CN110698839A - High dielectric constant polyphenyl ether/high impact polystyrene composition and preparation method thereof - Google Patents

High dielectric constant polyphenyl ether/high impact polystyrene composition and preparation method thereof Download PDF

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CN110698839A
CN110698839A CN201911136073.2A CN201911136073A CN110698839A CN 110698839 A CN110698839 A CN 110698839A CN 201911136073 A CN201911136073 A CN 201911136073A CN 110698839 A CN110698839 A CN 110698839A
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impact polystyrene
polyphenyl ether
viscosity
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CN110698839B (en
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王忠强
冯刚
蓝承东
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Guangdong Harmony New Materials Co Ltd
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    • C—CHEMISTRY; METALLURGY
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    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • C08L71/12—Polyphenylene oxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B9/00—Making granules
    • B29B9/02—Making granules by dividing preformed material
    • B29B9/06—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B9/00—Making granules
    • B29B9/12—Making granules characterised by structure or composition
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
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    • B29C2948/92504—Controlled parameter
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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Abstract

The invention relates to a high dielectric constant polyphenyl ether/high impact polystyrene composition and a preparation method thereof, wherein the high dielectric constant polyphenyl ether/high impact polystyrene composition is prepared from the following raw materials: high-viscosity polyphenyl ether resin, low-viscosity polyphenyl ether resin, high-impact polystyrene resin, 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 polyphenyl ether/high impact polystyrene 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

High dielectric constant polyphenyl ether/high impact polystyrene composition and preparation method thereof
Technical Field
The invention relates to the field of materials, in particular to a high dielectric constant polyphenyl ether/high impact polystyrene composition and a preparation method thereof.
Background
Polyphenylene Oxide (PPO) has the advantages of excellent mechanical property, heat resistance, electrical insulation and small creep deformation at high temperature, and the PPO has low density and hygroscopicity, high strength and good dimensional stability. However, pure PPO resin has high glass transition temperature, poor melt flowability and difficult molding processing, and needs to be processed at a high temperature of 300 ℃, thereby greatly limiting the application range of the PPO resin. In order to overcome the defects of PPO and expand the application field of the PPO, the PPO is modified by blending High Impact Polystyrene (HIPS) so as to improve the molding processability of the PPO and enable the PPO to be widely applied, but the PPO/HIPS composition with good processability and mechanical property is still difficult to obtain by the existing PPO/HIPS system.
Currently, some studies have been made in the prior art on PPO/HIPS systems, such as: chinese patent CN109735037A discloses a chemical resistance PPO/HIPS alloy material and a preparation method thereof, wherein the chemical resistance PPO/HIPS alloy material comprises the following components in parts by weight: 20-50 parts of polyphenyl ether, 35-66 parts of high impact polystyrene, 10-15 parts of flame retardant, 1-3 parts of ethylene-tetrafluoroethylene copolymer, 1-2 parts of hydrogenated styrene-butadiene block copolymer, 0.1-1 part of antioxidant and 0.1-1 part of lubricant; chinese patent CN105419210A discloses a wear-resistant reinforced PPO/HIPS material and a preparation method thereof, wherein the material comprises the following raw materials in parts by weight: 20-40 parts of HIPS resin, 5-30 parts of PPO resin, 3-8 parts of nitrile rubber, 3-8 parts of TPU resin, 10-30 parts of glass fiber, 10-15 parts of aramid fiber, 3-10 parts of molybdenum disulfide, 3-10 parts of calcium sulfate whisker, 1-10 parts of polytetrafluoroethylene, 0.5-1.5 parts of coupling agent, 0.5-1 part of lubricant and 0.2-0.8 part of antioxidant; chinese patent CN105199364A discloses a flame-retardant aging-resistant PPO-HIPS polymer alloy and a preparation method thereof, relating to a polymer alloy and a preparation method thereof, wherein the polymer alloy comprises the following components in parts by weight: PPO80-90, HIPS10-20, triune intumescent flame retardant 10-40, high-efficiency anti-aging agent 0.5-20, antibacterial agent 0.5-3, compatibilizer SEBS-g-MAH10-50, mica powder 1-20 and zinc oxide 0.1-5; chinese patent CN106947236A discloses a flame-retardant modified PPO-HIPS-mica powder composite material and a preparation method thereof, wherein the material is composed of the following raw materials in parts by weight: 650 parts of PPO powder, 350 parts of HIPS 150, 350 parts of mica powder, 20-60 parts of compatilizer, 40-70 parts of flexibilizer, 80-170 parts of flame retardant, 10-50 parts of anti-tick agent, 40-70 parts of flexibilizer, 3-20 parts of antioxidant, 3-20 parts of lubricant and 3-25 parts of toner; chinese patent CN108164973A discloses a high-dielectric polyphenylene oxide material and a preparation method and application thereof, wherein the polyphenylene oxide material comprises the following components in parts by weight: 30-70 parts of PPO, 20-40 parts of impact-resistant polystyrene (HIPS) foaming master batch, 3-10 parts of single-walled carbon nanotube, 0.5-1.5 parts of graphene, 10-20 parts of high dielectric filler, 1-4 parts of toughening agent, 0.3-0.8 part of antioxidant and 0.5-2 parts of lubricant; chinese patent CN108117739A discloses a PPO composite material with high frequency and high dielectric constant, which comprises the following raw materials in parts by weight: 20-29 parts of PPO resin, 60-70 parts of filler, 5-10 parts of dielectric additive and 1-1.5 parts of processing additive.
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 polyphenyl ether/high impact polystyrene composition can be directly molded by injection, and has extremely important use value and application prospect in the field of electrician with requirements on miniaturization, light weight and high reliability. However, the prior art has less research on the high dielectricity of the PPO/HIPS system.
