A weather-resistant ABS resin composite material, a preparation method thereof, and its application in automobile exterior parts

Abstract

The invention relates to the technical field of ABS resins and discloses a weather-resistant ABS resin composite material, a preparation method thereof, and application of the composite material in automotive exterior parts. The weather-resistant ABS resin composite material comprises 85-92 parts by weight of ABS resin, 8-15 parts by weight of grafted POE, 0.2-1 parts by weight of nano-titanium dioxide, etc.; a styrene polymer molecular chain is introduced into the side chain of the grafted POE, and the composite material has good compatibility with the ABS resin; the carboxyl groups contained in the composite material can interact with the surface of the nano-titanium dioxide, thereby improving the compatibility and dispersibility between the nano-titanium dioxide and the ABS resin, enhancing the material's resistance to ultraviolet aging and heat aging, and having excellent weather resistance. The composite material has better practical application in automotive exterior parts such as lampshades and air intake grilles.

Description

Technical Field

[0001] The present invention relates to the technical field of ABS resins, in particular to a weather-resistant ABS resin composite material, a preparation method thereof, and application thereof in automobile exterior trims. Background Art

[0002] Acrylonitrile-butadiene-styrene (ABS) resin is a common thermoplastic resin with high mechanical strength, high hardness, and excellent insulation properties. It is widely used in automotive parts, electronics, and the building materials industry. Ethylene-octene copolymer (POE) is a good elastomeric material that can improve the toughness and other properties of materials such as ABS. Because ABS resin contains olefinic groups in its molecular chain, it is susceptible to light aging and thermal oxidative aging, resulting in poor UV resistance, heat resistance, and weathering resistance. Therefore, additives such as UV absorbers and antioxidants are required.

[0003] Nano-titanium dioxide is inexpensive, readily available, and possesses high mechanical strength and excellent UV resistance. When added to polymer materials such as ABS, polystyrene, and natural rubber, it can improve the material's mechanical strength and UV aging resistance. Patent Publication No. CN117964993B discloses an ABS resin reinforcing additive, an ABS resin material, and a preparation method thereof. This additive utilizes a surfactant combined with nano-titanium dioxide to enhance its affinity for organic matter, improving the ABS resin's UV aging resistance and other properties. However, the ABS resin in this patent lacks good heat aging resistance, hindering its practical application in automotive exterior parts and other applications. Summary of the Invention

[0004] In view of the shortcomings of the existing technology, the present invention provides a weather-resistant ABS resin composite material, a preparation method thereof, and an application in automobile exterior parts, which solves the problems of ABS resin's poor UV resistance, heat aging resistance, and weather resistance.

[0005] In order to solve the above technical problems, the technical solution adopted by the present invention is: a weather-resistant ABS resin composite material and a preparation method thereof, comprising 85-92 parts by weight of ABS resin, 8-15 parts by weight of grafted POE, 0.2-1 parts by weight of nano-titanium dioxide, and 0.1-0.3 parts by weight of antioxidant; the preparation method is:

[0006] (1) Add glacial acetic acid, trimellitic anhydride, and 4-aminostyrene to a reaction vessel, stir the reaction, and then cool in an ice-water bath. Filter and wash the precipitate with water, then recrystallize and purify it in dichloromethane to obtain a styrene derivative. The reaction formula is:

[0007] .

[0008] (2) Ethylene-octene copolymer, styrene derivative and diisopropylbenzene peroxide are mixed, melt-grafted and extruded in a screw extruder to obtain grafted POE.

[0009] (3) Grafted POE and nano-titanium dioxide are mixed in a mixer once, and then ABS resin and antioxidant are added and mixed again. Finally, the material is melt-extruded in a screw extruder and pelletized to obtain a weather-resistant ABS resin composite material.

[0010] Preferably, the amount of trimellitic anhydride in (1) is 100 parts by weight, and the amount of 4-aminostyrene is 62-68 parts by weight.

[0011] Preferably, the reaction temperature in (1) is 120-130°C and the reaction time is 12-18 hours.

[0012] Preferably, the amount of ethylene-octene copolymer in (2) is 100 parts by weight, the amount of styrene derivative is 2-8 parts by weight, and the amount of dicumyl peroxide is 0.2-1 part by weight.

[0013] Preferably, the temperature of the middle screw extruder zones 1-6 in (2) is 150-170°C, and the screw speed is 30-50 r / min.

