Thermoplastic elastomer material containing core-shell microspheres and use thereof

Abstract

The present application relates to a kind of thermoplastic elastomer material containing core-shell microspheres and its application, belong to elastomer preparation technical field, acrylate, styrene, acrylonitrile and the like are used as monomer, under the initiation of initiator, free radical is generated and graft polymerization is carried out, again as shell layer, the emulsion of containing amide, polyether polyol and polyether siloxane and the like wax core is coated in inside to form core-shell microspheres, then melt blend with polyether copolyester elastomer matrix, the polyether, polyester segment contained in core-shell microspheres is similar with the polyether, polyester segment of polyether copolyester elastomer matrix, increase its compatibility in matrix, can be evenly distributed in matrix, thus the CVJ sheath made of material, in the process of use, core-shell microspheres itself can play the role of reducing friction, reducing noise, when core-shell microspheres experience a certain degree of friction, shell layer cracks, and the wax material in the inside is precipitated.

Description

Technical Field

[0001] This invention belongs to the field of elastomer preparation technology, and relates to a thermoplastic elastomer material containing core-shell microsphere particles and its application. Background Technology

[0002] Thermoplastic elastomers, with their excellent mechanical properties, chemical resistance, and ease of molding and processing, are widely used in many fields, especially in automotive parts manufacturing. Constant velocity joint (CVJ) bushings, as core protective components of automotive transmission systems, are typically manufactured using thermoplastic elastomers, particularly copolyether esters. Copolyether esters are the preferred material for CVJ bushings because they possess a range of mechanical and physical properties that meet specific requirements. They can withstand various stresses generated during vehicle operation, including torsional and tensile stresses, ensuring the bushing does not easily break or deform excessively. They also possess good flexibility to adapt to the movement of the CVJ at different sway angles, while also having a certain degree of rigidity to provide effective support and protection for the internal universal joint and drive shaft. In addition, coether ester has good chemical resistance to greases. Various greases, such as lubricating oil, exist in automotive transmission systems. Coether ester can maintain its stable performance even when in long-term contact with these greases and will not experience aging, swelling, or other problems due to grease corrosion, thus ensuring the service life of the CVJ sheath.

[0003] Chinese patent application CN112912441A discloses a copolyether resin formulation in which 1-4 wt% of polyether glycol (PTMEG) with a molecular weight preferably 800-3000 is added; particularly preferably, PTMEG with a molecular weight of 2000 is added. Because polysiloxane PDMS is incompatible with copolyether ester elastomers, it is difficult to add. Therefore, in the examples, polysiloxane encapsulated in poly[(meth)acrylate] is preferred, having an average particle size of 200-250 μm as determined by optical microscopy.

[0004] The invention application with publication number CN109476905A discloses an equal velocity joint sheath material made of a polymer composition. The polymer composition includes a thermoplastic polyester elastomer, a first fast diffusion wax (unsaturated diamide: ethylene dioleamide) and a second slow diffusion wax (unsaturated diamide: ethylene distearylamide). After 2500 hours, the weight loss of the first fast diffusion wax is greater than 0.6 wt%, and the weight loss of the second slow diffusion wax is less than 0.4 wt%.

[0005] The above solutions all involve directly adding wax or oil as an additive. Once the wax or oil separates, it provides lubrication and reduces the squeaking noise caused by friction during compression. However, during use, compression causes wax and oil films to separate from the surface of the sheath. These films are quickly used up or even disappear under the wash of rainwater. Relying on the separation of wax and oil for surface lubrication lacks long-term lubrication. Summary of the Invention

[0006] The purpose of this invention is to provide a thermoplastic elastomer material containing core-shell microspheres and its application, which improves the long-term lubricity and aging resistance of the sheath by melt blending core-shell microspheres and polyether copolyester elastomer.

[0007] The objective of this invention can be achieved through the following technical solutions:

[0008] A thermoplastic elastomer material containing core-shell microspheres is prepared by the following steps:

[0009] Step 1: The monomers containing double bonds are grafted and polymerized under the action of an initiator through emulsion polymerization, and the lubricating core emulsion is wrapped inside to obtain core-shell microspheres.

