CN110684347B

CN110684347B - Conductive polyamide 6/polyphenyl ether composition and preparation method thereof

Info

Publication number: CN110684347B
Application number: CN201911055607.9A
Authority: CN
Inventors: 王忠强; 丁佳; 李白羽
Original assignee: Guangdong Aldex New Material Co Ltd
Current assignee: Guangdong Aldex New Material Co Ltd
Priority date: 2019-10-31
Filing date: 2019-10-31
Publication date: 2022-03-25
Anticipated expiration: 2039-10-31
Also published as: CN110684347A

Abstract

The invention relates to a conductive polyamide 6/polyphenyl ether composition and a preparation method thereof, wherein the conductive polyamide 6/polyphenyl ether composition is prepared from the following raw materials: the low-viscosity polyamide 6 resin, the high-viscosity polyphenyl ether resin, the low-viscosity polyphenyl ether resin, a 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 gamma-aminopropyltriethoxysilane. The conductive polyamide 6/polyphenyl ether composition has excellent mechanical property, processing property and conductivity, and can be applied to manufacturing of automobiles, electronic and electric appliance elements and the like.

Description

Conductive polyamide 6/polyphenyl ether composition and preparation method thereof

Technical Field

The invention relates to the field of materials, in particular to a conductive polyamide 6/polyphenyl ether composition and a preparation method thereof.

Background

Polyamide 6(PA6) is a crystalline resin and is excellent in chemical resistance and processability, but has a large water absorption to cause a decrease in mechanical properties and a poor dimensional stability, while polyphenylene oxide (PPO) is an amorphous resin and has good mechanical properties and heat resistance but is poor in processability, chemical resistance and impact resistance. The polyamide 6/polyphenyl ether composition prepared by the polyamide 6 and the polyphenyl ether can overcome the defects of the polyamide 6 and the polyphenyl ether, and has the characteristics of high rigidity, small creep, high heat deformation temperature, good impact resistance and oil resistance and the like. From the microstructure, the conductive polyamide 6/polyphenylene ether composition forms a sea-island structure, polyamide 6 contributes to the composition to have good solvent resistance, paintability and molding processability, and polyphenylene ether contributes to the composition to have good heat resistance, rigidity and dimensional stability. However, since crystalline PA6 and amorphous PPO are thermodynamically incompatible, resulting in too large a domain size of the dispersed phase of the blend and weak interfacial force, resulting in insufficient strength and toughness of the material, the key to the preparation of polyamide 6/polyphenylene ether compositions is the compatibilization technique.

