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

Abstract

The application relates to the technical field of materials, and discloses a special wire based on electron accelerator irradiation crosslinking fluororubber and a preparation method thereof. The special wire is prepared by uniformly coating fluororubber coating material around a conductor and then performing electron accelerator irradiation crosslinking. The fluororubber coating material is prepared by taking fluororubber as a main raw material and taking basalt fiber modified components and the like as auxiliary materials and mixing and forming. The basalt fiber modified component is a macromolecular modifier with an alternating connection structure of siloxane and flexible long fatty chains grafted on the surface of basalt fiber. The macromolecular modifier can be crosslinked with the fluororubber in the subsequent irradiation crosslinking process, so that a three-dimensional crosslinking network with the basalt fiber as a crosslinking center is formed, the mechanical property of the fluororubber is enhanced, and the temperature resistance of the fluororubber is improved.

Description

TECHNICAL FIELD

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

[0002] The special wire refers to a cable product used in extreme working conditions (high temperature, corrosion, high voltage, radiation, etc.), and its design needs to break through the performance limit of conventional materials. In the fields of oil exploitation, aerospace, nuclear power industry, etc., traditional wires, such as PVC and XLPE insulated cables, 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, due to its unique molecular structure, endows it with excellent high and low temperature resistance, corrosion resistance and mechanical properties, and becomes one of the core materials of special wire.

[0003] Although fluororubber has excellent comprehensive performance, it is insufficient in low temperature resistance, and will become hard, lose elasticity, and even crack at lower temperatures, affecting the service life of the cable. Therefore, the use of fluororubber special wire in cold environments will be limited, and as a special cable, the mechanical properties of fluororubber are slightly insufficient, which greatly limits the further development of fluororubber in the field of wire and cable. Therefore, it is of great significance to improve fluororubber and improve its low temperature resistance and mechanical properties. SUMMARY

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

[0005] The purpose of the present application can be achieved by the following technical solutions:

[0006] A preparation method of a special wire based on electron accelerator irradiation cross-linked fluororubber, comprising the following steps:

[0007] Step 1, making fluororubber material coating material:

[0008] S1, adding fluororubber, basalt fiber modified component, crosslinking agent, antioxidant, carbon black and lubricant into a mixing machine, mixing at room temperature for 1-2h to form a rubber mixture;

[0009] S2, transferring the rubber mixture to an extruder for extrusion granulation, then extruding the obtained granules into a wire, and placing them in a temperature environment of 160-180℃ for pretreatment for 30-60min to form a fluororubber material coating material;

[0010] Step 2, preparing a special wire:

[0011] The fluorine rubber coating material is evenly coated around the conductor, then irradiation cross-linking is carried out by using an electron accelerator, and the irradiation energy is controlled to be 50-100 KGy, so that the special electric wire is formed.

[0012] As a further scheme of the present application, in the preparation process of the fluorine rubber coating material, the weight fractions of the raw materials are as follows: 78-85 parts of fluorine rubber, 2-4.5 parts of basalt fiber modified component, 3-5 parts of cross-linking agent, 0.5-1 part of anti-aging agent, 5-10 parts of carbon black, and 1-2 parts of lubricant.

[0013] As a further scheme of the present application, the molecular weight of the fluorine rubber is 450-500, and the fluorine content is 38-45%.

[0014] As a further scheme of the present application, the basalt fiber modified component is prepared by the following method:

[0015] Step one, the basalt fiber is added into an ethanol aqueous solution medium with a volume fraction of 60-70%, and after being uniformly dispersed, a silane coupling agent is added, and stirred and mixed uniformly, then the temperature is increased to 60-70℃, and after being kept warm and stirred for 3-6h, the temperature is decreased to discharge the material, and the solid material is collected to prepare a fiber intermediate;

[0016] Step two, the fiber intermediate is dispersed in a toluene solvent to form a uniformly dispersed solution, air is discharged by nitrogen, then 1,1,3,3-tetramethyl-1,3-di[2-(5-norbornene-2-yl)ethyl]disiloxane and a photoinitiator are added to the dispersion, after addition, mechanical stirring is uniformly carried out, a wavelength of 365nm ultraviolet lamp is used for irradiation for 20-40min, then a chain extension monomer is added to the dispersion, and irradiation is continued for 2-6h, the material is discharged, and the solid material is centrifuged, washed, and vacuum dried to prepare the basalt fiber modified component.

