CN111393828A - Low dielectric constant polyphenyl ether composition and preparation method thereof - Google Patents
Low dielectric constant polyphenyl ether composition and preparation method thereof Download PDFInfo
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- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
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Abstract
The invention relates to a low dielectric constant polyphenyl ether composition and a preparation method thereof, wherein the low dielectric constant polyphenyl ether composition is prepared from the following raw materials: polyphenylene ether resin, high impact polystyrene resin, polyphenylene ether grafted maleic anhydride, hydrogenated styrene-butadiene-styrene copolymer grafted maleic anhydride, hollow glass beads, polyhedral oligomeric silsesquioxane polymer, titanate coupling agent, polytetrafluoroethylene resin, hyperbranched polyester polymer, erucamide, N' -bis (2,2,6, 6-tetramethyl-4-piperidyl) -1, 3-benzenedicarboxamide, bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphate. The polyphenyl ether composition with the low dielectric constant has excellent mechanical property, processability and the low dielectric constant, and can be applied to shells, coatings, protective materials and the like of 5G base stations, micro base station systems, data communication terminals, antennas and radio frequency modules.
Description
Technical Field
The invention relates to the field of materials, in particular to a low-dielectric-constant polyphenyl ether composition and a preparation method thereof.
Background
Dielectric materials, also known as dielectrics, are electrically insulating materials. There are high dielectric materials and low dielectric materials, depending on the properties. With the rapid advance of electronic information technology, electronic products are being developed toward light weight, high performance and multiple functions, and development of low dielectric constant (D) having good performance is increasingly required for low dielectric materialsk<3) A material. Meanwhile, with the coming of the 5G era, the requirements on the transmission speed and the loss of electronic signals are higher than those of 4G products, generally, the dielectric constant of the 4G products for the resin material is only required to be less than 3.7(1GHz), and the dielectric constant of the 5G products for the resin material is required to be less than 3.2(1 GHz).
Generally, there are three methods for reducing the dielectric constant of a polymer, which are ① introducing fluorine atoms into a polymer molecular chain to reduce the stacking density of the molecular chain and increase the free movement space of the molecular chain, ② introducing a bulky structure (such as polyhedral oligomeric silsesquioxane polymer) or a microporous structure or introducing large molecular chain side groups (such as benzene rings) by a physical or chemical method, ③ reducing the dielectric constant of a blend by blending other materials with lower dielectric constant, such as blending with Polytetrafluoroethylene (PTFE) with a relative dielectric constant of 2.0(1GHz), or blending with materials such as polyhedral oligomeric silsesquioxane Polymer (POSS) which can increase the free volume, and the like.
The polyphenylene oxide (PPO) has good mechanical property, heat resistance, chemical stability and lower dielectric constant, can be continuously used within the temperature range of-160-190 ℃, and is the most excellent material for resisting creep property of thermoplastic engineering plastics. But the processing property of the polyphenyl ether is poor, the polyphenyl ether needs to be modified, the toughening and the strengthening of the polyphenyl ether are needed, and the dielectric constant of the blend needs to be reduced so as to meet the increasing requirements in the fields of electronic and electrical engineering, integrated circuit packaging, electromagnetic wave shielding and the like.
Currently, some studies on PPO dielectric systems are made in the prior art, such as: chinese patent CN 109575528A discloses a low-dielectric high-toughness reinforced PBT/PPO composition and a preparation method thereof, wherein the composition comprises the following raw materials, by weight, 45-85 parts of polybutylene terephthalate (PBT), 15-55 Parts of Polyphenylene Oxide (PPO), 100 parts of the sum of the polybutylene terephthalate and the polyphenylene oxide, 20-40 parts of glass fiber, 6-14 parts of a compatilizer, 0.6-1 part of an antioxidant, 5-20 parts of polytetrafluoroethylene, 0.2-1 part of a plasticizer, 0.2-1 part of a silane coupling agent, and the weight ratio of the plasticizer to the silane coupling agent is 1: 1-5: 1. Chinese patent CN 108117739A discloses a PPO composite material with high frequency and high dielectric constant, which comprises the following raw materials, 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. Chinese patent CN 110684338A discloses a thermoplastic composition relating to a thermoplastic composition with good dielectric and ductility properties, comprising: 29.9 to 84.9 wt% of a base resin comprising poly (p-phenylene oxide) (PPO), Polystyrene (PS) and an impact modifier, 15 to 70 wt% of a dielectric filler, and 0.1 to 10 wt% of an impact promoter comprising a polycarbonate-siloxane copolymer, a polyolefin-siloxane copolymer, or a combination thereof. Chinese patent CN108164973A discloses a high-dielectric polyphenyl ether material and a preparation method and application thereof, wherein the polyphenyl ether material comprises the following raw materials, 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 flexibilizer, 0.3-0.8 part of antioxidant and 0.5-2 parts of lubricant; chinese patent CN102408251A discloses a method for preparing a low dielectric constant mesoporous silica film material, which comprises the steps of adding P123 and PDMS-PEO into polymeric silica sol to form oligomeric silicate precursor solution, then aging, spin-coating on a silicon chip, and roasting to obtain the low dielectric constant mesoporous silica film material, wherein the polymeric silica sol is prepared by mixing TEOS, water, hydrochloric acid and ethanol and refluxing.
Disclosure of Invention
Based on the above, the invention aims to provide a low-dielectric-constant polyphenyl ether composition with excellent mechanical properties and processability, which can be applied to shells, coatings, protective materials and the like of 5G base stations, micro base station systems, data communication terminals, antennas and radio frequency modules.
In order to achieve the purpose, the invention adopts the following scheme:
a low-dielectric-constant polyphenyl ether composition is prepared from the following raw materials in parts by weight:
70-95 Parts of Polyphenylene Oxide (PPO),
5-30 parts of high impact polystyrene resin (HIPS),
the total of the parts by weight of the polyphenyl ether resin and the high impact polystyrene resin is 100 parts,
the intrinsic viscosity of the polyphenyl ether resin is 0.33-0.37 d L/g, the compressive strength of the hollow glass beads is not lower than 53MPa, and the number average molecular weight of the polytetrafluoroethylene resin is 1-10 ten thousand.
