene-2-yl)ethyl]disiloxane first undergo a click reaction with the basalt fiber intermediate material. After the chain extension monomer is added, the 1,1,3,3-tetramethyl-1,3-di[2-(5-norbornene-2-yl)ethyl]disiloxane and the chain extension monomer in the system can undergo a continuous and uninterrupted click reaction on the surface of the basalt fiber, thereby grafting a macromolecular modifier having an alternating connection structure of siloxane and a flexible long fatty chain on the surface of the basalt fiber. By controlling the amount of material added, the end of the macromolecular modifier can be a norbornene structure to obtain a basalt fiber modified component.

[0014] As a further embodiment of the present invention, the crosslinking agent is trimethylolpropane trimethacrylate or triallyl isocyanurate; the antioxidant is antioxidant 4010 or antioxidant 4010NA; and the lubricant is at least one of calcium stearate or zinc stearate.

[0015] A special electric wire based on electron accelerator irradiation cross-linked fluororubber is prepared by adopting the preparation method.

[0016] Beneficial effects of the present invention: The present invention prepares a basalt fiber modified component by grafting a macromolecular modifier having an alternating connection structure of siloxane and a flexible long fatty chain onto the surface of a basalt fiber. The macromolecular modifier structure contains a large amount of norbornene structures, which can achieve cross-linking with fluororubber during the subsequent radiation cross-linking process, thereby greatly enhancing the interface bonding performance of the basalt fiber and the fluororubber molecular chain, and forming a three-dimensional cross-linked network with the basalt fiber as the cross-linking center. On the one hand, this cross-linked network structure can utilize the stress dispersion and stress transfer effects of the basalt fiber to greatly enhance the mechanical properties, and can also utilize the alternating connection structure of siloxane and a flexible long fatty chain in the macromolecular modifier structure to improve the temperature resistance of the fluororubber.

[0017] Of course, any product implementing the present invention does not necessarily need to achieve all of the advantages described above at the same time. BRIEF DESCRIPTION OF THE DRAWINGS

[0018] In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the accompanying drawings required for describing the embodiments will be briefly introduced below. Obviously, the accompanying drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other accompanying drawings can be obtained based on these accompanying drawings without paying creative work.

[0019] Figure 1 The scanning electron microscope images of basalt fiber and basalt fiber modified components, where (1) is basalt fiber and (2) is basalt fiber modified component. DETAILED DESCRIPTION

[0020] The following will be combined with the drawings in the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0021] Example 1 Preparation of fluororubber coating material: S1. According to the weight ratio, 78 parts of fluororubber, 2 parts of basalt fiber modified component, 3 parts of crosslinking agent trimethylolpropane trimethacrylate, 0.5 parts of antioxidant 4010, 5 parts of carbon black and 1 part of lubricant calcium stearate were added to a mixer and mixed at room temperature for 1 hour to form a rubber mixture; S2. The rubber mixture is transferred to an extruder for extrusion granulation, and the obtained granules are extruded into wires, which are placed in a temperature environment of 160° C. for pretreatment for 60 minutes to form a fluororubber coating material.

[0022] The molecular weight of fluororubber is 490, and the fluorine content is 42%; carbon black is carbon black N330; the following are the same.

[0023] Example 2 Preparation of fluororubber coating material: S1. According to the weight ratio, 78 parts of fluororubber, 4.2 parts of basalt fiber modified component, 4 parts of crosslinking agent triallyl isocyanurate, 0.6 parts of antioxidant 4010NA, 8 parts of carbon black and 1.5 parts of lubricant zinc stearate were added to a mixer and mixed at room temperature for 1 hour to form a rubber mixture; S2. The rubber mixture is transferred to an extruder for extrusion granulation, and the obtained granules are extruded into wires, which are placed in a temperature environment of 170° C. for pretreatment for 40 minutes to form a fluororubber coating material.

[0024] Example 3 Preparation of fluororubber coating material: S1. According to the weight ratio, 85 parts of fluororubber, 4.5 parts of basalt fiber modified component, 5 parts of crosslinking agent triallyl isocyanurate, 1 part of antioxidant 4010NA, 10 parts of carbon black and 2 parts of lubricant zinc stearate were added to a mixer and mixed at room temperature for 2 hours to form a rubber mixture; S2. The rubber mixture is transferred to an extruder for extrusion granulation, and the obtained granules are extruded into wires, and the wires are placed in a temperature environment of 180° C. for pretreatment for 30 minutes to form a fluororubber coating material.

