High-strength oil-resistant cable material and preparation method thereof

Abstract

The application relates to the technical field of cable materials, and discloses a high-strength oil-resistant cable material and a preparation method thereof; the preparation method comprises the following operation steps: mixing polyether polyurethane resin and butyronitrile rubber at 70-90 DEG C for 3-6 minutes, adding modified microcapsules, an antioxidant, an ultraviolet absorber and a lubricant to continue mixing, and extruding and granulating at 120-160 DEG C to obtain the high-strength oil-resistant cable material. In the scheme, in order to solve the problem that the oil resistance of the cable material is affected by the poor compatibility of the polyphosphate flame retardant with the polyurethane resin due to the strong hydrophilicity of the polyphosphate flame retardant, the polyphosphate flame retardant is made into hydrophobic coated aluminum polyphosphate, and the microcapsules are prepared by taking the hydrophobic coated aluminum polyphosphate as a core material, so that the network compactness of the microcapsules is improved, and the oil resistance and the strength of the cable material are improved.

Description

Technical Field

[0001] This invention relates to the field of cable material technology, specifically a high-strength oil-resistant cable material and its preparation method. Background Technology

[0002] With the rapid development of the petrochemical, shipbuilding, oilfield exploration and industrial equipment electrification industries, special working condition wires and cables are in a complex environment of oil erosion, mechanical pulling and extrusion wear for a long time, and the comprehensive performance requirements of cable materials are constantly being upgraded.

[0003] Currently, most conventional oil-resistant cable materials on the market use ordinary polyolefin or general rubber base materials, with a single formula system. After long-term immersion in oil media, they are prone to volume expansion and material softening, resulting in a significant decrease in mechanical strength.

[0004] In summary, the preparation of a high-strength oil-resistant cable material is of great significance. Summary of the Invention

[0005] The purpose of this invention is to provide a high-strength oil-resistant cable material and its preparation method to solve the problems raised in the prior art.

[0006] To achieve the above objectives, the present invention provides the following technical solution: A high-strength oil-resistant cable material, wherein the raw materials of the high-strength oil-resistant cable material include the following components: by mass parts, 70-80 parts of polyether polyurethane resin, 10-15 parts of nitrile rubber, 18-22 parts of modified microcapsules, 0.1-0.2 parts of antioxidant, 0.1-0.2 parts of ultraviolet absorber, and 2-3 parts of lubricant.

[0007] A more optimized method for preparing the modified microcapsules is as follows: (1) Zinc oxide and aluminum tripolyphosphate are added to an ethanol aqueous solution and mixed evenly. Methyltrimethoxysilane and tetraethyl orthosilicate are added and stirred evenly. The temperature is raised to 50~70℃ and stirred for 4~6 hours. The mixture is filtered, washed and dried to obtain hydrophobically coated aluminum polyphosphate. (2) Hydroxylated sheet graphene and sodium dodecylbenzenesulfonate were added to deionized water and mixed to obtain an aqueous phase; 2,2-difluoro-1,3-diol was mixed with 1,6-hexanediisocyanate and triethylenediamine and stirred evenly, heated to 70~80℃ and stirred for 2~3 hours, cooled to room temperature, washed and dried to obtain a fluorinated prepolymer; the fluorinated prepolymer was mixed with hydrophobically coated aluminum polyphosphate and isophorone diisocyanate to obtain an oil phase, and under the action of a constant magnetic field throughout the process, the aqueous phase was added, and the mixture was emulsified by high-speed stirring for 2~4 minutes, stirred at room temperature for 1~3 hours, heated to 70~80℃ and stirred for 4~6 hours, washed and dried to obtain modified microcapsules.

[0008] An optimized ratio of zinc oxide, aluminum tripolyphosphate, methyltrimethoxysilane, and tetraethyl orthosilicate is (0.5~1.5):(2.5~4):(3~5):(6~8).

[0009] More optimized, the mass ratio of 2,2-difluoro-1,3-diol to 1,6-hexanediisocyanate and triethylenediamine is (2~3.2):5:(0.01~0.02).

