阅读说明：本技术 一种增强聚对苯二甲酸丁二醇酯组合物及其制备方法 (Reinforced polybutylene terephthalate composition and preparation method thereof ) 是由 王忠强 卢健体 丁佳 于 2020-04-08 设计创作，主要内容包括：本发明涉及一种增强聚对苯二甲酸丁二醇酯组合物及其制备方法,所述增强聚对苯二甲酸丁二醇酯组合物由以下原料制备而成：聚对苯二甲酸丁二醇酯A树脂、聚对苯二甲酸丁二醇酯B树脂、乙烯-辛烯共聚物接枝甲基丙烯酸缩水甘油酯、空心玻璃微珠、多面体低聚倍半硅氧烷聚合物、低介电常数玻璃纤维、钛酸酯偶联剂、聚四氟乙烯树脂、超支化聚酯聚合物、芥酸酰胺、抗氧剂CY和双(2,4-二枯基苯基)季戊四醇二亚磷酸酯。上述增强聚对苯二甲酸丁二醇酯组合物具有优异的力学性能、加工性能和低介电常数,可应用于5G基站、微基站系统、数据通讯终端、天线与射频模块的壳体和包覆、防护材料等。(The invention relates to a reinforced polybutylene terephthalate composition and a preparation method thereof, wherein the reinforced polybutylene terephthalate composition is prepared from the following raw materials: polybutylene terephthalate A resin, polybutylene terephthalate B resin, ethylene-octene copolymer grafted glycidyl methacrylate, 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 enhanced polybutylene terephthalate composition has excellent mechanical property, processability and low dielectric constant, and can be applied to shells, coatings, protective materials and the like of 5G base stations, micro base station systems, data communication terminals, antennas and radio frequency modules.)

1. The reinforced polybutylene terephthalate composition is characterized by being prepared from the following raw materials in parts by weight:

the intrinsic viscosity of the polybutylene terephthalate A resin is 0.95-1.00 d L/g, the intrinsic viscosity of the polybutylene terephthalate B resin is 0.75-0.80 d L/g, the compressive strength of the hollow glass beads is not lower than 53MPa, the number average molecular weight of the polytetrafluoroethylene resin is 1-10 ten thousand, and the dielectric constant (1GHz) of the low-dielectric-constant glass fiber is not higher than 4.5.

2. The reinforced polybutylene terephthalate composition of claim 1, which is prepared from the following raw materials in parts by weight:

3. the reinforced polybutylene terephthalate composition of claim 2, which is prepared from the following raw materials in parts by weight:

4. the reinforced polybutylene terephthalate composition according to any one of claims 1 to 3, wherein the ethylene-octene copolymer has a glycidyl methacrylate graft ratio of 1.2 to 1.8% to the glycidyl methacrylate.

5. The reinforced polybutylene terephthalate composition of any one of claims 1-3, wherein the polyhedral oligomeric silsesquioxane polymer has terminal groups that are epoxy groups; and/or the titanate coupling agent is a mono-alkoxy fatty acid titanate coupling agent.

6. A process for preparing a reinforced polybutylene terephthalate composition according to any one of claims 1 to 5, comprising the steps of:

(1) drying the polybutylene terephthalate A resin and the polybutylene terephthalate B resin, and then mixing the polybutylene terephthalate A resin and the polybutylene terephthalate B resin with the ethylene-octene copolymer grafted glycidyl methacrylate, 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 method according to claim 6, wherein the polybutylene terephthalate A resin and the polybutylene terephthalate B resin are dried at a temperature of 90 to 120 ℃ for 4 to 8 hours in the step (1); preferably, in the step (1), the polybutylene terephthalate A resin and the polybutylene terephthalate B resin are dried for 4-6 hours at the temperature of 100-110 ℃;

and/or the process parameters of the parallel twin-screw extruder in the step (3) comprise: the temperature of the first zone is 240-260 ℃, the temperature of the second zone is 245-265 ℃, the temperature of the third zone is 245-265 ℃, the temperature of the fourth zone is 250-270 ℃, the temperature of the fifth zone is 250-270 ℃, the temperature of the sixth zone is 245-265 ℃, the temperature of the seventh zone is 245-265 ℃, the temperature of the eighth zone is 245-265 ℃, the temperature of the die head is 245-265 ℃ and the rotation 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 245-255 ℃, the temperature of the second zone is 250-260 ℃, the temperature of the third zone is 250-260 ℃, the temperature of the fourth zone is 255-265 ℃, the temperature of the fifth zone is 255-265 ℃, the temperature of the sixth zone is 250-260 ℃, the temperature of the seventh zone is 250-260 ℃, the temperature of the eighth zone is 250-260 ℃, the temperature of the die head is 250-260 ℃, 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 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.

