CN111320848A - Low dielectric constant liquid crystal polymer composition and preparation method thereof - Google Patents
Low dielectric constant liquid crystal polymer composition and preparation method thereof Download PDFInfo
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/42—Mixtures of liquid crystal compounds covered by two or more of the preceding groups C09K19/06 - C09K19/40
- C09K19/46—Mixtures of liquid crystal compounds covered by two or more of the preceding groups C09K19/06 - C09K19/40 containing esters
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- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
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- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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Abstract
The invention relates to a low dielectric constant liquid crystal polymer composition and a preparation method thereof, wherein the low dielectric constant liquid crystal polymer composition is prepared from the following raw materials: liquid crystal polymer A resin, liquid crystal polymer B 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 and bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphate. The low dielectric constant liquid crystal polymer 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.
Description
Technical Field
The invention relates to the field of materials, in particular to a low dielectric constant liquid crystal polymer composition and a preparation method thereof.
Background
Dielectric materials, also known as dielectrics, are electrically insulating materials. There are high dielectric materials and low dielectric materials, depending on the properties. With the rapid advance of electronic information technology, electronic products are being developed toward light weight, high performance and multiple functions, and development of low dielectric constant (D) having good performance is increasingly required for low dielectric materialsk<3) A material. Meanwhile, with the coming of the 5G era, the requirements on the transmission speed and the loss of electronic signals are higher than those of 4G products, generally, the dielectric constant of the 4G products for the resin material is only required to be less than 3.7(1GHz), and the dielectric constant of the 5G products for the resin material is required to be less than 3.2(1 GHz).
Generally, there are three methods for reducing the dielectric constant of a polymer, ① introducing fluorine atoms into a polymer molecular chain to reduce the stacking density of the molecular chain and increase the free movement space of the molecular chain, ② introducing a bulky structure (such as polyhedral oligomeric silsesquioxane polymer) or a microporous structure or introducing large molecular chain side groups (such as benzene rings) by a physical or chemical method, ③ reducing the dielectric constant of a blend by blending other materials with lower dielectric constant, such as blending with Polytetrafluoroethylene (PTFE) with a relative dielectric constant of 2.0(1GHz), or blending with materials such as polyhedral oligomeric silsesquioxane Polymer (POSS) which can increase the free volume, and the like.
The liquid crystal polymer is a high molecular compound which can exist in a liquid crystal phase under a certain condition and is characterized by higher molecular mass and the orientation order and position order of molecules in a liquid state. According to the physical conditions for forming liquid crystal, the liquid crystal can be divided into Lyotropic Liquid Crystal Polymer (LLCP) and Thermotropic Liquid Crystal Polymer (TLCP), wherein the Thermotropic Liquid Crystal Polymer (TLCP) has low melt viscosity, easy processing, excellent mechanical property, higher chemical stability and thermal stability, but the thermotropic liquid crystal polymer has low notch impact strength, and needs to be toughened and enhanced and the dielectric constant of the blend needs to be reduced so as to meet the increasing demands in the fields of electronic and electrical engineering, integrated circuit packaging, electromagnetic wave shielding and the like.
Currently, some studies on LCP dielectric systems are made in the prior art, for example: chinese patent CN110769594A discloses an LCP high-frequency substrate with high Dk and low Df characteristics, which comprises at least one copper foil layer, at least one high-dielectric LCP core layer and at least one high-dielectric glue layer, wherein the high-dielectric LCP core layer is positioned between the copper foil layer and the high-dielectric glue layer, the high-dielectric LCP core layer is a core layer with a Dk value of 6-100 and a Df value of 0.002-0.010, and the high-dielectric glue layer is a glue layer with a Dk value of 6-100 and a Df value of 0.002-0.010; the thickness of the copper foil layer is 1-35 mu m; the thickness of the high-dielectric LCP core layer is 12-100 mu m, and the thickness of the high-dielectric glue layer is 12-100 mu m. Chinese patent CN 107849429a discloses an adhesive composition which has high adhesion not only to conventional polyimide and polyester films but also to low-polarity resin substrates such as LCP or metal substrates, can achieve high solder heat resistance, and is excellent in low dielectric characteristics and pot life properties; chinese patent CN 107848259a discloses a laminate which has high adhesion not only to conventional polyimide and polyester films but also to low-polarity resin substrates such as LCP and metal substrates, can obtain high solder heat resistance, and has excellent low dielectric characteristics and flame retardancy; chinese patent CN 107848259A discloses a low-dielectric low-loss 5G application material, which comprises an MPI material layer positioned in the middle and LCP material layers coated on the upper and lower sides of the MPI material layer, wherein the thickness of the MPI material layer is 25-75 μm, and the thickness of the LCP material layer is 12.5-50 μm; chinese patent CN 101921469A discloses a liquid crystal polyester blend composition, which comprises 100 weight parts of liquid crystal polyester blend and 0.1-300 weight parts of calcium titanate and/or barium titanate; wherein the liquid-crystalline polyester blend is obtainable by combining a liquid-crystalline polyester (A) (LCP A) and a liquid-crystalline polyester (B) (LCP B) in such a manner that the (LCP A)/(LCP B) weight ratio is from 99/1 to 80/20.
Disclosure of Invention
Based on the above, the invention aims to provide a low dielectric constant liquid crystal polymer composition with excellent mechanical properties and processability, which can be applied to shells, coatings, protective materials and the like of 5G base stations, micro base station systems, data communication terminals, antennas and radio frequency modules.
