ASA composite material and preparation method and application thereof in electric vehicle charging pile shell

Abstract

The present application relates to the technical field of polycarbonate ASA material, and discloses an ASA composite material and a preparation method and application thereof in an electric vehicle charging pile shell, wherein polycarbonate, ASA acrylonitrile-styrene-acrylate copolymer, poly(acrylonitrile-acrylate benzyl carbonate), an antioxidant and a processing aid are mixed and melt-extruded to obtain the ASA composite material.Poly(acrylonitrile-acrylate benzyl carbonate) contains the same carbonate group as polycarbonate, and the compatibility of the two is very good, and contains polyacrylonitrile and polyacrylate block molecular chains, and the side chain contains a benzene ring structure, which is similar to the structure of ASA acrylonitrile-styrene-acrylate copolymer, thereby playing a role of compatibilizing polycarbonate and ASA, so that the material has higher impact strength, tensile strength and elongation at break.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of polycarbonate ASA material, in particular to an ASA composite material and a preparation method thereof and application of the ASA composite material in an electric vehicle charging pile shell. BACKGROUND

[0002] ASA acrylonitrile-styrene-acrylate copolymer has good cold resistance, toughness and strength, and does not contain an alkenyl group, has excellent weather resistance, and is widely used in the fields of automobile charging piles, automobile interiors, electronics and electrical appliances, and buildings. The alloy material prepared by mixing ASA with polycarbonate, polymethyl methacrylate, polybutylene terephthalate and other materials has better mechanical properties.

[0003] ASA has poor compatibility with polycarbonate, and a compatibilizer such as styrene-maleic anhydride copolymer, maleic anhydride grafted ABS, etc. is usually added to improve the performance of the composite material. Patent No. CN109337327B discloses a weather-resistant matte PC / ASA alloy material, which is prepared by mixing bisphenol A polycarbonate resin, acrylate rubber-acrylonitrile-styrene graft copolymer, organic silicon toughening agent, compatibilizer ethylene-methyl acrylate-glycidyl methacrylate, etc. However, the compatibilizer has poor compatibilization effect, and the tensile strength of the alloy material is low. SUMMARY

[0004] In view of the deficiencies of the prior art, the present application 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] To solve the above technical problems, the technical scheme adopted by the present application is as follows: an ASA composite material and a preparation method thereof, 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 an antioxidant, and 0.36-0.5 parts by weight of a processing aid.

[0006] The preparation method of the ASA composite material is as follows:

[0007] (1) water, acrylonitrile, acrylate benzyl carbonate and an emulsifier are added to a reaction container, and then nitrogen is introduced after stirring, and azobisisobutyronitrile is added dropwise, and then filtered after stirring and reaction, washed with water and ethanol, and dried to obtain poly(acrylonitrile-acrylate benzyl carbonate).

[0008] (2) mixing polycarbonate, ASA acrylonitrile-styrene-acrylate copolymer, poly(acrylonitrile-acrylate benzyl carbonate), antioxidant, processing aid in a mixer, then melt extruding in a twin-screw extruder, the temperature of 1-6 zones is 210-260℃, the screw rotation speed is 200-400r / min, pelletizing, to obtain ASA composite material.

[0009] Preferably, the temperature of the reaction in (1) is 65-75℃, and the reaction time is 6-9h.

[0010] 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.

[0011] Preferably, the emulsifier in (1) is sodium dodecyl benzene sulfonate or sodium dodecyl sulfate.

[0012] Preferably, the antioxidant in (2) is antioxidant 1010 or antioxidant 1076.

[0013] Preferably, the processing aid in (2) is any one or combination of polyethylene wax, pentaerythritol stearate or ethylene bis-stearamide.

[0014] Preferably, the preparation method of acrylate benzyl carbonate is: adding dichloromethane, 84-102 parts by weight of hydroxyethyl acrylate monomer, 58-70 parts by weight of triethylamine into a reaction vessel, passing nitrogen, adding 100 parts by weight of benzyl chloroformate in an ice water bath, then stirring at 20-30℃ for 5-8h, filtering, distilling the filtrate under reduced pressure, separating by silica gel column chromatography, using petroleum ether and ethyl acetate solution as eluent, to obtain acrylate benzyl carbonate. The reaction formula is:

[0015] .

