High-weather-resistant anti-ultraviolet polypropylene modified master batch for automobile exterior trimming parts and preparation method of polypropylene modified master batch

Abstract

The invention provides a high-weather-resistance anti-ultraviolet polypropylene modified master batch which comprises the following components in parts by weight: 60-80 parts of polypropylene matrix resin, 10-20 parts of an inorganic anti-ultraviolet material ZnO / CeO2, 2-5 parts of an antioxidant and 2-5 parts of a plasticizer, and a preparation process of ZnO / CeO2 comprises the following steps: dissolving a zinc source and acetylacetone in ethanol to obtain a solution (1); dissolving a cerium source and EDTA (Ethylene Diamine Tetraacetic Acid) in ethanol to obtain a solution (2); mixing the solution (1) and the solution (2), adding urea, transferring into a polytetrafluoroethylene high-pressure reaction kettle, and performing solvothermal reaction; after solvothermal is finished, a product is annealed for 1-2 hours at 300-350 DEG C, and ZnO / CeO2 endows the polypropylene material with excellent anti-ultraviolet performance, antibacterial performance and mechanical performance.

Description

Technical Field

[0001] The present application belongs to the field of polymer technology, and specifically relates to a highly weather-resistant and UV-resistant polypropylene masterbatch, a preparation method thereof, and an automotive exterior trim. Background Art

[0002] Polypropylene is widely used in automotive interior and exterior components due to its lightweight, easy processing, excellent chemical resistance, and low cost. However, long-term exposure to complex and changing environments can cause polypropylene to age easily. Ultraviolet rays (particularly UVA 315–400 nm) in sunlight can break down the polypropylene's molecular chains, leading to embrittlement, powdering, surface cracking, and color fading and yellowing. Extreme temperature fluctuations—such as summer temperatures exceeding 80°C on the surface of exterior trims—accelerate surface oxidation reactions, while winter temperatures can cause brittle cracking.

[0003] To address these issues, existing technologies propose adding inorganic fillers, antioxidants, and UV absorbers to polypropylene matrix resins. For example, Chinese invention patent CN108841085A discloses a high-rigidity, high-heat-resistant polypropylene material and its preparation method. The polypropylene material comprises a polypropylene resin, an inorganic filler, a cycloolefin polymer, a color masterbatch, a nucleating agent, an antioxidant, an UV absorber, and a lubricant. This polypropylene material exhibits high powder filling, high crystallinity, and a low defect rate. By optimizing the formulation and combining it with a suitable injection molding process, the overall modulus, strength, and heat-resistant temperature of the finished injection molded product can be improved.

[0004] Chinese invention patent CN107652540A discloses a UV-resistant polypropylene composite material, its preparation method, and its application. This UV-resistant polypropylene composite material is composed of the following raw materials in percentage by weight: 50-70% polypropylene; 10-30% inorganic powder; 10-30% toughening agent; 0.1-2% antioxidant; 0.1-2% light stabilizer; 0.5-10% nucleating agent masterbatch; 0.1-2% lubricant; and 0.5-5% color masterbatch. Using a reactive UV absorber and an energy transfer agent as a light stabilizer, and incorporating a homemade nucleating agent masterbatch, the resulting polypropylene composite material maintains a gloss retention rate of over 80% after aging for 4000 hours, while meeting the grayscale requirement of talc-reinforced polypropylene for a grade 4 or higher. This significantly exceeds the OEM's requirement of 1500-2000 hours, making it well-suited for use in the strong sunlight and high-heat environments of automotive grilles.

[0005] Chinese invention patent CN110982170A discloses a polypropylene plastic for new energy vehicle interiors. The raw materials include modified polypropylene masterbatch, wheat straw, sugarcane bagasse, propylene oxide-modified corn starch, calcium fructose microcrystals, carbon nanotubes, nano-silicon carbide, nano-inorganic fillers and nucleating agents. The modified polypropylene masterbatch, wheat straw, sugarcane bagasse and propylene oxide-modified corn starch used as the main raw materials are abundant, low in price and environmentally friendly. The resulting plastic products have high strength, low production cost, biodegradability, antistatic, oxidation resistance and UV resistance, and can alleviate the problem of white pollution.

