Anti-aging material for automobile plastic parts and preparation method of anti-aging material

Abstract

The invention relates to the technical field of plastic production, and particularly discloses an anti-aging material for automobile plastic parts and a preparation method thereof.The anti-aging material is prepared from, by weight, 90-100 parts of polypropylene, 15-25 parts of functionalized ethylene propylene diene monomer, 8-12 parts of anti-aging reinforcing components, 1-3 parts of lubricant, 1.2-1.6 parts of cross-linking agent, 3-5 parts of thermal oxidation stabilizer and 0.5-0.7 part of antioxidant; the functional ethylene propylene diene monomer and the anti-aging reinforcing component are added, and the functional ethylene propylene diene monomer contains an ethylene propylene diene monomer structure, hydroxyl, a phosphonate group, an amido group and unsaturated double bonds, not only has good compatibility with a polypropylene base material, but also can react with the anti-aging reinforcing component, so that the overall cross-linking density is improved, and the anti-aging performance is improved. Migration and precipitation of the anti-aging reinforcing component are avoided, and meanwhile, the aging resistance and flame retardance of the material for the automobile plastic accessory are improved.

Description

Technical Field

[0001] The present application relates to the technical field of plastic production, and more specifically, to an aging-resistant material for automobile plastic parts and a preparation method thereof. Background Art

[0002] Polypropylene (PP) is widely used in complete vehicles and various component systems due to its excellent mechanical properties, low cost, low density, and ease of processing and molding. However, PP inherently suffers from poor aging resistance, and its molecular chains are easily broken by exposure to light and heat, resulting in reduced mechanical strength and service life. Furthermore, PP exhibits poor flame retardancy, releasing significant heat during combustion, which can pose significant risks. Therefore, improving PP's aging resistance and flame retardancy could significantly expand its application areas.

[0003] In the existing technology, ultraviolet absorbers and flame retardants are added to improve the aging resistance and flame retardancy of automobile plastic parts. However, these small molecule ultraviolet absorbers and flame retardants are easy to migrate and precipitate, which reduces the aging resistance and flame retardancy of automobile plastic parts.

[0004] Based on the above-mentioned defects, the present application provides an aging-resistant material for automotive plastic accessories and a preparation method thereof. Summary of the Invention

[0005] In order to solve the problems mentioned in the above background technology, the present application provides an aging-resistant material for automobile plastic parts and a preparation method thereof.

[0006] An aging-resistant material for automotive plastic parts, comprising the following raw materials in parts by weight: 90-100 parts of polypropylene, 15-25 parts of functionalized EPDM rubber, 8-12 parts of an anti-aging reinforcing component, 1-3 parts of a lubricant, 1.2-1.6 parts of a cross-linking agent, 3-5 parts of a thermal oxygen stabilizer, and 0.5-0.7 parts of an antioxidant;

[0007] The method for preparing the aging-resistant material for automobile plastic parts comprises the following steps:

[0008] Step S1, preparing materials: weighing corresponding weight portions of polypropylene, functionalized EPDM rubber, anti-aging reinforcement component, lubricant, thermal oxidation stabilizer and antioxidant for later use;

[0009] Step S2, melt extrusion: feeding polypropylene, functionalized EPDM rubber, anti-aging reinforcement component, lubricant, crosslinking agent, thermal oxygen stabilizer and antioxidant into a twin-screw extruder and extruding through a die to obtain a molten mixture;

[0010] Step S3, molding: Place the molten mixture prepared in step S2 in a torque rheometer, Refining, The material is unloaded, crushed, and placed in an injection molding machine for injection molding to obtain aging-resistant materials for automobile plastic parts.

[0011] Preferably, the lubricant is erucamide or ethylene bisstearamide.

[0012] Preferably, the cross-linking agent is dicumyl peroxide.

[0013] Preferably, the thermal oxygen stabilizer is Irganox 1010 or Irganox 168.

[0014] Preferably, the antioxidant is antioxidant 168 or antioxidant 1010.

[0015] Preferably, in step S2, the extrusion process of the twin-screw extruder is: zone 1 200-205°C, zone 2 205-210°C, zone 3 210-215°C, zone 4 215-220°C, zone 5 220-225°C, head temperature 225°C; screw speed is 90-100r / min.

[0016] Preferably, in step S3, during injection molding, the head temperature is 180-185° C., the injection pressure is 66-68 MPa, the extrusion rate is 1.1-1.4 g / s, the traction force is 6-6.2 N, and the moving speed is 0.32-0.34 m / min.

[0017] Preferably, in step S3, the banburying temperature is 155-165° C., and the banburying time is 10-15 min.

[0018] Preferably, the functionalized EPDM rubber is prepared by the following steps:

[0019] Step A1, adding EPDM rubber to n-hexane, stirring evenly, heating to 62-66° C., adding formic acid and Tween-80, stirring evenly, then adding hydrogen peroxide dropwise, stirring and reacting for 7-9 hours, then adding sodium carbonate aqueous solution, continuing to stir evenly, standing, washing, then adding to anhydrous ethanol, flocculating and precipitating for 2.4-3 hours, and drying to obtain epoxy-modified EPDM rubber, wherein the mass ratio of EPDM rubber, n-hexane, formic acid, Tween-80, hydrogen peroxide, sodium carbonate aqueous solution and anhydrous ethanol is 3.2-3.6:55-65:0.16-0.28:0.22-0.26:0.32-0.42:20-24:90-110, and the mass fraction of sodium carbonate aqueous solution is 0.04-0.08%;

[0020] In the above reaction process, n-hexane is used as a solvent, and the "formic acid-hydrogen peroxide" in-situ epoxidation method is used to convert the unsaturated double bonds in the EPDM rubber into epoxy groups to obtain epoxidized modified EPDM rubber;

[0021] Step A2: Add the epoxidized modified EPDM rubber to toluene, stir evenly, heat to 42-46° C., add a mixture a of a phosphorus-containing monomer, triethylamine, and anhydrous ethanol dropwise while stirring, heat to 74-80° C., continue stirring and reacting for 3.4-4.2 hours, filter, wash, and dry to obtain functionalized EPDM rubber, wherein the mass ratio of the epoxidized modified EPDM rubber, toluene, and the mixture a is 4.4-5.2:85-95:36-52, and the mass ratio of the phosphorus-containing monomer, triethylamine, and anhydrous ethanol in the mixture a is 3-3.4:0.04-0.06:30-40. In the above reaction process, using toluene as a solvent and triethylamine as a catalyst, the epoxidized modified EPDM rubber and the phosphorus-containing monomer undergo a ring-opening esterification reaction to obtain the functionalized EPDM rubber.

[0022] Preferably, the mass fraction of the hydrogen peroxide is 30-34%.

