Impact-resistant composite material for automobile plastic parts and preparation method of impact-resistant composite material

Abstract

The invention discloses an impact-resistant composite material for automobile plastic parts and a preparation method thereof, and relates to the field of automobile plastic parts, the impact-resistant composite material comprises the following raw materials by weight: 65-75 parts of polypropylene, 3-5 parts of a compatilizer, 15-20 parts of a modified ethylene-octylene copolymer, 1-1.5 parts of an anti-aging agent, 10-12 parts of talcum powder, 2-4 parts of a coupling agent, 0.6-0.8 part of a lubricant, and 0.3-0.5 part of an auxiliary agent. And the modified ethylene-octylene copolymer and the anti-aging agent are combined, so that the composite material is endowed with relatively strong impact resistance, flame retardance, smoke suppression and aging resistance.

Description

Technical Field

[0001] The present invention relates to the field of automobile plastic accessories, and in particular to an impact-resistant composite material for automobile plastic accessories and a preparation method thereof. Background Art

[0002] Polypropylene is a thermoplastic synthetic resin with excellent performance. It is a colorless and translucent polymer formed by the addition polymerization of propylene. It is one of the important general-purpose plastics. However, its low high-temperature melt strength, poor impact resistance and easy aging limit its use in materials for plastic accessories.

[0003] Cinnamate is a commonly used anti-UV aging agent. However, cinnamate UV absorbers not only have poor compatibility with polypropylene and low stability, but also have a short UV absorption range and limited UV absorption capacity. Therefore, they cannot effectively improve the material's UV aging resistance, which is not conducive to extending the material's service life, limiting their use in polypropylene composite materials for automotive plastic parts.

[0004] Previous studies have used POE (such as ethylene-octene copolymer) and montmorillonite in combination to improve the impact resistance and flame retardancy of polypropylene. However, montmorillonite has poor compatibility with both POE and polypropylene. Furthermore, when used alone for flame retardancy, montmorillonite's ability to promote charring is insufficient, preventing the formation of a dense carbon layer. This results in weak smoke suppression and, therefore, insufficient flame retardancy.

[0005] Based on this, a suitable modification method is needed to expand the ultraviolet absorption range of cinnamate ultraviolet absorbers, improve the charring ability and smoke suppression performance of montmorillonite, and apply them to polypropylene composites for automotive plastic accessories, so as to obtain polypropylene composites for automotive plastic accessories with better comprehensive performance such as aging resistance, impact resistance, flame retardancy and smoke suppression. Summary of the Invention

[0006] In order to solve the above technical problems, the present invention provides an impact-resistant composite material for automobile plastic parts and a preparation method thereof.

[0007] The purpose of the present invention can be achieved through the following technical solutions:

[0008] An impact-resistant composite material for automotive plastic parts, comprising the following raw materials in parts by weight: 65-75 parts of polypropylene, 3-5 parts of a compatibilizer, 15-20 parts of a modified ethylene-octene copolymer, 1-1.5 parts of an anti-aging agent, 10-12 parts of talc, 2-4 parts of a coupling agent, 0.6-0.8 parts of a lubricant, and 0.3-0.5 parts of an additive;

[0009] Furthermore, the compatibilizer is maleic anhydride grafted polypropylene; the coupling agent is 3-acryloxypropyl triethoxysilane; the lubricant is ethylene bisstearamide; and the auxiliary agent is tris(dipropylene glycol) phosphite;

[0010] The preparation of the impact-resistant composite material for automobile plastic parts comprises the following steps:

[0011] Polypropylene, modified ethylene-octene copolymer, talc, and a coupling agent are mixed and stirred at a low speed, and then a compatibilizer, an anti-aging agent, a lubricant, and an additive are added and stirred at a high speed to obtain a mixture; the mixture is extruded and granulated to obtain an impact-resistant composite material for automotive plastic parts;

[0012] The preparation of the impact-resistant composite material for automobile plastic parts comprises the following specific steps:

[0013] Mixing polypropylene, modified ethylene-octene copolymer, talc, and a coupling agent, stirring at 700-800 rpm for 5-7 minutes, adding a compatibilizer, an anti-aging agent, a lubricant, and an additive, and stirring at 1000-1200 rpm for 10-12 minutes to obtain a mixture; extruding and granulating the mixture to obtain an impact-resistant composite material for automotive plastic parts;

[0014] Furthermore, polypropylene needs to be dried at 80-90°C for 3-4 hours and used after cooling; the temperature during the preparation of the mixture is ≤60°C; during the extrusion granulation process, a twin-screw extruder is used with a screw speed of 300-400rpm, a material residence time of 2-3min, a feeding section temperature of 165-170°C, a melting section temperature of 180-190°C, a mixing section temperature of 200-210°C, a homogenization section temperature of 190-200°C, and a die head temperature of 195-205°C;

[0015] The modified ethylene-octene copolymer is prepared by the following steps:

[0016] Step G1: tributylphosphine, acetone, and potassium iodide are mixed, a protective gas is introduced, the mixture is stirred and heated, a chloroolefin is added, the mixture is refluxed and stirred, and post-processed to obtain product e1; product e1 and ethanol are mixed and stirred, an oxidant is added, and the mixture is heated and stirred to obtain product e2;

[0017] Step G2: mixing product e2, deionized water, and ethanol, grinding the mixture, adding nano-montmorillonite, continuing grinding, and post-processing to obtain product e3;

[0018] Step G3: Mix expanded graphite and potassium permanganate solution, heat and stir to obtain product e4; mix KH550, anhydrous ethanol and deionized water, heat and stir, add product e4, heat and continue stirring to obtain product e5; mix product e3, product e5, DMAC and tetrahydrofuran, and stir at room temperature to obtain product e6;

[0019] Step G4: In a protective gas atmosphere, nitrobenzoic acid and anhydrous tetrahydrofuran were mixed and stirred, and then methylenetriphenylphosphine was added, and the mixture was heated and refluxed with stirring to obtain product e7; product e7 was added to DMF and stirred, and then oxalyl chloride was added in an ice-water bath, and the mixture was heated and stirred to obtain product e8; product e6, toluene, and dimethyl sulfoxide were mixed, heated and ultrasonically dispersed, pyridine and potassium carbonate were added, stirred, and then a solution of product e8 was added in an ice-water bath. After the addition was complete, the mixture was stirred to obtain product e9;

[0020] Step G5: Mix product e9, toluene, and methanol, disperse them ultrasonically, add sodium sulfide and potassium bicarbonate, and heat and reflux with stirring to obtain product e10; mix ethylene-octene copolymer, product e10, toluene, and initiator, disperse them ultrasonically, and heat and stir to react to obtain modified ethylene-octene copolymer;

[0021] The preparation of the modified ethylene-octene copolymer comprises the following specific steps:

[0022] Step G1: tributylphosphine, acetone, and potassium iodide are mixed, followed by introduction of protective gas, and the mixture is heated to 40-45°C with stirring. A chloroolefin is added, and the mixture is refluxed with stirring for 4.5-5 hours. The mixture is filtered, washed with ethyl acetate, rotary evaporated, and vacuum dried at 35-40°C to obtain product e1. Product e1 and ethanol are mixed and stirred for 5-10 minutes, an oxidant is added, and the mixture is stirred at 50-55°C for 5-5.5 hours to obtain product e2.

