Anti-aging push-pull sleeve material for vehicle and anti-aging push-pull sleeve for vehicle

Abstract

The invention discloses an anti-aging push-and-pull sleeve material for a vehicle and an anti-aging push-and-pull sleeve for the vehicle, and belongs to the technical field of push-and-pull sleeves for the vehicle. The anti-aging push-pull sleeve material for the vehicle is prepared from the following raw material components in parts by mass: 45 to 63 parts of polypropylene, 2 to 3 parts of ultraviolet absorbent, 15 to 25 parts of flame retardant, 2.5 to 3.5 parts of ethylene propylene diene monomer, 2.5 to 3.5 parts of POE thermoplastic elastomer, 0.5 to 0.7 part of initiator, 3 to 4 parts of white carbon black, 1 to 2 parts of carbon black, 4 to 6 parts of silane coupling agent and 3 to 5 parts of lubricant. 2, 4 '-dihydroxybenzophenone or 2, 6, 4'-trihydroxy-4-methoxybenzophenone is adopted as the ultraviolet absorbent, and 2, 4 '-dihydroxybenzophenone or 2, 6, 4'-trihydroxy-4-methoxybenzophenone is adopted as the ultraviolet absorbent; 1, 1, 3, 3, 5, 5-hexa (styryloxy) triphosphorus heterocyclic triphosphazene is adopted as the flame retardant.

Description

Technical Field

[0001] This invention relates to the field of automotive push-pull sleeve technology, specifically to an anti-aging automotive push-pull sleeve material and an anti-aging automotive push-pull sleeve. Background Technology

[0002] With the rapid development of the automotive industry, the requirements for material performance in automotive components are increasing, especially in terms of durability, safety, and environmental adaptability. Push-pull sleeves, as key components in automotive control systems, are widely used in control mechanisms such as clutches, throttles, and gear shifts. They are exposed to complex environments such as the engine compartment or exterior of the vehicle body for extended periods, and must withstand the combined effects of temperature changes, ultraviolet radiation, and mechanical stress. Therefore, their materials must possess excellent mechanical properties, superior anti-aging capabilities, and necessary flame-retardant characteristics to ensure structural integrity and functional stability during long-term use.

[0003] Currently, automotive push-pull sleeves are mostly made of polypropylene (PP) or blends of it with other elastomers. Polypropylene is widely used due to its low density, low cost, ease of processing, and non-toxic and odorless properties; however, its weather resistance is poor, especially under ultraviolet light and heat-oxidation, it is prone to aging, leading to brittleness and cracking, thus affecting its service life. Furthermore, pure polypropylene lacks sufficient low-temperature toughness and has limited impact resistance, making it difficult to meet the demands of extreme working conditions. Although adding ethylene propylene diene monomer (EPDM) can improve the material's weather resistance and elasticity to some extent, the poor compatibility between EPDM and PP easily leads to phase separation, affecting the material's uniformity and mechanical properties. POE thermoplastic elastomer, as a novel ethylene-octene copolymer, possesses excellent low-temperature toughness, good processing rheology, and high cost-effectiveness. It can effectively improve the impact resistance of PP-based materials and enhance its blend compatibility with EPDM, and has been widely used in the field of plastic modification in recent years.

[0004] However, existing automotive push-pull sleeve materials still have shortcomings in terms of UV resistance, flame retardancy, and long-term thermal stability. Especially under high temperature, high humidity, and strong sunlight environments, these materials are prone to oxidative degradation, surface powdering, and decreased mechanical properties, severely limiting their service life and reliability. Furthermore, automotive fire safety requirements are becoming increasingly stringent, and traditional materials often struggle to simultaneously meet both mechanical performance and flame retardancy standards.

[0005] To address the aforementioned issues, the applicant has developed an anti-aging automotive push-pull sleeve material and an anti-aging automotive push-pull sleeve. Summary of the Invention

[0006] The purpose of this invention is to provide an anti-aging automotive push-pull sleeve material and an anti-aging automotive push-pull sleeve to solve the technical problems mentioned in the background art.

[0007] The technical solution to achieve the objective of this invention is: In a first aspect, the present invention provides an anti-aging automotive push-pull sleeve material, wherein, by mass parts, the raw material components include 45-63 parts by mass of polypropylene, 2-4 parts by mass of ultraviolet absorber, 15-25 parts by mass of flame retardant, 2.5-3.5 parts by mass of EPDM rubber, 2.5-3.5 parts by mass of POE thermoplastic elastomer, 0.5-0.7 parts by mass of initiator, 3-4 parts by mass of silica, 1-2 parts by mass of carbon black, 4-6 parts by mass of silane coupling agent, and 3-5 parts by mass of lubricant.

