CN111138815A - Low-dielectric-constant liquid crystal polymer and preparation method thereof - Google Patents
Low-dielectric-constant liquid crystal polymer and preparation method thereof Download PDFInfo
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- CN111138815A CN111138815A CN201911373943.8A CN201911373943A CN111138815A CN 111138815 A CN111138815 A CN 111138815A CN 201911373943 A CN201911373943 A CN 201911373943A CN 111138815 A CN111138815 A CN 111138815A
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
- C08K7/28—Glass
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/14—Glass
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Abstract
The invention provides a low dielectric constant liquid crystal polymer, which comprises the following components in parts by weight: 50-90 parts of wholly aromatic liquid crystal polyester resin; 10-30 parts of hollow glass beads; wherein the diameter of the hollow glass bead is 10-50 μm. The low dielectric constant liquid crystal polymer takes wholly aromatic liquid crystal polyester resin as a matrix material, hollow glass beads with the diameter of 10-50 mu m are added, the wholly aromatic liquid crystal polyester resin is modified by the hollow glass beads, the hollow glass beads are hollow and have hard shells, the shells are thin gas, and the hollow glass beads with the hollow structures are added, so that the hollow glass beads and the wholly aromatic liquid crystal polyester resin are mixed, and the overall dielectric constant of the prepared liquid crystal polymer is reduced.
Description
Technical Field
The invention relates to the field of high-molecular composite materials, in particular to a low-dielectric-constant liquid crystal polymer and a preparation method thereof.
Background
A Liquid Crystal Polymer (LCP) is an intermediate state polymer between a solid crystal and a liquid, and its molecular arrangement is not three-dimensionally ordered as in the solid crystal but is not disordered as in the liquid, but rather has a certain (one-dimensional or two-dimensional) order. It is a novel polymer material which generally exhibits liquid crystallinity in a molten state. The material has excellent heat resistance and forming processing performance.
Liquid crystal polymers can be further classified into lyotropic liquid crystal polymers and thermotropic liquid crystal polymers. The former is in a liquid crystal state in a solvent, and the latter is in a liquid crystal state due to a change in temperature. The thermotropic liquid crystal polymer has more excellent comprehensive performance and can be processed by injection molding and extrusion molding. The liquid crystal polymer has rigid main chain, compact molecular packing and high orientation during forming, and thus has small linear expansion coefficient, low forming shrinkage, outstanding strength and elastic modulus, excellent heat resistance, high load deformation temperature up to 340 deg.c. LCP has excellent electrical insulation performance and has better dielectric strength than common engineering plastics. As an electronic and electrical application device, the electrical property of the material is hardly influenced when the continuous use temperature is 200-300 ℃, so that the material is widely applied to the fields of precise electronic zero devices and the like.
The Dielectric Constant (Dk) is called the Dielectric Constant, and refers to the amount of electrostatic energy that can be stored under a potential gradient per unit. In Printed Circuit Boards (PCBs) and flexible circuit boards (FPCs) used for high frequencies, the dielectric constant of a material is a factor affecting the propagation speed of signals thereof, and the smaller the dielectric constant, the more advantageous the propagation of signals thereof. The dielectric constant of the liquid crystal polymer is large, and the dielectric constant with a large value influences the signal propagation speed in the process of preparing electronic parts, so that the use is influenced.
Disclosure of Invention
The invention aims to provide a low dielectric constant liquid crystal polymer and a preparation method thereof, and aims to solve the problem that the dielectric constant of liquid crystal polyester resin is high and the signal propagation speed is influenced in the prior art.
In order to achieve the purpose, the invention adopts the following technical scheme:
a low dielectric constant liquid crystal polymer comprises the following components in parts by weight:
50-90 parts of wholly aromatic liquid crystal polyester resin;
10-30 parts of hollow glass beads;
wherein the diameter of the hollow glass bead is 10-50 μm.
And, a method for preparing a low dielectric constant liquid crystal polymer, the method comprising the steps of:
weighing the components according to the low dielectric constant liquid crystal polymer;
drying the wholly aromatic liquid crystal polyester resin and the hollow glass beads;
mixing the dried wholly aromatic liquid crystal polyester resin and the hollow glass beads to obtain a first mixture;
and melting and mixing the first mixture, extruding, bracing, cooling and granulating to obtain the low dielectric constant liquid crystal polymer.