[0023] Furthermore, the usage ratio of tributylphosphine, acetone, potassium iodide, and chloroolefin is 21-23 g: 100-110 mL: 0.3-0.4 g: 16-20 g; the chloroolefin is selected from one of 11-chloro-1-undecene and 8-chloro-1-octene; the usage ratio of product e1, ethanol, and oxidant is 50-52 g: 150-160 mL: 20-22 g; the volume fraction of ethanol is 95%; and the oxidant is 3-chloroperoxybenzoic acid.

[0024] During the reaction process of step G1, tributylphosphine reacts with the chloroolefin to generate a quaternary phosphonium salt product containing a carbon-carbon double bond, namely, product e1; the carbon-carbon double bond of product e1 is oxidized to an epoxy group to obtain a quaternary phosphonium salt product containing an epoxy group, namely, product e2;

[0025] Step G2: Mix product e2, deionized water, and ethanol, grind for 30-35 minutes, add nano-montmorillonite, continue grinding for 2-2.5 hours, stir, filter, and wash with water until no white turbidity is produced by silver nitrate solution detection, and freeze-dry to obtain product e3;

[0026] Furthermore, the usage ratio of product e2, deionized water, ethanol, and nano-montmorillonite is 53-55 g: 1900-2000 mL: 400-500 mL: 28-30 g; the volume fraction of ethanol is 95%; and the concentration of the silver nitrate solution is 0.1-0.15 mol / L.

[0027] During the reaction of step G2, the quaternary phosphonium salt containing an epoxy group in product e2 intercalates and modifies the montmorillonite to obtain a modified montmorillonite product containing an epoxy group, namely product e3;

[0028] Step G3: After mixing expanded graphite and potassium permanganate solution, heat the mixture to 50-60°C and stir at constant temperature for 11-12 hours to obtain product e4; KH550, anhydrous ethanol, and deionized water are mixed, stirred at 40-45°C for 3-3.5 hours, product e4 is added, the temperature is raised to 70-80°C, and stirred for 4-4.5 hours to obtain product e5; product e3, product e5, DMAC, and tetrahydrofuran are mixed, and stirred at room temperature for 8-8.5 hours to obtain product e6;

[0029] Furthermore, the usage ratio of expanded graphite and potassium permanganate solution is 1-1.5 g:45-50 g; the potassium permanganate solution is obtained by mixing potassium permanganate and concentrated sulfuric acid in a mass ratio of 3-4 g:40-42 g; the mass fraction of concentrated sulfuric acid is 98%; the usage ratio of KH550, anhydrous ethanol, deionized water, and product e4 is 1-1.5 g:140-150 mL:15-20 mL:53-55 g; the usage ratio of product e3, product e5, DMAC, and tetrahydrofuran is 31-33 g:58-60 g:1800-1900 mL:500-600 mL;

[0030] During the reaction of step G3, the expanded graphite is oxidized by potassium permanganate solution, increasing the number of oxygen-containing groups on the surface to obtain product e4; KH550 is hydrolyzed to modify the surface of the expanded graphite with increased oxygen-containing groups to obtain amino-containing expanded graphite, i.e., product e5; the epoxy groups in product e3 react with the amino groups in product e5 to obtain a montmorillonite-expanded graphite graft product containing hydroxyl groups, i.e., product e6;

[0031] Step G4: In a protective gas atmosphere, nitrobenzoic acid and anhydrous tetrahydrofuran were mixed, stirred for 35-45 minutes, and then methylenetriphenylphosphine was added. The mixture was refluxed and stirred at 55-60°C for 5-5.5 hours to obtain product e7; product e7 was added to DMF and stirred for 10-15 minutes. Oxalyl chloride was added in an ice-water bath, and the mixture was stirred at 65-70°C for 1-1.5 hours to obtain product e8; product e6 was mixed with toluene and dimethyl sulfoxide, heated to 50-60°C, and ultrasonically dispersed for 1.5-2 hours. Pyridine and potassium carbonate were added and stirred for 10-15 minutes. The solution of product e8 was added in an ice-water bath and stirred for 6-6.5 hours after the addition to obtain product e9;

[0032] Furthermore, the usage ratio of nitrobenzoic acid, anhydrous tetrahydrofuran, and methylenetriphenylphosphine is 21-23 g:105-110 mL:30-32 g; the nitrobenzoic acid is 2-formyl-5-nitrobenzoic acid; the usage ratio of product e7, DMF, and oxalyl chloride is 18-20 g:70-80 mL:15-17 g; the usage ratio of the solution of product e6, toluene, dimethyl sulfoxide, pyridine, potassium carbonate, and product e8 is 10-12 g:400-500 mL:350-450 mL:0.05-0.07 g:26-28 g:90-95 mL; the solution of product e8 is obtained by adding 21-23 g of product e8 to 45-55 mL of dimethyl sulfoxide and stirring.

[0033] During the reaction of step G4, the formyl group of nitrobenzoic acid reacts with methylenetriphenylphosphine to obtain nitrobenzoic acid containing a terminal carbon-carbon double bond, i.e., product e7; the carboxyl group of product e7 reacts with oxalyl chloride to obtain product e8 containing an acyl chloride; the acyl chloride of product e8 reacts with the hydroxyl group of product e6 to obtain a montmorillonite-expanded graphite grafted product containing a terminal carbon-carbon double bond and a nitro group, i.e., product e9;

[0034] Step G5: Mix product e9, toluene, and methanol, and ultrasonically disperse them for 2-2.5 hours. Then, add sodium sulfide and potassium bicarbonate, raise the temperature to 70-75° C., and reflux with stirring for 8-8.5 hours to obtain product e10. Mix ethylene-octene copolymer, product e10, toluene, and initiator, and ultrasonically disperse them for 1-1.5 hours. Then, stir and react at a constant temperature of 120-130° C. for 6-7 hours to obtain a modified ethylene-octene copolymer.