[0014] Preferably, the temperature during the first mixing in (3) is 70-90°C and the time is 60-90 min; the temperature during the first mixing is 70-90°C and the time is 20-30 min.

[0015] Preferably, during melt extrusion in the (3) middle screw extruder, the temperature of zones 1-6 is 180-225°C, and the screw speed is 200-300 r / min.

[0016] Preferably, the weather-resistant ABS resin composite material is used in automobile exterior parts.

[0017] Beneficial technical effects: The present invention melt-grafts styrene derivatives onto ethylene-octene copolymers to produce grafted POE, which is then blended and granulated with ABS resin and nano-titanium dioxide to produce a weather-resistant ABS resin composite. The grafted POE incorporates styrene polymer chains into its side chains, enhancing the compatibility between POE and ABS resin and improving the mechanical properties of the composite.

[0018] The present invention introduces carboxyl groups into POE, which can interact with the surface of nano-titanium dioxide and coat the surface of the nano-titanium dioxide, thereby improving the compatibility and dispersibility between the nano-titanium dioxide and the ABS resin, and making the ABS composite material have higher tensile strength.

[0019] The nano-titanium dioxide of the present invention is uniformly dispersed in the ABS material under the coating effect of the grafted POE, which significantly improves the material's anti-ultraviolet aging performance. In addition, the styrene polymer molecular chain of the side chain of the grafted POE contains a high-temperature resistant imide ring, which is beneficial to improving the heat aging resistance of the composite material, so that the ABS composite material has higher weather resistance and has better practical application in automobile exterior decoration such as car lampshades and air intake grilles. BRIEF DESCRIPTION OF THE DRAWINGS

[0020] Figure 1 This is the infrared spectrum of the grafted POE of Example 1. DETAILED DESCRIPTION

[0021] The following is a clear and complete description of the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the 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.

[0022] The ABS resin, brand Toray 920-555, was sourced from Shanghai Shengyu Plastics Co., Ltd. The ethylene-octene copolymer, model C1055D, was sourced from Guangdong Yuming New Materials Technology Co., Ltd. The nano-titanium dioxide had an average particle size of 40 nm.

[0023] Example 1:

[0024] (1) Add 500 mL of glacial acetic acid, 30 g of trimellitic anhydride, and 18.6 g of 4-aminostyrene to a reaction vessel, heat to 120°C, stir, and reflux under condensation for 18 h. Cool in an ice-water bath, filter, wash the precipitate with water, and then recrystallize and purify it from dichloromethane to obtain a styrene derivative as an off-white solid with a yield of 36.2 g.

[0025] (2) 1 kg of ethylene-octene copolymer, 20 g of styrene derivative, and 2 g of diisopropylbenzene peroxide were mixed and melt-grafted in a screw extruder. The temperatures in zones 1-6 were 150°C, 160°C, 160°C, 170°C, 170°C, and 170°C, and the screw speed was 50 r / min. Grafted POE was obtained by extrusion. Figure 1 In the infrared spectrum, 1586 cm -1 It is the characteristic absorption peak of benzene ring, 1350cm -1 It is the absorption peak of the CN bond of the imide ring, 1725-1751cm -1 It is the absorption peak of C=O, 3451cm -1 It is the absorption peak of -OH in the carboxyl group.

[0026] (3) 0.8 kg grafted POE and 20 g nano-titanium dioxide were mixed in a mixer at 80 ° C for 60 min, and then 9.2 kg ABS resin and 17 g antioxidant 1076 were added and mixed for 20 min. Finally, the materials were melt-extruded in a screw extruder with the temperatures of zones 1-6 being 180 ° C, 200 ° C, 215 ° C, 225 ° C, 225 ° C, and 220 ° C, and the screw speed being 200 r / min. The materials were pelletized to obtain weather-resistant ABS resin composite materials.

[0027] Example 2:

[0028] (1) Add 600 mL of glacial acetic acid, 30 g of trimellitic anhydride, and 20.4 g of 4-aminostyrene to a reaction vessel, heat to 130°C, stir, and reflux for 12 h. Cool in an ice-water bath, filter, wash the precipitate with water, and then recrystallize and purify it from dichloromethane to obtain a styrene derivative as an off-white solid with a yield of 33.5 g.

