CN110643175B - High dielectric constant polyamide 6/polyphenyl ether composition and preparation method thereof - Google Patents
High dielectric constant polyamide 6/polyphenyl ether composition and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a high-dielectric-constant polyamide 6/polyphenyl ether composition and a preparation method thereof, wherein the high-dielectric-constant polyamide 6/polyphenyl ether composition is prepared from the following raw materials: the low-viscosity polyamide 6 resin, the high-viscosity polyphenylene oxide resin, the low-viscosity polyphenylene oxide 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 high-dielectric-constant filler, a silane coupling agent, polyvinylidene fluoride and a copper phthalocyanine oligomer. The high dielectric constant polyamide 6/polyphenyl ether composition has excellent mechanical property, processing property and high dielectric constant, and can be applied to the fields of communication, fine electrician and the like.
Description
Technical Field
The invention relates to the field of materials, in particular to a high-dielectric-constant 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 and the polyphenyl ether are prepared into the high-dielectric-constant polyamide 6/polyphenyl ether composition, so that the defects of the polyamide 6 and the polyphenyl ether can be overcome, and the composition 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 high dielectric constant polyamide 6/polyphenylene ether composition forms a sea-island structure, the polyamide 6 contributes to the composition to have good solvent resistance, coating property and molding processability, and the 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 high dielectric constant polyamide 6/polyphenylene ether compositions is compatibilization technology.
Currently, some studies on toughening compatibilization of PA6/PPO systems 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 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.
In the technical field of electrics and electronics, high dielectric constant materials with special functions in the aspect of energy storage have important functions, and meanwhile, with the development of industries such as communication, fine electricians and the like, the requirements on high energy storage density and high dielectric constant materials are increasing day by day. The high-dielectric-constant polyamide 6/polyphenyl ether composition can be directly molded by injection, and has extremely important use value and application prospect in the field of electricians with requirements on miniaturization, light weight and high reliability. However, the prior art has few studies on the high dielectricity of the PA6/PPO system.
Disclosure of Invention
Based on this, the invention aims to provide a polyamide 6/polyphenylene oxide composition with excellent mechanical properties, processability and high dielectric constant, which can be applied to the fields of communication, fine electrician and the like.
In order to achieve the purpose, the invention adopts the following scheme:
the high-dielectric-constant polyamide 6/polyphenyl ether composition is prepared from the following raw materials in parts by weight:
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 high-dielectric-constant filler is at least one of barium titanate, strontium titanate, barium sodium niobate and strontium niobate;
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 high dielectric constant polyamide 6/polyphenylene ether composition is prepared from the following raw materials in parts by weight:
in some of the embodiments, the high dielectric constant polyamide 6/polyphenylene ether composition is further preferably prepared from the following raw materials in parts by weight:
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 high dielectric constant filler is barium titanate; the silane coupling agent is at least one of gamma-aminopropyltriethoxysilane and gamma-aminopropyltrimethoxysilane.
Another object of the present invention is to provide a process for the preparation of a high dielectric constant polyamide 6/polyphenylene ether composition.
The preparation method of the high dielectric constant 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, pentaerythritol zinc, a high-dielectric-constant filler, a silane coupling agent, polyvinylidene fluoride and a copper phthalocyanine oligomer into a stirrer for mixing;
(2) adding the styrene-glycidyl methacrylate copolymer, toluene diisocyanate and hydrogenated styrene-isoprene copolymer grafted maleic anhydride 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 high dielectric constant polyamide 6/polyphenylene ether composition of the invention is as follows:
in order to overcome the defect of poor compatibility and processing performance of PA6 and PPO in a high-dielectric-constant polyamide 6/polyphenylene oxide composition, the invention improves the compatibility between PA6 and PPO by adding a copolymer of styrene and glycidyl methacrylate, toluene diisocyanate and hydrogenated styrene-isoprene copolymer grafted maleic anhydride, meanwhile, the hydrogenated styrene-isoprene copolymer grafted maleic anhydride can improve the notch impact strength of the PA6/PPO composition, the mechanical property of the PA6/PPO composition is ensured by adding high-viscosity polyphenyl ether resin, the processing property of the PA6/PPO composition is ensured by adding low-viscosity polyphenyl ether resin and low-viscosity polyamide 6 resin, the dielectric constant of the polyamide 6/polyphenyl ether composition is improved by compounding and using a high dielectric constant filler, polyvinylidene fluoride and copper phthalocyanine oligomer.
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, and can be prepared by blending PA6 and PPOProvides excellent color stability and melt stability while preventing thermal degradation of PA6 and PPO during high temperature and suppressing thermal oxidative discoloration due to long-term exposure, and also provides excellent color stability and melt stability 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.
