CN112625402B - Electroplating-grade LCP composite material, preparation method thereof and antenna - Google Patents
Electroplating-grade LCP composite material, preparation method thereof and antenna Download PDFInfo
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- CN112625402B CN112625402B CN202011411422.XA CN202011411422A CN112625402B CN 112625402 B CN112625402 B CN 112625402B CN 202011411422 A CN202011411422 A CN 202011411422A CN 112625402 B CN112625402 B CN 112625402B
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- C—CHEMISTRY; METALLURGY
- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01Q—ANTENNAS, i.e. RADIO AERIALS
- H01Q1/00—Details of, or arrangements associated with, antennas
- H01Q1/36—Structural form of radiating elements, e.g. cone, spiral, umbrella; Particular materials used therewith
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01Q—ANTENNAS, i.e. RADIO AERIALS
- H01Q1/00—Details of, or arrangements associated with, antennas
- H01Q1/36—Structural form of radiating elements, e.g. cone, spiral, umbrella; Particular materials used therewith
- H01Q1/38—Structural form of radiating elements, e.g. cone, spiral, umbrella; Particular materials used therewith formed by a conductive layer on an insulating support
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
- 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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
Abstract
The invention provides an electroplating LCP composite material, a preparation method thereof and an antenna, and relates to the technical field of high polymer materials. The electroplating-grade LCP composite material is mainly prepared from LCP composite resin, reinforcing filler and a coupling agent, wherein the LCP composite resin is prepared from LCP matrix raw materials and specific polymer gel, and the formed LCP composite resin has a structure that the polymer gel is uniformly dispersed in the LCP matrix raw materials to form the LCP resin. The LCP composite resin with the specific composition and structure is compounded with the reinforcing filler and the coupling agent, so that the electroplating LCP composite material has low dielectric loss and high tensile strength and can be used for electroplating treatment. The invention also provides a preparation method of the electroplating LCP composite material.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to an electroplating LCP composite material, a preparation method thereof and an antenna.
Background
With the arrival of the 5G era, the signal transmission frequency of the communication industry is higher and higher, so the dielectric loss requirement of the material is as low as possible, so that the signal attenuation is reduced, and the energy consumption is reduced. Liquid Crystal Polymer (LCP) has the characteristics of low dielectric loss and stability in a wide frequency range, so that the LCP meets the performance requirements of the future communication industry on materials. In the field of communications, antennas for receiving signals typically require plating. However, LCP has high chemical resistance, so that it is impossible to directly perform water plating. The metal coating of the product manufactured by the universal plating has poor binding force and rough surface, and is not beneficial to signal transmission.
There is relatively little research currently in the industry on the water-plating of LCP's. The prior art discloses LCP materials which have improved plating properties by the addition of thermoplastic elastomers having higher melt indices than LCP, and which can have plating bonds of up to 10N. However, since LCP has good flowability, there is a large limitation on the types of thermoplastic elastomers to be added, and the dielectric loss of LCP material is high. Therefore, there is a need for an LCP material that can satisfy low dielectric loss, high strength, and can be water-plated.
In view of the above, the present invention is particularly proposed to solve at least one of the above technical problems.
Disclosure of Invention
The first purpose of the present invention is to provide an electroplating grade LCP composite material, which has low dielectric loss and high bonding strength and can be subjected to water plating.
A second object of the present invention is to provide a method for preparing an electroplated grade LCP composite.
A third object of the present invention is to provide an antenna.
In order to achieve the purpose, the technical scheme of the invention is as follows:
the invention provides an electroplating LCP composite material, which comprises the following raw materials in percentage by mass:
70-99% of LCP composite resin, 0-30% of reinforcing filler and 0-2% of coupling agent;
the LCP composite resin takes LCP resin formed by LCP matrix raw materials as main resin, and high polymer gel is uniformly dispersed in the LCP resin;
the polymer gel comprises polyphenylene oxide resin and/or polystyrene resin.
Further, on the basis of the above technical solution of the present invention, the preparation method of the LCP composite resin includes the steps of:
and mixing the LCP matrix raw material and the high polymer gel, and carrying out polymerization reaction to obtain the LCP composite resin.
Further, on the basis of the technical scheme of the invention, the LCP composite resin is taken as a whole, and the mass ratio of the LCP resin formed by LCP matrix raw materials to the high polymer gel is (60-97%): (3% -40%);
preferably, the temperature of the polymerization reaction is 200-400 ℃ and the time is 1-24 h.
Further, on the basis of the technical scheme, the initial flow temperature of the LCP composite resin is 280-380 ℃;
preferably, the LCP composite resin has a dielectric constant of 2.5 to 3.5;
preferably, the dielectric loss of the LCP composite resin is 0 to 0.005.
Further, on the basis of the technical scheme of the invention, the reinforcing filler comprises fibrous reinforcing filler and/or powder reinforcing filler;
preferably, the fibrous reinforcing filler comprises any one of glass fiber, quartz fiber, basalt fiber, liquid crystal polymer fiber or polyether ketone fiber or a combination of at least two of the same;
preferably, the powder reinforcing filler comprises any one or a combination of at least two of silica, alumina, aluminum nitride, boron nitride, forsterite, barium titanate, calcium titanate, titanium dioxide or glass beads;
preferably, the coupling agent comprises any one of a titanate coupling agent, a silane coupling agent, a borate coupling agent, an aluminum-titanium composite coupling agent or an aluminate coupling agent or a combination of at least two of the two.
