CN111334042A - Low-dielectric-constant polyphenylene sulfide composition and preparation method thereof - Google Patents
Low-dielectric-constant polyphenylene sulfide composition and preparation method thereof Download PDFInfo
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L81/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen or carbon only; Compositions of polysulfones; Compositions of derivatives of such polymers
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- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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- C08L2205/08—Polymer mixtures characterised by other features containing additives to improve the compatibility between two polymers
Abstract
The invention relates to a low dielectric constant polyphenylene sulfide composition and a preparation method thereof, wherein the low dielectric constant polyphenylene sulfide composition is prepared from the following raw materials: polyphenylene sulfide resin, 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 polyphenylene sulfide composition with the low dielectric constant has excellent mechanical property, processability and the low dielectric constant, and can be applied to shells, cladding, 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 polyphenylene sulfide 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 (Dk <3) materials with good performance is increasingly required. 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.
Polyphenylene Sulfide (PPS) has the characteristics of excellent high temperature resistance, corrosion resistance, radiation resistance, flame retardance, balanced physical and mechanical properties, excellent dimensional stability, excellent electrical properties and the like, and is widely used as special engineering plastic after being filled and modified. However, polyphenylene sulfide has poor toughness, and it is necessary to toughen and strengthen polyphenylene sulfide, and blend other materials with lower dielectric constant to reduce the dielectric constant of the blend, so as to meet the increasing demands in the fields of electronics and electricians, integrated circuit packaging, electromagnetic wave shielding, etc.
Currently, some research is being done in the prior art on PPS dielectric systems, such as: chinese patent CN 108165010a discloses a high thermal conductivity low dielectric polyphenylene sulfide composite material and a preparation method thereof, the composite material comprises: 100 parts of polyphenylene sulfide resin, 10-40 parts of glass fiber, 30-60 parts of boron nitride, 5-15 parts of compatilizer, 0.8-3.0 parts of coupling agent, 1.0-5.0 parts of dispersing agent and 0.4-1.2 parts of antioxidant. Chinese patent CN 109705577A discloses a PPS with low dielectric coefficient, grinding particles of PPS toughening agent into powder by a grinder, then sieving by a high-density sieve, and reserving the toughening agent powder left under the sieve for later use; after the materials are processed, adding PPS resin, hollow glass beads, PPS toughening agent powder and low-dielectric-coefficient glass fibers into a high-speed mixer in proportion for mixing; and after the materials are mixed, taking out the materials, and putting the materials into a plastic extruding machine for extrusion molding. Chinese patent CN 110791096A discloses a 5G PPS film, which is prepared from the following raw materials in parts by weight: 65-80 parts of polyphenylene sulfide resin, 25-35 parts of hyperbranched polyimide, 10-15 parts of N-vinyl o-phenylene imine/[ (3,3, 3-trifluoro-1-propenyl) thio ] benzene/vinyl benzenesulfonic acid/isopropenyl boronic acid pinacol ester/vinyl trimethoxy silane copolymer, 5-8 parts of fluorine-phosphorus co-doped nano mica powder, 3-6 parts of fluorinated graphene and 0.5-1.5 parts of phosphorus pentoxide. Chinese patent CN108250751A discloses a polyphenylene sulfide resin composition with low dielectric constant and a preparation method thereof. The polyphenylene sulfide resin composition is mainly prepared from 20-80 parts by mass of PPS resin, 15-40 parts by mass of glass fiber, 0.5-10 parts by mass of hollow microspheres, 3-15 parts by mass of toughening agent, 0.3-3 parts by mass of antioxidant, 0.3-3 parts by mass of heat stabilizer, 0.5-2 parts by mass of lubricant and 0-3 parts by mass of nucleating agent. Chinese patent CN 108329692A discloses a polyphenylene sulfide resin composition with low dielectric constant and a preparation method thereof. The polyphenylene sulfide resin composition is mainly prepared from 20-80 parts by mass of PPS resin, 15-40 parts by mass of glass fiber, 0.3-5 parts by mass of cage-like silsesquioxane, 3-15 parts by mass of toughening agent, 0.3-3 parts by mass of antioxidant, 0.5-3 parts by mass of heat stabilizer, 0.3-3 parts by mass of lubricant and 0-3 parts by mass of nucleating agent.
Disclosure of Invention
Based on the above, the present invention provides a low dielectric constant polyphenylene sulfide composition with excellent mechanical properties and processability, which can be applied to housings, coatings, protective materials, etc. 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:
the low-dielectric-constant polyphenylene sulfide composition is prepared from the following raw materials in parts by weight:
80-98 Parts of Polyphenylene Sulfide (PPS),
1 to 10 parts of hydrogenated styrene-butadiene-styrene copolymer (SEBS),
1-10 parts of hydrogenated styrene-butadiene-styrene copolymer grafted maleic anhydride (SEBS-g-MAH),
the total of the parts by weight of the polyphenylene sulfide resin, the hydrogenated styrene-butadiene-styrene copolymer and the hydrogenated styrene-butadiene-styrene copolymer grafted maleic anhydride is 100 parts,
the number average molecular weight of the polyphenylene sulfide resin is 4.6-5.0 ten thousand; the compressive strength of the hollow glass beads is not lower than 53 MPa; the number average molecular weight of the polytetrafluoroethylene resin is 1-10 ten thousand.