In order to achieve the purpose, the invention adopts the following scheme:
a low dielectric constant liquid crystal polymer composition is prepared from the following raw materials in parts by weight:
60-93 parts of liquid crystal polymer A resin (LCP-A),
5-20 parts of liquid crystal polymer B resin (LCP-B),
2-20 parts of hydrogenated styrene-butadiene-styrene copolymer grafted maleic anhydride (SEBS-g-MAH),
the total weight of the liquid crystal polymer A resin, the liquid crystal polymer B resin and the hydrogenated styrene-butadiene-styrene copolymer grafted maleic anhydride is 100 parts,
the liquid crystal polymer A resin is polymerized by p-hydroxybenzoic acid and 2-hydroxy-6-naphthoic acid; the liquid crystal polymer B resin is polymerized by p-hydroxybenzoic acid, 4' -biphenol and terephthalic acid; 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 liquid crystal polymer composition is prepared from the following raw materials in parts by weight:
68-85 parts of liquid crystal polymer A resin (LCP-A),
9-16 parts of liquid crystal polymer B resin (LCP-B),
6-16 parts of hydrogenated styrene-butadiene-styrene copolymer grafted maleic anhydride (SEBS-g-MAH),
the total weight of the liquid crystal polymer A resin, the liquid crystal polymer B resin and the hydrogenated styrene-butadiene-styrene copolymer grafted maleic anhydride is 100 parts,
in some embodiments, the low-k liquid crystal polymer composition is further preferably prepared from the following raw materials in parts by weight:
72-78 parts of liquid crystal polymer A resin (LCP-A),
12-14 parts of liquid crystal polymer B resin (LCP-B),
10-14 parts of hydrogenated styrene-butadiene-styrene copolymer grafted maleic anhydride (SEBS-g-MAH),
the total weight of the liquid crystal polymer A resin, the liquid crystal polymer B resin 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 selected from at least one of epoxy cyclohexyl POSS and glycidol POSS.
In some of these embodiments, the titanate coupling agent is a monoalkoxy fatty acid titanate coupling agent.
Another object of the present invention is to provide a method for preparing a low dielectric constant liquid crystalline polymer composition.
The preparation method of the low dielectric constant liquid crystal polymer composition comprises the following steps:
(1) drying the liquid crystal polymer A resin and the liquid crystal polymer B resin, and then mixing the dried liquid crystal polymer A resin and the liquid crystal polymer B resin with 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 (in a stirrer);
(2) mixing the hollow glass microspheres, the polyhedral oligomeric silsesquioxane polymer, the titanate coupling agent, the hyperbranched polyester polymer and the erucamide (in another blender);
(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 liquid crystal polymer A resin and the liquid crystal polymer B resin in the step (1) are dried for 4-8 hours at a temperature of 110-140 ℃.
In some embodiments, the liquid crystal polymer A resin and the liquid crystal polymer B resin in the step (1) are dried for 4-6 hours at a temperature of 120-130 ℃.
In some of the embodiments, the process parameters of the parallel twin-screw extruder in step (3) include: the technological parameters comprise: the temperature of the first zone is 305-325 ℃, the temperature of the second zone is 310-330 ℃, the temperature of the third zone is 310-330 ℃, the temperature of the fourth zone is 315-335 ℃, the temperature of the fifth zone is 315-335 ℃, the temperature of the sixth zone is 310-330 ℃, the temperature of the seventh zone is 310-330 ℃, the temperature of the eighth zone is 310-330 ℃, the temperature of the die head is 310-330 ℃ and the rotation speed of the screw is 200-600 rpm.
The process parameters in the step (3) comprise: the temperature of the first zone is 310-320 ℃, the temperature of the second zone is 315-325 ℃, the temperature of the third zone is 315-325 ℃, the temperature of the fourth zone is 320-330 ℃, the temperature of the fifth zone is 320-330 ℃, the temperature of the sixth zone is 315-325 ℃, the temperature of the seventh zone is 315-325 ℃, the temperature of the eighth zone is 315-325 ℃, the temperature of the die head is 315-325 ℃, 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 length L of the screw to the diameter D of the screw is 35 to 45; and 2 meshing block areas and 1 reverse thread area are arranged on the screw rod.
In some embodiments, in step (1) and/or step (2), the mixing step is performed by using a stirrer, wherein the stirrer is a high-speed stirrer and the rotating speed is 500-1500 rpm.
The principle of the low dielectric constant liquid crystal polymer composition of the present invention is as follows:
in order to solve the defect of poor compatibility of LCP, low dielectric filler hollow glass microspheres (HGS) and polyhedral oligomeric silsesquioxane (POSS) in the low dielectric constant liquid crystal polymer composition, the compatibility between LCP and the low dielectric filler is improved by adding a compatilizer SEBS-g-MAH, the compatibility between LCP and the 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 LCP 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 LCP and low dielectric filler, and simultaneously improves the mechanical property and processability, so that the low dielectric constant liquid crystal polymer composition with excellent comprehensive properties is prepared.
The liquid crystal polymer A resin adopted by the invention is polymerized by p-hydroxybenzoic acid and 2-hydroxy-6-naphthoic acid, the melting point is 295 ℃, the processability is better, and the heat distortion temperature is general; the liquid crystal polymer B resin is polymerized by p-hydroxybenzoic acid, 4' -biphenol and terephthalic acid, the melting point is 335 ℃, the heat distortion temperature is high, and the processing performance is general. Therefore, the two liquid crystal polymer resins are compounded to obtain the low dielectric constant liquid crystal polymer composition with excellent heat distortion temperature and processability.
The compatibility of SEBS structural units in the compatilizer SEBS-g-MAH and LCP resin is good, 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 LCP, and react with a coupling agent for coating low dielectric fillers, so that the compatibility between the LCP and the low dielectric fillers is improved, and the impact property of the composition can be improved by the SEBS-g-MAH.
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 type framework, the intrinsic nanopores of the POSS enable the POSS to have a very low dielectric constant which is 2.1-2.5 (1GHz), the dielectric constant can be effectively reduced without obviously influencing the mechanical property of a blend, the POSS has good compatibility with a base material resin, the particle agglomeration can be effectively reduced, meanwhile, the POSS contains an inorganic core consisting of silicon and oxygen, the POSS has good thermal stability, the molecular size of the POSS is large, and the POSS has the effect of blocking the chain segment movement of polymer molecules, so that the addition of the POSS is also beneficial to improving the thermal stability of the composition.