[0010] In a more optimized configuration, the mass ratio of the hydroxylated sheet graphene to sodium dodecylbenzenesulfonate is 1:(0.05~0.1); the solid content of the aqueous phase is 8~15wt%. In the oil phase, the mass ratio of fluorinated prepolymer, hydrophobically coated aluminum polyphosphate, and isophorone diisocyanate is (4~6):2:1; the mass ratio of the oil phase to the water phase is 1:(3~4).

[0011] A more optimized method for preparing the hydroxylated sheet graphene is as follows: (1) Graphene oxide is ultrasonically dispersed in deionized water, an aqueous solution of FeCl2·4H2O and FeCl3·6H2O is added, ammonia is added to adjust the pH to 9-11, the mixture is stirred for 2-3 hours, washed and dried, and separated by magnetic adsorption to obtain magnetic graphene oxide; (2) Magnetic graphene oxide is ultrasonically dispersed in an aqueous ethanol solution, the pH is adjusted to 4-5, KH-560 aqueous ethanol solution is added, the mixture is heated to 60-75℃ and stirred for 5-6 hours, the pH is adjusted to 2-3, the temperature is raised to 80-90℃ and stirred for 3-4 hours, separated by magnetic adsorption, washed and dried to obtain hydroxylated sheet graphene.

[0012] In a more optimized manner, the mass ratio of graphene oxide, FeCl2·4H2O, and FeCl3·6H2O is 1:(0.3~0.4):(0.7~0.8); the mass ratio of magnetic graphene oxide to KH-560 ethanol aqueous solution is 1:(5~7); and the concentration of KH-560 ethanol aqueous solution is 13~17wt%.

[0013] In a more optimized configuration, the particle size of the graphene oxide is 1~3µm; and the loading of iron oxide in the hydroxylated sheet graphene is 15~20wt%.

[0014] A method for preparing a high-strength oil-resistant cable material includes the following steps: mixing polyether-type polyurethane resin and nitrile rubber at 70~90℃ for 3~6 minutes, adding modified microcapsules, antioxidants, ultraviolet absorbers and lubricants and continuing to mix, and extruding and granulating at 120~160℃ to obtain the high-strength oil-resistant cable material.

[0015] Compared with the prior art, the beneficial effects of the present invention are: In this scheme, cable material is prepared by melt extrusion of polyether polyurethane resin, polyphosphate flame retardant, antioxidant, ultraviolet absorber and lubricant. Polyether polyurethane resin has good moisture resistance but average oil resistance. Therefore, nitrile rubber is added to this scheme to improve oil resistance.

[0016] Polyphosphate flame retardants have good flame retardancy, but their strong hydrophilicity and poor interfacial compatibility with polyurethane resin affect the oil resistance of cable materials. To solve this problem, this solution loads a hydrophobic silicone coating layer onto the surface of the polyphosphate flame retardant, resulting in hydrophobic coated aluminum polyphosphate as a flame retardant. When the amount of tetraethyl orthosilicate added increases, the density of the silicone coating layer improves, but the overall rigidity increases, leading to more breakage during twin-screw extrusion. Although compounding with flexible methyltrimethoxysilane can improve processability, it will cause the silicone coating layer to have a porous structure, reducing the density of the silicone network. Under long-term immersion in oil media, oil molecules can easily penetrate inward, causing material performance degradation.

[0017] To further enhance the surface network density of hydrophobically coated aluminum polyphosphate, this method uses hydrophobically coated aluminum polyphosphate as the core material, compounded with a fluorinated prepolymer and isophorone diisocyanate as the oil phase; hydroxylated sheet graphene and sodium dodecylbenzene sulfonate are dispersed in deionized water as the aqueous phase; the oil and aqueous phases are mixed, emulsified, and heated to react, yielding modified microcapsules. The shell of these modified microcapsules contains polyurethane material, which significantly improves the compatibility between the polyphosphate flame retardant and the polyurethane resin, as well as the overall strength of the system; simultaneously, the fluorinated prepolymer effectively enhances the material's flexibility, preventing excessive rigidity.

