CN110760177B

CN110760177B - Conductive polyphenyl ether/high impact polystyrene composition and preparation method thereof

Info

Publication number: CN110760177B
Application number: CN201911128627.4A
Authority: CN
Inventors: 王忠强; 黄浩; 卢健体
Original assignee: Guangdong Aldex New Material Co Ltd
Current assignee: Guangdong Aldex New Material Co Ltd
Priority date: 2019-11-18
Filing date: 2019-11-18
Publication date: 2022-08-19
Anticipated expiration: 2039-11-18
Also published as: CN110760177A

Abstract

The invention relates to a conductive polyphenyl ether/high impact polystyrene composition and a preparation method thereof, wherein the conductive polyphenyl ether/high impact polystyrene composition is prepared from the following raw materials: the high-viscosity polyphenylene oxide resin, the low-viscosity polyphenylene oxide resin, the high-impact polystyrene resin, the styrene-glycidyl methacrylate copolymer, toluene diisocyanate, hydrogenated styrene-isoprene copolymer grafted maleic anhydride, N' -bis (2,2,6, 6-tetramethyl-4-piperidyl) -1, 3-benzenedicarboxamide, bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphate, pentaerythritol zinc, a graphene-carbon nanotube nano composite material and a silane coupling agent. The conductive polyphenyl ether/high impact polystyrene composition has excellent mechanical property and processing property, and can be applied to the electronic and electric appliance industry and the automobile industry.

Description

Conductive polyphenyl ether/high impact polystyrene composition and preparation method thereof

Technical Field

The invention relates to the field of materials, in particular to a conductive polyphenyl ether/high impact polystyrene composition and a preparation method thereof.

Background

Polyphenylene Oxide (PPO) has the advantages of excellent mechanical property, heat resistance, electrical insulation and small creep deformation at high temperature, and the PPO has low density and hygroscopicity, high strength and good dimensional stability. However, pure PPO resin has high glass transition temperature, poor melt flowability and difficult molding processing, and needs to be processed at a high temperature of 300 ℃, thereby greatly limiting the application range of the PPO resin. In order to overcome the defects of PPO and expand the application field of PPO, the PPO is modified by blending High Impact Polystyrene (HIPS) so as to improve the molding processability of the PPO, so that the PPO can be widely applied, but the PPO/HIPS composition with good processability, mechanical property and conductivity is still difficult to obtain in the existing PPO/HIPS system.

Carbon Nanotubes (CNTs) have high flexibility, low mass density and large aspect ratio, and a conductive carbon nanotube polymer composite can be obtained by using highly conductive carbon nanotubes as a filler, but the carbon nanotubes are easily entangled together due to van der waals forces during blending, which makes the carbon nanotubes difficult to disperse in the polymer. Graphene (Gr) with a two-dimensional structure is used as an isomer of carbon, the two-dimensional structure has unique electronic, thermal and mechanical properties, and can be used as a filler to improve the mechanical and electrical properties of a polymer composite material, but the Graphene needs to solve the dispersion problem and maintain a good lamellar structure in the polymer blending process.

Currently, some studies have been made in the prior art on PPO/HIPS systems, such as: chinese patent CN109735037A discloses a chemical resistance PPO/HIPS alloy material and a preparation method thereof, wherein the chemical resistance PPO/HIPS alloy material comprises the following components in parts by weight: 20-50 parts of polyphenyl ether, 35-66 parts of high impact polystyrene, 10-15 parts of a flame retardant, 1-3 parts of an ethylene-tetrafluoroethylene copolymer, 1-2 parts of a hydrogenated styrene-butadiene block copolymer, 0.1-1 part of an antioxidant and 0.1-1 part of a lubricant; chinese patent CN105419210A discloses a wear-resistant reinforced PPO/HIPS material and a preparation method thereof, wherein the material comprises the following raw materials in parts by weight: 20-40 parts of HIPS resin, 5-30 parts of PPO resin, 3-8 parts of nitrile rubber, 3-8 parts of TPU resin, 10-30 parts of glass fiber, 10-15 parts of aramid fiber, 3-10 parts of molybdenum disulfide, 3-10 parts of calcium sulfate whisker, 1-10 parts of polytetrafluoroethylene, 0.5-1.5 parts of coupling agent, 0.5-1 part of lubricant and 0.2-0.8 part of antioxidant; chinese patent CN105199364A discloses a flame-retardant aging-resistant PPO-HIPS polymer alloy and a preparation method thereof, relating to a polymer alloy and a preparation method thereof, wherein the polymer alloy comprises the following components in parts by mass: 80-90 parts of PPO, 10-20 parts of HIPS, 10-40 parts of three-in-one intumescent flame retardant, 0.5-20 parts of efficient anti-aging agent, 0.5-3 parts of antibacterial agent, 1-20 parts of compatibilizer SEBS-g-MAH10, 1-20 parts of mica powder and 0.1-5 parts of zinc oxide; chinese patent CN106947236A discloses a flame-retardant modified PPO-HIPS-mica powder composite material and a preparation method thereof, wherein the material is composed of the following raw materials in parts by weight: 650 parts of PPO powder, 150-350 parts of HIPS, 150-350 parts of mica powder, 20-60 parts of compatilizer, 40-70 parts of flexibilizer, 80-170 parts of flame retardant, 10-50 parts of anti-tick agent, 40-70 parts of flexibilizer, 3-20 parts of antioxidant, 3-20 parts of lubricant and 3-25 parts of toner; chinese patent CN110144109A discloses a weather-resistant high CTI halogen-free flame-retardant PPO/HIPS composite material and a preparation method thereof, wherein the composite material comprises the following components: 100 parts of PPO, 5-25 parts of HIPS10, 5-25 parts of toughening agent, 2-8 parts of light shielding agent, 5-15 parts of heat-resistant agent, 0.5-2 parts of light stabilizer, 10-25 parts of flame retardant, 1-5 parts of auxiliary flame retardant, 0.1-1 part of antioxidant and 0.1-1 part of lubricant by weight of 5 parts; chinese patent CN107541049A discloses a graphene-continuous glass fiber reinforced halogen-free flame-retardant weather-resistant PPO/HIPS alloy material, which is prepared from the following components in parts by weight: 480 parts of PPO 360-grade material, 320 parts of HIPS 240-grade material, 400 parts of continuous glass fiber 200-grade material, 5-15 parts of graphene, 10-20 parts of compatilizer, 50-80 parts of flexibilizer, 80-120 parts of flame retardant, 6-10 parts of antioxidant, 3-5 parts of composite light stabilizer, 4-8 parts of lubricant and 5-15 parts of metal oxide; chinese patent CN103483798A discloses an antistatic PPO/HIPS alloy and a preparation method thereof, wherein the alloy comprises the following raw materials in parts by weight: 100-120 parts of PPO, 30-50 parts of HIPS, 10-20 parts of a toughening agent, 3000.5-1 parts of an antioxidant, 6-10 parts of monoglyceride, 5-8 parts of ethoxylated lauryl tyramine, 8-12 parts of melamine phosphate, 1-3 parts of a heat stabilizer and 1-3 parts of a lubricant; chinese patent CN106118019A discloses a high-performance conductive engineering plastic, which is prepared by applying graphene to a polymer MPPO (polyphenylene oxide/high impact polystyrene blend modified alloy) matrix to form a high-conductivity and high-strength graphene/MPPO engineering plastic; chinese patent CN109233243A discloses a conductive MPPO engineering material with excellent comprehensive performance, which comprises the following components in percentage by mass: 35-50% of PPO resin, 10-15% of HIPS resin, 30-45% of self-made conductive fiber, 4-6% of toughening agent, 0.1-0.3% of coupling agent, 0.2-0.4% of antioxidant and 0.4-0.8% of lubricant; chinese patent CN102585481A discloses a conductive flame-retardant thermoplastic resin, in particular to a polyphenylene ether resin composition with conductive and flame-retardant effects, which comprises the following substances in parts by weight: 20-100 parts of polyphenyl ether, 5-30 parts of conductive agent, 5-25 parts of flame retardant and 5-15 parts of compatibilizer.