[0017] As a further scheme of the present application, in step one, the silane coupling agent is 3-mercaptopropyl trimethoxysilane or 3-mercaptopropyl triethoxysilane.

[0018] As a further scheme of the present application, in step two, the photoinitiator is any one of Irgacure 2959, Irgacure 184, or Irgacure 907.

[0019] As a further scheme of the present application, in step two, the chain extension monomer is any one of 1,5-pentanedithiol, 1,8-octanedithiol, 1,9-nonanedithiol, or 1,10-decanedithiol.

[0020] As a further scheme of the present application, in step two, the mass ratio of the fiber intermediate, 1,1,3,3-tetramethyl-1,3-bis[2-(5-norbornene-2-yl)ethyl]disiloxane and the chain extending monomer is 1:2.5-4:0.3-0.6.

[0021] In the above technical solution, first, the basalt fiber is surface modified by using a silane coupling agent containing a mercapto group to obtain a basalt fiber intermediate, then, under the condition of a photoinitiator and light irradiation, the unsaturated alkenyl functional group in the structure of 1,1,3,3-tetramethyl-1,3-bis[2-(5-norbornene-2-yl)ethyl]disiloxane first undergoes a click reaction with the basalt fiber intermediate, and after adding a chain extending monomer, the 1,1,3,3-tetramethyl-1,3-bis[2-(5-norbornene-2-yl)ethyl]disiloxane and the chain extending monomer in the system can continuously and uninterruptedly undergo a click reaction on the surface of the basalt fiber, so that a macromolecular modifier having an alternating connection structure of siloxane and flexible long fatty chain is grafted on the surface of the basalt fiber, and by controlling the addition amount of the material, the macromolecular modifier can have a norbornene structure at the end, and a basalt fiber modified component is obtained.

[0022] As a further scheme of the present application, 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.

[0023] A special wire based on electron accelerator irradiation crosslinked fluororubber is prepared by the above preparation method.

[0024] The present application has the following beneficial effects:

[0025] The present application grafts a macromolecular modifier having an alternating connection structure of siloxane and flexible long fatty chain on the surface of the basalt fiber to prepare a basalt fiber modified component, the macromolecular modifier has a large amount of norbornene structure in the structure, and can be crosslinked with fluororubber in a subsequent irradiation crosslinking process, so that the interface bonding performance of the basalt fiber and the fluororubber molecular chain is greatly enhanced, and a three-dimensional crosslinked network with the basalt fiber as the crosslinking center is formed, on the one hand, the crosslinked network structure can greatly enhance the mechanical properties by using the stress dispersion and stress transfer effect of the basalt fiber, and can also improve the temperature resistance of the fluororubber by using the alternating connection structure of siloxane and flexible long fatty chain in the structure of the macromolecular modifier.

[0026] Of course, any product implementing the present application does not necessarily need to achieve all the advantages described above. BRIEF DESCRIPTION OF DRAWINGS

[0027] In order to more clearly illustrate the technical solutions of the embodiments of the present application, the following will briefly introduce the drawings needed to be used in the description of the embodiments. Obviously, the drawings in the following description are only some embodiments of the present application, and other drawings can be obtained by those skilled in the art without any creative effort on the basis of these drawings.

[0028] Figure 1 Scanning electron microscope images of basalt fiber and basalt fiber modified component, wherein (1) is basalt fiber, and (2) is basalt fiber modified component. DETAILED DESCRIPTION

[0029] The technical solutions in the embodiments of the present application will be described clearly and completely in the following with reference to the drawings in the embodiments of the present application. Obviously, the described embodiments are only some embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without any creative effort belong to the scope of protection of the present application.