In some embodiments, the low dielectric constant polyphenylene sulfide composition is prepared from the following raw materials in parts by weight:
84-96 Parts of Polyphenylene Sulfide (PPS),
2-8 parts of hydrogenated styrene-butadiene-styrene copolymer (SEBS),
2-8 parts of hydrogenated styrene-butadiene-styrene copolymer grafted maleic anhydride (SEBS-g-MAH),
the total of the parts by weight of the polyphenylene sulfide resin, the hydrogenated styrene-butadiene-styrene copolymer and the hydrogenated styrene-butadiene-styrene copolymer grafted maleic anhydride is 100 parts,
in some embodiments, the low dielectric constant polyphenylene sulfide composition is further preferably prepared from the following raw materials in parts by weight:
88 to 92 Parts of Polyphenylene Sulfide (PPS),
4 to 6 parts of hydrogenated styrene-butadiene-styrene copolymer (SEBS),
4-6 parts of hydrogenated styrene-butadiene-styrene copolymer grafted maleic anhydride (SEBS-g-MAH),
the total of the parts by weight of the polyphenylene sulfide resin, the hydrogenated styrene-butadiene-styrene copolymer and the hydrogenated styrene-butadiene-styrene copolymer grafted maleic anhydride is 100 parts,
in some embodiments, the low dielectric constant polyphenylene sulfide composition is further preferably prepared from the following raw materials in parts by weight:
89-91 Parts of Polyphenylene Sulfide (PPS),
4 to 6 parts of hydrogenated styrene-butadiene-styrene copolymer (SEBS),
4-6 parts of hydrogenated styrene-butadiene-styrene copolymer grafted maleic anhydride (SEBS-g-MAH),
the total of the parts by weight of the polyphenylene sulfide resin, the hydrogenated styrene-butadiene-styrene copolymer and the hydrogenated styrene-butadiene-styrene copolymer grafted maleic anhydride is 100 parts,
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 epoxycyclohexylethyl-POSS and glycidyl-POSS.
In some of these embodiments, the titanate coupling agent is a monoalkoxy fatty acid titanate coupling agent.
The compressive strength of the hollow glass beads is 55-65 MPa; the number average molecular weight of the polytetrafluoroethylene resin is 3-7 ten thousand.
The invention also aims to provide a preparation method of the low-dielectric-constant polyphenylene sulfide composition.
The specific technical scheme comprises the following steps:
(1) drying the polyphenylene sulfide resin, and mixing the polyphenylene sulfide resin with the hydrogenated styrene-butadiene-styrene copolymer, the 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 (2) 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), performing melt extrusion, and granulating.
In some embodiments, the polyphenylene sulfide resin is dried at 90-100 ℃ for 4-6 hours in step (1). Preferably, the polyphenylene sulfide resin is dried at 90-100 ℃ for 4-6 hours in the step (1).
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 280-300 ℃, the temperature of the second zone is 285-305 ℃, the temperature of the third zone is 285-305 ℃, the temperature of the fourth zone is 290-310 ℃, the temperature of the fifth zone is 290-310 ℃, the temperature of the sixth zone is 285-305 ℃, the temperature of the seventh zone is 285-305 ℃, the temperature of the eighth zone is 285-305 ℃, the temperature of the die head is 285-305 ℃, 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 285-295 ℃, the temperature of the second zone is 290-300 ℃, the temperature of the third zone is 290-300 ℃, the temperature of the fourth zone is 295-305 ℃, the temperature of the fifth zone is 295-305 ℃, the temperature of the sixth zone is 290-300 ℃, the temperature of the seventh zone is 290-300 ℃, the temperature of the eighth zone is 290-300 ℃, the temperature of the die head is 290-300 ℃ 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 and the diameter D of the screw of the parallel double-screw extruder is 35-50; the screw of the parallel double-screw extruder 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 screw length L to the diameter D of the parallel twin-screw extruder is 35 to 45; and the screws of the parallel double-screw extruder are provided with 2 meshing block areas and 1 reverse thread area.
In some embodiments, in step (1) and/or 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 low dielectric constant polyphenylene sulfide composition of the invention has the following principle:
in order to solve the defect of poor compatibility and processability of PPS, low dielectric filler hollow glass microspheres (HGS) and polyhedral oligomeric silsesquioxane (POSS) in the low dielectric constant polyphenylene sulfide composition, the compatibility among PPS, SEBS and low dielectric filler is improved by adding a compatilizer SEBS-g-MAH, the compatibility between PPS and low dielectric filler is improved by adding a titanate coupling agent, and the effect of coating the low dielectric filler by the titanate coupling agent and the processability of the PPS composition are improved by adding a lubricating dispersant hyperbranched polyester polymer and erucamide. According to the invention, the addition of the auxiliary agent improves the interface bonding force and compatibility between PPS and the low dielectric filler, and simultaneously improves the mechanical property and the processing property of the PPS composition, so that the low dielectric constant polyphenylene sulfide composition with excellent comprehensive properties is prepared.
