ASA (Acrylonitrile Styrene Acrylate) composite material, preparation method and application of ASA composite material in shell of electric vehicle charging pile

Abstract

The invention relates to the technical field of polycarbonate ASA materials, and discloses an ASA composite material, a preparation method and application of the ASA composite material in an electric vehicle charging pile shell. Polycarbonate, ASA acrylonitrile-styrene-acrylate copolymer, poly (acrylonitrile-acrylate benzyl carbonate), an antioxidant and a processing aid are mixed and subjected to melt extrusion; the ASA composite material is obtained. Poly (acrylonitrile-acrylate benzyl carbonate) contains a carbonate group which is the same as that of polycarbonate, the polycarbonate and the poly (acrylonitrile-acrylate benzyl carbonate) have good compatibility, and contain polyacrylonitrile and polyacrylate block molecular chains, and the side chain contains a benzene ring structure which is similar to the structure of an ASA acrylonitrile-styrene-acrylate copolymer, so that the effect of compatibilizing the polycarbonate and the ASA is achieved; therefore, the material has higher impact strength, tensile strength and elongation at break.

Description

Technical Field

[0001] The present invention relates to the technical field of polycarbonate (ASA) materials, in particular to an ASA composite material, a preparation method thereof, and application thereof in an electric vehicle charging pile casing. Background Art

[0002] ASA acrylonitrile-styrene-acrylate copolymer has excellent cold resistance, toughness, and strength, and does not contain olefin groups, resulting in excellent weather resistance. It is widely used in automotive charging stations, automotive interiors, electronics, and construction. ASA is mixed with materials such as polycarbonate, polymethyl methacrylate, and polybutylene terephthalate to produce alloys with improved mechanical properties.

[0003] ASA and polycarbonate have poor compatibility, necessitating the addition of compatibilizers to enhance the composite's performance, such as styrene-maleic anhydride copolymer and maleic anhydride-grafted ABS. Patent publication number CN109337327B discloses a weather-resistant matte PC / ASA alloy material. This material is obtained by mixing bisphenol A polycarbonate resin, an acrylate rubber-acrylonitrile-styrene graft copolymer, an organosilicon toughening agent, and a compatibilizer, ethylene-methyl acrylate-glycidyl methacrylate. However, the compatibilizer's compatibilizing effect is poor, resulting in low tensile strength and other properties of the alloy. Summary of the Invention

[0004] In view of the deficiencies of the prior art, the present invention provides an ASA composite material and a preparation method, which solves the problem of poor compatibility between polycarbonate and ASA and improves the mechanical strength of the polycarbonate-ASA composite material.

[0005] In order to solve the above technical problems, the technical solution adopted by the present invention is: an ASA composite material and a preparation method, the ASA composite material comprising 60-75 parts by weight of polycarbonate, 25-40 parts by weight of ASA acrylonitrile-styrene-acrylate copolymer, 2-6 parts by weight of poly(acrylonitrile-acrylate benzyl carbonate), 0.2-0.3 parts by weight of antioxidant, and 0.36-0.5 parts by weight of processing aid.

[0006] The preparation method of ASA composite material is as follows: (1) Add water, acrylonitrile, benzyl acrylate carbonate, and an emulsifier into a reaction vessel, stir, and introduce nitrogen, add azobisisobutyronitrile dropwise, stir to react, filter, wash with water and ethanol, and dry to obtain poly(acrylonitrile-benzyl acrylate carbonate).

[0007] (2) Polycarbonate, ASA acrylonitrile-styrene-acrylate copolymer, poly(acrylonitrile-acrylate benzyl carbonate), antioxidant, and processing aid are mixed in a mixer, and then melt-extruded in a twin-screw extruder at a temperature of 210-260°C in zones 1-6 and a screw speed of 200-400 r / min, and pelletized to obtain an ASA composite material.

[0008] Preferably, the reaction temperature in (1) is 65-75°C and the reaction time is 6-9h.

