High-performance high-gloss ABS electromagnetic shielding plastic and preparation method thereof

Abstract

The invention provides a high-performance high-gloss ABS electromagnetic shielding plastic and a preparation method thereof. According to the method, the ABS resin is used as a matrix component, and the PMMA resin is added to be blended with the ABS resin, so that the specular reflectance can be improved, and the glossiness of the ABS resin is further improved. In addition, by adding the PANI-MAH-nanoFe3O4 composite filler, the ABS electromagnetic shielding plastic with both mechanical properties and electromagnetic shielding properties can be obtained.

Description

TECHNICAL FIELD

[0001] The present application relates to an ABS plastic and a preparation method thereof, in particular to a high-performance high-gloss ABS electromagnetic shielding plastic and a preparation method thereof. BACKGROUND

[0002] ABS plastic is a thermoplastic engineering plastic with two-phase structure, which is polymerized by three monomers of acrylonitrile (A), butadiene (B) and styrene (S) through emulsion, bulk or suspension polymerization. The two-phase structure includes a continuous phase and a dispersed phase. The continuous phase is a SAN (styrene-acrylonitrile copolymer) matrix, which provides rigidity, heat resistance and chemical stability; the dispersed phase is crosslinked polybutadiene rubber particles, which endow toughness and low-temperature impact resistance. Since its commercialization in 1948, the production of ABS plastic has ranked first among the five major general-purpose engineering plastics in the world, and it is widely used in the fields of automobiles, electronics and electrical appliances, home appliances, 3D printing, medical devices, etc.

[0003] ABS plastic is widely used as the shell of electronic and electrical appliances due to its easy processing, good toughness and low cost, but ABS itself is not conductive, which makes it difficult to meet the increasingly stringent electromagnetic compatibility (EMC) requirements. The ways to improve the electromagnetic shielding performance of ABS plastic include "conductive filler blending" and "surface metallization". The ABS plastic obtained by the "surface metallization approach" has high shielding effectiveness, but it increases the process and environmental pressure. The "conductive filler blending approach" is easy to realize complex structure and lightweight, but high shielding requires high filling, which damages the mechanical properties. Currently, the conductive filler blending approach is developing towards "low filling-high network efficiency", such as CNTs / graphene + magnetic particle synergy, foaming microstructure optimization, etc.

[0004] CN115109381A discloses a new composition of ABS composite material with electromagnetic shielding effect; the ABS composite material with electromagnetic shielding effect is obtained by adding an electromagnetic shielding agent made of carbon nanotubes and tungsten powder, so that it has electromagnetic shielding effect; especially by adding the electromagnetic shielding agent prepared by the method of the application, the prepared ABS composite material has more excellent electromagnetic shielding effect.

[0005] CN115746531A discloses a PC-ABS electromagnetic shielding composite material, which improves the absorption loss and multiple reflection attenuation by surface modification of carbon nanotubes. The hollow structure of carbon nanotubes can increase the dissipation path of electromagnetic waves and enhance the interface polarization effect. The "conductor-insulator" core-shell type nano-conductive filler with carbon nanotubes as the core and maleic anhydride as the shell is blended with PC / ABS substrate to prepare a PC / ABS electromagnetic shielding composite material which not only has excellent dielectric properties but also has good processability.

[0006] Although people have carried out extensive research on the electromagnetic shielding performance of ABS plastic, there are still deficiencies in the compatibility of electromagnetic shielding fillers in the ABS plastic matrix and the compounding of organic / inorganic electromagnetic shielding fillers, and the research on high-gloss electromagnetic shielding ABS plastic. SUMMARY

[0007] To solve the above technical problems, the application provides a high-performance high-gloss ABS electromagnetic shielding plastic and a preparation method thereof. The method uses ABS resin as a matrix component and adds PMMA resin for blending with the ABS resin, which can improve the specular reflectance and thus the gloss. In addition, by adding a PANI-MAH-nanoFe3O4 composite filler, an ABS electromagnetic shielding plastic with mechanical properties and electromagnetic shielding properties can be obtained.