Disclosure of Invention
Based on this, the invention aims to provide a polyphenyl ether/high impact polystyrene composition with excellent mechanical property, processing property 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:
a high dielectric constant polyphenyl ether/high impact polystyrene composition is prepared from the following raw materials in parts by weight:
35-50 parts of high-viscosity polyphenylene oxide (PPO),
25-40 parts of low-viscosity polyphenylene oxide (PPO),
10-40 parts of high impact polystyrene resin (HIPS),
the sum of the parts by weight of the high-viscosity polyphenyl ether resin, the low-viscosity polyphenyl ether resin and the high impact polystyrene resin is 100 parts,
Figure BDA0002279625990000031
the intrinsic viscosity of the high-viscosity polyphenyl ether resin is 0.45-0.51 dL/g; the intrinsic viscosity of the low-viscosity polyphenyl ether resin is 0.33-0.37 dL/g; the number average molecular weight of the high impact polystyrene resin is 17000-28000;
the 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 polyphenylene ether/high impact polystyrene composition is prepared from the following raw materials in parts by weight:
40-45 parts of high-viscosity polyphenylene oxide resin (PPO),
30-35 parts of low-viscosity polyphenylene oxide (PPO),
20-30 parts of high impact polystyrene resin (HIPS),
the sum of the parts by weight of the high-viscosity polyphenyl ether resin, the low-viscosity polyphenyl ether resin and the high impact polystyrene resin is 100 parts,
Figure BDA0002279625990000032
Figure BDA0002279625990000041
in some of the embodiments, the high dielectric constant polyphenylene ether/high impact polystyrene composition is further preferably prepared from the following raw materials in parts by weight:
42-44 parts of high-viscosity polyphenylene oxide resin (PPO),
31-33 parts of low-viscosity polyphenylene oxide (PPO),
23-28 parts of high impact polystyrene resin (HIPS),
the sum of the parts by weight of the high-viscosity polyphenyl ether resin, the low-viscosity polyphenyl ether resin and the high impact polystyrene resin is 100 parts,
Figure BDA0002279625990000042
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 polyphenylene ether/high impact polystyrene composition.
The preparation method of the high dielectric constant polyphenyl ether/high impact polystyrene composition comprises the following steps:
(1) drying the high-viscosity polyphenyl ether resin, the low-viscosity polyphenyl ether resin and the high-impact polystyrene resin at the temperature of 80-110 ℃ for 4-8 hours, cooling, and adding the cooled high-viscosity polyphenyl ether resin, the cooled low-viscosity polyphenyl ether resin, the cooled high-impact polystyrene resin, the N, N' -bis (2,2,6, 6-tetramethyl-4-piperidyl) -1, 3-benzenedicarboxamide, bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphate, 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 250-270 ℃, the temperature of the second zone is 255-275 ℃, the temperature of the third zone is 255-275 ℃, the temperature of the fourth zone is 260-280 ℃, the temperature of the fifth zone is 260-280 ℃, the temperature of the sixth zone is 260-280 ℃, the temperature of the seventh zone is 260-280 ℃, the temperature of the eighth zone is 255-275 ℃, the temperature of the die head is 255-275 ℃ and the rotation speed of the screw is 200-600 rpm.
In some embodiments, the high-viscosity polyphenylene ether resin, the low-viscosity polyphenylene ether resin and the high impact polystyrene resin are dried at a temperature of 90-100 ℃ for 4-6 hours in the step (1); the process parameters in the step (3) comprise: the temperature of the first zone is 255-265 ℃, the temperature of the second zone is 260-270 ℃, the temperature of the third zone is 260-270 ℃, the temperature of the fourth zone is 265-275 ℃, the temperature of the fifth zone is 265-275 ℃, the temperature of the sixth zone is 265-275 ℃, the temperature of the seventh zone is 265-275 ℃, the temperature of the eighth zone is 260-270 ℃, the temperature of the die head is 260-270 ℃, and the rotating speed of the screw is 300-500 rpm.
In some of these embodiments, the screw shape of the parallel twin screw extruder is a single thread; the ratio L/D of the length L of the screw to the diameter D of the screw is 35 to 50; the screw is provided with more than 1 (including 1) meshing block area and more than 1 (including 1) reverse thread area.
In some of these embodiments, the ratio L/D of the length L of the screw to the diameter D of the screw is 35 to 45; and 2 meshing block areas and 1 reverse thread area are arranged on the screw rod.
In some embodiments, in step (1) and/or step (2), the stirrer is a high-speed stirrer with a rotation speed of 500-.
The principle of the high dielectric constant polyphenylene ether/high impact polystyrene composition of the present invention is as follows:
in order to improve the compatibility between the polyphenyl ether resin and the high impact polystyrene resin in the high dielectric constant polyphenyl ether/high impact polystyrene composition and the defect of poor processing performance of the polyphenyl ether resin, the invention improves the compatibility between the polyphenyl ether resin and the high impact polystyrene resin by adding a styrene and glycidyl methacrylate copolymer and hydrogenated styrene-isoprene copolymer grafted maleic anhydride, wherein the compatibility between a styrene structural unit in the styrene and glycidyl methacrylate copolymer and the hydrogenated styrene-isoprene copolymer grafted maleic anhydride and the high impact polystyrene resin is very good, an epoxy group of the styrene and glycidyl methacrylate copolymer and an anhydride group of the hydrogenated styrene-isoprene copolymer grafted maleic anhydride can react with a terminal hydroxyl group of the polyphenyl ether resin, thereby improving the compatibility between the PPO and the HIPS. Due to the fact that the processing temperature of the polyphenyl ether resin is high, chain breakage of the polyphenyl ether resin is prone to occur in the processing process, and the generation of polyphenyl ether resin oligomer is reduced by utilizing the reaction of isocyanate groups of toluene diisocyanate and the terminal hydroxyl groups of PPO, and the mechanical property of the polyphenyl ether/high impact polystyrene composition with the high dielectric constant is guaranteed. The mechanical property of the PPO/HIPS composition is ensured by adding high-viscosity polyphenyl ether resin, the processability of the PPO/HIPS composition is ensured by adding low-viscosity polyphenyl ether resin and high-impact polystyrene resin, and the dielectric constant of the PPO/HIPS composition is improved by compounding and using high-dielectric-constant filler, polyvinylidene fluoride and copper phthalocyanine oligomer.