SEBS structural units in the compatilizer SEBS-g-MAH adopted by the invention have good compatibility with SEBS resin and PPS resin, and maleic anhydride groups of the SEBS-g-MAH and epoxy groups of the polyhedral oligomeric silsesquioxane polymer can react with terminal hydroxyl groups of hollow glass beads and terminal hydroxyl groups of PPS and react with a titanate coupling agent coating low dielectric filler, so that the compatibility between PPS and the low dielectric filler is improved; furthermore, SEBS-g-MAH can also improve the impact performance of the PPS 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 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 POSS has good thermal stability, is large in molecular size and has the effect of blocking the movement of polymer molecular chain segments, and the addition of POSS is favorable for improving the thermal stability of the composition.
The effect of the titanate coupling agent used in 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 PPS.
The polytetrafluoroethylene resin used in the invention has special lubricity and non-stickiness, is used as a modifier and a release agent of the PPS composition, and has a low dielectric constant of 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 PPS composition and the coating effect of the titanate coupling agent, and improve the dispersion degree of the low dielectric filler in the PPS 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 PPS composition and the coating effect of the titanate coupling agent, and improve the dispersion degree of the low dielectric filler in the PPS composition system, and has small influence on the mechanical property of the PPS 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 blending process of the PPS composition is better, and the hindered piperidyl can provide antioxidation and improve the dyeability of the PPS composition.
The melting point of the bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphate adopted by the invention is 239 ℃, the thermal decomposition temperature exceeds 350 ℃, the heat resistance and the hydrolysis resistance are good, and the method can be used in the blending process of a PPS (polyphenylene sulfide) compositionProvide excellent color stability and melt stability while preventing thermal degradation of the PPS composition during high temperature processing and suppressing thermal oxidative discoloration thereof due to long-term extrusion processing, and also provide a method for producing the PPS 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 PPS, low dielectric filler hollow glass microspheres (HGS) and polyhedral oligomeric silsesquioxane Polymers (POSS) in the existing low dielectric constant polyphenylene sulfide composition, the compatibility between the PPS and the low dielectric constant filler is improved by adding compatilizer SEBS-g-MAH, titanate coupling agent, lubricating dispersant hyperbranched polyester polymers and erucamide, the processing performance of the PPS composition is improved by adopting low molecular weight PTFE, the dielectric constant of the PPS composition is reduced by compounding HGS, POSS and PTFE, and yellowing phenomenon and thermal stability in the blending processing process of the low dielectric constant polyphenylene sulfide composition are improved by compounding N, N' -bis (2,2,6, 6-tetramethyl-4-piperidyl) -1, 3-phthalic amide and bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphate The raw material components are matched with each other, so that the obtained low-dielectric-constant polyphenylene sulfide composition has excellent mechanical property and processing property, and can be applied to shells, coating materials, 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 polyphenylene sulfide 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 sulfide composition according to an 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 sulfide composition of the embodiment of the invention is as follows (see fig. 1 for a flow chart of the preparation process):
wherein R is1＝SEBS，R2HGS or PPS;
as can be seen from the reaction formula, the maleic anhydride group of the SEBS-g-MAH can react with the terminal hydroxyl groups of the HGS and the PPS, and the epoxy group of the POSS can react with the terminal hydroxyl groups of the HGS and the PPS, so that the compatibility between the PPS and the low dielectric filler is improved.
The examples of the invention and the comparative examples used the following raw materials:
polyphenylene sulfide resin with a number average molecular weight of 4.8 ten thousand selected from Chongqing Polylion New Material science and technology Co;
polyphenylene sulfide resin with a number average molecular weight of 7.2 ten thousand selected from Chongqing Polylion New Material science and technology Co;
hydrogenated styrene-butadiene-styrene copolymer selected from kraton high performance polymers;
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;
epoxycyclohexylethyl-POSS selected from the American company Hybrid Plastics;
glycidyl-POSS selected from Hybrid Plastics, USA;
mono-alkoxy fatty acid titanate coupling agent (type is titanate coupling agent TC-130), selected from chemical auxiliary oil material factory of Tianchang 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 (the type is CYD-C600), the thermal decomposition temperature is more than or equal to 350 ℃, and the hyperbranched polyester polymer is selected from Wehaichen molecular new materials GmbH;
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 polyphenylene sulfide composition, which is prepared from the following raw materials in parts by weight:
80 parts of polyphenylene sulfide resin (the number average molecular weight is 4.8 ten thousand),
10 parts of hydrogenated styrene-butadiene-styrene copolymer,
10 parts of hydrogenated styrene-butadiene-styrene copolymer grafted maleic anhydride,
the total of the parts by weight of the polyphenylene sulfide resin, the hydrogenated styrene-butadiene-styrene copolymer and the hydrogenated styrene-butadiene-styrene copolymer grafted maleic anhydride is 100 parts,
the preparation method of the low-dielectric-constant polyphenylene sulfide composition comprises the following steps:
(1) drying the polyphenylene sulfide resin at the temperature of 80 ℃ for 8 hours, cooling, and adding the cooled polyphenylene sulfide resin, the 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 into a stirrer for mixing;
(2) adding the hollow glass beads, epoxy cyclohexyl ethyl-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 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 200 rpm.
The screw of the parallel double-screw extruder is in a single-thread shape, the ratio L/D of the length L and the diameter D of the screw is 35, and the screw is provided with 2 meshing block areas and 1 back-thread area; the stirrer in the step (1) and the step (2) is a high-speed stirrer, and the rotating speed is 1000 revolutions per minute.
