Stretch-resistant cable sheath material and preparation method thereof

Abstract

The invention discloses a tensile cable sheath material and a preparation method thereof. Comprising the following steps: step 1, mixing polyvinyl chloride, polyurethane-acrylate and polymer microspheres at 50-60 DEG C, then adding a lubricant, an antioxidant and a cross-linking agent, uniformly stirring, then raising the temperature to 90-100 DEG C, and adding a processing aid to obtain a mixed raw material; and 2, transferring the mixed raw material to a twin-screw plasticator for plastication, after uniform plastication, carrying out water-cooling bracing, pelletizing, and drying to obtain the cable sheath material. The preparation method has the beneficial effects that the polymer microspheres are prepared by an emulsion polymerization method and are introduced into the preparation process of the cable sheath, so that the tensile property, chemical corrosion resistance and aging resistance of the sheath are effectively improved.

Description

Technical Field

[0001] This invention belongs to the field of cable technology, specifically relating to a tensile-resistant cable sheath material and its preparation method. Background Technology

[0002] With the rapid development of industries such as power and communications, cable sheath materials need to possess higher mechanical strength, weather resistance, and anti-aging properties to adapt to long-term use in complex environments. Traditional cable sheath materials typically use polyvinyl chloride (PVC) or polyethylene (PE) as the main matrix. While they possess certain flexibility and insulation properties, they have significant shortcomings in tensile strength, chemical corrosion resistance, and long-term stability. For example, ordinary PVC sheath materials are prone to plastic deformation under long-term stress or extreme temperature conditions, leading to a decline in mechanical properties; while PE materials have poor weather resistance and are prone to aging and cracking under ultraviolet radiation or humid and hot environments.

[0003] In existing technologies, to improve the performance of sheath materials, inorganic fillers (such as calcium carbonate and talc) or elastomers (such as EPDM rubber) are typically added to enhance mechanical properties. However, these methods often lead to deterioration of material processing performance or uneven filler dispersion, affecting the uniformity and durability of the final product. Furthermore, some modification techniques rely on expensive nanomaterials or complex surface treatment processes, increasing production costs and limiting their industrial application.

[0004] Therefore, in order to solve the above problems, the present invention provides a tensile cable sheath material and its preparation method. Summary of the Invention

[0005] The purpose of this invention is to overcome the shortcomings of the prior art and provide a tensile cable sheath material and its preparation method.

[0006] The objective of this invention can be achieved through the following technical solutions: A method for preparing a tensile-resistant cable sheath material includes the following steps: Step 1: Mix polyvinyl chloride, polyurethane-acrylate, and polymer microspheres at 50-60℃, then add lubricant, antioxidant, and crosslinking agent, stir evenly, then raise the temperature to 90-100℃, add processing aids, and obtain mixed raw materials; Step 2: Transfer the mixed raw materials to a twin-screw plasticizer for plasticizing. After the plasticizing is uniform, the mixture is water-cooled, stretched, and granulated. After drying, the cable sheath material is obtained.

[0007] In a more optimized manner, the raw materials for the cable sheath material include the following components: by weight, 80-100 parts of polyvinyl chloride, 40-50 parts of polyurethane-acrylate, 0.75-1 parts of polymer microspheres, 1-2 parts of lubricant, 1-2 parts of antioxidant, and 2-3 parts of crosslinking agent.

[0008] The optimized preparation process of the polymer microspheres is as follows: (1) Mix γ-valerolactone, glycidyl methacrylate, styrene, butyl acrylate, benzoyl peroxide, and emulsifier, and stir magnetically until homogeneous to obtain the oil phase; mix polyvinyl alcohol and deionized water to obtain the aqueous phase; (2) Mix the oil phase and the water phase, emulsify them using a high-speed disperser, then put them into a polymerization reactor, purge with nitrogen, raise the temperature to 70-80℃, react for 8-10 hours, cool to room temperature after the reaction is complete, filter, wash, and dry to obtain polymer microspheres.

[0009] Ideally, the mass ratio of the oil phase to the water phase is (2-5):20.

[0010] More preferably, the oil phase raw material comprises the following components: by weight, 20-30 parts γ-valerolactone, 30-40 parts glycidyl methacrylate, 30-40 parts styrene, 10-12 parts butyl acrylate, 2-3 parts benzoyl peroxide, and 1-2 parts emulsifier; the aqueous phase raw material comprises the following components: by weight, 1-2 parts polyvinyl alcohol and 100-120 parts deionized water.