Technical Field

The invention relates to the field of materials, in particular to a reinforced polybutylene terephthalate composition and a preparation method thereof.

Background

Dielectric materials, also known as dielectrics, are electrically insulating materials. There are high dielectric materials and low dielectric materials, depending on the properties. With the rapid advance of electronic information technology, electronic products are being developed toward light weight, high performance and multiple functions, and development of low dielectric constant (D) having good performance is increasingly required for low dielectric materials_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.

Polybutylene terephthalate (PBT) is a crystalline linear saturated polyester, has excellent comprehensive properties, and can be widely applied to the fields of electronic and electric appliances, automobile industry and the like, for example, PBT can be used as a transformer, an energy-saving lamp holder, an igniter switch and the like. Structurally, in the repeating structural unit of the PBT, a benzene ring and a polar ester group which are difficult to move are arranged, and a conjugated system is formed between the benzene ring and the ester group, so that the rigidity of molecules is higher, the flexibility of molecular chains is lower, and the notch impact strength of the PBT is lower. Thus, there is a need to toughen and strengthen PBT and to lower the dielectric constant of PBT compositions by blending other lower dielectric constant materials to meet the increasing demands in the fields of electronics and electricians, integrated circuit packaging, and electromagnetic wave shielding.

Currently, some research is done in the prior art on PBT dielectric systems, for example: chinese patent CN 109575528A discloses a low-dielectric high-toughness reinforced PBT/PPO composition and a preparation method thereof, wherein the low-dielectric high-toughness reinforced PBT/PPO composition comprises the following raw materials in parts by weight: 45-85 parts of polybutylene terephthalate (PBT), 15-55 Parts of Polyphenylene Oxide (PPO), 100 parts of the sum of the parts by weight of the polybutylene terephthalate and the polyphenylene oxide, 20-40 parts of glass fiber, 6-14 parts of a compatilizer, 0.6-1 part of an antioxidant, 5-20 parts of polytetrafluoroethylene, 0.2-1 part of a plasticizer and 0.2-1 part of a silane coupling agent, wherein the weight ratio of the plasticizer to the silane coupling agent is 1: 1-5: 1; chinese patent CN 108102311A discloses a low-dielectric PBT/PETG alloy nano injection molding composite material and a preparation method and application thereof, wherein the preparation raw materials of the PBT/PETG alloy nano injection molding composite material comprise 30-50 parts by weight of PBT resin, 30-50 parts by weight of PETG resin, 30-40 parts by weight of glass fiber, 0.2-0.8 part by weight of antioxidant, 1-2 parts by weight of lubricant, 0.3-0.5 part by weight of anti-UV agent and 3-8 parts by weight of compatilizer; chinese patent CN 108752879A discloses a multi-effect PBT modified plastic and a preparation method thereof, wherein the modified plastic comprises the following components in parts by weight: 58 parts of PBT, 18 parts of polytetrafluoroethylene, 10 parts of glass bead master batch, 3 parts of alumina, 2 parts of antioxidant, 10 parts of heat-conducting filler, 2 parts of halogen-free flame retardant, 4 parts of alkali-free glass fiber, 4 parts of low-temperature modified toughening agent and 10 parts of acid glycidyl ester; chinese patent CN 109971139A discloses PBT-PET modified plastic for communication equipment, which comprises the following components in parts by weight: 25-55 parts of PBT, 30-75 parts of PET, 10-30 parts of vinylidene fluoride, 15-30 parts of tetrafluoroethylene, 1-5 parts of an ester exchange inhibitor, 20-30 parts of an inorganic filler and 0-5 parts of an auxiliary agent; chinese patent CN 109679304A discloses a PBT/PCT composite material, a preparation method and application thereof, wherein the PBT/PCT composite material comprises the following components in parts by weight: 30-45 parts of PBT, 4-20 parts of PCT, (5-10 parts of vinyl POSS, MAH) -g-PP and 25-40 parts of reinforcing material.

Disclosure of Invention

Based on the above, the invention aims to provide a reinforced polybutylene terephthalate composition with excellent mechanical properties, processability and low dielectric constant, which can be applied to shells, coatings, protective materials and the like of 5G base stations, micro base station systems, data communication terminals, antennas and radio frequency modules.

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

the reinforced polybutylene terephthalate composition is prepared from the following raw materials in parts by weight:

the intrinsic viscosity of the polybutylene terephthalate A resin is 0.95-1.00 d L/g, the intrinsic viscosity of the polybutylene terephthalate B resin is 0.75-0.80 d L/g, the compressive strength of the hollow glass beads is not lower than 53MPa, the number average molecular weight of the polytetrafluoroethylene resin is 1-10 ten thousand, and the dielectric constant (1GHz) of the low-dielectric-constant glass fiber is not higher than 4.5.

