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

Abstract

The invention discloses a high-strength cold-resistant cable material and a preparation method thereof. The cable material disclosed by the invention has the advantages of high strength, cold resistance, corrosion resistance, flame retardance and the like, and is widely applied to severe cold rural areas, wind power stations, solar equipment and the like. According to the cable material, the PVC resin serves as a main raw material, nitrile rubber with excellent cold resistance is added as an auxiliary raw material, various auxiliaries are added, the comprehensive performance of a matrix is improved, the toughness of the matrix is improved through the synergistic effect of the modified filler and the macromolecular plasticizer, and then the matrix still has good performance at low temperature; and the matrix has the advantages of high strength, cold resistance, corrosion resistance, flame retardance and the like.

Description

Technical Field

[0001] The invention relates to the field of cable materials, and in particular to a high-strength cold-resistant cable material and a preparation method thereof. Background Art

[0002] Cables are indispensable materials for industrial and agricultural production and modern life. my country is the world's largest cable producer, and the cable industry plays a very important role in my country's national economy. However, the impact strength of cable materials on the market is not high under low temperature conditions. Polyvinyl chloride is one of the commonly used raw materials for cable materials. It has the disadvantages of being hard, brittle, and lacking in impact resistance and flame retardancy. The effect of temperature on its products is very obvious. In low temperature environments, polyvinyl chloride products will quickly become brittle, and the products will not only become hard but also brittle. When subjected to external forces, they are very likely to break.

[0003] Traditional cable materials achieve toughening of polyvinyl chloride resin by adding rigid particles, especially inorganic rigid particles. Although it is widely accepted, the toughening effect of inorganic rigid particles is not significant, and there are problems such as poor compatibility between inorganic particles and resin. In addition, a large amount of small molecule plasticizers are added to the soft polyvinyl chloride material during its preparation. These plasticizers will migrate when used in a low temperature environment. As time goes by, PVC products will also become brittle and hard. Therefore, it is necessary to improve the dispersibility of inorganic particles in the resin to improve the toughening effect so that it still has good performance under cold conditions. At the same time, macromolecular plasticizers are used to avoid problems such as precipitation of plasticization. Therefore, it is necessary to develop a cable material with high strength, cold resistance, flame retardancy and corrosion resistance to meet actual needs. Summary of the invention

[0004] In order to solve the above technical problems, the present invention provides a high-strength cold-resistant cable material and a preparation method thereof.

[0005] The purpose of the present invention can be achieved through the following technical solutions: A high-strength cold-resistant cable material, comprising the following raw materials in parts by weight: 50-70 parts of PVC resin, 20-30 parts of nitrile rubber, 10-15 parts of modified filler, 0.5-1.2 parts of lubricant, 3-5 parts of antioxidant, 2-4 parts of stabilizer, 2-6 parts of macromolecular plasticizer, 0.4-1 parts of vulcanizer, and 0.1-0.4 parts of accelerator; The modified filler is prepared by the following steps: Step A1, adding 1,2,5,6-diepoxyhexane and sodium hydroxide into a reactor containing ethanol and stirring to mix evenly, then adding pentaerythritol phosphate and stirring evenly, raising the system temperature to 30-40° C., continuing the reaction for 3-5 hours, and after the reaction is completed, cooling to room temperature, centrifuging, washing, and drying to obtain a terminal hydroxyl flame retardant chain extender; Furthermore, the usage ratio of 1,2,5,6-diepoxyhexane, pentaerythritol phosphate, sodium hydroxide and ethanol is 0.05-0.15 mol: 0.011-0.031 mol: 0.1-0.2 g: 50-100 mL.

[0006] Step A2, mixing boric acid and trihydroxypropane in a reactor and stirring evenly, then adding the silicon dioxide solution into the reactor and mixing evenly, and heating to 80-90°C, stirring continuously for 20-40 minutes, heating to 400-600°C under nitrogen conditions, keeping warm for 2-3 hours, and then cooling, and then transferring the mixture to a reactor, keeping warm at 1400-1500°C for 1-3 hours, and then cooling, to obtain SiO2@CB4 nanomaterials; Furthermore, the dosage ratio of boric acid, trihydroxypropane and silicon dioxide solution is 0.15-0.25 mol: 0.18-0.3 mol: 30 mL, and the silicon dioxide solution is prepared by mixing and stirring nano silicon dioxide and ethanol in a dosage ratio of 0.5-1.5 g: 30 mL.