[0011] In this solution, the polymer microspheres prepared are different from other fillers. They do not contain pores, thus avoiding the problems of rupture and rebound. At the same time, since the sphere walls are made of organic polymer materials, they have both toughness and wear resistance, which can effectively improve the mechanical and physical properties of the substrate. In addition, the polymer microspheres are lightweight, and can significantly reduce the specific gravity of the substrate with extremely low addition amounts, achieving a lightweight effect. They also have advantages such as convenient processing, environmental protection and non-toxicity. Since the filled microspheres can be tightly bound to the substrate, they are not prone to sedimentation or precipitation, and the surface reactivity is inhibited, so no obvious precipitation phenomenon will appear on the outer surface of the substrate.

[0012] In a more optimized manner, the preparation process of the emulsifier is as follows: S1: Mix deionized water, ethanol, and hexadecyltrimethylammonium bromide, raise the temperature to 60-70℃, stir for 1-2 hours, then add 25wt% ammonia, cyclohexane, tetraethyl orthosilicate, and 3-aminopropyltrimethoxysilane, continue stirring for 3-4 hours, centrifuge, wash, transfer to acetone, raise the temperature to 70-80℃, react for 24 hours, wash, and dry to obtain the aminated support; S2: Vanillin, malononitrile, deionized water, and morpholine were mixed and reacted at room temperature for 1-2 hours. After the reaction was completed, dichloromethane and water were added for extraction. The organic phases were combined, dried with anhydrous sodium sulfate, and dichloromethane was removed by vacuum distillation. The mixture was then transferred to acetic acid, copper acetate was added, and the temperature was raised to 80-90℃. The reaction was carried out for 7-8 hours. After the reaction was completed, the mixture was poured into ice water, extracted with dichloromethane, dried and purified to obtain intermediate A. S3: Under a protective atmosphere, 2-hydroxy-3-vinylbenzaldehyde and N,N-dimethylformamide are mixed, the temperature is raised to 35-40℃, and a mixture of cyanuric chloride, triethylamine and N,N-dimethylformamide is slowly added dropwise. After the addition is complete, the mixture is stirred for 4-5 hours. After the reaction is complete, the mixture is cooled to room temperature, filtered, washed and dried to obtain intermediate B. S4: Mix intermediate A, intermediate B and acetonitrile, add sodium carbonate, raise the temperature to 80-90℃, react for 15-18h, after the reaction is completed, cool to room temperature, dissolve the crude product in N,N-dimethylformamide, pour into acetic acid solution, precipitate solid, and after further purification, obtain the modifier. S5: Mix the aminated carrier, modifier, and N,N-dimethylformamide, stir until homogeneous, add acetic acid, and react at room temperature for 10-12 hours. After the reaction is complete, filter, wash, and dry to obtain the emulsifier.

[0013] In this scheme, a micelle template is formed by the self-assembly of hexadecyltrimethylammonium bromide. Then, tetraethyl orthosilicate and 3-aminopropyltrimethoxysilane are used as inorganic and organic silicon sources, respectively, and undergo hydrolysis and condensation reactions under the catalysis of ammonia water to finally obtain an aminated support.

[0014] In this scheme, the aldehyde group of vanillin and the active methylene group of malononitrile undergo dehydration condensation under a weak base (morpholine) catalysis to form an α,β-unsaturated cyano structure. Subsequently, the cyano group in the malononitrile is selectively hydrated to an amide, preserving the conjugated system. The specific synthetic process is shown below: In this scheme, the phenolic hydroxyl group of 2-hydroxy-3-vinylbenzaldehyde acts as a nucleophile to attack the chlorotriazine ring of cyanuric chloride, undergoing a substitution reaction in the presence of triethylamine to form a stable triazine ring structure while retaining the reactive group; the specific synthetic process is shown below: In this scheme, the hydroxyl group in intermediate A and the chlorinated group in intermediate B undergo a substitution reaction under alkaline conditions of sodium carbonate to form a covalently linked macromolecular modifier; its structural formula is shown below: In this scheme, the aldehyde group retained in the modifier molecule reacts with the amino group on the surface of the aminated carrier under the catalysis of acetic acid to form an imine bond. At the same time, the acidic environment provided by acetic acid promotes the reaction equilibrium to shift towards the formation of imine. This covalent bond firmly anchors the organic modifier to the surface of the carrier, forming an emulsifier.