[0018] In hydroxylated sheet graphene, the sheet graphene has a larger specific surface area and two-dimensional structure, which can effectively improve the compactness of the modified microcapsule shell at low to medium addition levels. However, sheet graphene is prone to severe interlayer stacking. If the emulsification and dispersion are uneven and the interfacial bonding is poor, it can easily cause structural defects in the microcapsule shell and reduce oil resistance. In this scheme, magnetic nanoparticles are deposited on the surface of sheet graphene and then hydroxylated for use in modified microcapsules. An external magnetic field is applied during the emulsification reaction of oil and water phases and room temperature stirring to effectively suppress the graphene agglomeration and stacking problem, avoid uneven distribution of graphene in the microcapsule shell and polyurethane cable material system, and prevent the deterioration of the material's oil resistance and mechanical strength. Detailed Implementation

[0019] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0020] Material preparation: The preparation method of hydroxylated sheet graphene is as follows: (1) Weigh graphene oxide, FeCl2·4H2O and FeCl3·6H2O in a mass ratio of 1:0.3:0.7; ultrasonically disperse graphene oxide in deionized water, add aqueous solution of FeCl2·4H2O and FeCl3·6H2O, add ammonia to adjust pH to 11, stir for 3 hours, wash and dry, and separate by magnetic adsorption to obtain magnetic graphene oxide; (2) Magnetic graphene oxide is prepared by... Graphene and KH-560 ethanol aqueous solution were weighed at a mass ratio of 1:6; the concentration of KH-560 ethanol aqueous solution was 17wt%; magnetic graphene oxide was ultrasonically dispersed in ethanol aqueous solution, the pH was adjusted to 4.5, KH-560 (3-glycidyl etheroxypropyltrimethoxysilane) ethanol aqueous solution was added, the mixture was heated to 70℃ and stirred for 5 hours, the pH was adjusted to 2.5, the temperature was raised to 80℃ and stirred for 3 hours, the mixture was separated by magnetic adsorption, washed and dried to obtain hydroxylated sheet graphene. Example 1

[0021] The modified microcapsules are prepared as follows: (1) Zinc oxide, aluminum tripolyphosphate, methyltrimethoxysilane and tetraethyl orthosilicate are weighed in a mass ratio of 0.5:3.5:5:8; zinc oxide and aluminum tripolyphosphate are added to an ethanol aqueous solution and mixed evenly; methyltrimethoxysilane and tetraethyl orthosilicate are added and stirred evenly; the temperature is raised to 70°C and stirred for 5 hours; the mixture is filtered, washed and dried to obtain hydrophobic coated aluminum polyphosphate. (2) The mass ratio of hydroxylated sheet graphene to sodium dodecylbenzenesulfonate is 1:0.08; the hydroxylated sheet graphene and sodium dodecylbenzenesulfonate are added to deionized water and mixed to obtain an aqueous phase; the solid content of the aqueous phase is 15wt%; 2,2-difluoro-1,3-diol, 1,6-hexanediisocyanate, and triethylenediamine are weighed in a mass ratio of 3.1:5:0.015; 2,2-difluoro-1,3-diol, 1,6-hexanediisocyanate, and triethylenediamine are stirred evenly, and the temperature is raised to 80℃ and stirred for 2 hours. The mixture was cooled to room temperature, washed, and dried to obtain a fluorinated prepolymer. The fluorinated prepolymer, hydrophobically coated aluminum polyphosphate, and isophorone diisocyanate were weighed in a mass ratio of 4:2:1. The fluorinated prepolymer was mixed with the hydrophobically coated aluminum polyphosphate and isophorone diisocyanate to obtain an oil phase. Under the constant magnetic field of 400 mT applied throughout the process, an aqueous phase was added, and the mixture was emulsified by high-speed stirring for 4 minutes, stirred at room temperature for 3 hours, heated to 80℃ and stirred for 5 hours. After washing and drying, modified microcapsules were obtained. The mass ratio of the oil phase to the aqueous phase was 1:3. A method for preparing a high-strength, oil-resistant cable material includes the following steps: 77 parts of polyether-type polyurethane resin (model 58881) and 15 parts of nitrile rubber were mixed at 90°C for 4 minutes. Then, 20.8 parts of modified microcapsules, 0.1 parts of antioxidant 1010, 0.1 parts of UV-327 ultraviolet absorber, 1.5 parts of ethylene bis-stearamide, and 0.5 parts of zinc stearate were added and mixed further. The mixture was then extruded and granulated at 150°C to obtain high-strength oil-resistant cable material. Example 2