[0007] Step A3, adding SiO2@CB4 nanomaterial to the mixed solution, stirring at a speed of 1000-2000rpm for 10-15min, and then stirring at a speed of 300-600rpm for 20min, then raising the system temperature to 20-40°C, adding dibutyltin dilaurate and deionized water and stirring at a speed of 1500-2500rpm for 10-15min, raising the temperature to 45-75°C for continuous reaction for 3-5h, and then raising the temperature to 90°C for reaction for 2-4h to obtain a mixture, and then adding polyvinyl alcohol (weight average molecular weight of 30000) to the mixture and stirring for 30min. After the reaction is completed, centrifuging, washing, and drying to obtain a modified filler; Furthermore, the addition amount of SiO2@CB4 nanomaterial is 0.05-0.2‰ of the mass of isophorone diisocyanate; Furthermore, the mixed liquid is composed of the following components in the following mass ratios: 20%-70% of isophorone diisocyanate, 10%-80% of polyethylene adipate glycol (number average molecular weight of 1000-3000), and 5%-15% of terminal hydroxyl flame retardant chain extender; Furthermore, the addition amounts of dibutyltin dilaurate and deionized water are 100-300ppm and 40%-60% of the total mass of the mixed solution, respectively, and the amount of polyvinyl alcohol is 0.5%-1% of the total mass of the mixture in step A3.

[0008] The macromolecular plasticizer is prepared by the following steps: Step B1, under nitrogen conditions, methanetriacetic acid, 2-hydroxymethylmalonic acid and p-toluenesulfonic acid are added to a reactor, stirred and mixed evenly, and heated to 120-140° C. and refluxed for 2-4 hours, recorded as mixture 1; methanetriacetic acid, 2-hydroxymethylmalonic acid and p-toluenesulfonic acid are then added to mixture 1 to continue the reaction for 2 hours. After the reaction is completed, the nitrogen is stopped, and the temperature is maintained to reduce pressure and remove water, which is recorded as mixture 2; 2-hydroxymethylmalonic acid and p-toluenesulfonic acid are added to mixture 2, nitrogen is introduced, the temperature is maintained to continue the reaction for 2 hours, and then the reduced pressure reaction is performed for 2 hours. When no water is distilled out, it is cooled to room temperature, 10 mL of acetone is added, stirred and mixed for 10 minutes, and then recrystallized, filtered, and dried to obtain a carboxyl-terminated hyperbranched polyester; Further, the usage ratio of 2-hydroxymethylmalonic acid and p-toluenesulfonic acid in the carboxyl-terminated hyperbranched polyester is 0.28-0.44 mol: 0.08-0.24 g; Furthermore, the usage ratio of methanetriacetic acid, 2-hydroxymethylmalonic acid and p-toluenesulfonic acid in mixture 1 is 0.07-0.21 mol: 0.01-0.03 mol: 0.02-0.06 g, and the usage ratio of methanetriacetic acid, 2-hydroxymethylmalonic acid and p-toluenesulfonic acid in mixture 2 is 0.14-0.22 mol: 0.02-0.06 mol: 0.04-0.12 g.

[0009] Step B2, under nitrogen conditions, add the terminal carboxyl hyperbranched polyester, tridecanol and p-toluenesulfonic acid into a reactor, stir and mix evenly, heat to 130° C. and reflux for 2-3 hours, stop introducing nitrogen, maintain the temperature and reduce pressure to remove water, after anhydrous distillation, cool to room temperature, add 20 mL of acetone, stir and mix for 20 minutes, recrystallize, filter and dry to obtain a macromolecular plasticizer; Furthermore, the usage ratio of the carboxyl-terminated hyperbranched polyester, tridecanol and p-toluenesulfonic acid is 0.5-2 g: 4-10 g: 0.03-0.1 g.

[0010] A method for preparing a high-strength cold-resistant cable material comprises the following steps: Step S1, weighing raw materials by weight, stirring and mixing PVC resin, modified filler, antioxidant, lubricant and macromolecular plasticizer, kneading in a kneader at a temperature of 120-140° C. for 5-10 minutes, taking out and cooling, and obtaining a premix; Step S2: After the premix is ​​evenly mixed with the remaining raw materials, it is kneaded and granulated in a twin-screw extruder at a kneading temperature of 140-160° C. to obtain a high-strength cold-resistant cable material.