[0035] Furthermore, the usage ratio of product e9, toluene, methanol, sodium sulfide, and potassium bicarbonate is 14-16 g: 800-900 mL: 200-300 mL: 21-23 g: 1.5-2.5 g; the usage ratio of ethylene-octene copolymer, product e10, toluene, and initiator is 100-105 g: 10-11 g: 3000-3200 mL: 0.5-0.7 g; the initiator is azobisisobutyronitrile;

[0036] During the reaction of step G5, the nitro group in product e9 is selectively reduced to an amino group, retaining the terminal double bond, thereby obtaining a montmorillonite-expanded graphite grafted product containing a terminal carbon-carbon double bond and an amino group, namely, product e10; product e10 is grafted onto an ethylene-octene copolymer to obtain a modified ethylene-octene copolymer;

[0037] The preparation of the anti-aging agent comprises the following steps:

[0038] Step H1: After mixing a conjugated carboxylic acid and 1,4-dioxane, thionyl chloride and DMF are added, and the mixture is heated and stirred to obtain product f2; after mixing cinnamate and ethyl acetate, triethylamine and sodium dithionite are added, and the mixture is heated and stirred to obtain product f2;

[0039] Step H2, mixing the product f1 and DMSO to obtain a mixture s; adding the product f2 to DMSO and ethyl acetate, stirring, then adding sodium carbonate, continuing to stir, adding the mixture s in an ice-water bath, heating after the addition is complete, and stirring at a constant temperature to obtain the product f3;

[0040] Step H3, adding the product f3 to DMAC and stirring, then adding aminophenol and ammonium sulfate while heating, and continuing to stir to obtain an anti-aging agent;

[0041] The preparation of the anti-aging agent comprises the following specific steps:

[0042] Step H1: Mix and stir a conjugated carboxylic acid and 1,4-dioxane for 30-40 minutes, add thionyl chloride and DMF, heat to 45-50°C, and stir for 4.5-5 hours to obtain product f2; mix cinnamate and ethyl acetate for 25-35 minutes, add triethylamine and sodium dithionite, and stir for 2-2.5 hours at 50-60°C to obtain product f2;

[0043] Furthermore, the usage ratio of conjugated carboxylic acid, 1,4-dioxane, thionyl chloride, and DMF is 35-37 g: 105-115 mL: 18-20 g: 0.3-0.5 g; the conjugated carboxylic acid is ‌4-[(1E,3E,5E)-4-methyl-6-(2,6,6-trimethyl-1-cyclohexen-1-yl)-1,3,5-hexatrien-1-yl]benzoic acid (CAS No.: 91587-01-8, supplier: Taoshu Biological); the usage ratio of cinnamate, ethyl acetate, triethylamine, and sodium dithionite is 24-26 g: 110-120 mL: 3-4 g: 26-28 g; the cinnamate is ethyl (E)-3-(4-nitrophenyl)acrylate;

[0044] During the reaction of step H1, the conjugated carboxylic acid reacts with thionyl chloride to obtain product f1 containing an acyl chloride; the nitro group in the cinnamate is reduced to an amino group to obtain product f2;

[0045] Step H2, product f1 and DMSO were mixed and stirred for 20-25 minutes to obtain a mixture s; product f2 was added to DMSO and ethyl acetate, stirred for 15-25 minutes, and then sodium carbonate was added. The mixture s was added in an ice-water bath. After the addition was complete, the temperature was raised to 40-50°C and the reaction was stirred at this temperature for 7-7.5 hours to obtain product f3;

[0046] Furthermore, the usage ratio of product f1 and DMSO in the mixed solution s is 40-42 g: 85-90 mL; the usage ratio of product f2, DMSO, ethyl acetate, sodium carbonate, and mixed solution s is 22-24 g: 20-30 mL: 30-40 mL: 2.5-3.5 g: 130-140 mL;

[0047] During the reaction of step H2, the acyl chloride in product f1 reacts with the amino group in product f2 to obtain product f3;

[0048] Step H3, adding product f3 to DMAC and stirring for 30-40 minutes, raising the temperature to 80-90°C, adding aminophenol and ammonium sulfate, and continuing to stir and react for 9-9.5 hours to obtain an anti-aging agent;

[0049] Furthermore, the usage ratio of product f3, DMAC, aminophenol, and ammonium sulfate is 66-68 g:180-190 mL:16-18 g:3-3.5 g; the aminophenol is 5-aminobenzene-1,2,3-triol;

[0050] During the reaction of step H3, the ester group in the product f3 reacts with the amino group of the aminophenol to obtain a compound containing polyphenolic hydroxyl groups and having a larger conjugated system composed of polyvalent conjugated double bonds, benzene rings, and cinnamamide, i.e., an anti-aging agent;

[0051] Beneficial effects of the present invention: The present invention discloses an impact-resistant composite material for automobile plastic parts and a preparation method thereof. The impact-resistant composite material for automobile plastic parts is prepared from raw materials such as polypropylene, a compatibilizer, a modified ethylene-octene copolymer, and an aging resistance agent.

[0052] The modified ethylene-octene copolymer is obtained by reacting quaternary phosphonium salt-modified montmorillonite, silane-modified expanded graphite, 2-formyl-5-nitrobenzoic acid, etc. to obtain a montmorillonite-expanded graphite graft product containing a terminal carbon-carbon double bond and an amino group, namely product e10, which is then grafted with the ethylene-octene copolymer. After grafting with ethylene-octene copolymer, the compatibility and dispersion of montmorillonite and expanded graphite in the matrix are enhanced. Expanded graphite can promote the formation of a dense and stable carbon layer during combustion, and inhibit the release of smoke through porous absorption. After the expanded graphite is grafted with montmorillonite, an intramolecular synergistic flame retardant effect is produced, which makes up for the defects of montmorillonite's insufficient carbonization efficiency and weak smoke suppression performance. The amino group introduced by the reaction of 2-formyl-5-nitrobenzoic acid enables the modified ethylene-octene copolymer to produce chemical crosslinking with the compatibilizer, namely maleic anhydride grafted polypropylene, further enhancing the interfacial bonding strength between the modified ethylene-octene copolymer and polypropylene, thereby contributing to further improvement of impact resistance, flame retardancy and smoke suppression.

[0053] The anti-aging agent is a compound containing polyphenolic hydroxyl groups and having a large conjugated system composed of polyvalent conjugated double bonds, benzene rings, and cinnamamide, obtained by reacting (E)-3-(4-nitrophenyl) ethyl acrylate, 5-aminobenzene-1,2,3-triol, ‌4-[(1E,3E,5E)-4-methyl-6-(2,6,6-trimethyl-1-cyclohexene-1-yl)-1,3,5-hexatrien-1-yl]benzoic acid, etc. After reacting and combining ethyl (E)-3-(4-nitrophenyl)acrylate with ‌4-[(1E,3E,5E)-4-methyl-6-(2,6,6-trimethyl-1-cyclohexen-1-yl)-1,3,5-hexatrien-1-yl]benzoic acid, the cinnamate skeleton in the ethyl (E)-3-(4-nitrophenyl)acrylate is combined with multiple conjugated double bonds, expanding the ultraviolet absorption wavelength range and enhancing the ultraviolet absorption ability, thereby compensating for the insufficient ultraviolet absorption ability of the cinnamate. In addition, the multiple conjugated double bonds are similar to the structure of polypropylene, which enhances the compatibility of the anti-aging agent with polypropylene. 5-aminobenzene-1,2,3-triol is then added to the reaction to convert the cinnamate into the more stable cinnamamide. At the same time, multiple phenolic hydroxyl groups are introduced, which enhances the antioxidant effect of the anti-aging agent and can also react with maleic anhydride grafted polypropylene, further enhancing the compatibility of the anti-aging agent with polypropylene, thereby imparting better aging resistance to the material used in automotive plastic parts. DETAILED DESCRIPTION

[0054] The following is a clear and complete description of the technical solutions in the embodiments of the present invention. Obviously, the embodiments described are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making any creative efforts are within the scope of protection of the present invention.