[0015] More preferably, the amination carrier raw material comprises the following components by weight: 25-30 parts deionized water, 7-8 parts ethanol, 0.1-0.2 parts hexadecyltrimethylammonium bromide, 1-2 parts ammonia, 3-4 parts cyclohexane, 0.4-0.5 parts tetraethyl orthosilicate, 0.1-0.2 parts 3-aminopropyltrimethoxysilane, and 25-30 parts acetone; The intermediate A raw material comprises the following components by weight: 5-8 parts vanillin, 2-4 parts malononitrile, 100-120 parts deionized water, 0.1-0.2 parts morpholine, 100-150 parts acetic acid, and 2-3 parts copper acetate. The intermediate B raw material comprises the following components: by weight, 16-18 parts of 2-hydroxy-3-vinylbenzaldehyde, 200-250 parts of N,N-dimethylformamide, 10-12 parts of cyanuric chloride, and 1-2 parts of triethylamine; The modifier raw material includes the following components: by weight, 6-8 parts of intermediate A, 12-16 parts of intermediate B, 200-250 parts of acetonitrile, and 0.8-1 parts of sodium carbonate; The emulsifier raw material includes the following components: by weight, 12-18 parts of aminated carrier, 0.5-0.8 parts of modifier, 100-120 parts of N,N-dimethylformamide, and 1-2 parts of acetic acid.

[0016] Ideally, the plasticizing temperature is 165-175°C.

[0017] More preferably, the lubricant includes one or more of polyethylene wax, zinc stearate, and stearic acid; the antioxidant includes one or more of antioxidant 1010 and antioxidant 1076; the processing aid is MMA / styrene copolymer; and the crosslinking agent is dicumyl peroxide.

