ABS composite material as well as preparation method and application thereof

Abstract

The invention discloses an ABS (Acrylonitrile Butadiene Styrene) composite material as well as a preparation method and application thereof. The ABS composite material comprises the following components in parts by weight: 70-85 parts of ABS resin; 10 to 20 parts of reinforcing fiber; 3-8 parts of a gas-assisted forming regulator; wherein the gas-assisted forming regulator is prepared from a styrene-N-phenylmaleimide-maleic anhydride copolymer and polymethyl methacrylate, and the mass ratio of the styrene-N-phenylmaleimide-maleic anhydride copolymer to the polymethyl methacrylate is (0.4-2.6): 1. The styrene-N-phenylmaleimide-maleic anhydride copolymer and polymethyl methacrylate in a specific mass ratio are added into an ABS resin system filled with reinforced fibers to serve as gas-assisted forming regulators, so that the gas-assisted forming effect of the ABS composite material can be effectively improved, and meanwhile, the ABS composite material has relatively good impact performance.

Description

Technical Field

[0001] This invention belongs to the field of polymer materials technology, specifically relating to an ABS composite material, its preparation method, and its application. Background Technology

[0002] When injection molding large, thin-walled parts, the solidification of the material at the front end prevents the holding pressure from reaching the back end, resulting in shrinkage or dimensional defects at the back. Gas-assisted injection molding is an advanced plastic processing technology. This technology is widely used in the automotive industry (such as door handles, dashboards, and grilles) and home appliances (such as washing machine drums and television housings) to overcome the problem of shrinkage or dimensional defects at the back end during the injection molding of large, thin-walled parts.

[0003] Acrylonitrile-butadiene-styrene copolymer (ABS resin) is a commonly used material in gas-assisted molding due to its good processability and surface gloss. To improve the rigidity and strength of the parts, reinforcing fibers are added to modify it. However, the introduction of reinforcing fibers usually results in a "cutting" effect of the fibers, which changes the melt flowability and makes it unsuitable for gas-assisted molding. Summary of the Invention

[0004] The purpose of this invention is to overcome the defects in the prior art where the melt flow rate of fiber-reinforced ABS composite materials is too low or too high, making them unsuitable for gas-assisted molding, and to provide an ABS composite material.

[0005] Another object of the present invention is to provide a method for preparing the ABS composite material.

[0006] Another object of the present invention is to provide applications of the ABS composite material.

[0007] To achieve the above objectives, the present invention employs the following technical solution: An ABS composite material comprises the following components in parts by weight: 70-85 parts of ABS resin; 10-20 parts of reinforcing fiber; 3-8 parts of gas-assisted molding modifier; The gas-assisted molding modifier comprises styrene-N-phenylmaleimide-maleic anhydride copolymer and polymethyl methacrylate, with a mass ratio of (0.4~2.6):1.

[0008] This invention provides an ABS composite material that improves the gas-assisted molding effect of the ABS composite material by adding a gas-assisted molding modifier to the ABS resin system filled with reinforcing fibers. Specifically, the gas-assisted molding modifier can coat the reinforcing fibers, reducing the interfacial separation between them and the ABS resin; and the gas-assisted molding modifier can physically entangle or slightly chemically crosslink with the ABS resin to form a three-dimensional network structure, which can ensure molding stability during gas-assisted molding.

[0009] It should be noted that the ABS resin mentioned in this invention is 70 to 85 parts, for example, but not limited to 70 parts, 71 parts, 72 parts, 73 parts, 74 parts, 75 parts, 76 parts, 77 parts, 78 parts, 79 parts, 80 parts, 81 parts, 82 parts, 83 parts, 84 parts, or 85 parts, etc., and the specific values ​​between the above-mentioned values ​​are not exhaustively listed in this invention due to space limitations and for the sake of brevity.

[0010] It should be noted that, in the ABS composite material described in this invention, the ABS resin content is preferably not less than 80 wt%.

[0011] Preferably, the melt flow rate of the ABS resin at 220°C and 10kg is 15~30g / 10min.

[0012] Specifically, the test standard for the melt flow rate of the ABS resin is ISO 1133-1:2022.