[0010] Step 2: Use a twin-screw extruder to melt-blend polyether copolyester elastomer, core-shell microspheres, antioxidants and carbon black to obtain a thermoplastic elastomer material containing core-shell microspheres.

[0011] Furthermore, the preparation process of core-shell microspheres is as follows:

[0012] Acrylic esters, styrene, acrylonitrile, deionized water and emulsifier are added to a reaction vessel and stirred for 15-20 minutes. Then, ammonium persulfate initiator is added and mixed evenly. The mixture is then added dropwise to the core emulsion over 2-3 hours and kept at this temperature for 1.5 hours. The pH is adjusted to 7-8 with ammonia water. Calcium chloride aqueous solution is added under stirring conditions, stirred, filtered, washed, and dried to obtain core-shell microspheres.

[0013] Furthermore, the preparation process of the nuclear emulsion is as follows:

[0014] Acrylic esters, double-bonded lubricating oils, acrylic acid, deionized water, and emulsifiers are added to a reactor and stirred for 15-20 minutes to obtain a pre-emulsion. Deionized water, emulsifiers, sodium bicarbonate, and a portion of the pre-emulsion are added to the reactor. A 10wt% ammonium persulfate aqueous solution is added at 600-800 rpm and 60-62°C. The temperature is raised to 83-85°C and held for 15-20 minutes. The remaining pre-emulsion and a 10wt% ammonium persulfate aqueous solution are then added dropwise over 1.5 hours, and the mixture is held for 30 minutes to obtain a core emulsion.

[0015] Furthermore, the lubricant is one or a mixture of amides, polyether polyols, and polyether siloxanes.

[0016] Furthermore, acrylates are one or a mixture of methyl methacrylate, butyl acrylate, and prepolymer monomers containing double bonds.

[0017] Furthermore, the preparation process of the prepolymer containing double bonds is as follows:

[0018] 3,4-epoxycyclohexylmethyl methacrylate and p-aminodiphenylamine were added to a reaction vessel, and then hexafluoroisopropanol was added dropwise to the reaction vessel. The mixture was stirred and dissolved, and the reaction was carried out at 120-125℃ for 24-26 hours. The liquid was washed with a mixture of n-heptane and chloroform, and then distilled under reduced pressure to obtain a prepolymer monomer containing double bonds.

[0019] Furthermore, the ratio of 3,4-epoxycyclohexylmethyl methacrylate, p-aminodiphenylamine, and hexafluoroisopropanol is 46.7-56.7 g: 18.4-24.4 g: 40-50 mL.

[0020] Furthermore, the proportion of core-shell microsphere particles is 0.1-1%.

[0021] Furthermore, the melt blending time is 5-6 min, the rotation speed is 100-120 r / min, and the temperature is 175-180℃.

[0022] Application of a thermoplastic elastomer material containing core-shell microspheres in CVJ sheath material.

[0023] The beneficial effects of this invention are:

[0024] 1. This invention uses acrylates, styrene, acrylonitrile, etc. as monomers. Under the initiation of an initiator, free radicals are generated and grafted polymerized. Then, a core-shell microsphere is formed by encapsulating a waxy core emulsion containing amides, polyether polyols, and polyether siloxanes as a shell layer. This core-shell microsphere is then melt-blended with a polyether copolyester elastomer matrix. The polyether and polyester segments in the core-shell microsphere are similar to those in the polyether copolyester elastomer matrix, which increases its compatibility in the matrix and allows it to be evenly distributed in the matrix. The CVJ sheath made from this material can reduce friction and noise during use. When the core-shell microsphere has undergone a certain degree of friction, the shell cracks and the internal waxy substances precipitate out, but a wax film can still be formed on the surface of the CVJ sheath, reducing surface tension and providing lubrication and reducing friction noise, thus prolonging the lubrication effect.