[0016] Preferably, the hydroxyethyl acrylate monomer is hydroxyethyl acrylate or hydroxyethyl methacrylate.

[0017] Preferably, the ASA composite material is applied to the shell of electric vehicle charging pile.

[0018] The application has the beneficial technical effects that: acrylonitrile and benzyl acrylate carbonate are subjected to copolymerization reaction to obtain poly(acrylonitrile-benzyl acrylate carbonate), which is mixed with polycarbonate, ASA, polyethylene wax and other auxiliaries as a compatilizer to obtain an ASA composite material, the poly(acrylonitrile-benzyl acrylate carbonate) contains the same carbonate group as polycarbonate, and has good compatibility with polycarbonate, and contains 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 copolymer, thereby playing a role of compatibilizing polycarbonate and ASA, so that the material has higher impact strength, tensile strength and elongation at break, and the prepared composite material has excellent mechanical properties and good practical application in electric vehicle charging pile shell and the like. BRIEF DESCRIPTION OF DRAWINGS

[0019] Figure 1 is the infrared spectrum of poly(acrylonitrile-benzyl acrylate carbonate) of Example 1. DETAILED DESCRIPTION

[0020] In order for those skilled in the art to better understand the present application, the technical solutions in the embodiments of the present application will be described below in conjunction with the embodiments of the present application. Obviously, the described embodiments are only a part of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor should fall within the scope of protection of the present application.

[0021] The following polycarbonate is an aromatic polycarbonate, the model number is EGN2030CK 9005, and the source is Dongguan Kaiyuan Plastic Raw Material Co., Ltd. The ASA resin model number is LURANASA37019, and the source is Guangzhou Hongcheng Plastic Co., Ltd. The styrene-maleic anhydride copolymer model number is SMA31123, and the source is Dongguan Xinmiao New Material Co., Ltd.

[0022] Example 1

[0023] (1) 900 mL of dichloromethane, 20.4 g of hydroxyethyl methacrylate, 11.6 g of triethylamine were added to a reaction container, nitrogen was introduced, 20 g of benzyl chloroformate was added in an ice water bath, and then stirred at 20°C for 8 h, filtered, the filtrate was distilled under reduced pressure, separated by silica gel column chromatography, and the eluent was petroleum ether and ethyl acetate solution to obtain benzyl acrylate carbonate. The structural formula is .

[0024] (2) Into a reaction vessel were added 300 mL of water, 26 g of acrylonitrile, 74 g of benzyl acrylate carbonate, 2.7 g of sodium dodecylbenzenesulfonate, stirred, and then nitrogen was bubbled therethrough. 1.4 g of azobisisobutyronitrile was added dropwise, and heated to 75°C. The reaction was stirred for 6 h, filtered, washed with water and ethanol, and dried to obtain poly(acrylonitrile-benzyl acrylate carbonate). Figure 1 stretching vibration peaks of ester group and carbonate group -C=0- were observed at 1714-1727 cm -1 -1, 1487-1613 cm -1 -1 were characteristic peaks of benzene ring skeleton, and 2247 cm -1 -1 was a characteristic peak of cyano group -CN-.

[0025] (3) 7.5 kg of polycarbonate, 2.5 kg of ASA acrylonitrile-styrene-acrylate copolymer, 0.2 kg of poly(acrylonitrile-benzyl acrylate carbonate), 23 g of antioxidant 1076, 21 g of polyethylene wax, and 23 g of ethylene bis-stearamide were mixed in a mixer, and then melt-extruded in a twin-screw extruder with a temperature of 210°C, 235°C, 250°C, 260°C, 260°C, and 260°C in zones 1-6, and a screw rotation speed of 300 r / min. The pellets were obtained, and an ASA composite material was obtained.

[0026] Example 2

[0027] (1) Into a reaction vessel were added 800 mL of dichloromethane, 16.8 g of hydroxyethyl acrylate, and 14 g of triethylamine. Nitrogen was bubbled therethrough, and 20 g of benzyl chloroformate was added in an ice water bath. The reaction was stirred at 30°C for 5 h, filtered, and the filtrate was distilled under reduced pressure. Poly(acrylonitrile-benzyl acrylate carbonate) was separated by silica gel column chromatography with a solvent of petroleum ether and ethyl acetate. .