The low dielectric constant liquid crystal polymer takes wholly aromatic liquid crystal polyester resin as a matrix material, hollow glass beads with the diameter of 10-50 mu m are added, the wholly aromatic liquid crystal polyester resin is modified by the hollow glass beads with the diameter of 10-50 mu m, the hollow glass beads are hollow structures, have hard shells, are thin gases in the shells, and have the dielectric constant of air approximate to 1, and the hollow glass beads with the hollow structures are added, so that the hollow glass beads and the wholly aromatic liquid crystal polyester resin are mixed, the overall dielectric constant of the prepared liquid crystal polymer is reduced, and the use of the liquid crystal polyester compound in the fields of electronic devices and the like is effectively improved.
The preparation method of the low dielectric constant liquid crystal polymer provided by the invention comprises the steps of drying the wholly aromatic liquid crystal polyester resin and the hollow glass beads, mixing, melting and mixing the mixture, extruding, drawing into strips, cooling and granulating to obtain the low dielectric constant liquid crystal polymer. The preparation method can ensure that all components are fully dispersed and mutually act, so that the prepared low dielectric constant liquid crystal polymer has low dielectric constant performance. Meanwhile, the preparation method has the advantages of simple process, less used equipment and stable performance of the prepared material, effectively reduces the production cost and is suitable for large-scale use.
Detailed Description
In order to make the objects, technical solutions and technical effects of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments obtained by a person of ordinary skill in the art without any inventive step in connection with the embodiments of the present invention shall fall within the scope of protection of the present invention.
In the description of the present invention, it is to be understood that the terms "first", "second" and the like are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implying any number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature. In the description of the present invention, "a plurality" means two or more unless specifically defined otherwise.
The embodiment of the invention provides a low dielectric constant liquid crystal polymer, which comprises the following components in parts by weight:
50-90 parts of wholly aromatic liquid crystal polyester resin;
10-30 parts of hollow glass beads;
wherein the diameter of the hollow glass bead is 10-50 μm.
The low dielectric constant liquid crystal polymer takes wholly aromatic liquid crystal polyester resin as a matrix material, hollow glass beads with the diameter of 10-50 mu m are added, the wholly aromatic liquid crystal polyester resin is modified by the hollow glass beads with the diameter of 10-50 mu m, the hollow glass beads are hollow structures, air is filled in the hollow glass beads, the dielectric constant of the air is close to 1, the hollow glass beads with the hollow structures are added, the hollow glass beads and the wholly aromatic liquid crystal polyester resin are mixed, the overall dielectric constant of the prepared liquid crystal polymer is reduced, and the use of the liquid crystal polyester compound in the fields of electronic devices and the like is effectively improved.
Specifically, the low dielectric constant liquid crystal polymer comprises 50-90 parts of a wholly aromatic liquid crystal polyester resin formed by polymerizing monomers, preferably at least two selected from the group consisting of a free aromatic diol, an aromatic diamine, an aromatic hydroxylamine, an aromatic dicarboxylic acid, an aromatic hydroxycarboxylic acid, and an aromatic aminocarboxylic acid. The wholly aromatic liquid crystal polyester resin is composed of the monomers, so that the wholly aromatic liquid crystal polyester resin has better performance, and the low dielectric constant liquid crystal polymer has more excellent heat resistance, dimensional stability and high mechanical property.
More preferably, the wholly aromatic liquid crystalline polyester resin contains the following repeating unit:
repeating units derived from an aromatic diol:
-O-Ar-O-；
repeating units derived from an aromatic diamine:
-HN-Ar-NH-；
repeating units from aromatic hydroxylamine:
-HN-Ar-O-；
repeating units derived from aromatic dicarboxylic acids:
-OC-Ar-CO-；
repeating units derived from aromatic hydroxycarboxylic acids:
-O-Ar-CO-；
repeating units from aromatic aminocarboxylic acids:
-HN-Ar-CO-；
ar is one of phenylene and derivatives thereof, biphenylene and derivatives thereof, naphthalene and derivatives thereof, and aromatic compounds and derivatives thereof, wherein the two phenylenes are bonded by carbon or non-carbon elements. The wholly aromatic liquid crystal polyester resin is used as a matrix material of the low dielectric constant liquid crystal polymer, contains the repeating unit, and can ensure that the prepared low dielectric constant liquid crystal polymer has high thermal stability and stable size.