[0025] 2. This invention uses 3,4-epoxycyclohexylmethyl methacrylate and p-aminodiphenylamine as raw materials to synthesize a prepolymer monomer containing double bonds. The epoxy group of 3,4-epoxycyclohexylmethyl methacrylate undergoes a nucleophilic addition reaction with the amino group in p-aminodiphenylamine. The prepolymer monomer containing double bonds is then polymerized with monomers such as acrylates and styrene to form a shell layer, increasing the strength of the shell layer and uniformly loading the aniline structure onto the core-shell microspheres. This is then melt-blended with the matrix to improve its dispersion uniformity in the matrix. In conjunction with substances such as carbon black, it enhances the aging resistance of the material, thereby extending the service life of the CVJ sheath.

[0026] 3. The core-shell microspheres in this invention are grafted copolymerized with prepolymer monomers using unreacted double bonds remaining on the surface of the core emulsion. Simultaneously, hydrogen bonds are formed between the cyano groups of acrylonitrile and the carboxyl groups of the core layer, and van der Waals forces are generated between the styrene and the ester groups of the core layer. This ensures that the shell layer can tightly encapsulate the core particles, enhancing the interfacial bonding force between the core and shell. This results in a dense structure between the core and shell, ensuring structural stability. Under certain frictional forces, the core layer can break, releasing the waxy substances in the core layer for lubrication. At the same time, the dense structure of the shell layer can fix the aniline structure in the prepolymer monomer containing double bonds, preventing its migration. This improves both mechanical properties and aging resistance. Detailed Implementation

[0027] To further illustrate the technical means and effects of the present invention in achieving the intended purpose, the following detailed description of the specific implementation methods, features and effects of the present invention, in conjunction with preferred embodiments, is provided below.

[0028] Example 1: This example provides a thermoplastic elastomer material containing core-shell microspheres, prepared through the following steps:

[0029] S1: 51.7 g of 3,4-epoxycyclohexylmethyl methacrylate and 21.4 g of p-aminodiphenylamine were added to a reaction vessel, and then 45 mL of hexafluoroisopropanol was added dropwise to the reaction vessel. The mixture was stirred and dissolved, and stirred at 122 °C for 25 h. The epoxy group in 3,4-epoxycyclohexylmethyl methacrylate and the amino group in p-aminodiphenylamine underwent a nucleophilic addition reaction. The liquid was washed with a mixture of n-heptane and chloroform (volume ratio of n-heptane to chloroform was 3:1), and the mixture was distilled under reduced pressure for 1.5 h to obtain a prepolymer monomer containing double bonds.

[0030] S2: Add 4.5g methyl methacrylate, 34g vinyl-terminated polyether siloxane, 2.3g acrylic acid, 41.9g butyl acrylate, 187.5mL deionized water, and 1.4g emulsifier (sodium dodecylbenzenesulfonate) to a reactor and stir for 17min at 22℃ and 900r / min to obtain a pre-emulsion. Add 42.5mL deionized water, 0.9g emulsifier (sodium dodecylbenzenesulfonate), 0.6g sodium bicarbonate, and 28.8g pre-emulsion to a reactor and add 11.6g of 10wt% ammonium persulfate aqueous solution at 700r / min and 61℃. Heat to 84℃ and hold for 17min. Then, add 247.2g of pre-emulsion and 5.3g of 10wt% ammonium persulfate aqueous solution dropwise over 1.5h and hold for 30min to obtain a core emulsion.

[0031] S3: 4.0g methyl methacrylate, 8.0g prepolymer containing double bonds, 8.0g butyl acrylate, 10.0g styrene, 7.0g acrylonitrile, 125.0g deionized water and 1.9g emulsifier (sodium dodecylbenzene sulfonate) were added to the reactor and stirred for 17min at 22℃ and 900r / min. Then, 5.0g of 10wt% ammonium persulfate aqueous solution was added and mixed evenly. The mixture was then added dropwise to the core emulsion over 2.5h and kept at this temperature for 1.5h. The pH was adjusted to 7 with ammonia water. A 10wt% calcium chloride aqueous solution was slowly added at 350r / min and stirred for 12min. The mixture was then vacuum filtered, and the precipitate was washed four times with deionized water and dried at 62℃ for 5h to obtain core-shell microspheres.