[0030] Embodiment 1

[0031] Preparation of fluororubber material covering material:

[0032] S1, according to the weight fraction, 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 are added into a mixing machine, and mixed at room temperature for 1 h to form a rubber mixture;

[0033] S2, the rubber mixture is transferred to an extruder for extrusion granulation, and the obtained granules are extruded into a wire, and then placed in a temperature environment of 160℃ for pretreatment for 60 min to form a fluororubber material covering material.

[0034] The molecular weight of the fluororubber is 490, and the fluorine content is 42%; the carbon black is selected as carbon black N330; the following are the same.

[0035] Embodiment 2

[0036] Preparation of fluororubber material covering material:

[0037] S1, according to the weight fraction, 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 are added into a mixing machine, and mixed at room temperature for 1 h to form a rubber mixture;

[0038] S2, the rubber mixture is transferred to the extruder for extrusion granulation, and the obtained granules are extruded into a wire, and the wire is placed in a temperature environment of 170°C for pretreatment for 40 min to form a fluororubber material covering material.

[0039] Example 3

[0040] Preparation of the fluororubber material covering material:

[0041] S1, 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 are added into a mixer, and mixed at room temperature for 2 h to form a rubber mixture;

[0042] S2, the rubber mixture is transferred to the extruder for extrusion granulation, and the obtained granules are extruded into a wire, and the wire is placed in a temperature environment of 180°C for pretreatment for 30 min to form a fluororubber material covering material.

[0043] The basalt fiber modified component in the above examples is prepared by the following method:

[0044] Step one, 3.4g of basalt fiber is added to a 70% ethanol aqueous solution medium, after uniform dispersion, 2.5g of 3-mercaptopropyl triethoxysilane is added, stirred and mixed, then the temperature is raised to 65°C, and after 4h of incubation and stirring, the temperature is lowered and the solid material is collected to prepare a fiber intermediate;

[0045] Step two, 0.5g of the fiber intermediate is dispersed in toluene solvent to form a uniform dispersion liquid, nitrogen gas is used to remove air, then 1.5g of 1,1,3,3-tetramethyl-1,3-di[2-(5-norbornene-2-yl)ethyl]disiloxane and 0.1g of photoinitiator Irgacure 2959 are added to the dispersion liquid, after addition, mechanical stirring is uniform, then a wavelength of 365nm ultraviolet lamp is used for irradiation for 30min, then 0.2g of 1,10-decanedithiol is added to the dispersion liquid, and the irradiation is continued for 4h, the material is discharged, centrifuged to obtain the solid material, and after washing and vacuum drying treatment, the basalt fiber modified component is prepared.

[0046] Figure 1 Scanning electron micrographs of basalt fiber and basalt fiber modified component, wherein (1) is basalt fiber and (2) is basalt fiber modified component. As can be clearly observed from the figure, the surface roughness of the basalt fiber modified component is significantly increased, which is caused by the grafting of macromolecular modifier on the surface of the basalt fiber.

[0047] Comparative Example 1

[0048] Preparation of the fluororubber material covering material:

[0049] S1, 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 into a mixer, and mixed at room temperature for 1 h to form a rubber mixture;

[0050] S2, the rubber mixture was transferred to an extruder for extrusion granulation, and the obtained granules were extruded into a wire, and then placed in a temperature environment of 170℃ for pretreatment for 40 min to form a fluororubber coated material.

[0051] Comparative Example 2

[0052] Preparation of fluororubber coated material:

[0053] S1, 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 into a mixer, and mixed at room temperature for 1 h to form a rubber mixture;

[0054] S2, the rubber mixture was transferred to an extruder for extrusion granulation, and the obtained granules were extruded into a wire, and then placed in a temperature environment of 170℃ for pretreatment for 40 min to form a fluororubber coated material.

