Anti-static ASA composite material, its preparation method and application in communication equipment shell

Abstract

The application 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. Raw materials of the anti-static ASA composite material of the application 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, 0.3-0.5 parts by weight of a processing aid and the like; the graphene has good compatibility in the polycarbonate-ASA composite material, improves the mechanical properties such as impact strength of the composite material, the graphene is uniformly dispersed in the composite material, the volume resistivity is reduced, the anti-static performance is improved, and the application in the anti-static communication equipment plastic shell is better.

Description

Technical Field

[0001] This invention relates to the field of plastics technology, specifically to an antistatic ASA composite material, its preparation method, and its application in the housing of communication equipment. Background Technology

[0002] Acrylonitrile-styrene-acrylate copolymer (ASA) possesses high toughness, excellent mechanical properties, good high-temperature resistance, and certain antistatic properties, making it widely used in plastic housings for communication equipment, charging pile housings, and automotive interiors. Blending ASA with plastics such as polycarbonate and polyvinyl chloride can improve the toughness and impact strength of these plastics.

[0003] Polycarbonate (PC) is widely used due to its high strength, transparency, and excellent UV resistance. However, it suffers from poor toughness and antistatic properties. Adding impact-resistant resins and nanoparticles can improve these properties. Graphene possesses excellent mechanical properties and strong electrical conductivity, making it important for reinforcing and antistatic modification of plastics. Solving the graphene agglomeration problem and improving its compatibility with ASA and polycarbonate materials are research challenges. Patent CN114591588B discloses a PC / ASA composite material prepared using polycarbonate (PC) resin, ASA resin, graphene, flame retardant, and maleic anhydride-grafted polyethylene as raw materials. This composite material exhibits good notched impact strength, flame retardancy, and microwave absorption properties, and avoids the problem of poor antistatic properties in PC / ASA composite materials. Summary of the Invention

[0004] To address the shortcomings of existing technologies, this invention provides an antistatic ASA composite material and its preparation method, which solves the problem of poor dispersion of graphene in ASA and polycarbonate composite materials and improves the antistatic, mechanical and other properties of the composite material.

[0005] To solve the above-mentioned technical problems, the technical solution adopted by the present invention is: an antistatic ASA composite material and its preparation method, wherein the raw materials of the antistatic 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] Preparation method of antistatic ASA composite material:

[0007] (1) Add triethylamine, bisphenol A, and N,N-bis(2-hydroxyethyl)-3-aminopropionitrile to N,N-dimethylformamide, and dropwise add diacyl chloride monomer (structural formula: The polymerization reaction was carried out, followed by the addition of graphene oxide and N,N-dimethylformamide for grafting. After filtration, the product was washed sequentially with N,N-dimethylformamide and water, and then dried to obtain polyester-grafted graphene. The preparation reaction formula is as follows:

[0008] .

[0009] (2) Polycarbonate, acrylonitrile-styrene-acrylate copolymer, polyester-grafted graphene, antioxidant, and processing aid are mixed in a mixer, and then the material is melt-extruded in a twin-screw extruder and pelletized to obtain antistatic ASA composite material.

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

[0011] Preferably, the polymerization temperature 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, in (1), the diacyl chloride monomer is terephthaloyl chloride, malonyl chloride, glutaryl chloride or adipyl chloride.

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

[0016] Preferably, the antistatic ASA composite material is used in the housing of communication equipment.

[0017] The beneficial technical effects of this invention are as follows: Bisphenol A and N,N-bis(2-hydroxyethyl)-3-aminopropionitrile are polymerized with excess malonyl chloride to obtain a polyester polymer. The terminal acyl chloride groups then react with the hydroxyl groups on the surface of graphene oxide, thereby linking the polyester molecules to the graphene surface. Finally, the polymer is mixed with polycarbonate, ASA, etc., to obtain an antistatic ASA composite material.

[0018] The graphene-grafted polyester molecular chain of this invention contains ester groups, benzene rings, and cyano groups similar to those in ASA, which improves the compatibility between graphene and ASA. Furthermore, the polyester molecular chain contains a bisphenol A ester structure similar to that of bisphenol A polycarbonate, further improving the compatibility between graphene and polycarbonate. This results in excellent compatibility of graphene in polycarbonate-ASA composite materials, significantly improving the impact strength and other mechanical properties of the composite material. Moreover, the graphene is uniformly dispersed in the composite material, forming a continuous conductive path, reducing the volume resistivity, and improving the antistatic performance, leading to better practical applications in the plastic casing of antistatic communication equipment. Attached Figure Description

[0019] Figure 1 This is the infrared spectrum of polyester-grafted graphene. Detailed Implementation

[0020] The following acrylonitrile-styrene-acrylate copolymer (ASA), model number LURANASA37019, is sourced from Guangzhou Hongcheng Plastics Co., Ltd. The polycarbonate is bisphenol A polycarbonate, sourced from Wuhan Kanos Technology Co., Ltd.