The effect of the titanate coupling agent used in the present invention is attributed to its 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 of hydroxyl groups adsorbed on the surface of the low dielectric filler, while its organic phase has good compatibility with LCP.
The polytetrafluoroethylene resin adopted by the invention is mainly used as a modifier and a release agent of the 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 composition and the coating effect of the coupling agent, improve the dispersion degree of the low dielectric filler in the 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 composition and the coating effect of the coupling agent, improves the dispersion degree of the low dielectric filler in the composition system, and has little influence on the mechanical property of the 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 LCP blending process is better, and the hindered piperidyl can provide antioxidation and improve the dyeing property of the composition.
The bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphates adopted by the invention have the melting point of 239 ℃ and the thermal decomposition temperature of over 350 ℃, have good heat resistance and hydrolysis resistance, can provide excellent color stability and melt stability for LCP blending process, simultaneously prevent the LCP from thermal degradation in the high temperature process, inhibit thermo-oxidative discoloration caused by long-time extrusion processing, and provide Nitrogen Oxides (NO)x) 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 defect of poor compatibility of LCP, low dielectric filler hollow glass microspheres (HGS) and polyhedral oligomeric silsesquioxane Polymers (POSS) in the existing low dielectric constant liquid crystal polymer composition, the compatibility between the LCP and the low dielectric constant is improved by adding compatilizer SEBS-g-MAH, titanate coupling agent, lubricating dispersant hyperbranched polyester polymer and erucamide, the processability of the composition is improved by adopting low molecular weight PTFE, the dielectric constant of the composition is reduced by compounding HGS, POSS and PTFE, the yellowing phenomenon and the thermal stability of the liquid crystal polymer composition in the blending processing process 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 liquid crystal polymer 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 liquid crystal polymer 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 industrial production is facilitated.
Drawings
FIG. 1 is a flow chart of a process for preparing a low dielectric constant liquid crystal polymer 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 liquid crystal polymer composition of one 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 LCP;
as can be seen from the above reaction formula, the maleic anhydride group of the SEBS-g-MAH can react with the terminal hydroxyl groups of the HGS and the LCP, and the epoxy group of the POSS can react with the terminal hydroxyl groups of the HGS and the LCP, so as to improve the compatibility between the LCP and the low dielectric filler.
The examples of the invention and the comparative examples used the following raw materials:
liquid crystal polymer A resin, which is polymerized by p-hydroxybenzoic acid and 2-hydroxy-6-naphthoic acid and is selected from Seranii corporation, USA;
liquid crystal polymer B resin, which is polymerized by p-hydroxybenzoic acid, 4' -biphenol and terephthalic acid and is selected from Suwei corporation of America;
hydrogenated styrene-butadiene-styrene copolymer grafted maleic anhydride, maleic anhydride graft rate of 1%, selected from Shenyang Ketong plastics Co., Ltd;
the hollow glass microspheres have the compressive strength of 60MPa and are selected from New Material science and technology Limited company of Middling Steel group Maanshan Ministry;
the hollow glass microspheres have the compressive strength of 30MPa and are selected from New Material science and technology Limited company of Middling Steel group Maanshan Ministry;
epoxycyclohexyl POSS selected from Hybrid Plastics, usa;
glycidol POSS selected from the group consisting of Hybrid Plastics, USA;
mono-alkoxy fatty acid titanate coupling agent selected from chemical auxiliary oil material factories in Tianchan city;
polytetrafluoroethylene resin having a number average molecular weight of 5 ten thousand selected from the large-scale fluoroplastics (China) Co., Ltd;
polytetrafluoroethylene resin having a number average molecular weight of 200 ten thousand selected from the large-scale fluoroplastics (China) Co., Ltd;
the hyperbranched polyester polymer has a thermal decomposition temperature of more than or equal to 350 ℃, and is selected from Waishahen molecular new materials Co., Ltd;
erucamide, selected from the group consisting of Haimengteng New materials science and technology, Inc.;
n, N' -bis (2,2,6, 6-tetramethyl-4-piperidinyl) -1, 3-benzenedicarboxamide, selected from Toxongitai chemical Co., Ltd;
bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphate selected from Shanghai Yaozao Fine chemical Co., Ltd;
the present invention will be described in detail with reference to specific examples.
Example 1:
the embodiment provides a low dielectric constant liquid crystal polymer composition, which is prepared from the following raw materials in parts by weight:
60 parts of liquid crystal polymer A resin,
20 parts of liquid crystal polymer B resin,
20 parts of hydrogenated styrene-butadiene-styrene copolymer grafted maleic anhydride,
the total weight of the liquid crystal polymer A resin, the liquid crystal polymer B resin and the hydrogenated styrene-butadiene-styrene copolymer grafted maleic anhydride is 100 parts,
the preparation method of the low dielectric constant liquid crystal polymer composition comprises the following steps:
(1) drying the liquid crystal polymer A resin and the liquid crystal polymer B resin at the temperature of 110 ℃ for 8 hours, cooling, adding the cooled liquid crystal polymer A resin and liquid crystal polymer B resin and 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 into a stirrer for mixing;
(2) adding the hollow glass beads, epoxy cyclohexyl POSS, monoalkoxyl fatty acid titanate coupling agent, hyperbranched polyester polymer and erucamide into another stirrer for mixing;
(3) adding the mixed material obtained in the step (1) into a parallel double-screw extruder through a feeder, adding the mixed material obtained in the step (2) into the parallel double-screw extruder (totally eight zones) (for example, a fourth zone) in the lateral direction (for example, the fourth zone) for melt extrusion and granulation, wherein the process parameters comprise: the temperature in the first zone was 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 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 rotating speed of the stirrer in the step (1) and the step (2) is 1000 revolutions per minute.
