A kind of aging-resistant TPEE composite material and preparation method thereof

Abstract

The invention relates to the technical field of polymer material preparation, and discloses an aging-resistant TPEE composite material and a preparation method thereof. The aging-resistant TPEE composite material comprises the following raw materials: TPEE resin, maleic anhydride grafted polypropylene, a self-repairing aging-resistant composite material, a fire-resistant flame-retardant filler, a lubricant, and an ultraviolet absorber, wherein the self-repairing aging-resistant composite material is prepared by taking natural rubber as a polymer matrix, and sequentially introducing disulfide bonds and hindered phenol groups; the fire-resistant flame-retardant filler is prepared by taking illite as a carrier, and introducing a nitrogen-phosphorus synergistic flame retardant between its layers. The TPEE composite material prepared by the invention has excellent self-repairing performance, aging resistance, impact resistance, mechanical strength and flame retardancy, can meet the use requirements in various environments, has high safety, and has a long service life.

Description

Technical Field

[0001] The present invention relates to the technical field of polymer material preparation, and in particular to an aging-resistant TPEE composite material and a preparation method thereof. Background Art

[0002] TPEE material, or thermoplastic polyester elastomer material, is a high-performance elastomeric block copolymer with plastic properties. It has good melt stability, thermoplasticity and processability, as well as excellent oil resistance, low temperature resistance and chemical corrosion resistance. It is widely used in the fields of automobiles, rail transit, sporting goods, wires and cables, etc. However, ordinary TPEE materials have weak mechanical properties, poor aging resistance and high temperature resistance, and are not flame retardant. Therefore, in actual use, due to aging and changes in external stress, tiny cracks are easily generated on the surface of the material. The cracks expand over a long period of use, which not only affects the service life of the material, but also creates safety hazards, thus limiting the use of this material.

[0003] Therefore, people often improve TPEE materials when using them. For example, the patent with announcement number CN118063934B discloses a modified TPEE composite material and its preparation method. The TPEE composite material includes the following raw materials: TPEE resin, anti-melting drop flame retardant, ultraviolet absorber, antioxidant and lubricant, wherein the polyurethane segment can form an interpenetrating network with the TPEE resin to improve the compatibility between the organic phosphorus structure and the matrix. In the event of a fire, the carbamate structure in the anti-melting drop flame retardant has a lower thermal decomposition temperature than the polyester structure in the TPEE matrix, and will first absorb water and dehydrate to form a carbonized layer, isolating the TPEE matrix molecular chain, thereby inhibiting the occurrence of the melting drop phenomenon and exerting an excellent flame retardant effect. Although the patent gives the TPEE material excellent flame retardant and mechanical properties, it directly adds small molecule antioxidants to the antioxidant effect. When used for a long time, the small molecule antioxidants are easy to precipitate, affecting the aging resistance of the TPEE composite material. Summary of the invention

[0004] The purpose of the present invention is to provide an aging-resistant TPEE composite material and a preparation method thereof, which solves the following technical problems: (1) Ordinary TPEE materials have poor aging resistance and high temperature resistance, which affects the service life; (2) Ordinary TPEE materials have average impact resistance and mechanical strength, and are easily damaged when impacted; (3) Ordinary TPEE materials do not have self-repairing ability, and cannot be repaired in time when tiny cracks are generated due to aging or impact; (3) Ordinary TPEE materials do not have flame retardant ability, which poses a safety hazard when used.

[0005] The purpose of the present invention can be achieved by the following technical solutions:

[0006] A TPEE composite material that resists aging includes the following raw materials in parts by weight: 80-100 parts of TPEE resin, 10-15 parts of maleic anhydride grafted polypropylene, 8-12 parts of self-repairing aging-resistant composite materials, 6-8 parts of fire-resistant flame-retardant fillers, 3-5 parts of lubricants, and 1-3 parts of ultraviolet absorbers; the self-repairing aging-resistant composite material is prepared by using natural rubber as a polymer matrix and sequentially introducing disulfide bonds and hindered phenol groups; the fire-resistant flame-retardant filler is prepared by using illite as a carrier and introducing a nitrogen-phosphorus synergistic flame retardant between its layers.