In some embodiments, the reinforced polybutylene terephthalate composition is prepared from the following raw materials in parts by weight:

in some of the embodiments, the reinforced polybutylene terephthalate composition is further preferably prepared from the following raw materials in parts by weight:

in some embodiments, the ethylene-octene copolymer grafted with glycidyl methacrylate has a glycidyl methacrylate grafting ratio of 1.2-1.8%.

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 an epoxycyclohexyl polyhedral oligomeric silsesquioxane polymer and a glycidol polyhedral oligomeric silsesquioxane polymer.

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

The invention also aims to provide a preparation method of the reinforced polybutylene terephthalate composition, which has the advantages of simple process, easy control, low requirement on equipment, low investment and contribution to industrial production.

The preparation method of the reinforced polybutylene terephthalate composition comprises the following steps:

(1) drying the polybutylene terephthalate A resin and the polybutylene terephthalate B resin, and then mixing the polybutylene terephthalate A resin and the polybutylene terephthalate B resin with the ethylene-octene copolymer grafted glycidyl methacrylate, 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 (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 of the embodiments, the polybutylene terephthalate A resin and the polybutylene terephthalate B resin are dried at a temperature of 90 to 120 ℃ for 4 to 8 hours in the step (1).

In some embodiments, it is preferable that the polybutylene terephthalate A resin and the polybutylene terephthalate B resin are dried at a temperature of 100 to 110 ℃ 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 240-260 ℃, the temperature of the second zone is 245-265 ℃, the temperature of the third zone is 245-265 ℃, the temperature of the fourth zone is 250-270 ℃, the temperature of the fifth zone is 250-270 ℃, the temperature of the sixth zone is 245-265 ℃, the temperature of the seventh zone is 245-265 ℃, the temperature of the eighth zone is 245-265 ℃, the temperature of the die head is 245-265 ℃ and the rotation 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 245-255 ℃, the temperature of the second zone is 250-260 ℃, the temperature of the third zone is 250-260 ℃, the temperature of the fourth zone is 255-265 ℃, the temperature of the fifth zone is 255-265 ℃, the temperature of the sixth zone is 250-260 ℃, the temperature of the seventh zone is 250-260 ℃, the temperature of the eighth zone is 250-260 ℃, the temperature of the die head is 250-260 ℃, and the rotating speed of the screw is 300-500 rpm.

In some of these embodiments, the screw shape of the parallel twin screw extruder is a single flight.

In some of these embodiments, the parallel twin screw extruder has a ratio L/D of screw length L to diameter D of 35 to 50, preferably a ratio L/D of screw length L to diameter D of 35 to 45.

In some of the embodiments, the screws of the parallel twin-screw extruder are provided with more than 1 (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 polybutylene terephthalate composition of the invention is as follows:

in order to solve the defect of poor compatibility of PBT, low dielectric filler hollow glass microspheres (HGS), polyhedral oligomeric silsesquioxane Polymers (POSS) and low dielectric constant glass fibers (D glass fibers) in a reinforced polybutylene terephthalate composition, the invention improves the compatibility between the PBT and the low dielectric filler by adding a compatilizer POE-g-GMA, improves the compatibility between the PBT and the low dielectric filler by adding a titanate coupling agent, improves the effect of coating the low dielectric filler by the titanate coupling agent by adding a lubricating dispersant hyperbranched polyester polymer and erucamide, and improves the processability of the PBT composition. By adding the auxiliary agent, the interface bonding force and compatibility between the PBT and the low dielectric filler are improved, the mechanical property and the processing property of the PBT composition are improved, and the reinforced polybutylene terephthalate composition with excellent comprehensive properties is prepared.

The intrinsic viscosity of the polybutylene terephthalate A resin adopted by the invention is 0.95-1.00 d L/g, the mechanical property is good, but the processing property is general, while the intrinsic viscosity of the polybutylene terephthalate B resin adopted by the invention is 0.75-0.80 d L/g, the processing property is good, and the mechanical property is general, so that the enhanced polybutylene terephthalate composition with excellent mechanical property and processing property is obtained by compounding the two PBT resins.

Epoxy groups in the adopted compatilizer POE-g-GMA can react with terminal groups of PBT, terminal hydroxyl groups of hollow glass microspheres and the titanate coupling agent coated with the low dielectric filler, so that the compatibility between the PBT and the low dielectric filler is improved, and the impact property of the PBT composition can be improved by the POE-g-GMA.