[0055] Example 1

[0056] A modified ethylene-octene copolymer, the preparation of which comprises the following steps:

[0057] Step G1: tributylphosphine, acetone, and potassium iodide were mixed, nitrogen was introduced, the mixture was heated to 40°C with stirring, 8-chloro-1-octene was added, the mixture was refluxed and stirred for 4.5 hours, filtered, washed with ethyl acetate, rotary evaporated, and dried in vacuo at 40°C to obtain product e1; product e1 and ethanol were mixed and stirred for 5 minutes, 3-chloroperbenzoic acid was added, and the mixture was stirred and reacted at 50°C for 5 hours to obtain product e2; the amount ratio of tributylphosphine, acetone, potassium iodide, and 8-chloro-1-octene was 21g:100mL:0.3g:16g; the amount ratio of product e1, ethanol, and 3-chloroperbenzoic acid was 50g:150mL:20g; the volume fraction of ethanol was 95%;

[0058] Step G2: Mix product e2, deionized water, and ethanol, grind for 30 minutes, add nano-montmorillonite, continue grinding for 2 hours, stir, filter, and wash with water until no white turbidity is produced when detected by silver nitrate solution, and freeze-dry to obtain product e3; the amount ratio of product e2, deionized water, ethanol, and nano-montmorillonite is 53g:1900mL:400mL:28g; the volume fraction of ethanol is 95%; and the concentration of the silver nitrate solution is 0.1mol / L;

[0059] Step G3, after mixing expanded graphite and potassium permanganate solution, heating to 50°C, stirring at constant temperature for 11 hours to obtain product e4; KH550, anhydrous ethanol, and deionized water were mixed, stirred at 40°C for 3 hours, and product e4 was added, heated to 70°C, and stirred for 4 hours to obtain product e5; product e3, product e5, DMAC, and tetrahydrofuran were mixed, stirred at room temperature for 8 hours to obtain product e6; expanded graphite, permanganate The potassium solution was used in a ratio of 1 g:45 g; the potassium permanganate solution was prepared by mixing potassium permanganate and concentrated sulfuric acid in a mass ratio of 3 g:40 g; the mass fraction of concentrated sulfuric acid was 98%; the KH550, anhydrous ethanol, deionized water, and product e4 were used in a ratio of 1 g:140 mL:15 mL:53 g; the product e3, product e5, DMAC, and tetrahydrofuran were used in a ratio of 31 g:58 g:1800 mL:500 mL;

[0060] Step G4: In a nitrogen atmosphere, 2-formyl-5-nitrobenzoic acid and anhydrous tetrahydrofuran were mixed, stirred for 35 minutes, and then methylenetriphenylphosphine was added. The mixture was stirred under reflux at 55°C for 5 hours to obtain product e7. Product e7 was added to DMF and stirred for 10 minutes. Oxalyl chloride was added in an ice-water bath, and the mixture was stirred at 65°C for 1 hour to obtain product e8. Product e6, toluene, and dimethyl sulfoxide were mixed, heated to 50°C, and ultrasonically dispersed for 1.5 hours. Pyridine and potassium carbonate were added and stirred for 10 minutes. A solution of product e8 was added in an ice-water bath. After the addition, the mixture was stirred for 6 hours to obtain product e9; the usage ratio of 2-formyl-5-nitrobenzoic acid, anhydrous tetrahydrofuran, and methylenetriphenylphosphine was 21 g:105 mL:30 g; the usage ratio of product e7, DMF, and oxalyl chloride was 18 g:70 mL:15 g; the usage ratio of product e6, toluene, dimethyl sulfoxide, pyridine, potassium carbonate, and the solution of product e8 was 10 g:400 mL:350 mL:0.05 g:26 g:90 mL; the solution of product e8 was obtained by adding 21 g of product e8 to 45 mL of dimethyl sulfoxide and stirring;

[0061] Step G5: Mix product e9, toluene, and methanol, ultrasonically disperse them for 2 hours, add sodium sulfide and potassium bicarbonate, raise the temperature to 70°C, and reflux with stirring for 8 hours to obtain product e10; mix ethylene-octene copolymer (supplier: Suzhou Yitianli Plastic Co., Ltd., specification 25 kg / bag), product e10, toluene, and azobisisobutyronitrile, ultrasonically disperse them for 1 hour, and react at a constant temperature of 120°C with stirring for 6 hours to obtain a modified ethylene-octene copolymer; the amount ratio of product e9, toluene, methanol, sodium sulfide, and potassium bicarbonate is 14 g:800 mL:200 mL:21 g:1.5 g; the amount ratio of ethylene-octene copolymer, product e10, toluene, and azobisisobutyronitrile is 100 g:10 g:3000 mL:0.5 g.

[0062] Example 2

[0063] A modified ethylene-octene copolymer, the preparation of which comprises the following steps:

[0064] Step G1: tributylphosphine, acetone, and potassium iodide were mixed, nitrogen was introduced, and the mixture was heated to 43°C with stirring. 8-chloro-1-octene was added, and the mixture was refluxed and stirred for 4.8 hours. The mixture was filtered, washed with ethyl acetate, rotary evaporated, and dried in vacuo at 38°C to obtain product e1. Product e1 and ethanol were mixed and stirred for 8 minutes, 3-chloroperbenzoic acid was added, and the mixture was stirred and reacted at 53°C for 5.3 hours to obtain product e2. The dosage ratio of tributylphosphine, acetone, potassium iodide, and 8-chloro-1-octene was 22 g:105 mL:0.35 g:18 g; the dosage ratio of product e1, ethanol, and 3-chloroperbenzoic acid was 51 g:155 mL:21 g; and the volume fraction of ethanol was 95%.

[0065] Step G2: Mix product e2, deionized water, and ethanol, grind for 33 minutes, add nano-montmorillonite, continue grinding for 2.3 hours, stir, filter, wash with water until no white turbidity is produced when detected by silver nitrate solution, and freeze-dry to obtain product e3; the amount ratio of product e2, deionized water, ethanol, and nano-montmorillonite is 54g:1950mL:450mL:29g; the volume fraction of ethanol is 95%; the concentration of the silver nitrate solution is 0.13mol / L;

[0066] Step G3, after mixing expanded graphite and potassium permanganate solution, heating to 55 ° C, stirring at constant temperature for 11.5 hours to obtain product e4; KH550, anhydrous ethanol and deionized water were mixed, stirred at 43 ° C for 3.3 hours, product e4 was added, heated to 75 ° C, stirred for 4.3 hours to obtain product e5; product e3, product e5, DMAC and tetrahydrofuran were mixed, stirred at room temperature for 8.3 hours to obtain product e6; expanded graphite and high manganese The dosage ratio of potassium permanganate solution is 1.3 g:48 g; the potassium permanganate solution is prepared by mixing potassium permanganate and concentrated sulfuric acid in a mass ratio of 3.5 g:41 g; the mass fraction of concentrated sulfuric acid is 98%; the dosage ratio of KH550, anhydrous ethanol, deionized water, and product e4 is 1.3 g:145 mL:18 mL:54 g; the dosage ratio of product e3, product e5, DMAC, and tetrahydrofuran is 32 g:59 g:1850 mL:550 mL;