Further, on the basis of the technical scheme of the invention, the electroplating LCP composite material comprises the following raw materials in percentage by mass:
74 to 94 percent of LCP composite resin, 5 to 25 percent of reinforcing filler and 0.1 to 1.5 percent of coupling agent;
preferably, the electroplating-grade LCP composite material comprises the following raw materials in percentage by mass:
74-89% of LCP composite resin, 10-25% of reinforcing filler and 0.2-1% of coupling agent.
Further, on the basis of the technical scheme of the invention, the raw materials of the electroplating-grade LCP composite material also comprise an auxiliary agent, wherein the auxiliary agent comprises any one or a combination of at least two of an antistatic agent, a lubricant, a plasticizer, a heat stabilizer, a light stabilizer or an antioxidant;
preferably, the auxiliary agent accounts for 0-5% of the electroplating-grade LCP composite material by mass.
The invention also provides a preparation method of the electroplating LCP composite material, which comprises the following steps:
and (3) carrying out surface treatment on the reinforcing filler by using a coupling agent, mixing with the LCP composite resin and optionally an auxiliary agent, and forming to obtain the electroplating LCP composite material.
Further, on the basis of the technical scheme, the mixing and molding temperature is 280-380 ℃;
preferably, a twin-screw extruder is used for mixing and molding.
The invention also provides an antenna which is made of the electroplating LCP composite material or the electroplating LCP composite material prepared by the preparation method.
Compared with the prior art, the invention has the following technical effects:
(1) the invention provides an electroplating LCP composite material, which is mainly prepared from LCP composite resin, reinforcing filler and a coupling agent, wherein the LCP composite resin is prepared from LCP matrix raw materials and specific polymer gel, and the formed LCP composite resin has a structure that the polymer gel is uniformly dispersed in the LCP matrix raw materials to form the LCP resin. Through adopting the LCP composite resin with the specific composition and the structure, the reinforcing filler and the coupling agent are compounded, so that the electroplating LCP composite material has lower dielectric loss and higher tensile strength and can be used for electroplating treatment.
(2) The invention provides a preparation method of an electroplating LCP composite material, which is simple to operate, stable in process and suitable for industrial mass production.
(3) The invention provides an antenna which is made of the electroplating LCP composite material. In view of the advantages of the electroplating LCP composite material, the prepared antenna has lower dielectric loss, and the antenna has higher bonding strength with the metal plating layer on the surface of the antenna, thereby meeting the use requirement of the communication antenna in outdoor severe environment.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the implementation, and it should be understood that the described embodiments are some, but not all embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
According to a first aspect of the present invention there is provided an electroplated grade LCP composite comprising the following raw materials in mass fractions:
70-99% of LCP composite resin, 0-30% of reinforcing filler and 0-2% of coupling agent;
the LCP composite resin takes LCP resin formed by LCP matrix raw materials as main resin, and high polymer gel is uniformly dispersed in the LCP resin;
the polymer gel comprises polyphenylene oxide resin and/or polystyrene resin.
Specifically, the LCP composite resin of the present invention is made of an LCP matrix material and a specific type of polymer gel, and the formed LCP composite resin is mainly made of an LCP resin formed of the LCP matrix material, and the polymer gel is uniformly dispersed in the LCP resin.
The LCP base material used varies depending on the kind of LCP resin. The kind of the LCP matrix material is not particularly limited and may be selected according to the actual situation.
The polymer gel may include a polyphenylene ether resin and/or a polystyrene resin. By "and/or" herein is meant that the polymer gel may comprise only polyphenylene ether resin, or only polystyrene resin, or both polyphenylene ether resin and polystyrene resin.
Specifically, polyphenylene ether resin, also called poly 2, 6-dimethyl-1, 4-phenylene oxide (PPO or PPE), has low water absorption, and the dielectric constant and dielectric loss are one of the smallest varieties in engineering plastics, and are hardly affected by temperature and humidity. However, in the case of an organic solvent, stress cracking occurs and the fluidity thereof is poor. When the LCP composite resin and the LCP resin form a specific structure, the characteristic of poor flowability of the LCP composite resin is favorably improved, and the dielectric loss of the LCP resin can be further reduced. The formation of pore-forming is facilitated during the electroplating process, and the binding force after electroplating is improved.
In an alternative embodiment of the present invention, the polyphenylene ether resin has a number average molecular weight of 1000 to 50000, preferably 2000 to 20000. The polyphenylene ether resin typically, but not by way of limitation, has a number average molecular weight of 1000, 2000, 5000, 10000, 20000, 30000, 40000, or 50000.
In an alternative embodiment of the present invention, the polyphenylene ether resin has a hydroxyl equivalent weight of 10 to 1000, preferably 200 to 900. The polyphenylene ether resin typically has, but is not limited to, a hydroxyl equivalent weight of 10, 50, 100, 200, 300, 400, 500, 600, 700, 800, 900 or 1000.
Polystyrene resin has a very low dielectric loss tangent and is not affected by changes in frequency, ambient temperature, and humidity, but is inferior in solvent resistance and oxidation resistance. Polystyrene is soluble in many solvents with similar solubility parameters, such as acetone, tetrachloroethane, styrene, benzene, chloroform, xylene, toluene, carbon tetrachloride, methyl ethyl ketone, esters, etc., and insoluble in, but swellable by, mineral oil, aliphatic hydrocarbons, diethyl ether, phenol, etc. Many non-solvent materials, such as higher alcohols and oils, can stress crack or swell polystyrene.
The invention finds that the LCP composite resin formed by the polystyrene resin and the LCP resin is beneficial to improving the characteristic of poor fluidity of the LCP composite resin and can further reduce the dielectric loss of the LCP resin. The formation of pore-forming is facilitated during the electroplating process, and the binding force after electroplating is improved.