[0013] It should be noted that the gas-assisted molding regulator described in this invention is 3 to 8 parts, for example, but not limited to 3 parts, 3.2 parts, 3.5 parts, 3.8 parts, 4 parts, 4.2 parts, 4.5 parts, 4.8 parts, 5 parts, 5.2 parts, 5.5 parts, 5.8 parts, 6 parts, 6.2 parts, 6.5 parts, 6.8 parts, 7 parts, 7.2 parts, 7.5 parts, 7.8 parts, or 8 parts, etc., and the specific values ​​between the above values ​​are not exhaustively listed in this invention due to space limitations and for the sake of brevity.

[0014] Preferably, the content of the gas-assisted molding modifier in the ABS composite material is 2.8~8wt%.

[0015] It should be noted that the mass ratio of styrene-N-phenylmaleimide-maleic anhydride copolymer and polymethyl methacrylate in this invention is (0.4~2.6):1, for example, but not limited to, 0.4:1, 0.5:1, 0.6:1, 0.7:1, 0.8:1, 0.9:1, 1:1, 1.1:1, 1.2:1, 1.3:1, 1.4:1, 1.5:1, 1.6:1, 1.7:1, 1.8:1, 1.9:1, 2:1, 2.1:1, 2.2:1, 2.3:1, 2.4:1, 2.5:1, or 2.6:1, etc., and the specific values ​​between the above values ​​are not exhaustively listed in this invention due to space limitations and for the sake of brevity.

[0016] Preferably, the mass ratio of the styrene-N-phenylmaleimide-maleic anhydride copolymer to polymethyl methacrylate is (0.5~2.5):1.

[0017] More preferably, the mass ratio of styrene-N-phenylmaleimide-maleic anhydride copolymer to polymethyl methacrylate in the gas-assisted molding modifier is (1~2):1.

[0018] Preferably, the maleic anhydride content in the styrene-N-phenylmaleimide-maleic anhydride copolymer is 0.5~15wt%.

[0019] Preferably, the N-phenylmaleimide content in the styrene-N-phenylmaleimide-maleic anhydride copolymer is 15~60wt%.

[0020] Preferably, the styrene-N-phenylmaleimide-maleic anhydride copolymer has a melt flow rate of 1~90g / 10min at 265°C and 10kg.

[0021] Specifically, the test standard for the melt flow rate of the styrene-N-phenylmaleimide-maleic anhydride copolymer is ISO 1133-1:2022.

[0022] Preferably, the polymethyl methacrylate has a melt flow rate of 1~10g / 10min at 230°C and 3.8kg.

[0023] Specifically, the test standard for the melt flow rate of the polymethyl methacrylate described in this invention is ISO 1133-1:2022.

[0024] Preferably, the average retention length of the reinforcing fibers in the ABS composite material is 270~560μm.

[0025] More preferably, the average retention length of the reinforcing fibers in the ABS composite material is 300~500μm.

[0026] Specifically, the retention length of the reinforcing fiber is determined by a two-dimensional imaging method.

[0027] Specifically, the retention length of the reinforcing fiber can be adjusted by controlling the screw speed, screw combination, feeding method, etc.

[0028] Preferably, the reinforcing fibers comprise glass fibers and / or carbon fibers.

[0029] Preferably, the length of the glass fiber is 3~4.5mm.

[0030] Preferably, the average diameter of the glass fiber is 10~15μm.

[0031] Preferably, the ABS composite material further includes 1 to 5 parts of compatibilizer.

[0032] Preferably, the compatibilizer comprises ABS grafted maleic anhydride and / or ethylene-acrylate-maleic anhydride copolymer.

[0033] In some preferred embodiments, the maleic anhydride content in the ABS grafted with maleic anhydride is 8-12 wt%.

[0034] Preferably, without affecting the gas-assisted molding of the ABS composite material of the present invention, it further includes 0.2 to 3 parts of processing aids.

[0035] Preferably, the processing aids include, but are not limited to, antioxidants and / or lubricants.

[0036] Specifically, the antioxidant may be a commonly used antioxidant, such as, but not limited to, hindered phenolic antioxidants and / or phosphate antioxidants.

[0037] Specifically, the hindered phenolic antioxidant is one or more of N,N'-hexamethylene bis(3,5-di-tert-butyl-4-hydroxyphenylpropionamide) (Irganox 1098), pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (Irganox 1010), 1,6-hexanediol bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (Irganox 259), octadecyl β-(4-hydroxy-3,5-di-tert-butylphenyl)propionate (Irganox 1076), or 3,9-bis{2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)acrylic acid]-1,1-dimethyl}-2,4,8,10-tetraoxaspirocycloundecane (ADK AO-80).