[0023] Preferably, the phosphorus-containing monomer is prepared by the following steps:

[0024] Step B1, add tris(hydroxymethyl)aminomethane and p-hydroxycinnamic acid to anhydrous THF, stir evenly, and dropwise add a mixture b of N,N-dicyclohexylcarbodiimide, 4-dimethylaminopyridine and anhydrous THF while stirring, raise the temperature to reflux and react for 3-5 hours. After the reaction is completed, filter, wash and dry to obtain a polyhydroxy monomer, wherein the mass ratio of tris(hydroxymethyl)aminomethane, p-hydroxycinnamic acid, anhydrous THF and mixture b is 2-4:3-6:6 5-75:25-35, in the mixed solution b, the mass ratio of N,N-dicyclohexylcarbodiimide, 4-dimethylaminopyridine and anhydrous THF is 4.6-5.2:3-3.4:30-40. In the above reaction process, anhydrous THF is used as a solvent, N,N-dicyclohexylcarbodiimide is used as a dehydrating agent, 4-dimethylaminopyridine is used as an acylating agent, tris(hydroxymethyl)aminomethane and p-hydroxycinnamic acid undergo an amidation reaction to produce a polyhydroxy monomer;

[0025] Step B2, adding a polyhydroxy monomer, p-toluenesulfonic acid and (2-carboxyethyl)phenylphosphonic acid to anhydrous DMF, heating to 35-45°C, stirring evenly, then heating to 72-76°C, continuing to stir and react for 3.4-4.2 hours, rotary evaporation, washing, and drying to obtain a phosphorus-containing monomer, wherein the mass ratio of the polyhydroxy monomer, p-toluenesulfonic acid, (2-carboxyethyl)phenylphosphonic acid and anhydrous DMF is 3-5:0.08-0.12:2.4-4:40-50. In the above reaction process, using anhydrous DMF as solvent and p-toluenesulfonic acid as catalyst, the active hydroxyl groups on the polyhydroxy monomer and the carboxyl groups on the (2-carboxyethyl)phenylphosphonic acid undergo esterification reaction. After the reaction is completed, the remaining active hydroxyl groups can participate in the subsequent reaction process.

[0026] Preferably, the anti-aging enhancement component is prepared by the following steps:

[0027] Step C1, adding 2,4-dihydroxybenzophenone to anhydrous DMF, stirring evenly, adjusting the pH to 8-9, adding a mixture of itaconic anhydride and isopropanol c dropwise, controlling the dripping to be complete within 10 minutes, heating to 72-76°C, continuing stirring and reacting for 6-12 hours, then adjusting the pH to neutral, rotary evaporation, washing, and drying to obtain a carboxyl monomer, wherein the mass ratio of 2,4-dihydroxybenzophenone, anhydrous DMF, and the mixture c is 2.8-3.4:55-65:26-32, and the mass ratio of itaconic anhydride to isopropanol in the mixture c is 1.5-1.9:22. During the above reaction process, using anhydrous DMF as a solvent, the active hydroxyl group on 2,4-dihydroxybenzophenone and the anhydride on itaconic anhydride undergo a ring-opening esterification reaction to obtain a carboxyl monomer;

[0028] Step C2, ultrasonically mixing nano zinc oxide, deionized water, anhydrous ethanol and KH-560 for 28-32 minutes, heating to 46-52 ° C, stirring and reacting for 3.6-4.4 hours, centrifuging, washing and drying the precipitate to obtain epoxy zinc oxide, ultrasonically dispersing epoxy zinc oxide in anhydrous DMF, adding tetrabutylammonium bromide, carboxyl monomer and anhydrous DMF mixed solution d dropwise, controlling the dripping within 15 minutes, heating to 96-108 ° C, stirring and reacting for 1.8-2.4 hours, centrifuging, washing, and drying to obtain an anti-aging enhancement component, wherein nano zinc oxide, deionized water , anhydrous ethanol and KH-560 is 2.4-3.6:20-30:6:0.2-0.4, the mass ratio of epoxy zinc oxide, anhydrous DMF and mixed liquid d is 2-3:50-60:26-30, and in the mixed liquid d, the mass ratio of tetrabutylammonium bromide, carboxyl monomer and anhydrous DMF is 0.1:0.8-1.2:24. In the above reaction process, nano zinc oxide is first treated with KH-560 to obtain epoxy zinc oxide, and then under the action of tetrabutylammonium bromide, the carboxyl group of the carboxyl monomer and the epoxy zinc oxide undergo a ring-opening reaction to obtain the anti-aging enhancement component.

[0029] Compared with the prior art, the present invention has the following beneficial effects:

[0030] In order to improve the aging resistance and flame retardancy of the prepared materials for automotive plastic accessories, the present application starts from two aspects. First, functionalized EPDM rubber is added. The functionalized EPDM rubber is prepared by chemically bonding epoxidized modified EPDM rubber with a phosphorus-containing monomer. The presence of the EPDM rubber structure in the functionalized EPDM rubber itself has a highly saturated main chain structure, which can improve the aging resistance of the materials for automotive plastic accessories. The phosphorus-containing monomer also contains rich active hydroxyl groups, phosphonate groups, amide groups and unsaturated double bonds. On the one hand, the active hydroxyl groups can chemically react with the epoxidized modified EPDM rubber to increase the crosslinking degree of the functionalized EPDM rubber system, strengthen the intermolecular bonding force, and improve the aging resistance of the materials for automotive plastic accessories. On the other hand, as an anchor point, it undergoes a ring-opening reaction with the epoxy group of the anti-aging reinforcing component to further increase the crosslinking degree, thereby improving the automotive plastic accessories. The phosphate group and the ester group in the anti-aging reinforcing component can serve as an acid source, polypropylene can serve as a carbon source, and the amide group can serve as a nitrogen source. They constitute an expanding flame retardant system to improve the flame retardancy of materials for automotive plastic accessories. The presence of unsaturated double bonds can chemically cross-link with the anti-aging reinforcing component under the action of a cross-linking agent, thereby avoiding the migration and precipitation of the anti-aging reinforcing component, and further improving the aging resistance and flame retardancy of materials for automotive plastic accessories. Secondly, the addition of the anti-aging reinforcing component can, on the one hand, bring into play the UV resistance of nano zinc oxide and thus improve the aging resistance of materials for automotive plastic accessories. On the other hand, the carboxyl monomer grafted on the surface of the anti-aging reinforcing component has a benzophenone structure, which has high rigidity and good UV resistance. Introducing it into materials for automotive plastic accessories can synergize with the functionalized EPDM rubber to jointly improve the aging resistance and flame retardancy of materials for automotive plastic accessories. DETAILED DESCRIPTION

[0031] In order to make the implementation methods of the present application easier to understand, the present application will be described in detail below with reference to specific examples. These examples are only for illustration and are not intended to limit the scope of application of the present application.

[0032] The contents of the main raw materials and their components used in the examples and comparative examples are as follows:

[0033] The polypropylene is a standard sample of injection molding grade polypropylene commercially available from Suzhou Xinshengwang Plastics Co., Ltd., with the brand name HP500N and the product number HH6230V06DKU. The EPDM rubber is a standard sample of injection molding grade EPDM rubber commercially available from Dongguan Xiangyi New Materials Co., Ltd., with the brand name S5890F.

[0034] The present application is further described in detail below with reference to the following examples and comparative examples.

[0035] Preparation Examples 1-3 and Comparative Preparation Examples 1-3 provide methods for preparing functionalized core-shell particles.

[0036] Preparation Example 1

[0037] This preparation example provides a phosphorus-containing monomer, which is prepared by the following steps:

[0038] Step B1, adding tris(hydroxymethyl)aminomethane and p-hydroxycinnamic acid to anhydrous THF, stirring at a speed of 550 rpm for 16 minutes until uniform, and adding a mixture b of N, N-dicyclohexylcarbodiimide, 4-dimethylaminopyridine and anhydrous THF while stirring, and controlling the dripping within 15 minutes. After the dripping is completed, the temperature is raised to reflux for reaction for 3 hours. After the reaction is completed, the mixture is filtered, and then washed with anhydrous ethanol and deionized water three times each in sequence, and dried at 56°C to constant weight to obtain a polyhydroxy monomer, wherein the mass ratio of tris(hydroxymethyl)aminomethane, p-hydroxycinnamic acid, anhydrous THF and the mixture b is 2:3:65:25, and the mass ratio of N, N-dicyclohexylcarbodiimide, 4-dimethylaminopyridine and anhydrous THF in the mixture b is 4.6:3:30;

[0039] Step B2, add the polyhydroxy monomer, p-toluenesulfonic acid and (2-carboxyethyl)phenylphosphonic acid to anhydrous DMF, raise the temperature to 35 ° C, control the speed to 520 rpm, stir for 18 minutes until uniform, then raise the temperature to 72 ° C, maintain the speed unchanged, continue stirring and react for 3.4 hours, control the rotary evaporation temperature to 76 ° C to remove anhydrous DMF, wash with anhydrous ethanol and deionized water 3 times each, and dry at 60 ° C to constant weight to obtain a phosphorus-containing monomer, wherein the mass ratio of the polyhydroxy monomer, p-toluenesulfonic acid, (2-carboxyethyl)phenylphosphonic acid and anhydrous DMF is 3:0.08:2.4:40.

