CN111423723A

CN111423723A - Reinforced polyphenylene sulfide composition for 5G and preparation method thereof

Info

Publication number: CN111423723A
Application number: CN202010290560.0A
Authority: CN
Inventors: 王忠强; 卢健体; 丁佳; 韩春春
Original assignee: Guangdong Aldex New Material Co Ltd
Current assignee: Guangdong Aldex New Material Co Ltd
Priority date: 2020-04-14
Filing date: 2020-04-14
Publication date: 2020-07-17

Abstract

The invention relates to a reinforced polyphenylene sulfide composition for 5G and a preparation method thereof, wherein the reinforced polyphenylene sulfide composition for 5G is prepared from the following raw materials: polyphenylene sulfide resin, hydrogenated styrene-butadiene-styrene copolymer grafted maleic anhydride, hollow glass microspheres, polyhedral oligomeric silsesquioxane polymer, low dielectric constant glass fiber, titanate coupling agent, polytetrafluoroethylene resin, hyperbranched polyester polymer, erucamide, antioxidant CY and bis (2, 4-dicumylphenyl) pentaerythritol diphosphite. The reinforced polyphenylene sulfide composition for 5G has excellent mechanical property, processability and low dielectric constant, 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.

Description

Reinforced polyphenylene sulfide composition for 5G and preparation method thereof

Technical Field

The invention relates to the field of materials, in particular to a reinforced polyphenylene sulfide composition for 5G 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 developing toward light weight, high performance and multiple functions, and there is an increasing need to develop materials with low dielectric constant and good performanceLow dielectric constant (D)_k<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.

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; after the mixing is finished, 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 a low dielectric constant and a preparation method thereof, wherein 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 flexibilizer, 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 a low dielectric constant and a preparation method thereof, wherein 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 invention aims to provide a reinforced polyphenylene sulfide composition for 5G, which has excellent mechanical properties, processability and low dielectric constant and can be applied to a 5G base station, a micro base station system, a data communication terminal, a shell and a coating of an antenna and a radio frequency module, a protective material and the like.

In order to achieve the purpose, the invention adopts the following technical scheme:

the reinforced polyphenylene sulfide composition for 5G 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; the low dielectric constant glass fiber has a dielectric constant (1GHz) of not higher than 4.5.

In some embodiments, the reinforced polyphenylene sulfide composition for 5G 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),

in some embodiments, the reinforced polyphenylene sulfide composition for 5G 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),

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 the embodiments, the compressive strength of the hollow glass microspheres is 55-65 MPa.

In some of these embodiments, the polytetrafluoroethylene resin has a number average molecular weight of 3 to 7 ten thousand.

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 epoxycyclohexylethyl-POSS and/or glycidyl-POSS.

In some of these embodiments, the titanate coupling agent is a monoalkoxy fatty acid titanate coupling agent.

The invention also aims to provide the preparation method of the reinforced polyphenylene sulfide composition for 5G, which has the advantages of simple process, easiness in control, low requirement on equipment and contribution to industrial production.

The preparation method of the reinforced polyphenylene sulfide composition for 5G comprises the following steps:

(1) drying the polyphenylene sulfide resin, and then mixing the polyphenylene sulfide resin with the hydrogenated styrene-butadiene-styrene copolymer, the hydrogenated styrene-butadiene-styrene copolymer grafted maleic anhydride, polytetrafluoroethylene resin, an antioxidant CY and bis (2, 4-dicumylphenyl) pentaerythritol diphosphite (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 twin-screw extruder through a feeder, adding the mixed material obtained in the step (2) into the parallel twin-screw extruder in the lateral direction (for example, the fourth zone) of the parallel twin-screw extruder (total eight zones), and adding the low-dielectric-constant glass fiber into the parallel twin-screw extruder in the other lateral direction (for example, the third zone) of the parallel twin-screw extruder for melt extrusion and granulation.

