Polypropylene modified masterbatch for high-weather-resistance and ultraviolet-resistant automobile exterior parts and preparation method thereof

Abstract

The application provides a kind of high weather resistance ultraviolet resistant polypropylene modified master batch, its component includes: polypropylene matrix resin 60-80 parts by weight, inorganic ultraviolet resistant material ZnO / CeO2 10-20 parts, antioxidant 2-5 parts, plasticizer 2-5 parts, the preparation process of ZnO / CeO2 is as follows: zinc source and acetylacetone are dissolved in ethanol to obtain solution (1); cerium source and EDTA are dissolved in ethanol to obtain solution (2); solution (1) and solution (2) are mixed, urea is added, and the product is annealed at 300-350 DEG C for 1-2 hours after solvothermal reaction; ZnO / CeO2 endows polypropylene material with excellent ultraviolet resistance, antibacterial property and mechanical property.

Description

Technical Field

[0001] This application belongs to the field of polymer technology, specifically relating to a high weather-resistant and UV-resistant polypropylene masterbatch, its preparation method, and automotive exterior parts. Background Technology

[0002] Polypropylene (PP) is widely used in automotive interior and exterior parts due to its lightweight, ease of processing, good chemical resistance, and low cost. However, automotive exterior parts are constantly exposed to complex and changing environments, making PP prone to aging. Ultraviolet rays from sunlight (especially UVA 315–400 nm) can cause the PP molecular chains to break, leading to embrittlement, powdering, surface cracking, and discoloration (yellowing). Extreme temperature variations, such as temperatures exceeding 80°C in summer accelerating surface oxidation and low temperatures in winter potentially causing material brittleness and cracking, further exacerbate the problem.

[0003] To address the above issues, existing technologies propose adding inorganic fillers, antioxidants, and UV absorbers to the polypropylene matrix resin. For example, Chinese invention patent CN108841085A discloses a high-rigidity, high-heat-resistant polypropylene material and its preparation method. The polypropylene material includes polypropylene resin, inorganic fillers, cyclic olefin polymers, color masterbatch, nucleating agents, antioxidants, UV absorbers, and lubricants. This polypropylene material features high powder filling, high crystallinity, and a low defect rate. Through optimized formulation design and appropriate injection molding processes, the overall modulus, strength, and heat resistance of the injection-molded product can be improved.

[0004] Chinese invention patent CN107652540A discloses an anti-UV polypropylene composite material, its preparation method, and its application. This anti-UV polypropylene composite material is composed of the following raw materials in the indicated mass percentages: polypropylene 50-70%; inorganic powder 10-30%; toughening agent 10-30%; antioxidant 0.1-2%; light stabilizer 0.1-2%; nucleating agent masterbatch 0.5-10%; lubricant 0.1-2%; and color masterbatch 0.5-5%. Using a reactive UV absorber and energy transfer agent as light stabilizers, and incorporating a self-made nucleating agent masterbatch, the prepared polypropylene composite material, after aging for 4000 hours, maintains a gloss retention rate of over 80% while meeting the grayscale requirement of ≥4 for talc-reinforced polypropylene systems. This significantly exceeds the 1500-2000 hour requirement of OEMs, making it well-suited for use in high-light and high-heat environments, such as automotive grilles.

[0005] Chinese invention patent CN110982170A discloses a polypropylene plastic for use in the interior of new energy vehicles. The raw materials include modified polypropylene masterbatch, wheat straw, bagasse, propylene oxide modified corn starch, calcium cellulose microcrystals, carbon nanotubes, nano-silicon carbide, nano-inorganic fillers, and nucleating agents. The modified polypropylene masterbatch, wheat straw, bagasse, and propylene oxide modified corn starch used as the main raw materials are abundant, inexpensive, and environmentally friendly. Furthermore, the resulting plastic products are high-strength, low-cost, biodegradable, antistatic, oxidation-resistant, and UV-resistant, which can alleviate the problem of white pollution.

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

[0007] To address the aforementioned problems, this invention proposes a weather-resistant and UV-resistant polypropylene masterbatch, the components 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] The preparation process of the inorganic UV-resistant material ZnO / CeO2 is as follows:

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

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

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

[0012] (4) Transfer solution (3) into a polytetrafluoroethylene high-pressure reactor for solvothermal reaction;

[0013] (5) After filtering and washing the product from step (4), anneal it at 300-350℃ for 1-2 hours.