[0008] To achieve the above-mentioned purpose, the application adopts the following technical solutions: A high-performance high-gloss ABS electromagnetic shielding plastic, which is composed of the following raw materials in parts by weight: ABS resin 100 parts; PMMA 10-30 parts; Composite filler 20-35 parts; Compatibility agent 2-5 parts; Antioxidant 3-6 parts; UV absorber 1-3 parts; Lubricant 3-5 parts; Initiator 1-2 parts.

[0009] Further, the compatibility agent is one or a combination of two or more of a terpolymer of methyl methacrylate-glycidyl methacrylate-ethyl acrylate, a graft of ABS, styrene-acrylonitrile-glycidyl methacrylate, and a styrene-maleic anhydride copolymer; Further, the antioxidant is one or a combination of two or more of antioxidant 1010, antioxidant 1076, antioxidant 168, and antioxidant 626; Further, the UV absorber is one or a combination of two or more of UV-531, UV-327, and UV-1164; Further, the lubricant is one or a combination of two or more of butyl stearate, ethylene bis-stearyl amide, stearic amide, and calcium stearate.

[0010] Further, the initiator is one or a combination of two or more of benzoyl peroxide, dicumyl peroxide, and tert-butyl peroxybenzoate.

[0011] Further, the preparation process of the composite filler is as follows: Step one: Take HCl solution in a three-necked flask, add aniline monomer to start stirring, and use an ice bath to control the temperature of the flask at 0°C. Then, dissolve ammonium persulfate into the HCl solution to obtain a mixed solution, and add the mixed solution dropwise into the three-necked flask containing the aniline monomer to react. After the reaction, wash and dry to obtain conductive polyaniline; Step two: add the amino-containing silane coupling agent into an ethanol aqueous solution to hydrolyze and obtain a hydrolysis solution, add nano-magnetite into the hydrolysis solution, and reflux under stirring to react, filter, wash, and dry to obtain the amino-silane coupling agent modified nano-magnetite; Step three: Add the conductive polyaniline prepared in step one into DMF to stir and disperse uniformly to obtain a dispersion liquid, add maleic anhydride and triethylamine into the dispersion liquid to react for 4-5 h to obtain a reaction liquid, add the amino-silane coupling agent modified nano-magnetite obtained in step two into the reaction liquid to react for 2-4 h, cool to room temperature after the reaction, filter, and dry to obtain the composite filler.

[0012] Further, the preparation process of the composite filler is as follows: Step one: Take 30-40 ml of HCl solution with a concentration of 1 mol / L in a three-necked flask, add 10-20 g of aniline monomer to start stirring, and use an ice bath to control the temperature of the flask at 0°C. Then, dissolve 5-10 g of ammonium persulfate into 20-40 ml of HCl solution with a concentration of 1 mol / L to obtain a mixed solution, add the mixed solution dropwise into the three-necked flask containing the aniline monomer, the dropwise adding time of the mixed solution is 1-2 hours, the subsequent reaction time is 3-4 hours, the reaction temperature is always controlled at 0°C, and after the reaction, a dark green solution is obtained. After washing, place it in a vacuum drying box for drying treatment at 50-60°C for 2-4 h to obtain conductive polyaniline.

[0013] Step two: add 2-5 parts of amino-containing silane coupling agent into 50-100 ml of ethanol aqueous solution with a mass fraction of 80-90 wt% to hydrolyze, and use a pH adjuster to adjust the pH value of the ethanol aqueous solution to 8-11, hydrolyze for 4-5 h to obtain a hydrolysis solution, add 8-15 g of nano-magnetite into the hydrolysis solution, reflux under stirring to react for 2-5 h, filter, wash, and dry to obtain the amino-silane coupling agent modified nano-magnetite; Step three: 6-12 parts of the conductive polyaniline prepared in step one is added into 100-300 ml of DMF, and stirred and dispersed uniformly to obtain a dispersion liquid, 4-8 parts of maleic anhydride and 0.5-2 parts of triethylamine are added into the dispersion liquid, and reacted at 60-80°C for 4-5 hours to obtain a reaction liquid, then 5-10 parts of the amino silane coupling agent modified nano-Fe3O4 obtained in step two is added into the reaction liquid, and reacted at 60-80°C for 2-4 hours, and after the reaction is completed, the reaction liquid is cooled to room temperature, filtered, and dried to obtain the composite filler.