Disclosure of Invention

Based on the above, the invention aims to provide a polyphenyl ether/high impact polystyrene composition with excellent mechanical property, processability and electrical conductivity, which can be applied to the electronic and electrical industry and the automobile industry.

In order to achieve the purpose, the invention adopts the following scheme:

a conductive polyphenyl ether/high impact polystyrene composition is prepared from the following raw materials in parts by weight:

35-50 parts of high-viscosity polyphenylene oxide (PPO),

25-40 parts of low-viscosity polyphenylene oxide (PPO),

10-40 parts of high impact polystyrene resin (HIPS),

the sum of the parts by weight of the high-viscosity polyphenyl ether resin, the low-viscosity polyphenyl ether resin and the high impact polystyrene resin is 100 parts,

the intrinsic viscosity of the high-viscosity polyphenyl ether resin is 0.45-0.51 dL/g; the intrinsic viscosity of the low-viscosity polyphenyl ether resin is 0.33-0.37 dL/g; the number average molecular weight of the high impact polystyrene resin is 17000-28000;

the graphene-carbon nanotube nano composite material is prepared by mixing graphene oxide and a carboxylated carbon nanotube in a water phase, wherein the mass ratio of the graphene oxide to the carboxylated carbon nanotube is 1: 0.5 to 2;

the silane coupling agent is at least one of gamma-aminopropyltriethoxysilane, gamma-aminopropyltrimethoxysilane, N- (beta-aminoethyl) -gamma-aminopropyltriethoxysilane, N-beta- (aminoethyl) -gamma-aminopropyltrimethoxysilane, N-beta- (aminoethyl) -gamma-aminopropylmethyldimethoxysilane, gamma-aminopropylmethyldiethoxysilane and aniline methyltriethoxysilane.

In some of these embodiments, the conductive polyphenylene ether/high impact polystyrene composition is prepared from the following raw materials in parts by weight:

37-48 parts of high-viscosity polyphenylene oxide (PPO),

27-38 parts of low-viscosity polyphenylene oxide (PPO),

14-36 parts of high impact polystyrene resin (HIPS),

in some of the embodiments, the conductive polyphenylene ether/high impact polystyrene composition is further preferably prepared from the following raw materials in parts by weight:

41-45 parts of high-viscosity polyphenylene oxide resin (PPO),

30-34 parts of low-viscosity polyphenylene oxide (PPO),

20-30 parts of high impact polystyrene resin (HIPS),

in some embodiments, the mass fraction of the glycidyl methacrylate in the copolymer of styrene and glycidyl methacrylate is 2 to 4 wt%.

In some of the embodiments, the maleic anhydride grafting ratio of the hydrogenated styrene-isoprene copolymer grafted maleic anhydride is 0.8 to 1.5 wt%.

In some of these embodiments, the method for preparing graphene-carbon nanotube nanocomposites (Gr-CNTs) comprises the following steps: dispersing the graphene oxide in deionized water, then adding hydrazine hydrate and concentrated ammonia water, stirring, and reacting at 85-95 ℃ for 1-3 h to obtain graphene hydrosol; and then adding the carboxylated carbon nano tube into the graphene hydrosol, dispersing for 1-3 h, then carrying out centrifugal treatment on the obtained suspension at 2000-4000 rpm for 10-30 min, then carrying out centrifugal treatment at 13000-17000 rpm for 10-30 min to obtain a graphene-carbon nano tube nano composite material dispersion liquid, and drying to obtain the graphene-carbon nano tube nano composite material.

In some embodiments, the mass ratio of the graphene oxide to the carboxylated carbon nanotubes is 1kg: 0.8-1.2 kg.

In some embodiments, the mass volume ratio of the graphene oxide to the deionized water to the hydrazine hydrate to the concentrated ammonia water is 1kg: 0.8-1.2L: 0.8-1.2L: 6-8L.

In some of these embodiments, the method for preparing graphene-carbon nanotube nanocomposites (Gr-CNTs) comprises the following steps: dispersing 0.5kg of graphene oxide in 0.5L of deionized water through ultrasonic waves, adding 0.5L of hydrazine hydrate and 3.5L of concentrated ammonia water, stirring for 5-15 minutes, reacting at 85-95 ℃ for 1-3 hours to obtain graphene hydrosol, adding the carboxylated carbon nanotube into the graphene hydrosol, dispersing in the ultrasonic waves for 1-3 hours, centrifuging the obtained suspension at 2000-4000 rpm for 10-30 minutes, centrifuging at 13000-17000 rpm for 10-30 minutes to obtain a graphene-carbon nanotube nano composite material dispersion solution, performing suction filtration and washing, placing in an oven, and drying at 60-70 ℃ to obtain the graphene-carbon nanotube nano composite material.

In some of these embodiments, the silane coupling agent is at least one of gamma-aminopropyltriethoxysilane, gamma-aminopropyltrimethoxysilane.

It is another object of the present invention to provide a method for preparing a conductive polyphenylene ether/high impact polystyrene composition.