[0029] (2) 1 kg of ethylene-octene copolymer, 80 g of styrene derivative, and 10 g of diisopropylbenzene peroxide were mixed and melt-grafted in a screw extruder. The temperatures in zones 1-6 were 150°C, 160°C, 160°C, 170°C, 170°C, and 170°C, and the screw speed was 50 r / min. Grafted POE was obtained by extrusion.

[0030] (3) 1.2 kg grafted POE and 60 g nano-titanium dioxide were mixed in a mixer at 70 ° C for 90 min, and then 8.8 kg ABS resin and 30 g antioxidant 1076 were added and mixed for 30 min. Finally, the materials were melt-extruded in a screw extruder with the temperatures of zones 1-6 being 180 ° C, 200 ° C, 215 ° C, 225 ° C, 225 ° C, and 220 ° C, and the screw speed being 300 r / min. The materials were pelletized to obtain weather-resistant ABS resin composite materials.

[0031] Example 3:

[0032] (1) 1 kg of ethylene-octene copolymer, 50 g of a styrene derivative (prepared in the same manner as in Example 1), and 6.4 g of dicumyl peroxide were mixed and melt-grafted in a screw extruder at a screw speed of 30 r / min at a temperature of 150°C, 160°C, 160°C, 170°C, 170°C, and 170°C in zones 1-6 to obtain grafted POE.

[0033] (2) 1.5 kg grafted POE and 100 g nano-titanium dioxide were mixed in a mixer at 90 ° C for 60 min, and then 8.5 kg ABS resin and 10 g antioxidant 1076 were added and mixed for 30 min. Finally, the materials were melt-extruded in a screw extruder with the temperatures of zones 1-6 being 180 ° C, 200 ° C, 215 ° C, 225 ° C, 225 ° C, and 220 ° C, and the screw speed being 200 r / min. The materials were pelletized to obtain weather-resistant ABS resin composite materials.

[0034] Comparative Example 1:

[0035] (1) 0.8 kg of ethylene-octene copolymer and 20 g of nano-titanium dioxide were mixed in a mixer at 80 °C for 60 min, and then 9.2 kg of ABS resin and 17 g of antioxidant 1076 were added and mixed for 20 min. Finally, the materials were melt-extruded in a screw extruder with the temperatures of zones 1-6 being 180 °C, 200 °C, 215 °C, 225 °C, 225 °C, and 220 °C, and the screw speed being 200 r / min. The materials were pelletized to obtain ABS resin composite materials.

[0036] Comparative Example 2:

[0037] (1) 1 kg of ethylene-octene copolymer, 20 g of styrene, and 2 g of diisopropylbenzene peroxide were mixed and melt-grafted in a screw extruder. The temperatures in zones 1-6 were 150°C, 160°C, 160°C, 170°C, 170°C, and 170°C, and the screw speed was 50 r / min. Grafted POE was obtained by extrusion.

[0038] (2) 0.8 kg grafted POE and 20 g nano-titanium dioxide were mixed in a mixer at 80 ° C for 60 min, and then 9.2 kg ABS resin and 17 g antioxidant 1076 were added and mixed for 20 min. Finally, the materials were melt-extruded in a screw extruder with the temperatures of zones 1-6 being 180 ° C, 200 ° C, 215 ° C, 225 ° C, 225 ° C, and 220 ° C, and the screw speed being 200 r / min. The materials were pelletized to obtain ABS resin composite materials.

[0039] Comparative Example 3

[0040] (1) 1 kg of ethylene-octene copolymer, 20 g of 4-vinylbenzoic acid, and 2 g of diisopropylbenzene peroxide were mixed and melt-grafted in a screw extruder. The temperatures in zones 1-6 were 150°C, 160°C, 160°C, 170°C, 170°C, and 170°C, and the screw speed was 50 r / min. Grafted POE was obtained by extrusion.

[0041] (2) 0.8 kg grafted POE and 20 g nano-titanium dioxide were mixed in a mixer at 80 ° C for 60 min, and then 9.2 kg ABS resin and 17 g antioxidant 1076 were added and mixed for 20 min. Finally, the materials were melt-extruded in a screw extruder with the temperatures of zones 1-6 being 180 ° C, 200 ° C, 215 ° C, 225 ° C, 225 ° C, and 220 ° C, and the screw speed being 200 r / min. The materials were pelletized to obtain ABS resin composite materials.