The invention improves the dielectric constant of the polyamide 6/polyphenyl ether composition by compounding and using the high dielectric constant filler, polyvinylidene fluoride and copper phthalocyanine oligomer. The high dielectric constant fillers of barium titanate, strontium titanate, barium sodium niobate and strontium niobate have relaxor ferroelectrics with very high room temperature dielectric constants, and can effectively improve the compatibility between the high dielectric constant fillers and PA6 and PPO resin after being coated by a silane coupling agent, thereby reducing the influence of the high dielectric constant fillers on the mechanical property; polyvinylidene fluoride (PVDF) has high dielectric constant (100Hz is about 8 and dielectric loss is 0.04-0.2) and easy processability, and the dielectric constant of copper phthalocyanine oligomer (CuPc) can reach 105-106But the dispersion is difficult, and the composite use of PVDF and CuPc is helpful for the dispersion of CuPc in PA6 and PPO resin base materials, thereby improving the dielectric constant of the polyamide 6/polyphenylene oxide composition.
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 existing high dielectric constant polyamide 6/polyphenyl ether composition, the invention improves the compatibility between PA6 and PPO by adding styrene and glycidyl methacrylate copolymer, toluene diisocyanate and hydrogenated styrene-isoprene copolymer grafted maleic anhydride, improves the toughness of the high dielectric constant polyamide 6/polyphenyl ether composition by hydrogenated styrene-isoprene copolymer grafted maleic anhydride, ensures the mechanical property and processability of the high dielectric constant polyamide 6/polyphenyl ether composition by compounding high-viscosity and low-viscosity polyphenyl ether resin and low-viscosity polyamide 6 resin, and compounds 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 improve the yellowing phenomenon and the thermal stability in the blending processing process of the high dielectric constant polyamide 6/polyphenyl ether composition, a high dielectric constant filler, polyvinylidene fluoride and a copper phthalocyanine oligomer are compounded to improve the dielectric constant of the polyamide 6/polyphenyl ether composition, and the raw material components are matched with each other, so that the prepared high dielectric constant polyamide 6/polyphenyl ether composition has excellent mechanical property, processability and high dielectric constant, and can be applied to the fields of communication, fine electrician and the like.
The preparation method of the high dielectric constant 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 high dielectric constant polyamide 6/polyphenylene ether 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 high dielectric constant 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):
mechanism of reaction
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;
barium titanate selected from Zhengzhou chemical Limited;
gamma-aminopropyltriethoxysilane selected from Hubei Wuda organosilicon New materials GmbH;
gamma-aminopropyltrimethoxysilane selected from the group consisting of Hubei Wuda Silicone New materials GmbH;
polyvinylidene fluoride selected from Hubei Xin Mingtai chemical Co., Ltd;
copper phthalocyanine oligomer selected from sigma aldrich trade ltd;
hydrogenated styrene-butadiene-styrene copolymer grafted maleic anhydride, selected from Shenyangtotong plastics Co.
The present invention will be described in detail with reference to specific examples.
Example 1:
the embodiment of the invention relates to a high dielectric constant polyamide 6/polyphenyl ether composition, which is prepared from the following raw materials in parts by weight:
the preparation method of the high dielectric constant polyamide 6/polyphenyl ether composition comprises the following steps:
(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, pentaerythritol zinc, barium titanate, gamma-aminopropyltriethoxysilane, polyvinylidene fluoride and copper phthalocyanine oligomer into a high-speed stirrer (the rotating speed is 1000 revolutions per minute) for mixing;
(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;
(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:
the embodiment of the invention relates to a high dielectric constant polyamide 6/polyphenyl ether composition, which is prepared from the following raw materials in parts by weight:
the preparation method of the high dielectric constant polyamide 6/polyphenyl ether composition comprises the following steps:
(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, pentaerythritol zinc, barium titanate, gamma-aminopropyltrimethoxysilane, polyvinylidene fluoride and copper phthalocyanine oligomer into a high-speed stirrer (the rotating speed is 1000 revolutions per minute) for mixing;
(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;
(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:
the embodiment of the invention relates to a high dielectric constant polyamide 6/polyphenyl ether composition, which is prepared from the following raw materials in parts by weight:
the preparation method of the high dielectric constant polyamide 6/polyphenyl ether composition comprises the following steps:
(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, pentaerythritol zinc, barium titanate, gamma-aminopropyltriethoxysilane, polyvinylidene fluoride and copper phthalocyanine oligomer into a high-speed stirrer (the rotating speed is 1000 revolutions per minute) for mixing;
(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;
(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.
