Wear-resistant agent, irradiation flexible halogen-free wear-resistant cable material, preparation method of irradiation flexible halogen-free wear-resistant cable material and cable prepared from irradiation flexible halogen-free wear-resistant cable material

Abstract

The invention discloses a wear-resistant agent, which is prepared from the following ingredients in parts by weight: 2700 to 2900 parts of nano titanium dioxide; 2.1 to 2.3 parts of alkali; 28 to 70 parts of sodium metazincate; 2.3 to 2.5 parts of inorganic acid; wherein the wear-resistant agent further comprises active silica powder, a silane coupling agent, molybdenum disulfide and an organic solvent. The irradiation flexible halogen-free wear-resistant cable material provided by the invention has good mechanical properties, high flame retardance and good wear resistance, and is suitable for the cable industry.

Description

Technical Field

[0001] The invention relates to the field of electric wires and cables, and in particular to an anti-wear agent, an irradiated flexible halogen-free wear-resistant cable material, a preparation method thereof, and a cable. Background Art

[0002] With the global emphasis on environmental protection and safety regulations, the demand for low-smoke halogen-free cable materials is growing. In particular, driven by the rapid development of the new energy vehicle industry, the market size of the automotive cable industry continues to expand, and is expected to reach 55.33 billion yuan by 2025. This trend poses higher challenges to the performance requirements of wire and cable materials, but the current traditional PVC wires have problems such as poor flexibility, poor flame retardant effect and poor wear resistance. Therefore, it is necessary to develop a cable material with good processing performance, mechanical properties, flame retardant properties and good wear resistance. Summary of the invention

[0003] In view of the above-mentioned deficiencies in the prior art, the present invention proposes an anti-wear agent, an irradiated flexible halogen-free wear-resistant cable material, a preparation method and a protective cable made from the cable material, aiming to solve the problems of insufficient low-smoke flame retardant performance, toughness and wear resistance of current cable materials.

[0004] To achieve the above purpose, the present invention provides a wear-resistant agent, an irradiated flexible halogen-free wear-resistant cable material, a preparation method and a cable made from the cable material. A wear-resistant agent, the ingredients of which are measured by weight, include 2700-2900 parts of nano titanium dioxide; 2.1-2.3 parts of alkali; 28-70 parts of sodium metazincate; 2.3-2.5 parts of inorganic acid; wherein the ingredients of the wear-resistant agent also include active silicon micropowder, silane coupling agent, molybdenum disulfide and organic solvent.

[0005] Optionally, the active silicon micropowder is at least one of epoxy-modified active silicon micropowder, acyloxy-modified active silicon micropowder and vinyl-modified active silicon micropowder.

[0006] Optionally, the silane coupling agent is at least one of 3-aminopropyltriethoxysilane, γ-aminopropyltriethoxysilane and γ-glycidyloxypropyltrimethoxysilane.

[0007] Optionally, the base is a soluble base.

[0008] Optionally, the inorganic acid is at least one of hydrochloric acid and sulfuric acid.

[0009] Optionally, the organic solvent is at least one of ethanol, acetone, methanol, toluene and ethyl acetate.

[0010] An irradiated flexible halogen-free wear-resistant cable material, wherein the ingredients of the irradiated flexible halogen-free wear-resistant cable material are, by weight, 10-20 parts of LLDPE; 25-40 parts of EVA; 10-20 parts of POE; 5-10 parts of maleic anhydride grafted POE; 5-10 parts of toughening agent; 40-60 parts of compound flame retardant; 1-2 parts of lubricant; 1-2 parts of antioxidant; and 5-10 parts of the above-mentioned wear-resistant agent.

[0011] Optionally, the LLDPE has a melt flow rate of 3-8 g / 10 min at 190° C. / 2.16 kg.

[0012] Optionally, the EVA has a melt flow rate of 2-5 g / 10 min at 190° C. / 2.16 kg.

[0013] Optionally, the POE has a melt flow rate of 1-2 g / 10 min at 190° C. / 2.16 kg.

[0014] Optionally, the compatibilizer includes at least one of maleic anhydride grafted PE, maleic anhydride grafted EVA and maleic anhydride grafted POE.

[0015] Optionally, the toughening agent includes at least one of vinyl silicone rubber, fluororubber and other toughening agents.

[0016] Optionally, the compound flame retardant is compounded with an inorganic flame retardant, and the inorganic flame retardant includes aluminum hydroxide and magnesium hydroxide, wherein the weight ratio of aluminum hydroxide to magnesium hydroxide is (20-30): (20-30) compound flame retardant.

[0017] Optionally, the lubricant is at least one of fatty acids, fatty amides, metal soaps, and fatty alcohols.

[0018] In order to achieve the above-mentioned purpose, the present invention also proposes a method for preparing an irradiated flexible halogen-free wear-resistant cable material, comprising the following steps: preparing an anti-wear agent: preparing the anti-wear agent by a solution method from the above-mentioned nano titanium dioxide, alkali, sodium metazincate, acid, active silicon powder, silane coupling agent and molybdenum disulfide; preparing an irradiated flexible halogen-free wear-resistant cable material: pre-mixing LLDPE, EVA, POE, a compatibilizer, a toughening agent, a compound flame retardant, a lubricant, an antioxidant and an anti-wear agent, and then mixing them in an internal mixer to prepare a molten blend; granulating the molten blend in a twin-screw-single screw pelletizer, and then cooling, drying and irradiating the molten blend to finally obtain an irradiated flexible halogen-free wear-resistant cable material.