[0038] The phosphate ester antioxidant is one or more of tris(2,4-di-tert-butylphenyl) phosphite (Irganox 168), bis(2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphate (PEP-36), or 627A.

[0039] Commonly used lubricants can be selected in this invention. For example, but not limited to, one or more of erucamide, oleamide, vinyl bis-stearamide, polysiloxane, calcium stearate, magnesium stearate, zinc stearate, or PE wax.

[0040] Preferably, the ABS composite material comprises the following components calculated in parts by weight: 72-80 parts of ABS resin; 12-18 parts of reinforcing fiber; 4-7 parts of gas-assisted molding modifier; 1-5 parts compatibilizer; Processing aids: 0.2-3 parts.

[0041] The present invention also provides a method for preparing the above-mentioned ABS composite material, comprising the following steps: S1. Mix all components except the reinforcing fiber in proportion to obtain a premix; S2. The premixed material described in step S1 is fed into the extruder through the main feed port, and the reinforcing fiber is fed into the extruder through the side feed port and / or the main feed port. The ABS composite material is obtained by melt extrusion, cooling and pelletizing.

[0042] Specifically, the extruder mentioned in step S2 is a twin-screw extruder.

[0043] Specifically, the temperature of the twin-screw extruder is 180~190℃ in zone one, 200~210℃ in zone two, 210~220℃ in zone three, 210~220℃ in zone four, 200~210℃ in zone five, and 210~220℃ at the die head.

[0044] Specifically, the screw speed of the twin-screw extruder is 180~550 rpm.

[0045] Specifically, the length-to-diameter ratio of the twin-screw extruder is 36:1 to 48:1.

[0046] The present invention also provides the application of the above-mentioned ABS composite material in the preparation of appliance housings and / or automotive parts, especially suitable for gas-assisted molding of thin-walled parts.

[0047] An air-assisted molding part is made of the above-mentioned ABS composite material, such as the back cover of a large-size LCD TV, a car door panel, a car interior, or a car bumper.

[0048] Compared with the prior art, the present invention has the following beneficial effects: This invention provides an ABS composite material in which a specific mass ratio of styrene-N-phenylmaleimide-maleic anhydride copolymer and polymethyl methacrylate are added to an ABS resin system filled with reinforcing fibers as an air-assisted molding modifier, which can effectively improve the air-assisted molding effect of the ABS composite material and also has good impact performance. Detailed Implementation

[0049] The present invention will be further described in detail below with reference to specific embodiments. These embodiments are only used to explain the present invention and are not intended to limit the scope of the present invention. Unless otherwise specified, the experimental methods used in the following embodiments are conventional methods; the materials and reagents used are commercially available unless otherwise specified.