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 4:
the embodiment of the invention relates to a high dielectric constant polyamide 6/polyphenyl ether composition, which is prepared from the following raw materials in parts by weight:
the preparation method of the high dielectric constant polyamide 6/polyphenyl ether composition comprises the following steps:
(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, pentaerythritol zinc, barium titanate, gamma-aminopropyltriethoxysilane, polyvinylidene fluoride and copper phthalocyanine oligomer into a high-speed stirrer (the rotating speed is 1000 revolutions per minute) for mixing;
(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;
(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:
the embodiment of the invention relates to a high dielectric constant polyamide 6/polyphenyl ether composition, which is prepared from the following raw materials in parts by weight:
the preparation method of the high dielectric constant polyamide 6/polyphenyl ether composition comprises the following steps:
(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, pentaerythritol zinc, barium titanate, gamma-aminopropyltriethoxysilane, polyvinylidene fluoride and copper phthalocyanine oligomer into a high-speed stirrer (the rotating speed is 1000 revolutions per minute) for mixing;
(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;
(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:
the embodiment of the invention relates to a high dielectric constant polyamide 6/polyphenyl ether composition, which is prepared from the following raw materials in parts by weight:
the preparation method of the high dielectric constant polyamide 6/polyphenyl ether composition comprises the following steps:
(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, pentaerythritol zinc, barium titanate, gamma-aminopropyltriethoxysilane, polyvinylidene fluoride and copper phthalocyanine oligomer into a high-speed stirrer (the rotating speed is 1000 revolutions per minute) for mixing;
(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;
(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 7:
the embodiment of the invention relates to a high dielectric constant polyamide 6/polyphenyl ether composition, which is prepared from the following raw materials in parts by weight:
the preparation method of the high dielectric constant polyamide 6/polyphenyl ether composition comprises the following steps:
(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, pentaerythritol zinc, barium titanate, gamma-aminopropyltriethoxysilane, polyvinylidene fluoride and copper phthalocyanine oligomer into a high-speed stirrer (the rotating speed is 1000 revolutions per minute) for mixing;
(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;
(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 8:
the embodiment of the invention relates to a high dielectric constant polyamide 6/polyphenyl ether composition, which is prepared from the following raw materials in parts by weight:
the preparation method of the high dielectric constant polyamide 6/polyphenyl ether composition comprises the following steps:
(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, pentaerythritol zinc, barium titanate, gamma-aminopropyltriethoxysilane, polyvinylidene fluoride and copper phthalocyanine oligomer into a high-speed stirrer (the rotating speed is 1000 revolutions per minute) for mixing;
(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;
(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 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:
the comparative example is a high dielectric constant polyamide 6/polyphenylene oxide composition prepared from the following raw materials in parts by weight:
the preparation method of the high dielectric constant polyamide 6/polyphenyl ether composition comprises the following steps:
(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, pentaerythritol zinc, barium titanate, gamma-aminopropyltriethoxysilane, polyvinylidene fluoride and copper phthalocyanine oligomer into a high-speed stirrer (the rotating speed is 1000 revolutions per minute) for mixing;
(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;
(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.
Comparative example 2:
the comparative example is a high dielectric constant polyamide 6/polyphenylene oxide composition prepared from the following raw materials in parts by weight:
the preparation method of the high dielectric constant polyamide 6/polyphenyl ether composition comprises the following steps:
(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, pentaerythritol zinc, barium titanate, gamma-aminopropyltriethoxysilane, polyvinylidene fluoride and copper phthalocyanine oligomer into a high-speed stirrer (the rotating speed is 1000 revolutions per minute) for mixing;
(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;
(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.
Comparative example 3:
the comparative example is a high dielectric constant polyamide 6/polyphenylene oxide composition prepared from the following raw materials in parts by weight:
the preparation method of the high dielectric constant polyamide 6/polyphenyl ether composition comprises the following steps:
(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;
(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.
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.
Comparative example 4:
the comparative example is a high dielectric constant polyamide 6/polyphenylene oxide composition prepared from the following raw materials in parts by weight:
the preparation method of the high dielectric constant polyamide 6/polyphenyl ether composition comprises the following steps:
(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, pentaerythritol zinc, barium titanate, gamma-aminopropyltriethoxysilane, polyvinylidene fluoride and copper phthalocyanine oligomer into a high-speed stirrer (the rotating speed is 1000 revolutions per minute) for mixing;
(2) adding the styrene-glycidyl methacrylate copolymer, toluene diisocyanate and hydrogenated styrene-butadiene-styrene copolymer grafted maleic anhydride 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 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.
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; and d, changing the screw structure.