Example 2:
the embodiment provides a low dielectric constant liquid crystal polymer composition, which is prepared from the following raw materials in parts by weight:
93 parts of liquid crystal polymer A resin,
5 parts of liquid crystal polymer B resin,
2 parts of hydrogenated styrene-butadiene-styrene copolymer grafted maleic anhydride,
the total weight of the liquid crystal polymer A resin, the liquid crystal polymer B resin and the hydrogenated styrene-butadiene-styrene copolymer grafted maleic anhydride is 100 parts,
the preparation method of the low dielectric constant liquid crystal polymer composition comprises the following steps:
(1) drying the liquid crystal polymer A resin and the liquid crystal polymer B resin at the temperature of 140 ℃ for 4 hours, cooling, adding the cooled liquid crystal polymer A resin and liquid crystal polymer B resin and 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 into a stirrer for mixing;
(2) adding the hollow glass beads, the glycidol POSS, the monoalkoxy fatty acid titanate coupling agent, the hyperbranched polyester polymer and the erucamide into another stirrer for mixing;
(3) adding the mixed material obtained in the step (1) into a parallel double-screw extruder through a feeder, adding the mixed material obtained in the step (2) into the parallel double-screw extruder (totally eight zones) (for example, a fourth zone) in the lateral direction (for example, the fourth zone) for melt extrusion and granulation, wherein the process parameters comprise: the temperature in the first zone was 325 ℃, the temperature in the second zone was 330 ℃, the temperature in the third zone was 330 ℃, the temperature in the fourth zone was 335 ℃, the temperature in the fifth zone was 335 ℃, the temperature in the sixth zone was 330 ℃, the temperature in the seventh zone was 330 ℃, the temperature in the eighth zone was 330 ℃, the temperature in the die head was 330 ℃ and the screw speed was 600 rpm.
The screw of the parallel double-screw extruder is in a single-thread shape, the ratio L/D of the length L and the diameter D of the screw is 50, and the screw is provided with 2 meshing block areas and 1 back-thread area; the rotating speed of the stirrer in the step (1) and the step (2) is 1000 revolutions per minute.
Example 3:
the embodiment provides a low dielectric constant liquid crystal polymer composition, which is prepared from the following raw materials in parts by weight:
68 parts of a liquid crystal polymer A resin,
16 parts of liquid crystal polymer B resin,
16 parts of hydrogenated styrene-butadiene-styrene copolymer grafted maleic anhydride,
the total weight of the liquid crystal polymer A resin, the liquid crystal polymer B resin and the hydrogenated styrene-butadiene-styrene copolymer grafted maleic anhydride is 100 parts,
the preparation method of the low dielectric constant liquid crystal polymer composition comprises the following steps:
(1) drying the liquid crystal polymer A resin and the liquid crystal polymer B resin at the temperature of 120 ℃ for 6 hours, cooling, adding the cooled liquid crystal polymer A resin and liquid crystal polymer B resin and 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 into a stirrer for mixing;
(2) adding the hollow glass beads, the glycidol POSS, the monoalkoxy fatty acid titanate coupling agent, the hyperbranched polyester polymer and the erucamide into another stirrer for mixing;
(3) adding the mixed material obtained in the step (1) into a parallel double-screw extruder through a feeder, adding the mixed material obtained in the step (2) into the parallel double-screw extruder (totally eight zones) (for example, a fourth zone) in the lateral direction (for example, the fourth zone) for melt extrusion and granulation, wherein the process parameters comprise: the temperature in the first zone was 310 ℃, the temperature in the second zone was 315 ℃, the temperature in the third zone was 315 ℃, the temperature in the fourth zone was 320 ℃, the temperature in the fifth zone was 320 ℃, the temperature in the sixth zone was 315 ℃, the temperature in the seventh zone was 315 ℃, the temperature in the eighth zone was 315 ℃, the temperature in the die head was 315 ℃ and the screw speed was 300 rpm.
The screw of the parallel double-screw extruder is in a single-thread shape, the ratio L/D of the length L and the diameter D of the screw is 35, and the screw is provided with 2 meshing block areas and 1 back-thread area; the rotating speed of the stirrer in the step (1) and the step (2) is 1000 revolutions per minute.
Example 4:
the embodiment provides a low dielectric constant liquid crystal polymer composition, which is prepared from the following raw materials in parts by weight:
85 parts of liquid crystal polymer A resin,
9 parts of liquid crystal polymer B resin,
6 parts of hydrogenated styrene-butadiene-styrene copolymer grafted maleic anhydride,
the total weight of the liquid crystal polymer A resin, the liquid crystal polymer B resin and the hydrogenated styrene-butadiene-styrene copolymer grafted maleic anhydride is 100 parts,
the preparation method of the low dielectric constant liquid crystal polymer composition comprises the following steps:
(1) drying the liquid crystal polymer A resin and the liquid crystal polymer B resin at the temperature of 130 ℃ for 4 hours, cooling, adding the cooled liquid crystal polymer A resin and liquid crystal polymer B resin and 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 into a stirrer for mixing;
(2) adding the hollow glass beads, the glycidol POSS, the monoalkoxy fatty acid titanate coupling agent, the hyperbranched polyester polymer and the erucamide into another stirrer for mixing;
(3) adding the mixed material obtained in the step (1) into a parallel double-screw extruder through a feeder, adding the mixed material obtained in the step (2) into the parallel double-screw extruder (totally eight zones) (for example, a fourth zone) in the lateral direction (for example, the fourth zone) for melt extrusion and granulation, wherein the process parameters comprise: the temperature in the first zone was 320 ℃, the temperature in the second zone was 325 ℃, the temperature in the third zone was 325 ℃, the temperature in the fourth zone was 330 ℃, the temperature in the fifth zone was 330 ℃, the temperature in the sixth zone was 325 ℃, the temperature in the seventh zone was 325 ℃, the temperature in the eighth zone was 325 ℃, the temperature of the die head was 325 ℃ and the screw speed was 500 rpm.