[0011] Beneficial effects of the present invention: The cable material in the present invention has the advantages of high strength, cold resistance, corrosion resistance, flame retardancy, etc., and is widely used in cold rural areas, wind power stations, solar energy equipment, etc. The cable material of the present application uses PVC resin as the main raw material, and adds nitrile rubber with excellent cold resistance as an auxiliary raw material and various additives to improve the comprehensive performance of the matrix. The addition of modified fillers and macromolecular plasticizers synergistically improves the toughness of the matrix, thereby making the matrix still have good performance at low temperatures, and making the matrix have the advantages of high strength, cold resistance, corrosion resistance, flame retardancy, etc.

[0012] In the modified filler, firstly, the terminal hydroxyl group in pentaerythritol phosphate and the terminal epoxy group in 1,2,5,6-diepoxyhexane are used to undergo epoxidation reaction under alkaline conditions, thereby introducing phosphate into the chain extender to synthesize a terminal hydroxyl flame retardant chain extender; secondly, using boric acid and trihydroxypropane as raw materials, a layer of boron carbide is coated on the surface of silica to synthesize SiO2@CB4 nanomaterials; finally, the terminal hydroxyl flame retardant chain extender is used as one of the materials for synthesizing polyurethane, and a layer of polyurethane is coated on the surface of the SiO2@CB4 nanomaterial. In the modified filler, silica is used as the modified matrix and boron carbide is coated on its surface, which not only improves the dispersion of silica in the matrix, but also works synergistically to enhance the strength of the matrix; silica as an inorganic rigid particle mainly plays a stress concentration role in the matrix. When the matrix is ​​subjected to external force, silica can evenly disperse the external force in the matrix to avoid fracture at the force-bearing position, and can cause plastic deformation of the matrix, thereby absorbing a large amount of energy, thereby improving the toughness of the matrix; and the presence of polyurethane on the surface of SiO2@CB4 nanomaterials Not only the toughness of the matrix is ​​further improved, but also the flame retardant performance of the matrix is ​​improved. Among them, the phosphate structure contained in the polyurethane structure can decompose to produce phosphate free radicals and phosphate acetals during combustion. They can react with oxygen to form a protective layer on the surface of the matrix, thereby inhibiting the continuous combustion of the matrix, and can also promote the carbonization of the matrix to form a dense carbon layer on the surface of the matrix, thereby isolating oxygen and preventing the spread of flames; in addition, the soft elastic nature of the polyurethane also improves the toughness of the matrix, so that the matrix still has good mechanical properties at low temperatures.

[0013] In the macromolecular plasticizer, first, an esterification reaction occurs between methanetriacetic acid and 2-hydroxymethylmalonic acid to synthesize a carboxyl-terminated hyperbranched polyester; secondly, an esterification reaction occurs again between the carboxyl-terminated hyperbranched polyester and tridecanol, thereby introducing a long-chain hydrophobic alkyl group into the plasticizer. The macromolecular plasticizer introduces a long-chain alcohol-based structure, which improves the cold resistance and plasticizing efficiency of the matrix; the long-chain structure can also be entangled with the PVC resin in the matrix, thereby increasing the cross-linking density of the matrix, further improving the toughness of the matrix, and the long-chain hydrophobic structure also improves the hydrophobicity of the matrix surface, forming a hydrophobic film layer on the matrix surface, effectively inhibiting the corrosion of the matrix surface caused by corrosive substances in the air, thereby improving the corrosion resistance of the matrix; in addition, the hyperbranched structure of the plasticizer makes it contain a larger molecular weight, avoiding the migration, volatilization, dissolution and other phenomena of the plasticizer in the matrix due to the small molecular weight, and avoiding the environmental pollution caused by the above reasons, so that the PVC product can play a better role. DETAILED DESCRIPTION