[0019] Optionally, the preparation method of the wear-resistant agent comprises the following steps: dissolving nano titanium dioxide powder in water and then dispersing by ultrasonic, then adding alkali to adjust the pH value of the solution to alkaline, stirring the reaction and letting it stand, separating particles with a particle size greater than 1.5 μm by centrifugation, retaining the reaction solution, adding a certain amount of sodium metazincate solution to the reaction solution, adding acid by titration after the reaction to adjust the pH value of the solution to 5.5-6.5, then filtering and washing to obtain a filter cake, and heat treating the filter cake at 130-160° C. for 10-14 hours. The method comprises the following steps: obtaining titanium dioxide powder coated with zinc oxide, wherein the weight of sodium metazincate is 1%-2.5% of the nano titanium dioxide powder; adding active silicon micropowder, silane coupling agent and molybdenum disulfide into an organic solvent solution, ultrasonically stirring for 4-8 hours, and then adding the titanium dioxide powder coated with zinc oxide, wherein the weight ratio of active silicon micropowder, silane coupling agent, molybdenum disulfide and the titanium dioxide powder coated with zinc oxide is 1:2:1:1, continuing ultrasonic stirring, forming a mixture, and vacuum drying to obtain the wear-resistant agent.

[0020] In order to achieve the above object, the present invention further provides an irradiated flexible halogen-free wear-resistant cable, which is prepared by any of the above-mentioned preparation methods of irradiated flexible halogen-free wear-resistant cable materials.

[0021] Beneficial effects of the present invention: In the present invention, by selecting nano titanium dioxide, sodium metazincate, active silicon micropowder, silane coupling agent and molybdenum disulfide, etc., a synthetic wear-resistant agent is prepared, which has good compatibility and can have good dispersibility in the resin matrix, wherein the wear-resistant agent can act as the termination point of the silver streaks produced by the polymer material after being stretched by external force, and thus has a lubricating effect, improves the fluidity and compatibility between the various components of the material, improves the surface quality and wear resistance of the product, and combines the advantages of modified silicon micropowder and molybdenum disulfide to further improve the wear resistance. In the flame retardant process, the nano titanium dioxide component in the wear-resistant agent can act as a carbonizing agent to promote the carbonization of the material, and at the same time become a stable fulcrum of the carbon layer, forming a stable carbon layer, delaying the transfer of heat in the inner layer of the material, thereby improving the flame retardancy of the cable, and at the same time, the material can also be used as a halogen-free high smoke suppression synergist, compounded with halogen-free metal hydroxides, and has an excellent smoke suppression effect.

[0022] The present invention also uses the above-mentioned wear-resistant agent to prepare irradiated flexible halogen-free wear-resistant cable materials, LLDPE, EVA, POE and compatibilizer are used as matrix resins, and various components such as toughening agents, compound flame retardants, antioxidants, lubricants and wear-resistant agents are added to cooperate with each other. After appropriate irradiation, a unique soft and tough structure is formed. After the wear-resistant agent is added, a unique multi-layer coating structure is formed, which is beneficial to improving the wear resistance of the material and strengthening the compatibility of the various components of the material. A firm protective film can be formed on the surface of the object to make it have a lubricating effect, thereby improving processing fluidity and formability, and then improving the surface quality of the finished product. DETAILED DESCRIPTION

[0023] In order to make the purpose, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. It should be understood that the following embodiments are only used to explain the present invention and are not used to limit the present invention.

[0024] Unless defined otherwise, all technical and scientific terms used herein have the common meaning in the art to which the claimed subject matter belongs.

[0025] In order to facilitate the understanding of this embodiment, the symbols, instruments and terms are explained below:

[0026] LLDPE: Linear low density polyethylene, linear low density polyethylene, is non-toxic, tasteless, odorless milky white particles. Compared with LDPE, it has higher softening temperature and melting temperature, and has the advantages of high strength, good toughness, high rigidity, good heat resistance and cold resistance. It also has good resistance to environmental stress cracking, impact strength, tear strength and other properties, and is resistant to acids, alkalis, organic solvents, etc. and is widely used in industry, agriculture, medicine, health and daily necessities.

[0027] EVA: Ethylene Vinyl Acetate Copolymer, ethylene-vinyl acetate copolymer, is a general-purpose polymer with good chemical stability, aging resistance and ozone resistance. EVA materials have a wide range of applications, including the shoemaking industry, photovoltaic materials, and wires and cables.

[0028] POE: Polyolefinelastomer, polyolefin elastomer, is a synthetic polymer material. POE has a shorter branched chain distribution, which makes the material have excellent physical properties such as high elasticity, high strength, and high elongation. At the same time, its molecular bonds are saturated, which makes the material have excellent heat aging resistance and UV resistance. It is widely used in toughening and modification of automotive materials, shoe materials, construction, electronic appliances, daily necessities, medical equipment and other fields.

[0029] PE: Polyethylene is a thermoplastic resin made from the polymerization of ethylene monomers. It is mainly used to make films, packaging materials, containers, pipes, monofilaments, wires and cables, daily necessities, etc.

[0030] With the global emphasis on environmental protection and safety regulations, the demand for low-smoke halogen-free cable materials is growing. In particular, driven by the rapid development of the new energy vehicle industry, the market size of the automotive cable industry continues to expand, and is expected to reach 55.33 billion yuan by 2025. This trend poses higher challenges to the performance requirements of wire and cable materials. However, traditional PVC wires currently have problems such as poor flexibility, poor flame retardancy, and poor wear resistance. Therefore, it is necessary to develop a cable material with good processing performance, mechanical properties, flame retardancy, and good wear resistance.

[0031] To solve the above problems, the present invention provides an anti-wear agent, the ingredients of which, by weight, include 2700-2900 parts of nano titanium dioxide; 2.1-2.3 parts of alkali; 28-70 parts of sodium metazincate; and 2.3-2.5 parts of inorganic acid; wherein the ingredients of the anti-wear agent include active silicon micropowder, silane coupling agent, molybdenum disulfide and organic solvent.