[0007] Furthermore, the Shore hardness of the TPEE resin is 35-70D.

[0008] Furthermore, the lubricant is any one of stearic acid, sodium stearate, and zinc stearate; the ultraviolet absorber is any one of ultraviolet absorber UV-928, ultraviolet absorber UV-3030, and ultraviolet absorber UV-384.

[0009] Furthermore, the preparation method of the self-repairing anti-aging composite comprises the following steps:

[0010] S1: placing epoxidized natural rubber in toluene, mixing and stirring thoroughly, adding 2,2′-dithiodibenzoic acid and tetrabutylammonium bromide, heating to react, and collecting the product after reduced pressure distillation to obtain a self-healing rubber;

[0011] S2: Place the self-repairing rubber and 4-bromo-2,6-di-tert-butylphenol in N,N-dimethylformamide, add the accelerator after thorough mixing, raise the temperature to 55-65°C and react for 6-8h, collect the product after reduced pressure distillation, and obtain a self-repairing aging-resistant composite.

[0012] In this scheme, under the action of tetrabutylammonium bromide, the epoxy group in the epoxidized natural rubber structure undergoes a ring-opening reaction with the carboxyl group in the 2,2′-dithiodibenzoic acid structure to obtain a self-repairing rubber, and then under the action of an accelerator, the hydroxyl group in the self-repairing rubber structure undergoes a substitution reaction with the active bromine in the 4-bromo-2,6-di-tert-butylphenol structure to obtain a self-repairing aging-resistant composite. This self-repairing anti-aging composite has excellent compatibility with the TPEE matrix material. By taking epoxidized natural rubber as the polymer matrix material and adding it to the preparation process of the TPEE composite material, the toughness of the TPEE composite material can be effectively enhanced and its impact resistance can be improved. At the same time, the dynamic disulfide bonds in its structure have the function of breaking and repolymerizing, which can realize the ability of self-repair when the TPEE composite material is aged and cracked or damaged, and effectively prevent the further expansion of the cracks. In addition, the hindered phenol structure is introduced into its structure in a chemically bonded manner, which can capture the free radicals generated during the decomposition of organic matter and make them inactive, thereby terminating the aging reaction. Moreover, the effective ingredients are not easy to precipitate during long-term use, which can effectively improve the aging resistance of the TPEE composite material and give it a long service life.

[0013] Furthermore, in step S1, the temperature of the temperature-raising reaction is 85-90° C. and the time is 5-6 hours.

[0014] Furthermore, in step S2, the accelerator is any one of pyridine and potassium carbonate.

[0015] Furthermore, the preparation method of the fire-resistant flame-retardant filler comprises the following steps:

[0016] SS1: Place illite in anhydrous ethanol, ultrasonically disperse for 10-15 minutes, add 2-(methacryloyloxy)ethyl-2-(trimethylamino)ethyl phosphate, stir at a rate of 300-350r / min for 6-10 hours, then filter, wash, and vacuum dry to obtain modified illite;

[0017] SS2: Place the modified illite and maleimide butyric acid in deionized water, ultrasonically disperse for 5-10 minutes, add the initiator, heat to 55-60°C and react for 3-5 hours, filter, wash and dry to obtain a fire-resistant flame-retardant filler.

[0018] In this scheme, the silicate illite with a layered structure is intercalated and modified by 2-(methacryloyloxy)ethyl-2-(trimethylamino)ethyl phosphate containing a quaternary ammonium group and a double bond in its structure to obtain modified illite, and then under the action of an initiator, the double bonds on the surface of the modified illite react with the maleimide groups in the maleimidebutyric acid structure to undergo free radical polymerization to obtain a fire-resistant flame-retardant filler. This kind of fire-resistant flame-retardant filler uses layered silicate illite as a carrier and loads nitrogen-phosphorus synergistic flame retardant to form an organic-inorganic composite flame-retardant effective ingredient. At the same time, its structure contains carboxyl groups, which can enhance the compatibility of this kind of fire-resistant flame-retardant filler with TPEE composite materials, so that it can be evenly dispersed therein, which not only enhances the mechanical strength of the TPEE composite material, but also can effectively block oxygen in the event of a fire, forming a dense carbon layer to achieve a flame retardant effect, significantly improving the safety of TPEE composite materials. At the same time, the maleimide group in its structure has excellent high temperature resistance, which can effectively improve the stability of TPEE composite materials in high temperature environments and expand the application field of this kind of composite materials.