[0018] The beneficial effects of this invention are: This invention prepares polymer microspheres via emulsion polymerization and introduces them into the cable sheath manufacturing process, effectively improving the sheath's tensile strength, chemical corrosion resistance, and aging resistance. Details are as follows: Firstly, the aminated carrier prepared by the sol-gel method has the characteristics of small size and high specific surface area. Its surface is rich in silanol groups and amino groups, which can bond with hydrophobic modifiers to form amphiphilic emulsifiers. This emulsifier can form a dense and stable emulsion layer at the oil-water interface, effectively inhibiting oil droplet aggregation. At the same time, it has excellent mechanical strength and can withstand the shear force during processing, ensuring the stability of the emulsion. Secondly, in the proposed method, the modifier uses a triazine ring as a rigid backbone core. The benzene ring and conjugated double bonds contained therein can efficiently capture ultraviolet photons and induce the molecule to transition from the ground state to the excited state. At the same time, the absorbed ultraviolet energy is rapidly dissipated through non-radiative relaxation processes (such as thermal energy release), prompting the molecule to quickly return to the ground state, thereby effectively blocking the photodegradation reaction. Thirdly, the emulsifier in this design possesses multiple functional characteristics: First, the active double bond groups on its surface can undergo cross-linking reactions with other components in the polymer microspheres, constructing a dense three-dimensional network structure, thereby significantly enhancing the mechanical stability of the polymer microspheres; second, the emulsifier uses silica as a carrier substrate, an inorganic material that can uniformly disperse the stress field when the material is under stress, effectively eliminating local stress concentration and significantly improving the tensile strength of the composite material; furthermore, the unreacted double bond groups retained on the surface of the emulsifier can also form secondary cross-links with the sheath material. This molecular-level bonding not only enhances the material's resistance to chemical corrosion but also significantly improves its antioxidant degradation resistance, ensuring that the material maintains long-term stable performance during use. 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] Example 1: A method for preparing a tensile cable sheath material, comprising the following steps: Step 1: Mix 80 parts of polyvinyl chloride, 40 parts of polyurethane-acrylate, and 0.75 parts of polymer microspheres at 50°C, then add stearic acid, antioxidant 1010, and dicumyl peroxide, stir until homogeneous, then raise the temperature to 90°C and add MMA / styrene copolymer to obtain the mixed raw material; Step 2: Transfer the mixed raw materials to a twin-screw plasticizer and plasticize at 165°C. After the plasticizing is uniform, the mixture is water-cooled, stretched, and granulated. After drying, the cable sheath material is obtained. The preparation process of the polymer microspheres is as follows: (1) Mix 20 parts of γ-valerolactone, 30 parts of glycidyl methacrylate, 30 parts of styrene, 10 parts of butyl acrylate, 2 parts of benzoyl peroxide, and 1 part of emulsifier, and stir magnetically until homogeneous to obtain the oil phase; mix 1 part of polyvinyl alcohol and 100 parts of deionized water to obtain the aqueous phase; (2) The oil phase and the aqueous phase were mixed and emulsified using a high-speed disperser. Then the mixture was put into a polymerization reactor, purged with nitrogen, and the temperature was raised to 70°C. The reaction was carried out for 8 hours. After the reaction was completed, the mixture was cooled to room temperature, filtered, washed, and dried to obtain polymer microspheres. The mass ratio of the oil phase to the aqueous phase was 2:20. The preparation process of the emulsifier is as follows: S1: Mix 25 parts deionized water, 7 parts ethanol, and 0.1 parts hexadecyltrimethylammonium bromide, raise the temperature to 60°C, and stir for 1 hour. Then add 1 part 25 wt% ammonia, 3 parts cyclohexane, 0.4 parts tetraethyl orthosilicate, and 0.1 parts 3-aminopropyltrimethoxysilane, and continue stirring for 3 hours. Centrifuge, wash, and transfer to 25 parts acetone. Raise the temperature to 70°C and react for 24 hours. Wash and dry to obtain the aminated support. S2: Mix 5 parts vanillin, 2 parts malononitrile, 100 parts deionized water, and 0.1 parts morpholine. React at room temperature for 1 hour. After the reaction is complete, add dichloromethane and water for extraction. Combine the organic phases, add anhydrous sodium sulfate for drying, and remove dichloromethane by vacuum distillation. Then transfer to 100 parts acetic acid, add 2 parts copper acetate, raise the temperature to 80°C, and react for 7 hours. After the reaction is complete, pour the mixture into ice water, extract with dichloromethane, and dry and purify to obtain intermediate A. S3: Under a protective atmosphere, 16 parts of 2-hydroxy-3-vinylbenzaldehyde and 100 parts of N,N-dimethylformamide were mixed, the temperature was raised to 35°C, and a mixture of 10 parts of cyanuric chloride, 1 part of triethylamine and 100 parts of N,N-dimethylformamide was slowly added dropwise. After the addition was complete, the mixture was stirred and reacted for 4 hours. After the reaction was completed, the mixture was cooled to room temperature, filtered, washed and dried to obtain intermediate B. S4: Mix 6 parts of intermediate A, 12 parts of intermediate B, and 200 parts of acetonitrile, add 0.8 parts of sodium carbonate, raise the temperature to 80℃, react for 15 hours, after the reaction is completed, cool to room temperature, dissolve the crude product in N,N-dimethylformamide, pour into acetic acid solution, precipitate solid, and after further purification, obtain the modifier. S5: Mix 12 parts of aminated carrier, 0.5 parts of modifier, and 100 parts of N,N-dimethylformamide, stir well, add 1 part of acetic acid, and react at room temperature for 10 hours. After the reaction is complete, filter, wash, and dry to obtain emulsifier.