The preparation method of the conductive polyphenyl ether/high impact polystyrene composition comprises the following steps:

(1) drying the high-viscosity polyphenyl ether resin, the low-viscosity polyphenyl ether resin and the high-impact polystyrene resin at the temperature of 80-110 ℃ for 4-8 hours, cooling, and adding the cooled high-viscosity polyphenyl ether resin, the cooled low-viscosity polyphenyl ether resin, the cooled high-impact polystyrene resin, the N, N' -bis (2,2,6, 6-tetramethyl-4-piperidyl) -1, 3-benzenedicarboxamide, bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphate and pentaerythritol zinc into a stirrer for mixing;

(2) adding the styrene and glycidyl methacrylate copolymer, toluene diisocyanate, hydrogenated styrene-isoprene copolymer grafted maleic anhydride, the graphene-carbon nanotube nano composite material and the silane coupling agent into another stirrer for mixing;

(3) adding the mixed material obtained in the step (1) into a parallel double-screw extruder through a feeder, adding the mixed material obtained in the step (2) into the parallel double-screw extruder (totally eight zones) (for example, a fourth zone) in the lateral direction (for example, the fourth zone) for melt extrusion and granulation, wherein the process parameters comprise: the temperature of the first zone is 250-270 ℃, the temperature of the second zone is 255-275 ℃, the temperature of the third zone is 255-275 ℃, the temperature of the fourth zone is 260-280 ℃, the temperature of the fifth zone is 260-280 ℃, the temperature of the sixth zone is 260-280 ℃, the temperature of the seventh zone is 260-280 ℃, the temperature of the eighth zone is 255-275 ℃, the temperature of the die head is 255-275 ℃ and the rotation speed of the screw is 200-600 rpm.

In some embodiments, the high-viscosity polyphenylene ether resin, the low-viscosity polyphenylene ether resin and the high impact polystyrene resin are dried at a temperature of 90-100 ℃ for 4-6 hours in the step (1); the process parameters in the step (3) comprise: the temperature of the first zone is 255-265 ℃, the temperature of the second zone is 260-270 ℃, the temperature of the third zone is 260-270 ℃, the temperature of the fourth zone is 265-275 ℃, the temperature of the fifth zone is 265-275 ℃, the temperature of the sixth zone is 265-275 ℃, the temperature of the seventh zone is 265-275 ℃, the temperature of the eighth zone is 260-270 ℃, the temperature of the die head is 260-270 ℃, and the rotating speed of the screw is 300-500 rpm.

In some of these embodiments, the screw shape of the parallel twin screw extruder is a single thread; the ratio L/D of the length L of the screw to the diameter D of the screw is 35 to 50; the screw is provided with more than 1 (including 1) meshing block area and more than 1 (including 1) reverse thread area.

In some of these embodiments, the ratio L/D of the length L of the screw to the diameter D of the screw is 35 to 45; and 2 meshing block areas and 1 reverse thread area are arranged on the screw rod.

In some embodiments, in step (1) and/or step (2), the stirrer is a high-speed stirrer with a rotation speed of 500-.

The principle of the conductive polyphenylene ether/high impact polystyrene composition of the present invention is as follows:

in order to improve the compatibility between the polyphenyl ether resin and the high impact polystyrene resin in the conductive polyphenyl ether/high impact polystyrene composition and the defect of poor processing performance of the polyphenyl ether resin, the invention improves the compatibility between the polyphenyl ether resin and the high impact polystyrene resin by adding a styrene and glycidyl methacrylate copolymer and hydrogenated styrene-isoprene copolymer grafted maleic anhydride, wherein the compatibility between a styrene structural unit in the styrene and glycidyl methacrylate copolymer and the hydrogenated styrene-isoprene copolymer grafted maleic anhydride and the high impact polystyrene resin is very good, an epoxy group of the styrene and glycidyl methacrylate copolymer and an anhydride group of the hydrogenated styrene-isoprene copolymer grafted maleic anhydride can react with a terminal hydroxyl group of the polyphenyl ether resin, thereby improving the compatibility between the PPO and the HIPS. Due to the fact that the processing temperature of the polyphenyl ether resin is high, chain breakage of the polyphenyl ether resin is prone to occur in the processing process, and the generation of polyphenyl ether resin oligomer is reduced and the mechanical property of the conductive polyphenyl ether/high impact polystyrene composition is guaranteed by utilizing the reaction of the isocyanate group of toluene diisocyanate and the terminal hydroxyl group of PPO. The mechanical property of the PPO/HIPS composition is ensured by adding high-viscosity polyphenyl ether resin, and the processability of the PPO/HIPS composition is ensured by adding low-viscosity polyphenyl ether resin and high-impact polystyrene resin.

The melting point of the N, N' -bis (2,2,6, 6-tetramethyl-4-piperidyl) -1, 3-benzenedicarboxamide adopted by the invention is 272 ℃, the boiling point is more than 360 ℃, the thermal stability in the blending process of PPO and HIPS is better, and the hindered piperidyl of the antioxidant can provide an antioxidant effect and improve the dyeability of the copolymer; the bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphate has the melting point of 239 ℃ and the thermal decomposition temperature of more than 350 ℃, has good heat resistance and hydrolysis resistance, can provide excellent color stability and melt stability for PPO and HIPS in the blending process, can prevent the thermal degradation of PPO and HIPS in the high-temperature process, can inhibit the thermal oxidative discoloration caused by long time, and can also be provided in Nitrogen Oxide (NO) _x ) Color stability in gas environment, and prevention of discoloration of fumigant.

The pentaerythritol zinc adopted by the invention has the functions of lubrication and thermal stabilization, and simultaneously, when the pentaerythritol zinc is used as a thermal stabilizer alone, compared with a common zinc-containing compound (such as zinc oxide), the zinc-containing compound can effectively reduce the occurrence probability of zinc burning in the blending process.

According to the invention, the graphene-carbon nanotube nano composite material is adopted to improve the conductivity of the polyphenyl ether/high impact polystyrene composition, the carbon nanotubes can be embedded on the surface of the graphene through electrostatic action in the preparation process of the graphene-carbon nanotube nano composite material, so that the dispersion of the carbon nanotubes is facilitated, and the good lamellar structure of the graphene is maintained, and meanwhile, the silane coupling agent is adopted to improve the compatibility of the graphene-carbon nanotube nano composite material and the polyphenyl ether/high impact polystyrene composition, so that the dispersion of the graphene-carbon nanotube nano composite material in the polyphenyl ether/high impact polystyrene composition in the blending process is facilitated, and a high-efficiency conductive network is formed better.