The melting point of the N, N' -bis (2,2,6, 6-tetramethyl-4-piperidyl) -1, 3-benzenedicarboxamide adopted by the invention is 272 ℃, the boiling point is more than 360 ℃, the thermal stability in the blending process of PPO and HIPS is better, and the hindered piperidyl of the antioxidant can provide an antioxidant effect and improve the dyeability of the copolymer; the bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphate has the melting point of 239 ℃ and the thermal decomposition temperature of more than 350 ℃, has good heat resistance and hydrolysis resistance, can provide excellent color stability and melt stability for PPO and HIPS in the blending process, can prevent the thermal degradation of PPO and HIPS in the high-temperature process, can inhibit the thermal oxidative discoloration caused by long time, and can also be provided in Nitrogen Oxide (NO)x) Color stability in gas environment, and prevention of discoloration of fumigant.
The pentaerythritol zinc adopted by the invention has the functions of lubrication and thermal stabilization, and simultaneously, when the pentaerythritol zinc is used as a thermal stabilizer alone, compared with a common zinc-containing compound (such as zinc oxide), the zinc-containing compound can effectively reduce the occurrence probability of zinc burning in the blending process.
The invention adopts silane coupling agents, preferably gamma-aminopropyl triethoxysilane and gamma-aminopropyl trimethoxysilane, which all contain amino, and the additives can react with styrene and glycidyl methacrylate copolymer, toluene diisocyanate and hydrogenated styrene-isoprene copolymer grafted maleic anhydride, so that the interfacial bonding force and compatibility of the high dielectric constant filler, polyvinylidene fluoride and copper phthalocyanine oligomer and polyphenyl ether resin and high impact polystyrene resin are improved, and the influence of the interfacial bonding force and compatibility on the mechanical properties of the PPO/HIPS composition is reduced.
The invention improves the dielectric constant of the polyphenyl ether/high impact polystyrene 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 PPO resin and HIPS resin after being coated by the 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 of PVDF and CuPc is helpful for the dispersion of CuPc in the base materials of PPO resin and HIPS resin, thereby improving the dielectric constant of the polyphenyl ether/high impact polystyrene composition.
Compared with the prior art, the invention has the following beneficial effects:
in order to improve the compatibility between the polyphenyl ether resin and the high impact polystyrene resin and the defect of poor processing performance of the polyphenyl ether resin, the compatibility between the polyphenyl ether resin and the high impact polystyrene resin is improved by adding the styrene and glycidyl methacrylate copolymer and the hydrogenated styrene-isoprene copolymer grafted maleic anhydride, the generation of polyphenyl ether resin oligomers is reduced by adding the toluene diisocyanate, the mechanical property of the polyphenyl ether composition is ensured, meanwhile, the high-viscosity and low-viscosity polyphenyl ether resin is compounded to ensure the mechanical property and the processing performance of the high dielectric constant polyphenyl ether/high impact polystyrene composition, and N, N '-bis (2,2,6, 6-tetramethyl-4-piperidyl) -1, 3-phthalic amide, N' -bis (2,2, Bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphate and pentaerythritol zinc improve the yellowing phenomenon and the thermal stability of the high dielectric constant polyphenyl ether/high impact polystyrene composition in the blending processing process, a high dielectric constant filler, polyvinylidene fluoride and a copper phthalocyanine oligomer are compounded to improve the dielectric constant of the polyphenyl ether/high impact polystyrene composition, and the raw material components are matched with each other to ensure that the high dielectric constant polyphenyl ether/high impact polystyrene 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 polyphenyl ether/high impact polystyrene composition provided by the invention has the advantages of simple process, easiness in control and low requirement on equipment, and the used equipment is general polymer processing equipment, so that the investment is low, and the industrial production is facilitated.
Drawings
FIG. 1 is a flow chart of a process for preparing a high dielectric constant polyphenylene ether/high impact polystyrene composition in accordance with 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 polyphenylene ether/high impact polystyrene composition of one embodiment of the present invention is as follows (see FIG. 1 for a flow chart of the preparation process):
Figure BDA0002279625990000081
from the above reaction formula, the epoxy group of the styrene-glycidyl methacrylate copolymer and the anhydride group of the hydrogenated styrene-isoprene copolymer grafted maleic anhydride can react with the terminal hydroxyl group of the polyphenylene oxide resin, and meanwhile, the styrene structural unit in the styrene-glycidyl methacrylate copolymer and the hydrogenated styrene-isoprene copolymer grafted maleic anhydride has very good compatibility with the high impact polystyrene resin, so that the compatibility between the PPO and the HIPS is improved. In addition, the isocyanate group of the toluene diisocyanate can react with the terminal hydroxyl of the PPO, so that the generation of polyphenylene oxide resin oligomer is reduced, and the mechanical property of the high dielectric constant polyphenylene oxide/high impact polystyrene composition is ensured.