[0050] 1. Raw materials used in each embodiment and comparative example: ABS resin: ABS resin 1: KF-730, with a melt flow rate of 25g / 10min at 220℃ and 10kg, manufactured by Liaoning Kingfa Science & Technology Co., Ltd. ABS resin 2: ABS PA-757, with a melt flow rate of 22g / 10min at 220℃ and 10kg, manufactured by Zhenjiang Qimei Chemical Co., Ltd. Reinforcing fibers: Reinforcing fiber 1: ECS11-3.0-T436W, length 3mm, average diameter 11μm, manufacturer is Taishan Fiberglass Co., Ltd.; Reinforcing fiber 2: ECS10-4.5-534A, with a length of 4.5mm and an average diameter of 10μm, manufactured by Jushi Fiberglass Co., Ltd. Styrene-N-phenylmaleimide-maleic anhydride copolymer 1: HW-320, manufactured by Jiaxing Huawen Chemical Co., Ltd. Styrene-N-phenylmaleimide-maleic anhydride copolymer 2: MS-NB, manufactured by Nippon Denka; Polymethyl methacrylate 1: CM-205, with a melt flow rate of 2 g / 10 min at 230℃ and 3.8 kg, is manufactured by Zhenjiang Qimei Chemical Co., Ltd. Polymethyl methacrylate 2: CM-207, with a melt flow rate of 8 g / 10 min at 230℃ and 3.8 kg, is manufactured by Zhenjiang Qimei Chemical Co., Ltd. Gas-assisted molding modifier 1: A compound of styrene-N-phenylmaleimide-maleic anhydride copolymer 1 and polymethyl methacrylate 1 in a mass ratio of 1:1; Gas-assisted molding modifier 2: a compound of styrene-N-phenylmaleimide-maleic anhydride copolymer 1 and polymethyl methacrylate 2 in a mass ratio of 1:1; Gas-assisted molding modifier 3: a compound of styrene-N-phenylmaleimide-maleic anhydride copolymer 2 and polymethyl methacrylate 1 in a mass ratio of 1:1; Gas-assisted molding modifier 4: A compound of styrene-N-phenylmaleimide-maleic anhydride copolymer 1 and polymethyl methacrylate 1 in a mass ratio of 0.5:1; Gas-assisted molding modifier 5: a compound of styrene-N-phenylmaleimide-maleic anhydride copolymer 1 and polymethyl methacrylate 1 in a mass ratio of 2:1; Gas-assisted molding modifier 6: a compound of styrene-N-phenylmaleimide-maleic anhydride copolymer 1 and polymethyl methacrylate 1 in a mass ratio of 2.5:1; Gas-assisted molding regulator 7: A compound of styrene-maleic anhydride copolymer (SMA 700, maleic anhydride content of 18wt%, manufactured by Jiaxing Huawen) and polymethyl methacrylate 1 in a mass ratio of 1:1; Gas-assisted molding modifier 8: A compound of styrene-N-phenylmaleimide-maleic anhydride copolymer 1 and SMMA (NAS 21, manufactured by INEOS Styrenex) in a mass ratio of 1:1; Gas-assisted molding modifier 9: A compound of styrene-N-phenylmaleimide-maleic anhydride copolymer 1 and polymethyl methacrylate 1 in a mass ratio of 0.2:1; Gas-assisted molding modifier 10: a compound of styrene-N-phenylmaleimide-maleic anhydride copolymer 1 and polymethyl methacrylate 1 in a mass ratio of 3:1; Compatibilizer: ABS grafted with maleic anhydride, SMA 800, maleic anhydride content is 8wt%, manufacturer is Jiaxing Huawen; Processing aids: Antioxidants: A compound of hindered phenolic antioxidants and phosphate ester antioxidants in a 1:1 mass ratio, all of which are commercially available; Lubricant: Vinyl bis-stearamide, commercially available; It should be noted that the same raw materials used in the parallel experiments of the embodiments and comparative examples in this invention are from the same source.

[0051] 2. In each embodiment and comparative example, the ABS composite material was prepared according to the formulation in Table 1 by the following preparation method: S1. Add all components except the reinforcing fiber to a high-speed mixer in proportion and mix at 800 rpm for 4 minutes to obtain a uniform premix. S2. The premixed material described in step S1 is fed into a twin-screw extruder through the main feed port, and the reinforcing fiber is fed into the twin-screw extruder through the side feed port / main feed port. After melt extrusion, cooling, and pelletizing, ABS composite material is obtained. The temperature of the twin-screw extruder is 185℃ in zone 1, 205℃ in zone 2, 215℃ in zone 3, 215℃ in zone 4, 205℃ in zone 5, and 215℃ in the die head. The length-to-diameter ratio of the twin-screw extruder is 40:1. The retention length of the reinforcing fiber is adjusted by adjusting the screw speed and feeding method.

[0052] 3. Performance Testing: (1) Gas-assisted molding effect test: The ABS composite materials prepared in each example and comparative example were put into the injection molding machine and injected into square plates of 100×100×1mm and 100×100×1.5mm respectively. The molding temperature was 220℃, the injection pressure was 50%, and the injection speed was 50%. Gas-assisted molding was used, and the appearance of the front of the square plate was observed. If there was blow-through or shrinkage on the front, it was considered that the gas-assisted molding effect was not good.

[0053] (2) Notched impact strength test: The ABS composite materials prepared in each example and comparative example were tested according to standard ISO 180-2024, and the notch type was type 1A.

[0054] Examples 1-13 and Comparative Examples 1-7 Table 1. Amounts (parts by weight) and properties of each component in the ABS composite material in each embodiment.

[0055] Table 2. Amounts (parts by weight) and properties of each component in the ABS composite materials of each comparative example.