[0067] Step G4: In a nitrogen atmosphere, 2-formyl-5-nitrobenzoic acid and anhydrous tetrahydrofuran were mixed, stirred for 40 minutes, and then methylenetriphenylphosphine was added. The mixture was stirred at reflux at 58°C for 5.3 hours to obtain product e7; product e7 was added to DMF and stirred for 13 minutes. Oxalyl chloride was added in an ice-water bath, and the mixture was stirred at 68°C for 1.3 hours to obtain product e8; product e6, toluene, and dimethyl sulfoxide were mixed, heated to 55°C, ultrasonically dispersed for 1.8 hours, pyridine and potassium carbonate were added, stirred for 13 minutes, and a solution of product e8 was added in an ice-water bath. After the addition, the mixture was stirred for 6.3 hours to obtain product e9; the usage ratio of 2-formyl-5-nitrobenzoic acid, anhydrous tetrahydrofuran, and methylenetriphenylphosphine was 22 g:108 mL:31 g; the usage ratio of product e7, DMF, and oxalyl chloride was 19 g:75 mL:16 g; the usage ratio of product e6, toluene, dimethyl sulfoxide, pyridine, potassium carbonate, and the solution of product e8 was 11 g:450 mL:400 mL:0.06 g:27 g:93 mL; the solution of product e8 was prepared by adding 22 g of product e8 to 50 mL of dimethyl sulfoxide and stirring;

[0068] Step G5: Mix the product e9, toluene, and methanol, ultrasonically disperse them for 2.3 hours, add sodium sulfide and potassium bicarbonate, raise the temperature to 73°C, and reflux with stirring for 8.3 hours to obtain product e10; mix ethylene-octene copolymer (supplier: Suzhou Yitianli Plastic Co., Ltd., specification 25 kg / bag), product e10, toluene, and azobisisobutyronitrile, ultrasonically disperse them for 1.3 hours, and react at a constant temperature of 125°C with stirring for 6.5 hours to obtain a modified ethylene-octene copolymer; the amount ratio of product e9, toluene, methanol, sodium sulfide, and potassium bicarbonate is 15 g:850 mL:250 mL:22 g:2.0 g; the amount ratio of ethylene-octene copolymer, product e10, toluene, and azobisisobutyronitrile is 103 g:10.5 g:3100 mL:0.6 g.

[0069] Example 3

[0070] A modified ethylene-octene copolymer, the preparation of which comprises the following steps:

[0071] Step G1: tributylphosphine, acetone, and potassium iodide were mixed, nitrogen was introduced, and the mixture was heated to 45°C with stirring. 11-chloro-1-undecene was added, and the mixture was refluxed and stirred for 5 hours. The mixture was filtered, washed with ethyl acetate, rotary evaporated, and dried in vacuo at 40°C to obtain product e1; product e1 and ethanol were mixed and stirred for 10 minutes, 3-chloroperbenzoic acid was added, and the mixture was stirred and reacted at 55°C for 5.5 hours to obtain product e2; the amount ratio of tributylphosphine, acetone, potassium iodide, and 11-chloro-1-undecene was 23 g:110 mL:0.4 g:20 g; the amount ratio of product e1, ethanol, and 3-chloroperbenzoic acid was 52 g:160 mL:22 g; the volume fraction of ethanol was 95%;

[0072] Step G2: Mix product e2, deionized water, and ethanol, grind for 35 minutes, add nano-montmorillonite, continue grinding for 2.5 hours, stir, filter, wash with water until no white turbidity is produced when detected by silver nitrate solution, and freeze-dry to obtain product e3; the amount ratio of product e2, deionized water, ethanol, and nano-montmorillonite is 55g:2000mL:500mL:30g; the volume fraction of ethanol is 95%; the concentration of the silver nitrate solution is 0.15mol / L;

[0073] Step G3, after mixing expanded graphite and potassium permanganate solution, heating to 60 ° C, stirring at constant temperature for 12 hours to obtain product e4; KH550, anhydrous ethanol and deionized water were mixed, stirred at 45 ° C for 3.5 hours, product e4 was added, heated to 80 ° C, stirred for 4.5 hours to obtain product e5; product e3, product e5, DMAC and tetrahydrofuran were mixed, stirred at room temperature for 8.5 hours to obtain product e6; expanded graphite, high manganese The dosage ratio of potassium permanganate solution is 1.5 g:50 g; the potassium permanganate solution is obtained by mixing potassium permanganate and concentrated sulfuric acid in a mass ratio of 4 g:42 g; the mass fraction of concentrated sulfuric acid is 98%; the dosage ratio of KH550, anhydrous ethanol, deionized water, and product e4 is 1.5 g:150 mL:20 mL:55 g; the dosage ratio of product e3, product e5, DMAC, and tetrahydrofuran is 33 g:60 g:1900 mL:600 mL;

[0074] Step G4: In a nitrogen atmosphere, 2-formyl-5-nitrobenzoic acid and anhydrous tetrahydrofuran were mixed, stirred for 45 minutes, and then methylenetriphenylphosphine was added. The mixture was stirred at reflux at 60°C for 5.5 hours to obtain product e7. Product e7 was added to DMF and stirred for 15 minutes. Oxalyl chloride was added in an ice-water bath, and the mixture was stirred at 70°C for 1.5 hours to obtain product e8. Product e6, toluene, and dimethyl sulfoxide were mixed, heated to 60°C, ultrasonically dispersed for 2 hours, pyridine and potassium carbonate were added, stirred for 15 minutes, and a solution of product e8 was added in an ice-water bath. After the addition, the mixture was stirred for 6.5 hours to obtain product e9; the usage ratio of 2-formyl-5-nitrobenzoic acid, anhydrous tetrahydrofuran, and methylenetriphenylphosphine was 23 g:110 mL:32 g; the usage ratio of product e7, DMF, and oxalyl chloride was 20 g:80 mL:17 g; the usage ratio of product e6, toluene, dimethyl sulfoxide, pyridine, potassium carbonate, and the solution of product e8 was 12 g:500 mL:450 mL:0.07 g:28 g:95 mL; the solution of product e8 was obtained by adding 23 g of product e8 to 55 mL of dimethyl sulfoxide and stirring;

[0075] Step G5: Mix product e9, toluene, and methanol, ultrasonically disperse for 2.5 hours, add sodium sulfide and potassium bicarbonate, heat to 75°C, and reflux with stirring for 8.5 hours to obtain product e10; mix ethylene-octene copolymer (supplier: Suzhou Yitianli Plastic Co., Ltd., specification 25 kg / bag), product e10, toluene, and azobisisobutyronitrile, ultrasonically disperse for 1.5 hours, and react at a constant temperature of 130°C with stirring for 7 hours to obtain a modified ethylene-octene copolymer; the amount ratio of product e9, toluene, methanol, sodium sulfide, and potassium bicarbonate is 16 g:900 mL:300 mL:23 g:2.5 g; the amount ratio of ethylene-octene copolymer, product e10, toluene, and azobisisobutyronitrile is 105 g:11 g:3200 mL:0.7 g.