[0014] The technical solutions in the embodiments of the present invention are described clearly and completely below. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0015] Example 1 1) The modified filler is prepared by the following steps: Step A1, adding 0.05 mol 1,2,5,6-diepoxyhexane and 0.1 g sodium hydroxide into a reactor containing 50 mL ethanol and stirring to mix evenly, then adding 0.011 mol pentaerythritol phosphate and stirring evenly, raising the system temperature to 30° C., continuing the reaction for 3 h, and after the reaction is completed, cooling to room temperature, centrifuging, washing, and drying to obtain a terminal hydroxyl flame retardant chain extender; Step A2, 0.15 mol of boric acid and 0.18 mol of trihydroxypropane are mixed and stirred in a reactor, and then 30 mL of silica solution is added into the reactor and mixed and heated to 80°C, and stirred continuously for 20 min. Under nitrogen conditions, the temperature is raised to 400°C and kept warm for 2 h, and then cooled. The mixture is then transferred to a reactor, kept warm at 1400°C for 1 h, and then cooled to obtain SiO2@CB4 nanomaterials. The silica solution is prepared by mixing and stirring nano-silicon dioxide and ethanol in a dosage ratio of 0.5 g:30 mL; Step A3, adding SiO2@CB4 nanomaterials to the mixed solution, stirring at a speed of 1000 rpm for 10 min, stirring at a speed of 300 rpm for 20 min, then raising the system temperature to 25°C, adding dibutyltin dilaurate and deionized water and stirring at a speed of 1500 rpm for 10 min, heating to 45°C and continuing the reaction for 3 h, then raising the temperature to 90°C and reacting for 2 h to obtain a mixture, then adding polyvinyl alcohol (weight average molecular weight of 30,000) to the mixture and stirring for 30 min. After the reaction is completed, ionizing The modified filler is obtained by centrifuging, washing and drying. The amount of SiO2@CB4 nanomaterial added is 0.05-0.2‰ of the mass of isophorone diisocyanate. The mixed solution is composed of the following components in the following mass ratios: 50% of isophorone diisocyanate, 35% of polyethylene adipate glycol (number average molecular weight is 1000), and 15% of terminal hydroxyl flame retardant chain extender. The amounts of dibutyl tin dilaurate and deionized water added are 100ppm and 40% of the total mass of the mixed solution, respectively. The amount of polyvinyl alcohol used is 0.5% of the total mass of the mixture in step A3.

[0016] 2) The macromolecular plasticizer is prepared by the following steps: Step B1, under nitrogen conditions, 0.07 mol of methanetriacetic acid, 0.01 mol of 2-hydroxymethylmalonic acid and 0.02 g of p-toluenesulfonic acid were added to a reactor and stirred and mixed evenly, and heated to 120 ° C. and refluxed for 2 hours, recorded as mixture 1; 0.14 mol of methanetriacetic acid, 0.02 mol of 2-hydroxymethylmalonic acid and 0.04 g of p-toluenesulfonic acid were added to mixture 1 and the reaction was continued for 2 hours. After the reaction was completed, the nitrogen was stopped, and the temperature was maintained to reduce pressure and remove water, which was recorded as mixture 2; 0.28 mol of 2-hydroxymethylmalonic acid and 0.08 g of p-toluenesulfonic acid were added to mixture 2, nitrogen was introduced, the temperature was maintained to continue to react for 2 hours, and then the reaction was reduced in pressure for 2 hours. When no water was distilled out, it was cooled to room temperature, 10 mL of acetone was added, stirred and mixed for 10 minutes, recrystallized, filtered, and dried to obtain a carboxyl-terminated hyperbranched polyester; Step B2, under nitrogen conditions, 0.5g of terminal carboxyl hyperbranched polyester, 4g of tridecanol and 0.03g of p-toluenesulfonic acid were added to the reactor and stirred and mixed evenly, and heated to 130°C and refluxed for 2h, then the nitrogen was stopped, and the temperature was maintained to reduce pressure and remove water. After anhydrous distillation, it was cooled to room temperature, 20mL of acetone was added and stirred for 20min, recrystallized, filtered and dried to obtain a macromolecular plasticizer.

[0017] Example 2 1) The modified filler is prepared by the following steps: Step A1, adding 0.1 mol 1,2,5,6-diepoxyhexane and 0.15 g sodium hydroxide into a reactor containing 75 mL ethanol and stirring to mix evenly, then adding 0.021 mol pentaerythritol phosphate and stirring evenly, raising the system temperature to 35° C., continuing the reaction for 4 hours, and after the reaction is completed, cooling to room temperature, centrifuging, washing, and drying to obtain a terminal hydroxyl flame retardant chain extender; Step A2, 0.2 mol of boric acid and 0.24 mol of trihydroxypropane are mixed and stirred evenly in a reactor, and then 30 mL of silica solution is added into the reactor and mixed evenly, and heated to 85°C, and stirred continuously for 30 min, and heated to 500°C under nitrogen conditions, and kept warm for 2.5 h and then cooled, and then the mixture is transferred to a reactor, kept warm at 1450°C for 2 h and then cooled to obtain SiO2@CB4 nanomaterial, wherein the silica solution is prepared by mixing and stirring nano-silicon dioxide and ethanol in a dosage ratio of 1 g:30 mL; Step A3, add SiO2@CB4 nanomaterials to the mixed solution, stir at 1500 rpm for 10 min, then stir at 400 rpm for 20 min, then raise the system temperature to 30°C, add dibutyltin dilaurate and deionized water and stir at 2000 rpm for 10 min, then raise the temperature to 55°C and continue the reaction for 4 h, then raise the temperature to 90°C and react for 3 h to obtain a mixture, then add polyvinyl alcohol (weight average molecular weight of 30,000) to the mixture and stir for 30 min, after the reaction is completed , centrifuged, washed and dried to obtain the modified filler; the amount of SiO2@CB4 nanomaterial added is 0.1‰ of the mass of isophorone diisocyanate; the mixed solution is composed of the following components in the following mass ratio: 50% of isophorone diisocyanate, 40% of polyethylene adipate glycol (number average molecular weight is 2000), and 10% of terminal hydroxyl flame retardant chain extender; the amounts of dibutyl tin dilaurate and deionized water added are 200ppm and 50% of the total mass of the mixed solution, respectively, and the amount of polyvinyl alcohol used is 0.7% of the total mass of the mixture in step A3.