[0008] The anti-aging automotive push-pull sleeve material of this invention is composed of polypropylene, ethylene propylene diene monomer (EPDM) rubber, POE thermoplastic elastomer, ultraviolet absorber, flame retardant, initiator, silica, carbon black, silane coupling agent, and lubricant. Polypropylene, as the matrix resin, is a non-toxic, odorless, and tasteless milky-white highly crystalline polymer with low density, good mechanical properties, excellent molding and processing performance, high heat resistance, good chemical stability, almost no water absorption, resistance to most chemical corrosion, excellent electrical insulation, and pure, non-toxic properties. It is one of the lightest plastics currently available and is particularly suitable for lightweight applications. EPDM rubber possesses excellent weather resistance, heat resistance, and chemical resistance, significantly improving the long-term stability of the material in complex environments. POE thermoplastic elastomer exhibits excellent mechanical properties, rheological properties, and aging resistance due to its unique molecular structure. This material can be used as a rubber or for plastic modification. As a toughening agent and impact modifier, it can effectively improve the low-temperature toughness and flexibility of materials, while enhancing the compatibility of polypropylene and EPDM rubber blends. It also has a high cost-performance ratio and has gradually replaced EPDM rubber in many fields. This invention uses polypropylene, EPDM rubber and POE thermoplastic elastomer as composite base materials. By adding UV absorbers and flame retardants, the material's UV aging resistance, flame retardancy and overall weather resistance are further enhanced, giving it excellent comprehensive mechanical properties. It is suitable for components with high durability and safety requirements, such as automotive push-pull sleeves.

[0009] Furthermore, the ultraviolet absorber is 2,4'-dihydroxybenzophenone or 2,6,4'-trihydroxy-4-methoxybenzophenone.

[0010] Furthermore, the flame retardant comprises at least 1,1,3,3,5,5-hexa(styreneoxy)triphosphonic triphosphazene.

[0011] This invention uses 1,1,3,3,5,5-hexa(styreneoxy)triphosphazene as a flame retardant. This compound decomposes under high-temperature conditions, releasing phosphorus-containing free radicals (such as PO·) and nitrogen-containing gases (such as nitrogen and ammonia). The PO· free radicals can capture active free radicals in the flame (such as H· and HO·), thereby interrupting the chain combustion reaction; while inert gases such as nitrogen inhibit flame spread by diluting the oxygen concentration, achieving a gas-phase flame retardant effect. Simultaneously, phosphorus catalyzes the dehydration and carbonization of the polymer, forming a dense and continuous carbon layer that effectively isolates heat and oxygen transfer, preventing further pyrolysis of the internal materials, thus achieving a highly efficient flame-retardant effect in the condensed phase. Furthermore, the styrene oxide group in the 1,1,3,3,5,5-hexa(styreneoxy)triphosphazene heterocyclic phosphazene molecule exhibits good reactivity and compatibility, enabling it to interact with other raw material components such as the polypropylene matrix, EPDM rubber, and POE thermoplastic elastomer to a certain extent during processing, and even participate in grafting or crosslinking reactions in the presence of an initiator. These reactions… It enhances the interfacial bonding between components, reduces phase separation, and improves the uniformity and structural density of the composite material. This enhanced interfacial compatibility does not sacrifice the mechanical properties of the material; on the contrary, it effectively maintains or even improves the tensile strength of the material while providing excellent flame retardant effects, avoiding the "flame retardant-mechanical property inversion" problem common in traditional additive flame retardants. Furthermore, this flame retardant itself has high thermal stability, with a decomposition temperature higher than that of conventional polypropylene, ensuring that it will not decompose or fail during the molding process, thus guaranteeing the safety of the processing and the durability of the flame retardant effect.

[0012] Furthermore, the maleimide propyltriethoxysilane includes dicumyl peroxide.

[0013] Furthermore, the lubricant includes polyethylene wax.

[0014] Furthermore, the silane coupling agent comprises 3-(methacryloyloxy)propyltrimethoxysilane.