In some embodiments, the low dielectric constant polyphenylene ether composition is prepared from the following raw materials in parts by weight:
75-90 Parts of Polyphenylene Oxide (PPO),
10-25 parts of high impact polystyrene resin (HIPS),
the total of the parts by weight of the polyphenyl ether resin and the high impact polystyrene resin is 100 parts,
in some of the embodiments, the low dielectric constant polyphenylene ether composition is further preferably prepared from the following raw materials in parts by weight:
78-87 Parts of Polyphenylene Oxide (PPO),
13-22 parts of high impact polystyrene resin (HIPS),
the total of the parts by weight of the polyphenyl ether resin and the high impact polystyrene resin is 100 parts,
in some of the embodiments, the polyphenylene ether grafted maleic anhydride has a maleic anhydride grafting ratio of 0.8-1.2%.
In some of the embodiments, the maleic anhydride grafting ratio of the hydrogenated styrene-butadiene-styrene copolymer grafted maleic anhydride is 0.8 to 1.2%.
In some of these embodiments, the terminal group of the polyhedral oligomeric silsesquioxane polymer is an epoxy group. Specifically, the polyhedral oligomeric silsesquioxane polymer is at least one of glycidol POSS and epoxycyclohexyl POSS.
In some of these embodiments, the titanate coupling agent is a monoalkoxy fatty acid titanate coupling agent.
Another object of the present invention is to provide a process for preparing the above low dielectric constant polyphenylene ether composition.
The preparation method of the low dielectric constant polyphenyl ether composition comprises the following steps:
(1) drying the polyphenyl ether resin and the high impact polystyrene resin (cooling after drying), and mixing with polyphenyl ether grafted maleic anhydride, hydrogenated styrene-butadiene-styrene copolymer grafted maleic anhydride, polytetrafluoroethylene resin, N' -bis (2,2,6, 6-tetramethyl-4-piperidyl) -1, 3-benzenedicarboxamide and bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphate (in a stirrer);
(2) mixing the hollow glass beads, the polyhedral oligomeric silsesquioxane polymer, the titanate coupling agent, the hyperbranched polyester polymer and the erucamide (in another stirrer);
(3) and (3) adding the mixture mixed in the step (1) into a parallel double-screw extruder through a feeder, laterally adding the mixture mixed in the step (2) into the parallel double-screw extruder (total eight zones), performing melt extrusion, and granulating.
In some embodiments, the polyphenylene ether resin and the high impact polystyrene resin are dried at 80-110 ℃ for 4-8 hours in step (1); preferably, in the step (1), the polyphenylene ether resin and the high impact polystyrene resin are dried at a temperature of 90-100 ℃ for 4-6 hours.
In some of the embodiments, the process parameters of the parallel twin-screw extruder in step (3) include: the temperature of the first zone is 265-285 ℃, the temperature of the second zone is 270-290 ℃, the temperature of the third zone is 270-290 ℃, the temperature of the fourth zone is 275-295 ℃, the temperature of the fifth zone is 275-295 ℃, the temperature of the sixth zone is 270-290 ℃, the temperature of the seventh zone is 270-290 ℃, the temperature of the eighth zone is 270-290 ℃, the temperature of the die head is 270-290 ℃, and the rotating speed of the screw is 200-600 rpm.
In some of the embodiments, the process parameters of the parallel twin-screw extruder in step (3) include: the temperature of the first zone is 270-280 ℃, the temperature of the second zone is 275-285 ℃, the temperature of the third zone is 275-285 ℃, the temperature of the fourth zone is 280-290 ℃, the temperature of the fifth zone is 280-290 ℃, the temperature of the sixth zone is 275-285 ℃, the temperature of the seventh zone is 275-285 ℃, the temperature of the eighth zone is 275-285 ℃, the temperature of the die head is 275-285 ℃ 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 flight.
In some of these embodiments, the parallel twin screw extruder has a ratio L/D of screw length L to diameter D of 35 to 50, preferably a ratio L/D of screw length L to diameter D of 35 to 45.
In some of the embodiments, the screws of the parallel twin-screw extruder are provided with more than 1 intermeshing zone and more than 1 counter-thread zone; optionally, the screw is provided with 2 meshing block areas and 1 reverse thread area.
In some embodiments, in step (1), the mixing step is performed by using a stirrer, wherein the stirrer is a high-speed stirrer and the rotating speed is 500-1500 rpm.
In some embodiments, in the step (2), the mixing step is performed by using a stirrer, wherein the stirrer is a high-speed stirrer and the rotating speed is 500-1500 rpm.
The principle of the low dielectric constant polyphenylene ether composition of the invention is as follows:
in order to solve the defects of poor compatibility and processing performance of PPO, low dielectric fillers HGS and POSS in the low dielectric constant polyphenyl ether composition, the compatibility among PPO, HIPS and the low dielectric fillers is improved by adding compatilizers PPO-g-MAH and SEBS-g-MAH; adding titanate coupling agent to improve the compatibility between PPO and low dielectric filler; adding a lubricating dispersant hyperbranched polyester polymer and erucamide to improve the effect of coating the titanate coupling agent on the low dielectric filler and the processing performance of the PPO composition; according to the invention, the addition of the auxiliary agent improves the interface bonding force and compatibility between the PPO and the low dielectric filler, and simultaneously improves the mechanical property and the processing property of the PPO composition, so that the low dielectric constant polyphenyl ether composition with excellent comprehensive properties is prepared.
The compatibility of the polyphenylene oxide structural unit in the compatilizer PPO-g-MAH and the polyphenylene oxide resin is good, and the compatibility of the SEBS structural unit in the compatilizer SEBS-g-MAH and the HIPS resin is good; the maleic anhydride groups of the PPO-g-MAH and the SEBS-g-MAH and the epoxy groups of the polyhedral oligomeric silsesquioxane polymer can react with the terminal hydroxyl groups of the hollow glass microspheres and the PPO and react with a titanate coupling agent coating the low dielectric filler, so that the compatibility between the PPO and the low dielectric filler is improved; in addition, the SEBS-g-MAH can also improve the impact property of the PPO composition.
The hollow glass micro-beads (HGS) adopted by the invention are hollow spherical powdery inorganic nonmetallic materials, the main components of the hollow spherical powdery inorganic nonmetallic materials are soda lime borosilicate glass, and inert gases such as thin nitrogen, carbon dioxide and the like are filled in the cavity of the hollow spherical inorganic nonmetallic materials, so that the dielectric constant of the hollow glass micro-beads is only 1.2-1.5 (1 GHz).