[0018] 2) The macromolecular plasticizer is prepared by the following steps: Step B1, under nitrogen conditions, 0.14 mol of methanetriacetic acid, 0.02 mol of 2-hydroxymethylmalonic acid and 0.04 g of p-toluenesulfonic acid were added to a reactor and stirred and mixed evenly, and heated to 130 ° C. and refluxed for 3 h, recorded as mixture 1; 0.18 mol of methanetriacetic acid, 0.04 mol of 2-hydroxymethylmalonic acid and 0.08 g of p-toluenesulfonic acid were added to mixture 1 and the reaction was continued for 2 h. After the reaction was completed, the nitrogen was stopped, and the temperature was maintained to reduce pressure and remove water, which was recorded as mixture 2; 0.36 mol of 2-hydroxymethylmalonic acid and 0.16 g of p-toluenesulfonic acid were added to mixture 2, nitrogen was introduced, the temperature was maintained to continue to react for 2 h, and then the reaction was reduced in pressure for 2 h. When no water was distilled out, it was cooled to room temperature, 10 mL of acetone was added, stirred and mixed for 10 min, recrystallized, filtered, and dried to obtain a carboxyl-terminated hyperbranched polyester; Step B2, under nitrogen conditions, add 1g of terminal carboxyl hyperbranched polyester, 6g of tridecanol and 0.07g of p-toluenesulfonic acid into a reactor and stir and mix evenly, and heat to 130°C and reflux for 2.5h, stop passing nitrogen, maintain the temperature and reduce pressure to remove water, after anhydrous distillation, cool to room temperature, add 20mL of acetone and stir and mix for 20min, recrystallize, filter and dry to obtain a macromolecular plasticizer.

[0019] Example 3 1) The modified filler is prepared by the following steps: Step A1, adding 0.15 mol 1,2,5,6-diepoxyhexane and 0.2 g sodium hydroxide into a reactor containing 100 mL ethanol and stirring to mix evenly, then adding 0.031 mol pentaerythritol phosphate and stirring evenly, raising the system temperature to 40° C., continuing the reaction for 5 h, and after the reaction is completed, cooling to room temperature, centrifuging, washing, and drying to obtain a hydroxyl-terminated flame retardant chain extender; Step A2, 0.25 mol of boric acid and 0.3 mol of trihydroxypropane are mixed and stirred in a reactor, and then 30 mL of silica solution is added into the reactor and mixed and heated to 90° C., and stirred continuously for 40 min. Under nitrogen conditions, the temperature is raised to 600° C. and kept warm for 3 h, and then cooled. The mixture is then transferred to a reactor, kept warm at 1500° C. for 3 h, and then cooled to obtain SiO2@CB4 nanomaterials. The silica solution is prepared by mixing and stirring nano-silicon dioxide and ethanol in a dosage ratio of 1.5 g:30 mL; Step A3, add SiO2@CB4 nanomaterials to the mixed solution, stir at 2000 rpm for 15 min, then stir at 600 rpm for 20 min, then raise the system temperature to 40°C, add dibutyltin dilaurate and deionized water and stir at 2500 rpm for 15 min, then raise the temperature to 75°C and continue the reaction for 5 h, then raise the temperature to 90°C and react for 4 h to obtain a mixture, then add polyvinyl alcohol (weight average molecular weight of 30,000) to the mixture and stir for 30 min, and wait for the reaction to complete. After beaming, centrifugation, washing and drying are performed to obtain the modified filler; the addition amount of SiO2@CB4 nanomaterial is 0.2‰ of the mass of isophorone diisocyanate; the mixed solution is composed of the following components in the following mass ratio: 45% of isophorone diisocyanate, 50% of polyethylene adipate glycol (number average molecular weight is 3000), and 5% of terminal hydroxyl flame retardant chain extender; the addition amounts of dibutyl tin dilaurate and deionized water are 300ppm and 60% of the total mass of the mixed solution, respectively, and the amount of polyvinyl alcohol is 1% of the total mass of the mixture in step A3.