The screw of the parallel double-screw extruder is in a single-thread shape, the ratio L/D of the length L and the diameter D of the screw is 45, and the screw is provided with 2 meshing block areas and 1 back-thread area; the rotating speed of the stirrer in the step (1) and the step (2) is 1000 revolutions per minute.
Example 5:
the embodiment provides a low dielectric constant liquid crystal polymer composition, which is prepared from the following raw materials in parts by weight:
72 parts of liquid crystal polymer A resin,
14 parts of liquid crystal polymer B resin,
14 parts of hydrogenated styrene-butadiene-styrene copolymer grafted maleic anhydride,
the total weight of the liquid crystal polymer A resin, the liquid crystal polymer B resin and the hydrogenated styrene-butadiene-styrene copolymer grafted maleic anhydride is 100 parts,
the preparation method of the low dielectric constant liquid crystal polymer composition comprises the following steps:
(1) drying the liquid crystal polymer A resin and the liquid crystal polymer B resin at 125 ℃ for 5 hours, cooling, adding the cooled liquid crystal polymer A resin and the liquid crystal polymer B resin as well as 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 into a stirrer for mixing;
(2) adding the hollow glass beads, the glycidol POSS, the monoalkoxy fatty acid titanate coupling agent, the hyperbranched polyester polymer and the erucamide into another stirrer for mixing;
(3) adding the mixed material obtained in the step (1) into a parallel double-screw extruder through a feeder, adding the mixed material obtained in the step (2) into the parallel double-screw extruder (totally eight zones) (for example, a fourth zone) in the lateral direction (for example, the fourth zone) for melt extrusion and granulation, wherein the process parameters comprise: the temperature in the first zone was 315 deg.C, the temperature in the second zone was 320 deg.C, the temperature in the third zone was 320 deg.C, the temperature in the fourth zone was 325 deg.C, the temperature in the fifth zone was 325 deg.C, the temperature in the sixth zone was 320 deg.C, the temperature in the seventh zone was 320 deg.C, the temperature in the eighth zone was 320 deg.C, the temperature in the die head was 320 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 40, and the screw is provided with 2 meshing block areas and 1 back-thread area; the rotating speed of the stirrer in the step (1) and the step (2) is 1000 revolutions per minute.
Example 6:
the embodiment provides a low dielectric constant liquid crystal polymer composition, which is prepared from the following raw materials in parts by weight:
78 parts of a liquid crystal polymer A resin,
12 parts of liquid crystal polymer B resin,
10 parts of hydrogenated styrene-butadiene-styrene copolymer grafted maleic anhydride,
the total weight of the liquid crystal polymer A resin, the liquid crystal polymer B resin and the hydrogenated styrene-butadiene-styrene copolymer grafted maleic anhydride is 100 parts,
the preparation method of the low dielectric constant liquid crystal polymer composition comprises the following steps:
(1) drying the liquid crystal polymer A resin and the liquid crystal polymer B resin at 125 ℃ for 5 hours, cooling, adding the cooled liquid crystal polymer A resin and the liquid crystal polymer B resin as well as 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 into a stirrer for mixing;
(2) adding the hollow glass beads, the glycidol POSS, the monoalkoxy fatty acid titanate coupling agent, the hyperbranched polyester polymer and the erucamide into another stirrer for mixing;
(3) adding the mixed material obtained in the step (1) into a parallel double-screw extruder through a feeder, adding the mixed material obtained in the step (2) into the parallel double-screw extruder (totally eight zones) (for example, a fourth zone) in the lateral direction (for example, the fourth zone) for melt extrusion and granulation, wherein the process parameters comprise: the temperature in the first zone was 315 deg.C, the temperature in the second zone was 320 deg.C, the temperature in the third zone was 320 deg.C, the temperature in the fourth zone was 325 deg.C, the temperature in the fifth zone was 325 deg.C, the temperature in the sixth zone was 320 deg.C, the temperature in the seventh zone was 320 deg.C, the temperature in the eighth zone was 320 deg.C, the temperature in the die head was 320 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 40, and the screw is provided with 2 meshing block areas and 1 back-thread area; the rotating speed of the stirrer in the step (1) and the step (2) is 1000 revolutions per minute.
Example 7:
the embodiment provides a low dielectric constant liquid crystal polymer composition, which is prepared from the following raw materials in parts by weight:
75 parts of a liquid crystal polymer A resin,
13 parts of liquid crystal polymer B resin,
12 parts of hydrogenated styrene-butadiene-styrene copolymer grafted maleic anhydride,
the total weight of the liquid crystal polymer A resin, the liquid crystal polymer B resin and the hydrogenated styrene-butadiene-styrene copolymer grafted maleic anhydride is 100 parts,
the preparation method of the low dielectric constant liquid crystal polymer composition comprises the following steps:
(1) drying the liquid crystal polymer A resin and the liquid crystal polymer B resin at 125 ℃ for 5 hours, cooling, adding the cooled liquid crystal polymer A resin and the liquid crystal polymer B resin as well as 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 into a stirrer for mixing;
(2) adding the hollow glass beads, the glycidol POSS, the monoalkoxy fatty acid titanate coupling agent, the hyperbranched polyester polymer and the erucamide into another stirrer for mixing;
(3) adding the mixed material obtained in the step (1) into a parallel double-screw extruder through a feeder, adding the mixed material obtained in the step (2) into the parallel double-screw extruder (totally eight zones) (for example, a fourth zone) in the lateral direction (for example, the fourth zone) for melt extrusion and granulation, wherein the process parameters comprise: the temperature in the first zone was 315 deg.C, the temperature in the second zone was 320 deg.C, the temperature in the third zone was 320 deg.C, the temperature in the fourth zone was 325 deg.C, the temperature in the fifth zone was 325 deg.C, the temperature in the sixth zone was 320 deg.C, the temperature in the seventh zone was 320 deg.C, the temperature in the eighth zone was 320 deg.C, the temperature in the die head was 320 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 40, and the screw is provided with 2 meshing block areas and 1 back-thread area; the rotating speed of the stirrer in the step (1) and the step (2) is 1000 revolutions per minute.
