High-weather-resistance and high-brightness black PMMA / ABS (Polymethyl Methacrylate / Acrylonitrile Butadiene Styrene) composition and preparation method thereof

Abstract

The PMMA / ABS composition with high weather resistance and high bright black comprises the following components in percentage by weight: 47%-70% of PMMA resin, 15%-30% of SAN (Styrene Acrylonitrile Butadiene Styrene) resin, 15%-30% of MBS (Methyl Methacrylate-Butadiene-Styrene) flexibilizer, 0.1%-1% of toner and 1.0%-2.5% of processing aid. The alloy material obtained by the invention can be used as a new highlight black material to be applied to automobile exterior trimming parts, and is directly applied to highlight automobile exterior trimming parts which are not painted and have higher weather-proof requirements.

Description

Technical Field

[0001] The invention relates to a plastic alloy material, in particular to a high-weather-resistant, high-gloss black PMMA+ABS composition and a preparation method thereof. Background Art

[0002] As one of the general-purpose plastics, ABS has been widely used, but its weather resistance is poor and its hardness is low. It must be surface treated, such as painting and electroplating, when used in automotive exterior parts. PMMA has excellent weather resistance and high hardness, but is brittle. Therefore, in view of the difference in performance between the two, a PMMA / ABS alloy material is prepared, which can ensure the excellent weather resistance and certain toughness of the material, and also has a high-gloss black effect, so that it can be directly applied to automotive interior and exterior parts.

[0003] Patent application number: CN 114031888 A, a high-gloss PMMA, ABS composite material and a preparation method thereof, which improves the surface properties of PMMA / ABS by using homemade modified nanofillers to give it good gloss.

[0004] Patent application number: CN 111234443 A ， A PMMA / ABS spray-free resin with yellowing resistance and a preparation method thereof, wherein the impact performance of the material is ensured by introducing EEA-MAH, the yellowing resistance of the material is ensured by magnesium oxide, and the appearance effect of the spray-free material is ensured by adding pearlescent effect pigments through side feeding.

[0005] Patent application number: CN 114031888 A. The production process of homemade modified nanofillers is complicated and requires multiple steps. The products produced are limited to gloss and hardness. The mechanical properties, aging properties and whether the materials are suitable for the market are unknown. Patent application number: CN 111234443 A. It mainly improves the yellowing resistance of PMMA / ABS, but does not reflect the appearance gloss performance of the material, and the light aging test time in the patent is not reflected. The present invention mainly introduces suitable SAN and MBS toughening agents, and adjusts the ratio of PMMA, SAN and toughening agents to obtain a high-weather-resistant and high-gloss black PMMA+ABS composition that can be directly used for automotive exterior parts. Summary of the invention

[0006] A highly weather-resistant, high-gloss black PMMA+ABS composition comprising the following components (by weight percentage): PMMA resin 47%~70% SAN resin 15%~30% MBS toughening agent 15%~30% Color powder 0.1%~1% Processing aids 1.0%~2.5%.

[0007] The PMMA resin has a weight average molecular weight of 80,000-110,000 g / mol; preferably, it is a product of Mitsubishi Chemical Corporation, brand PMMA VH5001.

[0008] The SAN resin has an AN content of 20-30%; preferably, it is a product of Ningbo Formosa Chemical Industry Co., Ltd., brand SAN NF2200, with a weight average molecular weight of 80,000-130,000 g / mol.

[0009] The SAN resin 1 has an AN content of 30-40%; preferably, it is a product of Zhenjiang Chimei Company, brand SAN D-168, and has a weight average molecular weight of 14000-20000 g / mol.

[0010] The MBS toughening agent is a substance with a core-shell structure; preferably, it is a terpolymer with methyl methacrylate as the shell and cross-linked styrene-butadiene as the core, and its rubber particle size is 100-300nm; more preferably, it is a product of Rohm and Haas Company, brand EXL 2678.