[0015] Secondly, the present invention provides a method for preparing an anti-aging automotive push-pull sleeve material as described in the first aspect, comprising the following preparation steps: (1) Weigh and mix each raw material component; (2) Under nitrogen protection, the flame retardant weighed in step (1) is dissolved in 15 to 20 times the mass of the flame retardant in dimethyl sulfoxide to obtain solution A; the ultraviolet absorber weighed in step (1) is dissolved in 8 to 12 times the mass of the ultraviolet absorber in dimethyl sulfoxide, and then 0.005 to 0.02 times the mass of the ultraviolet absorber in catalyst is added. After stirring for 55 to 65 minutes, the temperature is raised to 120 to 130°C, and then solution A is added dropwise at 1 to 3 seconds. After the addition is completed, the temperature is kept constant for 110 to 130 minutes. Then sodium carbonate is added until the pH of the reaction system is neutral. Dimethyl sulfoxide is removed by vacuum distillation to obtain mixture A. (3) The polypropylene, EPDM rubber, POE thermoplastic elastomer, mixture A obtained in step (2), and 2 / 3 of the initiator weighed in step (1) are mixed evenly in a high-speed mixer and then added to a twin-screw extruder for melt mixing. Then, it is mixed evenly with silica, carbon black, silane coupling agent, lubricant, and the remaining initiator in a high-speed mixer. Finally, it is melt-mixed and extruded in a twin-screw extruder to obtain an anti-aging automotive push-pull sleeve material.

[0016] In the preparation of anti-aging automotive push-pull sleeve materials, this invention first premixes the flame retardant 1,1,3,3,5,5-hexa(styreneoxy)triphosphazene with a UV absorber, and introduces p-toluenesulfonic acid as a catalyst during the mixing process. Under the action of this acidic catalyst, the styrene groups in the flame retardant molecule undergo an alkylation reaction with the UV absorber. Some styrene groups are selectively introduced into the ortho position of the phenolic hydroxyl group of the UV absorber, generating styreneated phenol derivatives. This process not only achieves molecular-level synergy between the flame retardant and the UV absorber, but also produces a significant steric hindrance effect by introducing large-volume styrene groups into the ortho position of the phenolic antioxidant. This effect can effectively shield the phenolic hydroxyl group and inhibit its oxidation consumption under heat or oxygen, thereby significantly improving the antioxidant activity of the phenolic UV absorber. The process involves improving the flame retardancy and thermal stability of the material, extending its long-lasting protective effect. The material is then melt-blended with polypropylene, EPDM, POE thermoplastic elastomer, and an initiator, followed by further melt-blending with other raw material components and extrusion granulation. During this process, the initiator promotes grafting or cross-linking reactions between the polypropylene and the elastomer, enhancing the compatibility of the multiphase system. The pre-generated styrene-modified phenol derivative not only provides efficient UV absorption and antioxidant functions, but its styrene groups also exhibit good compatibility and interfacial interaction with olefin-containing components such as POE or EPDM, further improving the dispersibility of the UV absorber and flame retardant and the interfacial bonding strength with the matrix. The resulting anti-aging automotive push-pull sleeve material maintains excellent flame retardant properties while significantly improving the material's antioxidant capacity, long-term thermal stability, and overall mechanical properties.

[0017] Furthermore, the catalyst is p-toluenesulfonic acid.

[0018] Furthermore, the twin-screw extruder has a die head temperature of 160~170℃, a die head pressure of 1~10MPa, and a screw speed of 80~100r / min.

[0019] Thirdly, the present invention provides an anti-aging automotive push-pull sleeve, which comprises, from the inside out, an inner liner layer, a reinforcing layer, and an anti-aging outer covering layer; the anti-aging outer covering layer is made of the high and low temperature resistant automotive push-pull sleeve material described in the first aspect.

[0020] By adopting the above technical solution, the present invention has the following beneficial effects: (1) The anti-aging automotive push-pull sleeve material of the present invention is composed of polypropylene, ethylene propylene diene monomer (EPDM) rubber, POE thermoplastic elastomer, ultraviolet absorber, flame retardant, initiator, silica, carbon black, silane coupling agent, and lubricant. Among them, polypropylene, as the matrix resin, is a non-toxic, odorless, and tasteless milky white highly crystalline polymer with low density, good mechanical properties, excellent molding and processing performance, high heat resistance, good chemical stability, almost no water absorption, resistance to corrosion by most chemicals, excellent electrical insulation, and pure and non-toxic materials. It is one of the lightest plastic varieties currently available and is particularly suitable for lightweight applications. EPDM rubber has excellent weather resistance, heat resistance, and chemical resistance, which can significantly improve the long-term stability of the material in complex environments. POE thermoplastic elastomer exhibits excellent mechanical properties, rheological properties, and aging resistance due to its unique molecular structure. This material can be used as a rubber or for plastic modification. As a toughening agent and impact modifier, it can effectively improve the low-temperature toughness and flexibility of materials, while enhancing the compatibility of polypropylene and EPDM rubber blends. It also has a high cost-performance ratio and has gradually replaced EPDM rubber in many fields. This invention uses polypropylene, EPDM rubber and POE thermoplastic elastomer as composite base materials. By adding UV absorbers and flame retardants, the material's UV aging resistance, flame retardancy and overall weather resistance are further enhanced, giving it excellent comprehensive mechanical properties. It is suitable for components with high durability and safety requirements, such as automotive push-pull sleeves.