[0021] Following the method described in the journal *Zeitschrift für Naturforschung B*, 1 June 2005, "Cobalt Complexation with Unsymmetrical Tripodal Ligands," diethanolamine and acrylonitrile were reacted to prepare N,N-bis(2-hydroxyethyl)-3-aminopropionitrile, with the structural formula [structure omitted]. .

[0022] Example 1

[0023] (1) Add 22 mmol of triethylamine, 7 mmol of bisphenol A, and 3 mmol of N,N-bis(2-hydroxyethyl)-3-aminopropionitrile to 40 mL of N,N-dimethylformamide. Add 10.8 mmol of malonyl chloride dropwise in an ice-water bath. Stir and polymerize at 25 °C for 6 h. Then add 80 g of graphene oxide and 6 L of N,N-dimethylformamide. Stir and graft at 40 °C for 18 h. After filtration, wash thoroughly with N,N-dimethylformamide and water, and dry to obtain polyester-grafted graphene. Figure 1 In the infrared spectrum, 1512 cm⁻¹ -1 It is a characteristic peak of the benzene ring backbone in the graphene-grafted polyester molecular chain, at 1736 cm⁻¹. -1 The absorption peak is at 2227 cm⁻¹, corresponding to the ester group -C=O-. -1 It is the absorption peak of cyano-CN.

[0024] (2) Mix 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 in a mixer, and then melt-extrude the material in a twin-screw extruder. The temperatures of zones 1-6 are 210℃, 230℃, 245℃, 255℃, 265℃ and 265℃, and the screw speed is 300 r / min. The material is then pelletized to obtain an antistatic ASA composite material.

[0025] Example 2

[0026] (1) Add 20 mmol of triethylamine, 6.5 mmol of bisphenol A and 3.5 mmol of N,N-bis(2-hydroxyethyl)-3-aminopropionitrile to 30 mL of N,N-dimethylformamide. Add 10.4 mmol of terephthaloyl chloride dropwise in an ice-water bath. Stir and polymerize at 20 °C for 10 h. Then add 45 g of graphene oxide and 4 L of N,N-dimethylformamide. Stir and graft at 20 °C for 24 h. After filtration, wash thoroughly with N,N-dimethylformamide and water, and dry 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 temperatures of zones 1-6 were 210℃, 230℃, 245℃, 255℃, 265℃ and 265℃, and the screw speed was 400 r / min. The mixture was then pelletized to obtain an antistatic ASA composite material.

[0028] Example 3

[0029] (1) Add 20 mmol of triethylamine, 8 mmol of bisphenol A, and 2 mmol of N,N-bis(2-hydroxyethyl)-3-aminopropionitrile to 30 mL of N,N-dimethylformamide. Add 10.8 mmol of adipyl chloride dropwise in an ice-water bath. Stir the polymerization reaction at 35 °C for 6 h. Then add 30 g of graphene oxide and 2 L of N,N-dimethylformamide. Stir the grafting reaction at 40 °C for 18 h. After filtration, wash thoroughly with N,N-dimethylformamide and water, and dry to obtain polyester-grafted graphene.

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

[0031] Example 4

[0032] (1) Add 22 mmol of triethylamine, 7.5 mmol of bisphenol A and 2.5 mmol of N,N-bis(2-hydroxyethyl)-3-aminopropionitrile to 40 mL of N,N-dimethylformamide. Add 10.6 mmol of glutaryl chloride dropwise in an ice-water bath. Stir and polymerize at 25 °C for 7 h. Then add 60 g of graphene oxide and 5 L of N,N-dimethylformamide. Stir and graft at 50 °C for 18 h. After filtration, wash thoroughly with N,N-dimethylformamide and water, and dry to obtain polyester-grafted graphene.

[0033] (2) Mix 6 kg of polycarbonate, 4 kg of acrylonitrile-styrene-acrylate copolymer, 150 g of polyester-grafted graphene, 25 g of antioxidant 1076, 17 g of polyethylene wax, and 22 g of pentaerythritol stearate in a mixer, and then melt-extrude the material in a twin-screw extruder. The temperatures of zones 1-6 are 210℃, 230℃, 245℃, 255℃, 265℃, and 265℃, and the screw speed is 200 r / min. The mixture is then pelletized to obtain an antistatic ASA composite material.

[0034] Comparative Example 1

[0035] (1) Mix 8 kg of polycarbonate, 2 kg of acrylonitrile-styrene-acrylate copolymer, 30 g of graphene oxide, 22 g of antioxidant 1076, 18 g of polyethylene wax and 20 g of ethylene bis-stearamide in a mixer, and then melt-extrude the material in a twin-screw extruder. The temperatures of zones 1-6 are 210℃, 230℃, 245℃, 255℃, 265℃ and 265℃ respectively, and the screw speed is 300 r / min. The material is then pelletized to obtain an antistatic ASA composite material.