[0032] In the present invention, by selecting nano titanium dioxide, sodium metazincate, active silicon micropowder, silane coupling agent and molybdenum disulfide, etc., a synthetic wear-resistant agent is prepared, which has good compatibility and good dispersibility in the resin matrix. The wear-resistant agent can serve as the termination point of the silver streaks produced by the polymer material after being stretched by external force, so it has a lubricating effect, improves the fluidity and compatibility between the various components of the material, improves the surface quality and wear resistance of the product, and combines the advantages of modified silicon micropowder and molybdenum disulfide to further improve the wear resistance. In the flame retardant process, the nano titanium dioxide component in the wear-resistant agent can serve as a carbonizing agent to promote the carbonization of the material, and at the same time become a stable fulcrum of the carbon layer to form a stable carbon layer, delay the transfer of heat in the inner layer of the material, thereby improving the flame retardancy of the cable. At the same time, the material can also be used as a halogen-free high smoke suppression synergist, compounded with halogen-free metal hydroxides, and has an excellent smoke suppression effect.

[0033] Furthermore, the active silicon micropowder is at least one of epoxy-modified active silicon micropowder, acyloxy-modified active silicon micropowder and vinyl-modified active silicon micropowder.

[0034] In some embodiments, the active silicon powder is preferably epoxy-modified active silicon powder.

[0035] Furthermore, the silane coupling agent is at least one of 3-aminopropyltriethoxysilane, γ-aminopropyltriethoxysilane and γ-glycidyloxypropyltrimethoxysilane.

[0036] In some embodiments, the silane coupling agent is preferably 3-aminopropyltriethoxysilane.

[0037] Further, the base is a soluble base.

[0038] In some embodiments, the base is preferably sodium hydroxide.

[0039] Furthermore, the inorganic acid is at least one of hydrochloric acid and sulfuric acid.

[0040] In some embodiments, the inorganic acid is preferably hydrochloric acid.

[0041] Furthermore, the organic solvent is at least one of ethanol, acetone, methanol, toluene and ethyl acetate.

[0042] In some embodiments, the organic solvent is preferably ethanol.

[0043] The present invention also proposes an irradiated flexible halogen-free wear-resistant cable material, characterized in that the ingredients of the irradiated flexible halogen-free wear-resistant cable material, in parts by weight, include: 10-20 parts of LLDPE; 25-40 parts of EVA; 10-20 parts of POE; 5-10 parts of maleic anhydride grafted POE; 5-10 parts of toughening agent; 40-60 parts of compound flame retardant; 1-2 parts of lubricant; 1-2 parts of antioxidant; and 5-10 parts of the above-mentioned wear-resistant agent.

[0044] In some embodiments, the ingredients of the irradiated flexible halogen-free wear-resistant cable material, measured in parts by weight, preferably include: 10-20 parts of LLDPE; 25-40 parts of EVA; 10-20 parts of POE; 5-10 parts of maleic anhydride grafted POE; 5-10 parts of toughening agent; 40-60 parts of compound flame retardant; 1-2 parts of lubricant; 1-2 parts of antioxidant; and 5-10 parts of the above-mentioned wear-resistant agent.

[0045] Further, the melt flow rate of LLDPE at 190° C. / 2.16 kg is 3-8 g / 10 min.

[0046] In some embodiments, the melt flow rate of LLDPE at 190° C. / 2.16 kg is preferably 5 g / 10 min.

[0047] Further, the melt flow rate of EVA at 190° C. / 2.16 kg is 2-5 g / 10 min.

[0048] In some embodiments, the melt flow rate of EVA at 190° C. / 2.16 kg is preferably 3 g / 10 min.

[0049] Further, the melt flow rate of POE at 190° C. / 2.16 kg is 1-2 g / 10 min.

[0050] In some embodiments, the melt flow rate of POE at 190° C. / 2.16 kg is preferably 1.5 g / 10 min.

[0051] Furthermore, the compatibilizer includes at least one of maleic anhydride grafted PE, maleic anhydride grafted EVA and maleic anhydride grafted POE.

[0052] In some embodiments, the compatibilizer is preferably maleic anhydride grafted POE.

[0053] Furthermore, the toughening agent includes at least one of vinyl silicone rubber, fluororubber and other toughening agents.

[0054] In some embodiments, the toughening agent is preferably vinyl silicone rubber.

[0055] Furthermore, the compound flame retardant is compounded by an inorganic flame retardant, and the inorganic flame retardant includes aluminum hydroxide and magnesium hydroxide, wherein the weight ratio of aluminum hydroxide to magnesium hydroxide is (20-30): (20-30).

[0056] In some embodiments, the composite flame retardant is preferably aluminum hydroxide and magnesium hydroxide, and the weight ratio thereof is preferably (20-30): (20-30).

[0057] Furthermore, the lubricant is at least one of fatty acids, fatty amides, metal soaps, and fatty alcohols.

[0058] In some embodiments, the lubricant is preferably a fatty acid.