[0021] (2) The present invention uses 1,1,3,3,5,5-hexa(styreneoxy)triphosphazene as a flame retardant. This compound decomposes under high temperature conditions, releasing phosphorus-containing free radicals (such as PO·) and nitrogen-containing gases (such as nitrogen and ammonia). Among them, PO· free radicals can capture active free radicals (such as H· and HO·) in the flame, thereby interrupting the chain combustion reaction; while inert gases such as nitrogen inhibit the spread of flame by diluting the oxygen concentration, thus achieving a gas-phase flame retardant effect. Simultaneously, phosphorus catalyzes the dehydration and carbonization of the polymer, forming a dense and continuous carbon layer that effectively isolates heat and oxygen transfer, preventing further pyrolysis of the internal materials, thus achieving a highly efficient flame-retardant effect in the condensed phase. Furthermore, the styrene oxide group in the 1,1,3,3,5,5-hexa(styreneoxy)triphosphazene heterocyclic phosphazene molecule exhibits good reactivity and compatibility, enabling it to interact with other raw material components such as the polypropylene matrix, EPDM rubber, and POE thermoplastic elastomer to a certain extent during processing, and even participate in grafting or crosslinking reactions in the presence of an initiator. These reactions… It enhances the interfacial bonding between components, reduces phase separation, and improves the uniformity and structural density of the composite material. This enhanced interfacial compatibility does not sacrifice the mechanical properties of the material; on the contrary, it effectively maintains or even improves the tensile strength of the material while providing excellent flame retardant effects, avoiding the "flame retardant-mechanical property inversion" problem common in traditional additive flame retardants. Furthermore, this flame retardant itself has high thermal stability, with a decomposition temperature higher than that of conventional polypropylene, ensuring that it will not decompose or fail during the molding process, thus guaranteeing the safety of the processing and the durability of the flame retardant effect.

[0022] (3) In the preparation process of the anti-aging automotive push-pull sleeve material, the flame retardant 1,1,3,3,5,5-hexa(styreneoxy)triphosphazene is first premixed with the ultraviolet absorber, and p-toluenesulfonic acid is introduced as a catalyst during the mixing process. Under the action of the acidic catalyst, the styrene group in the flame retardant molecule undergoes an alkylation reaction with the ultraviolet absorber. Some styrene groups are selectively introduced into the ortho position of the phenolic hydroxyl group of the ultraviolet absorber to generate styreneated phenol derivatives. This process not only achieves molecular-level synergy between the flame retardant and the ultraviolet absorber, but also produces a significant steric hindrance effect by introducing a large volume of styrene group into the ortho position of the phenolic antioxidant. This effect can effectively shield the phenolic hydroxyl group and inhibit its oxidation consumption under heat or oxygen, thereby significantly improving the antioxidant capacity of the phenolic ultraviolet absorber. The process involves enhancing chemical activity and thermal stability to prolong the protective effect of the material. The material is then melt-blended with polypropylene, EPDM rubber, POE thermoplastic elastomer, and an initiator. This is followed by further melt-blending with other raw material components and extrusion granulation. During this process, the initiator promotes grafting or cross-linking reactions between the polypropylene and the elastomer, enhancing the compatibility of the multiphase system. The pre-generated styrene-modified phenol derivative not only provides efficient UV absorption and antioxidant functions, but its styrene groups also exhibit good compatibility and interfacial interaction with olefin-containing components such as POE or EPDM, further improving the dispersibility of the UV absorber and flame retardant and the interfacial bonding strength with the matrix. The resulting anti-aging automotive push-pull sleeve material maintains excellent flame retardant properties while significantly improving the material's antioxidant capacity, long-term thermal stability, and overall mechanical properties. Detailed Implementation

[0023] To better understand the above technical solution, the following will provide a detailed explanation of the technical solution in conjunction with specific implementation methods.

[0024] Based on the embodiments of this invention, all other embodiments obtained by those skilled in the art without inventive effort are within the scope of protection of this invention.

[0025] The following embodiments are only used to illustrate the technical solutions of the present invention more clearly, and should not be used to limit the scope of protection of the present invention.