[0009] Preferably, the amount of acrylonitrile in (1) is 22-36 parts by weight, the amount of acrylate benzyl carbonate is 64-78 parts by weight, the amount of emulsifier is 2.4-3.2 parts by weight, and the amount of azobisisobutyronitrile is 1-1.6 parts by weight.

[0010] Preferably, the emulsifier in (1) is sodium dodecylbenzenesulfonate or sodium dodecyl sulfate.

[0011] Preferably, the antioxidant in (2) is antioxidant 1010 or antioxidant 1076.

[0012] Preferably, the processing aid in (2) is any one or a combination of polyethylene wax, pentaerythritol stearate or ethylene bisstearamide.

[0013] Preferably, the preparation method of benzyl acrylate carbonate is as follows: dichloromethane, 84-102 parts by weight of hydroxyethyl acrylate monomer, and 58-70 parts by weight of triethylamine are added to a reaction vessel, nitrogen is introduced, 100 parts by weight of benzyl chloroformate is added in an ice-water bath, and then the mixture is stirred at 20-30° C. for 5-8 hours, filtered, and the filtrate is distilled under reduced pressure and separated by silica gel column chromatography using a petroleum ether and ethyl acetate solution as the eluent to obtain benzyl acrylate carbonate. The reaction formula is: .

[0014] Preferably, the hydroxyethyl acrylate monomer is hydroxyethyl acrylate or hydroxyethyl methacrylate.

[0015] Preferably, the ASA composite material is used in the housing of an electric vehicle charging pile.

[0016] The beneficial technical effects of the present invention include: copolymerization of acrylonitrile and benzyl acrylate carbonate to obtain poly(acrylonitrile-benzyl acrylate carbonate), which is mixed with polycarbonate, ASA, polyethylene wax and other additives as a compatibilizer to obtain an ASA composite material. The poly(acrylonitrile-benzyl acrylate carbonate) contains the same carbonate group as polycarbonate, and the two have good compatibility. The poly(acrylonitrile-benzyl acrylate carbonate) also contains polyacrylonitrile and polyacrylate block molecular chains, and the side chain contains a benzene ring structure, which is similar to the structure of the ASA acrylonitrile-styrene-acrylate copolymer, thereby compatibilizing the polycarbonate and ASA, and making the material have higher impact strength, tensile strength and elongation at break. The prepared composite material has excellent mechanical properties and has good practical applications in electric vehicle charging pile casings and other aspects. BRIEF DESCRIPTION OF THE DRAWINGS

[0017] Figure 1 This is the infrared spectrum of poly(acrylonitrile-benzyl acrylate carbonate) of Example 1. DETAILED DESCRIPTION

[0018] In order to enable those skilled in the art to better understand the solutions of the present invention, the technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention. Obviously, the embodiments described 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 creative efforts should fall within the scope of protection of the present invention.

[0019] The following polycarbonates are aromatic polycarbonates, model EGN2030CK 9005, sourced from Dongguan Kaiyuan Plastic Materials Co., Ltd. The ASA resin model is LURANASA37019, sourced from Guangzhou Hongcheng Plastics Co., Ltd. The styrene-maleic anhydride copolymer model is SMA31123, sourced from Dongguan Xinmiao New Materials Co., Ltd.

[0020] Example 1 (1) Add 900 mL of dichloromethane, 20.4 g of hydroxyethyl methacrylate, and 11.6 g of triethylamine to a reaction vessel, introduce nitrogen, add 20 g of benzyl chloroformate in an ice-water bath, and then stir and react at 20°C for 8 hours. Filter, distill the filtrate under reduced pressure, and separate by silica gel column chromatography using petroleum ether and ethyl acetate solution as eluent to obtain benzyl acrylate carbonate. The structural formula is .

