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 (PPO),

30-35 parts of low-viscosity polyphenylene oxide (PPO),

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

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),

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 polyphenyl ether/high impact polystyrene composition 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 styrene and glycidyl methacrylate copolymer and hydrogenated styrene-isoprene copolymer grafted maleic anhydride, wherein, the compatibility between styrene structural units 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, epoxy groups of the styrene and glycidyl methacrylate copolymer and anhydride groups of the hydrogenated styrene-isoprene copolymer grafted maleic anhydride can react with terminal hydroxyl groups 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 breaking 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, so that 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 is better in the blending process of PPO and HIPS, and the hindered piperidyl of the antioxidant can provide an antioxidant effect and improve the dyeability of a copolymer; the bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphate has the melting point of 239 ℃ and the thermal decomposition temperature of over 350 ℃, has good heat resistance and hydrolysis resistance, can provide excellent color stability and melt stability for PPO and HIPS in a blending process, can prevent the PPO and HIPS from thermal degradation in a high-temperature process, can inhibit thermal oxidative discoloration caused by a long time, and can also be provided for Nitrogen Oxide (NO)_x ) Color stability in gas environment, and prevention of discoloration due to fumigation.

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-aminopropyltriethoxysilane and gamma-aminopropyltrimethoxysilane, which all contain amino groups, 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, copper phthalocyanine oligomer and polyphenyl ether resin and high impact polystyrene resin are improved, and the influence of the high dielectric constant filler, polyvinylidene fluoride and copper phthalocyanine oligomer on the mechanical properties of the PPO/HIPS composition is reduced.

The invention uses high medium by compoundingThe electric constant filler, polyvinylidene fluoride and copper phthalocyanine oligomer are used for improving the dielectric constant of the polyphenyl ether/high impact polystyrene composition. 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 -10⁶ But 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 improve the defect of poor processability of the polyphenyl ether resin, the compatibility between the polyphenyl ether resin and the high impact polystyrene resin is improved by adding the copolymer of styrene and glycidyl methacrylate and the maleic anhydride grafted by the hydrogenated styrene-isoprene copolymer, and the generation of polyphenyl ether resin oligomer is reduced by adding toluene diisocyanate, so that 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 processability 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 diamide, N' -bis (2,2,6, 6-tetramethyl-4-piperidyl) and the like are compounded, 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, low requirement on equipment, low investment and contribution to industrial production, and all used equipment is general polymer processing equipment.

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):

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 raw materials used in the examples and comparative examples of the present invention were as follows:

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

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 (Shanghai) trade company;

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 e.g. 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 Achrom chemical Co., Ltd;

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 (shanghai) trade ltd;

hydrogenated styrene-butadiene-styrene copolymer grafted maleic anhydride, selected from Shenyankotong plastics, Inc.

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),

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

Example 2:

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

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

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

(1) drying the high-viscosity polyphenyl ether resin, the low-viscosity polyphenyl ether resin and the high-impact polystyrene resin at the temperature of 110 ℃ for 4 hours, cooling, and adding the cooled high-viscosity polyphenyl ether resin, the cooled low-viscosity polyphenyl ether resin, the cooled high-impact polystyrene resin 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;

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

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

Example 3:

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

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

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

(1) drying the high-viscosity polyphenyl ether resin, the low-viscosity polyphenyl ether resin and the high-impact polystyrene resin at the temperature of 90 ℃ for 6 hours, cooling, and adding the cooled high-viscosity polyphenyl ether resin, the cooled low-viscosity polyphenyl ether resin, the cooled high-impact polystyrene resin 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;

(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:

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

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

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

(1) drying the high-viscosity polyphenyl ether resin, the low-viscosity polyphenyl ether resin and the high-impact polystyrene resin at the temperature of 100 ℃ for 4 hours, cooling, and adding the cooled high-viscosity polyphenyl ether resin, the cooled low-viscosity polyphenyl ether resin, the cooled high-impact polystyrene resin 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;

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

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

Example 5:

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

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

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

(1) drying the high-viscosity polyphenyl ether resin, the low-viscosity polyphenyl ether resin and the high-impact polystyrene resin at the temperature of 95 ℃ for 5 hours, cooling, and adding the cooled high-viscosity polyphenyl ether resin, the cooled low-viscosity polyphenyl ether resin, the cooled high-impact polystyrene resin 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;

(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:

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),

(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 revolutions per minute) for mixing;

Example 7:

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),

Example 8:

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

The 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),

Comparative example 2:

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

Comparative example 3:

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.

(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.

Comparative example 4:

(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-phthalic diamide, bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphate, pentaerythritol zinc pentaerythritol, 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;

Comparative example 5

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

(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;

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

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.

In example 7, compared with example 8, the screw shape of the parallel twin-screw extruder of example 8 is double-screw, the ratio L/D of the length L of the screw to the diameter D of the screw is 50, the screw shape of the parallel twin-screw extruder of example 7 is single-screw, and the ratio L/D of the length L of the screw to the diameter D of the screw is 40, and by comparison, it can be found that the tensile strength, the notch impact strength and the melt index of the high dielectric constant polyphenylene ether/high impact polystyrene composition prepared by using the screw parameters of the parallel twin-screw extruder described in example 7 are 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

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:

40-45 parts of high-viscosity polyphenyl ether resin,

30-35 parts of low-viscosity polyphenyl ether resin,

20-30 parts of high impact polystyrene resin,

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;

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

42-44 parts of high-viscosity polyphenyl ether resin,

31-33 parts of low-viscosity polyphenyl ether resin,

23-28 parts of high impact polystyrene resin,

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 claimed in any one of claims 1 to 5, which comprises the steps of:

7. The 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 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.