[0036] Comparative Example 2

[0037] (1) Add 22 mmol of triethylamine, 7 mmol of bisphenol A and 3 mmol of N-methyldiethanolamine to 40 mL of N,N-dimethylformamide, add 10.8 mmol of malonyl chloride dropwise in an ice-water bath, and stir the polymerization reaction at 25 °C for 6 h. Then add 80 g of graphene oxide and 6 L of N,N-dimethylformamide, and stir the grafting reaction at 40 °C for 18 h. After filtration, wash thoroughly with N,N-dimethylformamide and water, and dry to obtain polyester-grafted graphene.

[0038] (2) Mix 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 in a mixer, and then melt-extrude the material in a twin-screw extruder. The temperatures of zones 1-6 are 210℃, 230℃, 245℃, 255℃, 265℃ and 265℃, and the screw speed is 300 r / min. The material is then pelletized to obtain an antistatic ASA composite material.

[0039] Comparative Example 3

[0040] (1) Add 22 mmol of triethylamine, 7 mmol of hydroquinone, and 3 mmol of N,N-bis(2-hydroxyethyl)-3-aminopropionitrile to 40 mL of N,N-dimethylformamide. Add 10.8 mmol of malonyl chloride dropwise in an ice-water bath. Stir the polymerization reaction at 25 °C for 6 h. Then add 80 g of graphene oxide and 6 L of N,N-dimethylformamide. Stir the grafting reaction at 40 °C for 18 h. After filtration, wash thoroughly with N,N-dimethylformamide and water, and dry to obtain polyester-grafted graphene.

[0041] (2) Mix 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 in a mixer, and then melt-extrude the material in a twin-screw extruder. The temperatures of zones 1-6 are 210℃, 230℃, 245℃, 255℃, 265℃ and 265℃, and the screw speed is 300 r / min. The material is then pelletized to obtain an antistatic ASA composite material.

[0042] The composite material was injection molded into test specimens using an injection molding machine. Impact strength was tested according to GB / T 1043.1-2008 standard, and tensile strength was tested according to GB / T 1040.1-2018 standard. Volume resistivity was tested according to ASTM D257-07 standard. Test results are shown in Table 1.

[0043] Table 1 Properties of composite materials

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

[0045] According to the test results in Table 1, the composite material obtained by blending polycarbonate, ASA and graphene oxide in Comparative Example 1 has low tensile properties and impact strength. This is mainly because graphene oxide is prone to agglomeration and has poor compatibility with polycarbonate and ASA, making it difficult to effectively improve the mechanical properties of the composite material. Furthermore, the poor dispersion of graphene oxide in the composite material makes it difficult to form a continuous conductive path, resulting in a high volume resistivity and poor antistatic performance.

[0046] Compared with Comparative Examples 1-3, Examples 1-4 used bisphenol A, N,N-bis(2-hydroxyethyl)-3-aminopropionitrile, and malonyl chloride esterification to carry out polymerization to obtain polyester polymers, which were then grafted onto the surface of graphene oxide. The grafted polyester molecular chains contain ester groups, benzene rings, and cyano groups similar to ASA, which improves the compatibility between graphene and ASA. Furthermore, the polyester molecular chains contain bisphenol A ester structures similar to bisphenol A polycarbonate, which improves the compatibility between graphene and polycarbonate. This results in good compatibility of graphene in polycarbonate-ASA composite materials, significantly improving the impact strength and other mechanical properties of the composite materials. In addition, the graphene is uniformly dispersed in the composite materials, forming continuous conductive pathways, reducing the volume resistivity, and improving the antistatic properties.

Claims

1. An antistatic ASA composite material, characterized in that, The raw materials of the antistatic 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 method for preparing the polyester-grafted graphene includes: adding triethylamine, bisphenol A, and N,N-bis(2-hydroxyethyl)-3-aminopropionitrile to N,N-dimethylformamide, adding diacyl chloride monomer dropwise in an ice-water bath to carry out a polymerization reaction, then adding graphene oxide and N,N-dimethylformamide to carry out a grafting reaction, filtering, washing with N,N-dimethylformamide and water in sequence, and drying to obtain polyester-grafted graphene; The ratio of 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.

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

3. The antistatic ASA composite material according to claim 1, characterized in that, The polymerization reaction is carried out at a temperature of 20-35℃ for 6-10 hours.

4. The antistatic ASA composite material according to claim 1, characterized in that, The grafting reaction is carried out at a temperature of 20-50℃ for 18-24 hours.

5. The antistatic ASA composite material according to claim 1, characterized in that, The diacyl chloride monomer is terephthaloyl chloride, malonyl chloride, glutaryl chloride, or adipyl chloride.

6. A method for preparing the antistatic ASA composite material as described in any one of claims 1-5, characterized in that, The preparation method includes: mixing polycarbonate, acrylonitrile-styrene-acrylate copolymer, polyester-grafted graphene, antioxidant, and processing aid in a mixer, then melting and extruding the material in a twin-screw extruder, and pelletizing it to obtain an antistatic ASA composite material.

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

8. The application of an antistatic ASA composite material obtained by the preparation method as described in claim 7 in the housing of a communication device.

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