[0040] Preparation Example 2

[0041] This preparation example provides a phosphorus-containing monomer, which is prepared by the following steps:

[0042] Step B1, adding tris(hydroxymethyl)aminomethane and p-hydroxycinnamic acid to anhydrous THF, stirring at a speed of 580 rpm for 20 minutes until uniform, and adding a mixture b of N, N-dicyclohexylcarbodiimide, 4-dimethylaminopyridine and anhydrous THF while stirring, and controlling the dripping within 15 minutes. After the dripping is completed, the temperature is raised to reflux for 4 hours. After the reaction is completed, the mixture is filtered, and then washed with anhydrous ethanol and deionized water 4 times each in sequence, and dried at 60°C to constant weight to obtain a polyhydroxy monomer, wherein the mass ratio of tris(hydroxymethyl)aminomethane, p-hydroxycinnamic acid, anhydrous THF and the mixture b is 3:4.5:70:30, and the mass ratio of N, N-dicyclohexylcarbodiimide, 4-dimethylaminopyridine and anhydrous THF in the mixture b is 4.9:3.2:35;

[0043] Step B2, add the polyhydroxy monomer, p-toluenesulfonic acid and (2-carboxyethyl)phenylphosphonic acid to anhydrous DMF, raise the temperature to 40 ° C, control the speed to 550 rpm, stir for 21 minutes until uniform, then raise the temperature to 74 ° C, maintain the speed unchanged, continue stirring and react for 3.7 hours, control the rotary evaporation temperature to 80 ° C to remove anhydrous DMF, wash with anhydrous ethanol and deionized water 4 times each, and dry at 64 ° C to constant weight, wherein the mass ratio of polyhydroxy monomer, p-toluenesulfonic acid, (2-carboxyethyl)phenylphosphonic acid and anhydrous DMF is 4:0.1:3.2:45.

[0044] Preparation Example 3

[0045] This preparation example provides a phosphorus-containing monomer, which is prepared by the following steps:

[0046] Step B1, adding tris(hydroxymethylaminomethane) and p-hydroxycinnamic acid to anhydrous THF, stirring at a speed of 610 rpm for 24 minutes until uniform, and adding a mixture b of N, N-dicyclohexylcarbodiimide, 4-dimethylaminopyridine and anhydrous THF while stirring, and controlling the dripping within 15 minutes. After the dripping is completed, the temperature is raised to reflux for reaction for 5 hours. After the reaction is completed, the mixture is filtered, washed with anhydrous ethanol and deionized water 5 times each, and dried at 64°C to constant weight to obtain a polyhydroxy monomer, wherein the mass ratio of tris(hydroxymethylaminomethane), p-hydroxycinnamic acid, anhydrous THF and the mixture b is 4:6:75:35, and the mass ratio of N, N-dicyclohexylcarbodiimide, 4-dimethylaminopyridine and anhydrous THF in the mixture b is 5.2:3.4:40;

[0047] Step B2, add the polyhydroxy monomer, p-toluenesulfonic acid and (2-carboxyethyl)phenylphosphonic acid to anhydrous DMF, raise the temperature to 45 ° C, control the speed to 580 rpm, stir for 24 minutes until uniform, then raise the temperature to 76 ° C, maintain the speed unchanged, continue stirring and react for 4.2 hours, control the rotary evaporation temperature to 84 ° C to remove anhydrous DMF, wash with anhydrous ethanol and deionized water 5 times each, and dry at 68 ° C to constant weight to obtain a phosphorus-containing monomer, wherein the mass ratio of the polyhydroxy monomer, p-toluenesulfonic acid, (2-carboxyethyl)phenylphosphonic acid and anhydrous DMF is 5:0.12:4:50.

[0048] Comparative Preparation Example 1

[0049] This comparative preparation example provides a phosphorus-containing monomer, which is prepared by the following steps:

[0050] Step B1, adding tris(hydroxymethyl)aminomethane and p-hydroxyphenylpropionic acid to anhydrous THF, stirring at a speed of 550 rpm for 16 minutes until uniform, and adding a mixture b of N, N-dicyclohexylcarbodiimide, 4-dimethylaminopyridine and anhydrous THF while stirring, and controlling the dripping within 15 minutes. After the dripping is completed, the temperature is raised to reflux for reaction for 3 hours. After the reaction is completed, the mixture is filtered, and then washed with anhydrous ethanol and deionized water three times each in sequence, and dried at 56°C to constant weight to obtain a polyhydroxy monomer, wherein the mass ratio of tris(hydroxymethyl)aminomethane, p-hydroxyphenylpropionic acid, anhydrous THF and the mixture b is 2:3:65:25, and the mass ratio of N, N-dicyclohexylcarbodiimide, 4-dimethylaminopyridine and anhydrous THF in the mixture b is 4.6:3:30;

[0051] Step B2, add the polyhydroxy monomer, p-toluenesulfonic acid and (2-carboxyethyl)phenylphosphonic acid to anhydrous DMF, raise the temperature to 35 ° C, control the speed to 520 rpm, stir for 18 minutes until uniform, then raise the temperature to 72 ° C, maintain the speed unchanged, continue stirring and react for 3.4 hours, control the rotary evaporation temperature to 76 ° C to remove anhydrous DMF, wash with anhydrous ethanol and deionized water 3 times each, and dry at 60 ° C to constant weight to obtain a phosphorus-containing monomer, wherein the mass ratio of the polyhydroxy monomer, p-toluenesulfonic acid, (2-carboxyethyl)phenylphosphonic acid and anhydrous DMF is 3:0.08:2.4:40.

[0052] Comparative Preparation Example 2

[0053] This comparative preparation example provides a phosphorus-containing monomer, which is prepared by the following steps:

[0054] Step B1, adding tris(hydroxymethyl)aminomethane and p-hydroxycinnamic acid to anhydrous THF, stirring at a speed of 550 rpm for 16 minutes until uniform, and adding a mixture b of N, N-dicyclohexylcarbodiimide, 4-dimethylaminopyridine and anhydrous THF while stirring, and controlling the dripping within 15 minutes. After the dripping is completed, the temperature is raised to reflux for reaction for 3 hours. After the reaction is completed, the mixture is filtered, and then washed with anhydrous ethanol and deionized water three times each in sequence, and dried at 56°C to constant weight to obtain a polyhydroxy monomer, wherein the mass ratio of tris(hydroxymethyl)aminomethane, p-hydroxycinnamic acid, anhydrous THF and the mixture b is 2:3:65:25, and the mass ratio of N, N-dicyclohexylcarbodiimide, 4-dimethylaminopyridine and anhydrous THF in the mixture b is 4.6:3:30;

[0055] Step B2, adding a polyhydroxy monomer, p-toluenesulfonic acid and o-carboxyphenylacetic acid to anhydrous DMF, raising the temperature to 35°C, controlling the rotation speed to 520 rpm, stirring for 18 minutes until uniform, then raising the temperature to 72°C, maintaining the rotation speed unchanged, and continuing to stir for 3.4 hours. The rotary evaporation temperature is controlled at 76°C to remove anhydrous DMF, and the mixture is washed with anhydrous ethanol and deionized water three times each, and dried at 60°C to constant weight to obtain a phosphorus-containing monomer, wherein the mass ratio of the polyhydroxy monomer, p-toluenesulfonic acid, o-carboxyphenylacetic acid and anhydrous DMF is 3:0.08:2.4:40.