In some embodiments, the polyphenylene sulfide resin is dried at 80-110 ℃ for 4-8 hours in step (1).

In some embodiments, it is preferable that the polyphenylene sulfide resin is dried at a temperature of 90 to 100 ℃ for 4 to 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 285-305 ℃, the temperature of the second zone is 290-310 ℃, the temperature of the third zone is 290-310 ℃, the temperature of the fourth zone is 295-315 ℃, the temperature of the fifth zone is 295-315 ℃, the temperature of the sixth zone is 290-310 ℃, the temperature of the seventh zone is 290-310 ℃, the temperature of the eighth zone is 290-310 ℃, the temperature of the die head is 290-310 ℃ 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 the preferred step (3) include: the temperature of the first zone is 290-300 ℃, the temperature of the second zone is 295-305 ℃, the temperature of the third zone is 295-305 ℃, the temperature of the fourth zone is 300-310 ℃, the temperature of the fifth zone is 300-310 ℃, the temperature of the sixth zone is 295-305 ℃, the temperature of the seventh zone is 295-305 ℃, the temperature of the eighth zone is 295-305 ℃, the temperature of the die head is 295-305 ℃ and the rotation 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 (including 1) intermeshing block zone and more than 1 (including 1) reverse-flight zone; preferably, the screw is provided with 2 meshing block areas and 1 reverse thread area.

In some embodiments, the mixing in step (1) 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, the mixing in step (2) 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 reinforced polyphenylene sulfide composition for 5G of the present invention is as follows:

in order to solve the defects of poor compatibility and processing performance of PPS and low dielectric filler hollow glass microspheres (HGS), polyhedral oligomeric silsesquioxane Polymers (POSS) and low dielectric constant glass fibers (D glass fibers) in a 5G reinforced polyphenylene sulfide composition, the compatibility among PPS, SEBS and low dielectric fillers is improved by adding a compatilizer SEBS-G-MAH, the compatibility between PPS and low dielectric fillers is improved by adding a titanate coupling agent, the effect of coating the low dielectric fillers by the titanate coupling agent is improved by adding a lubricating dispersant hyperbranched polyester polymer and erucamide, and the processing performance of the PPS composition is improved. By adding the auxiliary agent, the interface bonding force and compatibility between the PPS and the low dielectric filler are improved, the mechanical property and the processing property of the PPS composition are improved, the dielectric constant of the PPS composition is reduced, and the reinforced polyphenylene sulfide composition with excellent comprehensive performance and used for 5G is prepared.

The SEBS structural unit in the compatilizer SEBS-g-MAH adopted by the invention has good compatibility with SEBS resin and PPS resin, and the maleic anhydride group of the SEBS-g-MAH and the epoxy group of the polyhedral oligomeric silsesquioxane polymer can react with the terminal hydroxyl group of the hollow glass microsphere and the terminal group of PPS and react with the titanate coupling agent coating the low dielectric filler, so that the compatibility between the PPS and the low dielectric filler is improved, and the SEBS-g-MAH can improve the impact property 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, has internal nanopores so that the POSS has a very low dielectric constant of 2.1-2.5(1GHz), can effectively reduce the dielectric constant of the blend, does not obviously influence the mechanical property of the blend, has good compatibility with the base material resin, and can effectively reduce particle agglomeration. Meanwhile, POSS molecules contain inorganic cores composed of silicon and oxygen, so that the PPS composition 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 PPS composition.

The effect of the titanate coupling agent used in the invention is attributed to the effect on the interface, i.e. it can form chemical bridges between the inorganic filler and the organic polymer, which are coupled by the direct chemical action of its alkoxy groups with the trace amount of hydroxyl groups adsorbed on the surface of the low dielectric filler, while the organic phase has good compatibility with PPS.