[0011] The toner is a compound of red, yellow and blue powders and is commercially available.

[0012] The processing aids are antioxidants, light stabilizers and lubricants.

[0013] The antioxidants are hindered phenols and phosphites; preferably, the antioxidants purchased from Ciba Company.

[0014] The light stabilizer is a benzotriazole UV absorber, preferably a light stabilizer purchased from BASF.

[0015] The lubricant is pentaerythritol stearate; preferably the lubricant purchased from LOZA company. The highly weather-resistant, high-gloss black PMMA+ABS composition may further include the following components (by weight): 0.1% to 3% of SMA resin.

[0016] A method for preparing a high-weather-resistant, high-gloss black PMMA+ABS composition comprises the steps of: mixing the components according to weight percentage, and granulating with an extruder, wherein the extruder used is a twin-screw extruder, and the extrusion temperature is 210-230°C.

[0017] The alloy material obtained by the present invention can be used as a new high-gloss black material in automobile exterior decoration, and can be directly applied to non-painted high-gloss automobile exterior decoration parts with high weather resistance requirements. DETAILED DESCRIPTION

[0018] The dried PMMA resin, SAN resin, SMA resin, MBS toughening agent, color powder, antioxidant, light stabilizer and lubricant are mixed according to the composition formula in Table 1 and added into the main barrel of a twin-screw extruder (screw diameter is 35 mm, aspect ratio L / D=40). The main barrel is controlled at a temperature of 200°C-220°C, the twin screw speed is 400 rpm, and the extruded material strips are cooled in a water tank and pelletized to obtain the product of the present invention.

[0019] PMMA resin was purchased from Mitsubishi Chemical, brand PMMA VH5001.

[0020] SAN resin, with an AN content of 20-30%, was purchased from Ningbo Formosa Chemical Industry Co., Ltd., with the brand name SAN NF2200.

[0021] SAN resin 1, with an AN content of 30-40%, was purchased from Zhenjiang Chimei, with the brand name SAN D-168.

[0022] MBS toughening agent, purchased from Rohm and Haas, brand EXL 2678.

[0023] Color powder is a compound of red, yellow and blue powders.

[0024] Processing aids include antioxidants, light stabilizers, and light stabilizers.

[0025] The antioxidants are hindered phenols and phosphites; the antioxidants are purchased from Ciba.

[0026] The light stabilizer is a benzotriazole UV absorber; the light stabilizer was purchased from BASF.

[0027] The lubricant is pentaerythritol stearate, which is a lubricant purchased from LOZA Company.

[0028] SMA resin was purchased from Sartomer Company with the brand names SMA1000, SMA2000 and SMA17352.

[0029] The obtained product was dried at 80°C for 4 hours and then injection molded by an injection molding machine at a temperature of 210°C-230°C. The prepared specimens and samples were subjected to conventional mechanical property tests and weather resistance tests.

[0030] Table 1 Composition formula (parts by weight) composition Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Comparative Example 1 Comparative Example 2 PMMA resin 67 62 52 47 50 47 47 47 68.1 50 SAN resin 16.1 16.1 16.1 26.1 16.1 26.1 26.1 26.1 SAN resin 1 16.1 MBS toughening agent 15 20 30 25 25 24 24 24 30 25 SMA Resin 1 1 1 Toner 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 Processing Aids 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 The SMA resins in Examples 6, 7 and 8 are SMA1000, SMA2000 and SMA17352 respectively.

[0031] The product performance test methods are as follows: tensile strength refers to ISO 527 standard, tensile rate 50mm / min, flexural modulus refers to ISO 178 standard, bending rate 2mm / min, notched impact strength refers to ISO 179 standard, heat deformation temperature refers to ISO 75-2 standard, 0.45MPa.

[0032] Gloss test (20° angle) was carried out according to ISO 2813 and color L value was tested according to ISO 12647.

[0033] The weathering test was carried out according to ISO 4892-2 cycle 1 for 1000 hours.