In an alternative embodiment of the present invention, the polystyrene resin has a number average molecular weight of 1000 to 200000, preferably 10000 to 100000. The polystyrene resin typically, but not limited to, has a number average molecular weight of 1000, 2000, 5000, 10000, 20000, 40000, 50000, 60000, 80000, 100000, 120000, 140000, 150000, 160000, 180000, or 200000.
The addition of the high polymer gel in the LCP resin forming process can enable the high polymer gel to be uniformly dispersed in the LCP resin, and the obtained LCP composite resin has proper initial flow temperature, dielectric constant and dielectric loss.
Typical but non-limiting mass fractions of LCP composite resin in the electroplated grade LCP composite material are 70%, 72%, 75%, 78%, 80%, 82%, 85%, 88%, 90%, 92%, 94%, 95%, 96%, 98%, or 99%. Typical but non-limiting mass fractions of reinforcing fillers are 0%, 2%, 5%, 8%, 10%, 12%, 15%, 18%, 20%, 22%, 24%, 25%, 26%, 28% or 30%. Typical but not limiting mass fractions of coupling agent are 0%, 0.1%, 0.2%, 0.5%, 0.8%, 1.0%, 1.2%, 1.5%, 1.6%, 1.8% or 2.0%.
The electroplating LCP composite material provided by the invention is mainly prepared from LCP composite resin, reinforcing filler and a coupling agent, wherein the LCP composite resin is prepared from LCP matrix raw materials and specific polymer gel, and the formed LCP composite resin has a structure that the polymer gel is uniformly dispersed in the LCP matrix raw materials to form the LCP resin. The LCP composite resin with the specific composition and structure is compounded with the reinforcing filler and the coupling agent, so that the electroplating LCP composite material has low dielectric loss and high tensile strength and can be used for electroplating treatment.
The LCP resin formed has a different structure depending on the LCP matrix material. As an alternative embodiment of the present invention, the LCP resin includes at least one structural repeating unit of an aromatic hydroxycarboxylic acid repeating unit, an aromatic diol repeating unit, and an aromatic dicarboxylic acid repeating unit in its structure.
The aromatic hydroxycarboxylic acid repeating units are derived from at least one of the following, such as: 2-hydroxy-3-naphthoic acid, 2-hydroxy-6-naphthoic acid, 1-hydroxy-5-naphthoic acid, p-hydroxybenzoic acid, m-hydroxybenzoic acid, 4-hydroxy-4' -carboxydiphenyl ether, and aromatic hydroxycarboxylic acids in which a part of the hydrogen atoms in the aromatic ring of the above aromatic hydroxycarboxylic acids is substituted with one or more substituents selected from the group consisting of alkyl groups, aryl groups, halogen atoms, and the like. In the production of the LCP resin, the aromatic hydroxycarboxylic acid may be used alone, or two or more of the above aromatic hydroxycarboxylic acids may be used in combination.
The aromatic hydroxycarboxylic acid unit is preferably p-hydroxybenzoic acid and/or 2-hydroxy-6-naphthoic acid, and more preferably 2-hydroxy-6-naphthoic acid, from the viewpoint of obtaining excellent properties such as high heat resistance, low dielectric constant, and low loss.
The aromatic dicarboxylic acid repeating units are derived from at least one of the following, such as: 2,6 '-naphthalenedicarboxylic acid, isophthalic acid, terephthalic acid, 4' -biphenyldicarboxylic acid, 4 '-dicarboxylic acid-diphenylsulfide, 4' -dicarboxylic acid-diphenylether, and aromatic dicarboxylic acids in which a part of the hydrogen atoms in the aromatic ring of the aromatic dicarboxylic acid is substituted with one or more substituents selected from alkyl groups, aryl groups, halogen atoms, and the like. In the production of the LCP resin, the aromatic dicarboxylic acid may be used alone, or two or more of the above aromatic dicarboxylic acids may be used in combination.
The aromatic dicarboxylic acid unit is preferably terephthalic acid, isophthalic acid, 4 '-biphenyldicarboxylic acid, and 2, 6' -naphthalenedicarboxylic acid, and more preferably 4,4 '-biphenyldicarboxylic acid and 2, 6' -naphthalenedicarboxylic acid, from the viewpoint of obtaining excellent properties such as high heat resistance, low dielectric constant, and low loss.
The aromatic diol repeat units are derived from at least one of the following, such as: 2,6 ' -dihydroxynaphthalene, 1,5 ' -dihydroxynaphthalene, 4 ' -dihydroxybiphenyl, 4 ' -dihydroxybenzophenone, 1, 2-bis (4-hydroxyphenyl) ethane, 4 ' -dihydroxydiphenyl ether, 4 ' -dihydroxydiphenyl sulfone, 4 ' -dihydroxydiphenyl sulfide, bis (4-hydroxyphenyl) methane, resorcinol, hydroquinone and an aromatic diol in which a part of the hydrogen atoms in the aromatic ring of the aromatic diol is substituted with one or more substituents such as an alkyl group, an aryl group and a halogen atom. In the production of the LCP resin, the aromatic diol may be used alone, or two or more aromatic diols may be used in combination.
The aromatic diol unit is preferably 4,4 '-biphenol or hydroquinone, and more preferably 4, 4' -biphenol, from the viewpoint of obtaining excellent properties such as high heat resistance, low dielectric constant, and low loss.
As an alternative embodiment of the present invention, a method for preparing an LCP composite resin includes the steps of:
and mixing the LCP matrix raw material and the high polymer gel, and carrying out polymerization reaction to obtain the LCP composite resin.