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 high dielectric constant 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;
dielectric constant: the test frequency is 1GHz according to IEC 60250 standard.
The results of the performance tests are shown in table 2.
TABLE 2 Properties of the high dielectric constant 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 increases, mainly because PA6 is a crystalline plastic, the substrate itself has high tensile strength and good fluidity, and PPO is an amorphous plastic, the substrate itself has low tensile strength, and the main chain has rigid benzene rings, and the fluidity is poor. 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 dielectric constant (1GHz) of the barium titanate, polyvinylidene fluoride and copper phthalocyanine oligomer shows a trend of increasing change with increasing addition amount of the barium titanate, polyvinylidene fluoride and copper phthalocyanine oligomer. 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, and it was found by comparison that the tensile strength, notched impact strength, melt index and dielectric constant of the polyamide 6/polyphenylene ether composition prepared using the screw parameters of the parallel twin-screw extruder described in example 7 were better.
Example 7 compared with comparative example 1, comparative example 1 used a high viscosity polyphenylene ether resin with an intrinsic viscosity of 0.55dL/g, while example 7 used a high viscosity polyphenylene ether resin with an intrinsic viscosity of 0.48dL/g, the fluidity of the polyphenylene ether resin was greatly reduced with the increase of the intrinsic viscosity of the polyphenylene ether resin, and when the intrinsic viscosity of the polyphenylene ether resin was 0.55dL/g, the melt index of the high dielectric constant polyamide 6/polyphenylene ether composition was only 12g/10min, and the processability was poor; 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 notched impact strength of the high dielectric constant polyamide 6/polyphenylene ether composition prepared in comparative example 2 decreased as the intrinsic viscosities of the polyamide 6 resin and the polyphenylene ether resin decreased, and the tensile strength and notched impact strength were lower than those of example 7; example 7 in comparison with comparative example 3, in which no SG, TDI and SEPS-g-MAH were added, had poor compatibility of PA6 and PPO, and thus the tensile strength and notched impact strength of the prepared high dielectric constant polyamide 6/polyphenylene ether composition were much lower than those of example 7, and comparative example 3, in which no barium titanate, polyvinylidene fluoride, copper phthalocyanine oligomer was used, had a dielectric constant (1GHz) of only 3.6; 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 high dielectric constant polyamide 6/polyphenylene ether composition prepared in example 7 had higher tensile strength and higher notched impact strength than comparative example 4.
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 (9)
1. The high-dielectric-constant polyamide 6/polyphenyl ether composition is characterized by being prepared from the following raw materials in parts by weight:
68-72 parts of low-viscosity polyamide 6 resin,
14-16 parts of high-viscosity polyphenyl ether resin,
14-16 parts of low-viscosity polyphenyl ether resin,
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 high-dielectric-constant filler is at least one of barium titanate, strontium titanate, barium sodium niobate and strontium niobate;
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;
the preparation method of the high dielectric constant 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, pentaerythritol zinc, a high-dielectric-constant filler, a silane coupling agent, polyvinylidene fluoride and a copper phthalocyanine oligomer into a stirrer for mixing;
(2) adding the styrene-glycidyl methacrylate copolymer, toluene diisocyanate and hydrogenated styrene-isoprene copolymer grafted maleic anhydride 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 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 high dielectric constant polyamide 6/polyphenylene ether composition according to claim 1, which is prepared from the following raw materials in parts by weight:
70 parts of low-viscosity polyamide 6 resin,
15 parts of high-viscosity polyphenyl ether resin,
15 parts of low-viscosity polyphenyl ether resin,
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,
3. the high dielectric constant 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 high dielectric constant 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 high dielectric constant polyamide 6/polyphenylene ether composition according to claim 1 or 2, wherein the high dielectric constant filler is barium titanate; the silane coupling agent is at least one of gamma-aminopropyltriethoxysilane and gamma-aminopropyltrimethoxysilane.
6. A process for preparing a high dielectric constant polyamide 6/polyphenylene ether composition according to any of claims 1 to 5, comprising the steps of:
(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, pentaerythritol zinc, a high-dielectric-constant filler, a silane coupling agent, polyvinylidene fluoride and a copper phthalocyanine oligomer into a stirrer for mixing;
(2) adding the styrene-glycidyl methacrylate copolymer, toluene diisocyanate and hydrogenated styrene-isoprene copolymer grafted maleic anhydride 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 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.
7. The preparation method according to claim 6, 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.
8. The method according to claim 6, 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.
9. The method according to claim 6 or 7, wherein in step (1) and/or step (2), the stirrer is a high-speed stirrer with a rotation speed of 500 and 1500 rpm.
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