[0076] Example 4

[0077] An anti-aging agent, the preparation of which comprises the following steps:

[0078] Step H1, the conjugated carboxylic acid and 1,4-dioxane were mixed and stirred for 30 minutes, dichlorothionyl and DMF were added, the temperature was raised to 45°C, and the reaction was stirred for 4.5 hours to obtain product f2; (E)-3-(4-nitrophenyl) ethyl acrylate and ethyl acetate were mixed and stirred for 25 minutes, triethylamine and sodium dithionite were added, and the reaction was stirred at 50°C for 2 hours to obtain product f2; the amount ratio of conjugated carboxylic acid, 1,4-dioxane, dichlorothionyl and DMF was 35g:10 5mL:18g:0.3g; the conjugated carboxylic acid is ‌4-[(1E,3E,5E)-4-methyl-6-(2,6,6-trimethyl-1-cyclohexen-1-yl)-1,3,5-hexatrien-1-yl]benzoic acid (CAS No.: 91587-01-8, supplier: Taoshu Biological); the usage ratio of (E)-ethyl 3-(4-nitrophenyl)acrylate, ethyl acetate, triethylamine, and sodium dithionite is 24g:110mL:3g:26g;

[0079] Step H2, product f1 and DMSO were mixed and stirred for 20 minutes to obtain a mixed solution s; product f2 was added to DMSO and ethyl acetate, stirred for 15 minutes, and then sodium carbonate was added. The stirring was continued for 10 minutes, and the mixed solution s was added in an ice-water bath. After the addition was completed, the temperature was raised to 40°C, and the reaction was stirred at the constant temperature for 7 hours to obtain product f3; the amount ratio of product f1 and DMSO in the mixed solution s was 40 g:85 mL; the amount ratio of product f2, DMSO, ethyl acetate, sodium carbonate, and mixed solution s was 22 g:20 mL:30 mL:2.5 g:130 mL;

[0080] Step H3: Add product f3 to DMAC and stir for 30 minutes. Heat to 80°C, add 5-aminobenzene-1,2,3-triol and ammonium sulfate, and continue stirring and reacting for 9 hours to obtain an anti-aging agent. The amount ratio of product f3, DMAC, 5-aminobenzene-1,2,3-triol, and ammonium sulfate is 66 g:180 mL:16 g:3 g.

[0081] Example 5

[0082] An anti-aging agent, the preparation of which comprises the following steps:

[0083] Step H1: Conjugated carboxylic acid and 1,4-dioxane were mixed and stirred for 35 minutes, thionyl chloride and DMF were added, the temperature was raised to 48°C, and the reaction was stirred for 4.8 hours to obtain product f2; (E)-3-(4-nitrophenyl) ethyl acrylate and ethyl acetate were mixed and stirred for 30 minutes, triethylamine and sodium dithionite were added, and the reaction was stirred at 55°C for 2.3 hours to obtain product f2; the amount ratio of conjugated carboxylic acid, 1,4-dioxane, thionyl chloride, and DMF was 36g:11 0mL:19g:0.4g; the conjugated carboxylic acid is ‌4-[(1E,3E,5E)-4-methyl-6-(2,6,6-trimethyl-1-cyclohexen-1-yl)-1,3,5-hexatrien-1-yl]benzoic acid (CAS No.: 91587-01-8, supplier: Taoshu Biological); the usage ratio of (E)-3-(4-nitrophenyl)ethyl acrylate, ethyl acetate, triethylamine, and sodium dithionite is 25g:115mL:3.5g:27g;

[0084] Step H2, the product f1 and DMSO were mixed and stirred for 23 minutes to obtain a mixed solution s; the product f2 was added to DMSO and ethyl acetate, stirred for 20 minutes, and then sodium carbonate was added. The stirring was continued for 13 minutes, and the mixed solution s was added in an ice-water bath. After the addition was completed, the temperature was raised to 45°C, and the reaction was stirred at a constant temperature for 7.3 hours to obtain the product f3; the amount ratio of the product f1 and DMSO in the mixed solution s was 41 g:88 mL; the amount ratio of the product f2, DMSO, ethyl acetate, sodium carbonate, and mixed solution s was 23 g:25 mL:35 mL:3.0 g:135 mL;

[0085] Step H3: Add product f3 to DMAC and stir for 35 minutes. Heat to 85°C, add 5-aminobenzene-1,2,3-triol and ammonium sulfate, and continue stirring and reacting for 9.3 hours to obtain an anti-aging agent. The amount ratio of product f3, DMAC, 5-aminobenzene-1,2,3-triol, and ammonium sulfate is 67 g:185 mL:17 g:3.3 g.

[0086] Example 6

[0087] An anti-aging agent, the preparation of which comprises the following steps:

[0088] Step H1: Conjugated carboxylic acid and 1,4-dioxane were mixed and stirred for 40 minutes, thionyl chloride and DMF were added, the temperature was raised to 50°C, and the reaction was stirred for 5 hours to obtain product f2; (E)-3-(4-nitrophenyl) ethyl acrylate and ethyl acetate were mixed and stirred for 35 minutes, triethylamine and sodium dithionite were added, and the reaction was stirred at 60°C for 2.5 hours to obtain product f2; the amount ratio of conjugated carboxylic acid, 1,4-dioxane, thionyl chloride, and DMF was 37g:11 5mL:20g:0.5g; the conjugated carboxylic acid is ‌4-[(1E,3E,5E)-4-methyl-6-(2,6,6-trimethyl-1-cyclohexen-1-yl)-1,3,5-hexatrien-1-yl]benzoic acid (CAS No.: 91587-01-8, supplier: Taoshu Biological); the usage ratio of ethyl (E)-3-(4-nitrophenyl)acrylate, ethyl acetate, triethylamine, and sodium dithionite is 26g:120mL:4g:28g;

[0089] Step H2, product f1 and DMSO were mixed and stirred for 25 minutes to obtain a mixed solution s; product f2 was added to DMSO and ethyl acetate, stirred for 25 minutes, and then sodium carbonate was added. Stirring was continued for 15 minutes, and the mixed solution s was added in an ice-water bath. After the addition was completed, the temperature was raised to 50°C, and the reaction was stirred at a constant temperature for 7.5 hours to obtain product f3; the amount ratio of product f1 and DMSO in the mixed solution s was 42 g:90 mL; the amount ratio of product f2, DMSO, ethyl acetate, sodium carbonate, and mixed solution s was 24 g:30 mL:40 mL:3.5 g:140 mL;

[0090] Step H3: Add product f3 to DMAC and stir for 40 minutes. Heat to 90° C., add 5-aminobenzene-1,2,3-triol and ammonium sulfate, and continue stirring and reacting for 9.5 hours to obtain an anti-aging agent. The amount ratio of product f3, DMAC, 5-aminobenzene-1,2,3-triol, and ammonium sulfate is 68 g:190 mL:18 g:3.5 g.

[0091] Example 7

[0092] An impact-resistant composite material for automotive plastic parts, comprising the following raw materials in parts by weight: 65 parts of polypropylene, 3 parts of a compatibilizer, 15 parts of a modified ethylene-octene copolymer, 1 part of an anti-aging agent, 10 parts of talc, 2 parts of a coupling agent, 0.6 parts of a lubricant, and 0.3 parts of an additive; the compatibilizer is maleic anhydride-grafted polypropylene; the coupling agent is 3-acryloxypropyltriethoxysilane; the lubricant is ethylene bisstearamide; and the additive is tris(dipropylene glycol) phosphite.