The polytetrafluoroethylene resin adopted by the invention is mainly used as a modifier and a release agent of the PPS composition by utilizing the special lubricating property and non-stick property, and the dielectric constant 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 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, effectively solve the surface defects of the products, and simultaneously improve the glossiness of the surfaces of the products.

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 antioxidant CY (1,3, 5-tri (4-tert-butyl-3-hydroxy-2, 6-dimethylbenzyl) -1,3, 5-triazine-2, 4,6- (1H,3H,5H) -trione) adopted by the invention has excellent hydrolysis resistance, and can effectively inhibit thermal oxidation and degradation of the composition in the processing and using processes at high temperature; the bis (2, 4-dicumylphenyl) pentaerythritol diphosphite adopted by the invention has the main characteristics of high molecular weight, high steric hindrance, low volatilization and high phosphorus content (7.3%), is the highest molecular weight of all current commercial phosphite antioxidant products, has excellent high-temperature stability and migration precipitation resistance, can effectively prevent the composition from being easily yellowed or generating black spots in the high-temperature processing process, and provides effective high-temperature degradation protection.

Compared with the prior art, the invention has the following beneficial effects:

aiming at the defects of poor compatibility and processing performance of PPS and low dielectric filler hollow glass beads (HGS), polyhedral oligomeric silsesquioxane Polymer (POSS) and low dielectric constant glass fiber (D glass fiber) in the existing 5G reinforced polyphenylene sulfide composition, the compatibility between the PPS and the low dielectric filler is improved by adding a compatilizer SEBS-G-MAH, a titanate coupling agent, a lubricating dispersant hyperbranched polyester polymer and erucamide, the processing performance of the polyphenylene sulfide composition is improved by adopting low molecular weight PTFE, the dielectric constant of the polyphenylene sulfide composition is reduced by compounding HGS, POSS and PTFE, the yellowing phenomenon and the thermal stability of the 5G reinforced polyphenylene sulfide composition in the blending processing process are improved by compounding an antioxidant CY and bis (2, 4-dicumylphenyl) pentaerythritol diphosphite, the raw material components are matched with each other, so that the reinforced polyphenylene sulfide composition for 5G has excellent mechanical property, processability and low dielectric constant, and can be applied to 5G base stations, micro base station systems, data communication terminals, shells and coating materials of antennas and radio frequency modules, protective materials and the like.

The preparation method of the reinforced polyphenylene sulfide composition for 5G provided by the invention has the advantages of simple process, easiness in control and low requirement on equipment, and the used equipment is general polymer processing equipment, so that the investment is low, and the industrial production is facilitated.

Drawings

FIG. 1 is a flow chart of a process for preparing a reinforced polyphenylene sulfide composition for use in 5G, 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 reinforced polyphenylene sulfide composition for 5G according to an embodiment of the present 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;

glycidol-POSS selected from the group consisting of Hybrid Plastics, USA;

low dielectric constant glass fiber having a dielectric constant of 4.4 selected from the group consisting of Taishan glass fiber, Inc.;

common glass fiber with dielectric constant of 6.3 selected from Taishan glass fiber Co;

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.;

antioxidant CY selected from Cyanote, USA;

bis (2, 4-dicumylphenyl) pentaerythritol diphosphite selected from Dover corporation, USA.

The present invention will be described in detail with reference to specific examples.

Example 1

The embodiment of the invention relates to a reinforced polyphenylene sulfide composition for 5G, 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,

(1) drying the polyphenylene sulfide resin at the temperature of 80 ℃ for 8 hours, cooling, adding the cooled polyphenylene sulfide resin and the hydrogenated styrene-butadiene-styrene copolymer, the hydrogenated styrene-butadiene-styrene copolymer grafted maleic anhydride, polytetrafluoroethylene resin, an antioxidant CY and bis (2, 4-dicumylphenyl) pentaerythritol diphosphite into a stirrer for mixing, wherein the rotating speed of the stirrer is 1000 revolutions per minute;

(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, wherein the rotating speed of the stirrer is 1000 revolutions per minute;

(3) adding the mixed material obtained in the step (1) into a parallel twin-screw extruder through a feeder, adding the mixed material obtained in the step (2) into the parallel twin-screw extruder (totally eight zones) in a lateral direction (such as a fourth zone), and adding low-dielectric-constant glass fibers into the parallel twin-screw extruder in another lateral direction (such as a third 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 shape of the parallel twin-screw extruder is single thread, the ratio of the screw length L to the diameter D L/D is 35, and the screw is provided with 2 meshing block areas and 1 back-thread area.