[0025] The basalt fiber modified component in the above embodiment is prepared by the following method: Step 1: add 3.4 g of basalt fiber to a 70% ethanol aqueous solution medium, disperse evenly, then add 2.5 g of 3-mercaptopropyltriethoxysilane, stir and mix, then raise the temperature to 65°C, keep stirring for 4 hours, cool and discharge, collect the solid material, and obtain a fiber intermediate; Step 2: Disperse 0.5 g of the fiber intermediate in a toluene solvent to form a uniform dispersion, exhaust the air with nitrogen, and then add 1.5 g of 1,1,3,3-tetramethyl-1,3-di[2-(5-norbornene-2-yl)ethyl]disiloxane and 0.1 g of photoinitiator Irgacure 2959 to the dispersion. After the addition, stir mechanically to obtain a uniform dispersion. After irradiation with an ultraviolet lamp having a wavelength of 365 nm for 30 min, 0.2 g of 1,10-decanedithiol is added to the dispersion. The dispersion is further irradiated for 4 h, the material is discharged, the solid material is centrifuged, and the basalt fiber modified component is obtained after washing and vacuum drying.

[0026] Figure 1 The scanning electron microscope images of basalt fiber and basalt fiber modified components, where (1) is basalt fiber and (2) is basalt fiber modified component. It can be clearly observed from the figure that the surface roughness of the basalt fiber modified component is significantly increased, which is caused by the grafting of macromolecular modifiers on the surface of basalt fiber.

[0027] Comparative Example 1 Preparation of fluororubber coating material: S1. According to the weight ratio, 78 parts of fluororubber, 4.2 parts of basalt fiber, 4 parts of crosslinking agent triallyl isocyanurate, 0.6 parts of antioxidant 4010NA, 8 parts of carbon black and 1.5 parts of lubricant zinc stearate were added to a mixer and mixed at room temperature for 1 hour to form a rubber mixture; S2. The rubber mixture is transferred to an extruder for extrusion granulation, and the obtained granules are extruded into wires, which are placed in a temperature environment of 170° C. for pretreatment for 40 minutes to form a fluororubber coating material.

[0028] Comparative Example 2 Preparation of fluororubber coating material: S1. According to the weight ratio, 78 parts of fluororubber, 4 parts of crosslinking agent triallyl isocyanurate, 0.6 parts of antioxidant 4010NA, 8 parts of carbon black and 1.5 parts of lubricant zinc stearate were added to a mixer and mixed at room temperature for 1 hour to form a rubber mixture; S2. The rubber mixture is transferred to an extruder for extrusion granulation, and the obtained granules are extruded into wires, which are placed in a temperature environment of 170° C. for pretreatment for 40 minutes to form a fluororubber coating material.

[0029] Test Case Using an electron accelerator, the irradiation energy was controlled to be, and the fluororubber coating materials in the embodiments and comparative examples were irradiated and cross-linked, and then made into test specimens of various specifications, and various performance tests were carried out. The results are shown in Table 1: Table 1 - Test results

[0030] The test method of tear strength refers to the standard GB / T 529-2008; The test method for low temperature resistance is to place a sample with a specification of 10cm×10cm×5mm in a temperature environment of -50°C, take it out after 72 hours, observe whether the sample has cracks, etc., and evaluate its low temperature resistance.

[0031] According to the test results, although adding basalt fiber alone can improve the mechanical strength of fluororubber to a certain extent, due to the interface problem between them, the basalt fiber cannot be evenly dispersed, making it difficult for it to fully exert its own transfer load and stress effects, so the mechanical improvement effect is limited. The fluororubber coating made of basalt fiber modified components can not only show excellent mechanical properties, but also have excellent low temperature resistance, which can meet the use requirements of special environments.

[0032] Specific examples are used herein to illustrate the principles and implementation methods of the present invention. The description of the above embodiments is only used to help understand the method of the present invention and its core ideas, including the best mode, and also enable any technician in the field to practice the present invention, including making and using any device or system, and implementing any combined method. It should be pointed out that for ordinary technicians in this technical field, without departing from the principle of the present invention, the present invention can also be improved and modified, and these improvements and modifications also fall within the scope of protection of the claims of the present invention. The scope of patent protection of the present invention is defined by the claims and may include other embodiments that can be thought of by those skilled in the art. If these other embodiments have structural elements similar to the literal expression of the claims, or if they include equivalent structural elements that are not substantially different from the literal expression of the claims, then these other embodiments should also be included in the scope of the claims.