The polyhedral oligomeric silsesquioxane Polymer (POSS) adopted by the invention has a highly symmetrical cubic cage-shaped framework, and the intrinsic nanopores of the POSS enable the POSS to have a very low dielectric constant of 2.1-2.5 (1GHz), so that the dielectric constant of the blend can be effectively reduced, and the mechanical property of the blend cannot be obviously influenced; the compatibility of POSS and base material resin is good, and the particle agglomeration can be effectively reduced; meanwhile, POSS molecules contain inorganic cores composed of silicon and oxygen, so that the thermal stability is good, the molecular size is large, and the effect of blocking the movement of polymer molecular chain segments is achieved, and therefore, the addition of POSS is beneficial to improving the thermal stability of the low-dielectric-constant polyphenyl ether composition. In addition, the epoxy groups of POSS can react with the terminal hydroxyl groups of HGS and PPO, thereby improving the compatibility between PPO and low dielectric fillers.
The effect of the titanate coupling agent adopted by the invention is attributed to the influence on the interface, namely the titanate coupling agent can form a chemical bridge bond between the inorganic low dielectric filler and the organic polymer, the titanate coupling agent is coupled by the direct chemical action of the alkoxy of the titanate coupling agent and the trace hydroxyl adsorbed on the surface of the low dielectric filler, and the organic phase of the titanate coupling agent has good compatibility with PPO and HIPS.
The polytetrafluoroethylene resin adopted by the invention is mainly used as a modifier and a release agent of the low dielectric constant polyphenylene ether composition by utilizing the special lubricating property and non-stick property, and the dielectric constant of the polytetrafluoroethylene resin is lower and is only 2.0(1 GHz).
The hyperbranched polyester polymer adopted by the invention is a high temperature resistant dendritic structure additive with a polyester structural unit, which can obviously improve the processing fluidity of the PPO composition and the coating effect of the titanate coupling agent, and improve the dispersion degree of the low dielectric filler in the polyphenyl ether composition product, effectively solve the surface defect of the product, and simultaneously improve the surface glossiness of the product.
The erucamide adopted by the invention has higher melting point and good thermal stability, can obviously improve the processing fluidity of the PPO composition and the coating effect of a titanate coupling agent, improves the dispersion degree of low dielectric filler in the PPO composition, and has little influence on the mechanical property of the PPO composition.
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 PPO blending process is good, and the hindered piperidyl can provide antioxidation and improve the dyeability of the PPO composition.
The bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphate adopted by the invention has the melting point of 239 ℃ and the thermal decomposition temperature of over 350 ℃, has good heat resistance and hydrolysis resistance, can provide excellent color stability and melt stability for the blending process of a PPO composition, can prevent the thermal degradation of the PPO composition in the high-temperature process, and inhibit the thermal oxidative discoloration caused by long-time extrusion processing, and also provides a Nitrogen Oxide (NO) for the PPO compositionx) Color stability in gas environment, and prevention of discoloration of fumigant.
Compared with the prior art, the invention has the following beneficial effects:
aiming at the defects of poor compatibility and processing performance of PPO, low-dielectric-constant hollow glass microspheres (HGS) and polyhedral oligomeric silsesquioxane Polymers (POSS) in the existing low-dielectric-constant polyphenyl ether composition, the compatibility between PPO and the low-dielectric-constant polyphenyl ether is improved by adding compatilizers PPO-g-MAH, SEBS-g-MAH, titanate coupling agent, lubricating dispersant hyperbranched polyester polymer and erucamide, the processing performance of the low-dielectric-constant polyphenyl ether composition is improved by adopting low-viscosity PPO and low-molecular-weight PTFE, the dielectric constant of the low-dielectric-constant polyphenyl ether composition is reduced by compounding HGS, POSS and PTFE, N' -bis (2,2,6, 6-tetramethyl-4-piperidyl) -1, 3-phthalic amide and bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphate is used for improving the yellowing phenomenon and the thermal stability of the low-dielectric-constant polyphenyl ether composition in the blending processing process, and the raw material components are matched with each other, so that the obtained low-dielectric-constant polyphenyl ether composition has excellent mechanical property and processing property, and can be applied to shells, coatings, protective materials and the like of 5G base stations, micro base station systems, data communication terminals, antennas and radio frequency modules.
The preparation method of the low dielectric constant polyphenyl ether composition provided by the invention has the advantages of simple process, easiness in control and low requirements 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 low dielectric constant polyphenylene ether composition in accordance with one embodiment of the present invention.
Detailed Description
Experimental procedures according to the invention, in which no particular conditions are specified in the following examples, are generally carried out under conventional conditions, or under conditions recommended by the manufacturer. The various chemicals used in the examples are commercially available.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
The terms "comprising" and "having," and any variations thereof, are intended to cover non-exclusive inclusions. For example, a process, method, apparatus, article, or device that comprises a list of steps is not limited to only those steps or modules listed, but may alternatively include other steps not listed or inherent to such process, method, article, or device.
The "plurality" referred to in the present invention means two or more. "and/or" describes the association relationship of the associated objects, meaning that there may be three relationships, e.g., a and/or B, which may mean: a exists alone, A and B exist simultaneously, and B exists alone. The character "/" generally indicates that the former and latter associated objects are in an "or" relationship.
The reaction mechanism of the low dielectric constant polyphenylene ether composition according to an embodiment of the present invention is as follows (see fig. 1 for a flow chart of the preparation process):
wherein R is1PPO or SEBS, R2HGS or PPO;
as can be seen from the reaction formula, the maleic anhydride groups of PPO-g-MAH and SEBS-g-MAH can react with the terminal hydroxyl groups of HGS and PPO, and the epoxy groups of POSS can react with the terminal hydroxyl groups of HGS and PPO, so that the compatibility between PPO and low dielectric filler is improved.
The examples of the invention and the comparative examples used the following raw materials:
polyphenylene ether resin with an intrinsic viscosity of 0.35d L/g, selected from Nantong star synthetic materials GmbH;
polyphenylene ether resin with an intrinsic viscosity of 0.55d L/g, selected from Nantong star synthetic materials GmbH;
polyphenylene ether grafted maleic anhydride, the maleic anhydride grafting rate being 1%, selected from Nippon light corporation;
hydrogenated styrene-butadiene-styrene copolymer grafted maleic anhydride, maleic anhydride graft rate of 1%, selected from Shenyang Ketong plastics Co., Ltd;
the hollow glass microspheres have the compressive strength of 60MPa and are selected from New Material science and technology Limited company of Middling Steel group Maanshan Ministry;
the hollow glass microspheres have the compressive strength of 30MPa and are selected from New Material science and technology Limited company of Middling Steel group Maanshan Ministry;
epoxycyclohexyl POSS selected from Hybrid Plastics, usa;
glycidol POSS selected from the group consisting of Hybrid Plastics, USA;
mono-alkoxy fatty acid titanate coupling agent selected from chemical auxiliary oil material factories in Tianchan city;
polytetrafluoroethylene resin having a number average molecular weight of 5 ten thousand selected from the large-scale fluoroplastics (China) Co., Ltd;
polytetrafluoroethylene resin having a number average molecular weight of 200 ten thousand selected from the large-scale fluoroplastics (China) Co., Ltd;
the hyperbranched polyester polymer has a thermal decomposition temperature of more than or equal to 350 ℃, and is selected from Waishahen molecular new materials Co., Ltd;
erucamide, selected from the group consisting of Haimengteng New materials science and technology, Inc.;
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;
the present invention will be described in detail with reference to specific examples.