It is understood that the LCP composite resin is an LCP resin as a main resin, and a high polymer gel is added in the process of forming (polymerizing) the LCP matrix material into the LCP resin. The polymer gel is added at the initial stage of formation (initial stage of polymerization) or at the final stage of formation (final stage of polymerization), and is not limited herein.
It should be noted that the polymer gel is added during the polymerization, not after the polymerization is completed. The timing of the addition of the polymer gel is selected to ensure that the polymer gel is uniformly dispersed in the LCP resin polymerized from the LCP matrix material.
As an optional embodiment of the invention, the LCP composite resin is taken as a whole, and the mass ratio of the LCP resin formed by the LCP matrix raw material to the high polymer gel is (60-97%): (3% -40%); the typical but non-limiting mass ratio of LCP resin and polymer gel is 60%: 40% and 65%: 35% and 70%: 30% and 75%: 25% and 80%: 20% and 85%: 15% and 90%: 10% and 95%: 5%, or 97%: 3 percent.
As an alternative embodiment of the invention, the temperature of the polymerization reaction is 200-400 ℃ and the time is 1-24 h.
Typical but not limiting polymerization temperatures are 200 ℃, 220 ℃, 250 ℃, 260 ℃, 280 ℃, 300 ℃, 320 ℃, 350 ℃, 360 ℃, 380 ℃ or 400 ℃, and typical but not limiting polymerization times are 1h, 2h, 5h, 8h, 10h, 12h, 15h, 16h, 18h, 20h or 24 h.
The LCP composite resin has more proper initial flow temperature (greater than or equal to 280 ℃), dielectric constant (not greater than 3.5) and dielectric loss (not greater than 0.005) through the definition of the mass ratio of the LCP resin to the high polymer gel and the polymerization temperature.
As an optional embodiment of the invention, the initial flow temperature of the LCP composite resin is 280-380 ℃; typical but non-limiting initial flow temperatures for LCP composite resins are 280 ℃, 300 ℃, 320 ℃, 340 ℃, 350 ℃, 360 ℃ or 380 ℃.
As an alternative embodiment of the present invention, the LCP composite resin has a dielectric constant of 2.5 to 3.5; typical, but non-limiting, dielectric constants of LCP composite resins are 2.5, 2.6, 2.8, 3.0, 3.2, 3.4, or 3.5.
As an alternative embodiment of the present invention, the dielectric loss of the LCP composite resin is 0 to 0.005. Typical, but not limiting, dielectric losses for LCP composite resins are 0.001, 0.002, 0.003, 0.004, or 0.005.
As an alternative embodiment of the present invention, the reinforcing filler comprises a fibrous reinforcing filler and/or a powdery reinforcing filler;
preferably, the fibrous reinforcing filler comprises any one of glass fiber, quartz fiber, basalt fiber, liquid crystal polymer fiber or polyether ketone fiber or a combination of at least two of the same;
preferably, the powder reinforcing filler comprises any one of silica, alumina, aluminum nitride, boron nitride, forsterite, barium titanate, calcium titanate, titanium dioxide or glass beads or a combination of at least two of them.
The reinforcing filler mainly plays a role in increasing the mechanical strength of the material, and can adjust the dielectric property of the material, for example, the dielectric constant of the material can be increased to more than 4.0 by adding common glass fibers, or the dielectric constant of the material can be reduced to less than 2.0 by adding hollow glass beads, so that the cost is reduced.
As an alternative embodiment of the present invention, the coupling agent includes any one of a titanate coupling agent, a silane coupling agent, a borate coupling agent, an aluminum titanium composite coupling agent, or an aluminate coupling agent, or a combination of at least two thereof. Among them, the silane coupling agent preferably includes a mercapto-type silane coupling agent and/or an isocyanate-type coupling agent.
The coupling agent is mainly used for enhancing the bonding force between the reinforcing material and the LCP composite resin, and simultaneously can increase the hydrophilicity of the LCP composite material, thereby being beneficial to the subsequent water electroplating.
As an optional embodiment of the invention, the electroplating-grade LCP composite material comprises the following raw materials in percentage by mass:
74 to 94 percent of LCP composite resin, 5 to 25 percent of reinforcing filler and 0.1 to 1.5 percent of coupling agent;
preferably, the electroplating grade LCP composite material comprises the following raw materials in mass fraction:
74-89% of LCP composite resin, 10-25% of reinforcing filler and 0.2-1% of coupling agent.
By further limiting the dosage of each raw material in the electroplating LCP composite material, the composite material has high strength, the tensile strength is more than 100MPa, the dielectric property can be adjusted in a wide range, and the electroplating bonding force is more than 5N and can exceed 10N at most.
As an alternative embodiment of the present invention, the raw material of the electroplating-grade LCP composite further comprises an auxiliary agent, which comprises any one or a combination of at least two of an antistatic agent, a lubricant, a plasticizer, a heat stabilizer, a light stabilizer, or an antioxidant.
The electroplating LCP composite material can be endowed with corresponding characteristics by adding auxiliaries such as an antistatic agent, a lubricant, a plasticizer, a heat stabilizer, a light stabilizer or an antioxidant into the electroplating LCP composite material.
As an optional embodiment of the invention, the additive accounts for 0-5% of the mass fraction of the electroplating-grade LCP composite material.
The adjuvant is typically, but not limited to, 0%, 0.5%, 0.8%, 1.0%, 1.2%, 1.5%, 1.8%, 2.0%, 2.2%, 2.5%, 2.8%, 3.0%, 3.2%, 3.5%, 3.8%, 4.0%, 4.2%, 4.5%, 4.8%, or 5.0% by mass of the electroplating grade LCP composite.