[0021] (2) Add 300 mL of water, 26 g of acrylonitrile, 74 g of benzyl acrylate carbonate, and 2.7 g of sodium dodecylbenzenesulfonate to a reaction vessel, stir, and introduce nitrogen. Add 1.4 g of azobisisobutyronitrile dropwise, and heat to 75°C. Stir and react for 6 h. Filter, wash with water and ethanol, and dry to obtain poly(acrylonitrile-benzyl acrylate carbonate). Figure 1 In the infrared spectrum, 1714-1727 cm -1 It is the stretching vibration peak of ester group and carbonate group -C=O-. 1487-1613cm -1 It is the characteristic peak of the benzene ring skeleton, 2247cm -1 It is the characteristic peak of cyano -CN-.

[0022] (3) 7.5 kg of polycarbonate, 2.5 kg of ASA acrylonitrile-styrene-acrylate copolymer, 0.2 kg of poly(acrylonitrile-acrylate benzyl carbonate), 23 g of antioxidant 1076, 21 g of polyethylene wax, and 23 g of ethylene bisstearamide were mixed in a mixer and then melt-extruded in a twin-screw extruder with the temperatures in zones 1-6 being 210°C, 235°C, 250°C, 260°C, 260°C, and 260°C at a screw speed of 300 r / min. The mixture was pelletized to obtain an ASA composite material.

[0023] Example 2 (1) Add 800 mL of dichloromethane, 16.8 g of hydroxyethyl acrylate, and 14 g of triethylamine to a reaction vessel, introduce nitrogen, add 20 g of benzyl chloroformate in an ice-water bath, and then stir and react at 30°C for 5 hours, filter, and distill the filtrate under reduced pressure. Separate by silica gel column chromatography with petroleum ether and ethyl acetate solution as eluent to obtain benzyl acrylate carbonate. The structural formula is .

[0024] (2) Add 400 mL of water, 22 g of acrylonitrile, 78 g of benzyl acrylate carbonate, and 3.2 g of sodium dodecylbenzenesulfonate to a reaction vessel, stir, and introduce nitrogen. Add 1 g of azobisisobutyronitrile dropwise, and heat to 65°C. Stir and react for 9 h. Filter, wash with water and ethanol, and dry to obtain poly(acrylonitrile-benzyl acrylate carbonate).

[0025] (3) 7 kg of polycarbonate, 3 kg of ASA acrylonitrile-styrene-acrylate copolymer, 0.33 kg of poly(acrylonitrile-acrylate benzyl carbonate), 20 g of antioxidant 1076, 21 g of polyethylene wax, and 15 g of pentaerythritol stearate were mixed in a mixer and then melt-extruded in a twin-screw extruder at temperatures of 210°C, 235°C, 250°C, 260°C, 260°C, and 260°C in zones 1-6 at a screw speed of 400 r / min. The mixture was pelletized to obtain an ASA composite material.

[0026] Example 3 (1) 400 mL of water, 36 g of acrylonitrile, 64 g of benzyl acrylate carbonate (prepared in the same manner as in Example 1), and 2.4 g of sodium lauryl sulfate were added to a reaction vessel, stirred, and nitrogen was introduced. 1.6 g of azobisisobutyronitrile was added dropwise, and the mixture was heated to 70°C and stirred for 9 h. The mixture was filtered, washed with water and ethanol, and dried to obtain poly(acrylonitrile-benzyl acrylate carbonate).

[0027] (2) 6.5 kg of polycarbonate, 3.5 kg of ASA acrylonitrile-styrene-acrylate copolymer, 0.47 kg of poly(acrylonitrile-acrylate benzyl carbonate), 30 g of antioxidant 1010, 24 g of polyethylene wax, and 26 g of pentaerythritol stearate were mixed in a mixer and then melt-extruded in a twin-screw extruder at temperatures of 210°C, 235°C, 250°C, 260°C, 260°C, and 260°C in zones 1-6 at a screw speed of 200 r / min. The mixture was pelletized to obtain an ASA composite material.