[0019] Furthermore, in step SS1, the particle size of the illite is 0.8-1.5 μm.

[0020] Furthermore, in step SS2, the initiator is any one of benzoyl peroxide and diisopropylbenzene peroxide.

[0021] A method for preparing an aging-resistant TPEE composite material comprises the following steps:

[0022] Step 1: Place TPEE resin, maleic anhydride grafted polypropylene, self-repairing anti-aging composite, fire-resistant flame-retardant filler, lubricant, and ultraviolet absorber in a high-speed mixer, set the speed to 200-250r / min, heat to 160-170°C, and fully mix for 1-1.5h to obtain a mixture;

[0023] Step 2: Place the mixture in a twin-screw extruder, set the screw speed to 300-500r / min, the temperature of each zone of the extruder is: zone 1 temperature 170-180°C, zone 2 temperature 190-200°C, zone 3 temperature 210-220°C, zone 4 temperature 200-210°C, zone 5 temperature 180-190°C, extrusion temperature is 170-180°C, melt extrusion granulation, and obtain TPEE composite material after cooling.

[0024] Beneficial effects of the present invention:

[0025] The present invention participates in the preparation process of TPEE composite materials by preparing self-repairing aging-resistant composites and fire-resistant flame-retardant fillers, so that the composite materials have excellent self-repairing properties, aging resistance, impact resistance, mechanical strength and flame retardancy, can meet the use requirements in various environments, have high safety and long service life.

[0026] Of course, any product implementing the present invention does not necessarily need to achieve all of the advantages described above at the same time. BRIEF DESCRIPTION OF THE DRAWINGS

[0027] In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the accompanying drawings required for describing the embodiments will be briefly introduced below. Obviously, the accompanying drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other accompanying drawings can be obtained based on these accompanying drawings without paying creative work.

[0028] Figure 1 It is a thermal weight loss curve of illite, modified illite and refractory flame retardant filler in the embodiment of the present invention. DETAILED DESCRIPTION

[0029] The following will be combined with the drawings in the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0030] The preparation methods of the self-repairing anti-aging composite and the fire-resistant flame-retardant filler in the following embodiments and comparative examples of the present invention are as follows:

[0031] 1. Preparation of self-repairing anti-aging composites

[0032] S1: 3 g of epoxidized natural rubber was placed in 50 ml of toluene, and the mixture was thoroughly mixed and stirred. 2 g of 2,2′-dithiodibenzoic acid and 0.3 g of tetrabutylammonium bromide were added, and the mixture was heated to 85°C for reaction for 5 h. The product was collected after reduced pressure distillation to obtain a self-repairing rubber.

[0033] The acetylation method is used to test the hydroxyl content in the self-repairing rubber. The specific operation is as follows: 200 ml of ethyl acetate, 3 ml of 70% perchloric acid, and 10 ml of acetic anhydride are mixed, ice-water bath at 15°C for 30 minutes, and then 52.5 ml of acetic anhydride is added, shaken, and configured as an acylation reagent for use. 30 ml of pyridine is mixed with 10 ml of distilled water to prepare a hydrolysis reagent for use; 1 g of self-repairing rubber is taken as a sample, placed in 10 ml of ethyl acetate, 3 ml of acetylation reagent is added, mixed at room temperature for 30 minutes, 2 ml of distilled water is added, and 5 ml of hydrolysis reagent is added. After standing for 10 minutes, 2 ml of phenolphthalein indicator is added, and 0.7 mol / L standard potassium hydroxide solution is used for titration until the color in the solution changes and no longer changes for 30 seconds, that is, the titration end point is reached. At the same time, a blank experiment is performed, and the titration results are processed and calculated according to the following formula: Hydroxyl value (mgKOH / g) = (V 0 -V)×56.11C / M; where V 0 is the volume of standard potassium hydroxide titration solution consumed in the blank experiment, ml; V is the volume of standard potassium hydroxide titration solution consumed in the sample test, ml; C is the molar concentration of potassium hydroxide standard titration solution, mol / L; M is the sample mass fraction; 56.11 is the molar mass fraction of potassium hydroxide, g / mol; the hydroxyl value of the self-repairing rubber is calculated to be 14.9 mgKOH / g.