Specifically, the low dielectric constant liquid crystal polymer comprises 50-90 parts of wholly aromatic liquid crystal polyester resin, and if the addition amount is too large, the addition of hollow glass beads is influenced, the synergistic effect of the hollow glass beads and the hollow glass beads is further influenced, and the dielectric constant of the liquid crystal polymer cannot be well reduced; if the amount is too small, the low dielectric constant liquid crystal polymer matrix material will be too small, affecting the heat resistance, dimensional stability and mechanical properties of the low dielectric constant liquid crystal polymer. In a specific embodiment of the present invention, the specific addition parts of the wholly aromatic liquid crystalline polyester resin may be: 50 parts, 55 parts, 60 parts, 65 parts, 70 parts, 75 parts, 80 parts, 85 parts and 90 parts.
Specifically, the low dielectric constant liquid crystal polymer comprises 10-30 parts of hollow glass beads, and the diameter of the hollow glass beads is 10-50 microns. The hollow glass beads with the diameter of 10-50 mu m are used for modifying the wholly aromatic liquid crystal polyester resin, the hollow glass beads are of hollow structures, air is filled in the hollow glass beads, the dielectric constant of the air is close to 1, the hollow glass beads with the hollow structures are added to mix the hollow glass beads with the wholly aromatic liquid crystal polyester resin, the overall dielectric constant of the prepared liquid crystal polymer is reduced, and the use of the liquid crystal polyester compound in the fields of electronic devices and the like is effectively improved. In specific application, for example, the low dielectric constant liquid crystal polymer is subjected to injection molding to obtain a PCB or an FPC, and the low dielectric constant liquid crystal polymer obtained by modifying the wholly aromatic liquid crystal polyester resin by using the hollow glass beads is subjected to injection molding, so that the prepared PCB or FPC has a low dielectric constant and the signal propagation speed of the PCB or FPC is improved.
Specifically, the diameter of the hollow glass bead is 10-50 μm. The hollow glass beads with the diameter are selected for modification, if the diameter of the hollow glass beads is too small, the hollow glass beads are easy to agglomerate, so that the hollow glass beads are not uniformly distributed, the dielectric property of the liquid crystal polymer cannot be reduced, and other properties such as the mechanical property and the like of the prepared low dielectric constant liquid crystal polymer are influenced; if the diameter of the hollow glass beads is too large, the fusion of the hollow glass beads and the wholly aromatic liquid crystal polyester resin is incomplete, so that the hollow glass beads are unevenly distributed, the dielectric property of the liquid crystal polymer cannot be reduced, and other properties such as the mechanical property of the prepared low dielectric constant liquid crystal polymer are influenced. Preferably, the diameter of the hollow glass bead is 20-30 μm, and the hollow glass bead with the diameter can be uniformly mixed with the wholly aromatic liquid crystal polyester resin, so that the dielectric constant of the prepared liquid crystal composite is low, and the preparation method is favorable for being applied to the fields of electronic devices and the like.
Preferably, the wall thickness of the hollow glass bead is 1-2 μm. The hollow glass beads are guaranteed to be of a hollow structure and have a hard shell, the shell is internally thin gas, the dielectric constant of air is approximate to 1, the hollow glass beads are favorably and uniformly mixed with the wholly aromatic liquid crystal polyester resin, and the dielectric constant of the prepared liquid crystal compound is guaranteed to be low.