Meanwhile, the metal plating layer can be deposited on the surface of the LCP composite material by adopting the existing ABS electroplating process, so that the cost is low and the maintenance is convenient.
According to a second aspect of the present invention there is also provided a method of preparing an electroplated grade LCP composite, comprising the steps of:
and (3) carrying out surface treatment on the reinforcing filler by using a coupling agent, mixing with the LCP composite resin and optionally an auxiliary agent, and forming to obtain the electroplating LCP composite material.
In the present invention, "optional auxiliary" means that the auxiliary may be added or not added, and may be selectively added according to the actual situation.
The specific equipment used for kneading and molding is not limited here, as long as kneading and molding of each raw material can be achieved.
The preparation method of the electroplating LCP composite material has simple operation and stable process, and is suitable for industrial mass production.
As an optional implementation manner of the invention, the mixing and molding temperature is 280-380 ℃; typical but non-limiting kneading temperatures are 280 ℃, 300 ℃, 320 ℃, 340 ℃, 350 ℃, 360 ℃ or 380 ℃.
In an alternative embodiment of the present invention, a twin-screw extruder is used for kneading and molding.
According to a third aspect of the present invention, there is also provided an antenna made from the above electroplated LCP composite or the electroplated LCP composite made by the above method.
In view of the advantages of the electroplating LCP composite material, the prepared antenna has lower dielectric loss, and the antenna has higher bonding strength with the metal plating layer on the surface of the antenna, thereby meeting the use requirement of the communication antenna in outdoor severe environment.
The present invention will be further described with reference to specific examples and comparative examples.
Example 1
The embodiment provides an electroplating LCP composite material, which comprises the following raw materials in percentage by mass:
79% of LCP composite resin, 20% of reinforcing filler and 1% of coupling agent.
The LCP composite resin takes LCP resin formed by LCP matrix raw materials as main resin, and high polymer gel is uniformly dispersed in the LCP resin; the LCP resin comprises repeating units of p-hydroxybenzoic acid, 4-biphenol, terephthalic acid and isophthalic acid, the high polymer gel is polyphenyl ether resin (the number average molecular weight is 10000, the content of terminal hydroxyl is 900), the LCP composite resin is taken as a whole, and the mass ratio of the LCP resin to the high polymer gel is 90%: 10 percent; the reinforcing filler is quartz fiber; the coupling agent is titanate coupling agent (Nanjing eosin chemical industry group, model: SG-TnBT).
The preparation method of the LCP composite resin comprises the following steps:
2760g (20mol) of p-hydroxybenzoic acid, 1860g (10mol) of 4, 4-biphenol, 415g (2.5mol) of isophthalic acid, 1245g (7.5mol) of terephthalic acid, 4284g (42mol) of acetic anhydride and 5.28g (0.04mol) of potassium phenoxide are added into a reaction kettle provided with a stirring device, a thermometer and a reflux condenser, nitrogen is used for purging and replacing air in the reaction kettle, the temperature is raised to 140 ℃ and is kept for 2 hours for acetylation reaction, then the temperature is raised to 340 ℃, by-product acetic acid generated by polymerization of the mixture and unreacted acetic anhydride are timely discharged during the heating, finally the vacuum is pumped to 133Pa, and the vacuum pumping is stopped until the stirring torque rises.
Adding 618g of polyphenyl ether resin into a reaction kettle, continuously reacting for 30min, and then pressurizing and discharging with nitrogen to obtain a prepolymer; and crushing the prepared prepolymer, performing solid-phase tackifying under a vacuum condition, and keeping the temperature at 240 ℃ for 18 hours to obtain the LCP composite resin.
The LCP composite resin is detected to have the initial flow temperature of 320 ℃, the dielectric constant of 2.8 and the dielectric loss of 0.0012.
The preparation method of the electroplating-grade LCP composite material comprises the following steps:
adding the reinforcing filler into a high-speed mixer, adding the coupling agent after the temperature is raised to 130 ℃, continuously stirring for 2 hours, and taking out for later use;
and adding the LCP composite resin into a double-screw extruder through a main feeding machine, simultaneously adding the reinforcing filler treated by the coupling agent into a side feeding machine, carrying out melt extrusion at the temperature of 325 ℃, and carrying out granulation at the double-screw rotating speed of 300RMP to obtain the electroplating-grade LCP composite material.
Example 2
This example provides an electroplated grade LCP composite, except that the high polymer gel in the LCP composite resin is replaced by a polyphenylene ether resin with number average molecular weight of 10000 and terminal hydroxyl group content of 900, instead of a polyphenylene ether resin with number average molecular weight of 50000 and terminal hydroxyl group content of 300, the other raw materials and amounts are the same as in example 1.
The LCP composite resin is detected to have the initial flow temperature of 320 ℃, the dielectric constant of 2.8 and the dielectric loss of 0.0011.
The preparation method of the electroplated grade LCP composite provided in this example is the same as in example 1.
Example 3
This example provides an electroplated grade LCP composite material, except that 618g of polystyrene resin (number average molecular weight of 50000) is added to the LCP composite resin, i.e. the polymer gel in this example is a mixture of polyphenylene ether resin and polystyrene resin, and the other raw materials and amounts are the same as in example 1.
The LCP composite resin is detected to have the initial flow temperature of 315 ℃, the dielectric constant of 2.7 and the dielectric loss of 0.0012.
The preparation method of the above-mentioned electroplated grade LCP composite provided in this example is the same as in example 1.