[0022] The modified microcapsules are prepared as follows: (1) Zinc oxide, aluminum tripolyphosphate, methyltrimethoxysilane and tetraethyl orthosilicate are weighed in a mass ratio of 0.5:3.5:5:8; zinc oxide and aluminum tripolyphosphate are added to an ethanol aqueous solution and mixed evenly; methyltrimethoxysilane and tetraethyl orthosilicate are added and stirred evenly; the temperature is raised to 70°C and stirred for 5 hours; the mixture is filtered, washed and dried to obtain hydrophobic coated aluminum polyphosphate. (2) The mass ratio of hydroxylated sheet graphene to sodium dodecylbenzenesulfonate is 1:0.08; the hydroxylated sheet graphene and sodium dodecylbenzenesulfonate are added to deionized water and mixed to obtain an aqueous phase; the solid content of the aqueous phase is 15wt%; 2,2-difluoro-1,3-diol, 1,6-hexanediisocyanate, and triethylenediamine are weighed in a mass ratio of 3.1:5:0.015; 2,2-difluoro-1,3-diol, 1,6-hexanediisocyanate, and triethylenediamine are stirred evenly, and the temperature is raised to 80℃ and stirred for 2 hours. The mixture was cooled to room temperature, washed, and dried to obtain a fluorinated prepolymer. The fluorinated prepolymer, hydrophobically coated aluminum polyphosphate, and isophorone diisocyanate were weighed in a mass ratio of 4:2:1. The fluorinated prepolymer was mixed with the hydrophobically coated aluminum polyphosphate and isophorone diisocyanate to obtain an oil phase. Under the constant magnetic field of 400 mT applied throughout the process, an aqueous phase was added, and the mixture was emulsified by high-speed stirring for 4 minutes, stirred at room temperature for 3 hours, heated to 80℃ and stirred for 5 hours. After washing and drying, modified microcapsules were obtained. The mass ratio of the oil phase to the aqueous phase was 1:3. A method for preparing a high-strength, oil-resistant cable material includes the following steps: 77 parts of polyether-type polyurethane resin (model 58881) and 15 parts of nitrile rubber were mixed at 90°C for 4 minutes. Then, 18 parts of modified microcapsules, 0.1 parts of antioxidant 1010, 0.1 parts of UV-327 ultraviolet absorber, 1.5 parts of ethylene bis-stearamide, and 0.5 parts of zinc stearate were added and mixed further. The mixture was then extruded and granulated at 150°C to obtain high-strength oil-resistant cable material. Example 3

[0023] The modified microcapsules are prepared as follows: (1) Zinc oxide, aluminum tripolyphosphate, methyltrimethoxysilane and tetraethyl orthosilicate are weighed in a mass ratio of 0.5:3.5:5:8; zinc oxide and aluminum tripolyphosphate are added to an ethanol aqueous solution and mixed evenly; methyltrimethoxysilane and tetraethyl orthosilicate are added and stirred evenly; the temperature is raised to 70°C and stirred for 5 hours; the mixture is filtered, washed and dried to obtain hydrophobic coated aluminum polyphosphate. (2) The mass ratio of hydroxylated sheet graphene to sodium dodecylbenzenesulfonate is 1:0.08; the hydroxylated sheet graphene and sodium dodecylbenzenesulfonate are added to deionized water and mixed to obtain an aqueous phase; the solid content of the aqueous phase is 15wt%; 2,2-difluoro-1,3-diol, 1,6-hexanediisocyanate, and triethylenediamine are weighed in a mass ratio of 3.1:5:0.015; 2,2-difluoro-1,3-diol, 1,6-hexanediisocyanate, and triethylenediamine are stirred evenly, and the temperature is raised to 70~80℃ and stirred for 2~3 minutes. After cooling to room temperature for 2 hours, the mixture was washed and dried to obtain a fluorinated prepolymer. The fluorinated prepolymer, hydrophobically coated aluminum polyphosphate, and isophorone diisocyanate were weighed in a mass ratio of 4:2:1. The fluorinated prepolymer was mixed with the hydrophobically coated aluminum polyphosphate and isophorone diisocyanate to obtain an oil phase. Under the constant magnetic field of 400 mT applied throughout the mixture, an aqueous phase was added, and the mixture was emulsified by high-speed stirring for 4 minutes. The mixture was then stirred at room temperature for 3 hours, heated to 80°C, and stirred for 5 hours. After washing and drying, modified microcapsules were obtained. The mass ratio of the oil phase to the aqueous phase was 1:3. A method for preparing a high-strength, oil-resistant cable material includes the following steps: 77 parts of polyether-type polyurethane resin (model 58881) and 15 parts of nitrile rubber were mixed at 90°C for 4 minutes. Then, 22 parts of modified microcapsules, 0.1 parts of antioxidant 1010, 0.1 parts of UV-327 ultraviolet absorber, 1.5 parts of ethylene bis-stearamide, and 0.5 parts of zinc stearate were added and mixed further. The mixture was then extruded and granulated at 150°C to obtain high-strength oil-resistant cable material.