[0055] Test Example

[0056] The fluororubber coated materials in the examples and comparative examples were irradiated and crosslinked using an electron accelerator with a controlled irradiation energy of 2.5MeV, and then test samples of various specifications were prepared for performance testing, and the results are shown in Table 1:

[0057] Table 1-Test Results

[0058]

[0059] The test method for tear strength is referred to the standard GB / T 529-2008;

[0060] The test method for low temperature resistance is as follows: a sample with a specification of 10cm x 10cm x 5mm was placed in a temperature environment of -50℃, and after 72h, it was taken out and observed for cracking and other phenomena, and the low temperature resistance was evaluated.

[0061] According to the test results, although the basalt fiber can improve the mechanical strength of the fluorine rubber to a certain extent, the basalt fiber cannot be uniformly dispersed due to the interface problem between them, so it is difficult to play its full load transfer and stress effect, and therefore the improvement effect of mechanical property is limited. The fluorine rubber coating material prepared by using the basalt fiber modification component can not only exhibit excellent mechanical properties, but also has excellent low temperature resistance, and can meet the use requirements of special environment.

[0062] The principles and implementations of the present application are described herein by using specific examples, and the above examples are only used to help understand the method of the present application and its core idea, including the best mode, and also enable any person skilled in the art to practice the present application, including manufacturing and using any device or system, and implementing any combined method. It should be noted that for those skilled in the art, some improvements and modifications can be made to the present application without departing from the principles of the present application, and these improvements and modifications also fall within the protection scope of the claims of the present application. The scope of the patent protection of the present application is defined by the claims, and can 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.

[0063] The above examples are only used to illustrate the technical solutions of the present application, and not to limit them; although the present application has been described in detail with reference to the foregoing examples, those skilled in the art should understand that they can still modify the technical solutions recorded in the foregoing examples, or make equivalent replacement for part of the technical features; and these modifications or replacements will not make the essence of the corresponding technical solutions deviate from the spirit and scope of the technical solutions of the embodiments of the present application.

Claims

1. A method for preparing special wires of fluororubber cross-linked by electron accelerator irradiation, characterized in that: The following steps are involved: The first step is to make fluororubber coating material: S1. Add fluororubber, basalt fiber modified component, crosslinking agent, antioxidant, carbon black and lubricant into a mixer and mix at room temperature for 1-2 hours to form a rubber mixture; S2. Transferring the rubber mixture to an extruder for extrusion granulation, 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, and the irradiation energy is controlled to 50-100KGy to form a special wire; The basalt fiber modified component is prepared by the following method: Step 1: Modify basalt fiber using a silane coupling agent in an ethanol aqueous solution medium to obtain a fiber intermediate; Step 2: Disperse the fiber intermediate in toluene solvent to form a uniform dispersion, expel the air through nitrogen, and then add 1,1,3,3-tetramethyl-1,3-bis[2-(5-norbornene-2-yl)ethyl]disiloxane and a photoinitiator to the dispersion. After the addition, mechanically stir evenly, 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, centrifuge the solid material, wash, and vacuum dry to obtain a basalt fiber modified component; The mass ratio of the fiber intermediate, 1,1,3,3-tetramethyl-1,3-bis[2-(5-norbornene-2-yl)ethyl]disiloxane and chain extension monomer is 1:2.5-4:0.3-0.6; In step 1, the silane coupling agent is 3-mercaptopropyltrimethoxysilane or 3-mercaptopropyltriethoxysilane; In step 2, the chain extension monomer is any one of 1,5-pentanedithiol, 1,8-octanedithiol, 1,9-nonanedithiol or 1,10-decanedithiol.

2. The method for preparing a special 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 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 wire based on electron accelerator irradiation cross-linked fluororubber according to claim 1, characterized in that: In step 2, the photoinitiator is any one of Irgacure 2959, Irgacure 184 or Irgacure 907.

5. The method for preparing a special wire based on electron accelerator irradiation cross-linked fluororubber according to claim 1, 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.

6. A special wire based on electron accelerator irradiation cross-linked fluororubber, characterized in that: The method is as described in any one of claims 1 to 5.

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