[0021] Example 2: A method for preparing a tensile cable sheath material, comprising the following steps: Step 1: Mix 100 parts of polyvinyl chloride, 50 parts of polyurethane-acrylate, and 1 part of polymer microspheres at 60°C, then add stearic acid, antioxidant 1010, and dicumyl peroxide, stir until homogeneous, then raise the temperature to 100°C and add MMA / styrene copolymer to obtain mixed raw materials; Step 2: Transfer the mixed raw materials to a twin-screw plasticizer and plasticize them at 175°C. After the plasticizing is uniform, the mixture is water-cooled, stretched, and granulated. After drying, the cable sheath material is obtained. The preparation process of the polymer microspheres is as follows: (1) Mix 30 parts of γ-valerolactone, 40 parts of glycidyl methacrylate, 40 parts of styrene, 12 parts of butyl acrylate, 3 parts of benzoyl peroxide, and 2 parts of emulsifier, and stir magnetically until homogeneous to obtain the oil phase; mix 2 parts of polyvinyl alcohol and 120 parts of deionized water to obtain the aqueous phase; (2) The oil phase and the aqueous phase are mixed and emulsified using a high-speed disperser. Then, the mixture is added to a polymerization reactor, purged with nitrogen, and the temperature is raised to 80°C. The reaction is carried out for 10 hours. After the reaction is completed, the mixture is cooled to room temperature, filtered, washed, and dried to obtain polymer microspheres. The mass ratio of the oil phase to the aqueous phase is 5:20. The preparation process of the emulsifier is as follows: S1: Mix 30 parts deionized water, 8 parts ethanol, and 0.2 parts hexadecyltrimethylammonium bromide, raise the temperature to 70°C, and stir for 2 hours. Then add 2 parts 25 wt% ammonia, 4 parts cyclohexane, 0.5 parts tetraethyl orthosilicate, and 0.2 parts 3-aminopropyltrimethoxysilane, and continue stirring for 4 hours. After centrifugation and washing, transfer the mixture to 30 parts acetone, raise the temperature to 80°C, and react for 24 hours. After washing and drying, obtain the aminated support. S2: Mix 8 parts vanillin, 4 parts malononitrile, 120 parts deionized water, and 0.2 parts morpholine. React at room temperature for 2 hours. After the reaction is complete, add dichloromethane and water for extraction. Combine the organic phases, add anhydrous sodium sulfate for drying, and remove dichloromethane by vacuum distillation. Then transfer to 150 parts acetic acid, add 3 parts copper acetate, raise the temperature to 90°C, and react for 8 hours. After the reaction is complete, pour the mixture into ice water, extract with dichloromethane, and dry and purify to obtain intermediate A. S3: Under a protective atmosphere, 18 parts of 2-hydroxy-3-vinylbenzaldehyde and 120 parts of N,N-dimethylformamide were mixed, the temperature was raised to 40°C, and a mixture of 12 parts of cyanuric chloride, 2 parts of triethylamine and 130 parts of N,N-dimethylformamide was slowly added dropwise. After the addition was complete, the mixture was stirred for 5 hours. After the reaction was completed, the mixture was cooled to room temperature, filtered, washed and dried to obtain intermediate B. S4: Mix 8 parts of intermediate A, 16 parts of intermediate B, and 250 parts of acetonitrile, add 1 part of sodium carbonate, raise the temperature to 90℃, react for 18 hours, after the reaction is completed, cool to room temperature, dissolve the crude product in N,N-dimethylformamide, pour into acetic acid solution, precipitate solid, and after further purification, obtain the modifier. S5: Mix 18 parts of aminated carrier, 0.8 parts of modifier, and 120 parts of N,N-dimethylformamide, stir well, add 2 parts of acetic acid, and react at room temperature for 12 hours. After the reaction is complete, filter, wash, and dry to obtain emulsifier.