[0014] Further, the amino-containing silane coupling agent in step two is gamma-aminopropyl triethoxysilane or gamma-aminopropyl trimethoxysilane.

[0015] Further, the pH regulator in step two is sodium hydroxide or potassium hydroxide.

[0016] Further, the preparation method of the high-performance high-gloss ABS electromagnetic shielding plastic comprises the following steps: Step one: the raw materials are weighed according to the proportion, added into a high-speed mixer, and stirred and mixed for 10-20 minutes to form a first mixture; Step two: the first mixture is melted, extruded, granulated, and dried at a processing temperature of 180-220°C to obtain the high-performance high-gloss ABS electromagnetic shielding plastic.

[0017] Compared with the prior art, the present application has the following beneficial effects: The present application uses ABS resin as the base component, and by adding PMMA resin and blending with ABS resin, the specular reflectance can be improved, and thus the glossiness is improved. In addition, by adding the self-made PANI-MAH-nanoFe3O4 composite filler, ABS electromagnetic shielding plastic with mechanical properties and electromagnetic shielding properties can be obtained. The conductive polymer material polyaniline can improve the compatibility with ABS resin compared with ordinary inorganic conductive fillers. Further, the nano-Fe3O4 is a magnetic material, and the polyaniline molecular chain has amino groups, and by means of the two anhydride groups of maleic anhydride, the amino silane coupling agent modified nano-Fe3O4 is bonded with the polyaniline molecular chain, which can improve the stability and dispersibility of the nano-Fe3O4 in the polymer material. The polyaniline and nano-Fe3O4 composite filler obtained therefrom has good conductivity and magnetic permeability, and good compatibility with ABS resin, and the obtained ABS plastic has excellent electromagnetic shielding performance. In addition, the obtained composite filler contains unsaturated double bonds, which can polymerize with the double bonds in ABS under heating conditions, reduce the content of unsaturated double bonds in ABS molecules, improve the compatibility of ABS and the composite filler, and the aging resistance of the ABS plastic, and further improve the electromagnetic shielding performance of the ABS plastic.

[0018] The structure of the PANI-MAH-nanoFe3O4 composite filler in the application is shown as follows: DETAILED DESCRIPTION

[0019] The technical solutions in the application will be clearly and completely described below by combining with the embodiments in the application. Obviously, the described embodiments are only some of the embodiments of the application, not all the embodiments. Based on the embodiments in the application, all other embodiments obtained by those skilled in the art without creative work belong to the protection scope of the application. The specific conditions not mentioned in the embodiments are carried out according to the conventional conditions or the conditions suggested by the manufacturers. The reagents or instruments not mentioned by the manufacturers are all conventional products that can be purchased in the market.

[0020] The ABS resin is the ABS resin of Samsung Company in South Korea, and the model is SD-0150. The PMMA resin is the PMMA resin of CM Company in Taiwan, China, and the model is CM211. The nano-Fe3O4 is from Shanghai Yingcheng New Material Co., Ltd., and the particle size is 20 nm.

[0021] Synthesis Example 1 The preparation process of the composite filler is as follows: Step one: Take 36 ml of HCl solution with a concentration of 1 mol / L in a three-necked flask, add 13.4 g of aniline monomer and start stirring, and at the same time, control the temperature of the flask at 0 DEG C by ice bath. Then, dissolve 5.1 g of ammonium persulfate in 36 ml of HCl solution with a concentration of 1 mol / L to obtain a mixed solution, and drop the mixed solution into the three-necked flask with the aniline monomer dissolved therein. The dropping time of the mixed solution is 1 hour, and the subsequent reaction time is 3 hours. The reaction temperature is always controlled at 0 DEG C. After the reaction is completed, a dark green solution is obtained. After washing treatment, it is placed in a vacuum drying box and dried at 60 DEG C for 4 h to obtain conductive polyaniline.