[0059] In order to solve the above problems, the present invention also proposes a method for preparing an irradiated flexible halogen-free wear-resistant cable material, comprising the following steps:

[0060] S1: preparing an anti-wear agent: preparing an anti-wear agent by a solution method using the above-mentioned nano titanium dioxide, alkali, sodium metazincate, acid, active silicon micropowder, silane coupling agent and molybdenum disulfide;

[0061] In this scheme, by selecting nano titanium dioxide, sodium metazincate, active silicon micropowder, silane coupling agent and molybdenum disulfide, etc., a synthetic wear-resistant agent is prepared, which has good compatibility and good dispersibility in the resin matrix. The wear-resistant agent can act as the termination point of the silver streaks produced by the polymer material after being stretched by external force, so it has a lubricating effect, improves the fluidity and compatibility between the various components of the material, and improves the surface quality and wear resistance of the product. In addition, by combining the advantages of modified silicon micropowder and molybdenum disulfide, the wear resistance is further improved. In the flame retardant process, the nano titanium dioxide component in the wear-resistant agent can act as a carbonizing agent to promote the carbonization of the material, and at the same time become a stable fulcrum of the carbon layer, forming a stable carbon layer, delaying the transfer of heat in the inner layer of the material, thereby improving the flame retardancy of the cable. At the same time, the material can also be used as a halogen-free high smoke suppression synergist, and compounded with halogen-free metal hydroxides, it has an excellent smoke suppression effect.

[0062] S2: preparing irradiated flexible halogen-free wear-resistant cable material: pre-mixing LLDPE, EVA, POE, maleic anhydride grafted POE, toughening agent, compound flame retardant, lubricant, antioxidant and wear-resistant agent, and then mixing them in an internal mixer to prepare a melt blend irradiated flexible halogen-free wear-resistant cable material;

[0063] In some embodiments, internal mixing is performed in an internal mixer.

[0064] S3: The molten blend is granulated by a twin-screw-single screw granulator, and then cooled, dried and irradiated to finally obtain an irradiated flexible halogen-free wear-resistant cable material.

[0065] In some embodiments, the irradiated flexible halogen-free wear-resistant cable material can be irradiated with an irradiation dose of 6-12M to obtain an irradiated cross-linked flexible low-smoke halogen-free wear-resistant cable material.

[0066] Furthermore, the preparation method of the wear-resistant agent comprises the following steps:

[0067] The nano titanium dioxide powder is dissolved in water and then ultrasonically dispersed, and then alkali is added to adjust the pH value of the solution to alkaline, the reaction is stirred and allowed to stand, and particles with a particle size greater than 1.5 μm are separated by centrifugation, and the reaction solution is retained. A certain amount of sodium metazincate solution is added to the reaction solution, and acid is added by titration after the reaction to adjust the pH value of the solution to 5.5-6.5, and then filtered and washed to obtain a filter cake, and the filter cake is heat-treated at 130-160° C. for 10-14 hours to obtain titanium dioxide powder coated with zinc oxide, wherein the weight of sodium metazincate is 1%-2.5% of the nano titanium dioxide powder;

[0068] Active silicon micropowder, silane coupling agent and molybdenum disulfide are added to an organic solvent solution, ultrasonically stirred for 4-8 hours, and then titanium dioxide powder coated with zinc oxide is added, wherein the weight ratio of active silicon micropowder, silane coupling agent, molybdenum disulfide and titanium dioxide powder coated with zinc oxide is 1:2:1:1, ultrasonic stirring is continued, and after the mixture is formed, vacuum drying is performed to obtain a wear-resistant agent.

[0069] In some embodiments, nano titanium dioxide powder is added to a reaction device, and an appropriate amount of deionized water is added, and ultrasonic dispersion is performed for 0.5 h.

[0070] In some embodiments, the filter cake is heat treated at 150° C. for 12 hours to obtain zinc oxide-coated titanium dioxide powder.

[0071] In some embodiments, active silicon powder, silane coupling agent and molybdenum disulfide are added to an organic solvent solution and ultrasonically stirred for 5-7 hours.

[0072] In order to solve the above problems, the present invention also provides a flexible halogen-free wear-resistant cable, which is prepared by any of the above-mentioned preparation methods of irradiated flexible halogen-free wear-resistant cable materials.

[0073] The content of the present invention is explained below through specific examples and data.

[0074] Embodiment 1:

[0075] Weigh 2700 parts of fully ground nano titanium dioxide powder and add them to the reaction device, add an appropriate amount of deionized water, and ultrasonically disperse for 0.5h. Then add 2.1 parts of sodium hydroxide to adjust the solution pH to 9, and then stir at a constant speed for 2h. After the reaction is completed, let it stand for 1h, separate the particles with a particle size greater than 1.5μm by centrifugation, and retain the reaction solution. Add the reaction solution to the reaction device to ensure that the reaction device is constant temperature. Add 50 parts of Na2ZnO2 solution to it, and then gradually add 2.3 parts of hydrochloric acid to it within 1.5h to make the solution reach a certain pH value. Then quickly filter and wash the reaction solution to obtain a filter cake. Put the obtained filter cake into an oven and dry it at 150℃ for 12h. Finally, grind the obtained powder fully to obtain titanium dioxide powder coated with zinc oxide, in which the weight of sodium metazincrate is 1%-2.5% of the nano titanium dioxide powder. Active silicon micropowder, silane coupling agent and molybdenum disulfide are added to an ethanol solution and ultrasonically stirred for 5-7 hours, and then the coated titanium dioxide powder is added and ultrasonically stirred for 2-3 hours to form a mixture. The mixture is vacuum dried to obtain a self-made wear-resistant agent.

[0076] 15 parts of linear low-density polyethylene, 25 parts of ethylene-vinyl acetate copolymer, 10 parts of polyolefin elastomer, 8 parts of polyolefin elastomer grafted maleic anhydride, 8 parts of toughening agent, 25 parts of aluminum hydroxide, 25 parts of magnesium hydroxide, 1.5 parts of lubricant, 1.5 parts of antioxidant and 5 parts of homemade wear-resistant agent are mixed and kneaded, then extruded and granulated and irradiated to obtain irradiated flexible halogen-free wear-resistant cable material.