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

[0015] As a further preferred option, the solvothermal reaction conditions are 180~200℃ for 12~24 hours;

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

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

[0018] As a further preferred option, the cerium source is one or more of cerium acetate, cerium sulfate, and cerium nitrate;

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

[0020] As a further preferred option, the antioxidant is one or more of the following: phosphites, hindered amines, and hindered phenols.

[0021] Compared with the prior art, 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, and the difference in alcoholysis rates between Zn and Ce is adjusted through competitive coordination of acetylacetone and EDTA, resulting in an inorganic material with CeO2 particles grown on the ZnO surface. The flower-like high specific surface area increases the number of active sites, and the combination of the two can effectively broaden the UV absorption range, exhibiting excellent anti-UV aging properties. On the other hand, ZnO / CeO2 itself, as an inorganic filler, possesses excellent heat resistance and anti-aging properties, improving the strength and rigidity of polypropylene materials. Furthermore, ZnO / CeO2 can effectively enhance the antibacterial properties of the material. By adding this inorganic material alone to polypropylene, excellent UV resistance, mechanical properties, and antibacterial properties can be imparted to the polypropylene masterbatch. Attached Figure Description

[0023] Figure 1 Here is a SEM image of the ZnO / CeO2 prepared according to the present invention;

[0024] Figure 2 Here is a SEM image of the ZnO / CeO2 prepared according to the present invention; Detailed Implementation

[0025] To more clearly illustrate the technical solutions of the embodiments of the present invention, the accompanying drawings used in the embodiments will be briefly introduced below. It should be understood that the following drawings only show some embodiments of the present invention and should not be regarded as a limitation on the scope. For those skilled in the art, other related drawings can be obtained based on these drawings without creative effort.

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

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

[0031] (4) Transfer solution (3) into a polytetrafluoroethylene high-pressure reactor and react it at 180°C for 12 hours using a solvothermal method.

[0032] (5) After filtering and washing the product from step (4), anneal it at 300°C for 1 hour.

[0033] 80 parts of polypropylene matrix resin, 15 parts of inorganic UV-resistant material ZnO / CeO2, 2 parts of phosphite antioxidant, and 2 parts of dimethyl phthalate plasticizer were mixed in a high-speed mixer for 90 minutes, with the mixing temperature controlled at 120℃. After uniform mixing, the mixture was transferred to a screw extruder and extruded and granulated in a twin-screw extruder at 190℃ to obtain a polypropylene masterbatch with high weather resistance and UV resistance.

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

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

[0039] (4) Transfer solution (3) into a polytetrafluoroethylene high-pressure reactor and react it at 200°C for 12 hours using a solvothermal method.

[0040] (5) After filtering and washing the product from step (4), anneal it at 300°C for 1 hour.

[0041] 80 parts of polypropylene matrix resin, 10 parts of inorganic UV-resistant material ZnO / CeO2, 2 parts of hindered amine antioxidant, and 2 parts of butyl benzyl phthalate plasticizer were mixed in a high-speed mixer for 90 minutes, with the mixing temperature controlled at 120℃. After uniform mixing, the mixture was transferred to a screw extruder and extruded and granulated in a twin-screw extruder at 190℃ to obtain a polypropylene masterbatch with high weather resistance and UV resistance.

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

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

[0047] (4) Transfer solution (3) into a polytetrafluoroethylene high-pressure reactor and react it at 200°C for 12 hours using a solvothermal method.

[0048] (5) After filtering and washing the product from step (4), anneal it at 350°C for 1 hour.

[0049] 80 parts of polypropylene matrix resin, 15 parts of inorganic UV-resistant material ZnO / CeO2, 3 parts of phosphite antioxidant, and 3 parts of dimethyl phthalate plasticizer were mixed in a high-speed mixer for 90 minutes, with the mixing temperature controlled at 120℃. After uniform mixing, the mixture was transferred to a screw extruder and extruded and granulated in a twin-screw extruder at 230℃ to obtain a high 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) Dissolve the cerium source and EDTA in 80 mL of ethanol at a molar ratio of 1:2 to obtain solution (2);

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

[0055] (4) Transfer solution (3) into a polytetrafluoroethylene high-pressure reactor and react it at 200°C for 12 hours using a solvothermal method.