[0022] Step two: 3 parts of γ-aminopropyl triethoxysilane are added to 80 ml of 90wt% ethanol aqueous solution for hydrolysis, and a pH adjuster is used to adjust the pH value of the ethanol aqueous solution to 10. The hydrolysis is carried out for 4 h to obtain a hydrolysis solution. 10 g of nano-Fe3O4 is added to the above hydrolysis solution, and refluxed for 3 h under stirring. After filtration, washing and drying, the nano-Fe3O4 modified by the amino silane coupling agent is obtained. Step three: The conductive polyaniline prepared in step one was added into 100 ml DMF, and stirred to disperse uniformly to obtain a dispersion liquid. 4 parts of maleic anhydride and 1 part of triethylamine were added into the dispersion liquid, and reacted at 60°C for 4 hours to obtain a reaction liquid. Then 6 parts of the amino silane coupling agent modified nano-magnetic iron oxide obtained in step two was added into the reaction liquid, and reacted at 80°C for 3 hours. After the reaction was completed, the reaction liquid was cooled to room temperature, filtered, and dried to obtain the composite filler 1.

[0023] Synthesis Example 2 The preparation steps were the same as those in Synthesis Example 1, except that the preparation and addition of the conductive polyaniline were omitted, thereby obtaining the composite filler 2.

[0024] Synthesis Example 3 The preparation steps were the same as those in Synthesis Example 1, except that the preparation and addition of the amino silane coupling agent modified nano-magnetic iron oxide were omitted, thereby obtaining the composite filler 3.

[0025] Synthesis Example 4 The preparation steps were the same as those in Synthesis Example 1, except that the addition of the maleic anhydride was omitted, thereby obtaining the composite filler 4.

[0026] Example 1 Preparation of high-performance high-gloss ABS electromagnetic shielding plastic: The compositions of the raw materials of the components are as follows: ABS resin 100 parts; PMMA 15 parts; Composite filler 1 22 parts; Styrene-maleic anhydride copolymer 3 parts; Antioxidant 1076 4 parts; UV-327 2 parts; Butyl stearate 3 parts; Benzoyl peroxide 1 part.

[0027] The preparation method of the high-performance high-gloss ABS electromagnetic shielding plastic is as follows: Step one: weigh the raw materials according to the proportions, and add them into a high-speed mixer to stir and mix for 15 minutes to form a first mixture; Step two: melt, extrude, pelletize, and dry the first mixture at a processing temperature of 200°C to obtain the high-performance high-gloss ABS electromagnetic shielding plastic.

[0028] Example 2 Preparation of high-performance high-gloss ABS electromagnetic shielding plastic: The compositions of the raw materials of the components are as follows: ABS resin 100 parts; PMMA 18 parts; Composite filler 1 28 parts; Styrene-maleic anhydride copolymer 4 parts; Antioxidant 1010 4 parts; UV-531 1 part; Butyl stearate 3 parts; Dicumyl peroxide 1 part.

[0029] The preparation method of the high-performance high-gloss ABS electromagnetic shielding plastic is as follows: Step one: weigh each raw material according to the proportion, add it to the high-speed mixer and stir for 20 minutes to form a first mixture; Step two: melt, extrude, granulate and dry the first mixture at a processing temperature of 190°C to obtain the high-performance high-gloss ABS electromagnetic shielding plastic.

[0030] Example 3 Preparation of the high-performance high-gloss ABS electromagnetic shielding plastic: The composition of each component raw material is as follows: ABS resin 100 parts; PMMA 24 parts; Composite filler 1 32 parts; Styrene-maleic anhydride copolymer 5 parts; Antioxidant 1010 4 parts; UV-531 1 part; Butyl stearate 3 parts; Dicumyl peroxide 2 parts.

[0031] The preparation method of the high-performance high-gloss ABS electromagnetic shielding plastic is as follows: Step one: weigh each raw material according to the proportion, add it to the high-speed mixer and stir for 18 minutes to form a first mixture; Step two: melt, extrude, granulate and dry the first mixture at a processing temperature of 200°C to obtain the high-performance high-gloss ABS electromagnetic shielding plastic.

[0032] Comparative Example 1 Preparation of the high-performance high-gloss ABS electromagnetic shielding plastic: The composition of each component raw material is as follows: ABS resin 100 parts; PMMA 15 parts; Composite filler 2 22 parts; Styrene-maleic anhydride copolymer 3 parts; Antioxidant 1076 4 parts; UV-327 2 parts; Butyl stearate 3 parts; Benzoyl peroxide 1 part.