Compared with the prior art, the invention has the following beneficial effects:

in order to improve the compatibility between the polyphenyl ether resin and the high impact polystyrene resin and the defect of poor processing performance of the polyphenyl ether resin, the compatibility between the polyphenyl ether resin and the high impact polystyrene resin is improved by adding the copolymer of styrene and glycidyl methacrylate and the hydrogenated styrene-isoprene copolymer grafted maleic anhydride, the generation of polyphenyl ether resin oligomers is reduced by adding toluene diisocyanate, the mechanical property of the polyphenyl ether composition is ensured, meanwhile, the high-viscosity and low-viscosity polyphenyl ether resin is compounded to ensure the mechanical property and the processing performance of the conductive polyphenyl ether/high impact polystyrene composition, and N, N' -bis (2,2,6, 6-tetramethyl-4-piperidyl) -1, 3-phthalic amide, The bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphate and pentaerythritol zinc improve the yellowing phenomenon and the thermal stability of the conductive polyphenyl ether/high impact polystyrene composition in the blending processing process, the conductivity of the polyphenyl ether/high impact polystyrene composition is improved by adopting the graphene-carbon nanotube nano composite material, and the raw material components are matched with each other, so that the conductive polyphenyl ether/high impact polystyrene composition has excellent mechanical property, processing property and conductivity, and can be applied to the electronic and electric appliance industry and the automobile industry.

The preparation method of the conductive polyphenyl ether/high impact polystyrene composition provided by the invention has the advantages of simple process, easiness in control and low requirement on equipment, and the used equipment is general polymer processing equipment, so that the investment is low, and the industrial production is facilitated.

Drawings

FIG. 1 is a flow chart of a process for preparing a conductive polyphenylene ether/high impact polystyrene composition according to one embodiment of the present invention.

Detailed Description

In order to further understand the features and technical means of the present invention and achieve the specific objects and functions, the advantages and spirit of the present invention are further illustrated by the following embodiments.

The reaction mechanism of the conductive polyphenylene ether/high impact polystyrene composition of one embodiment of the present invention is as follows (see FIG. 1 for a flow chart of the preparation process):

from the above reaction formula, the epoxy group of the styrene-glycidyl methacrylate copolymer and the anhydride group of the hydrogenated styrene-isoprene copolymer grafted maleic anhydride can react with the terminal hydroxyl group of the polyphenylene oxide resin, and meanwhile, the styrene structural unit in the styrene-glycidyl methacrylate copolymer and the hydrogenated styrene-isoprene copolymer grafted maleic anhydride has very good compatibility with the high impact polystyrene resin, so that the compatibility between the PPO and the HIPS is improved. In addition, the isocyanate group of the toluene diisocyanate can react with the terminal hydroxyl of the PPO, so that the generation of polyphenylene oxide resin oligomer is reduced, and the mechanical property of the conductive polyphenylene oxide/high impact polystyrene composition is ensured.

The examples of the invention and the comparative examples used the following raw materials:

high viscosity polyphenylene ether resin with intrinsic viscosity of 0.48dL/g selected from Nantong star synthetic materials, Inc.;

a high viscosity polyphenylene ether resin having an intrinsic viscosity of 0.55dL/g selected from Nantong star synthetic materials, Inc.;

low viscosity polyphenylene ether resin with intrinsic viscosity of 0.35dL/g, selected from Nantong star synthetic materials GmbH;

low viscosity polyphenylene ether resin with intrinsic viscosity of 0.28dL/g, selected from Nantong star synthetic materials GmbH;

a high impact polystyrene resin having a number average molecular weight of 23000 selected from Taiwan Chimei industries, Ltd;

a copolymer of styrene and glycidyl methacrylate, the mass fraction of Glycidyl Methacrylate (GMA) being 3% by weight, selected from sigma aldrich trade ltd;

toluene diisocyanate selected from the group consisting of national pharmaceutical group chemical agents;

the hydrogenated styrene-isoprene copolymer was grafted with maleic anhydride, the maleic anhydride grafting ratio was 1.2 wt%, and was selected from the group consisting of the company clony, japan;

n, N' -bis (2,2,6, 6-tetramethyl-4-piperidinyl) -1, 3-benzenedicarboxamide, selected from Toxongitai chemical Co., Ltd;

bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphate selected from Shanghai Yaozao Fine chemical Co., Ltd;

pentaerythritol zinc selected from Zhaoqing Sendeli chemical industry Co., Ltd;

graphene oxide selected from the group consisting of institute of sciences, china, institute of academic organic chemistry, ltd;

carboxylated carbon nanotubes selected from the group consisting of the Chinese academy of sciences organic chemistry, Inc.;

gamma-aminopropyltriethoxysilane selected from Hubei Wuda New Silicone materials GmbH;

gamma-aminopropyltrimethoxysilane selected from the group consisting of Hubei Wuda Silicone New materials GmbH;

hydrogenated styrene-butadiene-styrene copolymer grafted maleic anhydride selected from Shenyangtotong plastics Co., Ltd;

carbon nanotube: selected from Nanjing Xiancheng nanomaterial science and technology Limited;

graphene: selected from Jiangsu Tiannai science and technology, Inc.

The present invention will be described in detail with reference to specific examples.

The preparation method of graphene-carbon nanotube nanocomposites (Gr-CNTs) described in the following examples is as follows: dispersing 0.5kg of graphene oxide in 0.5L of deionized water by ultrasonic waves, adding 0.5L of hydrazine hydrate and 3.5L of concentrated ammonia water, stirring for 10 minutes, reacting for 2 hours at 90 ℃ to obtain graphene hydrosol, adding 0.5kg of carboxylated carbon nanotubes into the graphene hydrosol, dispersing for 2 hours in the ultrasonic waves, centrifuging the obtained suspension at 3000rpm for 20 minutes, centrifuging at 15000rpm for 20 minutes to obtain a graphene-carbon nanotube nanocomposite dispersion solution, performing suction filtration and washing, placing in an oven, and drying at 65 ℃ to obtain the graphene-carbon nanotube nanocomposite.