Example 8:
the embodiment provides a low dielectric constant liquid crystal polymer composition, which is prepared from the following raw materials in parts by weight:
75 parts of a liquid crystal polymer A resin,
13 parts of liquid crystal polymer B resin,
12 parts of hydrogenated styrene-butadiene-styrene copolymer grafted maleic anhydride,
the total weight of the liquid crystal polymer A resin, the liquid crystal polymer B resin and the hydrogenated styrene-butadiene-styrene copolymer grafted maleic anhydride is 100 parts,
the preparation method of the low dielectric constant liquid crystal polymer composition comprises the following steps:
(1) drying the liquid crystal polymer A resin and the liquid crystal polymer B resin at 125 ℃ for 5 hours, cooling, adding the cooled liquid crystal polymer A resin and the liquid crystal polymer B resin as well as 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 into a stirrer for mixing;
(2) adding the hollow glass beads, the glycidol POSS, the monoalkoxy fatty acid titanate coupling agent, the hyperbranched polyester polymer and the erucamide into another stirrer for mixing;
(3) adding the mixed material obtained in the step (1) into a parallel double-screw extruder through a feeder, adding the mixed material obtained in the step (2) into the parallel double-screw extruder (totally eight zones) (for example, a fourth zone) in the lateral direction (for example, the fourth zone) for melt extrusion and granulation, wherein the process parameters comprise: the temperature in the first zone was 315 deg.C, the temperature in the second zone was 320 deg.C, the temperature in the third zone was 320 deg.C, the temperature in the fourth zone was 325 deg.C, the temperature in the fifth zone was 325 deg.C, the temperature in the sixth zone was 320 deg.C, the temperature in the seventh zone was 320 deg.C, the temperature in the eighth zone was 320 deg.C, the temperature in the die head was 320 deg.C, and.
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 rotating speed of the stirrer in the step (1) and the step (2) is 1000 revolutions per minute.
Comparative example 1:
the comparative example provides a low dielectric constant liquid crystal polymer composition, which is prepared from the following raw materials in parts by weight:
88 parts of liquid crystal polymer A resin,
12 parts of hydrogenated styrene-butadiene-styrene copolymer grafted maleic anhydride,
the total weight of the liquid crystal polymer A resin and the hydrogenated styrene-butadiene-styrene copolymer grafted maleic anhydride is 100 parts,
the preparation method of the low dielectric constant liquid crystal polymer composition comprises the following steps:
(1) drying the liquid crystal polymer A resin at 125 ℃ for 5 hours, cooling, adding the cooled liquid crystal polymer A resin and the hydrogenated styrene-butadiene-styrene copolymer grafted maleic anhydride, polytetrafluoroethylene resin, N' -bis (2,2,6, 6-tetramethyl-4-piperidyl) -1, 3-phthalic diamide, bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphate into a stirrer, and mixing;
(2) adding the hollow glass beads, the glycidol POSS, the monoalkoxy fatty acid titanate coupling agent, the hyperbranched polyester polymer and the erucamide into another stirrer for mixing;
(3) adding the mixed material obtained in the step (1) into a parallel double-screw extruder through a feeder, adding the mixed material obtained in the step (2) into the parallel double-screw extruder (totally eight zones) (for example, a fourth zone) in the lateral direction (for example, the fourth zone) for melt extrusion and granulation, wherein the process parameters comprise: the temperature in the first zone was 315 deg.C, the temperature in the second zone was 320 deg.C, the temperature in the third zone was 320 deg.C, the temperature in the fourth zone was 325 deg.C, the temperature in the fifth zone was 325 deg.C, the temperature in the sixth zone was 320 deg.C, the temperature in the seventh zone was 320 deg.C, the temperature in the eighth zone was 320 deg.C, the temperature in the die head was 320 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 40, and the screw is provided with 2 meshing block areas and 1 back-thread area; the rotating speed of the stirrer in the step (1) and the step (2) is 1000 revolutions per minute.
Comparative example 2:
the comparative example provides a low dielectric constant liquid crystal polymer composition, which is prepared from the following raw materials in parts by weight:
75 parts of a liquid crystal polymer A resin,
13 parts of liquid crystal polymer B resin,
12 parts of hydrogenated styrene-butadiene-styrene copolymer grafted maleic anhydride,
the total weight of the liquid crystal polymer A resin, the liquid crystal polymer B resin and the hydrogenated styrene-butadiene-styrene copolymer grafted maleic anhydride is 100 parts,
the preparation method of the low dielectric constant liquid crystal polymer composition comprises the following steps:
(1) drying the liquid crystal polymer A resin and the liquid crystal polymer B resin at 125 ℃ for 5 hours, cooling, adding the cooled liquid crystal polymer A resin and the liquid crystal polymer B resin as well as 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 into a stirrer for mixing;
(2) adding the hollow glass beads, the glycidol POSS, the monoalkoxy fatty acid titanate coupling agent, the hyperbranched polyester polymer and the erucamide into another stirrer for mixing;
(3) adding the mixed material obtained in the step (1) into a parallel double-screw extruder through a feeder, adding the mixed material obtained in the step (2) into the parallel double-screw extruder (totally eight zones) (for example, a fourth zone) in the lateral direction (for example, the fourth zone) for melt extrusion and granulation, wherein the process parameters comprise: the temperature in the first zone was 315 deg.C, the temperature in the second zone was 320 deg.C, the temperature in the third zone was 320 deg.C, the temperature in the fourth zone was 325 deg.C, the temperature in the fifth zone was 325 deg.C, the temperature in the sixth zone was 320 deg.C, the temperature in the seventh zone was 320 deg.C, the temperature in the eighth zone was 320 deg.C, the temperature in the die head was 320 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 40, and the screw is provided with 2 meshing block areas and 1 back-thread area; the rotating speed of the stirrer in the step (1) and the step (2) is 1000 revolutions per minute.