[0033] The preparation method of the high-performance high-gloss ABS electromagnetic shielding plastic is as follows: Step one: weigh each raw material according to the proportion, add it to the high-speed mixer and stir for 15 minutes to form a first mixture; Step two: melt, extrude, granulate and dry the first mixture at a processing temperature of 200°C to obtain the high-performance high-gloss ABS electromagnetic shielding plastic.

[0034] Comparative Example 2 Preparation of the high-performance high-gloss ABS electromagnetic shielding plastic: The composition of each component raw material is as follows: ABS resin 100 parts; PMMA 15 parts; Composite filler 3 22 parts; Styrene-maleic anhydride copolymer 3 parts; Antioxidant 1076 4 parts; UV-327 2 parts; Butyl stearate 3 parts; Benzoyl peroxide 1 part.

[0035] The preparation method of the high-performance high-gloss ABS electromagnetic shielding plastic is as follows: Step one: weigh each raw material according to the proportion, add it to the high-speed mixer and stir for 15 minutes to form a first mixture; Step two: melt, extrude, granulate and dry the first mixture at a processing temperature of 200°C to obtain the high-performance high-gloss ABS electromagnetic shielding plastic.

[0036] Comparative Example 3 Preparation of the high-performance high-gloss ABS electromagnetic shielding plastic: The composition of each component raw material is as follows: ABS resin 100 parts; PMMA 15 parts; Composite filler 4 22 parts; Styrene-maleic anhydride copolymer 3 parts; Antioxidant 1076 4 parts; UV-327 2 parts; Butyl stearate 3 parts; Benzoyl peroxide 1 part.

[0037] The preparation method of the high-performance high-gloss ABS electromagnetic shielding plastic is as follows: Step one: weigh each raw material according to the proportion, add to the high-speed mixer and stir for 15 minutes to form a first mixture; Step two: melt, extrude, granulate and dry the first mixture at a processing temperature of 200°C to obtain high-performance high-gloss ABS electromagnetic shielding plastic.

[0038] Comparative Example 4 Preparation of high-performance high-gloss ABS electromagnetic shielding plastic: The composition of each component raw material is as follows: ABS resin 100 parts; PMMA 15 parts; Composite filler 1 40 parts; Styrene-maleic anhydride copolymer 3 parts; Antioxidant 1076 4 parts; UV-327 2 parts; Butyl stearate 3 parts; Benzoyl peroxide 1 part.

[0039] The preparation method of high-performance high-gloss ABS electromagnetic shielding plastic is as follows: Step one: weigh each raw material according to the proportion, add to the high-speed mixer and stir for 15 minutes to form a first mixture; Step two: melt, extrude, granulate and dry the first mixture at a processing temperature of 200°C to obtain high-performance high-gloss ABS electromagnetic shielding plastic.

[0040] Performance test: After the high-performance high-gloss ABS electromagnetic shielding plastic prepared in Examples 1-3 and Comparative Examples 1-4 is prepared into a standard sample, its performance is detected.

[0041] The detection items include: gloss (reference standard ASTM D523); tensile strength (reference standard ASTM D638); bending strength (reference standard ASTM D790); electromagnetic shielding performance (reference standard ASTM D4935).

[0042] The results are shown in Table 1: Table 1 Comparison of properties of high-performance high-gloss ABS electromagnetic shielding plastic obtained from different examples and comparative examples

[0043] From the experimental results of Table 1, it can be seen that the high-performance high-gloss ABS electromagnetic shielding plastic prepared in the application not only has high gloss, tensile strength and bending strength, but also has good electromagnetic shielding performance. Further, compared with Example 1, Comparative Example 1 does not add conductive polyaniline, Comparative Example 2 does not add amino silane coupling agent modified nano-magnetic iron oxide, and Comparative Example 3 does not add maleic anhydride. The results show that the ABS plastic samples obtained in Comparative Examples 1-3 have different degrees of decline in tensile strength, bending strength and electromagnetic shielding efficiency compared with Example 1. Compared with Example 1, the amount of composite filler in Comparative Example 4 is too large, which further leads to the decline of the gloss and mechanical properties of the obtained ABS plastic sample.