[0024] Comparative Example 1 is based on Example 3, with hydrophobic coated aluminum polyphosphate added directly; the remaining operation steps are the same. The preparation method of hydrophobic coated aluminum polyphosphate is as follows: (1) Weigh zinc oxide, aluminum tripolyphosphate, methyltrimethoxysilane and tetraethyl orthosilicate in a mass ratio of 0.5:3.5:5:8; add zinc oxide and aluminum tripolyphosphate into an ethanol aqueous solution and mix evenly; add methyltrimethoxysilane and tetraethyl orthosilicate and stir evenly; heat to 70°C and stir for 5 hours; filter, wash and dry to obtain hydrophobic coated aluminum polyphosphate; A method for preparing a high-strength, oil-resistant cable material includes the following steps: 77 parts of polyether-type polyurethane resin (model 58881) and 15 parts of nitrile rubber were mixed at 90°C for 4 minutes. Then, 22 parts of hydrophobically coated aluminum polyphosphate, 0.1 parts of antioxidant 1010, 0.1 parts of UV-327 ultraviolet absorber, 1.5 parts of ethylene bis-stearamide, and 0.5 parts of zinc stearate were added and mixed for further mixing. The mixture was then extruded and granulated at 150°C to obtain high-strength oil-resistant cable material.

[0025] Comparative Example 2 is based on Example 3, except that the sheet-like graphene is replaced with spherical nano-silica; the remaining operation steps are the same. The preparation method of hydroxylated nano-silica is as follows: 60 nm nano-silica and KH-560 ethanol aqueous solution are weighed at a mass ratio of 1:6; the concentration of KH-560 ethanol aqueous solution is 17 wt%; the nano-silica is ultrasonically dispersed in the ethanol aqueous solution, the pH is adjusted to 4.5, KH-560 ethanol aqueous solution is added, the mixture is heated to 70℃ and stirred for 5 hours, the pH is adjusted to 2.5, the temperature is raised to 80℃ and stirred for 3 hours, the mixture is separated by magnetic adsorption, washed and dried to obtain hydroxylated nano-silica; The modified microcapsules are prepared as follows: (1) Zinc oxide, aluminum tripolyphosphate, methyltrimethoxysilane and tetraethyl orthosilicate are weighed in a mass ratio of 0.5:3.5:5:8; zinc oxide and aluminum tripolyphosphate are added to an ethanol aqueous solution and mixed evenly; methyltrimethoxysilane and tetraethyl orthosilicate are added and stirred evenly; the temperature is raised to 70°C and stirred for 5 hours; the mixture is filtered, washed and dried to obtain hydrophobic coated aluminum polyphosphate. (2) The mass ratio of hydroxylated nano-silica to sodium dodecylbenzenesulfonate was 1:0.08; the hydroxylated nano-silica and sodium dodecylbenzenesulfonate were added to deionized water and mixed to obtain an aqueous phase; the solid content of the aqueous phase was 15wt%; 2,2-difluoro-1,3-diol, 1,6-hexanediisocyanate, and triethylenediamine were weighed in a mass ratio of 3.1:5:0.015; 2,2-difluoro-1,3-diol, 1,6-hexanediisocyanate, and triethylenediamine were stirred evenly. The mixture was stirred at 80°C for 2 hours, cooled to room temperature, washed, and dried to obtain a fluorinated prepolymer. The fluorinated prepolymer, hydrophobically coated aluminum polyphosphate, and isophorone diisocyanate were weighed in a mass ratio of 4:2:1. The fluorinated prepolymer was mixed with the hydrophobically coated aluminum polyphosphate and isophorone diisocyanate to obtain an oil phase. The water phase was added, and the mixture was emulsified by high-speed stirring for 4 minutes, stirred at room temperature for 3 hours, heated to 80°C and stirred for 5 hours. The mixture was washed and dried to obtain modified microcapsules. The mass ratio of the oil phase to the water phase was 1:3.