[0093] The preparation of the impact-resistant composite material for automobile plastic parts comprises the following steps:

[0094] Polypropylene, the modified ethylene-octene copolymer obtained in Example 1, talc, and a coupling agent were mixed and stirred at 700 rpm for 5 min. A compatibilizer, an anti-aging agent obtained in Example 4, a lubricant, and an additive were added, and the mixture was stirred at 1000 rpm for 10 min to obtain a mixture. The mixture was extruded and granulated to obtain an impact-resistant composite material for automotive plastic parts. The polypropylene was dried at 80° C. for 3 h and used after cooling. The temperature during the preparation of the mixture was controlled at 50° C. During the extrusion granulation process, a twin-screw extruder was used with a screw speed of 300 rpm, a material residence time of 2.2 min, a feeding section temperature of 165° C., a melting section temperature of 180° C., a mixing section temperature of 200° C., a homogenizing section temperature of 190° C., and a die head temperature of 195° C.

[0095] Example 8

[0096] An impact-resistant composite material for automotive plastic parts, comprising the following raw materials in parts by weight: 70 parts of polypropylene, 4 parts of a compatibilizer, 18 parts of a modified ethylene-octene copolymer, 1.3 parts of an aging agent, 11 parts of talc, 3 parts of a coupling agent, 0.7 parts of a lubricant, and 0.4 parts of an additive; the compatibilizer is maleic anhydride-grafted polypropylene; the coupling agent is 3-acryloxypropyltriethoxysilane; the lubricant is ethylene bisstearamide; and the additive is tris(dipropylene glycol) phosphite.

[0097] The preparation of the impact-resistant composite material for automobile plastic parts comprises the following steps:

[0098] Polypropylene, the modified ethylene-octene copolymer obtained in Example 2, talc, and a coupling agent were mixed and stirred at 700 rpm for 6 min. A compatibilizer, an anti-aging agent obtained in Example 5, a lubricant, and an additive were added, and the mixture was stirred at 1100 rpm for 11 min to obtain a mixture. The mixture was extruded and granulated to obtain an impact-resistant composite material for automotive plastic parts. The polypropylene was dried at 85° C. for 3.5 h and used after cooling. The temperature during the preparation of the mixture was controlled at 50° C. During the extrusion granulation process, a twin-screw extruder was used with a screw speed of 300 rpm, a material residence time of 2.4 min, a feeding section temperature of 168° C., a melting section temperature of 185° C., a mixing section temperature of 205° C., a homogenizing section temperature of 195° C., and a die head temperature of 200° C.

[0099] Example 9

[0100] An impact-resistant composite material for automotive plastic parts, comprising the following raw materials in parts by weight: 75 parts of polypropylene, 5 parts of a compatibilizer, 20 parts of a modified ethylene-octene copolymer, 1.5 parts of an anti-aging agent, 12 parts of talc, 4 parts of a coupling agent, 0.8 parts of a lubricant, and 0.5 parts of an auxiliary agent; the compatibilizer is maleic anhydride-grafted polypropylene; the coupling agent is 3-acryloxypropyltriethoxysilane; the lubricant is ethylene bisstearamide; and the auxiliary agent is tris(dipropylene glycol) phosphite.

[0101] The preparation of the impact-resistant composite material for automobile plastic parts comprises the following steps:

[0102] Polypropylene, the modified ethylene-octene copolymer obtained in Example 3, talc, and a coupling agent were mixed and stirred at 800 rpm for 7 min. A compatibilizer, an anti-aging agent obtained in Example 6, a lubricant, and an additive were added, and the mixture was stirred at 1200 rpm for 12 min to obtain a mixture. The mixture was extruded and granulated to obtain an impact-resistant composite material for automotive plastic parts. The polypropylene was dried at 90° C. for 4 h and used after cooling. The temperature during the preparation of the mixture was controlled at 50° C. During the extrusion granulation process, a twin-screw extruder was used with a screw speed of 400 rpm, a material residence time of 3 min, a feeding section temperature of 170° C., a melting section temperature of 190° C., a mixing section temperature of 210° C., a homogenizing section temperature of 200° C., and a die head temperature of 205° C.

[0103] Comparative Example 1

[0104] Compared with Example 9, the product e10 grafted with the ethylene-octene copolymer used in step G5 of the preparation process of the modified ethylene-octene copolymer was replaced with the product e9. The rest of the process was exactly the same as Example 9 to prepare an impact-resistant composite material for automotive plastic parts.

[0105] Comparative Example 2

[0106] Compared with Example 9, the product e4 used in step G3 of the preparation of the modified ethylene-octene copolymer was replaced with zinc borate, and the rest was the same as in Example 9 to prepare an impact-resistant composite material for automotive plastic parts.

[0107] Comparative Example 3

[0108] Compared with Example 9, the ‌4-[(1E,3E,5E)-4-methyl-6-(2,6,6-trimethyl-1-cyclohexen-1-yl)-1,3,5-hexatrien-1-yl]benzoic acid in the preparation of the anti-aging agent was replaced with trans-5-phenyl-pentadienoic acid. The rest of the process was exactly the same as in Example 9 to prepare an impact-resistant composite material for automotive plastic parts.

[0109] Comparative Example 4

[0110] Compared with Example 9, 5-aminobenzene-1,2,3-triol in the preparation of the anti-aging agent was replaced with 4-amino-2,6-di-tert-butylphenol, and the rest was exactly the same as Example 9 to prepare an impact-resistant composite material for automotive plastic parts.

[0111] The impact-resistant composite material for automobile plastic parts prepared by the present invention is further tested for its effectiveness, and the test results are described below.

[0112] Impact resistance: Refer to GB / T1843-2008 "Determination of Izod Impact Strength of Plastics" to test the impact strength of the composite material. For each sample to be tested, five parallel samples were tested and the average value was taken.