Example 1:

the embodiment of the invention relates to a conductive polyphenyl ether/high impact polystyrene composition, which is prepared from the following raw materials in parts by weight:

35 parts of high-viscosity polyphenyl ether resin (the intrinsic viscosity is 0.48dL/g),

25 parts of low-viscosity polyphenylene ether resin (the intrinsic viscosity is 0.35dL/g),

40 parts of high impact polystyrene resin (23000 in number average molecular weight),

(1) drying the high-viscosity polyphenyl ether resin, the low-viscosity polyphenyl ether resin and the high-impact polystyrene resin at the temperature of 80 ℃ for 8 hours, cooling, and adding the cooled high-viscosity polyphenyl ether resin, the cooled low-viscosity polyphenyl ether resin, the cooled high-impact polystyrene resin, the N, N' -bis (2,2,6, 6-tetramethyl-4-piperidyl) -1, 3-benzenedicarboxamide, bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphate and pentaerythritol zinc into a high-speed stirrer (the rotating speed is 1000 revolutions per minute) for mixing;

(2) adding the styrene and glycidyl methacrylate copolymer, toluene diisocyanate, hydrogenated styrene-isoprene copolymer grafted maleic anhydride, the graphene-carbon nanotube nano composite material and gamma-aminopropyltriethoxysilane into another high-speed stirrer (the rotating speed is 1000 revolutions per minute) for mixing;

(3) adding the mixture mixed in the step (1) into a parallel double-screw extruder through a feeder, adding the mixture mixed in the step (2) into the side direction (the fourth zone) of the parallel double-screw extruder (total eight zones) for melt extrusion and granulation, wherein the process parameters comprise: the temperature of the first zone is 250 ℃, the temperature of the second zone is 255 ℃, the temperature of the third zone is 255 ℃, the temperature of the fourth zone is 260 ℃, the temperature of the fifth zone is 260 ℃, the temperature of the sixth zone is 260 ℃, the temperature of the seventh zone is 260 ℃, the temperature of the eighth zone is 255 ℃, the temperature of the die head is 255 ℃ and the rotation speed of the screw is 200 rpm.

The screw of the parallel double-screw extruder is in a single-thread shape, the ratio L/D of the length L and the diameter D of the screw is 35, and the screw is provided with 2 meshing block areas and 1 back-thread area.

Example 2:

50 parts of high-viscosity polyphenyl ether resin (the intrinsic viscosity is 0.48dL/g),

40 parts of low-viscosity polyphenylene ether resin (the intrinsic viscosity is 0.35dL/g),

10 parts of high impact polystyrene resin (23000 in number average molecular weight),

(1) drying the high-viscosity polyphenyl ether resin, the low-viscosity polyphenyl ether resin and the high-impact polystyrene resin at the temperature of 110 ℃ for 4 hours, cooling, and adding the cooled high-viscosity polyphenyl ether resin, the cooled low-viscosity polyphenyl ether resin, the cooled high-impact polystyrene resin, the N, N' -bis (2,2,6, 6-tetramethyl-4-piperidyl) -1, 3-benzenedicarboxamide, bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphate and pentaerythritol zinc into a high-speed stirrer (the rotating speed is 1000 revolutions per minute) for mixing;

(2) adding the styrene-glycidyl methacrylate copolymer, toluene diisocyanate, hydrogenated styrene-isoprene copolymer grafted maleic anhydride, the graphene-carbon nanotube nano composite material and gamma-aminopropyltrimethoxysilane into another high-speed stirrer (the rotating speed is 1000 revolutions per minute) for mixing;

(3) adding the mixture mixed in the step (1) into a parallel double-screw extruder through a feeder, adding the mixture mixed in the step (2) into the side direction (the fourth zone) of the parallel double-screw extruder (total eight zones) for melt extrusion and granulation, wherein the process parameters comprise: the temperature in the first zone was 270 ℃, the temperature in the second zone was 275 ℃, the temperature in the third zone was 275 ℃, the temperature in the fourth zone was 280 ℃, the temperature in the fifth zone was 280 ℃, the temperature in the sixth zone was 280 ℃, the temperature in the seventh zone was 280 ℃, the temperature in the eighth zone was 275 ℃, the temperature in the die head was 275 ℃ and the screw speed was 600 rpm.

The screw of the parallel double-screw extruder is in a single-thread shape, the ratio L/D of the length L and the diameter D of the screw is 50, and the screw is provided with 2 meshing block areas and 1 back-thread area.

Example 3:

37 parts of high-viscosity polyphenyl ether resin (the intrinsic viscosity is 0.48dL/g),

27 parts of low-viscosity polyphenylene ether resin (the intrinsic viscosity is 0.35dL/g),

36 parts of high impact polystyrene resin (23000 in number average molecular weight),

(1) drying the high-viscosity polyphenyl ether resin, the low-viscosity polyphenyl ether resin and the high-impact polystyrene resin at the temperature of 90 ℃ for 6 hours, cooling, and adding the cooled high-viscosity polyphenyl ether resin, the cooled low-viscosity polyphenyl ether resin, the cooled high-impact polystyrene resin, the N, N' -bis (2,2,6, 6-tetramethyl-4-piperidyl) -1, 3-benzenedicarboxamide, bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphate and pentaerythritol zinc into a high-speed stirrer (the rotating speed is 1000 revolutions per minute) for mixing;

(3) adding the mixture mixed in the step (1) into a parallel double-screw extruder through a feeder, adding the mixture mixed in the step (2) into the parallel double-screw extruder (totally eight zones) in the lateral direction (fourth zone) for melt extrusion, and granulating, wherein the process parameters comprise: the temperature in the first zone was 255 ℃, the temperature in the second zone was 260 ℃, the temperature in the third zone was 260 ℃, the temperature in the fourth zone was 265 ℃, the temperature in the fifth zone was 265 ℃, the temperature in the sixth zone was 265 ℃, the temperature in the seventh zone was 265 ℃, the temperature in the eighth zone was 260 ℃, the temperature in the die head was 260 ℃ and the screw speed was 300 rpm.

The shape of a screw of the parallel double-screw extruder is a single thread, the ratio L/D of the length L and the diameter D of the screw is 35, and the screw is provided with 2 meshing block areas and 1 reverse thread area.

Example 4:

48 parts of high-viscosity polyphenylene ether resin (the intrinsic viscosity is 0.48dL/g),

38 parts of low-viscosity polyphenylene ether resin (the intrinsic viscosity is 0.35dL/g),

14 parts of high impact polystyrene resin (23000 in number average molecular weight),

(1) drying the high-viscosity polyphenyl ether resin, the low-viscosity polyphenyl ether resin and the high-impact polystyrene resin at the temperature of 100 ℃ for 4 hours, cooling, and adding the cooled high-viscosity polyphenyl ether resin, the cooled low-viscosity polyphenyl ether resin, the cooled high-impact polystyrene resin, the N, N' -bis (2,2,6, 6-tetramethyl-4-piperidyl) -1, 3-benzenedicarboxamide, bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphate and pentaerythritol zinc into a high-speed stirrer (the rotating speed is 1000 revolutions per minute) for mixing;

(3) adding the mixture mixed in the step (1) into a parallel double-screw extruder through a feeder, adding the mixture mixed in the step (2) into the side direction (the fourth zone) of the parallel double-screw extruder (total eight zones) for melt extrusion and granulation, wherein the process parameters comprise: the temperature in the first zone was 265 deg.C, the temperature in the second zone was 270 deg.C, the temperature in the third zone was 270 deg.C, the temperature in the fourth zone was 275 deg.C, the temperature in the fifth zone was 275 deg.C, the temperature in the sixth zone was 275 deg.C, the temperature in the seventh zone was 275 deg.C, the temperature in the eighth zone was 270 deg.C, the temperature in the die head was 270 deg.C, and the screw speed was 500 rpm.