[0026] Comparative Example 3 is based on Example 3, but without depositing magnetic nanoparticles on the surface of the sheet-like graphene; the remaining operation steps are the same. The preparation method of hydroxylated sheet graphene is as follows: graphene oxide and KH-560 ethanol aqueous solution are weighed at a mass ratio of 1:6; the concentration of KH-560 ethanol aqueous solution is 17wt%; magnetic graphene oxide is ultrasonically dispersed in ethanol aqueous solution, the pH is adjusted to 4.5, KH-560 ethanol aqueous solution is added, heated to 70℃ and stirred for 5 hours, the pH is adjusted to 2.5, the temperature is raised to 80℃ and stirred for 3 hours, separated by magnetic adsorption, washed and dried to obtain hydroxylated sheet graphene; The modified microcapsules are prepared as follows: (1) Zinc oxide, aluminum tripolyphosphate, methyltrimethoxysilane and tetraethyl orthosilicate are weighed in a mass ratio of 0.5:3.5:5:8; zinc oxide and aluminum tripolyphosphate are added to an ethanol aqueous solution and mixed evenly; methyltrimethoxysilane and tetraethyl orthosilicate are added and stirred evenly; the temperature is raised to 70°C and stirred for 5 hours; the mixture is filtered, washed and dried to obtain hydrophobic coated aluminum polyphosphate. (2) The mass ratio of hydroxylated sheet graphene to sodium dodecylbenzenesulfonate is 1:0.08; the hydroxylated sheet graphene and sodium dodecylbenzenesulfonate are added to deionized water and mixed to obtain an aqueous phase; the solid content of the aqueous phase is 15wt%; 2,2-difluoro-1,3-diol, 1,6-hexanediisocyanate, and triethylenediamine are weighed in a mass ratio of 3.1:5:0.015; 2,2-difluoro-1,3-diol, 1,6-hexanediisocyanate, and triethylenediamine are stirred evenly and then... The mixture was heated to 70-80℃ and stirred for 2-3 hours, then cooled to room temperature, washed, and dried to obtain a fluorinated prepolymer. The fluorinated prepolymer, hydrophobically coated aluminum polyphosphate, and isophorone diisocyanate were weighed in a mass ratio of 4:2:1. The fluorinated prepolymer was mixed with the hydrophobically coated aluminum polyphosphate and isophorone diisocyanate to obtain an oil phase. The water phase was added, and the mixture was emulsified by high-speed stirring for 4 minutes, stirred at room temperature for 3 hours, heated to 80℃ and stirred for 5 hours. The mixture was then washed and dried to obtain modified microcapsules. The mass ratio of the oil phase to the water phase was 1:3.