Example 2

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,

(1) drying the polyphenylene sulfide resin at the temperature of 110 ℃ for 4 hours, cooling, adding the cooled polyphenylene sulfide resin and the hydrogenated styrene-butadiene-styrene copolymer, the hydrogenated styrene-butadiene-styrene copolymer grafted maleic anhydride, polytetrafluoroethylene resin, an antioxidant CY and bis (2, 4-dicumylphenyl) pentaerythritol diphosphite into a stirrer for mixing, wherein the rotating speed of the stirrer is 1000 revolutions per minute;

(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, wherein the rotating speed of the stirrer is 1000 revolutions per minute;

(3) adding the mixed material obtained in the step (1) into a parallel twin-screw extruder through a feeder, adding the mixed material obtained in the step (2) into the parallel twin-screw extruder (totally eight zones) in a lateral direction (such as a fourth zone), and adding low-dielectric-constant glass fibers into the parallel twin-screw extruder in another lateral direction (such as a third zone) for melt extrusion and granulation, wherein the process parameters comprise: the temperature in the first zone was 305 ℃, the temperature in the second zone was 310 ℃, the temperature in the third zone was 310 ℃, the temperature in the fourth zone was 315 ℃, the temperature in the fifth zone was 315 ℃, the temperature in the sixth zone was 310 ℃, the temperature in the seventh zone was 310 ℃, the temperature in the eighth zone was 310 ℃, the temperature in the die head was 310 ℃ and the screw speed was 600 rpm.

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

Example 3

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,

(1) drying the polyphenylene sulfide resin at the temperature of 90 ℃ for 6 hours, cooling, adding the cooled polyphenylene sulfide resin and the hydrogenated styrene-butadiene-styrene copolymer, the hydrogenated styrene-butadiene-styrene copolymer grafted maleic anhydride, polytetrafluoroethylene resin, an antioxidant CY and bis (2, 4-dicumylphenyl) pentaerythritol diphosphite into a stirrer for mixing, wherein the rotating speed of the stirrer is 1000 revolutions per minute;

(3) adding the mixed material obtained in the step (1) into a parallel twin-screw extruder through a feeder, adding the mixed material obtained in the step (2) into the parallel twin-screw extruder (totally eight zones) in a lateral direction (such as a fourth zone), and adding low-dielectric-constant glass fibers into the parallel twin-screw extruder in another lateral direction (such as a third 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 300 rpm.

Example 4

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,

(1) drying the polyphenylene sulfide resin at the temperature of 100 ℃ for 4 hours, cooling, adding the cooled polyphenylene sulfide resin and the hydrogenated styrene-butadiene-styrene copolymer, the hydrogenated styrene-butadiene-styrene copolymer grafted maleic anhydride, polytetrafluoroethylene resin, an antioxidant CY and bis (2, 4-dicumylphenyl) pentaerythritol diphosphite into a stirrer for mixing, wherein the rotating speed of the stirrer is 1000 revolutions per minute;

(3) adding the mixed material obtained in the step (1) into a parallel twin-screw extruder through a feeder, adding the mixed material obtained in the step (2) into the parallel twin-screw extruder (totally eight zones) in a lateral direction (such as a fourth zone), and adding low-dielectric-constant glass fibers into the parallel twin-screw extruder in another lateral direction (such as a third 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 shape of the parallel twin-screw extruder is single thread, the ratio of the screw length L to the diameter D L/D is 45, and the screw is provided with 2 meshing block areas and 1 back-thread area.