Example 1:
the embodiment provides a low-dielectric-constant polyphenyl ether composition, which is prepared from the following raw materials in parts by weight:
70 parts of polyphenyl ether resin (with the intrinsic viscosity of 0.35d L/g),
30 parts of high impact polystyrene resin,
the total of the parts by weight of the polyphenyl ether resin and the high impact polystyrene resin is 100 parts,
the preparation method of the low dielectric constant polyphenyl ether composition comprises the following steps:
(1) drying the polyphenyl ether resin and the high impact polystyrene resin at the temperature of 80 ℃ for 8 hours, cooling, and adding the cooled polyphenyl ether resin, the high impact polystyrene resin, the polyphenyl ether grafted maleic anhydride, the hydrogenated styrene-butadiene-styrene copolymer grafted maleic anhydride, the polytetrafluoroethylene resin, the N, N' -bis (2,2,6, 6-tetramethyl-4-piperidyl) -1, 3-benzenedicarboxamide and bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphate into a stirrer for mixing;
(2) adding the hollow glass beads, epoxy cyclohexyl POSS, monoalkoxyl fatty acid titanate coupling agent, hyperbranched polyester polymer and erucamide 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 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 270 deg.C, the temperature in the seventh zone was 270 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 of the length L of the screw to the diameter D of L/D is 35, the screw is provided with 2 meshing block areas and 1 back-thread area, and the stirrer in the step (1) and the step (2) is a high-speed stirrer with the rotating speed of 1000 revolutions per minute.
Example 2:
the embodiment provides a low-dielectric-constant polyphenyl ether composition, which is prepared from the following raw materials in parts by weight:
95 parts of polyphenyl ether resin (the intrinsic viscosity is 0.35d L/g),
5 parts of high impact polystyrene resin,
the total of the parts by weight of the polyphenyl ether resin and the high impact polystyrene resin is 100 parts,
the preparation method of the low dielectric constant polyphenyl ether composition comprises the following steps:
(1) drying the polyphenyl ether resin and the high impact polystyrene resin at the temperature of 110 ℃ for 4 hours, cooling, and adding the cooled polyphenyl ether resin, the high impact polystyrene resin, the polyphenyl ether grafted maleic anhydride, the hydrogenated styrene-butadiene-styrene copolymer grafted maleic anhydride, the polytetrafluoroethylene resin, the N, N' -bis (2,2,6, 6-tetramethyl-4-piperidyl) -1, 3-benzenedicarboxamide and bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphate into a stirrer for mixing;
(2) adding the hollow glass beads, the glycidol POSS, the monoalkoxy fatty acid titanate coupling agent, the hyperbranched polyester polymer and the erucamide 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 in the first zone was 285 deg.C, the temperature in the second zone was 290 deg.C, the temperature in the third zone was 290 deg.C, the temperature in the fourth zone was 295 deg.C, the temperature in the fifth zone was 295 deg.C, the temperature in the sixth zone was 290 deg.C, the temperature in the seventh zone was 290 deg.C, the temperature in the eighth zone was 290 deg.C, the temperature in the die head was 290 deg.C, and.
The screw of the parallel double-screw extruder is in a single-thread shape, the ratio of the length L of the screw to the diameter D of L/D is 50, the screw is provided with 2 meshing block areas and 1 back-thread area, and the stirrer in the step (1) and the step (2) is a high-speed stirrer with the rotating speed of 1000 revolutions per minute.
Example 3:
the embodiment provides a low-dielectric-constant polyphenyl ether composition, which is prepared from the following raw materials in parts by weight:
75 parts of polyphenyl ether resin (with the intrinsic viscosity of 0.35d L/g),
25 parts of high impact polystyrene resin,
the total of the parts by weight of the polyphenyl ether resin and the high impact polystyrene resin is 100 parts,
the preparation method of the low dielectric constant polyphenyl ether composition comprises the following steps:
(1) drying the polyphenyl ether resin and the high impact polystyrene resin at the temperature of 90 ℃ for 6 hours, cooling, and adding the cooled polyphenyl ether resin, the high impact polystyrene resin, the polyphenyl ether grafted maleic anhydride, the hydrogenated styrene-butadiene-styrene copolymer grafted maleic anhydride, the polytetrafluoroethylene resin, the N, N' -bis (2,2,6, 6-tetramethyl-4-piperidyl) -1, 3-benzenedicarboxamide and bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphate into a stirrer for mixing;
(2) adding the hollow glass beads, the glycidol POSS, the monoalkoxy fatty acid titanate coupling agent, the hyperbranched polyester polymer and the erucamide 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 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 275 ℃, the temperature in the seventh zone was 275 ℃, the temperature in the eighth zone was 275 ℃, the temperature in the die head was 275 ℃ and the screw speed was 300 rpm.
The screw of the parallel double-screw extruder is in a single-thread shape, the ratio of the length L of the screw to the diameter D of L/D is 35, the screw is provided with 2 meshing block areas and 1 back-thread area, and the stirrer in the step (1) and the step (2) is a high-speed stirrer with the rotating speed of 1000 revolutions per minute.