[0027] Comparative Example 4 is based on Example 3, except that 2,2-difluoro-1,3-diol is replaced with polyethylene glycol 400; the other operating steps are the same. The modified microcapsules are prepared as follows: (1) Zinc oxide, aluminum tripolyphosphate, methyltrimethoxysilane and tetraethyl orthosilicate are weighed in a mass ratio of 0.5:3.5:5:8; zinc oxide and aluminum tripolyphosphate are added to an ethanol aqueous solution and mixed evenly; methyltrimethoxysilane and tetraethyl orthosilicate are added and stirred evenly; the temperature is raised to 70°C and stirred for 5 hours; the mixture is filtered, washed and dried to obtain hydrophobic coated aluminum polyphosphate. (2) The mass ratio of hydroxylated sheet graphene to sodium dodecylbenzenesulfonate is 1:0.08; the hydroxylated sheet graphene and sodium dodecylbenzenesulfonate are added to deionized water and mixed to obtain an aqueous phase; the solid content of the aqueous phase is 15wt%; polyethylene glycol 400, 1,6-hexanediisocyanate, and triethylenediamine are weighed in a mass ratio of 8:5:0.015; polyethylene glycol 400, 1,6-hexanediisocyanate, and triethylenediamine are stirred evenly, heated to 80℃ and stirred for 2 hours, cooled to room temperature, and washed. The mixture was dried to obtain a fluorinated prepolymer. The fluorinated prepolymer, hydrophobically coated aluminum polyphosphate, and isophorone diisocyanate were weighed in a mass ratio of 4:2:1. The fluorinated prepolymer was mixed with the hydrophobically coated aluminum polyphosphate and isophorone diisocyanate to obtain an oil phase. Under the constant magnetic field of 400mT applied around the mixture, an aqueous phase was added. The mixture was emulsified by high-speed stirring for 4 minutes, stirred at room temperature for 3 hours, heated to 80℃ and stirred for 5 hours, washed and dried to obtain modified microcapsules. The mass ratio of the oil phase to the aqueous phase was 1:3.

[0028] Test 1: The high-strength oil-resistant cable materials prepared in Examples 1-3 and Comparative Examples 1-4 were placed in IRM903 test oil and IRM902 test oil at 100℃ for 168 hours, respectively; according to GB / T2951.11, the tensile strength (MPa) before and after oil resistance was tested, and the tensile strength reduction rate (%) was calculated. Table 1

[0029] Conclusions: Comparative Example 1, based on Example 3, directly added hydrophobically coated aluminum polyphosphate; the hydrophobically coated aluminum polyphosphate, through coating with methyltrimethoxysilane and tetraethyl orthosilicate, resulted in excessive pores and decreased network density, thus reducing oil resistance; Comparative Example 2, based on Example 3, replaced sheet graphene with spherical nano-silica; at the same addition amount, the surface area of ​​spherical nano-silica was less than that of sheet graphene, thus reducing oil resistance; Comparative Example 3, based on Example 3, did not deposit magnetic nanoparticles on the surface of sheet graphene; the introduction of magnetic nanomaterials can improve the dispersion of sheet graphene through magnetic field, thus reducing the oil resistance of Comparative Example 3; Comparative Example 4, based on Example 3, replaced 2,2-difluoro-1,3-diol with polyethylene glycol; the fluorine group has strong electronegativity, thus having good oil resistance, and replacing it with polyethylene glycol led to a decrease in oil resistance.

[0030] Test 2: The density, elongation at break, hardness, and flame retardancy of the high-strength oil-resistant cable material prepared in Example 3 were tested. The testing standard for density was GB / T1033.1; the testing standard for elongation at break was GB / T2951.11; the testing standard for hardness was GB / T2411; and the testing standard for flame retardancy was GB / T2406.2-2009. Table 2

[0031] It will be apparent to those skilled in the art that the present invention is not limited to the details of the exemplary embodiments described above, and that the invention can be implemented in other specific forms without departing from the spirit or essential characteristics of the invention. Therefore, the embodiments should be considered in all respects as exemplary and non-limiting, and the scope of the invention is defined by the appended claims rather than the foregoing description. Thus, it is intended that all variations falling within the meaning and scope of equivalents of the claims be included within the present invention.

Claims

1. A high strength oil resistant cable compound characterized in that: The raw materials of the high-strength oil-resistant cable material include the following components: by mass, 70-80 parts of polyether polyurethane resin, 10-15 parts of nitrile rubber, 18-22 parts of modified microcapsules, 0.1-0.2 parts of antioxidant, 0.1-0.2 parts of ultraviolet absorber, and 2-3 parts of lubricant.