[0077] Embodiment 2:

[0078] Weigh 2900 parts of fully ground nano titanium dioxide powder and add them to the reaction device, add an appropriate amount of deionized water, and ultrasonically disperse for 0.5h. Then add 2.3 parts of sodium hydroxide to adjust the solution pH to 9, and then stir at a constant speed for 2h. After the reaction is completed, let it stand for 1h, separate the particles with a particle size greater than 1.5μm by centrifugation, and retain the reaction solution. Add the reaction solution to the reaction device to ensure that the reaction device is constant temperature. Add 70 parts of Na2ZnO2 solution to it, and then gradually add 2.5 parts of hydrochloric acid to it within 1.5h to make the solution reach a certain pH value. Then quickly filter and wash the reaction solution to obtain a filter cake. Put the obtained filter cake into an oven and dry it at 150℃ for 12h. Finally, grind the obtained powder fully to obtain zinc oxide-coated titanium dioxide powder, in which the weight of sodium metazincrate is 1%-2.5% of the nano titanium dioxide powder. Active silicon micropowder, silane coupling agent and molybdenum disulfide are added to an ethanol solution and ultrasonically stirred for 5-7 hours, and then the coated titanium dioxide powder is added and ultrasonically stirred for 2-3 hours to form a mixture. The mixture is vacuum dried to obtain a self-made wear-resistant agent.

[0079] 15 parts of linear low-density polyethylene, 25 parts of ethylene-vinyl acetate copolymer, 10 parts of polyolefin elastomer, 8 parts of polyolefin elastomer grafted maleic anhydride, 8 parts of toughening agent, 25 parts of aluminum hydroxide, 25 parts of magnesium hydroxide, 1.5 parts of lubricant, 1.5 parts of antioxidant and 5 parts of homemade wear-resistant agent are mixed and kneaded, then extruded and granulated and irradiated to obtain irradiated flexible halogen-free wear-resistant cable material.

[0080] Embodiment 3:

[0081] Weigh 2800 parts of fully ground nano titanium dioxide powder and add them to the reaction device, add an appropriate amount of deionized water, and ultrasonically disperse for 0.5h. Then add 2.2 parts of sodium hydroxide to adjust the solution pH to 9, and then stir at a constant speed for 2h. After the reaction is completed, let it stand for 1h, separate the particles with a particle size greater than 1.5μm by centrifugation, and retain the reaction solution. Add the reaction solution to the reaction device to ensure that the reaction device is kept at a constant temperature. Add 50 parts of Na2ZnO2 solution to it, and then gradually add 2.4 parts of hydrochloric acid to it within 1.5h so that the solution reaches a certain pH value. Then quickly filter and wash the reaction solution to obtain a filter cake. Put the obtained filter cake into an oven and dry it at 150℃ for 12h. Finally, grind the obtained powder fully to obtain titanium dioxide powder coated with zinc oxide, in which the weight of sodium metazincrate is 1%-2.5% of the nano titanium dioxide powder. Active silicon micropowder, silane coupling agent and molybdenum disulfide are added to an ethanol solution and ultrasonically stirred for 5-7 hours, and then the coated titanium dioxide powder is added and ultrasonically stirred for 2-3 hours to form a mixture. The mixture is vacuum dried to obtain a self-made wear-resistant agent.

[0082] 10 parts of linear low-density polyethylene, 30 parts of ethylene-vinyl acetate copolymer, 10 parts of polyolefin elastomer, 8 parts of polyolefin elastomer grafted maleic anhydride, 8 parts of toughening agent, 25 parts of aluminum hydroxide, 25 parts of magnesium hydroxide, 1.5 parts of lubricant, 1.5 parts of antioxidant and 5 parts of homemade wear-resistant agent are mixed and kneaded, then extruded and granulated and irradiated to obtain irradiated flexible halogen-free wear-resistant cable material.

[0083] Embodiment 4:

[0084] The preparation method is the same as that of Example 3, except that:

[0085] 15 parts of linear low-density polyethylene, 25 parts of ethylene-vinyl acetate copolymer, 10 parts of polyolefin elastomer, 8 parts of polyolefin elastomer grafted maleic anhydride, 8 parts of toughening agent, 25 parts of aluminum hydroxide, 25 parts of magnesium hydroxide, 1.5 parts of lubricant, 1.5 parts of antioxidant and 5 parts of homemade wear-resistant agent are mixed and kneaded, then extruded and granulated and irradiated to obtain irradiated flexible halogen-free wear-resistant cable material.

[0086] Embodiment 5:

[0087] The preparation method is the same as that of Example 3, except that:

[0088] 12 parts of linear low-density polyethylene, 28 parts of ethylene-vinyl acetate copolymer, 10 parts of polyolefin elastomer, 8 parts of polyolefin elastomer grafted maleic anhydride, 8 parts of toughening agent, 25 parts of aluminum hydroxide, 25 parts of magnesium hydroxide, 1.5 parts of lubricant, 1.5 parts of antioxidant and 5 parts of homemade wear-resistant agent are mixed and kneaded, then extruded and granulated and irradiated to obtain irradiated flexible halogen-free wear-resistant cable material.

[0089] Embodiment 6:

[0090] The preparation method is the same as that of Example 3, except that:

[0091] 15 parts of linear low-density polyethylene, 25 parts of ethylene-vinyl acetate copolymer, 10 parts of polyolefin elastomer, 6 parts of polyolefin elastomer grafted maleic anhydride, 10 parts of toughening agent, 25 parts of aluminum hydroxide, 25 parts of magnesium hydroxide, 1.5 parts of lubricant, 1.5 parts of antioxidant and 5 parts of homemade wear-resistant agent are mixed and kneaded, then extruded and granulated and irradiated to obtain irradiated flexible halogen-free wear-resistant cable material.