[0113] Flame retardancy and smoke suppression: Refer to GB / T2406-1993 to test the limiting oxygen index of the composite material; refer to GB / T8323-2008 "Test method for combustion performance of plastics - Smoke density method" to test the maximum smoke density of the composite material;

[0114] Aging resistance: The composite material was placed in a radiant atmosphere with a radiation intensity of 0.84W / m 2 The impact strength retention rate was measured after aging for 2000 hours under the conditions of xenon lamp irradiation, 50℃ temperature and 60% relative humidity;

[0115] The results are recorded in Table 1;

[0116] Table 1: Test results Example 7 Example 8 Example 9 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 <![CDATA[Impact strength (kJ / m 2 )]]> 24.2 24.6 25.2 20.6 25.0 24.9 24.7 Limiting oxygen index (%) 31.5 32.2 32.8 27.1 25.3 32.5 32.3 Maximum smoke density 151 148 146 172 205 147 148 Impact strength retention rate (%) 95.4 96.1 96.8 89.2 96.5 85.7 87.6

[0117] According to the data in Table 1, the impact-resistant composite material for automotive plastic parts of the present invention exhibits strong impact resistance, flame retardancy, smoke suppression, and aging resistance. A comparison of Example 9 with Comparative Example 1 shows that replacing product e10, which is grafted onto the ethylene-octene copolymer in step G5 during the preparation of the modified ethylene-octene copolymer, with product e9—that is, replacing the amino groups in the modified ethylene-octene copolymer with nitro groups—degrades the composite material's impact resistance, flame retardancy, smoke suppression, and aging resistance. A comparison of Example 9 with Comparative Example 2 shows that replacing product e4, used in step G3 during the preparation of the modified ethylene-octene copolymer, with zinc borate degrades the composite material's flame retardancy and smoke suppression. Comparing Example 9 with Comparative Example 3 shows that replacing ‌4-[(1E,3E,5E)-4-methyl-6-(2,6,6-trimethyl-1-cyclohexen-1-yl)-1,3,5-hexatrien-1-yl]benzoic acid with trans-5-phenyl-pentadienoic acid during the preparation of the anti-aging agent reduces the aging resistance of the composite material. Comparing Example 9 with Comparative Example 4 shows that replacing 5-aminobenzene-1,2,3-triol with 4-amino-2,6-di-tert-butylphenol during the preparation of the anti-aging agent reduces the aging resistance of the composite material.

[0118] The above content is merely an example and explanation of the concept of the present invention. Those skilled in the art may make various modifications or additions to the described specific embodiments or replace them in a similar manner. As long as they do not deviate from the concept of the invention or exceed the scope defined by the claims, they should all fall within the scope of protection of the present invention.

Claims

1. An impact-resistant composite material for automotive plastic parts, characterized by: The invention comprises the following raw materials in parts by weight: 65-75 parts of polypropylene, 3-5 parts of compatibilizer, 15-20 parts of modified ethylene-octene copolymer, 1-1.5 parts of anti-aging agent, 10-12 parts of talc, 2-4 parts of coupling agent, 0.6-0.8 parts of lubricant, and 0.3-0.5 parts of auxiliary agent; The modified ethylene-octene copolymer is obtained by reacting quaternary phosphonium salt-modified montmorillonite, silane-modified expanded graphite, nitrobenzoic acid, etc. to obtain a montmorillonite-expanded graphite grafted product containing terminal carbon-carbon double bonds and amino groups, namely product e10, which is then grafted with the ethylene-octene copolymer.

2. The impact-resistant composite material for automotive plastic parts according to claim 1, characterized in that: The modified ethylene-octene copolymer is prepared by the following steps: Step G1: tributylphosphine, acetone, and potassium iodide are mixed, a protective gas is introduced, the mixture is stirred and heated, a chloroolefin is added, the mixture is refluxed and stirred, and post-processed to obtain product e1; product e1 and ethanol are mixed and stirred, an oxidant is added, and the mixture is heated and stirred to obtain product e2; Step G2: mixing product e2, deionized water, and ethanol, grinding the mixture, adding nano-montmorillonite, continuing grinding, and post-processing to obtain product e3; Step G3: Mix expanded graphite and potassium permanganate solution, heat and stir to obtain product e4; mix KH550, anhydrous ethanol and deionized water, heat and stir, add product e4, heat and continue stirring to obtain product e5; mix product e3, product e5, DMAC and tetrahydrofuran, and stir at room temperature to obtain product e6; Step G4: In a protective gas atmosphere, nitrobenzoic acid and anhydrous tetrahydrofuran were mixed and stirred, and then methylenetriphenylphosphine was added, and the mixture was heated and refluxed with stirring to obtain product e7; product e7 was added to DMF and stirred, and then oxalyl chloride was added in an ice-water bath, and the mixture was heated and stirred to obtain product e8; product e6, toluene, and dimethyl sulfoxide were mixed, heated and ultrasonically dispersed, pyridine and potassium carbonate were added, stirred, and then a solution of product e8 was added in an ice-water bath. After the addition was complete, the mixture was stirred to obtain product e9; Step G5: Mix the product e9, toluene, and methanol, disperse them ultrasonically, add sodium sulfide and potassium bicarbonate, heat and reflux with stirring to obtain product e10; mix the ethylene-octene copolymer, product e10, toluene, and initiator, disperse them ultrasonically, heat and stir to react, and obtain a modified ethylene-octene copolymer.

3. The impact-resistant composite material for automotive plastic parts according to claim 2, characterized in that: In step G1, the chlorinated olefin is selected from one of 11-chloro-1-undecene and 8-chloro-1-octene.

4. The impact-resistant composite material for automotive plastic parts according to claim 2, characterized in that: In step G3, the potassium permanganate solution is obtained by mixing potassium permanganate and concentrated sulfuric acid in a mass ratio of 3-4 g:40-42 g.

5. The impact-resistant composite material for automotive plastic parts according to claim 2, characterized in that: In step G4, the nitrobenzoic acid is 2-formyl-5-nitrobenzoic acid; and the solution of product e8 is obtained by adding 21-23 g of product e8 to 45-55 mL of dimethyl sulfoxide and stirring.

6. The impact-resistant composite material for automotive plastic parts according to claim 1, characterized in that: The preparation of the anti-aging agent comprises the following steps: Step H1: After mixing a conjugated carboxylic acid and 1,4-dioxane, thionyl chloride and DMF are added, and the mixture is heated and stirred to obtain product f2; after mixing cinnamate and ethyl acetate, triethylamine and sodium dithionite are added, and the mixture is heated and stirred to obtain product f2; Step H2, mixing the product f1 and DMSO to obtain a mixture s; adding the product f2 to DMSO and ethyl acetate, stirring, then adding sodium carbonate, continuing to stir, adding the mixture s in an ice-water bath, heating after the addition is complete, and stirring at a constant temperature to obtain the product f3; Step H3: Add product f3 to DMAC and stir, then add aminophenol and ammonium sulfate at elevated temperature, and continue stirring to obtain an anti-aging agent.

7. The impact-resistant composite material for automotive plastic parts according to claim 6, characterized in that: In step H1, the conjugated carboxylic acid is ‌4-[(1E,3E,5E)-4-methyl-6-(2,6,6-trimethyl-1-cyclohexen-1-yl)-1,3,5-hexatrien-1-yl]benzoic acid.

8. The impact-resistant composite material for automotive plastic parts according to claim 6, characterized in that: In step H1, the cinnamate is (E)-ethyl 3-(4-nitrophenyl)acrylate.

9. The impact-resistant composite material for automotive plastic parts according to claim 6, characterized in that: In step H3, the aminophenol is 5-aminobenzene-1,2,3-triol.

10. A method for preparing the impact-resistant composite material for automotive plastic parts according to any one of claims 1 to 9, characterized in that: The method comprises the following steps: mixing polypropylene, modified ethylene-octene copolymer, talcum powder and coupling agent, stirring at low speed, adding compatibilizer, anti-aging agent, lubricant and auxiliary agent, stirring at high speed to obtain a mixture; and extruding and granulating the mixture to obtain an impact-resistant composite material for automobile plastic parts.