[0033] The above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit the same. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that the technical solutions described in the aforementioned embodiments may still be modified, or some of the technical features may be replaced by equivalents. Such modifications or replacements will not cause the essence of the corresponding technical solutions to deviate from the spirit and scope of the technical solutions of the embodiments of the present invention.

Claims

1. A method for preparing a special wire of cross-linked fluororubber based on electron accelerator irradiation, characterized in that: The following steps are involved: The first step is to make fluororubber coating material: S1, adding fluororubber, basalt fiber modified component, crosslinking agent, antioxidant, carbon black and lubricant into a mixer, and mixing at room temperature for 1-2 hours to form a rubber mixture; S2, transferring the rubber mixture to an extruder for extrusion granulation, and then extruding the obtained granules into wires, and pre-treating the wires in a temperature environment of 160-180° C. for 30-60 minutes to form a fluororubber coating material; Step 2: Prepare special wires: The fluororubber coating material is evenly coated around the conductor, and then an electron accelerator is used for irradiation cross-linking. The irradiation energy is controlled to 50-100KGy to form a special wire.

2. The method for preparing a special electric wire based on electron accelerator irradiation cross-linked fluororubber according to claim 1, characterized in that: During the preparation of the fluororubber coating material, the weight proportions of the raw materials are as follows: 78-85 parts of fluororubber, 2-4.5 parts of basalt fiber modified component, 3-5 parts of crosslinking agent, 0.5-1 part of antioxidant, 5-10 parts of carbon black, and 1-2 parts of lubricant.

3. The method for preparing a special electric wire based on electron accelerator irradiation cross-linked fluororubber according to claim 1 or 2, characterized in that: The molecular weight of the fluororubber is 450-500, and the fluorine content is 38-45%.

4. The method for preparing a special electric wire based on electron accelerator irradiation cross-linked fluororubber according to claim 1, characterized in that: The basalt fiber modified component is prepared by the following method: Step 1: In an ethanol aqueous solution medium, basalt fiber is modified using a silane coupling agent to obtain a fiber intermediate; Step 2: Disperse the fiber intermediate in toluene solvent to form a uniform dispersion, exhaust the air through nitrogen, and then add 1,1,3,3-tetramethyl-1,3-di[2-(5-norbornene-2-yl)ethyl]disiloxane and a photoinitiator to the dispersion. After the addition, stir mechanically to make it uniform. Irradiate with an ultraviolet lamp with a wavelength of 365nm for 20-40min, then add the chain extension monomer to the dispersion, continue irradiation for 2-6h, discharge the material, centrifuge the solid material, wash it, and vacuum dry it to obtain a basalt fiber modified component.

5. The method for preparing a special electric wire based on electron accelerator irradiation cross-linked fluororubber according to claim 4, characterized in that: In step 1, the silane coupling agent is 3-mercaptopropyltrimethoxysilane or 3-mercaptopropyltriethoxysilane.

6. The method for preparing a special electric wire based on electron accelerator irradiation cross-linked fluororubber according to claim 4, characterized in that: In step 2, the photoinitiator is any one of Irgacure 2959, Irgacure 184 or Irgacure 907.

7. The method for preparing a special electric wire of fluororubber cross-linked by electron accelerator irradiation according to claim 4, characterized in that: In step 2, the chain extension monomer is any one of 1,5-pentanedithiol, 1,8-octanedithiol, 1,9-nonanedithiol or 1,10-decanedithiol.

8. The method for preparing a special electric wire of fluororubber cross-linked by electron accelerator irradiation according to claim 4, characterized in that: In step 2, the mass ratio of the fiber intermediate, 1,1,3,3-tetramethyl-1,3-di[2-(5-norbornene-2-yl)ethyl]disiloxane and the chain extension monomer is 1:2.5-4:0.3-0.

6.

9. The method for preparing a special electric wire based on electron accelerator irradiation cross-linked fluororubber according to claim 1 or 2, characterized in that: The cross-linking agent is trimethylolpropane trimethacrylate or triallyl isocyanurate; the antioxidant is antioxidant 4010 or antioxidant 4010NA; and the lubricant is at least one of calcium stearate or zinc stearate.

10. A special wire based on electron accelerator irradiation cross-linked fluororubber, characterized in that: The method is prepared according to any one of claims 1 to 9.

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