Preferably, the hollow glass bead is selected from any one of 3M iM16K, SHENNA K80, 3M VS5500, 3MS60HS and 3M K46. In a preferred embodiment of the invention, the hollow glass beads are made of 3MiM16K, 3M iM16K is a light-weight non-metal multifunctional material, the circularity rate is more than 97% due to good fluidity, the shape is regular, the viscosity and the internal stress of the product can be reduced, and further preferably, the 3M iM16K hollow glass beads have the diameter of 20 microns and the wall thickness of 1 micron. The glass beads 3M iM16K are added, the hollow glass beads are of hollow structures and have hard shells, the shell is thin gas, the dielectric constant of air is approximate to 1, the hollow glass beads with the hollow structures are added, so that the hollow glass beads and the wholly aromatic liquid crystal polyester resin are mixed, the overall dielectric constant of the prepared liquid crystal polymer is reduced, and the use of the liquid crystal polyester compound in the fields of electronic devices and the like is effectively improved.
Preferably, the low dielectric constant liquid crystal polymer comprises 10-30 parts of hollow glass beads; if the addition amount is too much, the hollow glass beads are easy to agglomerate, so that the distribution is uneven, the dielectric property of the liquid crystal polymer cannot be reduced, and other properties such as the mechanical property and the like of the prepared low dielectric constant liquid crystal polymer are influenced; if the amount of the glass beads added is too small, fusion between the glass beads and the wholly aromatic liquid crystal polyester resin is incomplete, resulting in non-uniform distribution of the glass beads, and failing to lower the dielectric properties of the liquid crystal polymer. In the specific embodiment of the present invention, the specific addition parts of the hollow glass beads may be: 10 parts, 15 parts, 20 parts, 25 parts and 30 parts.
Preferably, the low dielectric constant liquid crystal polymer further comprises 0-30 parts of a filler. If the amount of the hollow glass microspheres added is too large, the synergistic effect between the hollow glass microspheres and the wholly aromatic liquid crystalline polyester resin is affected, and the dielectric constant of the prepared liquid crystalline polyester composite is further affected. Preferably, the filler is at least one selected from talc, whiskers, wollastonite, mica, titanium dioxide, carbon black, calcium carbonate, clay, barium sulfate and silica. In the specific embodiment of the present invention, the specific addition parts of the filler may be 0 part, 5 parts, 10 parts, 15 parts, 20 parts, 25 parts, and 30 parts.
The low dielectric constant liquid crystal polymer is prepared by the following preparation method of the low dielectric constant liquid crystal polymer.
Correspondingly, the embodiment of the invention also provides a preparation method of the low dielectric constant liquid crystal polymer.
The method comprises the following steps:
s01, weighing each component according to the low dielectric constant liquid crystal polymer;
s02, drying the wholly aromatic liquid crystal polyester resin and the hollow glass beads;
s03, mixing the dried wholly aromatic liquid crystal polyester resin and the hollow glass beads to obtain a first mixture;
and S04, melting and mixing the first mixture, extruding, bracing, cooling and granulating to obtain the low dielectric constant liquid crystal polymer.
The preparation method of the low dielectric constant liquid crystal polymer provided by the invention comprises the steps of drying the wholly aromatic liquid crystal polyester resin and the hollow glass beads, mixing, melting and mixing the mixture, extruding, drawing into strips, cooling and granulating to obtain the low dielectric constant liquid crystal polymer. The preparation method can ensure that all components are fully dispersed and mutually act, so that the prepared low dielectric constant liquid crystal polymer has low dielectric constant performance. Meanwhile, the preparation method has the advantages of simple process, less used equipment and stable performance of the prepared material, effectively reduces the production cost and is suitable for large-scale use.
In the step S01, the components of the wholly aromatic liquid crystal polyester resin and the hollow glass beads are weighed according to the low dielectric constant liquid crystal polymer, and the addition amount of the components is as described above, and will not be described herein again for the sake of brevity.
Preferably, the method for preparing the wholly aromatic liquid crystalline polyester resin comprises the steps of:
s011, providing at least 2 monomer substances, and carrying out polycondensation reaction to prepare a wholly aromatic liquid crystal polyester prepolymer;
and S012, carrying out solid-phase polycondensation on the wholly aromatic liquid crystal polyester prepolymer to prepare the wholly aromatic liquid crystal polyester resin.