Example 2:
the embodiment provides a low-dielectric-constant polyphenylene sulfide composition, which is prepared from the following raw materials in parts by weight:
98 parts of polyphenylene sulfide resin (number average molecular weight 4.8 ten thousand),
1 part of hydrogenated styrene-butadiene-styrene copolymer,
1 part of hydrogenated styrene-butadiene-styrene copolymer grafted maleic anhydride,
the total of the parts by weight of the polyphenylene sulfide resin, the hydrogenated styrene-butadiene-styrene copolymer and the hydrogenated styrene-butadiene-styrene copolymer grafted maleic anhydride is 100 parts,
the preparation method of the low-dielectric-constant polyphenylene sulfide composition comprises the following steps:
(1) drying the polyphenylene sulfide resin at the temperature of 110 ℃ for 4 hours, cooling, and adding the cooled polyphenylene sulfide resin, the 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 into a stirrer for mixing;
(2) adding the hollow glass beads, glycidyl-POSS, monoalkoxy 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 300 deg.C, the temperature in the second zone was 305 deg.C, the temperature in the third zone was 305 deg.C, the temperature in the fourth zone was 310 deg.C, the temperature in the fifth zone was 310 deg.C, the temperature in the sixth zone was 305 deg.C, the temperature in the seventh zone was 305 deg.C, the temperature in the eighth zone was 305 deg.C, the temperature in the die was 305 deg.C, and the.
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; the stirrer in the step (1) and the step (2) is a high-speed stirrer, and the rotating speed is 1000 revolutions per minute.
Example 3:
the embodiment provides a low-dielectric-constant polyphenylene sulfide composition, which is prepared from the following raw materials in parts by weight:
84 parts of polyphenylene sulfide resin (the number average molecular weight is 4.8 ten thousand),
8 parts of hydrogenated styrene-butadiene-styrene copolymer,
8 parts of hydrogenated styrene-butadiene-styrene copolymer grafted maleic anhydride,
the total of the parts by weight of the polyphenylene sulfide resin, the hydrogenated styrene-butadiene-styrene copolymer and the hydrogenated styrene-butadiene-styrene copolymer grafted maleic anhydride is 100 parts,
the preparation method of the low-dielectric-constant polyphenylene sulfide composition comprises the following steps:
(1) drying the polyphenylene sulfide resin at the temperature of 90 ℃ for 6 hours, cooling, and adding the cooled polyphenylene sulfide resin, the 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 into a stirrer for mixing;
(2) adding the hollow glass beads, glycidyl-POSS, monoalkoxy 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 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 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; the stirrer in the step (1) and the step (2) is a high-speed stirrer, and the rotating speed is 1000 revolutions per minute.
Example 4:
the embodiment provides a low-dielectric-constant polyphenylene sulfide composition, which is prepared from the following raw materials in parts by weight:
96 parts of polyphenylene sulfide resin (number average molecular weight: 4.8 ten thousand),
2 parts of hydrogenated styrene-butadiene-styrene copolymer,
2 parts of hydrogenated styrene-butadiene-styrene copolymer grafted maleic anhydride,
the total of the parts by weight of the polyphenylene sulfide resin, the hydrogenated styrene-butadiene-styrene copolymer and the hydrogenated styrene-butadiene-styrene copolymer grafted maleic anhydride is 100 parts,
the preparation method of the low-dielectric-constant polyphenylene sulfide composition comprises the following steps:
(1) drying the polyphenylene sulfide resin at the temperature of 100 ℃ for 4 hours, cooling, and adding the cooled polyphenylene sulfide resin, the 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 into a stirrer for mixing;
(2) adding the hollow glass beads, glycidyl-POSS, monoalkoxy 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 295 deg.C, the temperature in the second zone was 300 deg.C, the temperature in the third zone was 300 deg.C, the temperature in the fourth zone was 305 deg.C, the temperature in the fifth zone was 305 deg.C, the temperature in the sixth zone was 300 deg.C, the temperature in the seventh zone was 300 deg.C, the temperature in the eighth zone was 300 deg.C, the temperature in the die head was 300 deg.C, and.
The screw of the parallel double-screw extruder is in a single-thread shape, the ratio L/D of the length L and the diameter D of the screw is 45, and the screw is provided with 2 meshing block areas and 1 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.
Example 5:
the embodiment provides a low-dielectric-constant polyphenylene sulfide composition, which is prepared from the following raw materials in parts by weight:
88 parts of polyphenylene sulfide resin (number average molecular weight 4.8 ten thousand),
6 parts of hydrogenated styrene-butadiene-styrene copolymer,
6 parts of hydrogenated styrene-butadiene-styrene copolymer grafted maleic anhydride,
the total of the parts by weight of the polyphenylene sulfide resin, the hydrogenated styrene-butadiene-styrene copolymer and the hydrogenated styrene-butadiene-styrene copolymer grafted maleic anhydride is 100 parts,
the preparation method of the low-dielectric-constant polyphenylene sulfide composition comprises the following steps:
(1) drying the polyphenylene sulfide resin at the temperature of 95 ℃ for 5 hours, cooling, and adding the cooled polyphenylene sulfide resin, the 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 into a stirrer for mixing;
(2) adding the hollow glass beads, glycidyl-POSS, monoalkoxy 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 290 ℃, the temperature in the second zone was 295 ℃, the temperature in the third zone was 295 ℃, the temperature in the fourth zone was 300 ℃, the temperature in the fifth zone was 300 ℃, the temperature in the sixth zone was 295 ℃, the temperature in the seventh zone was 295 ℃, the temperature in the eighth zone was 295 ℃, the temperature in the die head was 295 ℃ and the screw speed was 400 rpm.