[0034] S2: 3.2 g of self-repairing rubber and 3 g of 4-bromo-2,6-di-tert-butylphenol were placed in 60 ml of N,N-dimethylformamide, mixed thoroughly, and then 0.6 g of pyridine was added. The temperature was raised to 55°C and reacted for 6 h. The product was collected after reduced pressure distillation to obtain a self-repairing aging-resistant composite.

[0035] The acetylation method was used to test the content of hydroxyl groups in the self-repairing anti-aging composite. The specific operation was the same as step S1. After calculation, the hydroxyl value of the self-repairing anti-aging composite was 5.7 mgKOH / g, which was significantly lower than that of the self-repairing rubber. This was because the hydroxyl groups in the self-repairing rubber structure reacted with the active bromine in the 4-bromo-2,6-di-tert-butylphenol structure, resulting in consumption.

[0036] 2. Preparation of fire-resistant and flame-retardant fillers

[0037] SS1: 2 g of illite was placed in 80 ml of anhydrous ethanol, ultrasonically dispersed for 10 min, 1.6 g of 2-(methacryloyloxy)ethyl-2-(trimethylamino)ethyl phosphate was added, stirred at a rate of 300 r / min for 6 h, and then filtered, washed, and vacuum dried to obtain modified illite;

[0038] SS2: 2.5 g of modified illite and 2 g of maleimidobutyric acid were placed in 100 ml of deionized water, and after ultrasonic dispersion for 5 min, 0.3 g of benzoyl peroxide was added, and the temperature was raised to 55 °C for reaction for 3 h. After filtration, washing and drying, a fire-resistant flame-retardant filler was obtained.

[0039] Illite, modified illite and refractory flame retardant filler were analyzed by thermogravimetric analysis. Figure 1 It can be seen that at high temperature, the final mass retention rate of illite is 96.4%, and the lost part is caused by the thermal decomposition of crystal water; the final mass retention rate of modified illite is 55.1%, and the lost part is caused by the thermal decomposition of 2-(methacryloyloxy)ethyl-2-(trimethylamino)ethyl phosphate in the modified illite structure; the final mass retention rate of refractory flame retardant filler is 28.8%, and the lost part is caused by the thermal decomposition of organic matter in the structure.

[0040] Example 1, Preparation of TPEE composite material

[0041] Step 1: Place 80 parts of TPEE resin with a Shore hardness of 35D, 10 parts of maleic anhydride grafted polypropylene, 8 parts of self-repairing anti-aging composites, 6 parts of fire-resistant flame-retardant fillers, 3 parts of stearic acid, and 1 part of ultraviolet absorber UV-928 in a high-speed mixer, set the speed to 200r / min, heat to 160°C, and fully mix for 1h to obtain a mixture;

[0042] Step 2: Place the mixture in a twin-screw extruder, set the screw speed to 300r / min, the temperature of each zone of the extruder is: zone 1 temperature 170°C, zone 2 temperature 190°C, zone 3 temperature 210°C, zone 4 temperature 200°C, zone 5 temperature 180°C, extrusion temperature is 170°C, melt extrusion granulation, and obtain TPEE composite material after cooling.