[0020] 2) The macromolecular plasticizer is prepared by the following steps: Step B1, under nitrogen conditions, 0.21mol of methanetriacetic acid, 0.03mol of 2-hydroxymethylmalonic acid and 0.06g of p-toluenesulfonic acid were added to a reactor and stirred and mixed evenly, and heated to 140°C and refluxed for 4h, recorded as mixture 1; 0.22mol of methanetriacetic acid, 0.06mol of 2-hydroxymethylmalonic acid and 0.12g of p-toluenesulfonic acid were added to mixture 1 and the reaction was continued for 2h. After the reaction was completed, the nitrogen was stopped, and the temperature was maintained to reduce pressure and remove water, which was recorded as mixture 2; 0.44mol of 2-hydroxymethylmalonic acid and 0.24g of p-toluenesulfonic acid were added to mixture 2, nitrogen was introduced, the temperature was maintained to continue to react for 2h, and then the reaction was reduced in pressure for 2h. When no water was distilled out, it was cooled to room temperature, 10mL of acetone was added, stirred and mixed for 10min, recrystallized, filtered, and dried to obtain a carboxyl-terminated hyperbranched polyester; Step B2, under nitrogen conditions, add 2g of terminal carboxyl hyperbranched polyester, 10g of tridecanol and 0.1g of p-toluenesulfonic acid into a reactor and stir and mix evenly, and heat to 130°C and reflux for 3h, then stop passing nitrogen, maintain the temperature and reduce pressure to remove water, after anhydrous distillation, cool to room temperature, add 20mL of acetone and stir and mix for 20min, recrystallize, filter and dry to obtain a macromolecular plasticizer.

[0021] Example 4 A method for preparing a high-strength cold-resistant cable material comprises the following steps: 50-70 parts of PVC resin, 20-30 parts of nitrile rubber, 10-15 parts of the modified filler prepared in Example 1, 0.5-1.2 parts of magnesium stearate, 3-5 parts of antioxidant 1010, 2-4 parts of dibutyltin dilaurate, 2-6 parts of the macromolecular plasticizer prepared in Example 1, 0.4-1 parts of vulcanizing agent PDM, and 0.1-0.4 parts of accelerator CZ; Step S1, weighing raw materials by weight, stirring and mixing PVC resin, modified filler prepared in Example 1, antioxidant 1010, magnesium stearate and macromolecular plasticizer prepared in Example 1, kneading in a kneader at a temperature of 120-140° C. for 5-10 minutes, taking out and cooling, and obtaining a premix; Step S2: After the premix is ​​evenly mixed with the remaining raw materials, it is kneaded and granulated in a twin-screw extruder at a kneading temperature of 140-160° C. to obtain a high-strength cold-resistant cable material.

[0022] Example 5 A method for preparing a high-strength cold-resistant cable material comprises the following steps: 50-70 parts of PVC resin, 20-30 parts of nitrile rubber, 10-15 parts of the modified filler prepared in Example 2, 0.5-1.2 parts of magnesium stearate, 3-5 parts of antioxidant 1010, 2-4 parts of dibutyltin dilaurate, 2-6 parts of the macromolecular plasticizer prepared in Example 2, 0.4-1 parts of vulcanizing agent PDM, and 0.1-0.4 parts of accelerator CZ; Step S1, weighing raw materials by weight, stirring and mixing PVC resin, modified filler prepared in Example 2, antioxidant 1010, magnesium stearate and macromolecular plasticizer prepared in Example 2, kneading in a kneader at a temperature of 120-140° C. for 5-10 minutes, taking out and cooling, and obtaining a premix; Step S2: After the premix is ​​evenly mixed with the remaining raw materials, it is kneaded and granulated in a twin-screw extruder at a kneading temperature of 140-160° C. to obtain a high-strength cold-resistant cable material.