2. The high strength oil resistant cable material according to claim 1, wherein: The preparation method of the modified microcapsules is as follows: (1) Add zinc oxide and aluminum tripolyphosphate to an ethanol aqueous solution and mix evenly. Add methyltrimethoxysilane and tetraethyl orthosilicate and stir evenly. Heat to 50~70℃ and stir for 3~4 hours. Filter, wash and dry to obtain hydrophobic coated aluminum polyphosphate. (2) Hydroxylated sheet graphene and sodium dodecylbenzenesulfonate were added to deionized water and mixed to obtain an aqueous phase; 2,2-difluoro-1,3-diol was mixed with 1,6-hexanediisocyanate and triethylenediamine and stirred evenly, heated to 70~80℃ and stirred for 2~3 hours, cooled to room temperature, washed and dried to obtain a fluorinated prepolymer; the fluorinated prepolymer was mixed with hydrophobically coated aluminum polyphosphate and isophorone diisocyanate to obtain an oil phase, and under the action of a constant magnetic field throughout the process, the aqueous phase was added, and the mixture was emulsified by high-speed stirring for 2~4 minutes, stirred at room temperature for 1~3 hours, heated to 70~80℃ and stirred for 4~6 hours, washed and dried to obtain modified microcapsules.

3. The high strength oil resistant cable material according to claim 2, wherein: The mass ratio of zinc oxide, aluminum tripolyphosphate, methyltrimethoxysilane, and tetraethyl orthosilicate is (0.5~1.5):(2.5~4):(3~5):(6~8).

4. The high strength oil resistant cable material according to claim 2, wherein: The mass ratio of 2,2-difluoro-1,3-diol to 1,6-hexanediisocyanate and triethylenediamine is (2~3.2):5:(0.01~0.02).

5. The high strength oil resistant cable material according to claim 2, wherein: The mass ratio of the hydroxylated sheet graphene to sodium dodecylbenzenesulfonate is 1:(0.05~0.1); the solid content of the aqueous phase is 8~15wt%. In the oil phase, the mass ratio of fluorinated prepolymer, hydrophobically coated aluminum polyphosphate, and isophorone diisocyanate is (4~6):2:1; the mass ratio of the oil phase to the water phase is 1:(3~4).

6. The high strength oil resistant cable material according to claim 2, wherein: The method for preparing the hydroxylated sheet graphene is as follows: Graphene oxide is ultrasonically dispersed in deionized water, an aqueous solution of FeCl2·4H2O and FeCl3·6H2O is added, ammonia is added to adjust the pH to 9-11, the mixture is stirred for 2-3 hours, washed and dried, and separated by magnetic adsorption to obtain magnetic graphene oxide; the magnetic graphene oxide is ultrasonically dispersed in an ethanol aqueous solution, the pH is adjusted to 4-5, KH-560 ethanol aqueous solution is added, the mixture is heated to 60-75℃ and stirred for 5-6 hours, the pH is adjusted to 2-3, the temperature is raised to 80-90℃ and stirred for 3-4 hours, separated by magnetic adsorption, washed and dried to obtain hydroxylated sheet graphene.

7. The high strength oil resistant cable material according to claim 6, wherein: The mass ratio of graphene oxide, FeCl2·4H2O, and FeCl3·6H2O is 1:(0.3~0.4):(0.7~0.8); the mass ratio of magnetic graphene oxide to KH-560 ethanol aqueous solution is 1:(5~7); and the concentration of KH-560 ethanol aqueous solution is 13~17wt%.

8. The high strength oil resistant cable material according to claim 6, wherein: The graphene oxide has a particle size of 1~3µm; the hydroxylated sheet graphene has an iron oxide loading of 15~20wt%.

9. The process for the preparation of high strength oil resistant cable compound as claimed in claim 1, wherein: The process includes the following steps: mixing polyether-type polyurethane resin and nitrile rubber at 70~90℃ for 3~6 minutes, adding modified microcapsules, antioxidants, ultraviolet absorbers and lubricants and continuing to mix, then extruding and granulating at 120~160℃ to obtain high-strength oil-resistant cable material.

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