[0028] (2) Into a reaction vessel were added 400 mL of water, 22 g of acrylonitrile, 78 g of benzyl acrylate carbonate, and 3.2 g of sodium dodecylbenzenesulfonate. Nitrogen was bubbled therethrough after stirring, 1 g of azobisisobutyronitrile was added dropwise, and heated to 65°C. The reaction was stirred for 9 h, filtered, washed with water and ethanol, and dried to obtain poly(acrylonitrile-benzyl acrylate carbonate).

[0029] (3) 7 kg of polycarbonate, 3 kg of ASA acrylonitrile-styrene-acrylate copolymer, 0.33 kg of poly(acrylonitrile-benzyl acrylate 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 with a temperature of 210°C, 235°C, 250°C, 260°C, 260°C, and 260°C in zones 1-6, and a screw rotation speed of 400 r / min. The pellets were obtained, and an ASA composite material was obtained.

[0030] Example 3

[0031] (1) Into a reaction vessel were added 400 mL of water, 36 g of acrylonitrile, 64 g of benzyl acrylate ester (same preparation method as Example 1), 2.4 g of sodium dodecyl sulfate, stirred, and then nitrogen was bubbled in, 1.6 g of azobisisobutyronitrile was added dropwise, and heated to 70°C, stirred for 9 h, filtered, washed with water and ethanol, and dried to obtain poly(acrylonitrile-benzyl acrylate ester).

[0032] (2) 6.5 kg of polycarbonate, 3.5 kg of ASA acrylonitrile-styrene-acrylate copolymer, 0.47 kg of poly(acrylonitrile-benzyl acrylate ester), 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 with a temperature of 210°C, 235°C, 250°C, 260°C, 260°C, and 260°C in zones 1-6, and a screw rotation speed of 200 r / min, and pelletized to obtain an ASA composite material.

[0033] Example 4

[0034] (1) Into a reaction vessel were added 400 mL of water, 31 g of acrylonitrile, 69 g of benzyl acrylate ester (same preparation method as Example 2), 3 g of sodium dodecylbenzenesulfonate, stirred, and then nitrogen was bubbled in, 1.3 g of azobisisobutyronitrile was added dropwise, and heated to 65°C, stirred for 9 h, filtered, washed with water and ethanol, and dried to obtain poly(acrylonitrile-benzyl acrylate ester).

[0035] (2) 6 kg of polycarbonate, 4 kg of ASA acrylonitrile-styrene-acrylate copolymer, 0.6 kg of poly(acrylonitrile-benzyl acrylate ester), 30 g of antioxidant 1010, 20 g of polyethylene wax, and 23 g of ethylene bis-stearamide were mixed in a mixer, and then melt-extruded in a twin-screw extruder with a temperature of 210°C, 235°C, 250°C, 260°C, 260°C, and 260°C in zones 1-6, and a screw rotation speed of 400 r / min, and pelletized to obtain an ASA composite material.

[0036] Comparative Example 1

[0037] (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 bis-stearamide were mixed in a mixer, and then melt-extruded in a twin-screw extruder with a temperature of 210°C, 235°C, 250°C, 260°C, 260°C, and 260°C in zones 1-6, and a screw rotation speed of 300 r / min, and pelletized to obtain an ASA composite material.

[0038] Comparative Example 2

[0039] (1) Into a reaction vessel, 300 mL of water, 26 g of acrylonitrile, 74 g of allyl phenyl carbonate (CAS No. 16308-68-2), 2.7 g of sodium dodecyl benzene sulfonate were added, stirred, and then nitrogen was bubbled. 1.4 g of azobisisobutyronitrile was added dropwise, and heated to 75°C, and stirred for 6 h. Filtration, washing with water and ethanol, and drying gave poly(acrylonitrile-allyl phenyl carbonate).