[0028] Example 4 (1) 400 mL of water, 31 g of acrylonitrile, 69 g of benzyl acrylate carbonate (prepared in the same manner as in Example 2), and 3 g of sodium dodecylbenzenesulfonate were added to a reaction vessel, stirred, and nitrogen was introduced. 1.3 g of azobisisobutyronitrile was added dropwise, and the mixture was heated to 65°C and stirred for 9 h. The mixture was filtered, washed with water and ethanol, and dried to obtain poly(acrylonitrile-benzyl acrylate carbonate).

[0029] (2) 6 kg of polycarbonate, 4 kg of ASA acrylonitrile-styrene-acrylate copolymer, 0.6 kg of poly(acrylonitrile-acrylate benzyl carbonate), 30 g of antioxidant 1010, 20 g of polyethylene wax, and 23 g of ethylene bisstearamide were mixed in a mixer and then melt-extruded in a twin-screw extruder with the temperatures of zones 1-6 being 210°C, 235°C, 250°C, 260°C, 260°C, and 260°C, and the screw speed being 400 r / min. The mixture was pelletized to obtain an ASA composite material.

[0030] Comparative Example 1 (1) 7.5 kg of polycarbonate, 2.5 kg of ASA acrylonitrile-styrene-acrylate copolymer, 23 g of antioxidant 1076, 21 g of polyethylene wax, and 23 g of ethylene bisstearamide were mixed in a mixer and then melt-extruded in a twin-screw extruder with the temperatures in zones 1-6 being 210°C, 235°C, 250°C, 260°C, 260°C, and 260°C at a screw speed of 300 r / min. The mixture was pelletized to obtain an ASA composite material.

[0031] Comparative Example 2 (1) Add 300 mL of water, 26 g of acrylonitrile, 74 g of allylphenyl carbonate (CAS No. 16308-68-2), and 2.7 g of sodium dodecylbenzenesulfonate to a reaction vessel, stir, and introduce nitrogen. Add 1.4 g of azobisisobutyronitrile dropwise, and heat to 75°C. Stir and react for 6 h, filter, wash with water and ethanol, and dry to obtain poly(acrylonitrile-allylphenyl carbonate).

[0032] (2) 7.5 kg of polycarbonate, 2.5 kg of ASA acrylonitrile-styrene-acrylate copolymer, 0.2 kg of poly(acrylonitrile-allylphenyl carbonate), 23 g of antioxidant 1076, 21 g of polyethylene wax, and 23 g of ethylene bisstearamide were mixed in a mixer and then melt-extruded in a twin-screw extruder with the temperatures in zones 1-6 being 210°C, 235°C, 250°C, 260°C, 260°C, and 260°C, and the screw speed being 300 r / min. The mixture was pelletized to obtain an ASA composite material.

[0033] Comparative Example 3 (1) Add 900 mL of dichloromethane, 20.4 g of hydroxyethyl methacrylate, and 11.6 g of triethylamine to a reaction vessel, introduce nitrogen, add 20 g of isopropyl chloroformate in an ice-water bath, and then stir and react at 20°C for 8 hours. Filter, distill the filtrate under reduced pressure, and separate it by silica gel column chromatography using petroleum ether and ethyl acetate solution as eluent to obtain isopropyl acrylate carbonate. The structural formula is .

[0034] (2) Add 300 mL of water, 26 g of acrylonitrile, 74 g of isopropyl acrylate carbonate, and 2.7 g of sodium dodecylbenzenesulfonate to a reaction vessel, stir, and introduce nitrogen. Add 1.4 g of azobisisobutyronitrile dropwise, and heat to 75°C. Stir and react for 6 h. Filter, wash with water and ethanol, and dry to obtain poly(acrylonitrile-isopropyl acrylate carbonate).