[0032] Unreacted double bonds and carboxyl groups remain on the surface of the nuclei in the core emulsion. Methyl methacrylate, butyl acrylate, styrene, and acrylonitrile, when added dropwise, grow on the surface of the nuclei through graft copolymerization under the initiation of ammonium persulfate. The cyano groups of acrylonitrile form hydrogen bonds with the carboxyl groups of the core layer, and the ester groups of styrene generate van der Waals forces with the ester groups of the core layer, ensuring that the shell layer tightly covers the core layer and forms a clear core-shell structure. Calcium ions in calcium chloride, as divalent cations, can neutralize the negative charge on the surface of the core-shell particles, causing them to lose electrostatic repulsion and agglomerate and settle.

[0033] S4: Using a twin-screw extruder with an aspect ratio of 40 or higher, 100g of polyether copolyester elastomer, 0.55g of core-shell microspheres, 1.35g of antioxidant 618 and 5g of carbon black are melt-blended for 5 minutes at a melting speed of 110r / min and a melting temperature of 177℃ to obtain a thermoplastic elastomer material containing core-shell microspheres.

[0034] Example 2: This example provides a thermoplastic elastomer material containing core-shell microspheres, prepared through the following steps:

[0035] S1: 46.7g of 3,4-epoxycyclohexylmethyl methacrylate and 18.4g of p-aminodiphenylamine were added to a reaction vessel, and then 40mL of hexafluoroisopropanol was added dropwise to the reaction vessel. The mixture was stirred and dissolved, and stirred at 120℃ for 24h. The epoxy group in 3,4-epoxycyclohexylmethyl methacrylate and the amino group in p-aminodiphenylamine underwent a nucleophilic addition reaction. The liquid was washed with a mixture of n-heptane and chloroform (volume ratio of n-heptane to chloroform is 3:1), and the mixture was distilled under reduced pressure for 1.5h to obtain a prepolymer monomer containing double bonds.

[0036] S2: Add 4.0g methyl methacrylate, 28g vinyl-terminated polyether siloxane, 2.1g acrylic acid, 39.9g butyl acrylate, 175mL deionized water, and 1.3g emulsifier (sodium dodecylbenzenesulfonate) to a reactor and stir for 15min at 20℃ and 800r / min to obtain a pre-emulsion. Add 35mL deionized water, 0.8g emulsifier (sodium dodecylbenzenesulfonate), 0.4g sodium bicarbonate, and 25.8g pre-emulsion to a reactor and add 9.6g of 10wt% ammonium persulfate aqueous solution at 600r / min and 60℃. Heat to 83℃ and hold for 15min. Then, add 232.2g of pre-emulsion and 4.8g of 10wt% ammonium persulfate aqueous solution dropwise over 1.5h and hold for 30min to obtain a core emulsion.

[0037] S3: Add 3.0g methyl methacrylate, 6.0g prepolymer monomer containing double bonds, 6.0g butyl acrylate, 9.0g styrene, 6.0g acrylonitrile, 120.0g deionized water and 1.8g emulsifier (sodium dodecylbenzene sulfonate) to the reactor, stir for 15min at 20℃ and 800r / min, then add 4.0g of 10wt% ammonium persulfate aqueous solution, mix well, and dropwise into the core emulsion over 2h. Keep warm for 1.5h, adjust the pH to 7 with ammonia water, slowly add 10wt% calcium chloride aqueous solution at 300r / min, stir for 10min, vacuum filter, wash the precipitate three times with deionized water, and dry at 60℃ for 4h to obtain core-shell microspheres.

[0038] S4: Using a twin-screw extruder with an aspect ratio of 40 or higher, 100g of polyether copolyester elastomer, 0.1g of core-shell microspheres, 1.2g of antioxidant 618 and 4g of carbon black are melt-blended for 5 minutes at a melting speed of 100r / min and a melting temperature of 175℃ to obtain a thermoplastic elastomer material containing core-shell microspheres.