[0006] However, the polypropylene masterbatch obtained by existing technology has complex ingredients and high costs, and its weather resistance and UV resistance still cannot meet the standard requirements of commercial automobiles. Summary of the Invention

[0007] In order to solve the above problems, the present invention proposes a weather-resistant and UV-resistant polypropylene masterbatch, the ingredients of which, by weight, include: 60-80 parts of polypropylene matrix resin, 10-20 parts of inorganic UV-resistant material ZnO / CeO2, 2-5 parts of antioxidant, and 2-5 parts of plasticizer;

[0008] Among them, the preparation process of inorganic anti-ultraviolet material ZnO / CeO2 is as follows:

[0009] (1) dissolving a zinc source and acetylacetone in ethanol at a molar ratio of 1:(2-3) to obtain a solution (1);

[0010] (2) dissolving the cerium source and EDTA in ethanol at a molar ratio of 1:(1-2) to obtain solution (2);

[0011] (3) Mixing solution (1) and solution (2), adding urea, the molar ratio of zinc source: cerium source: urea is 1: (0.5-1): (2-3); mixing well to obtain solution (3);

[0012] (4) transferring the solution (3) into a polytetrafluoroethylene high-pressure reactor for solvent thermal reaction;

[0013] (5) The product of step (4) is filtered and washed, and then annealed at 300-350°C for 1-2 hours.

[0014] As a further preference, the volume of ethanol is 80-100 mL;

[0015] As a further preference, the solvent thermal reaction conditions are 180-200° C. for 12-24 hours;

[0016] As a further preference, the annealing atmosphere in step (5) is a nitrogen atmosphere, an air atmosphere or an argon atmosphere;

[0017] As a further preference, the zinc source is one or more of zinc acetate, zinc sulfate, zinc chloride, and zinc nitrate;

[0018] As a further preference, the cerium source is one or more of cerium acetate, cerium sulfate, and cerium nitric acid;

[0019] As a further preference, the plasticizer is dimethyl phthalate or butyl benzyl phthalate;

[0020] As a further preference, the antioxidant is one or more of phosphites, hindered amines, and hindered phenol antioxidants;

[0021] Compared with the existing technology, this application can achieve the following beneficial technical effects:

[0022] This application utilizes a one-step solvothermal method to obtain ZnO / CeO2. During the reaction, urea is introduced to initiate synergistic alcoholysis. Acetylacetone and EDTA are used for competitive coordination to adjust the alcoholysis rate difference of Zn / Ce, thereby obtaining an inorganic material in which CeO2 particles grow on the ZnO surface. The flower-shaped high specific surface area increases the active sites, and the combination of the two can effectively broaden the UV absorption range and has excellent anti-ultraviolet aging performance. On the other hand, ZnO / CeO2 itself, as an inorganic filler, has excellent heat resistance and aging resistance, and improves the strength and rigidity of polypropylene materials. In addition, ZnO / CeO2 can effectively improve the antibacterial properties of the material. By adding this inorganic material separately to polypropylene, the polypropylene masterbatch can be given excellent UV resistance, mechanical properties, and antibacterial properties. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] Figure 1 This is the SEM image of ZnO / CeO2 prepared in the present invention;

[0024] Figure 2 This is the SEM image of ZnO / CeO2 prepared in the present invention; DETAILED DESCRIPTION

[0025] In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the following briefly introduces the drawings required for use in the embodiments. It should be understood that the following drawings only illustrate certain embodiments of the present invention and therefore should not be regarded as limiting the scope. For ordinary technicians in this field, other relevant drawings can be obtained based on these drawings without paying any creative work.

[0026] Example 1

[0027] Preparation of ZnO / CeO2:

[0028] (1) Dissolve the zinc source and acetylacetone in 100 mL of ethanol at a molar ratio of 1:2 to obtain solution (1);

[0029] (2) dissolving the cerium source and EDTA in 100 mL of ethanol at a molar ratio of 1:2 to obtain solution (2);

[0030] (3) Mixing solution (1) and solution (2), adding urea, and the molar ratio of zinc source:cerium source:urea is 1:1:2; mixing well to obtain solution (3);

[0031] (4) Transfer solution (3) into a polytetrafluoroethylene autoclave and perform solvent thermal reaction at 180°C for 12 h;

[0032] (5) The product of step (4) was filtered, washed, and then annealed at 300°C for 1 hour.

[0033] 80 parts of polypropylene matrix resin, 15 parts of inorganic anti-ultraviolet material ZnO / CeO2, 2 parts of phosphite antioxidant, and 2 parts of dimethyl phthalate plasticizer are mixed in a high-speed mixer for 90 minutes, and the temperature of the mixing process is controlled at 120°C; after uniform mixing, the mixture is transferred to a screw extruder, and extruded and granulated in a twin-screw extruder at a temperature of 190°C to obtain a highly weather-resistant and anti-ultraviolet polypropylene masterbatch.