[0056] Preparation Examples 4-6 and Comparative Preparation Examples 3-4 provide a functionalized EPDM rubber.

[0057] Preparation Example 4

[0058] This preparation example provides a functionalized EPDM rubber, which is prepared by the following steps:

[0059] Step A1, adding EPDM rubber to n-hexane, stirring at a speed of 400 rpm for 12 minutes until uniform, heating to 62°C, adding formic acid and Tween-80, stirring for 14 minutes until uniform, then adding hydrogen peroxide with a mass fraction of 30% dropwise, controlling the dripping to be completed within 15 minutes, maintaining the speed unchanged, continuing to stir and react for 7 hours, then adding sodium carbonate aqueous solution, continuing to stir for 10 minutes until uniform, standing for 15 minutes, washing with deionized water three times, then adding anhydrous ethanol, flocculating and precipitating for 2.4 hours, and drying at 54°C to constant weight to obtain epoxy-modified EPDM rubber, wherein the mass ratio of EPDM rubber, n-hexane, formic acid, Tween-80, hydrogen peroxide, sodium carbonate aqueous solution and anhydrous ethanol is 3.2:55:0.16:0.22:0.32:20:90;

[0060] Step A2, add the epoxidized modified EPDM rubber to toluene, stir at a speed of 460 rpm for 18 minutes until uniform, heat to 42 ° C, and add the mixed solution a of the phosphorus-containing monomer, triethylamine and anhydrous ethanol prepared in Preparation Example 1 dropwise while stirring, and control the dripping within 10 minutes. After the dripping is completed, the temperature is raised to 74 ° C, the speed is maintained unchanged, and the stirring reaction is continued for 3.4 hours. Filter, wash with anhydrous ethanol and deionized water three times in sequence, and dry at 60 ° C to constant weight to obtain functionalized EPDM rubber, wherein the mass ratio of the epoxidized modified EPDM rubber, toluene and mixed solution a is 4.4:85:36, and the mass ratio of the phosphorus-containing monomer, triethylamine and anhydrous ethanol in the mixed solution a is 3:0.04:30.

[0061] Preparation Example 5

[0062] This preparation example provides a functionalized EPDM rubber, which is prepared by the following steps:

[0063] Step A1, adding EPDM rubber to n-hexane, stirring at a speed of 430 rpm for 16 minutes until uniform, heating to 64°C, adding formic acid and Tween-80, stirring for 16 minutes until uniform, then adding hydrogen peroxide with a mass fraction of 32%, controlling the dripping to be completed within 15 minutes, stirring and reacting for 8 hours, then adding a sodium carbonate aqueous solution with a mass fraction of 0.06%, continuing to stir for 11 minutes until uniform, standing for 20 minutes, washing with deionized water 4 times, then adding anhydrous ethanol, flocculating and precipitating for 2.7 hours, and drying at 58°C to constant weight to obtain epoxy-modified EPDM rubber, wherein the mass ratio of EPDM rubber, n-hexane, formic acid, Tween-80, hydrogen peroxide, sodium carbonate aqueous solution and anhydrous ethanol is 3.4:60:0.22:0.24:0.37:22:100;

[0064] Step A2, add the epoxidized modified EPDM rubber to toluene, stir at a speed of 500 rpm for 21 minutes until uniform, heat to 44 ° C, and add the mixed solution a of the phosphorus-containing monomer, triethylamine and anhydrous ethanol prepared in Preparation Example 2 dropwise while stirring, and control the dripping within 10 minutes. After the dripping is completed, the temperature is raised to 77 ° C, the speed is maintained unchanged, and the stirring reaction is continued for 3.8 hours. Filter, wash with anhydrous ethanol and deionized water 4 times in sequence, and dry at 64 ° C to constant weight to obtain functionalized EPDM rubber, wherein the mass ratio of the epoxidized modified EPDM rubber, toluene and mixed solution a is 4.8:90:44, and the mass ratio of the phosphorus-containing monomer, triethylamine and anhydrous ethanol in the mixed solution a is 3.2:0.05:35.

[0065] Preparation Example 6

[0066] This preparation example provides a functionalized EPDM rubber, which is prepared by the following steps:

[0067] Step A1, adding EPDM rubber to n-hexane, stirring at a speed of 460 rpm for 20 minutes until uniform, heating to 66°C, adding formic acid and Tween-80, stirring for 18 minutes until uniform, then adding 34% by mass of hydrogen peroxide, controlling the dripping to be completed within 15 minutes, maintaining the speed unchanged, stirring and reacting for 9 hours, then adding 0.08% by mass of sodium carbonate aqueous solution, continuing to stir for 12 minutes until uniform, standing for 25 minutes, washing with deionized water 5 times, then adding anhydrous ethanol, flocculating and precipitating for 3 hours, and drying at 62°C to constant weight to obtain epoxy-modified EPDM rubber, wherein the mass ratio of EPDM rubber, n-hexane, formic acid, Tween-80, hydrogen peroxide, sodium carbonate aqueous solution and anhydrous ethanol is 3.6:65:0.28:0.26:0.42:24:110;

[0068] Step A2, add the epoxidized modified EPDM rubber to toluene, stir at a speed of 540 rpm for 24 minutes until uniform, heat to 46 ° C, and add the mixed solution a of the phosphorus-containing monomer, triethylamine and anhydrous ethanol prepared in Preparation Example 3 dropwise while stirring, and control the dripping within 10 minutes. After the dripping is completed, the temperature is raised to 80 ° C, the speed is maintained unchanged, and the stirring reaction is continued for 4.2 hours. Filter, wash with anhydrous ethanol and deionized water 5 times in sequence, and dry at 68 ° C to constant weight to obtain functionalized EPDM rubber, wherein the mass ratio of the epoxidized modified EPDM rubber, toluene and mixed solution a is 5.2:95:52, and the mass ratio of the phosphorus-containing monomer, triethylamine and anhydrous ethanol in the mixed solution a is 3.4:0.06:40.

[0069] Comparative Preparation Example 3

[0070] This comparative preparation example provides a functionalized EPDM rubber, which is prepared by the following steps:

[0071] Step A1, adding EPDM rubber to n-hexane, stirring at a speed of 400 rpm for 12 minutes until uniform, heating to 62°C, adding formic acid and Tween-80, stirring for 14 minutes until uniform, then adding hydrogen peroxide with a mass fraction of 30% dropwise, controlling the dripping to be completed within 15 minutes, maintaining the speed unchanged, continuing to stir and react for 7 hours, then adding sodium carbonate aqueous solution, continuing to stir for 10 minutes until uniform, standing for 15 minutes, washing with deionized water three times, then adding anhydrous ethanol, flocculating and precipitating for 2.4 hours, and drying at 54°C to constant weight to obtain epoxy-modified EPDM rubber, wherein the mass ratio of EPDM rubber, n-hexane, formic acid, Tween-80, hydrogen peroxide, sodium carbonate aqueous solution and anhydrous ethanol is 3.2:55:0.16:0.22:0.32:20:90;

[0072] Step A2, add the epoxidized modified EPDM rubber to toluene, stir at a speed of 460 rpm for 18 minutes until uniform, heat to 42 ° C, and add dropwise the mixed solution a of the phosphorus-containing monomer, triethylamine and anhydrous ethanol prepared in Comparative Preparation Example 1 while stirring, and control the dripping within 10 minutes. After the dripping is completed, the temperature is raised to 74 ° C, the speed is maintained unchanged, and the stirring reaction is continued for 3.4 hours. Filter, wash with anhydrous ethanol and deionized water three times in sequence, and dry at 60 ° C to constant weight to obtain functionalized EPDM rubber, wherein the mass ratio of the epoxidized modified EPDM rubber, toluene and mixed solution a is 4.4:85:36, and the mass ratio of the phosphorus-containing monomer, triethylamine and anhydrous ethanol in the mixed solution a is 3:0.04:30.