[0026] The specific preparation method of 1,1,3,3,5,5-hexa(styreneoxy)triphosphonic triphosphazene is as follows: 8.16 g of 4-hydroxystyrene was dissolved in 100 mL of tetrahydrofuran, 1.63 g of sodium hydride was added, and the mixture was stirred at room temperature for 1 h. Then, 40 mL of tetrahydrofuran solution containing 2.60 g of hexachlorotriphosphonic triphosphazene was added at 1 s / drop, and the mixture was stirred at 50 °C for 48 h. After evaporating the solvent, the mixture was purified by recrystallization from methanol to obtain 1,1,3,3,5,5-hexa(styreneoxy)triphosphonic triphosphazene.

[0027] Initiators include dicumyl peroxide.

[0028] Lubricants include polyethylene wax.

[0029] Silane coupling agents include 3-(methacryloyloxy)propyltrimethoxysilane. Example 1

[0030] A method for preparing an anti-aging automotive push-pull sleeve material includes the following preparation steps: (1) Weigh and mix the raw materials as follows: 45 parts by mass of polypropylene, 2 parts by mass of UV absorber 2,4'-dihydroxybenzophenone, 15 parts by mass of flame retardant 1,1,3,3,5,5-hexa(styreneoxy)triphosphonic triphosphazene, 2.5 parts by mass of EPDM rubber, 2.5 parts by mass of POE thermoplastic elastomer, 1.5 parts by mass of initiator dicumyl peroxide, 4 parts by mass of silica, 1 part by mass of carbon black, 4 parts by mass of silane coupling agent, and 3 parts by mass of lubricant. (2) Under nitrogen protection, the flame retardant weighed in step (1) is dissolved in 15 times the mass of the flame retardant in dimethyl sulfoxide to obtain solution A; the ultraviolet absorber weighed in step (1) is dissolved in 8 times the mass of the ultraviolet absorber in dimethyl sulfoxide, and then 0.005 times the mass of the ultraviolet absorber in p-toluenesulfonic acid is added. After stirring for 55 min, the temperature is raised to 120℃, and then solution A is added drop by drop at 1s / drop. After the addition is completed, the temperature is kept constant for 110 min, and then sodium carbonate is added until the pH of the reaction system is neutral. Dimethyl sulfoxide is removed by vacuum distillation to obtain mixture A. (3) The polypropylene, EPDM rubber, POE thermoplastic elastomer, mixture A obtained in step (2), and 2 / 3 of the initiator weighed in step (1) are mixed in a high-speed mixer at 1800 r / min for 10 min until they are uniformly mixed. The mixture is then melt-blended in a twin-screw extruder. The mixture is then mixed with silica, carbon black, silane coupling agent, lubricant, and the remaining initiator in a high-speed mixer at 1800 r / min for 10 min until they are uniformly mixed. The mixture is then melt-blended in a twin-screw extruder to obtain an anti-aging automotive push-pull sleeve material. The die head temperature of the twin-screw extruder is 160℃, the die head pressure is 5MPa, and the screw speed is 100 r / min. Example 2

[0031] A method for preparing an anti-aging automotive push-pull sleeve material includes the following preparation steps: (1) Weigh and mix the raw materials as follows: 54 parts by mass of polypropylene, 3 parts by mass of UV absorber 2,6,4'-trihydroxy-4-methoxybenzophenone, 20 parts by mass of flame retardant 1,1,3,3,5,5-hexa(styreneoxy)triphosphonic triphosphazene, 3 parts by mass of EPDM rubber, 3 parts by mass of POE thermoplastic elastomer, 1.6 parts by mass of initiator dicumyl peroxide, 3.5 parts by mass of silica, 1.5 parts by mass of carbon black, 5 parts by mass of silane coupling agent, and 4 parts by mass of lubricant; (2) Under nitrogen protection, the flame retardant weighed in step (1) is dissolved in 17 times the mass of the flame retardant in dimethyl sulfoxide to obtain solution A; the ultraviolet absorber weighed in step (1) is dissolved in 10 times the mass of the ultraviolet absorber in dimethyl sulfoxide, and then 0.01 times the mass of the ultraviolet absorber in p-toluenesulfonic acid is added. After stirring for 60 min, the temperature is raised to 125℃, and then solution A is added dropwise at 2s / drop. After the addition is completed, the temperature is kept constant for 120 min, and then sodium carbonate is added until the pH of the reaction system is neutral. Dimethyl sulfoxide is removed by vacuum distillation to obtain mixture A. (3) The polypropylene, EPDM rubber, POE thermoplastic elastomer, mixture A obtained in step (2), and 2 / 3 of the initiator weighed in step (1) are mixed in a high-speed mixer at 2000 r / min for 15 min until uniform. The mixture is then melt-blended in a twin-screw extruder. The mixture is then mixed with silica, carbon black, silane coupling agent, lubricant, and the remaining initiator in a high-speed mixer at 2000 r / min for 15 min until uniform. The mixture is then melt-blended in a twin-screw extruder to obtain an anti-aging automotive push-pull sleeve material. The twin-screw extruder has a die head temperature of 165℃, a die head pressure of 5MPa, and a screw speed of 90 r / min. Example 3