[0040] (2) 7.5 kg of polycarbonate, 2.5 kg of ASA acrylonitrile-styrene-acrylate copolymer, 0.2 kg of poly(acrylonitrile-allyl phenyl carbonate), 23 g of antioxidant 1076, 21 g of polyethylene wax, and 23 g of ethylene bis-stearamide were mixed in a mixer, and then melt-extruded in a twin-screw extruder, with the temperature of 1-6 zones being 210°C, 235°C, 250°C, 260°C, 260°C, 260°C, and the screw rotation speed being 300 r / min. Pellets were obtained, and an ASA composite material was obtained.

[0041] Comparative Example 3

[0042] (1) Into a reaction vessel, 900 mL of dichloromethane, 20.4 g of hydroxyethyl methacrylate, and 11.6 g of triethylamine were added, nitrogen was bubbled, and 20 g of isopropyl chloroformate was added in an ice water bath. Then, stirring was performed at 20°C for 8 h. Filtration, distillation of the filtrate under reduced pressure, and separation by silica gel column chromatography, with a petroleum ether and ethyl acetate solution as the eluent, gave isopropyl acrylate carbonate. The structural formula is .

[0043] (2) Into a reaction vessel, 300 mL of water, 26 g of acrylonitrile, 74 g of isopropyl acrylate carbonate, and 2.7 g of sodium dodecyl benzene sulfonate were added, stirred, and then nitrogen was bubbled. 1.4 g of azobisisobutyronitrile was added dropwise, and heated to 75°C, and stirred for 6 h. Filtration, washing with water and ethanol, and drying gave poly(acrylonitrile-isopropyl acrylate carbonate).

[0044] (3) 7.5 kg of polycarbonate, 2.5 kg of ASA acrylonitrile-styrene-acrylate copolymer, 0.2 kg of poly(acrylonitrile-isopropyl acrylate carbonate), 23 g of antioxidant 1076, 21 g of polyethylene wax, and 23 g of ethylene bis-stearamide were mixed in a mixer, and then melt-extruded in a twin-screw extruder, with the temperature of 1-6 zones being 210°C, 235°C, 250°C, 260°C, 260°C, 260°C, and the screw rotation speed being 300 r / min. Pellets were obtained, and an ASA composite material was obtained.

[0045] Comparative Example 4

[0046] (1) 300 mL of water, 26 g of acrylonitrile, 74 g of benzyl methacrylate (CAS No. 2495-37-6), 2.7 g of sodium dodecylbenzenesulfonate were added to a reaction vessel, stirred, and then nitrogen was introduced, 1.4 g of azobisisobutyronitrile was added dropwise, and heated to 75°C, stirred for 6 h, filtered, washed with water and ethanol, and dried to obtain poly(acrylonitrile-benzyl methacrylate).

[0047] (2) 7.5 kg of polycarbonate, 2.5 kg of ASA acrylonitrile-styrene-acrylate copolymer, 0.2 kg of poly(acrylonitrile-benzyl methacrylate), 23 g of antioxidant 1076, 21 g of polyethylene wax, and 23 g of ethylene bis-stearamide were mixed in a mixer, then melt-extruded in a twin-screw extruder, the temperature of 1-6 zones was 210°C, 235°C, 250°C, 260°C, 260°C, 260°C, the screw rotation speed was 300 r / min, and pelletized to obtain an ASA composite material.

[0048] Comparative Example 5

[0049] (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 bis-stearamide were mixed in a mixer, then melt-extruded in a twin-screw extruder, the temperature of 1-6 zones was 210°C, 235°C, 250°C, 260°C, 260°C, 260°C, the screw rotation speed was 300 r / min, and pelletized to obtain an ASA composite material.

[0050] The polycarbonate was injection molded into a test strip by an injection molding machine. The impact strength was tested according to the GB / T 1043.1-2008 standard. The tensile strength was tested according to the GB / T 1040.1-2018 standard.

[0051] Table 1 Properties of ASA Composite Material

[0052]

[0053] The compatibility between the polycarbonate of Comparative Example 1 and the ASA acrylonitrile-styrene-acrylate copolymer was poor, resulting in low impact strength, tensile strength, and elongation at break of the composite material.