[0073] Comparative Preparation Example 4

[0074] This comparative preparation example provides a functionalized EPDM rubber, which is prepared by the following steps:

[0075] Step A1, adding EPDM rubber to n-hexane, stirring at a speed of 400 rpm for 12 minutes until uniform, heating to 62°C, adding formic acid and Tween-80, stirring for 14 minutes until uniform, then adding hydrogen peroxide with a mass fraction of 30% dropwise, controlling the dripping to be completed within 15 minutes, maintaining the speed unchanged, continuing to stir and react for 7 hours, then adding sodium carbonate aqueous solution, continuing to stir for 10 minutes until uniform, standing for 15 minutes, washing with deionized water three times, then adding anhydrous ethanol, flocculating and precipitating for 2.4 hours, and drying at 54°C to constant weight to obtain epoxy-modified EPDM rubber, wherein the mass ratio of EPDM rubber, n-hexane, formic acid, Tween-80, hydrogen peroxide, sodium carbonate aqueous solution and anhydrous ethanol is 3.2:55:0.16:0.22:0.32:20:90;

[0076] Step A2, add the epoxidized modified EPDM rubber to toluene, stir at a speed of 460 rpm for 18 minutes until uniform, heat to 42 ° C, and add dropwise the mixed solution a of the phosphorus-containing monomer, triethylamine and anhydrous ethanol prepared in Comparative Preparation Example 2 while stirring, and control the dripping within 10 minutes. After the dripping is completed, the temperature is raised to 74 ° C, the speed is maintained unchanged, and the stirring reaction is continued for 3.4 hours. Filter, wash with anhydrous ethanol and deionized water three times in sequence, and dry at 60 ° C to constant weight to obtain functionalized EPDM rubber, wherein the mass ratio of the epoxidized modified EPDM rubber, toluene and mixed solution a is 4.4:85:36, and the mass ratio of the phosphorus-containing monomer, triethylamine and anhydrous ethanol in the mixed solution a is 3:0.04:30.

[0077] Preparation Examples 7-9 and Comparative Preparation Examples 5-6 provide an anti-aging enhancement component.

[0078] Preparation Example 7

[0079] This preparation example provides an anti-aging enhancement component, which is prepared by the following steps:

[0080] Step C1, adding 2,4-dihydroxybenzophenone to anhydrous DMF, stirring at a speed of 460 rpm for 16 minutes until uniform, adjusting the pH value to 8 with a mass fraction of 2.2% sodium hydroxide aqueous solution, adding itaconic anhydride and isopropanol mixed solution c dropwise, controlling the dripping within 10 minutes, and heating to 72°C, maintaining the speed unchanged, and continuing to stir and react for 6 hours, and then adjusting the pH to neutral with a mass fraction of 0.6% hydrochloric acid aqueous solution, controlling the rotary evaporation temperature to 78°C to remove anhydrous DMF, washing with anhydrous ethanol and deionized water 3 times each, and drying at 62°C to constant weight to obtain a carboxyl monomer, wherein the mass ratio of 2,4-dihydroxybenzophenone, anhydrous DMF and mixed solution c is 2.8:55:26, and the mass ratio of itaconic anhydride and isopropanol in the mixed solution c is 1.5:22;

[0081] Step C2: Nano zinc oxide, deionized water, anhydrous ethanol and KH-560 were ultrasonically treated at a frequency of 30 kHz and a power of 450 W for 28 minutes, and the temperature was raised to 46° C. The mixture was stirred at a speed of 540 rpm for 3.6 hours, centrifuged, and the precipitate was washed three times with anhydrous ethanol and deionized water, and dried at 58° C. to a constant weight to obtain epoxy zinc oxide. The epoxy zinc oxide was ultrasonically dispersed in anhydrous DMF, and the ultrasonic frequency was controlled at 35 kHz and a power of 500 W for 20 minutes. Tetrabutylammonium bromide was added dropwise while stirring at a speed of 560 rpm. , carboxyl monomer and anhydrous DMF mixed solution d, after the dropwise addition, the temperature was raised to 96°C, the speed was maintained unchanged, and the stirring reaction was continued for 1.8 hours. After the reaction was completed, centrifugation was carried out, and the mixture was washed with anhydrous ethanol and deionized water for 3 times in sequence, and dried at 64°C to constant weight to obtain an anti-aging enhancement component, wherein the mass ratio of nano zinc oxide, deionized water, anhydrous ethanol and KH-560 was 2.4:20:6:0.2, the mass ratio of epoxy zinc oxide, anhydrous DMF and mixed solution d was 2:50:26, and the mass ratio of tetrabutylammonium bromide, carboxyl monomer and anhydrous DMF in the mixed solution d was 0.1:0.8:24.

[0082] Preparation Example 8

[0083] This preparation example provides an anti-aging enhancement component, which is prepared by the following steps:

[0084] Step C1, 2,4-dihydroxybenzophenone was added to anhydrous DMF, stirred at a speed of 480 rpm for 20 min until uniform, and the pH value was adjusted to 8.5 with a 2.5% mass fraction of sodium hydroxide aqueous solution, and a mixed solution c of itaconic anhydride and isopropanol was added dropwise, and the dripping was controlled within 10 min. After the dripping was completed, the temperature was raised to 74 ° C, the speed was maintained unchanged, and the stirring reaction was continued for 9 h, and then the pH was adjusted to neutral with a 0.8% mass fraction of hydrochloric acid aqueous solution. The rotary evaporation temperature was controlled to 80 ° C to remove anhydrous DMF, and the mixture was washed with anhydrous ethanol and deionized water 4 times each, and dried at 64 ° C to constant weight to obtain a carboxyl monomer, wherein the mass ratio of 2,4-dihydroxybenzophenone, anhydrous DMF and mixed solution c was 3.1:60:29, and the mass ratio of itaconic anhydride and isopropanol in the mixed solution c was 1.7:22;

[0085] Step C2: Nano zinc oxide, deionized water, anhydrous ethanol and KH-560 were ultrasonically treated at a frequency of 35 kHz and a power of 500 W for 30 min, and the temperature was raised to 49° C. The mixture was stirred at a speed of 570 rpm for 4 h, centrifuged, and the precipitate was washed and dried to obtain epoxy zinc oxide. The epoxy zinc oxide was ultrasonically dispersed in anhydrous DMF, and a mixture of tetrabutylammonium bromide, carboxyl monomer and anhydrous DMF was added dropwise. After the addition was completed, the temperature was raised to 102° C. and the speed was maintained unchanged. The reaction was continued with stirring for 2.1 hours. After the reaction was completed, the mixture was centrifuged, washed four times with anhydrous ethanol and deionized water, and dried at 66°C to constant weight to obtain an anti-aging enhancement component, wherein the mass ratio of nano-zinc oxide, deionized water, anhydrous ethanol and KH-560 was 3:25:6:0.3, the mass ratio of epoxy zinc oxide, anhydrous DMF and mixed solution d was 2.5:55:28, and in the mixed solution d, the mass ratio of tetrabutylammonium bromide, carboxyl monomer and anhydrous DMF was 0.1:1:24.