[0032] A method for preparing an anti-aging automotive push-pull sleeve material includes the following preparation steps: (1) Weigh and mix the raw materials as follows: 63 parts by mass of polypropylene, 4 parts by mass of UV absorber 2,6,4'-trihydroxy-4-methoxybenzophenone, 25 parts by mass of flame retardant 1,1,3,3,5,5-hexa(styreneoxy)triphosphonic triphosphazene, 3.5 parts by mass of EPDM rubber, 3.5 parts by mass of POE thermoplastic elastomer, 1.7 parts by mass of initiator dicumyl peroxide, 3 parts by mass of silica, 2 parts by mass of carbon black, 6 parts by mass of silane coupling agent, and 5 parts by mass of lubricant; (2) Under nitrogen protection, the flame retardant weighed in step (1) is dissolved in 20 times the mass of the flame retardant in dimethyl sulfoxide to obtain solution A; the ultraviolet absorber weighed in step (1) is dissolved in 12 times the mass of the ultraviolet absorber in dimethyl sulfoxide, and then 0.02 times the mass of the ultraviolet absorber in p-toluenesulfonic acid is added. After stirring for 65 min, the temperature is raised to 130℃, and then solution A is added dropwise at 3s / drop. After the addition is completed, the temperature is kept constant for 130 min, and then sodium carbonate is added until the pH of the reaction system is neutral. Dimethyl sulfoxide is removed by vacuum distillation to obtain mixture A. (3) The polypropylene, EPDM rubber, POE thermoplastic elastomer, mixture A obtained in step (2), and 2 / 3 of the initiator weighed in step (1) are mixed in a high-speed mixer at 2400 r / min for 20 min until uniform. The mixture is then melt-blended in a twin-screw extruder. The mixture is then mixed with silica, carbon black, silane coupling agent, lubricant, and the remaining initiator in a high-speed mixer at 2400 r / min for 20 min until uniform. The mixture is then melt-blended in a twin-screw extruder to obtain an anti-aging automotive push-pull sleeve material. The twin-screw extruder has a die head temperature of 170℃, a die head pressure of 5 MPa, and a screw speed of 80 r / min. Comparative Example 1

[0033] A method for preparing an anti-aging automotive push-pull sleeve material includes the following preparation steps: (1) Weigh and mix the raw materials as follows: 54 parts by weight of polypropylene, 3 parts by weight of UV absorber 2,4'-dihydroxybenzophenone or 2,6,4'-trihydroxy-4-methoxybenzophenone, 20 parts by weight of flame retardant, 3 parts by weight of EPDM rubber, 3 parts by weight of POE thermoplastic elastomer, 1.6 parts by weight of initiator dicumyl peroxide, 3.5 parts by weight of silica, 1.5 parts by weight of carbon black, 5 parts by weight of silane coupling agent, and 4 parts by weight of lubricant; (2) Under nitrogen protection, the flame retardant weighed in step (1) is dissolved in 17 times the mass of the flame retardant in dimethyl sulfoxide to obtain solution A; the ultraviolet absorber weighed in step (1) is dissolved in 10 times the mass of the ultraviolet absorber in dimethyl sulfoxide, and then 0.01 times the mass of the ultraviolet absorber in p-toluenesulfonic acid is added. After stirring for 60 min, the temperature is raised to 125℃, and then solution A is added dropwise at 2s / drop. After the addition is completed, the temperature is kept constant for 120 min, and then sodium carbonate is added until the pH of the reaction system is neutral. Dimethyl sulfoxide is removed by vacuum distillation to obtain mixture A. (3) The polypropylene, EPDM rubber, POE thermoplastic elastomer, mixture A obtained in step (2), and 2 / 3 of the initiator weighed in step (1) are mixed in a high-speed mixer at 2000 r / min for 15 min until uniform. The mixture is then melt-blended in a twin-screw extruder. The mixture is then mixed with silica, carbon black, silane coupling agent, lubricant, and the remaining initiator in a high-speed mixer at 2000 r / min for 15 min until uniform. The mixture is then melt-blended in a twin-screw extruder to obtain an anti-aging automotive push-pull sleeve material. The twin-screw extruder has a die head temperature of 165℃, a die head pressure of 5MPa, and a screw speed of 90 r / min.