[0054] The composite material of the embodiment 1-4 is added with poly(acrylonitrile-acrylate benzyl carbonate) as a compatibilizer, which contains the same carbonate group as polycarbonate, and has good compatibility with polycarbonate, and contains polyacrylonitrile and polyacrylate block molecular chains, and the side chain contains a benzene ring structure, which is similar to the structure of ASA acrylonitrile-styrene-acrylate copolymer, thereby playing a role of compatibilizing polycarbonate and ASA, and significantly improving the mechanical properties of the composite material, and having higher impact strength, tensile strength and elongation at break.

[0055] The comparative example 2 copolymerizes acrylonitrile and allyl phenyl carbonate to obtain poly(acrylonitrile-allyl phenyl carbonate), which does not contain polyacrylate block molecular chains, and has a large difference from the molecular chain structure of ASA, and has poor compatibilization effect on polycarbonate and ASA, thereby resulting in lower impact strength and other mechanical properties than the embodiment 1.

[0056] The comparative example 3 copolymerizes acrylonitrile and acrylate isopropyl carbonate to obtain poly(acrylonitrile-acrylate isopropyl carbonate), which does not contain a benzene ring structure, and has a large difference from the molecular chain structure of ASA, and has poor compatibilization effect on polycarbonate and ASA, thereby resulting in lower impact strength and other mechanical properties than the embodiment 1.

[0057] The comparative example 4 copolymerizes acrylonitrile and benzyl methacrylate to obtain poly(acrylonitrile-benzyl methacrylate), which does not contain a carbonate structure, and has poor compatibility with polycarbonate, and has poor compatibilization effect on polycarbonate and ASA, thereby resulting in lower impact strength and other mechanical properties of the material.

[0058] The comparative example 5 uses a conventional styrene-maleic anhydride copolymer as a compatibilizer, and the impact strength and other mechanical properties of the composite material are obviously lower than those of the embodiment 1, and the compatibilization effect is poor.

[0059] The above only describes the preferred embodiments of the present application, and does not limit the present application in any form. It should be noted that for ordinary skilled persons in the art, without departing from the principles of the present application, a number of improvements and refinements can be made, and these improvements and refinements should be considered as the protection scope of the present application.

Claims

1. An ASA composite material, characterized by, 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, 0.36-0.5 parts by weight of processing aid; The preparation method of the poly(acrylonitrile-acrylate benzyl carbonate) comprises the following steps: adding water, acrylonitrile, acrylate benzyl carbonate and emulsifier into a reaction container, stirring, then passing nitrogen, dropping azobisisobutyronitrile, filtering after stirring and reaction, washing, drying, and obtaining poly(acrylonitrile-acrylate benzyl carbonate). The structural formula of the acrylate benzyl carbonate is or .

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

3. The ASA composite of claim 1, wherein, The processing aid is any one or combination of polyethylene wax, pentaerythritol stearate or ethylene bis-stearamide.

4. The ASA composite of claim 1, wherein, The temperature of the reaction is 65-75℃, and the reaction time is 6-9h.

5. The ASA composite of claim 1, wherein, The amount of acrylonitrile is 22-36 parts by weight, the amount of acrylate benzyl carbonate is 64-78 parts by weight, and 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 of claim 5, wherein, The emulsifier is sodium dodecyl benzene sulfonate or sodium dodecyl sulfate.

7. The ASA composite of claim 5, wherein, The preparation method of the acrylate benzyl carbonate comprises the following steps: adding dichloromethane, 84-102 parts by weight of hydroxyethyl acrylate monomer, 58-70 parts by weight of triethylamine into a reaction container, passing nitrogen, adding 100 parts by weight of benzyl chloroformate in an ice water bath, then stirring and reacting at 20-30℃ for 5-8h, filtering, distilling the filtrate under reduced pressure, and separating by silica gel column chromatography to obtain acrylate benzyl carbonate.

8. The ASA composite of claim 7, wherein, The hydroxyethyl acrylate monomer is hydroxyethyl acrylate or hydroxyethyl methacrylate.

9. A process for the production of an ASA composite material as claimed in 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), antioxidant and processing aid in a mixer, then melt extruding in a twin-screw extruder, the temperature of 1-6 zones is 210-260℃, the screw rotation speed is 200-400r / min, and pelletizing to obtain the ASA composite material.

10. Application of the ASA composite material prepared by the preparation method of claim 9 in the outer shell of an electric vehicle charging pile.

Images