The examples of the invention and the comparative examples used the following raw materials:
high viscosity polyphenylene ether resin with intrinsic viscosity of 0.48dL/g, selected from Nantong star synthetic materials 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 0.28dL/g, selected from Nantong star synthetic materials GmbH;
a high impact polystyrene resin having a number average molecular weight of 23000 selected from Taiwan Chimei industries, Ltd;
a copolymer of styrene and glycidyl methacrylate, the mass fraction of Glycidyl Methacrylate (GMA) being 3% by weight, selected from sigma aldrich trade ltd;
toluene diisocyanate selected from the group consisting of national pharmaceutical group chemical agents;
the hydrogenated styrene-isoprene copolymer was grafted with maleic anhydride, the maleic anhydride grafting ratio was 1.2 wt%, and was selected from the group consisting of the company clony, japan;
n, N' -bis (2,2,6, 6-tetramethyl-4-piperidinyl) -1, 3-benzenedicarboxamide, selected from Toxongitai chemical Co., Ltd;
bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphate selected from Shanghai Yaozao Fine chemical Co., Ltd;
pentaerythritol zinc selected from Zhaoqing Sendeli chemical industry Co., Ltd;
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 polyphenyl ether/high impact polystyrene composition, which is prepared from the following raw materials in parts by weight:
35 parts of high-viscosity polyphenyl ether resin (the intrinsic viscosity is 0.48dL/g),
25 parts of low-viscosity polyphenylene ether resin (the intrinsic viscosity is 0.35dL/g),
40 parts of high impact polystyrene resin (23000 in number average molecular weight),
the sum of the parts by weight of the high-viscosity polyphenyl ether resin, the low-viscosity polyphenyl ether resin and the high impact polystyrene resin is 100 parts,
Figure BDA0002279625990000101
the preparation method of the high dielectric constant polyphenyl ether/high impact polystyrene composition comprises the following steps:
(1) drying the high-viscosity polyphenyl ether resin, the low-viscosity polyphenyl ether resin and the high-impact polystyrene resin at the temperature of 80 ℃ for 8 hours, cooling, and adding the cooled high-viscosity polyphenyl ether resin, the cooled low-viscosity polyphenyl ether resin, the cooled high-impact polystyrene resin and 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, 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 comprise: the temperature in the first zone was 250 ℃, the temperature in the second zone was 255 ℃, the temperature in the third zone was 255 ℃, the temperature in the fourth zone was 260 ℃, the temperature in the fifth zone was 260 ℃, the temperature in the sixth zone was 260 ℃, the temperature in the seventh zone was 255 ℃, the temperature in the eighth zone was 255 ℃, the temperature of the die head was 255 ℃ and the rotation speed of the screw 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 polyphenyl ether/high impact polystyrene composition, which is prepared from the following raw materials in parts by weight:
50 parts of high-viscosity polyphenyl ether resin (the intrinsic viscosity is 0.48dL/g),
40 parts of low-viscosity polyphenylene ether resin (the intrinsic viscosity is 0.35dL/g),
10 parts of high impact polystyrene resin (23000 in number average molecular weight),
the sum of the parts by weight of the high-viscosity polyphenyl ether resin, the low-viscosity polyphenyl ether resin and the high impact polystyrene resin is 100 parts,
Figure BDA0002279625990000121
the preparation method of the high dielectric constant polyphenyl ether/high impact polystyrene composition comprises the following steps:
(1) drying the high-viscosity polyphenyl ether resin, the low-viscosity polyphenyl ether resin and the high-impact polystyrene resin at the temperature of 110 ℃ for 4 hours, cooling, and adding the cooled high-viscosity polyphenyl ether resin, the cooled low-viscosity polyphenyl ether resin, the cooled high-impact polystyrene resin and 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, 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 comprise: the temperature in the first zone was 270 ℃, the temperature in the second zone was 275 ℃, the temperature in the third zone was 275 ℃, the temperature in the fourth zone was 280 ℃, the temperature in the fifth zone was 280 ℃, the temperature in the sixth zone was 280 ℃, the temperature in the seventh zone was 280 ℃, the temperature in the eighth zone was 275 ℃, the temperature in the die head was 275 ℃ and the screw speed was 600 rpm.
The screw of the parallel double-screw extruder is in a single-thread shape, the ratio L/D of the length L and the diameter D of the screw is 50, and the screw is provided with 2 meshing block areas and 1 back-thread area.
Example 3:
the embodiment of the invention relates to a high dielectric constant polyphenyl ether/high impact polystyrene composition, which is prepared from the following raw materials in parts by weight:
37 parts of high-viscosity polyphenyl ether resin (the intrinsic viscosity is 0.48dL/g),
27 parts of low-viscosity polyphenylene ether resin (the intrinsic viscosity is 0.35dL/g),
36 parts of high impact polystyrene resin (23000 in number average molecular weight),
the sum of the parts by weight of the high-viscosity polyphenyl ether resin, the low-viscosity polyphenyl ether resin and the high impact polystyrene resin is 100 parts,
Figure BDA0002279625990000131
the preparation method of the high dielectric constant polyphenyl ether/high impact polystyrene composition comprises the following steps:
(1) drying the high-viscosity polyphenyl ether resin, the low-viscosity polyphenyl ether resin and the high-impact polystyrene resin at the temperature of 90 ℃ for 6 hours, cooling, and adding the cooled high-viscosity polyphenyl ether resin, the cooled low-viscosity polyphenyl ether resin, the cooled high-impact polystyrene resin and 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, 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 comprise: the temperature in the first zone was 255 ℃, the temperature in the second zone was 260 ℃, the temperature in the third zone was 260 ℃, the temperature in the fourth zone was 265 ℃, the temperature in the fifth zone was 265 ℃, the temperature in the sixth zone was 265 ℃, the temperature in the seventh zone was 265 ℃, the temperature in the eighth zone was 260 ℃, the temperature in the die head was 260 ℃ and the screw speed was 300 rpm.