Comparative example 3:
the comparative example provides a low dielectric constant liquid crystal polymer composition, which is prepared from the following raw materials in parts by weight:
75 parts of a liquid crystal polymer A resin,
13 parts of liquid crystal polymer B resin,
12 parts of hydrogenated styrene-butadiene-styrene copolymer grafted maleic anhydride,
the total weight of the liquid crystal polymer A resin, the liquid crystal polymer B resin and the hydrogenated styrene-butadiene-styrene copolymer grafted maleic anhydride is 100 parts,
the preparation method of the low dielectric constant liquid crystal polymer composition comprises the following steps:
(1) drying the liquid crystal polymer A resin and the liquid crystal polymer B resin at 125 ℃ for 5 hours, cooling, adding the cooled liquid crystal polymer A resin and the liquid crystal polymer B resin as well as 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 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 315 deg.C, the temperature in the second zone was 320 deg.C, the temperature in the third zone was 320 deg.C, the temperature in the fourth zone was 325 deg.C, the temperature in the fifth zone was 325 deg.C, the temperature in the sixth zone was 320 deg.C, the temperature in the seventh zone was 320 deg.C, the temperature in the eighth zone was 320 deg.C, the temperature in the die head was 320 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 40, and the screw is provided with 2 meshing block areas and 1 back-thread area; the rotating speed of the stirrer in the step (1) and the step (2) is 1000 revolutions per minute.
Comparative example 4:
the comparative example provides a low dielectric constant liquid crystal polymer composition, which is prepared from the following raw materials in parts by weight:
75 parts of a liquid crystal polymer A resin,
13 parts of liquid crystal polymer B resin,
12 parts of hydrogenated styrene-butadiene-styrene copolymer grafted maleic anhydride,
the total weight of the liquid crystal polymer A resin, the liquid crystal polymer B resin and the hydrogenated styrene-butadiene-styrene copolymer grafted maleic anhydride is 100 parts,
the preparation method of the low dielectric constant liquid crystal polymer composition comprises the following steps:
(1) drying the liquid crystal polymer A resin and the liquid crystal polymer B resin at 125 ℃ for 5 hours, cooling, adding the cooled liquid crystal polymer A resin and the liquid crystal polymer B resin as well as 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 into a stirrer for mixing;
(2) adding the hollow glass beads, the glycidol POSS, the monoalkoxy fatty acid titanate coupling agent, the hyperbranched polyester polymer and the erucamide into another stirrer for mixing;
(3) adding the mixed material obtained in the step (1) into a parallel double-screw extruder through a feeder, adding the mixed material obtained in the step (2) into the parallel double-screw extruder (totally eight zones) (for example, a fourth zone) in the lateral direction (for example, the fourth zone) for melt extrusion and granulation, wherein the process parameters comprise: the temperature in the first zone was 315 deg.C, the temperature in the second zone was 320 deg.C, the temperature in the third zone was 320 deg.C, the temperature in the fourth zone was 325 deg.C, the temperature in the fifth zone was 325 deg.C, the temperature in the sixth zone was 320 deg.C, the temperature in the seventh zone was 320 deg.C, the temperature in the eighth zone was 320 deg.C, the temperature in the die head was 320 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 40, and the screw is provided with 2 meshing block areas and 1 back-thread area; the rotating speed of the stirrer in the step (1) and the step (2) is 1000 revolutions per minute.
Comparative example 5:
the comparative example provides a low dielectric constant liquid crystal polymer composition, which is prepared from the following raw materials in parts by weight:
75 parts of a liquid crystal polymer A resin,
13 parts of liquid crystal polymer B resin,
12 parts of hydrogenated styrene-butadiene-styrene copolymer grafted maleic anhydride,
the total weight of the liquid crystal polymer A resin, the liquid crystal polymer B resin and the hydrogenated styrene-butadiene-styrene copolymer grafted maleic anhydride is 100 parts,
the preparation method of the low dielectric constant liquid crystal polymer composition comprises the following steps:
(1) drying the liquid crystal polymer A resin and the liquid crystal polymer B resin at 125 ℃ for 5 hours, cooling, adding the cooled liquid crystal polymer A resin and the liquid crystal polymer B resin as well as 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 into a stirrer for mixing;
(2) adding the hollow glass beads, the glycidol POSS and the mono-alkoxy fatty acid titanate coupling agent into another stirrer for mixing;
(3) adding the mixed material obtained in the step (1) into a parallel double-screw extruder through a feeder, adding the mixed material obtained in the step (2) into the parallel double-screw extruder (totally eight zones) (for example, a fourth zone) in the lateral direction (for example, the fourth zone) for melt extrusion and granulation, wherein the process parameters comprise: the temperature in the first zone was 315 deg.C, the temperature in the second zone was 320 deg.C, the temperature in the third zone was 320 deg.C, the temperature in the fourth zone was 325 deg.C, the temperature in the fifth zone was 325 deg.C, the temperature in the sixth zone was 320 deg.C, the temperature in the seventh zone was 320 deg.C, the temperature in the eighth zone was 320 deg.C, the temperature in the die head was 320 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 40, and the screw is provided with 2 meshing block areas and 1 back-thread area; the rotating speed of the stirrer in the step (1) and the step (2) 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 compressive strength of the hollow glass beads is 30 MPa; c, 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 liquid crystalline polymer 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 330 ℃, and the load is 5 kg;
heat distortion temperature: testing according to GB/T1634.2-2004 standard, wherein the load is 0.45 MPa;
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 liquid crystalline Polymer compositions of the examples and comparative examples
In examples 1 to 7, in order to adjust the addition amounts of LCP-A, LCP-B, SEBS-g-MAH, HGS, POSS, titanate coupling agent, PTFE, hyperbranched polyester polymer, and erucamide, as can be seen from the table, as the addition amount of LCP increases (or the addition amount of SEBS-g-MAH decreases), the tensile strength and thermal deformation temperature thereof show an increasing trend, while the impact strength and melt index thereof show a decreasing trend, mainly because the tensile strength and thermal deformation temperature of the LCP substrate are higher, while the tensile strength and thermal deformation temperature of the SEBS-g-MAH itself are lower, and the processing flowability is better, and the toughening effect is 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 was a twin screw and the screw shape of the parallel twin-screw extruder of example 7 was a single screw, and it was found by comparison that the low dielectric constant liquid crystalline polymer composition prepared using the screw parameters of the parallel twin-screw extruder described in example 7 was better in tensile strength, notched impact strength, melt index and heat distortion temperature and lower in dielectric constant.