Example 4
This example provides an electroplated LCP composite material, except that the LCP composite resin in the electroplated LCP composite material was replaced by 69% by mass, the reinforcing filler was replaced by 30% by mass, and the amounts of the other raw materials were the same as in example 1.
The preparation method of the above-mentioned electroplated grade LCP composite provided in this example is the same as in example 1.
Example 5
This example provides an electroplated LCP composite material, except that the mass fraction of the LCP composite resin in the electroplated LCP composite material is replaced by 89%, the mass fraction of the reinforcing filler is replaced by 10%, and the amounts of the other raw materials and the preparation method are the same as those in example 1.
The preparation method of the above-mentioned electroplated grade LCP composite provided in this example is the same as in example 1.
Example 6
The embodiment provides an electroplating LCP composite material, which comprises the following raw materials in percentage by mass:
76.7 percent of LCP composite resin, 20 percent of reinforcing filler, 1 percent of coupling agent, 0.3 percent of antioxidant and 2 percent of plasticizer.
The LCP composite resin takes LCP resin formed by LCP matrix raw materials as main resin, and high polymer gel is uniformly dispersed in the LCP resin; the LCP resin comprises repeating units of p-hydroxybenzoic acid, 4-biphenol, terephthalic acid and isophthalic acid, the high polymer gel is polyphenyl ether resin (the number average molecular weight is 10000, the content of terminal hydroxyl is 900), the LCP composite resin is taken as a whole, and the mass ratio of the LCP resin to the high polymer gel is 90%: 10 percent; the reinforcing filler is quartz fiber; the coupling agent is titanate coupling agent (Nanjing eosin chemical industry group, model SG-TnBT); antioxidant (available from Bluggeman, model H161); the plasticizer was a polyester plasticizer (type W-2050, produced by Nippon DIC Co., Ltd.).
The LCP composite resin in this example was prepared in the same manner as in example 1.
The electroplated LCP composite was prepared in the same manner as in example 1, except that the coupling agent treated reinforcing filler was added in the preparation of the electroplated LCP composite, and the antioxidant and plasticizer were also added.
Example 7
The embodiment provides an electroplating LCP composite material, which comprises the following raw materials in percentage by mass:
79% of LCP composite resin, 20% of reinforcing filler and 1% of coupling agent.
The LCP composite resin takes LCP resin formed by LCP matrix raw materials as main resin, and high polymer gel is uniformly dispersed in the LCP resin; the LCP resin comprises the repeating units of p-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid, the high polymer gel is polyphenyl ether resin (the number average molecular weight is 10000, the content of terminal hydroxyl is 300), and the LCP composite resin is taken as a whole, and the mass ratio of the LCP resin to the high polymer gel is 90%: 10 percent; the reinforcing filler is hollow glass beads; the coupling agent is a silane coupling agent KH 550.
The preparation method of the LCP composite resin comprises the following steps:
4110g (30mol) of p-hydroxybenzoic acid, 1880g (10mol) of 6-hydroxy-2-naphthoic acid, 4488g of acetic anhydride and 1.2g of potassium acetate are added into a reaction kettle provided with a stirring device, a thermometer and a reflux condenser, nitrogen is used for purging and replacing air in the reaction kettle, the temperature is increased to 140 ℃ for heat preservation for 2 hours for acetylation reaction, then the temperature is increased to 340 ℃, by-product acetic acid generated by polymerization and unreacted acetic anhydride are timely discharged during the heating, finally, the vacuum pumping is carried out until the stirring torque rises, and the vacuum pumping is stopped.
Adding 586g of polyphenyl ether resin into a reaction kettle, continuously reacting for 30min, and then pressurizing and discharging with nitrogen to obtain a prepolymer; and crushing the prepared prepolymer, performing solid-phase tackifying under a vacuum condition, and keeping the temperature at 230 ℃ for 18 hours to obtain the LCP composite resin.
The LCP composite resin is detected to have the initial flow temperature of 300 ℃, the dielectric constant of 2.7 and the dielectric loss of 0.0009.
The preparation method of the electroplating LCP composite material comprises the following steps:
adding the reinforcing filler into a high-speed mixer, adding the coupling agent after the temperature is raised to 130 ℃, continuously stirring for 2 hours, and taking out for later use;
and adding the LCP composite resin into a double-screw extruder through a main feeding machine, simultaneously adding the reinforcing filler treated by the coupling agent into a side feeding machine, carrying out melt extrusion at the temperature of 310 ℃, and carrying out granulation at the double-screw rotating speed of 300RMP to obtain the electroplating-grade LCP composite material.
Example 8
This example provides an electroplated grade LCP composite material, which has the same raw materials and amounts as example 7 except that the high polymer gel in the LCP composite resin is replaced by a polystyrene resin (number average molecular weight is 10000) instead of a polyphenylene ether resin.
Through detection, the initial flow temperature of the LCP composite resin is 290 ℃, the dielectric constant is 2.7, and the dielectric loss is 0.0010.
This example provides an electroplated grade LCP composite prepared in the same manner as example 7.
Example 9
This example provides an electroplated LCP composite, which is prepared by replacing the high polymer gel in the LCP composite resin with a polystyrene resin (number average molecular weight 100000) and using the same materials and amounts as in example 7.
The LCP composite resin is detected to have the initial flow temperature of 295 ℃, the dielectric constant of 2.6 and the dielectric loss of 0.0009.
This example provides the same preparation method for the above-described electroplated grade LCP composite as example 7.
Comparative example 1
This comparative example provides an electroplating-grade LCP composite material, including the following raw materials by mass fraction:
68% of LCP composite resin, 30% of reinforcing filler and 2% of coupling agent.