Example 4:
the embodiment provides a low-dielectric-constant polyphenyl ether composition, which is prepared from the following raw materials in parts by weight:
90 parts of polyphenyl ether resin (with the intrinsic viscosity of 0.35d L/g),
10 parts of high impact polystyrene resin,
the total of the parts by weight of the polyphenyl ether resin and the high impact polystyrene resin is 100 parts,
the preparation method of the low dielectric constant polyphenyl ether composition comprises the following steps:
(1) drying the polyphenyl ether resin and the high impact polystyrene resin at the temperature of 100 ℃ for 4 hours, cooling, and adding the cooled polyphenyl ether resin, the high impact polystyrene resin, the polyphenyl ether grafted maleic anhydride, the hydrogenated styrene-butadiene-styrene copolymer grafted maleic anhydride, the polytetrafluoroethylene resin, the N, N' -bis (2,2,6, 6-tetramethyl-4-piperidyl) -1, 3-benzenedicarboxamide and bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphate into a stirrer for mixing;
(2) adding the hollow glass beads, the glycidol POSS, the monoalkoxy fatty acid titanate coupling agent, the hyperbranched polyester polymer and the erucamide 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 280 ℃, the temperature of the second zone is 285 ℃, the temperature of the third zone is 285 ℃, the temperature of the fourth zone is 290 ℃, the temperature of the fifth zone is 290 ℃, the temperature of the sixth zone is 285 ℃, the temperature of the seventh zone is 285 ℃, the temperature of the eighth zone is 285 ℃, the temperature of the die head is 285 ℃ and the rotating speed of the screw is 500 rpm.
The screw of the parallel double-screw extruder is in a single-thread shape, the ratio of the length L of the screw to the diameter D of L/D is 45, the screw is provided with 2 meshing block areas and 1 back-thread area, and the stirrer in the step (1) and the step (2) is a high-speed stirrer with the rotating speed of 1000 revolutions per minute.
Example 5:
the embodiment provides a low-dielectric-constant polyphenyl ether composition, which is prepared from the following raw materials in parts by weight:
78 parts of polyphenylene ether resin (with the intrinsic viscosity of 0.35d L/g),
22 parts of high impact polystyrene resin,
the total of the parts by weight of the polyphenyl ether resin and the high impact polystyrene resin is 100 parts,
the preparation method of the low dielectric constant polyphenyl ether composition comprises the following steps:
(1) drying the polyphenyl ether resin and the high impact polystyrene resin at the temperature of 95 ℃ for 5 hours, cooling, and adding the cooled polyphenyl ether resin, the high impact polystyrene resin, the polyphenyl ether grafted maleic anhydride, the hydrogenated styrene-butadiene-styrene copolymer grafted maleic anhydride, the polytetrafluoroethylene resin, the N, N' -bis (2,2,6, 6-tetramethyl-4-piperidyl) -1, 3-benzenedicarboxamide and bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphate into a stirrer for mixing;
(2) adding the hollow glass beads, the glycidol POSS, the monoalkoxy fatty acid titanate coupling agent, the hyperbranched polyester polymer and the erucamide 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 was 275 deg.C, the temperature of the second zone was 280 deg.C, the temperature of the third zone was 280 deg.C, the temperature of the fourth zone was 285 deg.C, the temperature of the fifth zone was 285 deg.C, the temperature of the sixth zone was 280 deg.C, the temperature of the seventh zone was 280 deg.C, the temperature of the eighth zone was 280 deg.C, the temperature of the die head was 280 deg.C, and.
The screw of the parallel double-screw extruder is in a single-thread shape, the ratio of the length L of the screw to the diameter D of L/D is 40, the screw is provided with 2 meshing block areas and 1 back-thread area, and the stirrer in the step (1) and the step (2) is a high-speed stirrer with the rotating speed of 1000 revolutions per minute.
Example 6:
the embodiment provides a low-dielectric-constant polyphenyl ether composition, which is prepared from the following raw materials in parts by weight:
87 parts of polyphenyl ether resin (with the intrinsic viscosity of 0.35d L/g),
13 parts of high impact polystyrene resin,
the total of the parts by weight of the polyphenyl ether resin and the high impact polystyrene resin is 100 parts,
the preparation method of the low dielectric constant polyphenyl ether composition comprises the following steps:
(1) drying the polyphenyl ether resin and the high impact polystyrene resin at the temperature of 95 ℃ for 5 hours, cooling, and adding the cooled polyphenyl ether resin, the high impact polystyrene resin, the polyphenyl ether grafted maleic anhydride, the hydrogenated styrene-butadiene-styrene copolymer grafted maleic anhydride, the polytetrafluoroethylene resin, the N, N' -bis (2,2,6, 6-tetramethyl-4-piperidyl) -1, 3-benzenedicarboxamide and bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphate into a stirrer for mixing;
(2) adding the hollow glass beads, the glycidol POSS, the monoalkoxy fatty acid titanate coupling agent, the hyperbranched polyester polymer and the erucamide 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 was 275 deg.C, the temperature of the second zone was 280 deg.C, the temperature of the third zone was 280 deg.C, the temperature of the fourth zone was 285 deg.C, the temperature of the fifth zone was 285 deg.C, the temperature of the sixth zone was 280 deg.C, the temperature of the seventh zone was 280 deg.C, the temperature of the eighth zone was 280 deg.C, the temperature of the die head was 280 deg.C, and.
The screw of the parallel double-screw extruder is in a single-thread shape, the ratio of the length L of the screw to the diameter D of L/D is 40, the screw is provided with 2 meshing block areas and 1 back-thread area, and the stirrer in the step (1) and the step (2) is a high-speed stirrer with the rotating speed of 1000 revolutions per minute.
Example 7:
the embodiment provides a low-dielectric-constant polyphenyl ether composition, which is prepared from the following raw materials in parts by weight:
82 parts of polyphenyl ether resin (with the intrinsic viscosity of 0.35d L/g),
18 parts of high impact polystyrene resin,
the total of the parts by weight of the polyphenyl ether resin and the high impact polystyrene resin is 100 parts,
the preparation method of the low dielectric constant polyphenyl ether composition comprises the following steps:
(1) drying the polyphenyl ether resin and the high impact polystyrene resin at the temperature of 95 ℃ for 5 hours, cooling, and adding the cooled polyphenyl ether resin, the high impact polystyrene resin, the polyphenyl ether grafted maleic anhydride, the hydrogenated styrene-butadiene-styrene copolymer grafted maleic anhydride, the polytetrafluoroethylene resin, the N, N' -bis (2,2,6, 6-tetramethyl-4-piperidyl) -1, 3-benzenedicarboxamide and bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphate into a stirrer for mixing;
(2) adding the hollow glass beads, the glycidol POSS, the monoalkoxy fatty acid titanate coupling agent, the hyperbranched polyester polymer and the erucamide 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 was 275 deg.C, the temperature of the second zone was 280 deg.C, the temperature of the third zone was 280 deg.C, the temperature of the fourth zone was 285 deg.C, the temperature of the fifth zone was 285 deg.C, the temperature of the sixth zone was 280 deg.C, the temperature of the seventh zone was 280 deg.C, the temperature of the eighth zone was 280 deg.C, the temperature of the die head was 280 deg.C, and.