[0023] Example 6 A method for preparing a high-strength cold-resistant cable material comprises the following steps: 50-70 parts of PVC resin, 20-30 parts of nitrile rubber, 10-15 parts of the modified filler prepared in Example 3, 0.5-1.2 parts of magnesium stearate, 3-5 parts of antioxidant 1010, 2-4 parts of dibutyltin dilaurate, 2-6 parts of the macromolecular plasticizer prepared in Example 3, 0.4-1 parts of vulcanizing agent PDM, and 0.1-0.4 parts of accelerator CZ; Step S1, weighing raw materials by weight, stirring and mixing PVC resin, modified filler prepared in Example 3, antioxidant 1010, magnesium stearate and macromolecular plasticizer prepared in Example 3, kneading in a kneader at a temperature of 120-140° C. for 5-10 minutes, taking out and cooling, and obtaining a premix; Step S2: After the premix is ​​evenly mixed with the remaining raw materials, it is kneaded and granulated in a twin-screw extruder at a kneading temperature of 140-160° C. to obtain a high-strength cold-resistant cable material.

[0024] Comparative Example 1 This comparative example is a cable material, which differs from Example 6 in that an equal amount of silicon dioxide is used to replace the modified filler prepared in Example 3, and the rest are the same.

[0025] Comparative Example 2 This comparative example is a cable material, which differs from Example 6 in that an equal amount of dioctyl adipate is used to replace the macromolecular plasticizer prepared in Example 3, and the rest are the same.

[0026] The cable materials prepared in Examples 4-6 and Comparative Examples 1-2 were subjected to performance tests: flame retardant performance test: oxygen index was measured according to the method of GB / T 2406.2-2009 "Determination of Combustion Behavior by Oxygen Index Method for Plastics"; corrosion resistance test: power cable samples were immersed in 20wt% sodium hydroxide solution and 20wt% sodium chloride solution under the same conditions for 168h, and then taken out to observe surface corrosion; tensile strength test: tested according to standard GB / T16421-1996; low temperature impact embrittlement temperature test: tested according to GB / T5470-2008 standard; the test results are shown in the following table:

[0027] It can be seen from the above table that the cable material in the present invention has high strength, flame retardancy, corrosion resistance, and still has good mechanical properties at low temperatures.

[0028] The above contents are merely examples and explanations of the concept of the present invention. The technicians in this technical field may make various modifications or additions to the specific embodiments described or replace them in a similar manner. As long as they do not deviate from the scope defined by the concept of the invention, they should all fall within the protection scope of the present invention.

Claims

1. A high-strength cold-resistant cable material, characterized in that: 50-70 parts of PVC resin, 20-30 parts of nitrile rubber, 10-15 parts of modified filler, 0.5-1.2 parts of lubricant, 3-5 parts of antioxidant, 2-4 parts of stabilizer, 2-6 parts of macromolecular plasticizer, 0.4-1 parts of vulcanizing agent, 0.1-0.4 parts of accelerator; The modified filler is prepared by the following steps: Step A1, adding 1,2,5,6-diepoxyhexane and sodium hydroxide into a reactor containing ethanol and stirring to mix evenly, then adding pentaerythritol phosphate and stirring evenly, raising the system temperature to 30-40° C., continuing the reaction for 3-5 hours, and after the reaction is completed, cooling to room temperature, centrifuging, washing, and drying to obtain a terminal hydroxyl flame retardant chain extender; Step A2, mixing boric acid and trihydroxypropane in a reactor and stirring evenly, then adding the silicon dioxide solution into the reactor and mixing evenly, and heating to 80-90°C, stirring continuously for 20-40 minutes, heating to 400-600°C under nitrogen conditions, keeping warm for 2-3 hours, and then cooling, and then transferring the mixture to a reactor, keeping warm at 1400-1500°C for 1-3 hours, and then cooling, to obtain SiO2@CB4 nanomaterials; Step A3, adding SiO2@CB4 nanomaterial to the mixed solution, stirring at a speed of 1000-2000rpm for 10-15min, and then stirring at a speed of 300-600rpm for 20min, then raising the system temperature to 20-40°C, adding dibutyltin dilaurate and deionized water and stirring at a speed of 1500-2500rpm for 10-15min, then heating to 45-75°C and continuing to react for 3-5h, then raising the temperature to 90°C and reacting for 2-4h to obtain a mixture, and then adding polyvinyl alcohol to the mixture and stirring for 30min. After the reaction is completed, centrifuging, washing, and drying to obtain a modified filler.

2. A high-strength cold-resistant cable material according to claim 1, characterized in that: In step A1, the usage ratio of 1,2,5,6-diepoxyhexane, pentaerythritol phosphate, sodium hydroxide and ethanol is 0.05-0.15 mol: 0.011-0.031 mol: 0.1-0.2 g: 50-100 mL.