[0022] Example 3: A method for preparing a tensile cable sheath material, comprising the following steps: Step 1: Mix 90 parts of polyvinyl chloride, 45 parts of polyurethane-acrylate, and 0.875 parts of polymer microspheres at 55°C, then add stearic acid, antioxidant 1010, and dicumyl peroxide, stir until homogeneous, then raise the temperature to 95°C and add MMA / styrene copolymer to obtain the mixed raw material; Step 2: Transfer the mixed raw materials to a twin-screw plasticizer and plasticize them at 170°C. After the plasticizing is uniform, the mixture is water-cooled, stretched, and granulated. After drying, the cable sheath material is obtained. The preparation process of the polymer microspheres is as follows: (1) Mix 25 parts γ-valerolactone, 35 parts glycidyl methacrylate, 35 parts styrene, 11 parts butyl acrylate, 2.5 parts benzoyl peroxide, and 1.5 parts emulsifier, and stir magnetically until homogeneous to obtain the oil phase; mix 1.5 parts polyvinyl alcohol and 110 parts deionized water to obtain the aqueous phase; (2) The oil phase and the aqueous phase were mixed and emulsified using a high-speed disperser. Then the mixture was placed in a polymerization reactor, purged with nitrogen, and the temperature was raised to 75°C. The reaction was carried out for 9 hours. After the reaction was completed, the mixture was cooled to room temperature, filtered, washed, and dried to obtain polymer microspheres. The mass ratio of the oil phase to the aqueous phase was 3.5:20. The preparation process of the emulsifier is as follows: S1: Mix 27.5 parts deionized water, 7.5 parts ethanol, and 0.15 parts hexadecyltrimethylammonium bromide, raise the temperature to 65°C, and stir for 1.5 h. Then add 1.5 parts 25 wt% ammonia, 3.5 parts cyclohexane, 0.45 parts tetraethyl orthosilicate, and 0.15 parts 3-aminopropyltrimethoxysilane, and continue stirring for 3.5 h. After centrifugation and washing, transfer to 27.5 parts acetone, raise the temperature to 75°C, and react for 24 h. After washing and drying, obtain the aminated support. S2: 6.5 parts vanillin, 3 parts malononitrile, 110 parts deionized water, and 0.15 parts morpholine were mixed and reacted at room temperature for 1.5 h. After the reaction was completed, dichloromethane and water were added for extraction. The organic phases were combined, dried with anhydrous sodium sulfate, and dichloromethane was removed by vacuum distillation. The mixture was then transferred to 125 parts acetic acid, 2.5 parts copper acetate were added, the temperature was raised to 85 °C, and the reaction was carried out for 7.5 h. After the reaction was completed, the mixture was poured into ice water, extracted with dichloromethane, dried and purified to obtain intermediate A. S3: Under a protective atmosphere, 17 parts of 2-hydroxy-3-vinylbenzaldehyde and 110 parts of N,N-dimethylformamide were mixed, the temperature was raised to 37.5℃, and a mixture of 11 parts of cyanuric chloride, 1.5 parts of triethylamine and 115 parts of N,N-dimethylformamide was slowly added dropwise. After the addition was complete, the mixture was stirred and reacted for 4.5 h. After the reaction was completed, the mixture was cooled to room temperature, filtered, washed and dried to obtain intermediate B. S4: Mix 7 parts of intermediate A, 14 parts of intermediate B, and 225 parts of acetonitrile, add 0.9 parts of sodium carbonate, raise the temperature to 85℃, and react for 16.5 h. After the reaction is completed, cool to room temperature, dissolve the crude product in N,N-dimethylformamide, pour it into acetic acid solution, precipitate the solid, and further purify to obtain the modifier. S5: Mix 15 parts of aminated carrier, 0.65 parts of modifier, and 110 parts of N,N-dimethylformamide, stir well, add 1.5 parts of acetic acid, and react at room temperature for 11 hours. After the reaction is complete, filter, wash, and dry to obtain emulsifier.

[0023] Comparative Example 1: No polymer microspheres were added; all other aspects were the same as in Example 3, as detailed below: Step 1: Mix 90 parts of polyvinyl chloride and 45 parts of polyurethane-acrylate at 55°C, then add stearic acid, antioxidant 1010 and dicumyl peroxide, stir evenly, then raise the temperature to 95°C and add MMA / styrene copolymer to obtain mixed raw materials; Step 2: Transfer the mixed raw materials to a twin-screw plasticizer and plasticize at 170°C. After the plasticizing is uniform, the mixture is water-cooled, stretched, and granulated. After drying, the cable sheath material is obtained.

[0024] Comparative Example 2: In the preparation of polymer microspheres, alkylphenol polyoxyethylene ether was used to replace the emulsifier prepared in Example 3, and the rest was the same as in Example 3, as follows: Step 1: Mix 90 parts of polyvinyl chloride, 45 parts of polyurethane-acrylate, and 0.875 parts of polymer microspheres at 55°C, then add stearic acid, antioxidant 1010, and dicumyl peroxide, stir until homogeneous, then raise the temperature to 95°C and add MMA / styrene copolymer to obtain the mixed raw material; Step 2: Transfer the mixed raw materials to a twin-screw plasticizer and plasticize them at 170°C. After the plasticizing is uniform, the mixture is water-cooled, stretched, and granulated. After drying, the cable sheath material is obtained. The preparation process of the polymer microspheres is as follows: (1) Mix 25 parts γ-valerolactone, 35 parts glycidyl methacrylate, 35 parts styrene, 11 parts butyl acrylate, 2.5 parts benzoyl peroxide, and 1.5 parts alkylphenol polyoxyethylene ether, and stir magnetically until homogeneous to obtain the oil phase; mix 1.5 parts polyvinyl alcohol and 110 parts deionized water to obtain the aqueous phase; (2) The oil phase and the water phase are mixed and emulsified using a high-speed disperser. Then, the mixture is added to a polymerization reactor, purged with nitrogen, and the temperature is raised to 75°C. The reaction is carried out for 9 hours. After the reaction is completed, the mixture is cooled to room temperature, filtered, washed, and dried to obtain polymer microspheres. The mass ratio of the oil phase to the water phase is 3.5:20.