[0086] Preparation Example 9

[0087] This preparation example provides an anti-aging enhancement component, which is prepared by the following steps:

[0088] Step C1, 2,4-dihydroxybenzophenone was added to anhydrous DMF, stirred at a speed of 500 rpm for 24 minutes until uniform, and the pH value was adjusted to 9 with a mass fraction of 2.8% sodium hydroxide aqueous solution, and a mixed solution c of itaconic anhydride and isopropanol was added dropwise, and the dripping was controlled within 10 minutes. After the dripping was completed, the temperature was raised to 76°C, the speed was maintained unchanged, and the stirring reaction was continued for 12 hours. The pH was then adjusted to neutral with a mass fraction of 1% hydrochloric acid aqueous solution, and the rotary evaporation temperature was controlled to 84°C to remove anhydrous DMF. The mixture was washed with anhydrous ethanol and deionized water 5 times each, and dried at 66°C to constant weight to obtain a carboxyl monomer, wherein the mass ratio of 2,4-dihydroxybenzophenone, anhydrous DMF and mixed solution c was 3.4:65:32, and the mass ratio of itaconic anhydride and isopropanol in the mixed solution c was 1.9:22;

[0089] Step C2: Nano zinc oxide, deionized water, anhydrous ethanol and KH-560 were ultrasonically treated at a frequency of 40 kHz and a power of 550 W for 32 minutes. The temperature was raised to 52° C. and stirred at a speed of 600 rpm for 4.4 hours. The mixture was centrifuged, washed and dried to obtain epoxy zinc oxide. The epoxy zinc oxide was ultrasonically dispersed in anhydrous DMF, and a mixture of tetrabutylammonium bromide, carboxyl monomer and anhydrous DMF was added dropwise. After the addition was completed, the temperature was raised to 108° C. and the speed was maintained unchanged. The reaction was continued with stirring for 2.4 hours. After the reaction was completed, the mixture was centrifuged, washed with anhydrous ethanol and deionized water for 5 times, and dried at 68°C to constant weight to obtain an anti-aging enhancement component, wherein the mass ratio of nano zinc oxide, deionized water, anhydrous ethanol and KH-560 was 3.6:30:6:0.4, the mass ratio of epoxy zinc oxide, anhydrous DMF and mixed solution d was 3:60:30, and in the mixed solution d, the mass ratio of tetrabutylammonium bromide, carboxyl monomer and anhydrous DMF was 0.1:1.2:24.

[0090] Comparative Preparation Example 5

[0091] This comparative preparation example provides an anti-aging enhancement component, which is prepared by the following steps:

[0092] Step C1, adding 2,4-dihydroxybenzoic acid to anhydrous DMF, stirring at a speed of 460 rpm for 16 minutes until uniform, adjusting the pH value to 8 with a 2.2% mass fraction of sodium hydroxide aqueous solution, adding itaconic anhydride and isopropanol mixed solution c dropwise, controlling the dripping within 10 minutes, and heating to 72°C, maintaining the speed unchanged, and continuing to stir and react for 6 hours, then adjusting the pH to neutral with a 0.6% mass fraction of hydrochloric acid aqueous solution, controlling the rotary evaporation temperature to 78°C to remove anhydrous DMF, washing with anhydrous ethanol and deionized water three times each, and drying at 62°C to constant weight to obtain a carboxyl monomer, wherein the mass ratio of 2,4-dihydroxybenzoic acid, anhydrous DMF and mixed solution c is 2.8:55:26, and the mass ratio of itaconic anhydride and isopropanol in the mixed solution c is 1.5:22;

[0093] Step C2: Nano zinc oxide, deionized water, anhydrous ethanol and KH-560 were ultrasonically treated at a frequency of 30 kHz and a power of 450 W for 28 minutes, and the temperature was raised to 46° C. The mixture was stirred at a speed of 540 rpm for 3.6 hours, centrifuged, and the precipitate was washed three times with anhydrous ethanol and deionized water, and dried at 58° C. to a constant weight to obtain epoxy zinc oxide. The epoxy zinc oxide was ultrasonically dispersed in anhydrous DMF, and the ultrasonic frequency was controlled at 35 kHz and a power of 500 W for 20 minutes. Tetrabutylammonium bromide was added dropwise while stirring at a speed of 560 rpm. , carboxyl monomer and anhydrous DMF mixed solution d, after the dropwise addition, the temperature was raised to 96°C, the speed was maintained unchanged, and the stirring reaction was continued for 1.8 hours. After the reaction was completed, centrifugation was carried out, and the mixture was washed with anhydrous ethanol and deionized water for 3 times in sequence, and dried at 64°C to constant weight to obtain an anti-aging enhancement component, wherein the mass ratio of nano zinc oxide, deionized water, anhydrous ethanol and KH-560 was 2.4:20:6:0.2, the mass ratio of epoxy zinc oxide, anhydrous DMF and mixed solution d was 2:50:26, and the mass ratio of tetrabutylammonium bromide, carboxyl monomer and anhydrous DMF in the mixed solution d was 0.1:0.8:24.

[0094] Comparative Preparation Example 6

[0095] This comparative preparation example provides an anti-aging enhancement component, which is prepared by the following steps:

[0096] Step C1, 2,4-dihydroxybenzophenone was added to anhydrous DMF, stirred at a speed of 460 rpm for 16 minutes until uniform, and the pH value was adjusted to 8 with a mass fraction of 2.2% sodium hydroxide aqueous solution, and a mixed solution c of phthalic anhydride and isopropanol was added dropwise, and the dripping was controlled within 10 minutes. After the dripping was completed, the temperature was raised to 72°C, the speed was maintained unchanged, and the stirring reaction was continued for 6 hours. The pH was then adjusted to neutral with a mass fraction of 0.6% hydrochloric acid aqueous solution, and the rotary evaporation temperature was controlled to 78°C to remove anhydrous DMF, and the mixture was washed with anhydrous ethanol and deionized water 3 times each, and dried at 62°C to constant weight to obtain a carboxyl monomer, wherein the mass ratio of 2,4-dihydroxybenzophenone, anhydrous DMF and mixed solution c was 2.8:55:26, and the mass ratio of phthalic anhydride and isopropanol in the mixed solution c was 1.5:22;

[0097] Step C2: Nano zinc oxide, deionized water, anhydrous ethanol and KH-560 were ultrasonically treated at a frequency of 30 kHz and a power of 450 W for 28 minutes, and the temperature was raised to 46° C. The mixture was stirred at a speed of 540 rpm for 3.6 hours, centrifuged, and the precipitate was washed three times with anhydrous ethanol and deionized water, and dried at 58° C. to a constant weight to obtain epoxy zinc oxide. The epoxy zinc oxide was ultrasonically dispersed in anhydrous DMF, and the ultrasonic frequency was controlled at 35 kHz and a power of 500 W for 20 minutes. Tetrabutylammonium bromide was added dropwise while stirring at a speed of 560 rpm. , carboxyl monomer and anhydrous DMF mixed solution d, after the dropwise addition, the temperature was raised to 96°C, the speed was maintained unchanged, and the stirring reaction was continued for 1.8 hours. After the reaction was completed, centrifugation was carried out, and the mixture was washed with anhydrous ethanol and deionized water for 3 times in sequence, and dried at 64°C to constant weight to obtain an anti-aging enhancement component, wherein the mass ratio of nano zinc oxide, deionized water, anhydrous ethanol and KH-560 was 2.4:20:6:0.2, the mass ratio of epoxy zinc oxide, anhydrous DMF and mixed solution d was 2:50:26, and the mass ratio of tetrabutylammonium bromide, carboxyl monomer and anhydrous DMF in the mixed solution d was 0.1:0.8:24.