[0092] Embodiment 7:

[0093] The preparation method is the same as that of Example 3, except that:

[0094] 12 parts of linear low-density polyethylene, 28 parts of ethylene-vinyl acetate copolymer, 10 parts of polyolefin elastomer, 6 parts of polyolefin elastomer grafted maleic anhydride, 10 parts of toughening agent, 25 parts of aluminum hydroxide, 25 parts of magnesium hydroxide, 1.5 parts of lubricant, 1.5 parts of antioxidant and 5 parts of homemade wear-resistant agent are mixed and kneaded, then extruded and granulated and irradiated to obtain irradiated flexible halogen-free wear-resistant cable material.

[0095] Embodiment 8:

[0096] The preparation method is the same as that of Example 3, except that:

[0097] 10 parts of linear low-density polyethylene, 30 parts of ethylene-vinyl acetate copolymer, 10 parts of polyolefin elastomer, 6 parts of polyolefin elastomer grafted maleic anhydride, 10 parts of toughening agent, 25 parts of aluminum hydroxide, 25 parts of magnesium hydroxide, 1.5 parts of lubricant, 1.5 parts of antioxidant and 5 parts of homemade wear-resistant agent are mixed and kneaded, then extruded and granulated and irradiated to obtain irradiated flexible halogen-free wear-resistant cable material.

[0098] Comparative Example 1:

[0099] The preparation method is the same as that of Example 3, except that:

[0100] 15 parts of linear low-density polyethylene, 30 parts of ethylene-vinyl acetate copolymer, 10 parts of polyolefin elastomer, 8 parts of polyolefin elastomer grafted maleic anhydride, 8 parts of toughening agent, 25 parts of aluminum hydroxide, 25 parts of magnesium hydroxide, 1.5 parts of lubricant and 1.5 parts of antioxidant are mixed and kneaded, then extruded and granulated and irradiated to obtain irradiated flexible halogen-free wear-resistant cable material.

[0101] Comparative Example 2:

[0102] The preparation method is the same as that of Example 3, except that:

[0103] 15 parts of linear low-density polyethylene, 25 parts of ethylene-vinyl acetate copolymer, 10 parts of polyolefin elastomer, 8 parts of polyolefin elastomer grafted maleic anhydride, 8 parts of toughening agent, 27.5 parts of aluminum hydroxide, 27.5 parts of magnesium hydroxide, 1.5 parts of lubricant and 1.5 parts of antioxidant are mixed and kneaded, then extruded and granulated and irradiated to obtain irradiated flexible halogen-free wear-resistant cable material.

[0104] Comparative Example 3:

[0105] The preparation method is the same as that of Example 3, except that:

[0106] 12 parts of linear low-density polyethylene, 28 parts of ethylene-vinyl acetate copolymer, 10 parts of polyolefin elastomer, 8 parts of polyolefin elastomer grafted maleic anhydride, 8 parts of toughening agent, 25 parts of aluminum hydroxide, 25 parts of magnesium hydroxide, 1.5 parts of lubricant and 1.5 parts of antioxidant are mixed and kneaded, then extruded and granulated and irradiated to obtain irradiated flexible halogen-free wear-resistant cable material.

[0107] Comparative Example 4:

[0108] Weigh 2600 parts of fully ground nano titanium dioxide powder and add them to the reaction device, add appropriate amount of deionized water, and ultrasonically disperse for 0.5h. Then add 2.1 parts of sodium hydroxide to adjust the solution pH to 9, and then stir at a constant speed for 2h. After the reaction is completed, let it stand for 1h, separate the particles with a particle size greater than 1.5μm by centrifugation, and retain the reaction solution. Add the reaction solution to the reaction device to ensure that the reaction device is constant temperature. Add 28 parts of Na2ZnO2 solution to it, and then gradually add 2.3 parts of hydrochloric acid to it within 1.5h so that the solution reaches a certain pH value. Then quickly filter and wash the reaction solution to obtain a filter cake. Put the obtained filter cake into an oven and dry it at 150℃ for 12h. Finally, grind the obtained powder fully to obtain titanium dioxide powder coated with zinc oxide, in which the weight of sodium metazincrate is 1%-2.5% of the nano titanium dioxide powder. Active silicon micropowder, silane coupling agent and molybdenum disulfide are added to an ethanol solution and ultrasonically stirred for 5-7 hours, and then the coated titanium dioxide powder is added and ultrasonically stirred for 2-3 hours to form a mixture. The mixture is vacuum dried to obtain a self-made wear-resistant agent.

[0109] 15 parts of linear low-density polyethylene, 25 parts of ethylene-vinyl acetate copolymer, 10 parts of polyolefin elastomer, 8 parts of polyolefin elastomer grafted maleic anhydride, 8 parts of toughening agent, 25 parts of aluminum hydroxide, 25 parts of magnesium hydroxide, 1.5 parts of lubricant, 1.5 parts of antioxidant and 5 parts of homemade wear-resistant agent are mixed and kneaded, then extruded and granulated and irradiated to obtain irradiated flexible halogen-free wear-resistant cable material.

[0110] Comparative Example 5:

[0111] Weigh 3000 parts of fully ground nano titanium dioxide powder and add them to the reaction device, add appropriate amount of deionized water, and ultrasonically disperse for 0.5h. Then add 2.3 parts of sodium hydroxide to adjust the solution pH to 9, and then stir at a constant speed for 2h. After the reaction is completed, let it stand for 1h, separate the particles with a particle size greater than 1.5μm by centrifugation, and retain the reaction solution. Add the reaction solution to the reaction device to ensure that the reaction device is constant temperature. Add 80 parts of Na2ZnO2 solution to it, and then gradually add 2.5 parts of hydrochloric acid to it within 1.5h so that the solution reaches a certain pH value. Then quickly filter and wash the reaction solution to obtain a filter cake. Put the obtained filter cake into an oven and dry it at 150℃ for 12h. Finally, grind the obtained powder fully to obtain titanium dioxide powder coated with zinc oxide, in which the weight of sodium metazincrate is 1%-2.5% of the nano titanium dioxide powder. Active silicon micropowder, silane coupling agent and molybdenum disulfide are added to an ethanol solution and ultrasonically stirred for 5-7 hours, and then the coated titanium dioxide powder is added and ultrasonically stirred for 2-3 hours to form a mixture. The mixture is vacuum dried to obtain a self-made wear-resistant agent.