The 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 polyphenyl ether/high impact polystyrene composition, which is prepared from the following raw materials in parts by weight:
48 parts of high-viscosity polyphenylene ether resin (the intrinsic viscosity is 0.48dL/g),
38 parts of low-viscosity polyphenylene ether resin (the intrinsic viscosity is 0.35dL/g),
14 parts of high impact polystyrene resin (23000 in number average molecular weight),
the sum of the parts by weight of the high-viscosity polyphenyl ether resin, the low-viscosity polyphenyl ether resin and the high impact polystyrene resin is 100 parts,
the preparation method of the high dielectric constant polyphenyl ether/high impact polystyrene composition comprises the following steps:
(1) drying the high-viscosity polyphenyl ether resin, the low-viscosity polyphenyl ether resin and the high-impact polystyrene resin at the temperature of 100 ℃ for 4 hours, cooling, and adding the cooled high-viscosity polyphenyl ether resin, the cooled low-viscosity polyphenyl ether resin, the cooled high-impact polystyrene resin and 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, 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 comprise: the temperature in the first zone was 265 deg.C, the temperature in the second zone was 270 deg.C, the temperature in the third zone was 270 deg.C, the temperature in the fourth zone was 275 deg.C, the temperature in the fifth zone was 275 deg.C, the temperature in the sixth zone was 275 deg.C, the temperature in the seventh zone was 275 deg.C, the temperature in the eighth zone was 270 deg.C, the temperature in the die head was 270 deg.C, and.
The screw 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 polyphenyl ether/high impact polystyrene composition, which is prepared from the following raw materials in parts by weight:
39 parts of high-viscosity polyphenyl ether resin (the intrinsic viscosity is 0.48dL/g),
29 parts of low-viscosity polyphenylene ether resin (with the intrinsic viscosity of 0.35dL/g),
32 parts of high impact polystyrene resin (23000 in number average molecular weight),
the sum of the parts by weight of the high-viscosity polyphenyl ether resin, the low-viscosity polyphenyl ether resin and the high impact polystyrene resin is 100 parts,
Figure BDA0002279625990000151
the preparation method of the high dielectric constant polyphenyl ether/high impact polystyrene composition comprises the following steps:
(1) drying the high-viscosity polyphenyl ether resin, the low-viscosity polyphenyl ether resin and the high-impact polystyrene resin at the temperature of 95 ℃ for 5 hours, cooling, and adding the cooled high-viscosity polyphenyl ether resin, the cooled low-viscosity polyphenyl ether resin, the cooled high-impact polystyrene resin and 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, 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 comprise: the temperature in the first zone was 260 ℃, the temperature in the second zone was 265 ℃, the temperature in the third zone was 265 ℃, the temperature in the fourth zone was 270 ℃, the temperature in the fifth zone was 270 ℃, the temperature in the sixth zone was 270 ℃, the temperature in the seventh zone was 270 ℃, the temperature in the eighth zone was 265 ℃, the temperature in the die head was 265 ℃ and the screw speed was 400 rpm.
The 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 polyphenyl ether/high impact polystyrene composition, which is prepared from the following raw materials in parts by weight:
46 parts of high-viscosity polyphenylene ether resin (the intrinsic viscosity is 0.48dL/g),
36 parts of low-viscosity polyphenylene ether resin (the intrinsic viscosity is 0.35dL/g),
18 parts of high impact polystyrene resin (23000 in number average molecular weight),
the sum of the parts by weight of the high-viscosity polyphenyl ether resin, the low-viscosity polyphenyl ether resin and the high impact polystyrene resin is 100 parts,
Figure BDA0002279625990000161
Figure BDA0002279625990000171
the preparation method of the high dielectric constant polyphenyl ether/high impact polystyrene composition comprises the following steps:
(1) drying the high-viscosity polyphenyl ether resin, the low-viscosity polyphenyl ether resin and the high-impact polystyrene resin at the temperature of 95 ℃ for 5 hours, cooling, and adding the cooled high-viscosity polyphenyl ether resin, the cooled low-viscosity polyphenyl ether resin, the cooled high-impact polystyrene resin and 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, 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 comprise: the temperature in the first zone was 260 ℃, the temperature in the second zone was 265 ℃, the temperature in the third zone was 265 ℃, the temperature in the fourth zone was 270 ℃, the temperature in the fifth zone was 270 ℃, the temperature in the sixth zone was 270 ℃, the temperature in the seventh zone was 270 ℃, the temperature in the eighth zone was 265 ℃, the temperature in the die head was 265 ℃ and the screw speed was 400 rpm.
The 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 polyphenyl ether/high impact polystyrene composition, which is prepared from the following raw materials in parts by weight:
43 parts of high-viscosity polyphenylene ether resin (the intrinsic viscosity is 0.48dL/g),
32 parts of low-viscosity polyphenylene ether resin (the intrinsic viscosity is 0.35dL/g),
25 parts of high impact polystyrene resin (23000 in number average molecular weight),
the sum of the parts by weight of the high-viscosity polyphenyl ether resin, the low-viscosity polyphenyl ether resin and the high impact polystyrene resin is 100 parts,
the preparation method of the high dielectric constant polyphenyl ether/high impact polystyrene composition comprises the following steps:
(1) drying the high-viscosity polyphenyl ether resin, the low-viscosity polyphenyl ether resin and the high-impact polystyrene resin at the temperature of 95 ℃ for 5 hours, cooling, and adding the cooled high-viscosity polyphenyl ether resin, the cooled low-viscosity polyphenyl ether resin, the cooled high-impact polystyrene resin and 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, 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 comprise: the temperature in the first zone was 260 ℃, the temperature in the second zone was 265 ℃, the temperature in the third zone was 265 ℃, the temperature in the fourth zone was 270 ℃, the temperature in the fifth zone was 270 ℃, the temperature in the sixth zone was 270 ℃, the temperature in the seventh zone was 270 ℃, the temperature in the eighth zone was 265 ℃, the temperature in the die head was 265 ℃ and the screw speed was 400 rpm.