[0042] Comparative Example 4

[0043] (1) Add 500 mL of glacial acetic acid, 23.1 g of phthalic anhydride, and 18.6 g of 4-aminostyrene to a reaction vessel, heat to 120°C, stir and reflux for 18 hours, cool in an ice-water bath, filter, wash the precipitate with water, and then recrystallize and purify it in dichloromethane to obtain a styrene derivative. The structural formula is .

[0044] (2) 1 kg of ethylene-octene copolymer, 20 g of styrene derivative, and 2 g of diisopropylbenzene peroxide were mixed and melt-grafted in a screw extruder. The temperatures in zones 1-6 were 150°C, 160°C, 160°C, 170°C, 170°C, and 170°C, and the screw speed was 50 r / min. Grafted POE was obtained by extrusion.

[0045] (3) 0.8 kg grafted POE and 20 g nano-titanium dioxide were mixed in a mixer at 80 °C for 60 min, and then 9.2 kg ABS resin and 17 g antioxidant 1076 were added and mixed for 20 min. Finally, the materials were melt-extruded in a screw extruder with the temperatures of zones 1-6 being 180 °C, 200 °C, 215 °C, 225 °C, 225 °C, and 220 °C, and the screw speed being 200 r / min. The materials were pelletized to obtain ABS resin composite materials.

[0046] ABS resin composite materials were injection molded into test specimens using an injection molding machine. Tensile strength was tested according to GB / T 1040.1-2018. Each specimen was tested three times and the average value was taken.

[0047] ABS resin composites were subjected to UV aging tests in a UV aging chamber (wavelength 280-315nm, power 180W) for 30 days. After aging at room temperature for 2 hours, the tensile strength was retested. Each sample group was tested three times, and the average value was taken to calculate the UV tensile strength retention rate W. W = A / A0 × 100%. A0 is the initial tensile strength, and A is the tensile strength after UV aging.

[0048] ABS resin composites were heat aged at 120°C in a forced air drying oven for 30 days, then left at room temperature for 2 hours. The tensile strength was then tested and the UV tensile strength retention rate, Q, was calculated. Q = A1 / A0 × 100%. The tensile strength was then tested again, with each group of specimens tested three times. The average was taken and the UV tensile strength retention rate, W, was calculated. W = A / A0 × 100%. A0 is the initial tensile strength, and A is the tensile strength after heat aging.

[0049] Table 1 Strength test of ABS resin composite materials

[0050] Initial tensile strength (MPa) Tensile strength after UV aging (MPa) UV aging retention rate (%) Tensile strength after heat aging (MPa) Thermal aging retention rate (%) Example 1 38.74 36.85 95.12 35.06 90.50 Example 2 44.71 43.52 97.34 41.15 92.04 Example 3 39.89 39.32 98.57 37.04 92.86 Comparative Example 1 34.25 31.53 92.06 29.70 86.72 Comparative Example 2 36.17 33.34 92.18 31.49 87.06 Comparative Example 3 38.40 36.61 95.34 33.72 87.81 Comparative Example 4 36.88 34.26 92.90 33.24 90.13

[0051] After testing, the tensile strength of the ABS resin composite material of Comparative Example 1 is low, mainly because the compatibility between the ABS resin, ethylene-octene copolymer and nano-titanium dioxide is poor, which affects the mechanical properties of the material, and the dispersion of nano-titanium dioxide in the ABS resin is poor, which is not conducive to improving the UV aging resistance of the ABS resin, resulting in a large decrease in tensile strength after UV aging and a low retention rate. In addition, the heat resistance of the composite material is poor, and the retention rate of tensile strength after thermal aging is low.

[0052] In Examples 1 to 3, ethylene-octene copolymers were melt-grafted using styrene derivatives, and styrene polymer molecular chains were introduced into the side chains of POE, thereby improving the compatibility between POE and ABS resin, which is beneficial to improving the mechanical properties of the composite material. The introduced styrene polymer molecular chains contain carboxyl groups, which can interact with the surface of nano-titanium dioxide and be coated on the surface of nano-titanium dioxide, thereby improving the compatibility and dispersibility between nano-titanium dioxide and ABS resin, so that the ABS composite material has higher tensile strength. At the same time, nano-titanium dioxide is uniformly dispersed in the ABS material, significantly improving the UV resistance of the material, and the tensile strength retention rate after UV aging is high. The styrene polymer molecular chains of the side chains of POE contain high-temperature resistant imide rings, which are beneficial to improving the heat resistance of the composite material, and the tensile strength retention rate after heat aging is high.