[0112] 15 parts of linear low-density polyethylene, 25 parts of ethylene-vinyl acetate copolymer, 10 parts of polyolefin elastomer, 8 parts of polyolefin elastomer grafted maleic anhydride, 8 parts of toughening agent, 25 parts of aluminum hydroxide, 25 parts of magnesium hydroxide, 1.5 parts of lubricant, 1.5 parts of antioxidant and 5 parts of homemade wear-resistant agent are mixed and kneaded, then extruded and granulated and irradiated to obtain irradiated flexible halogen-free wear-resistant cable material.

[0113] The components and important preparation variables of Examples 1-8 and Comparative Examples 1-5 are summarized in Table 1.

[0114] Table 1. Components of Examples 1-8 and Comparative Examples 1-5 of the present invention

[0115]

[0116] According to relevant test standards, the irradiated flexible halogen-free wear-resistant cable materials in the above Examples 1-8 and Comparative Examples 1-5 were tested for tensile strength, elongation at break, hardness, scratch resistance and flame retardancy, and the test results were recorded in the following Table 2:

[0117] Table 2. Performance of Examples 1-8 and Comparative Examples 1-5

[0118]

[0119] According to the test results above, it can be seen that 5 parts of wear-resistant agent are added in Examples 1-8. The tensile strength of Example 4 is 12.88MPa, the elongation at break is 374%, the change rate of tensile strength after aging is -7.2%, the change rate of elongation at break after aging is -20.3%, and the flame retardant grade is V-0; compared with Example 4, Comparative Example 2 does not add a homemade wear-resistant agent, but adds multiple parts of flame retardant. The elongation at break of Comparative Example 2 is 294%, which is significantly lower than that of Example 2. The change rate of tensile strength after aging and the elongation at break after aging are significantly lower than those of Example 2, and its scratch resistance is also reduced. The results show that the mechanical properties of Comparative Example 2 are reduced, and the number of wear resistance times is also greatly reduced. This result shows that the homemade wear-resistant agent has good compatibility and can have good dispersibility in the resin matrix. Among them, zinc oxide-coated titanium dioxide and molybdenum disulfide form a protective film on the surface of the material, so it has a lubricating effect, improves fluidity and formability, and improves the surface quality and wear resistance of the product. Comparative Example 3 did not add the homemade wear-resistant agent. The experimental results showed that the mechanical properties of Comparative Example 3 decreased after aging, and the number of scratch resistance decreased to 95 times; compared with Comparative Example 3, Example 3 added 5 parts of homemade wear-resistant agent, and its tensile strength was 12MPa, the elongation at break was 392%, the tensile strength change rate after aging was -6.1%, the elongation at break change rate after aging was -16.1%, and the flame retardant grade was V-0, indicating that the homemade wear-resistant agent has good flame retardant synergy, and zinc oxide coated titanium dioxide promotes carbonization of the material, thereby improving the flame retardant properties of the cable material.The components of the wear-resistant agent in Example 1, Example 2 and Example 3 are added in the same component ratio. The experimental results show that Example 1, Example 2 and Example 3 all have good tensile strength and elongation at break, and the hardness of the three is not much different. The number of scratch resistance changes accordingly, but the data are excellent in the overall experiment; in Example 3 and Example 4, the formula of the wear-resistant agent is the same, and the ratio of the basic materials added to the two is different. The physical and mechanical properties and the number of scratch resistance of Example 4 are better than those of Example 3 as a whole. The experimental data show that under the action of the same wear-resistant agent, the added material formula has a greater influence on the physical and mechanical properties and scratch resistance of the prepared irradiated flexible halogen-free wear-resistant cable material; in Comparative Example 4, the addition amount of nano titanium dioxide is 2600 parts, and in Comparative Example 5, the addition amount of nano titanium dioxide is 3000 parts, and the addition amount of nano titanium dioxide is not within the 2700-29 00 parts, the wear-resistant agent prepared in Example 4 and the wear-resistant agent prepared in Example 5 added materials such as nano-silicon dioxide which were different from the parts of this formula. After the scratch resistance test, the scratch resistance of the irradiated flexible halogen-free wear-resistant cable material prepared in Example 4 was 123 times, and the scratch resistance of the irradiated flexible halogen-free wear-resistant cable material prepared in Example 5 was 113 times. Compared with 76 times of scratch resistance in Example 1 without adding wear-resistant agent, 98 times of scratch resistance in Example 2 without adding wear-resistant agent, and 95 times of scratch resistance in Example 3 without adding wear-resistant agent, it can be obviously seen that the scratch resistance of Comparative Examples 4 and 5 is slightly increased, but because the addition amount of materials such as nano-silicon dioxide does not conform to this formula, the prepared wear-resistant agent does not produce corresponding wear-resistant effect, and the wear resistance of the prepared irradiated flexible halogen-free wear-resistant cable material is not significantly improved, and the scratch resistance performance requirement cannot be met. Therefore, the irradiated flexible halogen-free wear-resistant cable material proposed in the present invention not only has good processing performance, mechanical properties and flame retardant properties, but also has good wear resistance, and has broad application prospects in the industrial cable and new energy cable industries.