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 on toughening compatibilization and electrical conductivity of PA6/PPO system are made in the prior art, such as: chinese patent CN106084763A discloses a fatigue-resistant low-warpage PA6/PPO alloy material, wherein a compatibilizer SEBS-g-MAH and a toughener SBS are added into a PA6 and PPO system; chinese patent CN107083055A discloses a conductive PA6/PPO alloy material and a preparation method thereof, wherein the conductive PA6/PPO alloy material comprises, by mass, 35-60 parts of nylon 6, 40-65 parts of modified polyphenyl ether, 2-8 parts of a toughening agent, 0.5-5 parts of carbon nanotubes, 1-10 parts of conductive carbon black, 0.1-5 parts of a compatilizer and 0.1-3.0 parts of an antioxidant, wherein the toughening agent is one or two of maleic anhydride grafted ethylene-1-octene copolymer or methacrylic acid-butadiene-styrene copolymer, and the compatilizer is one or two of epoxy resin or modified epoxy resin with the molecular weight of 100-120 and the epoxy equivalent of 30-550 g/eq; chinese patent CN102417711A discloses a permanent antistatic master batch and a preparation method thereof, wherein the antistatic master batch comprises the following components in percentage by weight: 1-15% of alkali metal salt, 0.5-2% of antioxidant, 0.5-2% of heat stabilizer, 0-10% of auxiliary antistatic agent and 71-95% of high polymer material containing polyether block, wherein the high polymer material containing polyether block is a compound of polyoxyethylene and polyether ester amide in a weight ratio of 5: 1; chinese patent CN102732003A discloses a flame-retardant glass fiber reinforced PA6/PPO alloy composition and a preparation method thereof, wherein the composition comprises the following components in percentage by weight: PA 620-41%, PPO 20-41%, compatilizer 0-10%, compound flame-retardant master batch 0-15%, glass fiber 20-40%, antioxidant 0.1-1%, lubricating dispersant 0.1-1%; chinese patent CN103146176A discloses a PPO/PA alloy modified compatibilizer and a PPO/PA alloy, wherein the compatibilizer is a graft copolymer of polyphenyl ether, glycidyl methacrylate and styrene, and the PPO/PA alloy using the compatibilizer comprises the following components in parts by weight: 50-59.5% of polyphenyl ether, 31.5-40.4% of nylon, 0.1-18% of compatibilizer and 0.1-0.5% of antioxidant; chinese patent CN108587108A discloses a high impact PPO/PA alloy material and a preparation method thereof, wherein the PPO/PA alloy material is composed of PPO resin, PA resin, a compatilizer, a flexibilizer and an antioxidant, and specifically comprises the following raw materials in parts by weight: 30-70 parts of PPO resin, 30-70 parts of PA resin, 3-10 parts of compatilizer, 5-15 parts of toughening agent and 0.1-1 part of antioxidant, wherein the compatilizer is PPO-g-MAH, and the toughening agent is SEBS-g-MAH; chinese patent CN108276758A discloses a high-filling PPO/PA alloy material with a good surface and a preparation method thereof, wherein the high-filling PPO/PA alloy material is composed of eight components of PPO resin, PA resin, PS resin, carbon fiber, a compatilizer, a toughening agent, a flow modifier and an antioxidant; according to the weight ratio: 10-50 parts of PPO resin, 10-60 parts of PA resin, 5-20 parts of PS resin, 20-40 parts of carbon fiber, 3-10 parts of compatilizer, 5-15 parts of toughening agent, 0.2-2 parts of flow modifier and 0.1-1 part of antioxidant, wherein the compatilizer is PPO-g-MAH, and the toughening agent is one or more of SEBS, SEBS-g-MAH and POE-g-MAH; chinese patent CN107236280A discloses a conductive heat-resistant PPO/PPA flame-retardant composition and a preparation method thereof; the composition comprises the following components in percentage by mass: 10-40% of PPO; PPA 10-45%; 10-35% of a conductive agent; 3-8% of a compatilizer; 10-20% of a flame retardant; 0.3-0.8% of antioxidant, wherein the conductive agent is a mixture composed of graphene, conductive carbon black and carbon fibers, and the compatilizer is at least one of PPO-g-MAH and SEBS-g-MAH; chinese patent CN109370211A discloses a PA/PPO alloy suitable for electrostatic spraying and a preparation method thereof; the PA/PPO alloy comprises the following components in parts by weight: 15-40 parts of PPO resin, 45-70 parts of nylon (PA), 3-15 parts of a toughening agent, 0.2-3 parts of a compatilizer, 1-5 parts of Conductive Carbon Black (CCB), 2-10 parts of Expanded Graphite (EG) and 0.2-2 parts of other additives; chinese patent CN105153692A discloses an electroplatable PA66-PPO-MPI engineering plastic alloy and a preparation method thereof, the engineering plastic alloy consists of PA66 resin, PPO resin, MPI resin, conductive filler, compatilizer and auxiliary agent, wherein the conductive filler is selected from one or more of graphene, conductive carbon black, copper powder, aluminum powder, silver powder, nickel powder, silver-plated copper powder, silver-plated nickel powder and silver-plated glass beads; chinese patent CN104119666A discloses a conductive PPO material and a preparation method thereof, wherein the conductive PPO material comprises the following components in percentage by weight: PPO 50-60%, GPPS 10-15%, SMA 2-8%, SEBS-MA 2-5%, conductive carbon black 15-30%, surfactant 1-3%, lubricant 0.5-2%, and antioxidant 0.3-0.5%, wherein the sum of the contents of the components is 100%.