The 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 polyphenyl ether/high impact polystyrene composition, which is prepared from the following raw materials in parts by weight:
43 parts of high-viscosity polyphenylene ether resin (the intrinsic viscosity is 0.48dL/g),
32 parts of low-viscosity polyphenylene ether resin (the intrinsic viscosity is 0.35dL/g),
25 parts of high impact polystyrene resin (23000 in number average molecular weight),
the sum of the parts by weight of the high-viscosity polyphenyl ether resin, the low-viscosity polyphenyl ether resin and the high impact polystyrene resin is 100 parts,
Figure BDA0002279625990000191
the preparation method of the high dielectric constant polyphenyl ether/high impact polystyrene composition comprises the following steps:
(1) drying the high-viscosity polyphenyl ether resin, the low-viscosity polyphenyl ether resin and the high-impact polystyrene resin at the temperature of 95 ℃ for 5 hours, cooling, and adding the cooled high-viscosity polyphenyl ether resin, the cooled low-viscosity polyphenyl ether resin, the cooled high-impact polystyrene resin and 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, 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 comprise: the temperature in the first zone was 260 ℃, the temperature in the second zone was 265 ℃, the temperature in the third zone was 265 ℃, the temperature in the fourth zone was 270 ℃, the temperature in the fifth zone was 270 ℃, the temperature in the sixth zone was 270 ℃, the temperature in the seventh zone was 270 ℃, the temperature in the eighth zone was 265 ℃, the temperature in the die head was 265 ℃ and the screw speed was 400 rpm.
The shape of a screw of the parallel double-screw extruder is double-thread, the ratio L/D of the length L and the diameter D of the screw is 50, and the screw is provided with 2 meshing block areas and 1 back-thread area.
Comparative example 1:
the comparative example is a high dielectric constant polyphenyl ether/high impact polystyrene composition, which is prepared from the following raw materials in parts by weight:
43 parts of high-viscosity polyphenylene ether resin (with the intrinsic viscosity of 0.55dL/g),
32 parts of low-viscosity polyphenylene ether resin (the intrinsic viscosity is 0.35dL/g),
25 parts of high impact polystyrene resin (23000 in number average molecular weight),
the sum of the parts by weight of the high-viscosity polyphenyl ether resin, the low-viscosity polyphenyl ether resin and the high impact polystyrene resin is 100 parts,
Figure BDA0002279625990000201
Figure BDA0002279625990000211
the preparation method of the high dielectric constant polyphenyl ether/high impact polystyrene composition comprises the following steps:
(1) drying the high-viscosity polyphenyl ether resin, the low-viscosity polyphenyl ether resin and the high-impact polystyrene resin at the temperature of 95 ℃ for 5 hours, cooling, and adding the cooled high-viscosity polyphenyl ether resin, the cooled low-viscosity polyphenyl ether resin, the cooled high-impact polystyrene resin and 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, 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 comprise: the temperature in the first zone was 260 ℃, the temperature in the second zone was 265 ℃, the temperature in the third zone was 265 ℃, the temperature in the fourth zone was 270 ℃, the temperature in the fifth zone was 270 ℃, the temperature in the sixth zone was 270 ℃, the temperature in the seventh zone was 270 ℃, the temperature in the eighth zone was 265 ℃, the temperature in the die head was 265 ℃ and the screw speed was 400 rpm.
The 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 polyphenyl ether/high impact polystyrene composition, which is prepared from the following raw materials in parts by weight:
43 parts of high-viscosity polyphenylene ether resin (the intrinsic viscosity is 0.48dL/g),
32 parts of low-viscosity polyphenylene ether resin (the intrinsic viscosity is 0.28dL/g),
25 parts of high impact polystyrene resin (23000 in number average molecular weight),
the sum of the parts by weight of the high-viscosity polyphenyl ether resin, the low-viscosity polyphenyl ether resin and the high impact polystyrene resin is 100 parts,
Figure BDA0002279625990000221
the preparation method of the high dielectric constant polyphenyl ether/high impact polystyrene composition comprises the following steps:
(1) drying the high-viscosity polyphenyl ether resin, the low-viscosity polyphenyl ether resin and the high-impact polystyrene resin at the temperature of 95 ℃ for 5 hours, cooling, and adding the cooled high-viscosity polyphenyl ether resin, the cooled low-viscosity polyphenyl ether resin, the cooled high-impact polystyrene resin and 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, 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 comprise: the temperature in the first zone was 260 ℃, the temperature in the second zone was 265 ℃, the temperature in the third zone was 265 ℃, the temperature in the fourth zone was 270 ℃, the temperature in the fifth zone was 270 ℃, the temperature in the sixth zone was 270 ℃, the temperature in the seventh zone was 270 ℃, the temperature in the eighth zone was 265 ℃, the temperature in the die head was 265 ℃ and the screw speed was 400 rpm.
The 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 polyphenyl ether/high impact polystyrene composition, which is prepared from the following raw materials in parts by weight:
43 parts of high-viscosity polyphenylene ether resin (the intrinsic viscosity is 0.48dL/g),
32 parts of low-viscosity polyphenylene ether resin (the intrinsic viscosity is 0.35dL/g),
25 parts of high impact polystyrene resin (23000 in number average molecular weight),
the sum of the parts by weight of the high-viscosity polyphenyl ether resin, the low-viscosity polyphenyl ether resin and the high impact polystyrene resin is 100 parts,
0.2 portion of N, N' -bis (2,2,6, 6-tetramethyl-4-piperidyl) -1, 3-benzenedicarboxamide,
0.2 part of bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphate,
0.2 part of pentaerythritol zinc.