In the above step S011, the monomer substance is selected from at least two of a free aromatic diol, an aromatic diamine, an aromatic hydroxylamine, an aromatic dicarboxylic acid, an aromatic hydroxycarboxylic acid, and an aromatic aminocarboxylic acid. The wholly aromatic liquid crystal polyester resin is composed of the monomers, so that the wholly aromatic liquid crystal polyester resin has better performance, and the low dielectric constant liquid crystal polymer has more excellent heat resistance, dimensional stability and high mechanical property.
Preferably, the monomer substance is pretreated by an acylation reagent, and the activity of the monomer substance is further improved by the pretreatment, so that the polycondensation reaction is facilitated. Further preferably, the acylating agent includes, but is not limited to, an acetylating agent. In a preferred embodiment of the invention, the monomer material is pretreated with an acetylating reagent to increase the activity of the monomer.
Further, in the step of performing a polycondensation reaction to prepare the wholly aromatic liquid crystalline polyester prepolymer, the polycondensation reaction is selected from a solution polycondensation method or a bulk polycondensation method. By adopting the polycondensation reaction, the wholly aromatic liquid crystal polyester prepolymer can be prepared simply, conveniently and rapidly, and the subsequent reaction is facilitated.
In the step S012, the wholly aromatic liquid crystal polyester prepolymer is subjected to a solid phase polycondensation reaction to prepare the wholly aromatic liquid crystal polyester resin. Preferably, the wholly aromatic liquid crystalline polyester prepolymer is subjected to a solid phase polycondensation reaction, and a heating treatment is required. The problem of heat treatment is further determined by the monomer species selected for reaction, since there are differences in the monomer species selected for reaction. More preferably, the heat treatment is performed by a method selected from the group consisting of a hot plate, hot air, and high-temperature fluid. Further, in order to remove by-products of the solid state polycondensation reaction, purging with an inert gas or purging with a vacuum may be employed.
In the above step S02, the wholly aromatic liquid crystal polyester resin and the hollow glass beads are dried; the drying treatment is carried out for removing moisture and ensuring that each component is dried; if drying treatment is not carried out, bubbles can be generated in the product in the subsequent process of preparing the low dielectric constant liquid crystal polyester compound, and the product performance is influenced.
Preferably, the temperature of the drying treatment is 130-160 ℃, and the drying treatment is carried out under the temperature condition, so that the drying treatment effect of each component can be better. Further preferably, the drying time is 6 to 7 hours. In a preferred embodiment of the present invention, the temperature of the drying process is 140 ℃, and the time of the drying process is 6 hours.
In the step S03, the wholly aromatic liquid crystalline polyester resin and the hollow glass beads after the drying process are mixed to obtain a first mixture. Preferably, the mixing treatment is performed by an automatic mixer, and other methods for achieving the mixing treatment can also be used.
In the step S04, the first mixture is melt-kneaded, extruded, pulled into a string, cooled, and pelletized to obtain the low dielectric constant liquid crystal polymer. Preferably, a double-screw extruder is adopted, the obtained mixed first mixture is put into the double-screw extruder for melt mixing, and then the low dielectric constant liquid crystal polyester compound is prepared through extrusion, drawing, cooling and granulation.
In a preferred embodiment of the present invention, if the low dielectric constant liquid crystal polyester composite further comprises a filler, the method for preparing the low dielectric constant liquid crystal polyester composite comprises the following steps:
weighing the components according to the low-dielectric-constant liquid crystal polyester compound;
drying the wholly aromatic liquid crystal polyester resin, the hollow glass beads and the filler;
mixing the dried wholly aromatic liquid crystal polyester resin, the hollow glass beads and the filler to obtain a second mixture;
and melting and mixing the second mixture, extruding, bracing, cooling and granulating to obtain the low dielectric constant liquid crystal polymer.
The preparation method comprises the steps of drying the wholly aromatic liquid crystal polyester resin, the hollow glass beads and the filler, mixing, melting and mixing the mixture, extruding, bracing, cooling and granulating to obtain the low dielectric constant liquid crystal polymer. The preparation method can ensure that all components are fully dispersed and mutually act, so that the prepared low-dielectric-constant liquid crystal polyester compound has low dielectric constant performance. Meanwhile, the preparation method has the advantages of simple process, less used equipment and stable performance of the prepared material, effectively reduces the production cost and is suitable for large-scale use.