[0025] Testing: (1) The tensile properties of the cable sheath materials obtained in the examples and comparative examples were tested according to GB / T1040.2-2006; (2) The cable sheath materials obtained in the examples and comparative examples were immersed in 1 mol / L hydrochloric acid solution for 24 h, and the mass change and tensile strength retention rate were measured; (3) The cable sheath materials obtained in the examples and comparative examples were subjected to aging tests according to GB / T16422.2-2022; among which, thermal aging was aging at 100℃ for 168 h, and light aging was irradiated under a xenon arc lamp for 1000 h; the data obtained are shown in the table below: Conclusion: The polymer microspheres prepared by emulsion polymerization in this invention, when introduced into cable sheath materials, significantly improve the tensile strength, chemical corrosion resistance, and aging resistance of the materials. As shown in Table 1, the tensile strengths of Examples 1 to 3 reached 32.1 MPa, 33.5 MPa, and 33.8 MPa, respectively, which are much higher than 22.8 MPa of Comparative Example 1 and 25.6 MPa of Comparative Example 2. After immersion in hydrochloric acid for 24 hours, the mass change rate of the examples was only 2.88%-3.21%, and the tensile strength retention rate was 85.6%-89.7%, while the mass change rate of Comparative Example 1 was as high as 9.97%, and the tensile strength retention rate was only 68.6%. In the thermal aging and light aging tests, the tensile strength retention rate of the examples both exceeded 94%, while that of Comparative Example 1 decreased to 70.1% and 74.6%, respectively. In addition, the performance of the examples using the self-made emulsifier was better than that of Comparative Example 2 using the commercial emulsifier, indicating that the emulsifier and polymer microspheres designed in this invention have significant advantages in improving the overall performance of the materials.

[0026] In the description of this specification, the references to terms such as "an embodiment," "example," "specific example," etc., indicate that a specific feature, structure, material, or characteristic described in connection with that embodiment or example is included in at least one embodiment or example of the present invention. In this specification, the illustrative expressions of the above terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in one or more embodiments or examples.

[0027] The above description is merely an example and illustration of the present invention. Those skilled in the art can make various modifications or additions to the specific embodiments described, or use similar methods to replace them, as long as they do not deviate from the invention or exceed the scope defined in the claims, all of which should fall within the protection scope of the present invention.

Claims

1. A tensile-resistant cable sheath material, characterized in that: The raw materials for the cable sheath material include the following components by weight: 80-100 parts polyvinyl chloride, 40-50 parts polyurethane-acrylate, 0.75-1 parts polymer microspheres, 1-2 parts lubricant, 1-2 parts antioxidant, and 2-3 parts crosslinking agent. The preparation process of the polymer microspheres is as follows: (1) Mix γ-valerolactone, glycidyl methacrylate, styrene, butyl acrylate, benzoyl peroxide, and emulsifier, and stir magnetically until homogeneous to obtain the oil phase; mix polyvinyl alcohol and deionized water to obtain the aqueous phase; (2) Mix the oil phase and the water phase, emulsify them using a high-speed disperser, then put them into a polymerization reactor, purge with nitrogen, raise the temperature to 70-80℃, react for 8-10 hours, cool to room temperature after the reaction is complete, filter, wash, and dry to obtain polymer microspheres.

2. The tensile cable sheath material according to claim 1, characterized in that: The mass ratio of the oil phase to the water phase is (2-5):

20.

3. The tensile cable sheath material according to claim 1, characterized in that: The oil phase raw material comprises the following components: by weight, 20-30 parts γ-valerolactone, 30-40 parts glycidyl methacrylate, 30-40 parts styrene, 10-12 parts butyl acrylate, 2-3 parts benzoyl peroxide, and 1-2 parts emulsifier; the aqueous phase raw material comprises the following components: by weight, 1-2 parts polyvinyl alcohol and 100-120 parts deionized water.

