Anti-static ASA composite material, preparation method thereof and application of anti-static ASA composite material in communication equipment shell

Abstract

The invention relates to the technical field of plastics, and discloses an anti-static ASA composite material, a preparation method thereof and application of the anti-static ASA composite material in a communication equipment shell. The antistatic ASA composite material is prepared from the following raw materials in parts by weight: 60 to 80 parts of polycarbonate, 20 to 40 parts of acrylonitrile-styrene-acrylate copolymer, 0.3 to 1.5 parts of polyester grafted graphene, 0.3 to 0.5 part of processing aid and the like. Graphene has good compatibility in the polycarbonate-ASA composite material, the impact strength and other mechanical properties of the composite material are improved, graphene is uniformly dispersed in the composite material, the volume resistivity is reduced, the antistatic performance is improved, and the composite material has better practical application in the aspect of antistatic communication equipment plastic shells.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of plastics, in particular to an anti-static ASA composite material, a preparation method thereof and application thereof in a communication device shell. BACKGROUND

[0002] Acrylonitrile-styrene-acrylate copolymer (ASA) has high toughness, excellent mechanical properties, good high-temperature resistance and certain anti-static performance, and is widely used in communication device plastic shells, charging pile shells, automotive interiors and the like. Blending and modifying ASA with polycarbonate, polyvinyl chloride and other plastics can improve the toughness, impact strength and other properties of the plastics.

[0003] Polycarbonate has high strength, high transparency and excellent ultraviolet resistance, and is widely used. However, the toughness and anti-static performance of polycarbonate are poor. Adding impact-resistant resins, nano-particles and other fillers can improve the toughness and anti-static performance of polycarbonate. Graphene has excellent mechanical properties and strong conductivity, and has important applications in the reinforcement and anti-static modification of plastics and the like. Solving the problem of graphene agglomeration and improving the compatibility between graphene and ASA, polycarbonate and other materials are research difficulties. Patent No. CN114591588B discloses a PC / ASA composite material prepared from polycarbonate PC resin, ASA resin, graphene, flame retardant, maleic anhydride grafted polyethylene and the like, which has good notched impact strength, flame retardant performance and wave absorption performance. However, the anti-static performance of the PC / ASA composite material is poor. SUMMARY

[0004] In view of the deficiencies of the prior art, the present application provides an anti-static ASA composite material and a preparation method thereof, which solves the problem of poor dispersibility of graphene in ASA and polycarbonate composite materials, and improves the anti-static and mechanical properties of the composite material.

[0005] To solve the above technical problems, the technical scheme adopted by the present application is as follows: an anti-static ASA composite material and a preparation method thereof, the raw materials of the anti-static ASA composite material include 60-80 parts by weight of polycarbonate, 20-40 parts by weight of acrylonitrile-styrene-acrylate copolymer, 0.3-1.5 parts by weight of polyester grafted graphene, 0.15-0.25 parts by weight of antioxidant, and 0.3-0.5 parts by weight of processing aid.

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

[0007] (1) adding triethylamine, bisphenol A, N,N-bis(2-hydroxyethyl)-3-aminopropionitrile into N,N-dimethylformamide, and adding diacyl chloride monomer (the structural formula is ), and then adding graphene oxide, N,N-dimethylformamide to conduct grafting reaction, and then filtering, washing with N,N-dimethylformamide and water in sequence, and drying to obtain the polyester grafted graphene.

[0008] .

[0009] (2) mixing polycarbonate, acrylonitrile-styrene-acrylate copolymer, polyester grafted graphene, antioxidant, and processing aid in a mixing machine, and then melt-extruding the materials in a twin-screw extruder, and pelletizing to obtain the antistatic ASA composite material.

[0010] Preferably, the antioxidant is antioxidant 1010 or antioxidant 1076; and the processing aid is any one or combination of polyethylene wax, pentaerythritol stearate, or ethylene bis-stearamide.