[0053] In Comparative Example 2, styrene was used to melt-graft the ethylene-octene copolymer, thereby introducing a polystyrene molecular chain, improving the compatibility between POE and ABS resin, and facilitating improvement of the tensile strength of the composite material. However, the grafted POE does not contain a carboxyl group and cannot interact with the surface of the nano-titanium dioxide, making it difficult to improve the compatibility and dispersibility between the nano-titanium dioxide and the ABS resin. As a result, the tensile strength of the ABS composite material and the tensile strength retention rate after UV aging are lower than those in Example 1. The grafted POE also does not contain a high-temperature-resistant imide ring and has poor high-temperature resistance, resulting in a lower tensile strength after heat aging than in Example 1.

[0054] In Comparative Example 3, ethylene-octene copolymer was melt-grafted using 4-vinylbenzoic acid. The obtained grafted POE did not contain a high-temperature-resistant imide ring and had poor high-temperature resistance, resulting in a lower tensile strength after heat aging than that in Example 1.

[0055] The styrene derivative and the grafted POE of Comparative Example 4 do not contain a carboxyl group, and cannot improve the inability to interact with the surface of nano-titanium dioxide, making it difficult to improve the compatibility and dispersibility between nano-titanium dioxide and ABS resin, resulting in the tensile strength of the ABS composite material and the tensile strength retention rate after UV aging being lower than that of Example 1.

[0056] The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the technical concept of the present invention, various simple variations of the technical solution of the present invention may be made, including combining the various technical features in any other appropriate manner. These simple variations and combinations should also be regarded as disclosed in the present invention and fall within the scope of protection of the present invention.

Claims

1. A weather-resistant ABS resin composite material, characterized in that: The weather-resistant ABS resin composite material comprises 85-92 parts by weight of ABS resin, 8-15 parts by weight of grafted POE, 0.2-1 parts by weight of nano-titanium dioxide, and 0.1-0.3 parts by weight of an antioxidant; The preparation method of the grafted POE comprises the following steps: (1) Add glacial acetic acid, trimellitic anhydride, and 4-aminostyrene to a reaction vessel, stir for reaction, and then cool in an ice-water bath. Filter and wash the precipitate with water, and then recrystallize and purify it in dichloromethane to obtain a styrene derivative; Among them, the structural formula of the styrene derivative is: ； (2) Ethylene-octene copolymer, styrene derivative and diisopropylbenzene peroxide are mixed, melt-grafted and extruded in a screw extruder to obtain grafted POE.

2. The weather-resistant ABS resin composite material according to claim 1, characterized in that: The amount of trimellitic anhydride used in (1) is 100 parts by weight, and the amount of 4-aminostyrene is 62-68 parts by weight.

3. The weather-resistant ABS resin composite material according to claim 1, characterized in that: The reaction temperature in (1) is 120-130°C, and the reaction time is 12-18 hours.

4. The weather-resistant ABS resin composite material according to claim 1, characterized in that: The amount of the ethylene-octene copolymer in (2) is 100 parts by weight, the amount of the styrene derivative is 2-8 parts by weight, and the amount of dicumyl peroxide is 0.2-1 part by weight.

5. The weather-resistant ABS resin composite material according to claim 1, characterized in that: The temperature of the screw extruder zones 1-6 in (2) is 150-170°C, and the screw speed is 30-50 r / min.

6. A method for preparing a weather-resistant ABS resin composite material according to any one of claims 1 to 5, characterized in that: The preparation method comprises: mixing grafted POE and nano-titanium dioxide in a mixer once, then adding ABS resin and antioxidant, mixing again, and finally melting and extruding the materials in a screw extruder, and pelletizing to obtain a weather-resistant ABS resin composite material.

7. The method for preparing the weather-resistant ABS resin composite material according to claim 6, wherein: The temperature during the first mixing is 70-90° C., and the time is 60-90 min; the temperature during the second mixing is 70-90° C., and the time is 20-30 min.

8. The method for preparing the weather-resistant ABS resin composite material according to claim 6, wherein: During melt extrusion, the temperature of zones 1-6 is 180-225° C., and the screw speed is 200-300 r / min.

9. Use of the weather-resistant ABS resin composite material according to any one of claims 1 to 5 in automobile exterior parts.

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