[0098] Examples 1-3 and Comparative Examples 1-4 provide an aging-resistant material for automotive plastic parts and a preparation method thereof.

[0099] Example 1

[0100] This embodiment provides an aging-resistant material for automotive plastic parts, comprising the following raw materials in parts by weight:

[0101] 90 parts of polypropylene, 15 parts of the functionalized EPDM rubber prepared in Preparation Example 4, 8 parts of the anti-aging reinforcement component prepared in Preparation Example 7, 1 part of erucamide, 1.2 parts of dicumyl peroxide, 3 parts of Irganox 1010, and 1680.5 parts of an antioxidant;

[0102] The aging-resistant material for automobile plastic parts comprises the following steps:

[0103] Step S1, preparing materials: weighing corresponding weight portions of polypropylene, functionalized EPDM rubber, anti-aging reinforcement component, erucamide, Irganox 1010 and antioxidant 168 for later use;

[0104] Step S2, melt extrusion: polypropylene, functionalized EPDM rubber, anti-aging reinforcement component, lubricant, dicumyl peroxide, Irganox 1010, and antioxidant 168 are fed into a twin-screw extruder and extruded through a die head to obtain a molten mixture, wherein the extrusion process of the twin-screw extruder is as follows: zone 1 200° C., zone 2 205° C., zone 3 210° C., zone 4 215° C., zone 5 220° C., and die head temperature 225° C.; the screw speed is 90 r / min;

[0105] Step S3, molding: The molten mixture prepared in step S2 was placed in a torque rheometer, mixed at 155° C. for 10 min, discharged, crushed, and placed in an injection molding machine for injection molding to obtain an aging-resistant material for automotive plastic parts. During injection molding, the head temperature was 180° C., the injection pressure was 66 MPa, the extrusion rate was 1.1 g / s, the traction force was 6 N, and the moving speed was 0.32 m / min.

[0106] Example 2

[0107] This embodiment provides an aging-resistant material for automotive plastic parts, comprising the following raw materials in parts by weight:

[0108] 95 parts of polypropylene, 20 parts of the functionalized EPDM rubber prepared in Preparation Example 5, 10 parts of the anti-aging reinforcing component prepared in Preparation Example 8, 2 parts of ethylene bisstearamide, 1.4 parts of dicumyl peroxide, 4 parts of Irganox 168, and 0.6 parts of antioxidant 1010;

[0109] The aging-resistant material for automobile plastic parts comprises the following steps:

[0110] Step S1, preparing materials: weighing corresponding weight portions of polypropylene, functionalized EPDM rubber, anti-aging reinforcement component, ethylene bisstearamide, Irganox 168 and antioxidant 1010 for later use;

[0111] Step S2, melt extrusion: polypropylene, functionalized EPDM rubber, anti-aging reinforcement component, lubricant, dicumyl peroxide, Irganox 168, and antioxidant 1010 are fed into a twin-screw extruder and extruded through a die head to obtain a molten mixture, wherein the extrusion process of the twin-screw extruder is as follows: zone 1 202° C., zone 2 207° C., zone 3 212° C., zone 4 217° C., zone 5 222° C., die head temperature 225° C.; screw speed 95 r / min;

[0112] Step S3, molding: The molten mixture prepared in step S2 was placed in a torque rheometer, mixed at 160° C. for 12.5 min, discharged, crushed, and placed in an injection molding machine for injection molding to obtain an aging-resistant material for automotive plastic parts. During injection molding, the head temperature was 182° C., the injection pressure was 67 MPa, the extrusion rate was 1.25 g / s, the traction force was 6.1 N, and the moving speed was 0.33 m / min.

[0113] Example 3

[0114] This embodiment provides an aging-resistant material for automotive plastic parts, comprising the following raw materials in parts by weight:

[0115] 100 parts of polypropylene, 25 parts of the functionalized EPDM rubber prepared in Preparation Example 6, 12 parts of the anti-aging reinforcement component prepared in Preparation Example 9, 3 parts of erucamide, 1.6 parts of dicumyl peroxide, 5 parts of Irganox 1010, and 1680.7 parts of an antioxidant;

[0116] The aging-resistant material for automobile plastic parts comprises the following steps:

[0117] Step S1, preparing materials: weighing corresponding weight portions of polypropylene, functionalized EPDM rubber, anti-aging reinforcement component, erucamide, dicumyl peroxide, Irganox 1010 and antioxidant 168 for later use;

[0118] Step S2, melt extrusion: polypropylene, functionalized EPDM rubber, anti-aging reinforcement component, lubricant, Irganox 1010, and antioxidant 168 are fed into a twin-screw extruder and extruded through a die head to obtain a molten mixture, wherein the extrusion process of the twin-screw extruder is as follows: zone 1 205°C, zone 2 210°C, zone 3 215°C, zone 4 220°C, zone 5 225°C, and die head temperature 225°C; the screw speed is 100 r / min;

[0119] Step S3, molding: The molten mixture prepared in step S2 was placed in a torque rheometer, mixed at 165° C. for 15 min, discharged, crushed, and placed in an injection molding machine for injection molding to obtain an aging-resistant material for automotive plastic parts. The injection molding process was performed at a head temperature of 185° C., an injection pressure of 68 MPa, an extrusion rate of 1.4 g / s, a traction force of 6.2 N, and a moving speed of 0.34 m / min.

[0120] Comparative Example 1

[0121] Comparative Example 1 is the same as Example 1, except that the functionalized EPDM rubber in Example 1 is replaced by the functionalized EPDM rubber prepared in Comparative Preparation Example 3.

[0122] Comparative Example 2

[0123] Comparative Example 1 is the same as Example 1, except that the functionalized EPDM rubber in Example 1 is replaced by the functionalized EPDM rubber prepared in Comparative Preparation Example 4.

[0124] Comparative Example 3

[0125] Comparative Example 3 is the same as Example 1, except that the anti-aging enhancement component in Example 1 is replaced by the anti-aging enhancement component prepared in Comparative Preparation Example 5.

[0126] Comparative Example 4

[0127] Comparative Example 4 is the same as Example 1, except that the anti-aging enhancement component in Example 1 is replaced by the anti-aging enhancement component prepared in Comparative Preparation Example 6.

[0128] Performance Testing

[0129] The following performance tests were performed on the materials for automotive plastic parts prepared in Examples 1-3 and Comparative Examples 1-4:

[0130] Tensile strength test: tested in accordance with ASTM D638-2010 standard, thickness 3.0mm specimen, unit: MPa;

[0131] High temperature aging test: The automotive plastic parts materials prepared in Examples 1-3 and Comparative Examples 1-4 were placed in a 150°C oven for 1000 hours to test various properties.

[0132] UV aging test: The automotive plastic parts materials prepared in Examples 1-3 and Comparative Examples 1-4 were placed in a UV box and irradiated for 1500 hours to test various properties. Light source: UVA-340, light intensity: 0.76W, cycle conditions: 8 hours of illumination (BPT: 60°C), 4 hours of condensation (BPT: 50°C) (GB / T16422.3).

[0133] Flame retardancy test: Measure the horizontal burning velocity according to the automotive interior material combustion test regulations (FMVSS.302) to determine the flame retardancy of the material;

[0134] Table 1 Performance test of aging-resistant materials for automotive plastic parts

[0135] As can be seen from Table 1, compared with Comparative Examples 1-4, the tensile strength and tensile strength retention of the automotive plastic parts materials prepared in Examples 1-3 are better, and the horizontal burning velocity is lower, indicating that the automotive plastic parts materials prepared in the present invention have excellent aging resistance and flame retardant properties.