[0034] The flame retardant is prepared by compounding aluminum diethylphosphonate and melamine polyphosphate at a mass ratio of 2:1. Comparative Example 2

[0035] A method for preparing an anti-aging automotive push-pull sleeve material includes the following preparation steps: (1) Weigh and mix the raw materials as follows: 54 parts by mass of polypropylene, 3 parts by mass of UV absorber UV-531, 20 parts by mass of flame retardant 1,1,3,3,5,5-hexa(styreneoxy)triphosphonic triphosphazene, 3 parts by mass of EPDM rubber, 3 parts by mass of POE thermoplastic elastomer, 1.6 parts by mass of initiator dicumyl peroxide, 3.5 parts by mass of silica, 1.5 parts by mass of carbon black, 5 parts by mass of silane coupling agent, and 4 parts by mass of lubricant. (2) Under nitrogen protection, the flame retardant weighed in step (1) is dissolved in 17 times the mass of the flame retardant in dimethyl sulfoxide to obtain solution A; the ultraviolet absorber weighed in step (1) is dissolved in 10 times the mass of the ultraviolet absorber in dimethyl sulfoxide, and then 0.01 times the mass of the ultraviolet absorber in p-toluenesulfonic acid is added. After stirring for 60 min, the temperature is raised to 125℃, and then solution A is added dropwise at 2s / drop. After the addition is completed, the temperature is kept constant for 120 min, and then sodium carbonate is added until the pH of the reaction system is neutral. Dimethyl sulfoxide is removed by vacuum distillation to obtain mixture A. (3) The polypropylene, EPDM rubber, POE thermoplastic elastomer, mixture A obtained in step (2), and 2 / 3 of the initiator weighed in step (1) are mixed in a high-speed mixer at 2000 r / min for 15 min until uniform. The mixture is then melt-blended in a twin-screw extruder. The mixture is then mixed with silica, carbon black, silane coupling agent, lubricant, and the remaining initiator in a high-speed mixer at 2000 r / min for 15 min until uniform. The mixture is then melt-blended in a twin-screw extruder to obtain an anti-aging automotive push-pull sleeve material. The twin-screw extruder has a die head temperature of 165℃, a die head pressure of 5MPa, and a screw speed of 90 r / min. Comparative Example 3

[0036] A method for preparing an anti-aging automotive push-pull sleeve material includes the following preparation steps: (1) Weigh and mix the raw materials as follows: 54 parts by mass of polypropylene, 3 parts by mass of UV absorber 2,6,4'-trihydroxy-4-methoxybenzophenone, 20 parts by mass of flame retardant 1,1,3,3,5,5-hexa(styreneoxy)triphosphonic triphosphazene, 3 parts by mass of EPDM rubber, 3 parts by mass of POE thermoplastic elastomer, 1.6 parts by mass of initiator dicumyl peroxide, 3.5 parts by mass of silica, 1.5 parts by mass of carbon black, 5 parts by mass of silane coupling agent, and 4 parts by mass of lubricant; (2) The polypropylene, EPDM rubber, POE thermoplastic elastomer, flame retardant, and 2 / 3 of the initiator weighed in step (1) are mixed in a high-speed mixer at 2000 r / min for 15 min until uniform. The mixture is then melt-blended in a twin-screw extruder. The mixture is then mixed with UV absorber, silica, carbon black, silane coupling agent, lubricant, and the remaining initiator in a high-speed mixer at 2000 r / min for 15 min until uniform. The mixture is then melt-blended and extruded in a twin-screw extruder to obtain an anti-aging automotive push-pull sleeve material. The twin-screw extruder has a die head temperature of 165℃, a die head pressure of 5MPa, and a screw speed of 90 r / min. Example of effect

[0037] Table 1 below shows the performance test results of the anti-aging automotive push-pull sleeve materials prepared in Examples 1-3 and Comparative Examples 1-3: Table 1

[0038] As shown in Table 1, the anti-aging automotive push-pull sleeve materials obtained in Examples 1-3 have good mechanical properties, flame retardancy, and aging resistance.

[0039] The difference between Comparative Example 1 and Example 2 is that the flame retardant is obtained by compounding aluminum diethylphosphinate and melamine polyphosphate in a mass ratio of 2:1, instead of 1,1,3,3,5,5-hexa(styreneoxy)triphosphonic triphosphazene. The resulting anti-aging automotive push-pull sleeve material has weaker mechanical properties, UV aging resistance, and ozone aging resistance.