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 base material resin, and can effectively reduce particle agglomeration. Meanwhile, POSS molecules contain inorganic cores composed of silicon and oxygen, so that the thermal stability is good, the molecular size is large, and the effect of blocking the movement of polymer molecular chain segments is achieved, and therefore, the addition of POSS is beneficial to improving the thermal stability of the PBT composition.

The effect of the titanate coupling agent adopted by the invention is attributed to the influence on the interface, namely, the titanate coupling agent can form a chemical bridge bond between the inorganic 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 absorbed on the surface of the low dielectric filler, and the organic phase of the titanate coupling agent has good compatibility with PBT.

The polytetrafluoroethylene resin adopted by the invention is mainly used as a modifier and a release agent of the PBT composition by utilizing the special lubricating property and non-stick property, and the dielectric constant of the polytetrafluoroethylene resin is lower and is only 2.0(1 GHz).

The hyperbranched polyester polymer adopted by the invention is a high temperature resistant dendritic structure additive with a polyester structural unit, which can obviously improve the processing fluidity of the PBT composition and the coating effect of the titanate coupling agent, and improve the dispersion degree of the low dielectric filler in the PBT composition system, effectively solve the surface defects of the product, and simultaneously improve the glossiness of the surface 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 PBT composition and the coating effect of the titanate coupling agent, and improve the dispersion degree of the low dielectric filler in the composition system, and has little influence on the mechanical property of the PBT 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 PBT composition in the processes of processing at high temperature and using; 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 in all current commercial phosphite antioxidant products, has excellent high-temperature stability and migration precipitation resistance, can effectively prevent the phenomena that the PBT composition is easy to yellow or generates 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 defect of poor compatibility of PBT, low dielectric filler hollow glass microspheres (HGS), polyhedral oligomeric silsesquioxane Polymers (POSS) and low dielectric constant glass fibers (D glass fibers) in the existing reinforced polybutylene terephthalate composition, the compatibility between PBT and the low dielectric filler is improved by adding compatilizer POE-g-GMA, titanate coupling agent, lubricating dispersant hyperbranched polyester polymer and erucamide, the processing performance of the PBT composition is improved by adopting low molecular weight PTFE (polytetrafluoroethylene), the dielectric constant of the PBT composition is reduced by compounding HGS, POSS and PTFE, the yellowing phenomenon and the thermal stability of the reinforced polybutylene terephthalate composition in the blending processing process are improved by compounding antioxidant CY and bis (2, 4-dicumyl phenyl) pentaerythritol diphosphite, and the raw material components are matched with each other to ensure that the reinforced polybutylene terephthalate composition has excellent strength The material has the advantages of chemical property, processing property and 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.

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

Drawings

FIG. 1 is a flow diagram of a process for preparing a reinforced polybutylene terephthalate composition in accordance with one embodiment of the 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 polybutylene terephthalate composition of one embodiment of the invention is as follows (see FIG. 1 for a flow chart of the preparation process):

wherein R is₁POE-g-GMA or POSS, R₂PBT, HGS or titanate coupling agents.

As can be seen from the above reaction formula, the epoxy groups of POE-g-GMA and POSS can react with the terminal hydroxyl groups of PBT, HGS or titanate coupling agent, thereby improving the compatibility between PBT and low dielectric filler.

The examples of the invention and the comparative examples used the following raw materials:

polybutylene terephthalate A resin with the intrinsic viscosity of 1.00d L/g, which is selected from Nantong star synthetic materials GmbH;

polybutylene terephthalate B resin with the intrinsic viscosity of 0.75d L/g, which is selected from Nantong star synthetic materials GmbH;

the ethylene-octene copolymer is grafted with glycidyl methacrylate, the grafting ratio of the glycidyl methacrylate is 1.5 percent, and the ethylene-octene copolymer is selected from new molecular material science and technology company of Nantong Ri;

the hollow glass microspheres have the compressive strength of 60MPa and are selected from New Material science and technology Limited company of Middling Steel group Maanshan Ministry;

the hollow glass microspheres have the compressive strength of 30MPa and are selected from New Material science and technology Limited company of Middling Steel group Maanshan Ministry;

epoxycyclohexyl POSS selected from Hybrid Plastics, usa;

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

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 selected from chemical auxiliary oil material factories in Tianchan city;

polytetrafluoroethylene resin having a number average molecular weight of 5 ten thousand selected from the large-scale fluoroplastics (China) Co., Ltd;

polytetrafluoroethylene resin having a number average molecular weight of 200 ten thousand selected from the large-scale fluoroplastics (China) Co., Ltd;

the hyperbranched polyester polymer has a thermal decomposition temperature of more than or equal to 350 ℃, and is selected from Waishahen molecular new materials Co., Ltd;

erucamide, selected from the group consisting of Haimengteng New materials science and technology, Inc.;

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.