[0035] (3) 7.5 kg of polycarbonate, 2.5 kg of ASA acrylonitrile-styrene-acrylate copolymer, 0.2 kg of poly(acrylonitrile-acrylate isopropyl carbonate), 23 g of antioxidant 1076, 21 g of polyethylene wax, and 23 g of ethylene bisstearamide were mixed in a mixer and then melt-extruded in a twin-screw extruder with the temperatures in zones 1-6 being 210°C, 235°C, 250°C, 260°C, 260°C, and 260°C at a screw speed of 300 r / min. The mixture was pelletized to obtain an ASA composite material.

[0036] Comparative Example 4 (1) Add 300 mL of water, 26 g of acrylonitrile, 74 g of benzyl methacrylate (CAS No. 2495-37-6), and 2.7 g of sodium dodecylbenzenesulfonate to a reaction vessel, stir, and introduce nitrogen. Add 1.4 g of azobisisobutyronitrile dropwise, and heat to 75°C. Stir and react for 6 h. Filter, wash with water and ethanol, and dry to obtain poly(acrylonitrile-benzyl acrylate).

[0037] (2) 7.5 kg of polycarbonate, 2.5 kg of ASA acrylonitrile-styrene-acrylate copolymer, 0.2 kg of poly(acrylonitrile-benzyl acrylate), 23 g of antioxidant 1076, 21 g of polyethylene wax, and 23 g of ethylene bisstearamide were mixed in a mixer and then melt-extruded in a twin-screw extruder with the temperatures in zones 1-6 being 210°C, 235°C, 250°C, 260°C, 260°C, and 260°C, and the screw speed being 300 r / min. The mixture was pelletized to obtain an ASA composite material.

[0038] Comparative Example 5 (1) 7.5 kg of polycarbonate, 2.5 kg of ASA acrylonitrile-styrene-acrylate copolymer, 0.2 kg of styrene-maleic anhydride copolymer, 23 g of antioxidant 1076, 21 g of polyethylene wax, and 23 g of ethylene bisstearamide were mixed in a mixer and then melt-extruded in a twin-screw extruder with the temperatures of zones 1-6 being 210°C, 235°C, 250°C, 260°C, 260°C, and 260°C, and the screw speed being 300 r / min. The mixture was pelletized to obtain an ASA composite material.

[0039] Polycarbonate was injection molded into test specimens. Impact strength was tested according to GB / T 1043.1-2008. Tensile strength was tested according to GB / T 1040.1-2018.

[0040] Table 1 Properties of ASA composites

[0041] The compatibility between the polycarbonate of Comparative Example 1 and the ASA acrylonitrile-styrene-acrylate copolymer is very poor, resulting in low impact strength, tensile strength and elongation at break of the composite material.

[0042] Poly(acrylonitrile-benzyl acrylate carbonate) was added as a compatibilizer to the composite materials of Examples 1-4. Poly(acrylonitrile-benzyl acrylate carbonate) contains the same carbonate groups as polycarbonate, and the two are highly compatible. The composite materials also contain polyacrylonitrile and polyacrylate block molecular chains, and the side chains contain benzene ring structures, which are similar to the structure of ASA acrylonitrile-styrene-acrylate copolymers. This acts as a compatibilizer for polycarbonate and ASA, significantly improving the mechanical properties of the composite materials, resulting in higher impact strength, tensile strength, and elongation at break.

[0043] In Comparative Example 2, acrylonitrile and allyl phenyl carbonate were copolymerized to obtain poly(acrylonitrile-allyl phenyl carbonate) which did not contain polyacrylate block molecular chains and had a significant difference in molecular chain structure from ASA. It had a poor compatibilizing effect on polycarbonate and ASA, resulting in mechanical properties such as impact strength being lower than those in Example 1.

[0044] In Comparative Example 3, acrylonitrile and isopropyl acrylate carbonate were copolymerized to obtain poly(acrylonitrile-isopropyl acrylate carbonate) which did not contain a benzene ring structure and had a significant difference in molecular chain structure from ASA. It had a poor compatibilizing effect on polycarbonate and ASA, resulting in mechanical properties such as impact strength being lower than those in Example 1.