Disclosure of Invention

Based on the above, the invention aims to provide a conductive polyamide 6/polyphenyl ether composition with excellent mechanical property, processability and conductivity, which can be applied to manufacturing of automobiles, electronic and electric appliance components and the like.

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

the conductive polyamide 6/polyphenyl ether composition is prepared from the following raw materials in parts by weight:

60-80 parts of low-viscosity polyamide 6 resin (PA6),

10-20 parts of high-viscosity polyphenylene oxide resin (PPO),

10-20 parts of low-viscosity polyphenylene oxide (PPO),

the sum of the parts by weight of the low-viscosity polyamide 6 resin, the high-viscosity polyphenyl ether resin and the low-viscosity polyphenyl ether resin is 100 parts,

the intrinsic viscosity of the low-viscosity polyamide 6 resin is 1.01-1.33 dL/g; 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 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 embodiments, the conductive polyamide 6/polyphenylene ether composition is prepared from the following raw materials in parts by weight:

64-76 parts of low-viscosity polyamide 6 resin (PA6),

12-18 parts of high-viscosity polyphenylene oxide resin (PPO),

12-18 parts of low-viscosity polyphenylene oxide (PPO),

in some of the embodiments, the conductive polyamide 6/polyphenylene ether composition is further preferably prepared from the following raw materials in parts by weight:

68-72 parts of low-viscosity polyamide 6 resin (PA6),

14-16 parts of high-viscosity polyphenylene oxide resin (PPO),

14-16 parts of low-viscosity polyphenylene oxide (PPO),

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-to-volume ratio of the graphene oxide, the deionized water, the hydrazine hydrate and 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 the conductive polyamide 6/polyphenylene ether composition.

The preparation method of the conductive polyamide 6/polyphenyl ether composition comprises the following steps:

(1) drying the low-viscosity polyamide 6 resin at the temperature of 110-140 ℃ for 4-8 hours, drying the high-viscosity polyphenylene ether resin and the low-viscosity polyphenylene ether resin at the temperature of 80-110 ℃ for 4-8 hours, cooling, and adding the cooled low-viscosity polyamide 6 resin, the high-viscosity polyphenylene ether resin, the low-viscosity polyphenylene ether 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 240-260 ℃, the temperature of the second zone is 245-265 ℃, the temperature of the third zone is 245-265 ℃, the temperature of the fourth zone is 250-270 ℃, the temperature of the fifth zone is 250-270 ℃, the temperature of the sixth zone is 245-265 ℃, the temperature of the seventh zone is 245-265 ℃, the temperature of the eighth zone is 245-265 ℃, the temperature of the die head is 245-265 ℃ and the rotation speed of the screw is 200-600 rpm.

In some embodiments, in the step (1), the low-viscosity polyamide 6 resin is dried at a temperature of 120-130 ℃ for 4-6 hours, and the high-viscosity polyphenylene ether resin and the low-viscosity polyphenylene ether resin are dried at a temperature of 90-100 ℃ for 4-6 hours; the process parameters in the step (3) comprise: the temperature of the first zone is 245-255 ℃, the temperature of the second zone is 250-260 ℃, the temperature of the third zone is 250-260 ℃, the temperature of the fourth zone is 255-265 ℃, the temperature of the fifth zone is 255-265 ℃, the temperature of the sixth zone is 250-260 ℃, the temperature of the seventh zone is 250-260 ℃, the temperature of the eighth zone is 250-260 ℃, the temperature of the die head is 250-260 ℃, 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 polyamide 6/polyphenylene ether composition of the invention is as follows:

in order to solve the defect of poor compatibility and processability of PA6 and PPO in the conductive polyamide 6/polyphenylene oxide composition, the compatibility between PA6 and PPO is improved by adding the copolymer of styrene and glycidyl methacrylate, toluene diisocyanate and the hydrogenated styrene-isoprene copolymer grafted maleic anhydride, meanwhile, the notch impact strength of the PA6/PPO composition can be improved by adding the hydrogenated styrene-isoprene copolymer grafted maleic anhydride, the mechanical property of the PA6/PPO composition is ensured by adding the high-viscosity polyphenylene oxide resin, and the processability of the PA6/PPO composition is ensured by adding the low-viscosity polyphenylene oxide resin and the low-viscosity polyamide 6 resin.

The styrene-glycidyl methacrylate copolymer, the toluene diisocyanate and the hydrogenated styrene-isoprene copolymer grafted maleic anhydride adopted by the invention can effectively improve the interfacial adhesion between PA6 and PPO and improve the compatibility between the PA6 and the PPO. The styrene structural unit in the copolymer of styrene and glycidyl methacrylate has good compatibility with PPO, and the epoxy group of glycidyl methacrylate can react with the terminal amino group of PA6 and the terminal hydroxyl group of PPO, so that the compatibility between PA6 and PPO is improved; the isocyanate group of the toluene diisocyanate can react with the terminal amino group and the terminal carboxyl group of PA6 and the terminal hydroxyl group of PPO, so that the compatibility between PA6 and PPO is improved; the styrene structural unit in the hydrogenated styrene-isoprene copolymer grafted maleic anhydride has good compatibility with PPO, and the anhydride group of the maleic anhydride can react with the terminal amino group of PA6 and the terminal hydroxyl group of PPO, so that the compatibility between PA6 and PPO is improved.

The melting point of 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 PA6 and PPO is better, the amide group can react with the end group of PA6 resin to improve the compatibility, and the hindered piperidyl can provide the antioxidation and improve the dyeing property of the copolymer.

The bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphate adopted by the invention has the melting point of 239 ℃ and the thermal decomposition temperature of over 350 ℃, has good heat resistance and hydrolysis resistance, can provide excellent color stability and melt stability for the blending process of PA6 and PPO, can prevent thermal degradation of PA6 and PPO in the high-temperature process, inhibits thermo-oxidative discoloration caused by long time, and also provides a Nitrogen Oxide (NO) for_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 polyamide 6/polyphenyl ether 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, the graphene can be kept in a good lamellar structure, meanwhile, the silane coupling agent is adopted to improve the compatibility of the graphene-carbon nanotube nano composite material and the polyamide 6/polyphenyl ether composition, so that the dispersion of the graphene-carbon nanotube nano composite material in the polyamide 6/polyphenyl ether 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:

aiming at the defect of poor compatibility and processability of PA6 and PPO in the conventional conductive polyamide 6/polyphenyl ether composition, the compatibility between PA6 and PPO is improved by adding a styrene-glycidyl methacrylate copolymer, toluene diisocyanate and hydrogenated styrene-isoprene copolymer grafted maleic anhydride, the toughness of the conductive polyamide 6/polyphenyl ether composition is improved by the hydrogenated styrene-isoprene copolymer grafted maleic anhydride, the mechanical property and the processability of the conductive polyamide 6/polyphenyl ether composition are ensured by compounding high-viscosity and low-viscosity polyphenyl ether resin and low-viscosity polyamide 6 resin, and N, N' -bis (2,2,6, 6-tetramethyl-4-piperidyl) -1, 3-phthalic amide, PPO, 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 polyamide 6/polyphenyl ether composition in the blending processing process, the conductivity of the polyamide 6/polyphenyl ether composition is improved by adopting the graphene-carbon nanotube nano composite material, and the prepared conductive polyamide 6/polyphenyl ether composition has excellent mechanical property, processing property and conductivity due to the mutual matching of the raw material components, and can be applied to the manufacturing of automobiles, electronic and electric appliance elements and the like.