The screw of the parallel double-screw extruder is in a single-thread shape, the ratio of the length L of the screw to the diameter D of L/D is 40, the screw is provided with 2 meshing block areas and 1 back-thread area, and the stirrer in the step (1) and the step (2) is a high-speed stirrer with the rotating speed of 1000 revolutions per minute.
Example 8:
the embodiment provides a low-dielectric-constant polyphenyl ether composition, which is prepared from the following raw materials in parts by weight:
82 parts of polyphenyl ether resin (with the intrinsic viscosity of 0.35d L/g),
18 parts of high impact polystyrene resin,
the total of the parts by weight of the polyphenyl ether resin and the high impact polystyrene resin is 100 parts,
the preparation method of the low dielectric constant polyphenyl ether composition comprises the following steps:
(1) drying the polyphenyl ether resin and the high impact polystyrene resin at the temperature of 95 ℃ for 5 hours, cooling, and adding the cooled polyphenyl ether resin, the high impact polystyrene resin, the polyphenyl ether grafted maleic anhydride, the hydrogenated styrene-butadiene-styrene copolymer grafted maleic anhydride, the polytetrafluoroethylene resin, the N, N' -bis (2,2,6, 6-tetramethyl-4-piperidyl) -1, 3-benzenedicarboxamide and bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphate into a stirrer for mixing;
(2) adding the hollow glass beads, the glycidol POSS, the monoalkoxy fatty acid titanate coupling agent, the hyperbranched polyester polymer and the erucamide 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 was 275 deg.C, the temperature of the second zone was 280 deg.C, the temperature of the third zone was 280 deg.C, the temperature of the fourth zone was 285 deg.C, the temperature of the fifth zone was 285 deg.C, the temperature of the sixth zone was 280 deg.C, the temperature of the seventh zone was 280 deg.C, the temperature of the eighth zone was 280 deg.C, the temperature of the die head was 280 deg.C, and.
The screw shape of the parallel double-screw extruder is double-thread, the ratio L/D of the length L of the screw to the diameter D of the screw is 40, the screw is provided with 2 meshing block areas and 1 back-thread area, the stirrer in the step (1) and the step (2) is a high-speed stirrer, and the rotating speed is 1000 revolutions per minute.
Comparative example 1:
the comparative example provides a low dielectric constant polyphenylene ether composition, which is prepared from the following raw materials in parts by weight:
82 parts of polyphenyl ether resin (with the intrinsic viscosity of 0.55d L/g),
18 parts of high impact polystyrene resin,
the total of the parts by weight of the polyphenyl ether resin and the high impact polystyrene resin is 100 parts,
the preparation method of the low dielectric constant polyphenyl ether composition comprises the following steps:
(1) drying the polyphenyl ether resin and the high impact polystyrene resin at the temperature of 95 ℃ for 5 hours, cooling, and adding the cooled polyphenyl ether resin, the high impact polystyrene resin, the polyphenyl ether grafted maleic anhydride, the hydrogenated styrene-butadiene-styrene copolymer grafted maleic anhydride, the polytetrafluoroethylene resin, the N, N' -bis (2,2,6, 6-tetramethyl-4-piperidyl) -1, 3-benzenedicarboxamide and bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphate into a stirrer for mixing;
(2) adding the hollow glass beads, the glycidol POSS, the monoalkoxy fatty acid titanate coupling agent, the hyperbranched polyester polymer and the erucamide 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 was 275 deg.C, the temperature of the second zone was 280 deg.C, the temperature of the third zone was 280 deg.C, the temperature of the fourth zone was 285 deg.C, the temperature of the fifth zone was 285 deg.C, the temperature of the sixth zone was 280 deg.C, the temperature of the seventh zone was 280 deg.C, the temperature of the eighth zone was 280 deg.C, the temperature of the die head was 280 deg.C, and.
The screw of the parallel double-screw extruder is in a single-thread shape, the ratio of the length L of the screw to the diameter D of L/D is 40, the screw is provided with 2 meshing block areas and 1 back-thread area, and the stirrer in the step (1) and the step (2) is a high-speed stirrer with the rotating speed of 1000 revolutions per minute.
Comparative example 2:
the comparative example provides a low dielectric constant polyphenylene ether composition, which is prepared from the following raw materials in parts by weight:
82 parts of polyphenyl ether resin (with the intrinsic viscosity of 0.35d L/g),
18 parts of high impact polystyrene resin,
the total of the parts by weight of the polyphenyl ether resin and the high impact polystyrene resin is 100 parts,
the preparation method of the low dielectric constant polyphenyl ether composition comprises the following steps:
(1) drying the polyphenyl ether resin and the high impact polystyrene resin at the temperature of 95 ℃ for 5 hours, cooling, and adding the cooled polyphenyl ether resin, the high impact polystyrene resin, the polyphenyl ether grafted maleic anhydride, the hydrogenated styrene-butadiene-styrene copolymer grafted maleic anhydride, the polytetrafluoroethylene resin, the N, N' -bis (2,2,6, 6-tetramethyl-4-piperidyl) -1, 3-benzenedicarboxamide and bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphate into a stirrer for mixing;
(2) adding the hollow glass beads, the glycidol POSS, the monoalkoxy fatty acid titanate coupling agent, the hyperbranched polyester polymer and the erucamide 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 was 275 deg.C, the temperature of the second zone was 280 deg.C, the temperature of the third zone was 280 deg.C, the temperature of the fourth zone was 285 deg.C, the temperature of the fifth zone was 285 deg.C, the temperature of the sixth zone was 280 deg.C, the temperature of the seventh zone was 280 deg.C, the temperature of the eighth zone was 280 deg.C, the temperature of the die head was 280 deg.C, and.
The screw of the parallel double-screw extruder is in a single-thread shape, the ratio of the length L of the screw to the diameter D of L/D is 40, the screw is provided with 2 meshing block areas and 1 back-thread area, and the stirrer in the step (1) and the step (2) is a high-speed stirrer with the rotating speed of 1000 revolutions per minute.