[0034] Example 2

[0035] Preparation of ZnO / CeO2:

[0036] (1) Dissolve the zinc source and acetylacetone in 100 mL of ethanol at a molar ratio of 1:2 to obtain solution (1);

[0037] (2) dissolving the cerium source and EDTA in 100 mL of ethanol at a molar ratio of 1:2 to obtain solution (2);

[0038] (3) Mixing solution (1) and solution (2), adding urea, and the molar ratio of zinc source:cerium source:urea is 1:1:2; mixing well to obtain solution (3);

[0039] (4) Transfer solution (3) into a polytetrafluoroethylene autoclave and perform solvent thermal reaction at 200°C for 12 hours;

[0040] (5) The product of step (4) was filtered, washed, and then annealed at 300°C for 1 hour.

[0041] 80 parts of polypropylene matrix resin, 10 parts of inorganic anti-ultraviolet material ZnO / CeO2, 2 parts of hindered amine antioxidant, and 2 parts of butyl benzyl phthalate plasticizer are mixed in a high-speed mixer for 90 minutes, and the temperature of the mixing process is controlled at 120°C; after uniform mixing, the mixture is transferred to a screw extruder, and extruded and granulated in a twin-screw extruder at a temperature of 190°C to obtain a highly weather-resistant and anti-ultraviolet polypropylene masterbatch.

[0042] Example 3

[0043] Preparation of ZnO / CeO2:

[0044] (1) Dissolve the zinc source and acetylacetone in 100 mL of ethanol at a molar ratio of 1:2 to obtain solution (1);

[0045] (2) dissolving the cerium source and EDTA in 100 mL of ethanol at a molar ratio of 1:2 to obtain solution (2);

[0046] (3) Mixing solution (1) and solution (2), adding urea, and the molar ratio of zinc source:cerium source:urea is 1:1:3; mixing well to obtain solution (3);

[0047] (4) Transfer solution (3) into a polytetrafluoroethylene autoclave and perform solvent thermal reaction at 200°C for 12 hours;

[0048] (5) The product of step (4) was filtered, washed, and then annealed at 350°C for 1 hour.

[0049] 80 parts of polypropylene matrix resin, 15 parts of inorganic UV-resistant ZnO / CeO2, 3 parts of phosphite antioxidant, and 3 parts of dimethyl phthalate plasticizer were mixed in a high-speed mixer for 90 minutes at a temperature of 120°C. After uniform mixing, the mixture was transferred to a screw extruder and extruded and granulated in a twin-screw extruder at a temperature of 230°C to obtain a highly weather-resistant and UV-resistant polypropylene masterbatch.

[0050] Example 4

[0051] Preparation of ZnO / CeO2:

[0052] (1) Dissolve the zinc source and acetylacetone in 80 mL of ethanol at a molar ratio of 1:2.5 to obtain solution (1);

[0053] (2) dissolving the cerium source and EDTA in 80 mL of ethanol at a molar ratio of 1:2 to obtain solution (2);

[0054] (3) Mixing solution (1) and solution (2), adding urea, and the molar ratio of zinc source:cerium source:urea is 1:1:3; mixing well to obtain solution (3);

[0055] (4) Transfer solution (3) into a polytetrafluoroethylene autoclave and perform solvent thermal reaction at 200°C for 12 hours;

[0056] (5) The product of step (4) was filtered, washed, and then annealed at 300°C for 1 hour.

[0057] 80 parts of polypropylene matrix resin, 15 parts of inorganic anti-ultraviolet material ZnO / CeO2, 3 parts of phosphite antioxidant, and 3 parts of dimethyl phthalate plasticizer are mixed in a high-speed mixer for 90 minutes. The temperature of the mixing process is controlled at 120°C. After mixing evenly, the mixture is transferred to a screw extruder and extruded and granulated in a twin-screw extruder at a temperature of 230°C to obtain a weather-resistant and anti-ultraviolet polypropylene masterbatch.

[0058] Comparative Example 1

[0059] Preparation of ZnO:

[0060] (1) Dissolve the zinc source and acetylacetone in 100 mL of ethanol at a molar ratio of 1:2 to obtain solution (1);

[0061] (2) adding urea to solution (1) with a molar ratio of zinc source to urea of ​​1:2; mixing well to obtain solution (2);

[0062] (3) Transfer solution (2) into a polytetrafluoroethylene autoclave and perform solvent thermal reaction at 180°C for 12 hours;

[0063] (4) The product of step (3) was filtered, washed, and then annealed at 300°C for 1 hour.

[0064] 80 parts of polypropylene matrix resin, 15 parts of inorganic anti-UV material ZnO, 2 parts of phosphite antioxidant, and 2 parts of dimethyl phthalate plasticizer were mixed in a high-speed mixer for 90 minutes at a temperature of 120°C. After uniform mixing, the mixture was transferred to a screw extruder and extruded and granulated in a twin-screw extruder at a temperature of 190°C to obtain a weather-resistant and anti-UV polypropylene masterbatch.