The screw of the parallel double-screw extruder is in a single-thread shape, the ratio L/D of the length L and the diameter D of the screw is 40, and the screw is provided with 2 meshing block areas and 1 back-thread area; the stirrer in the step (1) and the step (2) is a high-speed stirrer, and the rotating speed is 1000 revolutions per minute.
Example 6:
the embodiment provides a low-dielectric-constant polyphenylene sulfide composition, which is prepared from the following raw materials in parts by weight:
92 parts of polyphenylene sulfide resin (number average molecular weight: 4.8 ten thousand),
4 parts of hydrogenated styrene-butadiene-styrene copolymer,
4 parts of hydrogenated styrene-butadiene-styrene copolymer grafted maleic anhydride,
the total of the parts by weight of the polyphenylene sulfide resin, the hydrogenated styrene-butadiene-styrene copolymer and the hydrogenated styrene-butadiene-styrene copolymer grafted maleic anhydride is 100 parts,
the preparation method of the low-dielectric-constant polyphenylene sulfide composition comprises the following steps:
(1) drying the polyphenylene sulfide resin at the temperature of 95 ℃ for 5 hours, cooling, and adding the cooled polyphenylene sulfide resin, the 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 into a stirrer for mixing;
(2) adding the hollow glass beads, glycidyl-POSS, monoalkoxy 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 290 ℃, the temperature in the second zone was 295 ℃, the temperature in the third zone was 295 ℃, the temperature in the fourth zone was 300 ℃, the temperature in the fifth zone was 300 ℃, the temperature in the sixth zone was 295 ℃, the temperature in the seventh zone was 295 ℃, the temperature in the eighth zone was 295 ℃, the temperature in the die head was 295 ℃ and the screw speed was 400 rpm.
The screw of the parallel double-screw extruder is in a single-thread shape, the ratio L/D of the length L and the diameter D of the screw is 40, and the screw is provided with 2 meshing block areas and 1 back-thread area; the stirrer in the step (1) and the step (2) is a high-speed stirrer, and the rotating speed is 1000 revolutions per minute.
Example 7:
the embodiment provides a low-dielectric-constant polyphenylene sulfide composition, which is prepared from the following raw materials in parts by weight:
90 parts of polyphenylene sulfide resin (number average molecular weight 4.8 ten thousand),
5 parts of hydrogenated styrene-butadiene-styrene copolymer,
5 parts of hydrogenated styrene-butadiene-styrene copolymer grafted maleic anhydride,
the total of the parts by weight of the polyphenylene sulfide resin, the hydrogenated styrene-butadiene-styrene copolymer and the hydrogenated styrene-butadiene-styrene copolymer grafted maleic anhydride is 100 parts,
the preparation method of the low-dielectric-constant polyphenylene sulfide composition comprises the following steps:
(1) drying the polyphenylene sulfide resin at the temperature of 95 ℃ for 5 hours, cooling, and adding the cooled polyphenylene sulfide resin, the 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 into a stirrer for mixing;
(2) adding the hollow glass beads, glycidyl-POSS, monoalkoxy 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 290 ℃, the temperature in the second zone was 295 ℃, the temperature in the third zone was 295 ℃, the temperature in the fourth zone was 300 ℃, the temperature in the fifth zone was 300 ℃, the temperature in the sixth zone was 295 ℃, the temperature in the seventh zone was 295 ℃, the temperature in the eighth zone was 295 ℃, the temperature in the die head was 295 ℃ and the screw speed was 400 rpm.
The screw of the parallel double-screw extruder is in a single-thread shape, the ratio L/D of the length L and the diameter D of the screw is 40, and the screw is provided with 2 meshing block areas and 1 back-thread area; the stirrer in the step (1) and the step (2) is a high-speed stirrer, and the rotating speed is 1000 revolutions per minute.
Example 8:
the embodiment provides a low-dielectric-constant polyphenylene sulfide composition, which is prepared from the following raw materials in parts by weight:
90 parts of polyphenylene sulfide resin (number average molecular weight 4.8 ten thousand),
5 parts of hydrogenated styrene-butadiene-styrene copolymer,
5 parts of hydrogenated styrene-butadiene-styrene copolymer grafted maleic anhydride,
the total of the parts by weight of the polyphenylene sulfide resin, the hydrogenated styrene-butadiene-styrene copolymer and the hydrogenated styrene-butadiene-styrene copolymer grafted maleic anhydride is 100 parts,
the preparation method of the low-dielectric-constant polyphenylene sulfide composition comprises the following steps:
(1) drying the polyphenylene sulfide resin at the temperature of 95 ℃ for 5 hours, cooling, and adding the cooled polyphenylene sulfide resin, the 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 into a stirrer for mixing;
(2) adding the hollow glass beads, glycidyl-POSS, monoalkoxy 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 290 ℃, the temperature in the second zone was 295 ℃, the temperature in the third zone was 295 ℃, the temperature in the fourth zone was 300 ℃, the temperature in the fifth zone was 300 ℃, the temperature in the sixth zone was 295 ℃, the temperature in the seventh zone was 295 ℃, the temperature in the eighth zone was 295 ℃, the temperature in the die head was 295 ℃ and the screw speed was 400 rpm.