[0039] Example 3: This example provides a thermoplastic elastomer material containing core-shell microspheres, prepared through the following steps:

[0040] S1: 56.7 g of 3,4-epoxycyclohexylmethyl methacrylate and 24.4 g of p-aminodiphenylamine were added to a reaction vessel, and then 50 mL of hexafluoroisopropanol was added dropwise to the reaction vessel. The mixture was stirred and dissolved, and stirred at 125 °C for 26 h. The epoxy group in 3,4-epoxycyclohexylmethyl methacrylate and the amino group in p-aminodiphenylamine underwent a nucleophilic addition reaction. The liquid was washed with a mixture of n-heptane and chloroform (volume ratio of n-heptane to chloroform was 3:1), and the mixture was distilled under reduced pressure for 1.5 h to obtain a prepolymer monomer containing double bonds.

[0041] S2: Add 5.0g methyl methacrylate, 40g vinyl-terminated polyether siloxane, 2.5g acrylic acid, 43.9g butyl acrylate, 200mL deionized water, and 1.5g emulsifier (sodium dodecylbenzenesulfonate) to a reactor and stir for 20min at 25℃ and 1000r / min to obtain a pre-emulsion. Add 50mL deionized water, 1.0g emulsifier (sodium dodecylbenzenesulfonate), 0.8g sodium bicarbonate, and 31.8g pre-emulsion to a reactor and add 13.6g of 10wt% ammonium persulfate aqueous solution at 800r / min and 62℃. Heat to 85℃ and maintain the temperature for 20min. Then, add 262.2g of pre-emulsion and 5.8g of 10wt% ammonium persulfate aqueous solution dropwise over 1.5h and maintain the temperature for 30min to obtain a core emulsion.

[0042] S3: Add 5.0g methyl methacrylate, 10.0g prepolymer monomer containing double bonds, 10.0g butyl acrylate, 11.0g styrene, 8.0g acrylonitrile, 130.0g deionized water and 2.0g emulsifier (sodium dodecylbenzene sulfonate) to the reactor. Stir for 20min at 25℃ and 1000r / min. Then add 6.0g of 10wt% ammonium persulfate aqueous solution and mix well. Add the mixture dropwise to the core emulsion over 3h and keep warm for 1.5h. Adjust the pH to 8 with ammonia water. Slowly add 10wt% calcium chloride aqueous solution at 400r / min and stir for 15min. Vacuum filter the mixture. Wash the precipitate 5 times with deionized water and dry it at 65℃ for 6h to obtain core-shell microspheres.

[0043] S4: Using a twin-screw extruder with an aspect ratio of 40 or higher, 100g of polyether copolyester elastomer, 1g of core-shell microspheres, 1.5g of antioxidant 618 and 6g of carbon black are melt-blended for 6 minutes at a melting speed of 120r / min and a melting temperature of 180℃ to obtain a thermoplastic elastomer material containing core-shell microspheres.

[0044] Example 4: This example provides a thermoplastic elastomer material containing core-shell microspheres. The difference from Example 1 is that no prepolymer monomer containing double bonds is added in step S3, and a thermoplastic elastomer material containing core-shell microspheres is prepared.

[0045] Example 5: This example provides a thermoplastic elastomer material containing core-shell microspheres. The difference from Example 1 is that oleamide is used instead of vinyl-terminated polyether siloxane in step S2 to prepare the thermoplastic elastomer material containing core-shell microspheres.

[0046] Example 6: This example provides a thermoplastic elastomer material containing core-shell microspheres. The difference from Example 1 is that 12g of oleamide is added in step S2, and the amount of vinyl-terminated polyether ester siloxane is adjusted to 16g to prepare the thermoplastic elastomer material containing core-shell microspheres.

[0047] Example 7: This example provides a thermoplastic elastomer material containing core-shell microspheres. The difference from Example 1 is that the amount of core-shell microspheres added in step S4 is adjusted to 1g, and a thermoplastic elastomer material containing core-shell microspheres is prepared.