[0120] The above are only preferred embodiments of the present invention, and do not limit the patent scope of the present invention. For those skilled in the art, the present invention may have various changes and variations. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the patent protection scope of the present invention.

Claims

1. A wear-resistant agent, characterized in that: The ingredients of the wear-resistant agent are measured by weight, including Nano titanium dioxide 2700-2900 parts; 2.1-2.3 parts of alkali; 28-70 parts of sodium metazincate; 2.3-2.5 parts of inorganic acid; The ingredients of the wear-resistant agent also include active silicon micropowder, silane coupling agent, molybdenum disulfide and organic solvent.

2. The anti-wear agent according to claim 1, characterized in that The active silicon micropowder is at least one of epoxy-modified active silicon micropowder, acyloxy-modified active silicon micropowder and vinyl-modified active silicon micropowder.

3. The anti-wear agent according to claim 1, characterized in that The silane coupling agent is at least one of 3-aminopropyltriethoxysilane, γ-aminopropyltriethoxysilane and γ-glycidyloxypropyltrimethoxysilane.

4. The anti-wear agent according to claim 1, characterized in that The base is a soluble base.

5. The anti-wear agent according to claim 1, characterized in that The inorganic acid is at least one of hydrochloric acid and sulfuric acid.

6. The anti-wear agent according to claim 1, characterized in that The organic solvent is at least one of ethanol, acetone, methanol, toluene and ethyl acetate.

7. An irradiated flexible halogen-free wear-resistant cable material, characterized in that: The ingredients of the irradiated flexible halogen-free wear-resistant cable material are measured in parts by weight and include: LLDPE 10-20 parts; EVA 25-40 parts; POE 10-20 parts; Compatibilizer 5-10 parts; 5-10 parts of toughening agent; 40-60 parts of compound flame retardant; 1-2 parts of lubricant; 1-2 parts of antioxidant; 5-10 parts of the anti-wear agent according to claims 1 to 6.

8. The irradiated flexible halogen-free wear-resistant cable material according to claim 7, characterized in that: The LLDPE has a melt flow rate of 3-8 g / 10 min at 190° C. / 2.16 kg.

9. The irradiated flexible halogen-free wear-resistant cable material according to claim 7, characterized in that: The EVA has a melt flow rate of 2-5 g / 10 min at 190° C. / 2.16 kg.

10. The flame-retardant, low-smoke, oil-resistant TPE sheath material irradiated flexible halogen-free wear-resistant cable material according to claim 7, characterized in that: The melt flow rate of the POE at 190° C. / 2.16 kg is 1-2 g / 10 min.

11. The irradiated flexible halogen-free wear-resistant cable material according to claim 7, characterized in that: The compatibilizer includes at least one of maleic anhydride grafted PE, maleic anhydride grafted EVA and maleic anhydride grafted POE.

12. The irradiated flexible halogen-free wear-resistant cable material according to claim 7, characterized in that: The toughening agent includes at least one of vinyl silicone rubber, fluororubber and other toughening agents.

13. The irradiated flexible halogen-free wear-resistant cable material according to claim 7, characterized in that: The compound flame retardant is compounded with an inorganic flame retardant, and the inorganic flame retardant includes aluminum hydroxide and magnesium hydroxide, wherein the weight ratio of aluminum hydroxide to magnesium hydroxide is (20-30): (20-30).

14. The irradiated flexible halogen-free wear-resistant cable material according to claim 7, characterized in that: The lubricant is at least one of fatty acids, fatty amides, metal soaps, and fatty alcohols.

15. A method for preparing an irradiated flexible halogen-free wear-resistant cable material, characterized in that: The following steps are involved: Preparation of anti-wear agent: preparing the anti-wear agent by solution method using the nano titanium dioxide, alkali, sodium metazincate, acid, active silicon powder, silane coupling agent and molybdenum disulfide as described in claims 1 to 5; Preparation of irradiated flexible halogen-free wear-resistant cable material: LLDPE, EVA, POE, maleic anhydride grafted POE, toughening agent, compound flame retardant, lubricant, antioxidant and wear agent are pre-mixed uniformly, and then mixed in an internal mixer to prepare a molten blend; the molten blend is granulated in a twin-screw-single screw pelletizer, and then cooled, dried and irradiated to finally obtain an irradiated flexible halogen-free wear-resistant cable material.

16. The method for preparing the irradiated flexible halogen-free wear-resistant cable material according to claim 15, characterized in that: The preparation method of the wear-resistant agent comprises the following steps: The nano titanium dioxide powder is dissolved in water and then ultrasonically dispersed, and then alkali is added to adjust the pH value of the solution to alkaline, the reaction is stirred and allowed to stand, and particles with a particle size greater than 1.5 μm are separated by centrifugation, and the reaction solution is retained. A certain amount of sodium metazincate solution is added to the reaction solution, and acid is added by titration after the reaction to adjust the pH value of the solution to 5.5-6.5, and then filtered and washed to obtain a filter cake, and the filter cake is heat-treated at 130-160° C. for 10-14 hours to obtain titanium dioxide powder coated with zinc oxide, wherein the weight of sodium metazincate is 1%-2.5% of the nano titanium dioxide powder; Active silicon micropowder, silane coupling agent and molybdenum disulfide are added to an organic solvent solution, ultrasonically stirred for 4-8 hours, and then titanium dioxide powder coated with zinc oxide is added, wherein the weight ratio of active silicon micropowder, silane coupling agent, molybdenum disulfide and titanium dioxide powder coated with zinc oxide is 1:2:1:1, ultrasonic stirring is continued, and after the mixture is formed, vacuum drying is performed to obtain the wear-resistant agent.

17. An irradiated flexible halogen-free wear-resistant cable, characterized in that: The cable is prepared by the preparation method of claim 7.

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