The shape of a screw of the parallel double-screw extruder is double-thread, the ratio L/D of the length L and the diameter D of the screw is 40, and the screw is provided with 2 meshing block areas and 1 back-thread area; 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 sulfide composition, which is prepared from the following raw materials in parts by weight:
90 parts of polyphenylene sulfide resin (number average molecular weight 7.2 ten thousand),
5 parts of hydrogenated styrene-butadiene-styrene copolymer,
5 parts of hydrogenated styrene-butadiene-styrene copolymer grafted maleic anhydride,
the total of the parts by weight of the polyphenylene sulfide resin, the hydrogenated styrene-butadiene-styrene copolymer and the hydrogenated styrene-butadiene-styrene copolymer grafted maleic anhydride is 100 parts,
the preparation method of the low-dielectric-constant polyphenylene sulfide composition comprises the following steps:
(1) drying the polyphenylene sulfide resin at the temperature of 95 ℃ for 5 hours, cooling, and adding the cooled polyphenylene sulfide resin, the 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 into a stirrer for mixing;
(2) adding the hollow glass beads, glycidyl-POSS, monoalkoxy 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 290 ℃, the temperature in the second zone was 295 ℃, the temperature in the third zone was 295 ℃, the temperature in the fourth zone was 300 ℃, the temperature in the fifth zone was 300 ℃, the temperature in the sixth zone was 295 ℃, the temperature in the seventh zone was 295 ℃, the temperature in the eighth zone was 295 ℃, the temperature in the die head was 295 ℃ and the screw speed was 400 rpm.
The screw of the parallel double-screw extruder is in a single-thread shape, the ratio L/D of the length L and the diameter D of the screw is 40, and the screw is provided with 2 meshing block areas and 1 back-thread area; the 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 2:
the comparative example provides a low dielectric constant polyphenylene sulfide composition, which is prepared from the following raw materials in parts by weight:
90 parts of polyphenylene sulfide resin (number average molecular weight 4.8 ten thousand),
5 parts of hydrogenated styrene-butadiene-styrene copolymer,
5 parts of hydrogenated styrene-butadiene-styrene copolymer grafted maleic anhydride,
the total of the parts by weight of the polyphenylene sulfide resin, the hydrogenated styrene-butadiene-styrene copolymer and the hydrogenated styrene-butadiene-styrene copolymer grafted maleic anhydride is 100 parts,
the preparation method of the low-dielectric-constant polyphenylene sulfide composition comprises the following steps:
(1) drying the polyphenylene sulfide resin at the temperature of 95 ℃ for 5 hours, cooling, and adding the cooled polyphenylene sulfide resin, the 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 into a stirrer for mixing;
(2) adding the hollow glass beads, glycidyl-POSS, monoalkoxy 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 290 ℃, the temperature in the second zone was 295 ℃, the temperature in the third zone was 295 ℃, the temperature in the fourth zone was 300 ℃, the temperature in the fifth zone was 300 ℃, the temperature in the sixth zone was 295 ℃, the temperature in the seventh zone was 295 ℃, the temperature in the eighth zone was 295 ℃, the temperature in the die head was 295 ℃ and the screw speed was 400 rpm.
The screw of the parallel double-screw extruder is in a single-thread shape, the ratio L/D of the length L and the diameter D of the screw is 40, and the screw is provided with 2 meshing block areas and 1 back-thread area; the 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 3:
the comparative example provides a low dielectric constant polyphenylene sulfide composition, which is prepared from the following raw materials in parts by weight:
90 parts of polyphenylene sulfide resin (number average molecular weight 4.8 ten thousand),
5 parts of hydrogenated styrene-butadiene-styrene copolymer,
5 parts of hydrogenated styrene-butadiene-styrene copolymer grafted maleic anhydride,
the total of the parts by weight of the polyphenylene sulfide resin, the hydrogenated styrene-butadiene-styrene copolymer and the hydrogenated styrene-butadiene-styrene copolymer grafted maleic anhydride is 100 parts,
the preparation method of the low-dielectric-constant polyphenylene sulfide composition comprises the following steps:
(1) drying the polyphenylene sulfide resin at the temperature of 95 ℃ for 5 hours, cooling, and adding the cooled polyphenylene sulfide resin, the 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 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 in the first zone was 290 ℃, the temperature in the second zone was 295 ℃, the temperature in the third zone was 295 ℃, the temperature in the fourth zone was 300 ℃, the temperature in the fifth zone was 300 ℃, the temperature in the sixth zone was 295 ℃, the temperature in the seventh zone was 295 ℃, the temperature in the eighth zone was 295 ℃, the temperature in the die head was 295 ℃ and the screw speed was 400 rpm.