[0056] (5) After filtering and washing the product from step (4), anneal it at 300°C for 1 hour.

[0057] 80 parts of polypropylene matrix resin, 15 parts of inorganic UV-resistant material ZnO / CeO2, 3 parts of phosphite antioxidant, and 3 parts of dimethyl phthalate plasticizer were mixed in a high-speed mixer for 90 minutes, with the mixing temperature controlled at 120℃. After uniform mixing, the mixture was transferred to a screw extruder and extruded and granulated in a twin-screw extruder at 230℃ to obtain weather-resistant and UV-resistant 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) Add solution (1) to urea, with a zinc source:urea molar ratio of 1:2; mix well to obtain solution (2);

[0062] (3) Transfer solution (2) into a polytetrafluoroethylene high-pressure reactor and react it at 180°C for 12 hours using a solvothermal method.

[0063] (4) After filtering and washing the product from step (3), anneal it at 300°C for 1 hour.

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

[0065] Comparative Example 2

[0066] Preparation of CeO2:

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

[0068] (2) Add solution (1) to urea, with a molar ratio of cerium source to urea of ​​1:2; mix well to obtain solution (2);

[0069] (3) Transfer solution (2) into a polytetrafluoroethylene high-pressure reactor and react it at 180°C for 12 hours using a solvothermal method.

[0070] (4) After filtering and washing the product from step (3), anneal it at 300°C for 1 hour.

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

[0072] Polypropylene masterbatch was injection molded into standard samples of 75mm×150mm×2mm, and the weather resistance of polypropylene PP under ultraviolet light was evaluated according to SAE J2020 standard.

[0073] Ultraviolet light source: UVA-340 fluorescent lamp; Cycling conditions: Ultraviolet irradiation stage: 60°C, 8 hours; Condensation stage: 50°C, 4 hours (no UV, only condensation); Cycle period: 100 hours.

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

[0075] Color difference 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 high-weather-resistant ultraviolet-resistant polypropylene masterbatch, ingredients of which comprise, by weight parts: Polypropylene base resin 60-80 parts, inorganic anti-ultraviolet material ZnO / CeO2 10-20 parts, antioxidant 2-5 parts, plasticizer 2-5 parts, The preparation process of the inorganic anti-ultraviolet material ZnO / CeO2 is as follows: The zinc source and acetylacetone are dissolved in ethanol according to a molar ratio of 1: (2-3) to obtain solution (1); the zinc source is one or more of zinc acetate, zinc sulfate, zinc chloride and zinc nitrate; The cerium source and EDTA are dissolved in ethanol according to a molar ratio of 1: (1-2) to obtain solution (2); the cerium source is one or more of cerium acetate, cerium sulfate and cerium nitrate; (3) Mix solution (1) and solution (2), add urea, and the molar ratio of zinc source:cerium source:urea is 1: (0.5-1): (2-3); mix uniformly to obtain solution (3); (4) Transfer solution (3) into a polytetrafluoroethylene high-pressure reaction kettle and perform solvothermal reaction; the solvothermal reaction conditions are 180-200℃ for 12-24 hours; (5) After filtering and washing the product of step (4), anneal at 300-350℃ for 1-2 hours.

2. The high-weather-resistant anti-ultraviolet polypropylene master batch according to claim 1, wherein the volume of ethanol in steps (1)-(2) is 80-100 mL.

3. The high-weather-resistant anti-ultraviolet polypropylene master batch according to claim 1, wherein the annealing atmosphere of step (5) is nitrogen atmosphere, air atmosphere or argon atmosphere.

4. The high-weather-resistant anti-ultraviolet polypropylene master batch according to claim 1, wherein the plasticizer is dimethyl phthalate or butyl benzyl phthalate.

5. The high-weather-resistant anti-ultraviolet polypropylene master batch according to claim 1, wherein the antioxidant is one or more of phosphite, hindered amine and hindered phenol antioxidants.

6. A polypropylene masterbatch for automotive exterior applications, characterized in that Prepared by the method of any one of claims 1-5.

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