[0034] The test results are shown in Table 2 Table 2 Conventional mechanical properties and weathering test results performance Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Comparative Example 1 Comparative Example 2 Tensile Strength 60 55 51 53 52 57 58 57 45 38 Flexural modulus 2372 2311 2267 2289 2256 2300 2380 2320 1668 2201 Notched impact strength 7 9 14 12 12 12.5 13 12.7 9 15 Heat Deflection Temperature 93 91 90 91 91 93 93 93 90 93 Glossiness 86 86 84 85 85 86 89 87 72 50 L value 23.2 23.7 24.1 23.5 23.5 23.5 23.4 23.4 26.1 30.7 Grayscale after weathering test Level 4-5 Level 4 Level 4 Level 4 Level 4 Level 4 Level 4 Level 4 Level 4 Level 3-4 ΔE after weathering test 0.87 0.93 1.03 0.92 0.96 0.91 0.9 0.91 0.94 2.01 Compared with the control example 1, the addition of a suitable SAN resin in the system of the embodiment 3 is conducive to a lower L value of the material, and also greatly improves the glossiness of the material, and the appearance is darker and brighter.

[0035] Compared with Control Example 2, the acrylonitrile content (AN) of the SAN resin in Example 5 is too high and the molecular weight is too large, which has a great impact on the L value and glossiness, resulting in extremely poor appearance and poor effect in xenon lamp aging.

[0036] Compared with Example 4, in Examples 6 to 8, 1 part of SMA in the system replaces the MBS toughening agent, and the glossiness of the material is improved, and the tensile strength and impact strength are also improved.

Claims

1. A highly weather-resistant, high-gloss black PMMA / ABS composition comprising the following components (percentage by weight): PMMA resin 47%~70% SAN resin 15%~30% MBS toughening agent 15%~30% Color powder 0.1%~1% Processing aids 1.0%~2.5% The SAN resin has an AN content of 20-30%.

2. A highly weather-resistant, high-gloss black PMMA / ABS composition comprising the following components (by weight): PMMA resin 47%~70% SAN resin 15%~30% MBS toughening agent 15%~30% Color powder 0.1%~1% Processing aids 1.0%~2.5% SMA resin 0.1%~3% The SAN resin has an AN content of 20-30%.

3. The highly weather-resistant, high-gloss black PMMA / ABS composition according to claim 1 or 2, characterized in that: The weight average molecular weight of the PMMA resin is 80,000-110,000 g / mol.

4. The highly weather-resistant, high-gloss black PMMA / ABS composition according to claim 1 or 2, characterized in that: The SAN resin is the brand SAN NF2200 produced by Ningbo Formosa Chemical Industry Co., Ltd.

5. The highly weather-resistant, high-gloss black PMMA / ABS composition according to claim 1 or 2, characterized in that: The MBS toughening agent is a substance with a core-shell structure.

6. The highly weather-resistant, high-gloss black PMMA / ABS composition according to claim 1 or 2, characterized in that: The toner is a composite of red, yellow and blue powders.

7. The highly weather-resistant, high-gloss black PMMA / ABS composition according to claim 1 or 2, characterized in that: The processing aids are antioxidants, light stabilizers, and lubricants; the antioxidants are hindered phenols and phosphites; the light stabilizers are benzotriazole UV absorbers; and the lubricants are pentaerythritol stearate.

8. The highly weather-resistant, high-gloss black PMMA / ABS composition according to claim 2, characterized in that: The SMA resin is produced by Sartomer Company and has the brands of SMA1000, SMA2000 and SMA17352 or more.

9. The method for preparing the highly weather-resistant, high-gloss black PMMA / ABS composition according to any one of claims 1 to 8, comprising the steps of: mixing the components according to weight percentage, and granulating them using an extruder, wherein the extruder used is a twin-screw extruder, and the extrusion temperature is 210-230°C.