Comparative example 3:
the comparative example provides a low dielectric constant polyphenylene ether composition, which is prepared from the following raw materials in parts by weight:
82 parts of polyphenyl ether resin (with the intrinsic viscosity of 0.35d L/g),
18 parts of high impact polystyrene resin,
the total of the parts by weight of the polyphenyl ether resin and the high impact polystyrene resin is 100 parts,
the preparation method of the low dielectric constant polyphenyl ether composition comprises the following steps:
(1) drying the polyphenyl ether resin and the high impact polystyrene resin at the temperature of 95 ℃ for 5 hours, cooling, and adding the cooled polyphenyl ether resin, the high impact polystyrene resin, the polyphenyl ether grafted maleic anhydride, the hydrogenated styrene-butadiene-styrene copolymer grafted maleic anhydride, the polytetrafluoroethylene resin, the N, N' -bis (2,2,6, 6-tetramethyl-4-piperidyl) -1, 3-benzenedicarboxamide and bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphate into a stirrer for mixing;
(2) adding the monoalkoxy fatty acid titanate coupling agent, the hyperbranched polyester polymer and the erucamide 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 was 275 deg.C, the temperature of the second zone was 280 deg.C, the temperature of the third zone was 280 deg.C, the temperature of the fourth zone was 285 deg.C, the temperature of the fifth zone was 285 deg.C, the temperature of the sixth zone was 280 deg.C, the temperature of the seventh zone was 280 deg.C, the temperature of the eighth zone was 280 deg.C, the temperature of the die head was 280 deg.C, and.
The screw of the parallel double-screw extruder is in a single-thread shape, the ratio of the length L of the screw to the diameter D of L/D is 40, the screw is provided with 2 meshing block areas and 1 back-thread area, and the stirrer in the step (1) and the step (2) is a high-speed stirrer with the rotating speed of 1000 revolutions per minute.
Comparative example 4:
the comparative example provides a low dielectric constant polyphenylene ether composition, which is prepared from the following raw materials in parts by weight:
82 parts of polyphenyl ether resin (with the intrinsic viscosity of 0.35d L/g),
18 parts of high impact polystyrene resin,
the total of the parts by weight of the polyphenyl ether resin and the high impact polystyrene resin is 100 parts,
the preparation method of the low dielectric constant polyphenyl ether composition comprises the following steps:
(1) drying the polyphenyl ether resin and the high impact polystyrene resin at the temperature of 95 ℃ for 5 hours, cooling, and adding the cooled polyphenyl ether resin, the high impact polystyrene resin, the polyphenyl ether grafted maleic anhydride, the hydrogenated styrene-butadiene-styrene copolymer grafted maleic anhydride, the polytetrafluoroethylene resin, the N, N' -bis (2,2,6, 6-tetramethyl-4-piperidyl) -1, 3-benzenedicarboxamide and bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphate into a stirrer for mixing;
(2) adding the hollow glass beads, the glycidol POSS, the monoalkoxy fatty acid titanate coupling agent, the hyperbranched polyester polymer and the erucamide 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 was 275 deg.C, the temperature of the second zone was 280 deg.C, the temperature of the third zone was 280 deg.C, the temperature of the fourth zone was 285 deg.C, the temperature of the fifth zone was 285 deg.C, the temperature of the sixth zone was 280 deg.C, the temperature of the seventh zone was 280 deg.C, the temperature of the eighth zone was 280 deg.C, the temperature of the die head was 280 deg.C, and.
The screw of the parallel double-screw extruder is in a single-thread shape, the ratio of the length L of the screw to the diameter D of L/D is 40, the screw is provided with 2 meshing block areas and 1 back-thread area, and the stirrer in the step (1) and the step (2) is a high-speed stirrer with the rotating speed of 1000 revolutions per minute.
Comparative example 5:
the comparative example provides a low dielectric constant polyphenylene ether composition, which is prepared from the following raw materials in parts by weight:
82 parts of polyphenyl ether resin (with the intrinsic viscosity of 0.35d L/g),
18 parts of high impact polystyrene resin,
the total of the parts by weight of the polyphenyl ether resin and the high impact polystyrene resin is 100 parts,
the preparation method of the low dielectric constant polyphenyl ether composition comprises the following steps:
(1) drying the polyphenyl ether resin and the high impact polystyrene resin at the temperature of 95 ℃ for 5 hours, cooling, and adding the cooled polyphenyl ether resin, the high impact polystyrene resin, the polyphenyl ether grafted maleic anhydride, the hydrogenated styrene-butadiene-styrene copolymer grafted maleic anhydride, the polytetrafluoroethylene resin, the N, N' -bis (2,2,6, 6-tetramethyl-4-piperidyl) -1, 3-benzenedicarboxamide and bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphate into a stirrer for mixing;
(2) adding the hollow glass beads, the glycidol POSS and the mono-alkoxy fatty acid titanate coupling agent into another stirrer for mixing;
(3) adding the mixed material obtained in the step (1) into a parallel double-screw extruder through a feeder, adding the mixed material obtained in the step (2) into the parallel double-screw extruder (totally eight zones) (for example, a fourth zone) in the lateral direction (for example, the fourth zone) for melt extrusion and granulation, wherein the process parameters comprise: the temperature of the first zone was 275 deg.C, the temperature of the second zone was 280 deg.C, the temperature of the third zone was 280 deg.C, the temperature of the fourth zone was 285 deg.C, the temperature of the fifth zone was 285 deg.C, the temperature of the sixth zone was 280 deg.C, the temperature of the seventh zone was 280 deg.C, the temperature of the eighth zone was 280 deg.C, the temperature of the die head was 280 deg.C, and.
The screw of the parallel double-screw extruder is in a single-thread shape, the ratio of the length L of the screw to the diameter D of L/D is 40, the screw is provided with 2 meshing block areas and 1 back-thread area, and the stirrer in the step (1) and the step (2) is a high-speed stirrer with the rotating speed of 1000 revolutions per minute.
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
Remarks that a, the screw structure is changed, b, the intrinsic viscosity of the polyphenyl ether resin is 0.55d L/g, c, the compressive strength of the hollow glass beads is 30MPa, d, the number average molecular weight of the polytetrafluoroethylene resin is 200 ten thousand;
wherein, the N, N' -bis (2,2,6, 6-tetramethyl-4-piperidyl) -1, 3-benzenedicarboxamide and bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphate of the above examples and comparative examples were added in amounts of 0.2 parts each.
The low dielectric constant polyphenylene ether compositions prepared in the above examples and comparative examples were subjected to the following property tests:
tensile property: testing according to GB/T1040-2006 standard, wherein the stretching speed is 50 mm/min;
impact properties: 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: the test frequency is 1GHz according to the test of GB/T5597-1999 standard. For the present composition, the lower the dielectric constant, the better.
The results of the performance tests are shown in table 2.