The screw of the parallel double-screw extruder is in a single-thread shape, the ratio L/D of the length L and the diameter D of the screw is 45, and the screw is provided with 2 meshing block areas and 1 reverse-thread area.

Example 5:

39 parts of high-viscosity polyphenylene ether resin (intrinsic viscosity 0.48dL/g),

29 parts of low-viscosity polyphenylene ether resin (the intrinsic viscosity is 0.35dL/g),

32 parts of high impact polystyrene resin (23000 in number average molecular weight),

(1) drying the high-viscosity polyphenyl ether resin, the low-viscosity polyphenyl ether resin and the high-impact polystyrene resin at the temperature of 95 ℃ for 5 hours, cooling, and adding the cooled high-viscosity polyphenyl ether resin, the cooled low-viscosity polyphenyl ether resin, the cooled high-impact polystyrene resin, the N, N' -bis (2,2,6, 6-tetramethyl-4-piperidyl) -1, 3-benzenedicarboxamide, bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphate and pentaerythritol zinc into a high-speed stirrer (the rotating speed is 1000 revolutions per minute) for mixing;

(3) adding the mixture mixed in the step (1) into a parallel double-screw extruder through a feeder, adding the mixture mixed in the step (2) into the side direction (the fourth zone) of the parallel double-screw extruder (total eight zones) for melt extrusion and granulation, wherein the process parameters comprise: the temperature of the first zone was 260 ℃, the temperature of the second zone was 265 ℃, the temperature of the third zone was 265 ℃, the temperature of the fourth zone was 270 ℃, the temperature of the fifth zone was 270 ℃, the temperature of the sixth zone was 270 ℃, the temperature of the seventh zone was 270 ℃, the temperature of the eighth zone was 265 ℃, the temperature of the die head was 265 ℃ and the screw speed was 400 rpm.

The screw of the parallel double-screw extruder is in a single-thread shape, the ratio L/D of the length L and the diameter D of the screw is 40, and the screw is provided with 2 meshing block areas and 1 back-thread area.

Example 6:

46 parts of high-viscosity polyphenylene ether resin (the intrinsic viscosity is 0.48dL/g),

36 parts of low-viscosity polyphenylene ether resin (the intrinsic viscosity is 0.35dL/g),

18 parts of high impact polystyrene resin (23000 in number average molecular weight),

(3) adding the mixture mixed in the step (1) into a parallel double-screw extruder through a feeder, adding the mixture mixed in the step (2) into the side direction (the fourth zone) of the parallel double-screw extruder (total eight zones) for melt extrusion and granulation, wherein the process parameters comprise: the temperature in the first zone was 260 ℃, the temperature in the second zone was 265 ℃, the temperature in the third zone was 265 ℃, the temperature in the fourth zone was 270 ℃, the temperature in the fifth zone was 270 ℃, the temperature in the sixth zone was 270 ℃, the temperature in the seventh zone was 270 ℃, the temperature in the eighth zone was 265 ℃, the temperature in the die head was 265 ℃ and the screw speed was 400 rpm.

Example 7:

43 parts of high-viscosity polyphenylene ether resin (intrinsic viscosity 0.48dL/g),

32 parts of low-viscosity polyphenylene ether resin (the intrinsic viscosity is 0.35dL/g),

25 parts of high impact polystyrene resin (23000 in number average molecular weight),

(2) adding the styrene and glycidyl methacrylate copolymer, toluene diisocyanate, hydrogenated styrene-isoprene copolymer grafted maleic anhydride, the graphene-carbon nanotube nanocomposite and gamma-aminopropyltriethoxysilane into another high-speed stirrer (the rotating speed is 1000 revolutions per minute) for mixing;

(3) adding the mixture mixed in the step (1) into a parallel double-screw extruder through a feeder, adding the mixture mixed in the step (2) into the parallel double-screw extruder (totally eight zones) in the lateral direction (fourth zone) for melt extrusion, and granulating, wherein the process parameters comprise: the temperature in the first zone was 260 ℃, the temperature in the second zone was 265 ℃, the temperature in the third zone was 265 ℃, the temperature in the fourth zone was 270 ℃, the temperature in the fifth zone was 270 ℃, the temperature in the sixth zone was 270 ℃, the temperature in the seventh zone was 270 ℃, the temperature in the eighth zone was 265 ℃, the temperature in the die head was 265 ℃ and the screw speed was 400 rpm.

The parallel double-screw extruder is characterized in that a screw of the parallel double-screw extruder is in a single-thread shape, the ratio L/D of the length L and the diameter D of the screw is 40, and the screw is provided with 2 meshing block areas and 1 reverse-thread area.

Example 8:

43 parts of high-viscosity polyphenylene ether resin (the intrinsic viscosity is 0.48dL/g),

The shape of a screw of the parallel double-screw extruder is double-thread, the ratio L/D of the length L and the diameter D of the screw is 50, and the screw is provided with 2 meshing block areas and 1 back-thread area.

Comparative example 1:

the comparative example is a conductive polyphenyl ether/high impact polystyrene composition, which is prepared from the following raw materials in parts by weight:

43 parts of high-viscosity polyphenylene ether resin (with the intrinsic viscosity of 0.55dL/g),

(2) adding the styrene-glycidyl methacrylate copolymer, toluene diisocyanate and hydrogenated styrene-isoprene copolymer grafted maleic anhydride into another high-speed stirrer (the rotating speed is 1000 rpm) for mixing;

Comparative example 2:

32 parts of low-viscosity polyphenylene ether resin (the intrinsic viscosity is 0.28dL/g),

Comparative example 3:

(2) adding the graphene-carbon nanotube nano composite material and gamma-aminopropyltriethoxysilane into another high-speed stirrer (the rotating speed is 1000 revolutions per minute) for mixing;

Comparative example 4:

(2) adding the styrene and glycidyl methacrylate copolymer, toluene diisocyanate, hydrogenated styrene-butadiene-styrene copolymer grafted maleic anhydride, the graphene-carbon nanotube nano composite material and gamma-aminopropyltriethoxysilane into another high-speed stirrer (the rotating speed is 1000 revolutions per minute) for mixing;

(3) adding the mixture mixed in the step (1) into a parallel double-screw extruder through a feeder, adding the mixture mixed in the step (2) into the parallel double-screw extruder (totally eight zones) in the lateral direction (fourth zone) for melt extrusion, and granulating, wherein the process parameters comprise: the temperature of the first zone was 260 ℃, the temperature of the second zone was 265 ℃, the temperature of the third zone was 265 ℃, the temperature of the fourth zone was 270 ℃, the temperature of the fifth zone was 270 ℃, the temperature of the sixth zone was 270 ℃, the temperature of the seventh zone was 270 ℃, the temperature of the eighth zone was 265 ℃, the temperature of the die head was 265 ℃ and the screw speed was 400 rpm.