[0045] In Comparative Example 4, acrylonitrile and benzyl methacrylate were copolymerized to obtain poly(acrylonitrile-benzyl acrylate) which did not contain a carbonate structure, had low compatibility with polycarbonate, and had a poor compatibilizing effect on polycarbonate and ASA, resulting in low mechanical properties such as impact strength of the material.

[0046] In Comparative Example 5, conventional styrene-maleic anhydride copolymer was used as the compatibilizer. The mechanical properties of the composite material, such as impact strength, were significantly lower than those in Example 1, and the compatibilization effect was poor.

[0047] The above description is merely a preferred embodiment of the present invention and does not constitute any limitation thereto. It should be noted that those skilled in the art may make various improvements and modifications without departing from the principles of the present invention, and such improvements and modifications shall also be considered within the scope of protection of the present invention.

Claims

1. An ASA composite material, characterized in that The ASA composite material comprises 60-75 parts by weight of polycarbonate, 25-40 parts by weight of ASA acrylonitrile-styrene-acrylate copolymer, 2-6 parts by weight of poly(acrylonitrile-acrylate benzyl carbonate), 0.2-0.3 parts by weight of antioxidant, and 0.36-0.5 parts by weight of processing aid; The preparation method of poly(acrylonitrile-benzyl carbonate acrylate) comprises the following steps: adding water, acrylonitrile, benzyl carbonate acrylate, and an emulsifier into a reaction container, stirring, introducing nitrogen, adding azobisisobutyronitrile dropwise, stirring for reaction, filtering, washing, and drying to obtain poly(acrylonitrile-benzyl carbonate acrylate).

2. The ASA composite material according to claim 1, characterized in that The antioxidant is antioxidant 1010 or antioxidant 1076.

3. The ASA composite material according to claim 1, characterized in that The processing aid is any one or a combination of polyethylene wax, pentaerythritol stearate or ethylene bisstearamide.

4. The ASA composite material according to claim 1, characterized in that The reaction temperature is 65-75° C., and the reaction time is 6-9 h.

5. The ASA composite material according to claim 1, characterized in that The amount of acrylonitrile used is 22-36 parts by weight, the amount of acrylate benzyl carbonate is 64-78 parts by weight, the amount of emulsifier is 2.4-3.2 parts by weight, and the amount of azobisisobutyronitrile is 1-1.6 parts by weight.

6. The ASA composite material according to claim 5, characterized in that The emulsifier is sodium dodecylbenzenesulfonate or sodium dodecyl sulfate.

7. The ASA composite material according to claim 5, characterized in that The preparation method of the benzyl acrylate carbonate comprises the following steps: adding dichloromethane, 84-102 parts by weight of hydroxyethyl acrylate monomer, and 58-70 parts by weight of triethylamine into a reaction vessel, introducing nitrogen, adding 100 parts by weight of benzyl chloroformate in an ice-water bath, stirring the mixture at 20-30° C. for reaction for 5-8 hours, filtering the mixture, and distilling the filtrate under reduced pressure. The filtrate is then separated by silica gel column chromatography to obtain the benzyl acrylate carbonate.

8. The ASA composite material according to claim 7, characterized in that The hydroxyethyl acrylate monomer is hydroxyethyl acrylate or hydroxyethyl methacrylate.

9. A method for preparing the ASA composite material according to any one of claims 1 to 8, characterized in that: The preparation method comprises the following steps: mixing polycarbonate, ASA acrylonitrile-styrene-acrylate copolymer, poly(acrylonitrile-acrylate benzyl carbonate), an antioxidant, and a processing aid in a mixer, then melt-extruding in a twin-screw extruder, with the temperature in zones 1-6 being 210-260°C and the screw speed being 200-400 r / min, and pelletizing to obtain an ASA composite material.

10. Use of the ASA composite material obtained by the preparation method according to claim 9 in the housing of an electric vehicle charging pile.

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