4. The tensile cable sheath material according to claim 1, characterized in that: The preparation process of the emulsifier is as follows: S1: Mix deionized water, ethanol, and hexadecyltrimethylammonium bromide, raise the temperature to 60-70℃, stir for 1-2 hours, then add 25wt% ammonia, cyclohexane, tetraethyl orthosilicate, and 3-aminopropyltrimethoxysilane, continue stirring for 3-4 hours, centrifuge, wash, transfer to acetone, raise the temperature to 70-80℃, react for 24 hours, wash, and dry to obtain the aminated support; S2: Vanillin, malononitrile, deionized water, and morpholine were mixed and reacted at room temperature for 1-2 hours. After the reaction was completed, dichloromethane and water were added for extraction. The organic phases were combined, dried with anhydrous sodium sulfate, and dichloromethane was removed by vacuum distillation. The mixture was then transferred to acetic acid, copper acetate was added, and the temperature was raised to 80-90℃. The reaction was carried out for 7-8 hours. After the reaction was completed, the mixture was poured into ice water, extracted with dichloromethane, dried and purified to obtain intermediate A. S3: Under a protective atmosphere, 2-hydroxy-3-vinylbenzaldehyde and N,N-dimethylformamide are mixed, the temperature is raised to 35-40℃, and a mixture of cyanuric chloride, triethylamine and N,N-dimethylformamide is slowly added dropwise. After the addition is complete, the mixture is stirred for 4-5 hours. After the reaction is complete, the mixture is cooled to room temperature, filtered, washed and dried to obtain intermediate B. S4: Mix intermediate A, intermediate B and acetonitrile, add sodium carbonate, raise the temperature to 80-90℃, react for 15-18h, after the reaction is completed, cool to room temperature, dissolve the crude product in N,N-dimethylformamide, pour into acetic acid solution, precipitate solid, and after further purification, obtain the modifier. S5: Mix the aminated carrier, modifier, and N,N-dimethylformamide, stir until homogeneous, add acetic acid, and react at room temperature for 10-12 hours. After the reaction is complete, filter, wash, and dry to obtain the emulsifier.

5. The tensile cable sheath material according to claim 4, characterized in that: The amination carrier raw material comprises the following components by weight: 25-30 parts deionized water, 7-8 parts ethanol, 0.1-0.2 parts hexadecyltrimethylammonium bromide, 1-2 parts ammonia, 3-4 parts cyclohexane, 0.4-0.5 parts tetraethyl orthosilicate, 0.1-0.2 parts 3-aminopropyltrimethoxysilane, and 25-30 parts acetone; The intermediate A raw material comprises the following components by weight: 5-8 parts vanillin, 2-4 parts malononitrile, 100-120 parts deionized water, 0.1-0.2 parts morpholine, 100-150 parts acetic acid, and 2-3 parts copper acetate. The intermediate B raw material comprises the following components: by weight, 16-18 parts of 2-hydroxy-3-vinylbenzaldehyde, 200-250 parts of N,N-dimethylformamide, 10-12 parts of cyanuric chloride, and 1-2 parts of triethylamine; The modifier raw material includes the following components: by weight, 6-8 parts of intermediate A, 12-16 parts of intermediate B, 200-250 parts of acetonitrile, and 0.8-1 parts of sodium carbonate; The emulsifier raw material includes the following components: by weight, 12-18 parts of aminated carrier, 0.5-0.8 parts of modifier, 100-120 parts of N,N-dimethylformamide, and 1-2 parts of acetic acid.

6. A method for preparing a tensile cable sheath material according to any one of claims 1-5, characterized in that: Includes the following steps: Step 1: Mix polyvinyl chloride, polyurethane-acrylate, and polymer microspheres at 50-60℃, then add lubricant, antioxidant, and crosslinking agent, stir evenly, then raise the temperature to 90-100℃, add processing aids, and obtain mixed raw materials; Step 2: Transfer the mixed raw materials to a twin-screw plasticizer for plasticizing. After the plasticizing is uniform, the mixture is water-cooled, stretched, and granulated. After drying, the cable sheath material is obtained.

7. The method for preparing a tensile cable sheath material according to claim 6, characterized in that: The plasticizing temperature is 165-175℃.

8. The method for preparing a tensile cable sheath material according to claim 6, characterized in that: The lubricant includes one or more of polyethylene wax, zinc stearate, and stearic acid; the antioxidant includes one or more of antioxidant 1010 and antioxidant 1076; the processing aid is MMA / styrene copolymer; and the crosslinking agent is dicumyl peroxide.

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