[0043] Example 2, Preparation of TPEE composite material

[0044] Step 1: Place 90 parts of TPEE resin with a Shore hardness of 50D, 12 parts of maleic anhydride grafted polypropylene, 10 parts of self-repairing anti-aging composite, 7 parts of fire-resistant flame-retardant filler, 4 parts of sodium stearate, and ultraviolet absorber UV-3030 in a high-speed mixer, set the speed to 220r / min, heat to 165°C, and fully mix for 1.2h to obtain a mixture;

[0045] Step 2: Place the mixture in a twin-screw extruder, set the screw speed to 400r / min, the temperature of each zone of the extruder is: zone 1 temperature 175°C, zone 2 temperature 195°C, zone 3 temperature 215°C, zone 4 temperature 205°C, zone 5 temperature 185°C, extrusion temperature is 175°C, melt extrusion granulation, and obtain TPEE composite material after cooling.

[0046] Example 3, Preparation of TPEE composite material

[0047] Step 1: Place 100 parts of TPEE resin with a Shore hardness of 75D, 15 parts of maleic anhydride grafted polypropylene, 12 parts of self-repairing anti-aging composite, 8 parts of fire-resistant flame-retardant filler, 5 parts of zinc stearate, and ultraviolet absorber UV-384 in a high-speed mixer, set the speed to 250r / min, heat to 170°C, and fully mix for 1.5h to obtain a mixture;

[0048] Step 2: Place the mixture in a twin-screw extruder, set the screw speed to 500r / min, the temperature of each zone of the extruder is: zone 1 temperature 180°C, zone 2 temperature 200°C, zone 3 temperature 220°C, zone 4 temperature 210°C, zone 5 temperature 190°C, extrusion temperature is 180°C, melt extrusion granulation, and obtain TPEE composite material after cooling.

[0049] Comparative Example 1, Preparation of TPEE Composite Material

[0050] Step 1, 90 parts of TPEE resin with a Shore hardness of 50D, 12 parts of maleic anhydride grafted polypropylene, 7 parts of fire-resistant flame retardant filler, 4 parts of sodium stearate, and ultraviolet absorber UV-3030 are placed in a high-speed mixer, the speed is set to 220r / min, the temperature is raised to 165°C, and the mixture is fully mixed for 1.2h to obtain a mixture;

[0051] Step 2: Place the mixture in a twin-screw extruder, set the screw speed to 400r / min, the temperature of each zone of the extruder is: zone 1 temperature 175°C, zone 2 temperature 195°C, zone 3 temperature 215°C, zone 4 temperature 205°C, zone 5 temperature 185°C, extrusion temperature is 175°C, melt extrusion granulation, and obtain TPEE composite material after cooling.

[0052] Comparative Example 2, Preparation of TPEE Composite Material

[0053] Step 1: Place 90 parts of TPEE resin with a Shore hardness of 50D, 12 parts of maleic anhydride grafted polypropylene, 10 parts of self-repairing anti-aging composite, 4 parts of sodium stearate, and ultraviolet absorber UV-3030 in a high-speed mixer, set the speed to 220 r / min, heat to 165° C., and fully mix for 1.2 hours to obtain a mixture;

[0054] Step 2: Place the mixture in a twin-screw extruder, set the screw speed to 400r / min, the temperature of each zone of the extruder is: zone 1 temperature 175°C, zone 2 temperature 195°C, zone 3 temperature 215°C, zone 4 temperature 205°C, zone 5 temperature 185°C, extrusion temperature is 175°C, melt extrusion granulation, and obtain TPEE composite material after cooling.

[0055] Comparative Example 3, Preparation of TPEE Composite Material

[0056] Step 1: Place 90 parts of TPEE resin with a Shore hardness of 50D, 12 parts of maleic anhydride grafted polypropylene, 10 parts of self-repairing rubber, 7 parts of fire-resistant flame-retardant filler, 4 parts of sodium stearate, and ultraviolet absorber UV-3030 in a high-speed mixer, set the speed to 220 r / min, heat to 165° C., and fully mix for 1.2 hours to obtain a mixture;

[0057] Step 2: Place the mixture in a twin-screw extruder, set the screw speed to 400r / min, the temperature of each zone of the extruder is: zone 1 temperature 175°C, zone 2 temperature 195°C, zone 3 temperature 215°C, zone 4 temperature 205°C, zone 5 temperature 185°C, extrusion temperature is 175°C, melt extrusion granulation, and obtain TPEE composite material after cooling.