[0048] Example 8: This example provides a thermoplastic elastomer material containing core-shell microspheres. The difference from Example 1 is that in step S2, allyl-terminated polyether polyol is used instead of vinyl-terminated polyether ester siloxane to prepare the thermoplastic elastomer material containing core-shell microspheres.

[0049] Comparative Example 1: This comparative example provides a thermoplastic elastomer material containing core-shell microsphere particles. The difference from Example 1 is that core-shell microsphere particles are not added in step S4 to prepare the thermoplastic elastomer material.

[0050] The thermoplastic elastomer materials containing core-shell microspheres prepared in Examples 1-8 and the thermoplastic elastomer material prepared in Comparative Example 1 were subjected to performance tests:

[0051] Mechanical property testing: Shore D hardness: According to the national standard ASTM D2240, the sample thickness required for hardness testing is greater than or equal to 6 mm, the temperature is 23±2℃, and different positions of the sample are tested.

[0052] Tensile properties: According to the national standard GB / T528-1998, the required specimens are dumbbell-shaped. Test results include tensile strength, elongation at break, and other properties.

[0053] The thermoplastic elastomer materials containing core-shell microspheres prepared in Examples 1-8 and the thermoplastic elastomer material prepared in Comparative Example 1, in their molten plasticized state, were extruded into a mold cavity using an Ossberger blow molding machine. The piston was extruded upwards, forming a preform in the mold cavity. The preform was then pulled into the mold, and air was blown in to cause the preform to expand inside the mold, tightly adhere to the mold, and be shaped to form the CVJ sheath.

[0054] Squeaking test: The angle between the drive shaft and the universal joint was 40°, the rotation speed was 150 r / min, and the cycle was 100 seconds. During the rotation, liquid and solid were uniformly applied to the outside of the sleeve: (1) 30s spray liquid (30 mL), (2) 10s add solid (10 g), (3) 60s rotate only; the spray liquid was water or an aqueous solution of antifreeze chemicals, which consisted of 15 wt% calcium chloride, 15 wt% calcium hydroxide and 70 wt% tap water, and the solid was sand with an average diameter preferably from 0.1-1.2 mm. The noise was measured using a microphone (National Instruments GRAS 1 / 2” free field response microphone) placed at an appropriate distance from the sleeve (14 cm from the sleeve) and pointing directly at the sleeve ripples, and converted to dB(A). The average time within one rotation of the sleeve was obtained. When the noise level of 78 dB(A) was measured for two consecutive cycles, the squeaking noise was emitted and the experiment was stopped. The highest number of cycles to this point was recorded as the "number of cycles before the squeaking".

[0055] Anti-aging performance: Referring to GB / T3511-2018, the test samples were cut into dumbbell-shaped strips, which were then vertically suspended on a fixture. The fixture was placed on a flat area with an open view outdoors, free from tall buildings and trees, to simulate the aging resistance of the CVJ sheath under outdoor use conditions. The aging time was set to 50 days. The surface color of the aged rubber samples was observed.

[0056] Table 1 Performance Test Overview

[0057]

[0058] As shown in Table 1, the tensile strength and elongation at break of Examples 1-8 are all higher than those of Comparative Example 1, indicating that the prepolymer containing double bonds can undergo graft copolymerization with shell monomers such as methyl methacrylate and styrene. The resulting core-shell microspheres have good compatibility with the polyether copolyester elastomer. This may be because the polyether lipid segments of the core-shell microspheres are similar to the polyether polyester segments of the polyether copolyester elastomer, which can significantly improve the interfacial compatibility between the core-shell microspheres and the polyether copolyester elastomer matrix.

[0059] As shown in Table 1, the number of cycles before the squeaking sound in Examples 1-8 was higher than that in Comparative Example 1. This indicates that the thermoplastic elastomer materials containing core-shell microspheres in Examples 1-8 can still effectively reduce friction and noise under harsh conditions such as rain and sandstorms. This may be because during the friction process, the shell layer cracks and precipitates waxy substances such as amides, polyether polyols, and polyether siloxanes from the core layer. These waxy substances can still form a wax film on the CVJ sheath surface, reducing surface tension, providing lubrication, and reducing friction noise.