The screw of the parallel double-screw extruder is in a single-thread shape, the ratio L/D of the length L and the diameter D of the screw is 40, and the screw is provided with 2 meshing block areas and 1 back-thread area; the 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 4:
the comparative example provides a low dielectric constant polyphenylene sulfide composition, which is prepared from the following raw materials in parts by weight:
90 parts of polyphenylene sulfide resin (number average molecular weight 4.8 ten thousand),
5 parts of hydrogenated styrene-butadiene-styrene copolymer,
5 parts of hydrogenated styrene-butadiene-styrene copolymer grafted maleic anhydride,
the total of the parts by weight of the polyphenylene sulfide resin, the hydrogenated styrene-butadiene-styrene copolymer and the hydrogenated styrene-butadiene-styrene copolymer grafted maleic anhydride is 100 parts,
the preparation method of the low-dielectric-constant polyphenylene sulfide composition comprises the following steps:
(1) drying the polyphenylene sulfide resin at the temperature of 95 ℃ for 5 hours, cooling, and adding the cooled polyphenylene sulfide resin, the 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 into a stirrer for mixing;
(2) adding the hollow glass beads, glycidyl-POSS, monoalkoxy 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 290 ℃, the temperature in the second zone was 295 ℃, the temperature in the third zone was 295 ℃, the temperature in the fourth zone was 300 ℃, the temperature in the fifth zone was 300 ℃, the temperature in the sixth zone was 295 ℃, the temperature in the seventh zone was 295 ℃, the temperature in the eighth zone was 295 ℃, the temperature in the die head was 295 ℃ and the screw speed was 400 rpm.
The screw of the parallel double-screw extruder is in a single-thread shape, the ratio L/D of the length L and the diameter D of the screw is 40, and the screw is provided with 2 meshing block areas and 1 back-thread area; the 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 5:
the comparative example provides a low dielectric constant polyphenylene sulfide composition, which is prepared from the following raw materials in parts by weight:
90 parts of polyphenylene sulfide resin (number average molecular weight 4.8 ten thousand),
5 parts of hydrogenated styrene-butadiene-styrene copolymer,
5 parts of hydrogenated styrene-butadiene-styrene copolymer grafted maleic anhydride,
the total of the parts by weight of the polyphenylene sulfide resin, the hydrogenated styrene-butadiene-styrene copolymer and the hydrogenated styrene-butadiene-styrene copolymer grafted maleic anhydride is 100 parts,
the preparation method of the low-dielectric-constant polyphenylene sulfide composition comprises the following steps:
(1) drying the polyphenylene sulfide resin at the temperature of 95 ℃ for 5 hours, cooling, and adding the cooled polyphenylene sulfide resin, the 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 into a stirrer for mixing;
(2) adding the hollow glass beads, glycidyl-POSS and monoalkoxyl 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 in the first zone was 290 ℃, the temperature in the second zone was 295 ℃, the temperature in the third zone was 295 ℃, the temperature in the fourth zone was 300 ℃, the temperature in the fifth zone was 300 ℃, the temperature in the sixth zone was 295 ℃, the temperature in the seventh zone was 295 ℃, the temperature in the eighth zone was 295 ℃, the temperature in the die head was 295 ℃ and the screw speed was 400 rpm.
The screw of the parallel double-screw extruder is in a single-thread shape, the ratio L/D of the length L and the diameter D of the screw is 40, and the screw is provided with 2 meshing block areas and 1 back-thread area; the stirrer in the step (1) and the step (2) is a high-speed stirrer, and the rotating speed is 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
Remarking: a, changing a screw structure; b, the number average molecular weight of the polyphenylene sulfide resin is 7.2 ten thousand; c, the compressive strength of the hollow glass beads is 30 MPa; 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 sulfide compositions prepared in the above examples and comparative examples were subjected to the following performance 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 300 ℃, 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 the Low dielectric constant polyphenylene sulfide compositions of the examples and comparative examples
Examples 1 to 7 are to adjust the addition amounts of PPS, SEBS-g-MAH, HGS, POSS, titanate coupling agent, PTFE, hyperbranched polyester polymer, and erucamide, and as can be seen from the table, as the addition amount of PPS increases (or the addition amount of SEBS, SEBS-g-MAH), the tensile strength thereof shows a tendency of increasing change, and the impact strength and melt index thereof show a tendency of decreasing change, mainly because the tensile strength of the PPS base material is high, while the tensile strength of SEBS and SEBS-g-MAH themselves is low, and the processing fluidity thereof is good, and the function of toughening is also achieved; 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 in comparison with example 8, the screw shape of the parallel twin-screw extruder of example 8 is double-screw thread, the screw shape of the parallel twin-screw extruder of example 7 is single-screw thread, and by comparison, it can be found that the low dielectric constant polyphenylene sulfide composition prepared by using the screw parameters of the parallel twin-screw extruder described in example 7 has better tensile strength, notch impact strength and melt index, and lower dielectric constant.