The kind and preparation method of LCP composite resin was the same as in example 1, and the preparation method of plating grade LCP composite material was the same as in example 1.
Comparative example 2
This comparative example provides an electroplated-grade LCP composite, except that the high polymer gel in the LCP composite resin was replaced with a thermoplastic elastomer TPE (DuPont G4774, USA), and the amounts of the other raw materials, the preparation method of the LCP composite resin, and the preparation method of the electroplated-grade LCP composite were the same as those of example 1.
The LCP composite resin is detected to have the initial flow temperature of 317 ℃, the dielectric constant of 2.9 and the dielectric loss of 0.0015.
Comparative example 3
This comparative example provides an electroplating-grade LCP composite, except that the high polymer gel in the LCP composite resin was replaced with thermoplastic elastomer TPO (exxonmobil chemical CMV241), and the amounts of the other raw materials, the preparation method of the LCP composite resin, and the preparation method of the electroplating-grade LCP composite were the same as in example 1.
The LCP composite resin is detected to have the initial flow temperature of 314 ℃, the dielectric constant of 3.0 and the dielectric loss of 0.0018.
Comparative example 4
This comparative example provides an electroplated-grade LCP composite, except that the high polymer gel in the LCP composite resin was replaced with thermoplastic elastomer TPU (cigarette tai wanghua polyurethane gmbh, WHT-2195), and the amounts of the other raw materials, the preparation method of the LCP composite resin, and the preparation method of the electroplated-grade LCP composite were the same as in example 1.
The LCP composite resin is detected to have the initial flow temperature of 312 ℃, the dielectric constant of 3.0 and the dielectric loss of 0.0017.
Comparative example 5
This comparative example provides an electroplating-grade LCP composite material, including the following raw materials by mass fraction:
71.1 percent of LCP resin, 7.9 percent of high polymer gel, 20 percent of reinforcing filler and 1 percent of coupling agent.
Wherein the LCP resin is prepared from LCP matrix raw materials, and the high polymer gel is polyphenyl ether resin (with the number average molecular weight of 10000 and the content of terminal hydroxyl groups of 900); the reinforcing filler is quartz fiber; the coupling agent is titanate coupling agent (Nanjing eosin chemical industry group, model: SG-TnBT).
The preparation method of the LCP resin comprises the following steps:
2760g (20mol) of p-hydroxybenzoic acid, 1860g (10mol) of 4, 4-biphenol, 415g (2.5mol) of isophthalic acid, 1245g (7.5mol) of terephthalic acid, 4284g (42mol) of acetic anhydride and 5.28g (0.04mol) of potassium phenoxide are added into a reaction kettle provided with a stirring device, a thermometer and a reflux condenser, nitrogen is used for purging and replacing air in the reaction kettle, the temperature is raised to 140 ℃ and is kept for 2 hours for acetylation reaction, then the temperature is raised to 340 ℃, by-product acetic acid generated by polymerization and unreacted acetic anhydride are timely discharged during the heating, finally the vacuum is pumped to 133Pa, the vacuum pumping is stopped after the stirring torque rises, the reaction is continued for 30min, and then nitrogen is used for pressurizing and discharging to obtain a prepolymer.
And crushing the prepared prepolymer, performing solid-phase tackifying under a vacuum condition, and keeping the temperature at 240 ℃ for 18 hours to obtain the LCP resin.
The preparation method of the electroplating LCP composite material comprises the following steps:
adding the reinforcing filler into a high-speed mixer, adding the coupling agent after the temperature is raised to 130 ℃, continuously stirring for 2 hours, and taking out for later use;
and uniformly mixing the high polymer gel and the LCP resin, adding the mixture into a double-screw extruder through a main feeding machine, simultaneously adding a reinforcing filler treated by a coupling agent into a side feeding machine, carrying out melt extrusion at the temperature of 325 ℃, and carrying out granulation at the double-screw rotating speed of 300RMP to obtain the electroplating-grade LCP composite material.
Comparative example 6
The present comparative example provides a liquid crystalline polymer composite of the prior art comprising the following raw materials in weight percent:
44% of liquid crystal polymer resin (LCP), 10% of polyamide resin (PA6), 20% of thermoplastic elastomer (TPE), 5% of glass fiber, 20% of inorganic mineral powder silicon oxide and KH 5501% of silane coupling agent.
The preparation method of the liquid crystal polymer composite for environment-friendly electroplating comprises the following steps:
(1) LCP, PA6 and TPE are added into an internal mixer through a main feeder to carry out melt polymerization to obtain a blend for later use;
(2) adding inorganic mineral powder silicon oxide into a high-speed mixer, adding a coupling agent KH550 for reaction when the temperature of the inorganic mineral powder silicon oxide is raised to 120 ℃, and taking out for later use, wherein the reaction time is 25 min;
(3) and (2) adding the blend obtained in the step (1) into a double-screw extruder through a main feeder, simultaneously adding the inorganic mineral powder silicon oxide and the glass fiber 301HP which are processed in the step (2) into a side feeder, mixing, controlling the temperature at 305 ℃ for melt extrusion, and granulating at the double-screw rotating speed of 300RMP to obtain the liquid crystal polymer compound.
To verify the technical effects of the respective examples and comparative examples, the following experiments were conducted.
Experimental example 1
The dielectric loss, tensile properties, plating bonding strength and high temperature resistance of the LCP composite materials provided in examples 1 to 9 and comparative examples 1 to 6 were measured, and the specific results are shown in table 1.