Further, specific examples are described.
Example 1
Low dielectric constant liquid crystal polymer
The low dielectric constant liquid crystal polymer comprises 75 parts of wholly aromatic liquid crystal polyester resin; 25 parts of hollow glass microspheres; wherein the diameter of the hollow glass bead is 20 μ M, and the model is 3M iM 16K.
The preparation method of the low dielectric constant liquid crystal polymer comprises the following steps: weighing the components according to the low dielectric constant liquid crystal polymer; drying the wholly aromatic liquid crystal polyester resin and the hollow glass beads at 130 ℃ for 4 hours; putting the wholly aromatic liquid crystal polyester resin and the hollow glass beads which are subjected to drying treatment into an automatic mixer, and uniformly mixing to obtain a first mixture; and putting the first mixture into a double-screw extruder for melt mixing, and then extruding, drawing strips, cooling and granulating to prepare the low-dielectric-constant liquid crystal polymer.
Example 2
Low dielectric constant liquid crystal polymer
The low dielectric constant liquid crystal polymer comprises 85 parts of wholly aromatic liquid crystal polyester resin; 15 parts of hollow glass beads; wherein the diameter of the hollow glass bead is 20 μ M, and the model is 3M iM 16K.
The preparation method of the low dielectric constant liquid crystal polymer comprises the following steps: weighing the components according to the low dielectric constant liquid crystal polymer; drying the wholly aromatic liquid crystal polyester resin and the hollow glass beads at 130 ℃ for 4 hours; putting the wholly aromatic liquid crystal polyester resin and the hollow glass beads which are subjected to drying treatment into an automatic mixer, and uniformly mixing to obtain a first mixture; and putting the first mixture into a double-screw extruder for melt mixing, and then extruding, drawing strips, cooling and granulating to prepare the low-dielectric-constant liquid crystal polymer.
Example 3
Low dielectric constant liquid crystal polymer
The low dielectric constant liquid crystal polymer comprises 75 parts of wholly aromatic liquid crystal polyester resin; 15 parts of hollow glass beads; 15 parts of glass fiber; wherein the diameter of the hollow glass bead is 20 μ M, and the model is 3M iM 16K.
The preparation method of the low dielectric constant liquid crystal polymer comprises the following steps: weighing the components according to the low dielectric constant liquid crystal polymer; drying the wholly aromatic liquid crystal polyester resin, the hollow glass beads and the glass fibers at 130 ℃ for 4 hours; putting the wholly aromatic liquid crystal polyester resin, the hollow glass beads and the glass fibers after drying treatment into an automatic mixer, and uniformly mixing to obtain a first mixture; and putting the first mixture into a double-screw extruder for melt mixing, and then extruding, drawing strips, cooling and granulating to prepare the low-dielectric-constant liquid crystal polymer.
Example 4
Low dielectric constant liquid crystal polymer
The low dielectric constant liquid crystal polymer includes, for example, 70 parts of wholly aromatic liquid crystal polyester resin; 10 parts of hollow glass beads; 20 parts of glass fiber; wherein the diameter of the hollow glass bead is 20 μ M, and the model is 3M iM 16K.
The preparation method of the low dielectric constant liquid crystal polymer comprises the following steps: weighing the components according to the low dielectric constant liquid crystal polymer; drying the wholly aromatic liquid crystal polyester resin, the hollow glass beads and the glass fibers at 130 ℃ for 4 hours; putting the wholly aromatic liquid crystal polyester resin, the hollow glass beads and the glass fibers after drying treatment into an automatic mixer, and uniformly mixing to obtain a first mixture; and putting the first mixture into a double-screw extruder for melt mixing, and then extruding, drawing strips, cooling and granulating to prepare the low-dielectric-constant liquid crystal polymer.
Comparative example 1
Low dielectric constant liquid crystal polymer
The low dielectric constant liquid crystal polymer includes 100 parts of a wholly aromatic liquid crystal polyester resin, which is the same as the wholly aromatic liquid crystal polyester resin in any one of embodiments 1 to 4.