[0011] Preferably, the temperature of the polymerization reaction in (1) is 20-35℃, and the reaction time is 6-10h.

[0012] Preferably, the temperature of the grafting reaction in (1) is 20-50℃, and the reaction time is 18-24h.

[0013] Preferably, the ratio of triethylamine, bisphenol A, N,N-bis(2-hydroxyethyl)-3-aminopropionitrile, diacyl chloride monomer, and graphene oxide in (1) is (2-2.2) mol:(0.65-0.8) mol:(0.2-0.35) mol:(1.04-1.1) mol:(3-8) kg.

[0014] Preferably, the diacyl chloride monomer in (1) is terephthaloyl chloride, malonyl chloride, glutaryl chloride, or adipoyl chloride.

[0015] Preferably, the temperature of zone 1-6 of the twin-screw extruder is 210-265℃, and the screw rotation speed is 200-400r / min.

[0016] Preferably, the antistatic ASA composite material is applied to a communication equipment shell.

[0017] The present application has the beneficial technical effects that: bisphenol A, N,N-bis(2-hydroxyethyl)-3-aminopropionitrile, and excess malonyl chloride are esterified to conduct polymerization reaction, polyester polymer is obtained, the terminal acid chloride groups react with the hydroxyl groups on the surface of graphene, thereby the polyester molecules are grafted to the surface of graphene, and finally mixed with polycarbonate, ASA, etc., to obtain the antistatic ASA composite material.

[0018] The polyester grafted graphene contains ester groups, benzene rings and cyano groups similar to ASA, improves the compatibility of graphene and ASA, and the polyester molecular chain contains a bisphenol A ester structure similar to bisphenol A polycarbonate, improves the compatibility between graphene and polycarbonate, makes graphene have good compatibility in polycarbonate-ASA composite material, significantly improves the mechanical properties such as impact strength of the composite material, and graphene is uniformly dispersed in the composite material to form a continuous conductive path, reduces the volume resistivity, improves the anti-static performance, and has better practical application in anti-static communication equipment plastic shell. BRIEF DESCRIPTION OF DRAWINGS

[0019] Figure 1 is an infrared spectrum of polyester grafted graphene. DETAILED DESCRIPTION

[0020] The following acrylonitrile-styrene-acrylate copolymer (ASA) is LURAN ASA37019 from Guangzhou Hongcheng Plastic Co., Ltd. The polycarbonate is bisphenol A polycarbonate from Wuhan Kanos Technology Co., Ltd.

[0021] According to the method of the journal Zeitschrift fur Naturforschung B, 1 June 2005, document “Cobalt Complexation with Unsymmetrical Tripodal Ligands”, diethanolamine and acrylonitrile are reacted to prepare N,N-bis(2-hydroxyethyl)-3-aminopropionitrile, the structure is .

[0022] Example 1

[0023] (1) 22 mmol of triethylamine, 7 mmol of bisphenol A, 3 mmol of N,N-bis(2-hydroxyethyl)-3-aminopropionitrile are added to 40 mL of N,N-dimethylformamide, 10.8 mmol of malonyl chloride is added dropwise in an ice water bath, and the polymerization reaction is stirred at 25°C for 6 h, then 80 g of graphene oxide is added, 6 L of N,N-dimethylformamide is added, and the grafting reaction is stirred at 40°C for 18 h. After filtration, it is washed with N,N-dimethylformamide and water, and dried to obtain polyester grafted graphene. Figure 1 The infrared spectrum of is 1512 cm -1 is the characteristic peak of the benzene ring skeleton in the polyester molecular chain of graphene grafted polyester, 1736 cm -1 is the absorption peak of ester group-C=O-, and 2227 cm -1 is the absorption peak of cyano group-CN.