Wherein, the test conditions of the dielectric loss are as follows: the frequency was measured at 10GHz using an apparatus Agilent N5230A, clamp SPDR.
Tensile Strength dumbbell-shaped test specimens were prepared according to ISO 527-2012 test method for tensile Properties of plastics, with a tensile speed of 2mm/min and a longitudinal axis of tension, and the tensile strength at failure of the test specimens was recorded. The sample should be conditioned for no less than 40 hours at 23 + -2 deg.C (73.4 + -3.6 deg.F) and 50 + -5% relative humidity prior to testing.
The plating adhesion refers to the bonding strength between the plating and the base resin or the intermediate plating, i.e., the force required to peel the plating per unit surface area from the base resin or the intermediate plating. The LCP composite materials prepared in each example and comparative example were prepared into 60 × 120 × 2mm plates by an injection molding machine, then plated by an ABS plating line, cut into a 10 × 80mm strip on the surface of the plate with a knife, adhered to the width of the strip-shaped plating layer with 3M adhesive paper, and then tested by a universal testing machine for the maximum force required to separate the plating layer from the plate, which was the plating bonding force.
The high temperature performance test was performed by preparing the LCP composite material of each example and comparative example into 20 pieces of 60 x 120 x 2mm sheet material, and then using reflow soldering, all the temperatures were set to 275 ℃ and the residence time was 60 s. The high-temperature resistance of the material is judged by observing the deformation of the plates, and the less the number of the deformed plates is, the better the high-temperature resistance is.
TABLE 1
As can be seen from the data in Table 1, each example of the present invention provides LCP composites having superior properties to the comparative examples. Specifically, the LCP composite material of each embodiment of the invention has low dielectric loss which can be as low as 0.0011, high mechanical strength (tensile strength), excellent temperature resistance, and plating layer bonding force after electroplating which is more than 5N and can be more than 10N at most.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (18)
1. An electroplating LCP composite material is characterized by comprising the following raw materials in percentage by mass:
70-99% of LCP composite resin, 0-30% of reinforcing filler and 0-2% of coupling agent;
the LCP composite resin takes LCP resin formed by LCP matrix raw materials as main resin, and high polymer gel is uniformly dispersed in the LCP resin;
the high polymer gel is polyphenyl ether resin and/or polystyrene resin;
the preparation method of the LCP composite resin comprises the following steps:
and mixing the LCP matrix raw material and the high polymer gel, and carrying out polymerization reaction to obtain the LCP composite resin.
2. A plated grade LCP composite material according to claim 1, wherein the LCP matrix material forms an LCP resin to polymer gel mass ratio of (60% to 97%) with the LCP composite resin as a whole: (3% -40%).
3. A plated grade LCP composite according to claim 1, wherein the temperature of the polymerisation reaction is 200-.
4. An electroplated grade LCP composite as claimed in claim 2, wherein the LCP composite resin onset flow temperature is 280-380 ℃.
5. An electroplated grade LCP composite as claimed in claim 2, wherein the LCP composite resin has a dielectric constant of 2.5-3.5.
6. An electroplated grade LCP composite as claimed in claim 2, wherein the dielectric loss of the LCP composite resin is 0-0.005.
7. An electroplated-grade LCP composite as claimed in claim 1, wherein the reinforcing filler comprises a fibrous reinforcing filler and/or a powdered reinforcing filler.
8. An electroplated grade LCP composite of claim 7, wherein the fibrous reinforcing filler comprises any one of, or a combination of at least two of, glass fibers, quartz fibers, basalt fibers, liquid crystal polymer fibers, or polyetherketone fibers.
9. An electroplated grade LCP composite as claimed in claim 7, wherein the powder reinforcing filler comprises any one or combination of at least two of silica, alumina, aluminum nitride, boron nitride, forsterite, barium titanate, calcium titanate, titanium dioxide or glass beads.
10. The electroplated grade LCP composite of claim 1, wherein the coupling agent comprises any one of a titanate coupling agent, a silane coupling agent, a borate coupling agent, an aluminum titanium composite coupling agent, or an aluminate coupling agent, or a combination of at least two thereof.
11. An electroplated grade LCP composite as claimed in any one of claims 1 to 10, comprising the following raw materials in mass fraction:
74 to 94 percent of LCP composite resin, 5 to 25 percent of reinforcing filler and 0.1 to 1.5 percent of coupling agent.
12. The electroplated grade LCP composite of any one of claims 1 to 10, comprising the following raw materials in mass fraction:
74-89% of LCP composite resin, 10-25% of reinforcing filler and 0.2-1% of coupling agent.
13. An electroplated-grade LCP composite of any one of claims 1 to 10, wherein the raw materials of the electroplated-grade LCP composite further comprise an auxiliary agent, the auxiliary agent comprising any one or a combination of at least two of an antistatic agent, a lubricant, a plasticizer, a heat stabilizer, a light stabilizer, or an antioxidant.
14. The electroplated grade LCP composite of claim 13, wherein the adjuvant comprises 0-5% by weight of the electroplated grade LCP composite.
15. A method of making an electroplated grade LCP composite of any one of claims 1 to 14, comprising the steps of:
and (3) carrying out surface treatment on the reinforcing filler by using a coupling agent, mixing with the LCP composite resin and optionally an auxiliary agent, and forming to obtain the electroplating LCP composite material.
16. The method as claimed in claim 15, wherein the mixing temperature is 280-380 ℃.
17. The method according to claim 15, wherein the kneading and molding are carried out by a twin-screw extruder.
18. An antenna made from a plated grade LCP composite material according to any one of claims 1 to 14 or made by the method of any one of claims 15 to 17.
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