The preparation method of the conductive polyamide 6/polyphenyl ether 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 polyamide 6/polyphenylene ether composition according to one embodiment of the 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 polyamide 6/polyphenylene ether composition according to one embodiment of the present invention is as follows (see FIG. 1 for a flow chart of the preparation process):

as can be seen from the reaction formula, the epoxy group of the copolymer of styrene and glycidyl methacrylate can chemically react with the terminal amino group of PA6 and the terminal hydroxyl group of PPO, so that the compatibility between PA6 and PPO is improved; the isocyanate group of the toluene diisocyanate can react with the terminal amino group and the terminal carboxyl group of PA6 and the terminal hydroxyl group of PPO, so that the compatibility between PA6 and PPO is improved; anhydride groups in the hydrogenated styrene-isoprene copolymer grafted maleic anhydride can react with terminal amino groups of PA6 and terminal hydroxyl groups of PPO, so that the compatibility between PA6 and PPO is improved.

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

low-viscosity polyamide 6 resin with the intrinsic viscosity of 1.17dL/g, and is selected from Shanyang Ba Ling petrochemical company, Hunan;

low-viscosity polyamide 6 resin with the intrinsic viscosity of 1.05dL/g and selected from Hunan Yueyangba Ling petrochemical company Limited;

low-viscosity polyamide 6 resin with the intrinsic viscosity of 0.97dL/g, and is selected from Shanyang Ba Ling petrochemical company, Hunan;

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

high viscosity polyphenylene ether resin with intrinsic viscosity of 0.46dL/g, selected from Nantong star synthetic materials GmbH;

high viscosity polyphenylene ether resin with intrinsic viscosity of 0.55dL/g, selected from Nantong star synthetic materials GmbH;

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 0.34dL/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 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 national academy of sciences 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 organosilicon New 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 polyamide 6/polyphenyl ether composition, which is prepared from the following raw materials in parts by weight:

60 parts of low-viscosity polyamide 6 resin (the intrinsic viscosity is 1.17dL/g),

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

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

(1) drying the low-viscosity polyamide 6 resin at the temperature of 110 ℃ for 8 hours, drying the high-viscosity polyphenylene ether resin and the low-viscosity polyphenylene ether resin at the temperature of 80 ℃ for 8 hours, cooling, and adding the cooled low-viscosity polyamide 6 resin, the cooled high-viscosity polyphenylene ether resin, the cooled low-viscosity polyphenylene ether resin, the cooled 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 are as follows: the temperature in the first zone was 240 ℃, the temperature in the second zone was 245 ℃, the temperature in the third zone was 245 ℃, the temperature in the fourth zone was 250 ℃, the temperature in the fifth zone was 250 ℃, the temperature in the sixth zone was 245 ℃, the temperature in the seventh zone was 245 ℃, the temperature in the eighth zone was 245 ℃, the temperature in the die head was 245 ℃ and the screw speed was 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:

80 parts of low-viscosity polyamide 6 resin (the intrinsic viscosity is 1.05dL/g),

10 parts of high-viscosity polyphenylene ether resin (the intrinsic viscosity is 0.46dL/g),

10 parts of low-viscosity polyphenylene ether resin (the intrinsic viscosity is 0.34dL/g),

(1) drying the low-viscosity polyamide 6 resin at the temperature of 140 ℃ for 4 hours, drying the high-viscosity polyphenylene ether resin and the low-viscosity polyphenylene ether resin at the temperature of 110 ℃ for 4 hours, cooling, and adding the cooled low-viscosity polyamide 6 resin, the cooled high-viscosity polyphenylene ether resin, the cooled low-viscosity polyphenylene ether resin, the cooled 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 are as follows: 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 265 ℃, the temperature in the seventh zone was 265 ℃, the temperature in the eighth zone was 265 ℃, the temperature in the die head was 265 ℃ 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:

64 parts of low-viscosity polyamide 6 resin (the intrinsic viscosity is 1.17dL/g),

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

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

(1) drying the low-viscosity polyamide 6 resin at the temperature of 120 ℃ for 6 hours, drying the high-viscosity polyphenylene ether resin and the low-viscosity polyphenylene ether resin at the temperature of 90 ℃ for 6 hours, cooling, and adding the cooled low-viscosity polyamide 6 resin, the cooled high-viscosity polyphenylene ether resin, the cooled low-viscosity polyphenylene ether resin, the cooled 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 are as follows: the temperature in the first zone was 245 ℃, the temperature in the second zone was 250 ℃, the temperature in the third zone was 250 ℃, the temperature in the fourth zone was 255 ℃, the temperature in the fifth zone was 255 ℃, the temperature in the sixth zone was 250 ℃, the temperature in the seventh zone was 250 ℃, the temperature in the eighth zone was 250 ℃, the temperature of the die head was 250 ℃ and the rotation speed of the screw was 300 rpm.

Example 4:

76 parts of low-viscosity polyamide 6 resin (the intrinsic viscosity is 1.17dL/g),

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

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

(1) drying the low-viscosity polyamide 6 resin at 130 ℃ for 4 hours, drying the high-viscosity polyphenylene ether resin and the low-viscosity polyphenylene ether resin at 100 ℃ for 4 hours, cooling, and adding the cooled low-viscosity polyamide 6 resin, the cooled high-viscosity polyphenylene ether resin, the cooled low-viscosity polyphenylene ether resin, the cooled 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 are as follows: 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 260 ℃, the temperature in the seventh zone was 260 ℃, the temperature in the eighth zone was 260 ℃, the temperature in the die head was 260 ℃ 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:

68 parts of low-viscosity polyamide 6 resin (the intrinsic viscosity is 1.17dL/g),

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

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

(1) drying the low-viscosity polyamide 6 resin at 125 ℃ for 5 hours, drying the high-viscosity polyphenylene ether resin and the low-viscosity polyphenylene ether resin at 95 ℃ for 5 hours, cooling, and adding the cooled low-viscosity polyamide 6 resin, the cooled high-viscosity polyphenylene ether resin, the cooled low-viscosity polyphenylene ether resin, the cooled 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 are as follows: the temperature in the first zone was 250 deg.C, the temperature in the second zone was 255 deg.C, the temperature in the third zone was 255 deg.C, the temperature in the fourth zone was 260 deg.C, the temperature in the fifth zone was 260 deg.C, the temperature in the sixth zone was 255 deg.C, the temperature in the seventh zone was 255 deg.C, the temperature in the eighth zone was 255 deg.C, the temperature in the die head was 255 deg.C, 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:

72 parts of low-viscosity polyamide 6 resin (the intrinsic viscosity is 1.17dL/g),

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

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

Example 7:

70 parts of low-viscosity polyamide 6 resin (the intrinsic viscosity is 1.17dL/g),

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

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

Example 8:

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 40, and the screw is provided with 2 meshing block areas and 1 back-thread area.

Comparative example 1:

15 parts of high-viscosity polyphenyl ether resin (the intrinsic viscosity is 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:

70 parts of low-viscosity polyamide 6 resin (with the intrinsic viscosity of 0.97dL/g),

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

Comparative example 3:

(1) drying the low-viscosity polyamide 6 resin at 125 ℃ for 5 hours, drying the high-viscosity polyphenylene ether resin and the low-viscosity polyphenylene ether resin at 95 ℃ for 5 hours, cooling, and adding the cooled low-viscosity polyamide 6 resin, the cooled high-viscosity polyphenylene ether resin, the cooled low-viscosity polyphenylene ether resin, the cooled N, N' -bis (2,2,6, 6-tetramethyl-4-piperidyl) -1, 3-benzenedicarboxamide, the cooled bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphate, zinc pentaerythritol, a graphene-carbon nanotube nanocomposite and gamma-aminopropyltriethoxysilane into a high-speed stirrer (the rotating speed is 1000 revolutions per minute) for mixing;