[0024] (2) 8 kg of polycarbonate, 2 kg of acrylonitrile-styrene-acrylate copolymer, 30 g of polyester grafted graphene, 22 g of antioxidant 1076, 18 g of polyethylene wax, 20 g of ethylene bis-stearamide were mixed in a mixer, and then the material was melt-extruded in a twin-screw extruder, the temperature of 1-6 zones was 210°C, 230°C, 245°C, 255°C, 265°C, 265°C, the screw rotation speed was 300 r / min, and pelletizing was performed to obtain an anti-static ASA composite material.

[0025] Example 2

[0026] (1) 20 mmol of triethylamine, 6.5 mmol of bisphenol A, and 3.5 mmol of N,N-bis(2-hydroxyethyl)-3-aminopropionitrile were added to 30 mL of N,N-dimethylformamide, 10.4 mmol of terephthaloyl chloride was added dropwise in an ice water bath, the polymerization reaction was stirred at 20°C for 10 h, then 45 g of oxidized graphene and 4 L of N,N-dimethylformamide were added, the grafting reaction was stirred at 20°C for 24 h, after filtration, N,N-dimethylformamide and water were used for sufficient washing, and drying was performed to obtain polyester grafted graphene.

[0027] (2) 7.5 kg of polycarbonate, 2.5 kg of acrylonitrile-styrene-acrylate copolymer, 60 g of polyester grafted graphene, 15 g of antioxidant 1010, 14 g of polyethylene wax, and 16 g of ethylene bis-stearamide were mixed in a mixer, and then the material was melt-extruded in a twin-screw extruder, the temperature of 1-6 zones was 210°C, 230°C, 245°C, 255°C, 265°C, 265°C, the screw rotation speed was 400 r / min, and pelletizing was performed to obtain an anti-static ASA composite material.

[0028] Example 3

[0029] (1) 20 mmol of triethylamine, 6.5 mmol of bisphenol A, and 3.5 mmol of N,N-bis(2-hydroxyethyl)-3-aminopropionitrile were added to 30 mL of N,N-dimethylformamide, 10.4 mmol of terephthaloyl chloride was added dropwise in an ice water bath, the polymerization reaction was stirred at 20°C for 10 h, then 45 g of oxidized graphene and 4 L of N,N-dimethylformamide were added, the grafting reaction was stirred at 20°C for 24 h, after filtration, N,N-dimethylformamide and water were used for sufficient washing, and drying was performed to obtain polyester grafted graphene.

[0030] (2) 7 kg polycarbonate, 3 kg acrylonitrile-styrene-acrylate copolymer, 100 g polyester grafted graphene, 15 g antioxidant 1010, 23 g polyethylene wax, 27 g pentaerythritol stearate were mixed in a mixer, and then the material was melt-extruded in a twin-screw extruder, the temperature of 1-6 zones was 210°C, 230°C, 245°C, 255°C, 265°C, 265°C, the screw rotation speed was 300 r / min, and the pelletizing was performed to obtain an antistatic ASA composite material.

[0031] Example 4

[0032] (1) 22 mmol triethylamine, 7.5 mmol bisphenol A, 2.5 mmol N,N-bis(2-hydroxyethyl)-3-aminopropionitrile were added to 40 mL N,N-dimethylformamide, 10.6 mmol glutaroyl chloride was added dropwise in an ice water bath, the polymerization was stirred at 25°C for 7 h, then 60 g oxidized graphene, 5 L N,N-dimethylformamide were added, the grafting reaction was stirred at 50°C for 18 h, after filtration, N,N-dimethylformamide and water were used for washing, and drying was performed to obtain polyester grafted graphene.

[0033] (2) 6 kg polycarbonate, 4 kg acrylonitrile-styrene-acrylate copolymer, 150 g polyester grafted graphene, 25 g antioxidant 1076, 17 g polyethylene wax, 22 g pentaerythritol stearate were mixed in a mixer, and then the material was melt-extruded in a twin-screw extruder, the temperature of 1-6 zones was 210°C, 230°C, 245°C, 255°C, 265°C, 265°C, the screw rotation speed was 200 r / min, and the pelletizing was performed to obtain an antistatic ASA composite material.