Example 5

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,

(1) drying the polyphenylene sulfide resin at the temperature of 95 ℃ for 5 hours, cooling, adding the cooled polyphenylene sulfide resin and the hydrogenated styrene-butadiene-styrene copolymer, the hydrogenated styrene-butadiene-styrene copolymer grafted maleic anhydride, polytetrafluoroethylene resin, an antioxidant CY and bis (2, 4-dicumylphenyl) pentaerythritol diphosphite into a stirrer for mixing, wherein the rotating speed of the stirrer is 1000 revolutions per minute;

(3) adding the mixed material obtained in the step (1) into a parallel twin-screw extruder through a feeder, adding the mixed material obtained in the step (2) into the parallel twin-screw extruder (totally eight zones) in a lateral direction (such as a fourth zone), and adding low-dielectric-constant glass fibers into the parallel twin-screw extruder in another lateral direction (such as a third 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 shape of the parallel twin-screw extruder is single thread, the ratio of the screw length L to the diameter D L/D is 40, and the screw is provided with 2 meshing block areas and 1 back-thread area.

Example 6

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,

Example 7

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,

Example 8

5 parts of hydrogenated styrene-butadiene-styrene copolymer,

The shape of the screw of the parallel double-screw extruder is double-thread, the ratio of the length L of the screw to the diameter D L/D is 40, and the screw is provided with 2 meshing block areas and 1 back-thread area.

Comparative example 1

90 parts of polyphenylene sulfide resin (number average molecular weight 7.2 ten thousand),

5 parts of hydrogenated styrene-butadiene-styrene copolymer,

Comparative example 2

5 parts of hydrogenated styrene-butadiene-styrene copolymer,

Comparative example 3

5 parts of hydrogenated styrene-butadiene-styrene copolymer,

(2) adding the mono-alkoxy fatty acid titanate coupling agent, the hyperbranched polyester polymer and the erucamide into another stirrer for mixing, wherein the rotating speed of the stirrer is 1000 revolutions per minute;

Comparative example 4

5 parts of hydrogenated styrene-butadiene-styrene copolymer,

Comparative example 5

5 parts of hydrogenated styrene-butadiene-styrene copolymer,

(2) adding the hollow glass beads, the glycidol-POSS and the monoalkoxyl fatty acid titanate coupling agent into another stirrer for mixing, wherein the rotating speed of the stirrer is 1000 revolutions per minute;

Comparative example 6

5 parts of hydrogenated styrene-butadiene-styrene copolymer,

(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), and adding common glass fiber into the parallel double-screw extruder (totally eight zones) (for example, a third zone) in the other side direction (for example, the third 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 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; e, the D glass fiber is changed into the common glass fiber, and the dielectric constant of the glass fiber is 6.3.

Wherein, the antioxidant CY and the bis (2, 4-dicumylphenyl) pentaerythritol diphosphite of the above examples and comparative examples are added in an amount of 0.2 part.

The reinforced polyphenylene sulfide compositions for 5G 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 reinforced polyphenylene sulfide compositions for 5G of examples and comparative examples