[0040] The difference between Comparative Example 2 and Example 2 is that the UV absorber used is UV-531 instead of 2,6,4'-trihydroxy-4-methoxybenzophenone, resulting in a less mechanical and ozone-resistant anti-aging automotive push-pull sleeve material.

[0041] The difference between Comparative Example 3 and Example 2 is that in the anti-aging automotive push-pull sleeve material, polypropylene, EPDM rubber, POE thermoplastic elastomer, flame retardant, and 2 / 3 of the initiator are melt-blended and then melt-blended with UV absorber, silica, carbon black, silane coupling agent, lubricant, and the remaining initiator. The resulting anti-aging automotive push-pull sleeve material has weaker mechanical properties and ozone aging resistance.

[0042] The specific embodiments described above further illustrate the purpose, technical solution, and beneficial effects of the present invention. It should be understood that the above descriptions are merely specific embodiments of the present invention and are not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. An anti-aging automotive push-pull sleeve material, characterized in that, By mass, the raw material components include 45-63 parts polypropylene, 2-4 parts ultraviolet absorber, 15-25 parts flame retardant, 2.5-3.5 parts EPDM rubber, 2.5-3.5 parts POE thermoplastic elastomer, 0.5-0.7 parts initiator, 3-4 parts silica, 1-2 parts carbon black, 4-6 parts silane coupling agent, and 3-5 parts lubricant.

2. The anti-aging automotive push-pull sleeve material according to claim 1, characterized in that, The ultraviolet absorber is 2,4'-dihydroxybenzophenone or 2,6,4'-trihydroxy-4-methoxybenzophenone.

3. The anti-aging automotive push-pull sleeve material according to claim 1, characterized in that, The flame retardant comprises at least 1,1,3,3,5,5-hexa(styreneoxy)triphosphonic triphosphazene.

4. The anti-aging automotive push-pull sleeve material according to claim 1, characterized in that, The initiator includes dicumyl peroxide.

5. The anti-aging automotive push-pull sleeve material according to claim 1, characterized in that, The lubricant includes polyethylene wax.

6. The anti-aging automotive push-pull sleeve material according to claim 1, characterized in that, The silane coupling agent includes 3-(methacryloyloxy)propyltrimethoxysilane.

7. A method for preparing an anti-aging automotive push-pull sleeve material as described in any one of claims 1 to 6, characterized in that, The preparation steps include the following: (1) Weigh and mix each raw material component; (2) Under nitrogen protection, the flame retardant weighed in step (1) is dissolved in 15 to 20 times the mass of the flame retardant in dimethyl sulfoxide to obtain solution A; the ultraviolet absorber weighed in step (1) is dissolved in 8 to 12 times the mass of the ultraviolet absorber in dimethyl sulfoxide, and then 0.005 to 0.02 times the mass of the ultraviolet absorber in catalyst is added. After stirring for 55 to 65 minutes, the temperature is raised to 120 to 130°C, and then solution A is added dropwise at 1 to 3 seconds. After the addition is completed, the temperature is kept constant for 110 to 130 minutes. Then sodium carbonate is added until the pH of the reaction system is neutral. Dimethyl sulfoxide is removed by vacuum distillation to obtain mixture A. (3) The polypropylene, EPDM rubber, POE thermoplastic elastomer, mixture A obtained in step (2), and 2 / 3 of the initiator weighed in step (1) are mixed evenly in a high-speed mixer and then added to a twin-screw extruder for melt mixing. Then, it is mixed evenly with silica, carbon black, silane coupling agent, lubricant, and the remaining initiator in a high-speed mixer. Finally, it is melt-mixed and extruded in a twin-screw extruder to obtain an anti-aging automotive push-pull sleeve material.

8. The method for preparing the anti-aging automotive push-pull sleeve material according to claim 7, characterized in that, The catalyst used is p-toluenesulfonic acid.

9. The method for preparing the anti-aging automotive push-pull sleeve material according to claim 7, characterized in that, The twin-screw extruder has a die head temperature of 160~170℃, a die head pressure of 1~10MPa, and a screw speed of 80~100r / min.

10. An anti-aging automotive push-pull sleeve, characterized in that, From the inside out, it includes an inner lining tube layer, a reinforcing layer, and an anti-aging outer coating layer; the anti-aging outer coating layer is made of the high and low temperature resistant automotive push-pull sleeve material as described in any one of claims 1 to 6.

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