[0034] Comparative Example 1

[0035] (1) 8 kg polycarbonate, 2 kg acrylonitrile-styrene-acrylate copolymer, 30 g oxidized graphene, 22 g antioxidant 1076, 18 g polyethylene wax, 20 g ethylene bis-stearamide were mixed in a mixer, and then the material was melt-extruded in a twin-screw extruder, the temperature of 1-6 zones was 210°C, 230°C, 245°C, 255°C, 265°C, 265°C, the screw rotation speed was 300 r / min, and the pelletizing was performed to obtain an antistatic ASA composite material.

[0036] Comparative Example 2

[0037] (1) Into 40 mL of N,N-dimethylformamide, 22 mmol of triethylamine, 7 mmol of bisphenol A, and 3 mmol of N-methyldiethanolamine were added, 10.8 mmol of malonyl chloride was added dropwise in an ice water bath, and the polymerization reaction was stirred at 25°C for 6 h. Then, 80 g of graphene oxide and 6 L of N,N-dimethylformamide were added, and the grafting reaction was stirred at 40°C for 18 h. After filtration, N,N-dimethylformamide and water were used for sufficient washing, and drying was performed to obtain polyester grafted graphene.

[0038] (2) 8 kg of polycarbonate, 2 kg of acrylonitrile-styrene-acrylate copolymer, 30 g of polyester grafted graphene, 22 g of antioxidant 1076, 18 g of polyethylene wax, and 20 g of ethylene bis-stearamide were mixed in a mixer, and then the materials were melt-extruded in a twin-screw extruder with a temperature of 210°C, 230°C, 245°C, 255°C, 265°C, and 265°C in zones 1-6, and a screw rotation speed of 300 r / min. Pellets were obtained, and an anti-static ASA composite material was obtained.

[0039] Comparative Example 3

[0040] (1) Into 40 mL of N,N-dimethylformamide, 22 mmol of triethylamine, 7 mmol of bisphenol A, and 3 mmol of N-methyldiethanolamine were added, 10.8 mmol of malonyl chloride was added dropwise in an ice water bath, and the polymerization reaction was stirred at 25°C for 6 h. Then, 80 g of graphene oxide and 6 L of N,N-dimethylformamide were added, and the grafting reaction was stirred at 40°C for 18 h. After filtration, N,N-dimethylformamide and water were used for sufficient washing, and drying was performed to obtain polyester grafted graphene.

[0041] (2) 8 kg of polycarbonate, 2 kg of acrylonitrile-styrene-acrylate copolymer, 30 g of polyester grafted graphene, 22 g of antioxidant 1076, 18 g of polyethylene wax, and 20 g of ethylene bis-stearamide were mixed in a mixer, and then the materials were melt-extruded in a twin-screw extruder with a temperature of 210°C, 230°C, 245°C, 255°C, 265°C, and 265°C in zones 1-6, and a screw rotation speed of 300 r / min. Pellets were obtained, and an anti-static ASA composite material was obtained.

[0042] The composite material was injection molded into a test sample 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, and the volume resistivity was tested according to the ASTM D257-07 standard. The test results are shown in Table 1.

[0043] Table 1 Properties of the composite material

[0044] impact strength (kJ / m 2 ) Tensile strength (MPa) Elongation at break (%) Volume resistivity (Ω-m) Example 1 56.5 66.8 88.2 2.58 x 10 12 ]] Example 2 63.7 71.2 95.6 8.61 x 10 8 ]]> Example 3 72.5 74.3 81.1 5.29 x 10 3 <!-- 4 -->]]> Example 4 73.9 65.8 60.2 6.73 x 10 2 ]] Comparative Example 1 49.2 61.5 77.8 3.70 x 10 13 ]] Comparative Example 2 53.0 63.9 81.5 6.17 x 10 12 ]]> Comparative Example 3 55.4 65.1 85.7 7.25 x 10 12 ]]>

[0045] According to the test results in Table 1, the comparative example 1 blends polycarbonate, ASA and graphene oxide, and the tensile properties and impact strength of the obtained composite material are low, mainly because the graphene oxide is prone to agglomeration, and the compatibility with polycarbonate and ASA is poor, which is difficult to effectively improve the mechanical properties of the composite material, and the dispersion of graphene oxide in the composite material is poor, which is difficult to form a continuous conductive path, resulting in a large volume resistivity and poor antistatic performance.