Comparative example 5:

(2) adding the styrene-glycidyl methacrylate copolymer, toluene diisocyanate, hydrogenated styrene-isoprene copolymer grafted maleic anhydride, carbon nano tubes and gamma-aminopropyltriethoxysilane into another high-speed stirrer (the rotating speed is 1000 revolutions per minute) for mixing;

Comparative example 6:

(2) adding the styrene and glycidyl methacrylate copolymer, toluene diisocyanate, hydrogenated styrene-isoprene copolymer grafted maleic anhydride, graphene and gamma-aminopropyltriethoxysilane into another high-speed stirrer (the rotating speed is 1000 revolutions per minute) for mixing;

Comparative example 7:

(2) adding the styrene and glycidyl methacrylate copolymer, hydrogenated styrene-isoprene copolymer grafted maleic anhydride, the graphene-carbon nanotube nano composite material and gamma-aminopropyltriethoxysilane into another high-speed stirrer (the rotating speed is 1000 revolutions per minute) for mixing;

The following is a list of raw material compositions of examples and comparative examples (table 1).

TABLE 1 summary of the parts by weight of the raw materials of the examples and comparative examples

Remarking: a, changing a screw structure; b, the intrinsic viscosity of the high-viscosity PPO is 0.55 dL/g; c, the intrinsic viscosity of the low-viscosity PPO is 0.28 dL/g; d, replacing SEPS-g-MAH with SEBS-g-MAH; e, replacing Gr-CNTs with carbon nanotubes; f, replacing Gr-CNTs with graphene.

The N, N' -bis (2,2,6, 6-tetramethyl-4-piperidyl) -1, 3-benzenedicarboxamide, bis (2, 6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphate and pentaerythritol zinc of the above examples and comparative examples were added in amounts of 0.2 parts, respectively.

The conductive polyphenylene ether/high impact polystyrene compositions prepared in the above examples and comparative examples were subjected to the following property tests:

tensile property: testing according to GB/T1040-2006 standard, wherein the stretching speed is 50 mm/min;

impact properties: according to the test of GB/T1843-2008 standard, the thickness of the sample strip is 4 mm;

melt index: testing according to GB/T3682-2000 standard, wherein the testing temperature is 280 ℃, and the load is 5 kg;

volume resistivity: according to the test of GB/T1410-2006 standard, the smaller the volume resistivity is, the better the conductivity is.

The results of the performance tests are shown in table 2.

TABLE 2 Properties of the conductive polyphenylene ether/high impact polystyrene compositions of the examples and comparative examples

In examples 1 to 7, the addition amounts of the high-viscosity polyphenylene ether resin, the low-viscosity polyphenylene ether resin, the high-impact polystyrene resin, SG, TDI and SEPS-g-MAH were adjusted, and it can be seen from the table that as the addition amount of the high-impact polystyrene resin decreased (or the addition amount of the polyphenylene ether resin increased), the tensile strength exhibited an increasing trend of change, while the notched impact strength and melt index exhibited a decreasing trend of change, primarily because the HIPS base resin was lower in strength and better in toughness and flowability, and SG and SEPS-g-MAH can improve the compatibility between the polyphenyl ether resin and the high impact polystyrene resin, thereby improving the mechanical property of the conductive polyphenyl ether/high impact polystyrene composition, but the strength of SG and SEPS-g-MAH is lower, too much addition thereof adversely affects the mechanical properties of the conductive polyphenylene ether/high impact polystyrene composition. Meanwhile, TDI can reduce the generation of polyphenylene oxide resin oligomer, and the addition of TDI ensures the mechanical property of the polyphenylene oxide/high impact polystyrene composition. The volume resistivity thereof shows a decreasing trend of change as the addition amount of Gr-CNTs increases, and when the addition amount of Gr-CNTs exceeds 10 parts, the volume resistivity thereof does not change much. By comparison, example 7 has the best overall performance.

Example 7 compared with example 8, the screw shape of the parallel twin-screw extruder of example 8 was double-screw, the ratio L/D of the length L of the screw to the diameter D of the screw was 50, the screw shape of the parallel twin-screw extruder of example 7 was single-screw, and the ratio L/D of the length L of the screw to the diameter D of the screw was 40, and it was found by comparison that the tensile strength, the notched impact strength and the melt index of the conductive polyphenylene ether/high impact polystyrene composition prepared using the screw parameters of the parallel twin-screw extruder described in example 7 were better.

Example 7 in comparison with comparative example 1, comparative example 1 used a high viscosity polyphenylene ether resin having an intrinsic viscosity of 0.55dL/g, whereas example 7 used a high viscosity polyphenylene ether resin having an intrinsic viscosity of 0.48dL/g, and the fluidity thereof was greatly reduced as the intrinsic viscosity of the polyphenylene ether resin was increased, and when the intrinsic viscosity of the polyphenylene ether resin was 0.55dL/g, the melt index of the conductive polyphenylene ether/high impact polystyrene composition was only 5.5g/10min, and the processability was poor, and comparative example 1 did not use Gr-CNTs, and the volume resistivity thereof was 10 ^15～16 Omega cm; example 7 in comparison with comparative example 2, comparative example 2 used a low-tack polyphenylene ether resin having an intrinsic viscosity of 0.28dL/g, whereas example 7 used a low-tack polyphenylene ether resin having an intrinsic viscosity of 0.35dL/g, and as the intrinsic viscosity of the polyphenylene ether resin decreased, the tensile strength and notched impact strength decreased, and the conductive polyphenylene ether/high impact polystyrene composition prepared in comparative example 2 had lower tensile strength and notched impact strength than those of example 7; example 7 compared to comparative example 3, comparative example 3 had no addition of SG, TDI and SEPS-g-MAH, and had a general compatibility of PPO and HIPS, so that the resulting conductive polyphenylene ether/high impact polystyrene composition had lower tensile strength and notched impact strength than example 7; example 7 compares with comparative example 4Example 4 used SEBS-g-MAH and example 7 used SEPS-g-MAH, the polyphenylene ether/high impact polystyrene composition prepared in example 7 had higher tensile and notched impact strengths than those of comparative example 4; example 7 compared with comparative examples 5 and 6, comparative example 5 uses carbon nanotubes, comparative example 6 uses graphene, and example 7 uses Gr-CNTs, since the carbon nanotubes or graphene used alone are prone to agglomeration, which affects the conductivity of the polymer and the mechanical properties and processability of the material, the polyphenylene ether/high impact polystyrene composition prepared in example 7 has better conductivity, tensile strength, notched impact strength and melt index than comparative examples 5 and 6; example 7 in comparison to comparative example 7, the PPO/HIPS composition produced polyphenylene ether resin oligomers to affect mechanical properties due to the absence of toluene diisocyanate added in comparative example 7, resulting in a polyphenylene ether/high impact polystyrene composition prepared in comparative example 7 having lower tensile strength and lower notched impact strength than example 7.