[0136] This specific embodiment is merely an explanation of the present application and is not a limitation of the present application. After reading this specification, those skilled in the art may make non-creative modifications to the present embodiment as needed, but as long as they are within the scope of the claims of the present application, they are protected by the patent law.

Claims

1. An aging-resistant material for automotive plastic parts, characterized in that: Including parts by weight of raw materials: 90-100 parts of polypropylene, 15-25 parts of functionalized EPDM rubber, 8-12 parts of anti-aging reinforcement component, 1-3 parts of lubricant, 1.2-1.6 parts of crosslinking agent, 3-5 parts of thermal oxygen stabilizer and 0.5-0.7 parts of antioxidant; The functionalized EPDM rubber is firstly prepared by in-situ epoxidation of EPDM rubber and formic acid-hydrogen peroxide to obtain epoxidized modified EPDM rubber, and then reacted with a phosphorus-containing monomer through a ring-opening esterification reaction to obtain the functionalized EPDM rubber; The phosphorus-containing monomer is prepared by an amidation reaction between tris(hydroxymethyl)aminomethane and p-hydroxycinnamic acid to obtain a polyhydroxy monomer, which is then esterified with (2-carboxyethyl)phenylphosphonic acid. The anti-aging enhancement component is firstly prepared by subjecting 2,4-dihydroxybenzophenone and itaconic anhydride to a ring-opening esterification reaction to obtain a carboxyl monomer, and then undergoing a ring-opening reaction with epoxy zinc oxide to obtain the anti-aging enhancement component.

2. The aging-resistant material for automobile plastic parts according to claim 1, characterized in that: The functionalized EPDM rubber is prepared by the following steps: Step A1, adding EPDM rubber to n-hexane, stirring evenly, heating to 62-66° C., adding formic acid and Tween-80, stirring evenly, then adding hydrogen peroxide dropwise, stirring and reacting for 7-9 hours, then adding sodium carbonate aqueous solution, continuing to stir evenly, standing, washing, then adding anhydrous ethanol, flocculating and precipitating for 2.4-3 hours, and drying to obtain epoxy-modified EPDM rubber; Step A2: Add the epoxidized modified EPDM rubber to toluene, stir evenly, raise the temperature to 42-46°C, add dropwise a mixture of the phosphorus-containing monomer, triethylamine, and anhydrous ethanol while stirring, raise the temperature to 74-80°C, continue stirring and react for 3.4-4.2 hours, filter, wash, and dry to obtain the functionalized EPDM rubber.

3. The aging-resistant material for automobile plastic parts according to claim 2, characterized in that: In step A1, the mass ratio of EPDM rubber, n-hexane, formic acid, Tween-80, hydrogen peroxide, sodium carbonate aqueous solution and anhydrous ethanol is 3.2-3.6:55-65:0.16-0.28:0.22-0.26:0.32-0.42:20-24:90-110.

4. The aging-resistant material for automobile plastic parts according to claim 2, characterized in that: In step A2, the mass ratio of epoxidized modified EPDM rubber, toluene and mixed solution a is 4.4-5.2:85-95:36-52. In the mixed solution a, the mass ratio of phosphorus-containing monomer, triethylamine and anhydrous ethanol is 3-3.4:0.04-0.06:30-40.

5. The aging-resistant material for automobile plastic parts according to claim 2, characterized in that: The phosphorus-containing monomer is prepared by the following steps: Step B1, adding tris(hydroxymethyl)aminomethane and p-hydroxycinnamic acid to anhydrous THF, stirring evenly, adding a mixture of N,N-dicyclohexylcarbodiimide, 4-dimethylaminopyridine and anhydrous THF dropwise while stirring, heating to reflux for 3-5 hours, and filtering, washing and drying after the reaction to obtain a polyhydroxy monomer; Step B2: Add the polyhydroxy monomer, p-toluenesulfonic acid and (2-carboxyethyl)phenylphosphonic acid to anhydrous DMF, heat to 35-45°C, stir evenly, then heat to 72-76°C, continue stirring and react for 3.4-4.2 hours, rotary evaporate, wash, and dry to obtain the phosphorus-containing monomer.

6. The aging-resistant material for automobile plastic parts according to claim 5, characterized in that: In step B1, the mass ratio of tris(hydroxymethyl)aminomethane, p-hydroxycinnamic acid, anhydrous THF and mixed solution b is 2-4:3-6:65-75:25-35, and in mixed solution b, the mass ratio of N,N-dicyclohexylcarbodiimide, 4-dimethylaminopyridine and anhydrous THF is 4.6-5.2:3-3.4:30-40.

7. The aging-resistant material for automobile plastic parts according to claim 5, characterized in that: In the step B2, the mass ratio of the polyhydroxy monomer, p-toluenesulfonic acid, (2-carboxyethyl)phenylphosphonic acid and anhydrous DMF is 3-5:0.08-0.12:2.4-4:40-50.

8. The aging-resistant material for automobile plastic parts according to claim 1, characterized in that: The anti-aging enhancement component is prepared by the following steps: Step C1, adding 2,4-dihydroxybenzophenone to anhydrous DMF, stirring evenly, adjusting the pH to 8-9, adding dropwise a mixture of itaconic anhydride and isopropanol (c), heating to 72-76°C, continuing stirring and reacting for 6-12 hours, then adjusting the pH to neutral, rotary evaporation, washing, and drying to obtain a carboxyl monomer; Step C2, ultrasonically mix nano zinc oxide, deionized water, anhydrous ethanol and KH-560 for 28-32 minutes, heat to 46-52°C, stir and react for 3.6-4.4 hours, centrifuge, wash and dry the precipitate to obtain epoxy zinc oxide, ultrasonically disperse the epoxy zinc oxide in anhydrous DMF, dropwise add a mixture d of tetrabutylammonium bromide, carboxyl monomer and anhydrous DMF, heat to 96-108°C, stir and react for 1.8-2.4 hours, centrifuge, wash and dry after the reaction to obtain the anti-aging enhancement component.

9. The aging-resistant material for automobile plastic parts according to claim 8, characterized in that: In the step C1, the mass ratio of 2,4-dihydroxybenzophenone, anhydrous DMF and mixed solution c is 2.8-3.4:55-65:26-32, the mass ratio of itaconic anhydride and isopropyl alcohol in the mixed solution c is 1.5-1.9:22, in the step C2, the mass ratio of nano-zinc oxide, deionized water, anhydrous ethanol and KH-560 is 2.4-3.6:20-30:6:0.2-0.4, the mass ratio of epoxy zinc oxide, anhydrous DMF and mixed solution d is 2-3:50-60:26-30, and the mass ratio of tetrabutylammonium bromide, carboxyl monomer and anhydrous DMF in the mixed solution d is 0.1:0.8-1.2:

24.

10. A method for preparing an aging-resistant material for automobile plastic parts according to any one of claims 1 to 9, characterized in that: The following steps are involved: Step S1, preparing materials: weighing corresponding weight portions of polypropylene, functionalized EPDM rubber, anti-aging reinforcement component, lubricant, thermal oxidation stabilizer and antioxidant for later use; Step S2, melt extrusion: feeding polypropylene, functionalized EPDM rubber, anti-aging reinforcement component, lubricant, crosslinking agent, thermal oxygen stabilizer and antioxidant into a twin-screw extruder and extruding through a die to obtain a molten mixture; Step S3, molding: placing the molten mixture prepared in step S2 in a torque rheometer, mixing, unloading, crushing, and placing in an injection molding machine for injection molding to obtain an aging-resistant material for automotive plastic parts.

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