[0046] Compared with the comparative examples 1-3, the examples 1-4 use bisphenol A, N,N-bis(2-hydroxyethyl)-3-aminopropyl cyanate, and malonyl chloride to esterify and polymerize to obtain polyester polymers, and then graft them onto the surface of graphene oxide. The grafted polyester molecular chain contains ester groups, benzene rings and cyano groups similar to ASA, which improves the compatibility of graphene and ASA, and the polyester molecular chain contains bisphenol A ester structure similar to bisphenol A polycarbonate, which improves the compatibility between graphene and polycarbonate, so that graphene has good compatibility in polycarbonate-ASA composite material, and the impact strength and other mechanical properties of the composite material are significantly improved. And the graphene is uniformly dispersed in the composite material to form a continuous conductive path, which reduces the volume resistivity and improves the antistatic performance.

Claims

1. An antistatic ASA composite material, characterized by, The raw materials of the anti-static ASA composite material include 60-80 parts by weight of polycarbonate, 20-40 parts by weight of acrylonitrile-styrene-acrylate copolymer, 0.3-1.5 parts by weight of polyester grafted graphene, 0.15-0.25 parts by weight of antioxidant, and 0.3-0.5 parts by weight of processing aid. The preparation method of the polyester grafted graphene comprises the following steps: adding triethylamine, bisphenol A, and N,N-bis(2-hydroxyethyl)-3-aminopropionitrile into N,N-dimethylformamide, adding diacyl chloride monomer dropwise in an ice water bath, performing polymerization reaction, then adding graphene oxide and N,N-dimethylformamide, performing grafting reaction, filtering, washing with N,N-dimethylformamide and water in sequence, and drying to obtain the polyester grafted graphene.

2. The anti-static ASA composite material according to claim 1, characterized in that, The antioxidant is antioxidant 1010 or antioxidant 1076; and the processing aid is any one or combination of polyethylene wax, pentaerythritol stearate, or ethylene bis-stearamide.

3. The anti-static ASA composite material according to claim 1, characterized in that, The temperature of the polymerization reaction is 20-35℃, and the reaction time is 6-10h.

4. The anti-static ASA composite material according to claim 1, characterized in that, The temperature of the grafting reaction is 20-50℃, and the reaction time is 18-24h.

5. The anti-static ASA composite material according to claim 1, characterized in that, The ratio of the triethylamine, bisphenol A, N,N-bis(2-hydroxyethyl)-3-aminopropionitrile, diacyl chloride monomer, and graphene oxide is (2-2.2) mol:(0.65-0.8) mol:(0.2-0.35) mol:(1.04-1.1) mol:(3-8) kg.

6. The anti-static ASA composite material according to claim 1, characterized in that, The diacyl chloride monomer is terephthaloyl chloride, malonyl chloride, glutaryl chloride, or adipoyl chloride.

7. A process for the production of an antistatic ASA composite material according to any one of claims 1 to 6, characterized in that, The preparation method comprises the following steps: mixing polycarbonate, acrylonitrile-styrene-acrylate copolymer, polyester grafted graphene, antioxidant, and processing aid in a mixer, then melt-extruding the materials in a twin-screw extruder, and pelletizing to obtain the anti-static ASA composite material.

8. The method for preparing the antistatic ASA composite material according to claim 7, characterized in that, The temperature of the 1-6 zones of the twin-screw extruder is 210-265℃, and the screw rotation speed is 200-400r / min.

9. Application of the anti-static ASA composite material obtained by the preparation method of claim 8 to a communication device shell.

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