Example 7 in comparison with comparative example 1, comparative example 1 did not use a liquid crystal polymer B resin, and therefore comparative example 1 had lower tensile strength and lower heat distortion temperature than example 7; 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 composition was higher than that of example 7 since comparative example 3 did not add HGS and POSS having low dielectric constants; 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 the composition to break, and the prepared composition has poorer tensile strength, notch impact strength and melt index and higher 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 dispersants can function as the titanate coupling agent for dispersion, the monoalkoxy fatty acid titanate coupling agent has a poor effect of coating the hollow glass microspheres and the glycidyl POSS, the interfacial bonding force and compatibility of the LCP composition with the low dielectric filler are reduced, and the processability of the composition is deteriorated, so that the tensile strength, notched impact strength and melt index of the composition prepared in comparative example 5 are worse, 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 liquid crystal polymer composition is characterized by being prepared from the following raw materials in parts by weight:
60-93 parts of liquid crystal polymer A resin,
5-20 parts of liquid crystal polymer B resin,
2-20 parts of hydrogenated styrene-butadiene-styrene copolymer grafted maleic anhydride,
the total weight of the liquid crystal polymer A resin, the liquid crystal polymer B resin and the hydrogenated styrene-butadiene-styrene copolymer grafted maleic anhydride is 100 parts,
the liquid crystal polymer A resin is polymerized by p-hydroxybenzoic acid and 2-hydroxy-6-naphthoic acid; the liquid crystal polymer B resin is polymerized by p-hydroxybenzoic acid, 4' -biphenol and terephthalic acid; 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 liquid crystal polymer composition of claim 1, prepared from the following raw materials in parts by weight:
68-85 parts of liquid crystal polymer A resin,
9-16 parts of liquid crystal polymer B resin,
6-16 parts of hydrogenated styrene-butadiene-styrene copolymer grafted maleic anhydride,
the total weight of the liquid crystal polymer A resin, the liquid crystal polymer B resin and the hydrogenated styrene-butadiene-styrene copolymer grafted maleic anhydride is 100 parts,
3. the low dielectric constant liquid crystal polymer composition of claim 2, prepared from the following raw materials in parts by weight:
72-78 parts of liquid crystal polymer A resin,
12-14 parts of liquid crystal polymer B resin,
10-14 parts of hydrogenated styrene-butadiene-styrene copolymer grafted maleic anhydride,
the total weight of the liquid crystal polymer A resin, the liquid crystal polymer B resin and the hydrogenated styrene-butadiene-styrene copolymer grafted maleic anhydride is 100 parts,
4. the low dielectric constant liquid crystal polymer 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%; and/or the terminal group of the polyhedral oligomeric silsesquioxane polymer is an epoxy group.
5. The low dielectric constant liquid crystal polymer composition of any one of claims 1 to 3, wherein the titanate coupling agent is a monoalkoxy fatty acid titanate coupling agent.
6. A method for preparing the low dielectric constant liquid crystal polymer composition of any one of claims 1 to 5, comprising the steps of:
(1) drying the liquid crystal polymer A resin and the liquid crystal polymer B resin, and mixing with 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;
(2) mixing the hollow glass beads, the polyhedral oligomeric silsesquioxane polymer, the titanate coupling agent, the hyperbranched polyester polymer and the erucamide;
(3) and (3) adding the mixture mixed in the step (1) into a parallel double-screw extruder through a feeder, adding the mixture mixed in the step (2) into the parallel double-screw extruder in the lateral direction, performing melt extrusion, and granulating.
7. The method according to claim 6, wherein the liquid crystal polymer A resin and the liquid crystal polymer B resin are dried at a temperature of 110 to 140 ℃ for 4 to 8 hours in the step (1); preferably, the liquid crystal polymer A resin and the liquid crystal polymer B are dried for 4-6 hours at the temperature of 120-130 ℃ 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 305-325 ℃, the temperature of the second zone is 310-330 ℃, the temperature of the third zone is 310-330 ℃, the temperature of the fourth zone is 315-335 ℃, the temperature of the fifth zone is 315-335 ℃, the temperature of the sixth zone is 310-330 ℃, the temperature of the seventh zone is 310-330 ℃, the temperature of the eighth zone is 310-330 ℃, the temperature of the die head is 310-330 ℃ 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 310-320 ℃, the temperature of the second zone is 315-325 ℃, the temperature of the third zone is 315-325 ℃, the temperature of the fourth zone is 320-330 ℃, the temperature of the fifth zone is 320-330 ℃, the temperature of the sixth zone is 315-325 ℃, the temperature of the seventh zone is 315-325 ℃, the temperature of the eighth zone is 315-325 ℃, the temperature of the die head is 315-325 ℃, 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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