Examples 1 to 7 are to adjust the addition amounts of PPS, SEBS-g-MAH, HGS, POSS, D glass fiber, titanate coupling agent, PTFE, hyperbranched polyester polymer, and erucamide, and as can be seen from table 2, as the addition amount of PPS increases (or the addition amount of SEBS, SEBS-g-MAH decreases), the tensile strength thereof tends to increase, while the impact strength and melt index thereof tend to decrease, mainly because the tensile strength of the PPS substrate 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 to example 8, the screw shape of the parallel twin screw extruder of example 8 was a twin screw flight and the screw shape of the parallel twin screw extruder of example 7 was a single screw flight, and by comparison it was found that the tensile strength, notched impact strength and melt index of the reinforced polyphenylene sulfide composition for 5G 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 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, whose flowability was greatly reduced as the number average molecular weight of the polyphenylene sulfide resin was increased, and its melt index of the reinforced polyphenylene sulfide composition for 5G was only 5G/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 polyphenylene sulfide composition is higher than that of example 7 since comparative example 3 does not add HGS and POSS with low dielectric constant; example 7 compared with comparative example 4, the molecular weight of the polytetrafluoroethylene resin used in comparative example 4 is 200 ten thousand, the processing fluidity is poor during the processing of a parallel twin-screw extruder, and extrusion swelling is easy to occur to cause broken strands of the polyphenylene sulfide composition, and the prepared polyphenylene sulfide composition has poorer tensile strength, notch impact strength and melt index and higher dielectric constant; example 7 compared with 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 in the polyphenylene sulfide composition, the monoalkoxy fatty acid titanate coupling agent is poor 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 polyphenylene sulfide composition is poor, so that the polyphenylene sulfide composition prepared in comparative example 5 is poorer in tensile strength, notched impact strength and melt index, and higher in dielectric constant; example 7 in comparison with comparative example 6, comparative example 6 used a common glass fiber having a dielectric constant of 6.3, so that the polyphenylene sulfide composition prepared had a much higher dielectric constant than example 7.

The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.

The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.

Claims

1. The reinforced polyphenylene sulfide composition for 5G is characterized by being prepared from the following raw materials in parts by weight:

2. The reinforced polyphenylene sulfide composition for 5G according to claim 1, which is prepared from the following raw materials in parts by weight:

3. the reinforced polyphenylene sulfide composition for 5G according to claim 2, wherein the composition is prepared from the following raw materials in parts by weight:

4. the reinforced polyphenylene sulfide composition for 5G 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 reinforced polyphenylene sulfide composition for 5G according to any one of claims 1-3, 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 preparation method of the reinforced polyphenylene sulfide composition for 5G, according to any one of claims 1 to 5, comprising the steps of:

(1) drying the polyphenylene sulfide resin, and then mixing with the hydrogenated styrene-butadiene-styrene copolymer, the hydrogenated styrene-butadiene-styrene copolymer grafted maleic anhydride, a polytetrafluoroethylene resin, an antioxidant CY and bis (2, 4-dicumylphenyl) pentaerythritol diphosphite;

(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 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 in the lateral direction, adding the low-dielectric-constant glass fiber into the parallel double-screw extruder in the other 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 285-305 ℃, the temperature of the second zone is 290-310 ℃, the temperature of the third zone is 290-310 ℃, the temperature of the fourth zone is 295-315 ℃, the temperature of the fifth zone is 295-315 ℃, the temperature of the sixth zone is 290-310 ℃, the temperature of the seventh zone is 290-310 ℃, the temperature of the eighth zone is 290-310 ℃, the temperature of the die head is 290-310 ℃ 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 290-300 ℃, the temperature of the second zone is 295-305 ℃, the temperature of the third zone is 295-305 ℃, the temperature of the fourth zone is 300-310 ℃, the temperature of the fifth zone is 300-310 ℃, the temperature of the sixth zone is 295-305 ℃, the temperature of the seventh zone is 295-305 ℃, the temperature of the eighth zone is 295-305 ℃, the temperature of the die head is 295-305 ℃ and the rotation 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 of the screw length L to the diameter D L/D of the parallel twin-screw extruder 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-thread areas.

9. The method of claim 8, wherein the ratio of the length L of the screw to the diameter D L/D is 35-45, and the screw is provided with 2 intermeshing lands and 1 counter-flight land.

10. The method according to any one of claims 6 to 9, wherein the mixing in step (1) and/or step (2) is performed using a mixer having a rotation speed of 500 to 1500 rpm.