[0044] The above is only an example and description of the concept of the present application. Those skilled in the art can make various modifications or supplements to the described specific embodiments or use similar ways to replace them, as long as they do not deviate from the concept of the present application or exceed the defined range, which should belong to the protection scope of the present application.

Claims

1. A high performance high gloss ABS electromagnetic shielding plastic characterized in that, According to parts by weight, raw materials consisting of: ABS resin 100 parts; PMMA 10-30 parts; Composite filler 20-35 parts; Compatibility agent 2-5 parts; Antioxidant 3-6 parts; UV absorber 1-3 parts; Lubricant 3-5 parts; Initiator 1-2 parts.

2. A high performance high gloss ABS electromagnetic shielding plastic as claimed in claim 1, wherein, The preparation process of the composite filler is as follows: Step one: Take HCl solution in a three-necked flask, add aniline monomer to start stirring, and at the same time use ice bath to control the temperature of the flask at 0℃. Then, dissolve ammonium persulfate into the HCl solution to obtain a mixed solution, and add the mixed solution dropwise into the three-necked flask containing the aniline monomer for reaction. After the reaction, wash and dry to obtain conductive polyaniline; Step two: add amino-containing silane coupling agent into ethanol aqueous solution to hydrolyze and obtain a hydrolysis solution, add nano-magnetite into the hydrolysis solution, and reflux under stirring, filter, wash, and dry to obtain nano-magnetite modified by amino silane coupling agent; Step three: Add the conductive polyaniline prepared in step one into DMF to stir and disperse uniformly to obtain a dispersion liquid, add maleic anhydride and triethylamine into the dispersion liquid, react for 4-5 hours to obtain a reaction liquid, add the nano-magnetite modified by amino silane coupling agent obtained in step two into the reaction liquid, react for 2-4 hours, cool to room temperature after the reaction, filter, and dry to obtain the composite filler.

3. A high performance high gloss ABS electromagnetic shielding plastic as claimed in claim 1 wherein, The compatibility agent is one or a combination of two or more of a terpolymer of methyl methacrylate-glycidyl methacrylate-ethyl acrylate, a graft of ABS, styrene-acrylonitrile-glycidyl methacrylate, and a styrene-maleic anhydride copolymer.

4. A high performance high gloss ABS electromagnetic shielding plastic as claimed in claim 1 wherein, The antioxidant is one or a combination of two or more of antioxidant 1010, antioxidant 1076, antioxidant 168, and antioxidant 626.

5. A high performance high gloss ABS electromagnetic shielding plastic as claimed in claim 1 wherein, The UV absorber is one or a combination of two or more of UV-531, UV-327, and UV-1164.

6. A high performance high gloss ABS electromagnetic shielding plastic as defined in claim 1 wherein, The lubricant is one or a combination of two or more of butyl stearate, ethylene bis-stearyl amide, stearic amide, and calcium stearate.

7. The high-performance, high-gloss ABS electromagnetic shielding plastic as described in claim 1, characterized in that, The initiator is one or a combination of two or more of benzoyl peroxide, dicumyl peroxide, and tert-butyl perbenzoate.

8. A high performance high gloss ABS electromagnetic shielding plastic as claimed in claim 2, wherein, The amino-containing silane coupling agent in step two is γ-aminopropyl triethoxysilane or γ-aminopropyl trimethoxysilane.

9. A high performance high gloss ABS electromagnetic shielding plastic as claimed in claim 2, wherein, The pH regulator in step two is sodium hydroxide or potassium hydroxide.

10. A method for preparing a high-performance, high-gloss ABS electromagnetic shielding plastic as described in any one of claims 1-9, characterized in that, The preparation method comprises the following steps: Step one: weigh each raw material according to the proportion, add into a high-speed mixer, and stir and mix for 10-20 minutes to form a first mixture; Step two: melt, extrude, granulate, and dry the first mixture at a processing temperature of 180-220℃ to obtain high-performance high-gloss ABS electromagnetic shielding plastic.

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