[0058] Comparative Example 4, Preparation of TPEE Composite Material

[0059] Step 1: Place 90 parts of TPEE resin with a Shore hardness of 50D, 12 parts of maleic anhydride grafted polypropylene, 10 parts of self-repairing anti-aging composite, 7 parts of modified illite, 4 parts of sodium stearate, and ultraviolet absorber UV-3030 in a high-speed mixer, set the speed to 220r / min, heat to 165°C, and fully mix for 1.2h to obtain a mixture;

[0060] Step 2: Place the mixture in a twin-screw extruder, set the screw speed to 400r / min, the temperature of each zone of the extruder is: zone 1 temperature 175°C, zone 2 temperature 195°C, zone 3 temperature 215°C, zone 4 temperature 205°C, zone 5 temperature 185°C, extrusion temperature is 175°C, melt extrusion granulation, and obtain TPEE composite material after cooling.

[0061] Performance Testing

[0062] ① The TPEE composite materials prepared in Examples 1 to 3 were made into samples that met the specifications. The samples were tested according to the reference standard GB / T1040-2006 and the samples treated in an aging box at 80°C for 72 hours were subjected to tensile strength tests to determine the mechanical strength and aging resistance of the samples. A 3 cm long and 0.5 mm wide crack was scratched on the surface of the sample with a blade, and the sample was repaired at 100°C for 36 hours. The tensile strength of the sample was tested again, and the repair rate was calculated with reference to the following formula: Repair rate = tensile strength after repair × 100% / initial tensile strength to determine the repair ability of the sample. The specific test results are shown in the table below:

[0063]

[0064] It can be seen from the above table that the samples prepared in Examples 1 to 3 all have excellent mechanical strength, aging resistance and self-repairing ability. In the sample prepared in Comparative Example 1, no self-repairing aging-resistant composite was added, and the self-repairing performance and aging resistance were poor, but fire-resistant flame-retardant fillers were added thereto, and the tensile strength was good. In the sample prepared in Comparative Example 2, no fire-resistant flame-retardant fillers were added, and the tensile strength was poor, but self-repairing aging-resistant composites were added thereto, and the self-repairing ability and aging resistance were good. In the sample prepared in Comparative Example 3, self-repairing rubber and fire-resistant flame-retardant fillers were directly added, and the mechanical strength was high and the repair performance was good, but the aging resistance was poor. In the sample prepared in Comparative Example 4, modified illite and self-repairing aging-resistant composite were directly added, and it had good mechanical strength, aging resistance and repair performance.

[0065] ② Examples 1 to 3 and Comparative Examples 1 to 4 were made into samples that met the specifications. The impact strength of the samples was tested with reference to the standard GB / T1043.1-2008 to determine the impact resistance of the samples; the Vicat softening temperature of the samples was tested with reference to the standard GB / T1633-2000 to determine the high temperature resistance of the samples; the vertical burning test was performed on the samples with reference to the UL-94 flame retardant grade standard to determine the flame retardant grade of the samples; the specific test results are shown in the following table:

[0066]

[0067] It can be seen from the above table that the samples prepared in Examples 1 to 3 all have excellent impact resistance, high temperature resistance and flame retardant effects, while the sample prepared in Comparative Example 1 has poor impact resistance, the sample prepared in Comparative Example 2 has average high temperature resistance, the sample prepared in Comparative Example 3 has excellent impact resistance, high temperature resistance and flame retardant effects, and the sample prepared in Comparative Example 4 has flame retardant and high temperature resistance that are not as good as those in the examples.

[0068] In the description of this specification, the description with reference to the terms "one embodiment", "some embodiments", "example", "specific example", or "some examples" etc. means that the specific features, structures, materials or characteristics described in conjunction with the embodiment or example are included in at least one embodiment or example of the present invention. In this specification, the schematic representations of the above terms do not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described may be combined in any one or more embodiments or examples in a suitable manner. In addition, those skilled in the art may combine and combine the different embodiments or examples described in this specification and the features of the different embodiments or examples, without contradiction.