The preparation method of the high dielectric constant polyphenyl ether/high impact polystyrene composition comprises the following steps:
(1) drying the high-viscosity polyphenyl ether resin, the low-viscosity polyphenyl ether resin and the high-impact polystyrene resin at the temperature of 95 ℃ for 5 hours, cooling, and adding the cooled high-viscosity polyphenyl ether resin, the cooled low-viscosity polyphenyl ether resin, the cooled high-impact polystyrene resin, the N, N' -bis (2,2,6, 6-tetramethyl-4-piperidyl) -1, 3-benzenedicarboxamide, bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphate and pentaerythritol zinc into a high-speed stirrer (the rotating speed is 1000 revolutions per minute) for mixing;
(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 260 ℃, the temperature in the second zone was 265 ℃, the temperature in the third zone was 265 ℃, the temperature in the fourth zone was 270 ℃, the temperature in the fifth zone was 270 ℃, the temperature in the sixth zone was 270 ℃, the temperature in the seventh zone was 270 ℃, the temperature in the eighth zone was 265 ℃, the temperature in the die head was 265 ℃ and the screw speed was 400 rpm.
The 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 polyphenyl ether/high impact polystyrene composition, which is prepared from the following raw materials in parts by weight:
43 parts of high-viscosity polyphenylene ether resin (the intrinsic viscosity is 0.48dL/g),
32 parts of low-viscosity polyphenylene ether resin (the intrinsic viscosity is 0.35dL/g),
25 parts of high impact polystyrene resin (23000 in number average molecular weight),
the sum of the parts by weight of the high-viscosity polyphenyl ether resin, the low-viscosity polyphenyl ether resin and the high impact polystyrene resin is 100 parts,
Figure BDA0002279625990000241
the preparation method of the high dielectric constant polyphenyl ether/high impact polystyrene composition comprises the following steps:
(1) drying the high-viscosity polyphenyl ether resin, the low-viscosity polyphenyl ether resin and the high-impact polystyrene resin at the temperature of 95 ℃ for 5 hours, cooling, and adding the cooled high-viscosity polyphenyl ether resin, the cooled low-viscosity polyphenyl ether resin, the cooled high-impact polystyrene resin and 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, 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 comprise: the temperature in the first zone was 260 ℃, the temperature in the second zone was 265 ℃, the temperature in the third zone was 265 ℃, the temperature in the fourth zone was 270 ℃, the temperature in the fifth zone was 270 ℃, the temperature in the sixth zone was 270 ℃, the temperature in the seventh zone was 270 ℃, the temperature in the eighth zone was 265 ℃, the temperature in the die head was 265 ℃ and the screw speed was 400 rpm.
The 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 5
The comparative example is a high dielectric constant polyphenyl ether/high impact polystyrene composition, which is prepared from the following raw materials in parts by weight:
43 parts of high-viscosity polyphenylene ether resin (the intrinsic viscosity is 0.48dL/g),
32 parts of low-viscosity polyphenylene ether resin (the intrinsic viscosity is 0.35dL/g),
25 parts of high impact polystyrene resin (23000 in number average molecular weight),
the sum of the parts by weight of the high-viscosity polyphenyl ether resin, the low-viscosity polyphenyl ether resin and the high impact polystyrene resin is 100 parts,
Figure BDA0002279625990000251
the preparation method of the high dielectric constant polyphenyl ether/high impact polystyrene composition comprises the following steps:
(1) drying the high-viscosity polyphenyl ether resin, the low-viscosity polyphenyl ether resin and the high-impact polystyrene resin at the temperature of 95 ℃ for 5 hours, cooling, and adding the cooled high-viscosity polyphenyl ether resin, the cooled low-viscosity polyphenyl ether resin, the cooled high-impact polystyrene resin and 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, 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 and the 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 comprise: the temperature in the first zone was 260 ℃, the temperature in the second zone was 265 ℃, the temperature in the third zone was 265 ℃, the temperature in the fourth zone was 270 ℃, the temperature in the fifth zone was 270 ℃, the temperature in the sixth zone was 270 ℃, the temperature in the seventh zone was 270 ℃, the temperature in the eighth zone was 265 ℃, the temperature in the die head was 265 ℃ and the screw speed was 400 rpm.
The 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, changing a screw structure; b, the intrinsic viscosity of the high-viscosity PPO is 0.55 dL/g; c, the intrinsic viscosity of the low-viscosity PPO is 0.28 dL/g; and d, replacing SEPS-g-MAH with SEBS-g-MAH.
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 polyphenylene ether/high impact polystyrene compositions prepared in the above examples and comparative examples were subjected to the following property tests:
tensile property: testing according to GB/T1040-2006 standard, wherein the stretching speed is 50 mm/min;
impact properties: according to the test of GB/T1843-2008 standard, the thickness of the sample strip is 4 mm;
melt index: testing according to GB/T3682-2000 standard, wherein the testing temperature is 280 ℃, and the load is 5 kg;
dielectric constant: testing according to IEC 60250 standard, wherein the testing frequency is 1 GHz;
the results of the performance tests are shown in table 2.