(2) adding the mixture mixed in the step (1) into a parallel double-screw extruder through a feeder for melt extrusion and granulation, wherein the process parameters are as follows: the temperature in the first zone was 250 deg.C, the temperature in the second zone was 255 deg.C, the temperature in the third zone was 255 deg.C, the temperature in the fourth zone was 260 deg.C, the temperature in the fifth zone was 260 deg.C, the temperature in the sixth zone was 255 deg.C, the temperature in the seventh zone was 255 deg.C, the temperature in the eighth zone was 255 deg.C, the temperature in the die head was 255 deg.C, and the screw speed was 400 rpm.

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;

Comparative example 5:

(2) adding the styrene-glycidyl methacrylate copolymer, toluene diisocyanate, hydrogenated styrene-isoprene copolymer grafted maleic anhydride, carbon nano tubes, graphene 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 composition parts by weight of the raw materials of the examples and comparative examples

Remarking: a, the intrinsic viscosity of the high-viscosity PPO is 0.55 dL/g; b, the intrinsic viscosity of the low-viscosity PA6 is 0.97dL/g, and the intrinsic viscosity of the low-viscosity PPO is 0.28 dL/g; c, replacing SEPS-g-MAH with SEBS-g-MAH; d, changing the screw structure; e, replacing 5 parts of each of the Gr-CNTs by the carbon nano tube and the graphene.

The amounts of 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 used in the above examples and comparative examples were 0.2 parts.

The conductive polyamide 6/polyphenylene ether 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: the thickness of the sample strip is 4mm according to the test of GB/T1843-2008 standard;

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 electrically conductive Polyamide 6/polyphenylene ether compositions of the examples and comparative examples

In examples 1 to 7, the addition amounts of the low-viscosity polyamide 6 resin, the high-viscosity polyphenylene ether resin, the low-viscosity polyphenylene ether resin, SG, TDI, and SEPS-g-MAH were adjusted, and it can be seen from the table that as the addition amount of the low-viscosity polyamide 6 resin decreases (or the addition amount of the polyphenylene ether resin increases), the tensile strength and the melt index thereof decrease, and the notch impact strength thereof decreases after increasing, mainly because PA6 is a crystalline plastic, the tensile strength of the base material itself is high and the fluidity thereof is good, and PPO is an amorphous plastic, the tensile strength of the base material itself is not high, and the fluidity thereof is poor because the base material itself has rigid benzene rings in the main chain. Meanwhile, the addition amounts of SG, TDI and SEPS-g-MAH are increased, so that the compatibility between two phases of PA6 and PPO can be effectively improved, and the notch impact strength of PA6/PPO is improved, but the tensile strength of the PA6/PPO is influenced on the contrary by excessive addition of SG, TDI and SEPS-g-MAH. 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, the overall performance of example 7 is best.