TABLE 2 Properties of Low dielectric constant polyphenylene ether compositions of examples and comparative examples
Examples 1 to 7 are to adjust the addition amounts of PPO, HIPS, PPO-g-MAH, SEBS-g-MAH, HGS, POSS, titanate coupling agent, PTFE, hyperbranched polyester polymer, and erucamide, and it can be seen from the table that as the addition amount of PPO increases (or the addition amounts of HIPS, SEBS-g-MAH decrease), the tensile strength thereof tends to increase, while the impact strength and melt index tend to decrease, mainly because the PPO base material has a higher tensile strength, but the HIPS and SEBS-g-MAH have lower tensile strengths and better processing flowability, and simultaneously, the functions of toughening; as the addition amount of HGS and POSS is reduced, the dielectric constant of the material shows a trend of increasing. By comparison, the overall performance of example 7 is best.
Example 7 the screw shape of the parallel twin screw extruder of example 8 was a twin screw and the screw shape of the parallel twin screw extruder of example 7 was a single screw as compared to example 8. by comparison, it was found that the tensile strength, notched impact strength and melt index of the low dielectric constant polyphenylene ether composition prepared using the screw parameters of the parallel twin screw extruder described in example 7 was better and the dielectric constant was lower.
Example 7 compared to comparative example 1, comparative example 1 used a polyphenylene ether resin with an intrinsic viscosity of 0.55d L/g and example 7 used a polyphenylene ether resin with an intrinsic viscosity of 0.35d L/g, the flowability of which decreased greatly with increasing intrinsic viscosity of the polyphenylene ether resin, and the melt index of the low dielectric constant polyphenylene ether composition was only 3g/10min when the intrinsic viscosity of the polyphenylene ether resin was 0.55d L/g, example 7 compared to comparative example 2 used hollow glass microspheres with a compressive strength of 30MPa and example 7 used a compressive strength of 60MPa, and example 7 compared to comparative example 2 used a hollow glass microsphere with a compressive strength of 60MPa, and because of the lower compressive strength of the hollow glass microspheres of comparative example 2, the composition broke easily during parallel twin screw extruder processing, losing its reinforcing and low dielectric constant properties, resulting in a substantial decrease in mechanical properties, and the dielectric constant increases, and example 7 compared to comparative example 3, because comparative example 3 did not add HGS and POSS of low dielectric constant, the composition of which has a dielectric constant higher than example 7, and comparative example 4, the hyperbranched polymer composition prepared by parallel extruder, and the hyperbranched polyester resin, and the low dielectric constant of the high tensile strength of the PPO-epoxy resin, and the PPO-epoxy resin, the PPO-epoxy resin of the epoxy.
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 low-dielectric-constant polyphenyl ether composition is characterized by being prepared from the following raw materials in parts by weight:
the intrinsic viscosity of the polyphenyl ether resin is 0.33-0.37 d L/g, the compressive strength of the hollow glass beads is not lower than 53MPa, and the number average molecular weight of the polytetrafluoroethylene resin is 1-10 ten thousand.
2. The low dielectric constant polyphenylene ether composition according to claim 1, which is prepared from the following raw materials in parts by weight:
3. the low dielectric constant polyphenylene ether composition according to claim 2, which is prepared from the following raw materials in parts by weight:
4. the low dielectric constant polyphenylene ether composition according to any one of claims 1 to 3, wherein the polyphenylene ether is grafted with maleic anhydride at a maleic anhydride grafting ratio of 0.8 to 1.2%; and/or the maleic anhydride grafting rate of the hydrogenated styrene-butadiene-styrene copolymer grafted maleic anhydride is 0.8-1.2%.
5. The low dielectric constant polyphenylene ether composition according to any one of claims 1 to 3, wherein the terminal group of the polyhedral oligomeric silsesquioxane polymer is an epoxy group; and/or the titanate coupling agent is a mono-alkoxy fatty acid titanate coupling agent.
6. A method for producing a low dielectric constant polyphenylene ether composition according to any one of claims 1 to 5, comprising the steps of:
(1) drying the polyphenyl ether resin and the high impact polystyrene resin, and mixing with polyphenyl ether grafted maleic anhydride, hydrogenated styrene-butadiene-styrene copolymer grafted maleic anhydride, polytetrafluoroethylene resin, N' -bis (2,2,6, 6-tetramethyl-4-piperidyl) -1, 3-phthalic diamide and bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphate;
(2) mixing the hollow glass beads, the polyhedral oligomeric silsesquioxane polymer, the titanate coupling agent, the hyperbranched polyester polymer and the erucamide;
(3) and (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.
7. The method according to claim 6, wherein the process parameters of the parallel twin-screw extruder in the step (3) include: the temperature of the first zone is 265-285 ℃, the temperature of the second zone is 270-290 ℃, the temperature of the third zone is 270-290 ℃, the temperature of the fourth zone is 275-295 ℃, the temperature of the fifth zone is 275-295 ℃, the temperature of the sixth zone is 270-290 ℃, the temperature of the seventh zone is 270-290 ℃, the temperature of the eighth zone is 270-290 ℃, the temperature of the die head is 270-290 ℃, and the rotating speed of the screw is 200-600 rpm; preferably, the process parameters of the parallel twin-screw extruder in the step (3) comprise: the temperature of the first zone is 270-280 ℃, the temperature of the second zone is 275-285 ℃, the temperature of the third zone is 275-285 ℃, the temperature of the fourth zone is 280-290 ℃, the temperature of the fifth zone is 280-290 ℃, the temperature of the sixth zone is 275-285 ℃, the temperature of the seventh zone is 275-285 ℃, the temperature of the eighth zone is 275-285 ℃, the temperature of the die head is 275-285 ℃, and the rotating speed of the screw is 300-500 rpm;
and/or, in the step (1), the polyphenyl ether resin and the high impact polystyrene resin are dried for 4-8 hours at the temperature of 80-110 ℃; preferably, in the step (1), the polyphenylene ether resin and the high impact polystyrene resin are dried at a temperature of 90-100 ℃ for 4-6 hours.
8. The production method according to claim 6, wherein the screw shape of the parallel twin-screw extruder is a single-screw, and/or the ratio of the screw length L to the diameter D of the parallel twin-screw extruder L/D is 35 to 50, and/or the screw of the parallel twin-screw extruder is provided with 1 or more intermeshing land areas and 1 or more counter-screw land areas.
9. The preparation method of claim 8, wherein the ratio L/D of the length L of the screw to the diameter D is 35-45, and the screw is provided with 2 meshing block areas and 1 reverse thread area.
10. The method according to any one of claims 6 to 9, wherein the mixing step is performed using a stirrer having a rotation speed of 500 to 1500 rpm in the step (1) and/or the step (2).
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