3. A high-strength cold-resistant cable material according to claim 1, characterized in that: In step A2, the dosage ratio of boric acid, trihydroxypropane and silicon dioxide solution is 0.15-0.25 mol: 0.18-0.3 mol: 30 mL, and the silicon dioxide solution is prepared by mixing and stirring nano-silicon dioxide and ethanol in a dosage ratio of 0.5-1.5 g: 30 mL.

4. A high-strength cold-resistant cable material according to claim 1, characterized in that: In step A3, the amount of SiO2@CB4 nanomaterial added is 0.05-0.2‰ of the mass of isophorone diisocyanate.

5. The high-strength cold-resistant cable material according to claim 1, characterized in that: The mixed solution in step A3 is composed of the following components in the following mass ratios: 20%-70% of isophorone diisocyanate, 10%-80% of polyethylene adipate glycol, and 5%-15% of terminal hydroxyl flame retardant chain extender.

6. A high-strength cold-resistant cable material according to claim 1, characterized in that: In step A3, the addition amounts of dibutyltin dilaurate and deionized water are 100-300ppm and 40%-60% of the total mass of the mixed solution, respectively, and the amount of polyvinyl alcohol is 0.5%-1% of the total mass of the mixture in step A3.

7. A high-strength cold-resistant cable material according to claim 1, characterized in that: The macromolecular plasticizer is prepared by the following steps: Step B1, under nitrogen conditions, methanetriacetic acid, 2-hydroxymethylmalonic acid and p-toluenesulfonic acid are added to a reactor, stirred and mixed evenly, and heated to 120-140° C. and refluxed for 2-4 hours, recorded as mixture 1; methanetriacetic acid, 2-hydroxymethylmalonic acid and p-toluenesulfonic acid are then added to mixture 1 to continue the reaction for 2 hours. After the reaction is completed, the nitrogen is stopped, and the temperature is maintained to reduce pressure and remove water, which is recorded as mixture 2; 2-hydroxymethylmalonic acid and p-toluenesulfonic acid are added to mixture 2, nitrogen is introduced, the temperature is maintained to continue the reaction for 2 hours, and then the reduced pressure reaction is performed for 2 hours. When no water is distilled out, it is cooled to room temperature, 10 mL of acetone is added, stirred and mixed for 10 minutes, and then recrystallized, filtered, and dried to obtain a carboxyl-terminated hyperbranched polyester; Step B2, under nitrogen conditions, add the terminal carboxyl hyperbranched polyester, tridecanol and p-toluenesulfonic acid into a reactor and stir and mix evenly, and heat to 130 ° C. and reflux for 2-3h, then stop passing nitrogen, maintain the temperature and reduce pressure to remove water, and after anhydrous distillation, cool to room temperature, add 20mL of acetone and stir and mix for 20min, recrystallize, filter and dry to obtain a macromolecular plasticizer.

8. A high-strength cold-resistant cable material according to claim 7, characterized in that: In step B1, the amount ratio of 2-hydroxymethylmalonic acid and p-toluenesulfonic acid in the terminal carboxyl hyperbranched polyester is 0.28-0.44 mol: 0.08-0.24 g; the amount ratio of methanetriacetic acid, 2-hydroxymethylmalonic acid and p-toluenesulfonic acid in mixture 1 is 0.07-0.21 mol: 0.01-0.03 mol: 0.02-0.06 g; the amount ratio of methanetriacetic acid, 2-hydroxymethylmalonic acid and p-toluenesulfonic acid in mixture 2 is 0.14-0.22 mol: 0.02-0.06 mol: 0.04-0.12 g.

9. A high-strength cold-resistant cable material according to claim 7, characterized in that: In step B2, the usage ratio of the terminal carboxyl hyperbranched polyester, tridecanol and p-toluenesulfonic acid is 0.5-2g:4-10g:0.03-0.1g.

10. The method for preparing a high-strength cold-resistant cable material according to claim 1, characterized in that: The following steps are involved: Step S1, weighing raw materials by weight, stirring and mixing PVC resin, modified filler, antioxidant, lubricant and macromolecular plasticizer, kneading in a kneader at a temperature of 120-140° C. for 5-10 minutes, taking out and cooling, and obtaining a premix; Step S2: After the premix is ​​evenly mixed with the remaining raw materials, it is kneaded and granulated in a twin-screw extruder at a kneading temperature of 140-160° C. to obtain a high-strength cold-resistant cable material.

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