Example 7 the screw shape of the parallel twin-screw extruder of example 8 was a twin screw and the screw shape of the parallel twin-screw extruder of example 7 was a single screw, as compared to example 8, it was found by comparison that the tensile strength, notched impact strength, melt index and conductivity of the electrically conductive polyamide 6/polyphenylene ether composition prepared using the screw parameters of the parallel twin-screw extruder described in example 7 was 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 as the intrinsic viscosity of the polyphenylene ether resin increased, the fluidity of the polyphenylene ether resin decreased greatly, and when the polyphenylene ether resin was moldedThe conductive polyamide 6/polyphenylene ether composition has a melt index of only 17g/10min at an intrinsic viscosity of 0.55dL/g, and comparative example 1 has no addition of Gr-CNTs and a volume resistivity of 10^15～16Ω · cm, much higher than example 7; example 7 in comparison with comparative example 2, comparative example 2 used a low-tack polyamide 6 resin having an intrinsic viscosity of 0.97dL/g and a low-tack polyphenylene ether resin having an intrinsic viscosity of 0.28dL/g, whereas example 7 used a low-tack polyamide 6 resin having an intrinsic viscosity of 1.17dL/g and a low-tack polyphenylene ether resin having an intrinsic viscosity of 0.35dL/g, the tensile strength and the notched impact strength of the conductive polyamide 6/polyphenylene ether composition prepared in comparative example 2 were lower than those of example 7 as the intrinsic viscosities of the polyamide 6 resin and the polyphenylene ether resin were lower; example 7 compared to comparative example 3, which had no addition of SG, TDI and SEPS-g-MAH, had poor compatibility of PA6 and PPO, and the dispersion of Gr-CNTs in the matrix was also affected, so that the tensile strength, notched impact strength and electrical conductivity of the prepared conductive polyamide 6/polyphenylene ether composition were much lower than those of example 7; example 7 in comparison to comparative example 4, which used SEBS-g-MAH in comparative example 4, and SEPS-g-MAH in example 7, the conductive polyamide 6/polyphenylene ether composition prepared in example 7 had higher tensile strength and notched impact strength than comparative example 4. Example 7 compared with comparative example 5, comparative example 5 directly adds separate graphene and carbon nanotubes, while example 7 uses graphene-carbon nanotube nanocomposite, and graphene and carbon nanotubes are more easily agglomerated in the resin matrix during blending, so that the tensile strength, notched impact strength and volume resistivity of the composite are affected, and thus the tensile strength, notched impact strength and conductivity of the conductive polyamide 6/polyphenylene ether composition prepared in comparative example 5 are inferior to those of 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 polyamide 6/polyphenyl ether 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;

(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 240-260 ℃, the temperature of the second zone is 245-265 ℃, the temperature of the third zone is 245-265 ℃, the temperature of the fourth zone is 250-270 ℃, the temperature of the fifth zone is 250-270 ℃, the temperature of the sixth zone is 245-265 ℃, the temperature of the seventh zone is 245-265 ℃, the temperature of the eighth zone is 245-265 ℃, the temperature of the die head is 245-265 ℃ 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 polyamide 6/polyphenylene ether composition according to claim 1, characterized by being prepared from the following raw materials in parts by weight:

3. the conductive polyamide 6/polyphenylene ether composition according to 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 polyamide 6/polyphenylene ether composition according to claim 1 or 2, wherein the maleic anhydride graft ratio in the hydrogenated styrene-isoprene copolymer grafted maleic anhydride is 0.8 to 1.5 wt%.

5. The conductive polyamide 6/polyphenylene ether composition according to claim 1 or 2, wherein the graphene-carbon nanotube nanocomposite material 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 polyamide 6/polyphenylene ether composition according to claim 1 or 2, wherein the silane coupling agent is at least one of γ -aminopropyltriethoxysilane and γ -aminopropyltrimethoxysilane.

7. A process for the preparation of a conductive polyamide 6/polyphenylene ether composition according to any of claims l-6, comprising the steps of:

8. The preparation method according to claim 7, wherein in the step (1), the low-viscosity polyamide 6 resin is dried at a temperature of 120 to 130 ℃ for 4 to 6 hours, and the high-viscosity polyphenylene ether resin and the low-viscosity polyphenylene ether 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 245-255 ℃, the temperature of the second zone is 250-260 ℃, the temperature of the third zone is 250-260 ℃, the temperature of the fourth zone is 255-265 ℃, the temperature of the fifth zone is 255-265 ℃, the temperature of the sixth zone is 250-260 ℃, the temperature of the seventh zone is 250-260 ℃, the temperature of the eighth zone is 250-260 ℃, the temperature of the die head is 250-260 ℃, and the rotating speed of the screw is 300-500 rpm.

9. The production method according to claim 7 or 8, 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.