[0069] The above contents are merely examples and explanations of the concept of the present invention. The technicians in this technical field may make various modifications or additions to the specific embodiments described or replace them in a similar manner. As long as they do not deviate from the scope defined by the concept of the invention, they should all fall within the protection scope of the present invention.

Claims

1. An aging-resistant TPEE composite material, characterized in that: The invention comprises the following raw materials in parts by weight: 80-100 parts of TPEE resin, 10-15 parts of maleic anhydride grafted polypropylene, 8-12 parts of self-repairing anti-aging composite, 6-8 parts of fire-resistant flame-retardant filler, 3-5 parts of lubricant, and 1-3 parts of ultraviolet absorber; the self-repairing anti-aging composite is prepared by taking natural rubber as a polymer matrix, and sequentially introducing disulfide bonds and hindered phenol groups; the fire-resistant flame-retardant filler is prepared by taking illite as a carrier, and introducing nitrogen-phosphorus synergistic flame retardant between its layers; The preparation method of the self-repairing anti-aging composite comprises the following steps: S1: placing epoxidized natural rubber in toluene, mixing and stirring thoroughly, adding 2,2′-dithiodibenzoic acid and tetrabutylammonium bromide, heating to react, and collecting the product after reduced pressure distillation to obtain a self-healing rubber; S2: Place the self-repairing rubber and 4-bromo-2,6-di-tert-butylphenol in N,N-dimethylformamide, add the accelerator after thorough mixing, raise the temperature to 55-65°C and react for 6-8h, collect the product after reduced pressure distillation, and obtain a self-repairing aging-resistant composite.

2. The aging-resistant TPEE composite material according to claim 1, characterized in that: The Shore hardness of the TPEE resin is 35-70D.

3. The aging-resistant TPEE composite material according to claim 1, characterized in that: The lubricant is any one of stearic acid, sodium stearate and zinc stearate; the ultraviolet absorber is any one of ultraviolet absorber UV-928, ultraviolet absorber UV-3030 and ultraviolet absorber UV-384.

4. The aging-resistant TPEE composite material according to claim 1, characterized in that: In step S1, the temperature of the temperature-raising reaction is 85-90° C. and the time is 5-6 hours.

5. The aging-resistant TPEE composite material according to claim 1, characterized in that: In step S2, the accelerator is any one of pyridine and potassium carbonate.

6. The aging-resistant TPEE composite material according to claim 1, characterized in that: The preparation method of the fire-resistant flame-retardant filler comprises the following steps: SS1: Place illite in anhydrous ethanol, ultrasonically disperse for 10-15 minutes, add 2-(methacryloyloxy)ethyl-2-(trimethylamino)ethyl phosphate, stir at a rate of 300-350r / min for 6-10 hours, then filter, wash, and vacuum dry to obtain modified illite; SS2: Place the modified illite and maleimide butyric acid in deionized water, ultrasonically disperse for 5-10 minutes, add the initiator, heat to 55-60°C and react for 3-5 hours, filter, wash and dry to obtain a fire-resistant flame-retardant filler.

7. The aging-resistant TPEE composite material according to claim 6, characterized in that: In step SS1, the particle size of the illite is 0.8-1.5 μm.

8. The aging-resistant TPEE composite material according to claim 6, characterized in that: In step SS2, the initiator is any one of benzoyl peroxide and diisopropylbenzene peroxide.

9. A method for preparing the aging-resistant TPEE composite material according to claim 1, characterized in that: The following steps are involved: Step 1: Place TPEE resin, maleic anhydride grafted polypropylene, self-repairing anti-aging composite, fire-resistant flame-retardant filler, lubricant, and ultraviolet absorber in a high-speed mixer, set the speed to 200-250r / min, heat to 160-170°C, and fully mix for 1-1.5h to obtain a mixture; Step 2: Place the mixture in a twin-screw extruder, set the screw speed to 300-500r / min, the temperature of each zone of the extruder is: zone 1 temperature 170-180°C, zone 2 temperature 190-200°C, zone 3 temperature 210-220°C, zone 4 temperature 200-210°C, zone 5 temperature 180-190°C, extrusion temperature is 170-180°C, melt extrusion granulation, and obtain TPEE composite material after cooling.

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