The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.

The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.

Claims

1. The conductive polyphenyl ether/high impact polystyrene composition is characterized by being prepared from the following raw materials in parts by weight:

the graphene-carbon nanotube nano composite material is obtained by mixing graphene oxide and a carboxylated carbon nanotube in a water phase, wherein the mass ratio of the graphene oxide to the carboxylated carbon nanotube is 1: 0.5-2;

the silane coupling agent is at least one of gamma-aminopropyltriethoxysilane, gamma-aminopropyltrimethoxysilane, N- (beta-aminoethyl) -gamma-aminopropyltriethoxysilane, N-beta- (aminoethyl) -gamma-aminopropyltrimethoxysilane, N-beta- (aminoethyl) -gamma-aminopropylmethyldimethoxysilane, gamma-aminopropylmethyldiethoxysilane and aniline methyltriethoxysilane;

(2) adding the styrene and glycidyl methacrylate copolymer, toluene diisocyanate, hydrogenated styrene-isoprene copolymer grafted maleic anhydride, the graphene-carbon nanotube nanocomposite and the silane coupling agent into another stirrer for mixing;

(3) adding the mixture mixed in the step (1) into a parallel double-screw extruder through a feeder, adding the mixture mixed in the step (2) into the parallel double-screw extruder in the lateral direction, performing melt extrusion, and granulating, wherein the process parameters comprise: the temperature of the first zone is 250-270 ℃, the temperature of the second zone is 255-275 ℃, the temperature of the third zone is 255-275 ℃, the temperature of the fourth zone is 260-280 ℃, the temperature of the fifth zone is 260-280 ℃, the temperature of the sixth zone is 260-280 ℃, the temperature of the seventh zone is 260-280 ℃, the temperature of the eighth zone is 255-275 ℃, the temperature of the die head is 255-275 ℃ and the rotation speed of the screw is 200-600 rpm;

the screw shape of the parallel double-screw extruder is a single thread; the ratio L/D of the length L of the screw to the diameter D of the screw is 35 to 50; the screw is provided with more than 1 meshing block area and more than 1 reverse thread area.

2. The conductive polyphenylene ether/high impact polystyrene composition of claim 1, which is prepared from the following raw materials in parts by weight:

3. the conductive polyphenylene ether/high impact polystyrene composition as claimed in claim 1 or 2, wherein the mass fraction of glycidyl methacrylate in the copolymer of styrene and glycidyl methacrylate is 2 to 4 wt%.

4. The conductive polyphenylene ether/high impact polystyrene composition as claimed in claim 1 or 2, wherein the maleic anhydride grafting ratio in the hydrogenated styrene-isoprene copolymer grafted maleic anhydride is 0.8 to 1.5 wt%.

5. The conductive polyphenylene ether/high impact polystyrene composition of claim 1 or 2, wherein the graphene-carbon nanotube nanocomposite is prepared by a method comprising the steps of: dispersing the graphene oxide in deionized water, then adding hydrazine hydrate and concentrated ammonia water, stirring, and reacting at 85-95 ℃ for 1-3 h to obtain graphene hydrosol; and then adding the carboxylated carbon nano tube into the graphene hydrosol, dispersing for 1-3 h, then carrying out centrifugal treatment on the obtained suspension at 2000-4000 rpm for 10-30 min, then carrying out centrifugal treatment at 13000-17000 rpm for 10-30 min to obtain a graphene-carbon nano tube nano composite material dispersion liquid, and drying to obtain the graphene-carbon nano tube nano composite material.

6. The conductive polyphenylene ether/high impact polystyrene composition of claim 1 or 2, wherein the silane coupling agent is at least one of γ -aminopropyltriethoxysilane, γ -aminopropyltrimethoxysilane.

7. A method for preparing a conductive polyphenylene ether/high impact polystyrene composition as defined in any one of claims 1 to 6, comprising the steps of:

(3) adding the mixture mixed in the step (1) into a parallel double-screw extruder through a feeder, laterally adding the mixture mixed in the step (2) into the parallel double-screw extruder, performing melt extrusion, and granulating, wherein the process parameters comprise that the temperature of a first zone is 250-270 ℃, the temperature of a second zone is 255-275 ℃, the temperature of a third zone is 255-275 ℃, the temperature of a fourth zone is 260-280 ℃, the temperature of a fifth zone is 260-280 ℃, the temperature of a sixth zone is 260-280 ℃, the temperature of a seventh zone is 255-275 ℃, the temperature of a die head is 255-275 ℃, and the rotation speed of a screw is 200-600 rpm;

8. The method according to claim 7, wherein in the step (1), the high-viscosity polyphenylene ether resin, the low-viscosity polyphenylene ether resin and the high impact polystyrene resin are dried at a temperature of 90 to 100 ℃ for 4 to 6 hours; the process parameters in the step (3) comprise: the temperature of the first zone is 255-265 ℃, the temperature of the second zone is 260-270 ℃, the temperature of the third zone is 260-270 ℃, the temperature of the fourth zone is 265-275 ℃, the temperature of the fifth zone is 265-275 ℃, the temperature of the sixth zone is 265-275 ℃, the temperature of the seventh zone is 265-275 ℃, the temperature of the eighth zone is 260-270 ℃, the temperature of the die head is 260-270 ℃, and the rotating speed of the screw is 300-500 rpm.

9. The method according to claim 7, wherein the ratio L/D of the screw length L to the diameter D is 35 to 45; and 2 meshing block areas and 1 reverse thread area are arranged on the screw rod.