[0065] Comparative Example 2

[0066] Preparation of CeO2:

[0067] (1) dissolving a cerium source and EDTA in 100 mL of ethanol at a molar ratio of 1:2 to obtain solution (1);

[0068] (2) adding urea to solution (1) with a molar ratio of cerium source to urea of ​​1:2; mixing uniformly to obtain solution (2);

[0069] (3) Transfer solution (2) into a polytetrafluoroethylene autoclave and perform solvent thermal reaction at 180°C for 12 hours;

[0070] (4) The product of step (3) was filtered, washed, and then annealed at 300°C for 1 hour.

[0071] 80 parts of polypropylene matrix resin, 15 parts of inorganic anti-UV material CeO2, 2 parts of phosphite antioxidant, and 2 parts of dimethyl phthalate plasticizer were mixed in a high-speed mixer for 90 minutes at a temperature of 120°C. After uniform mixing, the mixture was transferred to a screw extruder and extruded and granulated in a twin-screw extruder at a temperature of 190°C to obtain a highly weather-resistant and anti-UV polypropylene masterbatch.

[0072] The polypropylene masterbatch was injection molded into a 75mm×150mm×2mm standard sample, and the weather resistance of polypropylene (PP) under UV light was evaluated according to the SAE J2020 standard.

[0073] UV light source: UVA-340 fluorescent lamp; cycle conditions: UV illumination stage: 60°C, for 8 hours; condensation stage: 50°C, for 4 hours (no UV, only condensation); cycle period: 100h.

[0074] After the test, color difference, tensile strength (ISO 527 standard), and impact strength (ISO 180 standard) were tested. The results are shown in Table 1. As can be seen from the table below, Examples 1-4 are superior to Comparative Examples 1-2 in terms of color difference, tensile strength, and impact strength.

[0075] Chromatic Aberration Tensile strength (Mpa) Impact strength (KJ / m2) Example 1 0.7 29.4 8.4 Example 2 1.1 28.3 7.3 Example 3 1.3 27.7 8.1 Example 4 0.8 24.9 8.0 Comparative Example 1 2.1 21.1 6.5 Comparative Example 2 1.9 22.3 5.9

Claims

1. A highly weather-resistant and UV-resistant polypropylene masterbatch, comprising, by weight: 60-80 parts of polypropylene matrix resin, 10-20 parts of inorganic anti-ultraviolet material ZnO / CeO2, 2-5 parts of antioxidant, and 2-5 parts of plasticizer.

2. The highly weather-resistant and UV-resistant polypropylene masterbatch according to claim 1, wherein the preparation process of the inorganic UV-resistant material ZnO / CeO2 is as follows: (1) dissolving a zinc source and acetylacetone in ethanol at a molar ratio of 1:(2-3) to obtain a solution (1); (2) dissolving the cerium source and EDTA in ethanol at a molar ratio of 1:(1-2) to obtain solution (2); (3) Mixing solution (1) and solution (2), adding urea, the molar ratio of zinc source: cerium source: urea is 1: (0.5-1): (2-3); mixing well to obtain solution (3); (4) transferring the solution (3) into a polytetrafluoroethylene high-pressure reactor for solvent thermal reaction; (5) The product of step (4) is filtered and washed, and then annealed at 300-350°C for 1-2 hours.

3. The highly weather-resistant and UV-resistant polypropylene masterbatch according to claim 2, wherein the volume of ethanol in steps (1)-(2) is 80-100 mL.

4. The highly weather-resistant and UV-resistant polypropylene masterbatch according to claim 2, wherein the solvent thermal reaction conditions are 180-200°C for 12-24 hours.

5. The highly weather-resistant and UV-resistant polypropylene masterbatch according to claim 2, wherein the annealing atmosphere in step (5) is a nitrogen atmosphere, an air atmosphere, or an argon atmosphere.

6. The highly weather-resistant and UV-resistant polypropylene masterbatch according to claim 2, wherein the zinc source is one or more of zinc acetate, zinc sulfate, zinc chloride, and zinc nitrate.

7. The highly weather-resistant and UV-resistant polypropylene masterbatch according to claim 2, wherein the cerium source is one or more of cerium acetate, cerium sulfate, and cerium nitric acid.

8. The highly weather-resistant and UV-resistant polypropylene masterbatch according to claim 2, wherein the plasticizer is dimethyl phthalate or butyl benzyl phthalate.

9. The highly weather-resistant and UV-resistant polypropylene masterbatch according to claim 2, wherein the antioxidant is one or more of phosphites, hindered amines, and hindered phenol antioxidants.

10. A polypropylene masterbatch for automobile exterior, characterized in that: The method according to any one of claims 1 to 9 is used to prepare the present invention.

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