[0060] As shown in Table 1, the surface color of Examples 1-3 and Examples 5-8 did not change significantly after aging for 50 days, while the surface color of Examples 4 and Comparative Example 1 changed slightly after aging for 50 days. This indicates that the prepolymer monomer containing double bonds has good aging resistance. This may be because the aniline structure in the prepolymer monomer containing double bonds has good aging resistance. When it is added as a monomer to the shell layer during the preparation process, it undergoes graft polymerization with other monomers in the shell layer, allowing it to be evenly distributed in the shell layer. Together with carbon black, it plays a synergistic role in aging resistance and can also prevent its migration.

[0061] The above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention in any way. Although the present invention has been disclosed above with reference to preferred embodiments, it is not intended to limit the present invention. Any person skilled in the art can make some modifications or alterations to the above-disclosed technical content to create equivalent embodiments without departing from the scope of the present invention. Any simple modifications, equivalent changes and alterations made to the above embodiments based on the technical essence of the present invention without departing from the scope of the present invention shall still fall within the scope of the present invention.

Claims

1. A thermoplastic elastomer material containing core-shell microspheres, characterized in that, Prepared by the following steps: Step 1: The monomers containing double bonds are grafted and polymerized under the action of an initiator by emulsion polymerization, and the lubricating core emulsion is wrapped inside to obtain core-shell microspheres. Step 2: Use a twin-screw extruder to melt-blend polyether copolyester elastomer, core-shell microspheres, antioxidants and carbon black to obtain a thermoplastic elastomer material containing core-shell microspheres; The preparation process of the core-shell microspheres described in step one is as follows: Methyl methacrylate, prepolymer monomers containing double bonds, butyl acrylate, styrene, acrylonitrile, deionized water and emulsifier are added to a reaction vessel and stirred for 15-20 minutes. Then, ammonium persulfate initiator is added and mixed evenly. The mixture is then added dropwise to the core emulsion over 2-3 hours and kept at this temperature for 1.5 hours. The pH is adjusted to 7-8 with ammonia water. Calcium chloride aqueous solution is added under stirring conditions, stirred, filtered, washed, and dried to obtain core-shell microspheres. The preparation process of the nuclear emulsion is as follows: Methyl methacrylate, double-bonded lubricating oil, acrylic acid, butyl acrylate, deionized water, and emulsifier are added to a reaction vessel and stirred for 15-20 minutes to obtain a pre-emulsion. Deionized water, emulsifier, sodium bicarbonate, and a portion of the pre-emulsion are added to the reaction vessel. A 10wt% ammonium persulfate aqueous solution is added at 600-800 r / min and 60-62℃. The temperature is raised to 83-85℃ and held for 15-20 minutes. The remaining pre-emulsion and a 10wt% ammonium persulfate aqueous solution are then added dropwise over 1.5 hours and held for 30 minutes to obtain a core emulsion. The lubricating oil is one or a mixture of amides, polyether polyols and polyether siloxanes; The preparation process of the prepolymer containing double bonds is as follows: Add 46.7-56.7 g of 3,4-epoxycyclohexylmethyl methacrylate and 18.4-24.4 g of p-aminodiphenylamine to a reaction vessel, then add 40-50 mL of hexafluoroisopropanol dropwise to the reaction vessel, stir to dissolve, and react with stirring at 120-125 °C for 24-26 h. Wash the liquid with a mixture of n-heptane and chloroform, and distill under reduced pressure to obtain a prepolymer monomer containing double bonds.

2. The thermoplastic elastomer material containing core-shell microspheres according to claim 1, characterized in that, The proportion of core-shell microspheres in step two is 0.1-1%.

3. The thermoplastic elastomer material containing core-shell microspheres according to claim 1, characterized in that, The melt blending time in step two is 5-6 min, the rotation speed is 100-120 r / min, and the temperature is 175-180℃.

4. The application of a thermoplastic elastomer material containing core-shell microspheres according to any one of claims 1-3 in CVJ sheath material.

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