TABLE 2 Properties of the high dielectric constant polyphenylene ether/high impact polystyrene compositions of the examples and comparative examples
Figure BDA0002279625990000271
Figure BDA0002279625990000281
In examples 1 to 7, the addition amounts of the high-viscosity polyphenylene ether resin, the low-viscosity polyphenylene ether resin, the high-impact polystyrene resin, SG, TDI and SEPS-g-MAH were adjusted, and it can be seen from the table that as the addition amount of the high-impact polystyrene resin was decreased (or the addition amount of the polyphenylene ether resin was increased), the tensile strength exhibited an increasing trend of change, while the notched impact strength and melt index exhibited a decreasing trend of change, primarily because the HIPS base resin was lower in strength and better in toughness and flowability, and SG and SEPS-g-MAH can improve the compatibility between the polyphenyl ether resin and the high impact polystyrene resin, thereby improving the mechanical property of the high dielectric constant polyphenyl ether/high impact polystyrene composition, but the strength of SG and SEPS-g-MAH is lower, too much addition thereof adversely affects the mechanical properties of the high dielectric constant polyphenylene ether/high impact polystyrene composition. Meanwhile, TDI can reduce the generation of polyphenyl ether resin oligomer, and the mechanical property of the polyphenyl ether/high impact polystyrene composition is ensured by the addition of TDI. 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 in comparison with example 8, the screw shape of the parallel twin-screw extruder of example 8 was a twin-screw flight, the ratio L/D of the length L of the screw to the diameter D of the screw was 50, the screw shape of the parallel twin-screw extruder of example 7 was a single-screw flight, and the ratio L/D of the length L of the screw to the diameter D of the screw was 40, and it was found by comparison that the tensile strength, notched impact strength and melt index of the high dielectric constant polyphenylene ether/high impact polystyrene composition prepared using the screw parameters of the parallel twin-screw extruder described in example 7 were better.
Example 7 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 polyphenylene ether/high impact polystyrene composition was only 4.9g/10min, and the processability was not good; example 7 in comparison with comparative example 2, comparative example 2 used a low-tack polyphenylene ether resin having an intrinsic viscosity of 0.28dL/g, whereas example 7 used a low-tack polyphenylene ether resin having an intrinsic viscosity of 0.35dL/g, and as the intrinsic viscosity of the polyphenylene ether resin decreased, the tensile strength and notched impact strength decreased, and the tensile strength and notched impact strength of the high dielectric constant polyphenylene ether/high impact polystyrene composition prepared in comparative example 2 were lower than those of example 7; example 7 compared with comparative example 3, comparative example 3 has no SG, TDI and SEPS-g-MAH, and has common PPO and HIPS compatibility, so that the tensile strength and the notch impact strength of the prepared high dielectric constant polyphenyl ether/high impact polystyrene composition are lower than those of example 7, and comparative example 3 has no barium titanate, polyvinylidene fluoride and copper phthalocyanine oligomer, and has a dielectric constant (1GHz) of only 3.4; 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 polyphenylene ether/high impact polystyrene composition prepared in example 7 had higher tensile and notched impact strengths than those of comparative example 4; example 7 in comparison to comparative example 5, the PPO/HIPS composition produced polyphenylene ether resin oligomers to affect mechanical properties due to the absence of toluene diisocyanate added in comparative example 5, resulting in a high dielectric constant polyphenylene ether/high impact polystyrene composition prepared in comparative example 5 having lower tensile strength and lower notched impact strength than example 7.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.

Claims (10)

1. The high-dielectric-constant polyphenyl ether/high-impact polystyrene composition is characterized by being prepared from the following raw materials in parts by weight:
the intrinsic viscosity of the high-viscosity polyphenyl ether resin is 0.45-0.51 dL/g; the intrinsic viscosity of the low-viscosity polyphenyl ether resin is 0.33-0.37 dL/g; the number average molecular weight of the high impact polystyrene resin is 17000-28000;
the 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.
2. The high dielectric constant polyphenylene ether/high impact polystyrene composition of claim 1, which is prepared from the following raw materials in parts by weight:
Figure FDA0002279625980000021
3. the high dielectric constant polyphenylene ether/high impact polystyrene composition as claimed in claim 1 or 2, wherein the mass fraction of glycidyl methacrylate in the copolymer of styrene and glycidyl methacrylate is 2 to 4 wt%.
4. The high dielectric constant polyphenylene ether/high impact polystyrene composition as claimed in 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 polyphenylene ether/high impact polystyrene composition of 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 method for preparing a high dielectric constant polyphenylene ether/high impact polystyrene composition as defined in any one of claims 1 to 5, comprising the steps of:
(1) drying the high-viscosity polyphenyl ether resin, the low-viscosity polyphenyl ether resin and the high-impact polystyrene resin at the temperature of 80-110 ℃ for 4-8 hours, cooling, and adding the cooled high-viscosity polyphenyl ether resin, the cooled low-viscosity polyphenyl ether resin, the cooled high-impact polystyrene resin, the N, N' -bis (2,2,6, 6-tetramethyl-4-piperidyl) -1, 3-benzenedicarboxamide, bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphate, 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 250-270 ℃, the temperature of the second zone is 255-275 ℃, the temperature of the third zone is 255-275 ℃, the temperature of the fourth zone is 260-280 ℃, the temperature of the fifth zone is 260-280 ℃, the temperature of the sixth zone is 260-280 ℃, the temperature of the seventh zone is 260-280 ℃, the temperature of the eighth zone is 255-275 ℃, the temperature of the die head is 255-275 ℃ and the rotation speed of the screw is 200-600 rpm.
7. The preparation method according to claim 6, wherein in the step (1), the high-viscosity polyphenylene ether resin, the low-viscosity polyphenylene ether resin and the high-impact polystyrene resin are dried at a temperature of 90 to 100 ℃ for 4 to 6 hours; the process parameters in the step (3) comprise: the temperature of the first zone is 255-265 ℃, the temperature of the second zone is 260-270 ℃, the temperature of the third zone is 260-270 ℃, the temperature of the fourth zone is 265-275 ℃, the temperature of the fifth zone is 265-275 ℃, the temperature of the sixth zone is 265-275 ℃, the temperature of the seventh zone is 265-275 ℃, the temperature of the eighth zone is 260-270 ℃, the temperature of the die head is 260-270 ℃, and the rotating speed of the screw is 300-500 rpm.
8. The production method according to claim 6 or 7, wherein the screw shape of the parallel twin-screw extruder is a single-screw 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.
9. The method according to claim 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.
10. 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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