Example 7 in comparison with comparative example 1, comparative example 1 used a polyphenylene sulfide resin having a number average molecular weight of 7.2 ten thousand, while example 7 used a polyphenylene sulfide resin having a number average molecular weight of 4.8 ten thousand, and the flowability of the polyphenylene sulfide resin was greatly reduced as the number average molecular weight of the polyphenylene sulfide resin was increased, and the melt index of the low dielectric constant polyphenylene sulfide composition was only 6g/10min when the number average molecular weight of the polyphenylene sulfide resin was 7.2 ten thousand; example 7 compared with comparative example 2, the compressive strength of the hollow glass bead used in comparative example 2 was 30MPa, while the compressive strength of the hollow glass bead used in example 7 was 60MPa, and since the compressive strength of the hollow glass bead used in comparative example 2 was low, the hollow glass bead was easily broken during the parallel twin-screw extruder processing, and lost the characteristics of reinforcement and low dielectric constant, resulting in a great decrease in mechanical properties and an increase in dielectric constant; example 7 compared to comparative example 3, the dielectric constant of the PPS composition is higher than that of example 7 since comparative example 3 does not add HGS and POSS having low dielectric constants; example 7 compared with comparative example 4, the polytetrafluoroethylene resin used in comparative example 4 has a molecular weight of 200 ten thousand, is less flowable during processing in a parallel twin-screw extruder, and is prone to extrusion swelling, which leads to breakage of the PPS composition, while the PPS composition prepared is poorer in tensile strength, notched impact strength, and melt index, and is higher in dielectric constant; example 7 compared to comparative example 5, since comparative example 5 does not add the hyperbranched polyester polymer and erucamide, and the two lubricating and dispersing agents can play a role in promoting the dispersion of the titanate coupling agent, the monoalkoxy fatty acid titanate coupling agent is less effective in coating the hollow glass microspheres and the glycidyl-POSS, the interfacial bonding force and compatibility of the polyphenylene sulfide composition and the low dielectric filler are reduced, and the processability of the PPS composition is poor, so that the tensile strength, the notched impact strength and the melt index of the PPS composition prepared in comparative example 5 are poorer, and the dielectric constant is higher.
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 polyphenylene sulfide composition is characterized by being prepared from the following raw materials in parts by weight:
the number average molecular weight of the polyphenylene sulfide resin is 4.6-5.0 ten thousand; the compressive strength of the hollow glass beads is not lower than 53 MPa; the number average molecular weight of the polytetrafluoroethylene resin is 1-10 ten thousand.
2. The low-dielectric-constant polyphenylene sulfide composition of claim 1, which is prepared from the following raw materials in parts by weight:
3. the low-dielectric-constant polyphenylene sulfide composition of claim 2, which is prepared from the following raw materials in parts by weight:
4. the low dielectric constant polyphenylene sulfide composition according to any one of claims 1 to 3, wherein the maleic anhydride grafting ratio of the hydrogenated styrene-butadiene-styrene copolymer grafted maleic anhydride is 0.8 to 1.2%.
5. The low dielectric constant polyphenylene sulfide composition of any one of claims 1 to 3, wherein the titanate coupling agent is a monoalkoxy fatty acid titanate coupling agent; and/or the terminal group of the polyhedral oligomeric silsesquioxane polymer is an epoxy group.
6. The preparation method of the low dielectric constant polyphenylene sulfide composition as defined in any one of claims 1 to 5, comprising the steps of:
(1) drying the polyphenylene sulfide resin, and mixing the polyphenylene sulfide resin with the hydrogenated styrene-butadiene-styrene copolymer, the 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;
(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 preparation method according to claim 6, wherein the polyphenylene sulfide resin is dried at a temperature of 80 to 110 ℃ for 4 to 8 hours in the step (1); preferably, the polyphenylene sulfide resin is dried for 4-6 hours at the temperature of 90-100 ℃ in the step (1);
and/or the process parameters of the parallel twin-screw extruder in the step (3) comprise: the temperature of the first zone is 280-300 ℃, the temperature of the second zone is 285-305 ℃, the temperature of the third zone is 285-305 ℃, the temperature of the fourth zone is 290-310 ℃, the temperature of the fifth zone is 290-310 ℃, the temperature of the sixth zone is 285-305 ℃, the temperature of the seventh zone is 285-305 ℃, the temperature of the eighth zone is 285-305 ℃, the temperature of the die head is 285-305 ℃, 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 285-295 ℃, the temperature of the second zone is 290-300 ℃, the temperature of the third zone is 290-300 ℃, the temperature of the fourth zone is 295-305 ℃, the temperature of the fifth zone is 295-305 ℃, the temperature of the sixth zone is 290-300 ℃, the temperature of the seventh zone is 290-300 ℃, the temperature of the eighth zone is 290-300 ℃, the temperature of the die head is 290-300 ℃ and the rotating speed of the screw is 300-500 rpm.
8. The production method according to claim 6 or 7, wherein the screw shape of the parallel twin-screw extruder is a single-screw thread; and/or the ratio L/D of the length L and the diameter D of the screw of the parallel double-screw extruder is 35-50; and/or more than 1 meshing block area and more than 1 reverse thread area are arranged on the screw of the parallel double-screw extruder.
9. The method according to claim 8, wherein the ratio L/D of the screw length L to the diameter D is 35 to 45; and 2 meshing block areas and 1 reverse thread area are arranged on the screw rod.
10. The method according to claim 6 or 7, wherein the mixing step is performed by 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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| CN113861688A (en) * | 2021-10-28 | 2021-12-31 | 江西聚真科技发展有限公司 | Low-dielectric polyphenylene sulfide composite material and preparation method thereof |
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