Comparative example 2
Low dielectric constant liquid crystal polymer
The low dielectric constant liquid crystal polymer includes, for example, 70 parts of wholly aromatic liquid crystal polyester resin; 0 part of hollow glass microspheres; 30 parts of glass fiber.
The preparation method of the low dielectric constant liquid crystal polymer comprises the following steps: weighing the components according to the low dielectric constant liquid crystal polymer; drying the wholly aromatic liquid crystal polyester resin and the glass fiber at 130 ℃ for 4 hours; putting the wholly aromatic liquid crystal polyester resin and the glass fiber after drying treatment into an automatic mixer, and uniformly mixing to obtain a first mixture; and putting the first mixture into a double-screw extruder for melt mixing, and then extruding, drawing strips, cooling and granulating to prepare the low-dielectric-constant liquid crystal polymer.
In order to verify the properties of the composites prepared in the examples and comparative examples of the present invention, the composites obtained in the examples and comparative examples were used as injection molding materials, injection-molded using an injection molding machine, and the properties of the composites in the examples and comparative examples were tested and evaluated by the following methods:
(1) dielectric constant
The dielectric constant measurements referred to in the examples of the present invention were in accordance with ASTM D-150.
Results analysis As shown in Table 1 below, from Table 1, the low dielectric constant liquid crystal polymer prepared in example 1 had a dielectric constant of 2.69Hz, the low dielectric constant liquid crystal polymer prepared in example 2 had a dielectric constant of 2.88Hz, the low dielectric constant liquid crystal polymer prepared in example 3 had a dielectric constant of 3.01Hz, the low dielectric constant liquid crystal polymer prepared in example 4 had a dielectric constant of 3.30Hz, the low dielectric constant liquid crystal polymer prepared in comparative example 1 had a dielectric constant of 3.23Hz, and the low dielectric constant liquid crystal polymer prepared in comparative example 2 had a dielectric constant of 3.84 Hz.
From the above analysis, examples 1-2 and comparative example 1, in which examples 1-2 added both of the wholly aromatic liquid crystalline polyester resin and the hollow glass beads, did not add a filler, whereas comparative example 1 was only one of the wholly aromatic liquid crystalline polyester resin. The examples 1-2 showed a significant decrease in dielectric constant as compared to the low dielectric constant liquid crystal polymer prepared in comparative example 1, which demonstrates that the dielectric constant of the low dielectric constant liquid crystal polymer can be significantly decreased when only hollow glass beads are added to the wholly aromatic liquid crystal polyester resin, and that the decrease in dielectric constant is greater as the addition ratio of the hollow glass beads is higher.
Further analysis was conducted, and examples 3 to 4 and comparative example 2 each added a filler, wherein examples 3 and 4 each added three substances of wholly aromatic liquid crystalline polyester resin, hollow glass beads and filler, and comparative example 2 added two substances of wholly aromatic liquid crystalline polyester resin and filler. As can be seen from the comparison of examples 3 to 4 with the ratio 2, the higher the ratio of hollow glass microspheres added, the larger the reduction in dielectric constant. Comparing comparative example 1 and comparative example 2, one can obtain: when the filler glass fiber is added, the strength of the liquid crystal polyester can be improved by adding the glass fiber, but the dielectric constant can also be improved.
The low dielectric constant liquid crystal polymer takes wholly aromatic liquid crystal polyester resin as a matrix material, hollow glass beads with the diameter of 10-50 mu m are added, the wholly aromatic liquid crystal polyester resin is modified by the hollow glass beads with the diameter of 10-50 mu m, the hollow glass beads are hollow structures, have hard shells, are thin gases in the shells, and have the dielectric constant of air approximate to 1, and the hollow glass beads with the hollow structures are added, so that the hollow glass beads and the wholly aromatic liquid crystal polyester resin are mixed, the overall dielectric constant of the prepared liquid crystal polymer is reduced, and the use of the liquid crystal polyester compound in the fields of electronic devices and the like is effectively improved.