[0056] As shown in Table 1, the ABS composite material prepared by this invention has good gas-assisted molding effect and good notched impact performance. Specifically, the gas-assisted molding effect is good at a thickness of 1.5 mm, and preferably good at a thickness of 1 mm; the notched impact performance is ≥8 KJ / m. 2 Preferably ≥9.5KJ / m 2 .

[0057] As can be seen from Comparative Examples 1-4 and Comparative Example 7, if other substances are used to replace the gas-assisted molding modifier of the present invention, or if the mass ratio of styrene-N-phenylmaleimide-maleic anhydride copolymer and polymethyl methacrylate in the gas-assisted molding modifier is too low or too high, the resulting ABS composite material cannot be used for gas-assisted molding.

[0058] As can be seen from Comparative Examples 5 and 6, if the amount of gas-assisted molding modifier added is too much or too little, the resulting ABS composite material cannot be used for gas-assisted molding.

[0059] Obviously, the above embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not intended to limit the implementation of the present invention. Those skilled in the art can make other variations or modifications based on the above description. It is neither necessary nor possible to exhaustively describe all embodiments here. Any modifications, equivalent substitutions, and improvements made within the spirit and principles of the present invention should be included within the scope of protection of the claims of the present invention.

Claims

1. An ABS composite material, characterized in that, Includes the following components, calculated in parts by weight: 70-85 parts of ABS resin; 10-20 parts of reinforcing fiber; 3-8 parts of gas-assisted molding modifier; The gas-assisted molding modifier comprises styrene-N-phenylmaleimide-maleic anhydride copolymer and polymethyl methacrylate, with a mass ratio of (0.4~2.6):

1.

2. The ABS composite material according to claim 1, characterized in that, The mass ratio of styrene-N-phenylmaleimide-maleic anhydride copolymer to polymethyl methacrylate in the gas-assisted molding modifier is (0.5~2.5):1; preferably, the mass ratio of styrene-N-phenylmaleimide-maleic anhydride copolymer to polymethyl methacrylate in the gas-assisted molding modifier is (1~2):

1.

3. The ABS composite material according to claim 1, characterized in that, The retention length of the reinforcing fibers in the ABS composite material is 270~560μm; preferably, the retention length of the reinforcing fibers in the ABS composite material is 300~500μm.

4. The ABS composite material according to claim 1, characterized in that, The melt flow rate of the ABS resin at 220°C and 10 kg is 15~30 g / 10 min.

5. The ABS composite material according to claim 1, characterized in that, Satisfy at least one of the following: (a) The maleic anhydride content in the styrene-N-phenylmaleimide-maleic anhydride copolymer is 0.5~15wt%; (b) The melt flow rate of the polymethyl methacrylate at 230°C and 3.8 kg is 1~10 g / 10 min.

6. The ABS composite material according to claim 1, characterized in that, At least one of the following three conditions must be met: (a) It also includes 1 to 5 parts of a compatibilizer; said compatibilizer includes ABS grafted maleic anhydride and / or ethylene-acrylate-maleic anhydride copolymer; (b) The reinforcing fibers include glass fibers and / or carbon fibers; (c) It also includes 0.2 to 3 parts of processing aids; said processing aids include antioxidants and / or lubricants.

7. A method for preparing the ABS composite material according to any one of claims 1 to 6, characterized in that, Includes the following steps: S1. Mix all components except the reinforcing fiber in proportion to obtain a premix; S2. The premixed material described in step S1 is fed into the extruder through the main feed port, and the reinforcing fiber is fed into the extruder through the side feed port. After melt extrusion, cooling, and pelletizing, ABS composite material is obtained.

8. A gas-assisted molding modifier, characterized in that, The gas-assisted molding modifier comprises styrene-N-phenylmaleimide-maleic anhydride copolymer and polymethyl methacrylate, with a mass ratio of (0.4~2.6):

1.

9. The gas-assisted molding modifier of claim 8 is used to adjust the gas-assisted molding properties of glass fiber reinforced ABS composite materials, characterized in that, The glass fiber reinforced ABS composite material comprises the following components in parts by weight: 70-85 parts of ABS resin; 10-20 parts of reinforcing fiber; 3-8 parts of gas-assisted molding modifier.

10. A component, characterized in that, It is prepared using the ABS composite material described in any one of claims 1 to 6.

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