TABLE 1
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (10)
1. A low dielectric constant liquid crystal polymer is characterized by comprising the following components in parts by weight:
50-90 parts of wholly aromatic liquid crystal polyester resin;
10-30 parts of hollow glass beads;
wherein the diameter of the hollow glass bead is 10-50 μm.
2. The low dielectric constant liquid crystal polymer of claim 1, wherein the wall thickness of the hollow glass microspheres is 1-2 μm.
3. The low dielectric constant liquid crystal polymer of claim 1, wherein the hollow glass beads have a type selected from any one of 3M iM16K, shen na K80, 3M VS5500, 3M S60HS, and 3MK 46.
4. The low dielectric constant liquid crystal polymer according to any one of claims 1 to 3, wherein the low dielectric constant liquid crystal polymer further comprises 0 to 30 parts of a filler.
5. The low dielectric constant liquid crystal polymer of claim 4, wherein the filler is at least one selected from talc, whiskers, wollastonite, mica, titanium dioxide, carbon black, calcium carbonate, clay, barium sulfate, and silica.
6. A preparation method of a low dielectric constant liquid crystal polymer is characterized by comprising the following steps:
weighing the components according to any one of claims 1 to 5;
drying the wholly aromatic liquid crystal polyester resin and the hollow glass beads;
mixing the dried wholly aromatic liquid crystal polyester resin and the hollow glass beads to obtain a first mixture;
and melting and mixing the first mixture, extruding, bracing, cooling and granulating to obtain the low dielectric constant liquid crystal polymer.
7. The method for preparing a low dielectric constant liquid crystal polymer according to claim 6, wherein the drying temperature is 130 to 160 ℃.
8. The method of preparing a low dielectric constant liquid crystal polymer of claim 6, wherein the method of preparing the wholly aromatic liquid crystal polyester resin comprises the steps of:
providing at least 2 monomer substances, and carrying out polycondensation reaction to prepare a wholly aromatic liquid crystal polyester prepolymer;
and carrying out solid-phase polycondensation on the wholly aromatic liquid crystal polyester prepolymer to prepare the wholly aromatic liquid crystal polyester resin.
9. The method of claim 8, wherein the step of performing a polycondensation reaction to obtain the wholly aromatic liquid crystalline polyester prepolymer is a solution polycondensation method or a bulk polycondensation method.
10. The method of claim 8, wherein the monomer material is pre-treated with an acylating agent.
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| CN112625439A (en) * | 2020-12-28 | 2021-04-09 | 广东优巨先进新材料股份有限公司 | Low-dielectric polyaramide liquid crystal composite material and preparation method and application thereof |
| CN113004663A (en) * | 2021-02-05 | 2021-06-22 | 桂林理工大学 | Low-dielectric alloy material and preparation method and application thereof |
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| US11722759B2 (en) | 2019-03-20 | 2023-08-08 | Ticona Llc | Actuator assembly for a camera module |
| US12032272B2 (en) | 2019-03-20 | 2024-07-09 | Ticona Llc | Polymer composition for use in a camera module |
| US11555113B2 (en) | 2019-09-10 | 2023-01-17 | Ticona Llc | Liquid crystalline polymer composition |
| US12035467B2 (en) | 2020-02-26 | 2024-07-09 | Ticona Llc | Circuit structure |
| CN112625439A (en) * | 2020-12-28 | 2021-04-09 | 广东优巨先进新材料股份有限公司 | Low-dielectric polyaramide liquid crystal composite material and preparation method and application thereof |
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| CN113667281A (en) * | 2021-09-13 | 2021-11-19 | 宁夏清研高分子新材料有限公司 | Low-dielectric-constant TLCP material and preparation method thereof |
| CN113861716A (en) * | 2021-09-30 | 2021-12-31 | 珠海万通特种工程塑料有限公司 | Liquid crystal polymer composition and application thereof |
| CN113881194A (en) * | 2021-09-30 | 2022-01-04 | 重庆沃特智成新材料科技有限公司 | Low-dielectric-constant liquid crystal polymer and preparation method and application thereof |
| CN113861716B (en) * | 2021-09-30 | 2023-04-07 | 珠海万通特种工程塑料有限公司 | Liquid crystal polymer composition and application thereof |
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