CN111073224A - Low-warpage liquid crystal polymer and preparation method thereof - Google Patents
Low-warpage liquid crystal polymer and preparation method thereof Download PDFInfo
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- CN111073224A CN111073224A CN201911363994.2A CN201911363994A CN111073224A CN 111073224 A CN111073224 A CN 111073224A CN 201911363994 A CN201911363994 A CN 201911363994A CN 111073224 A CN111073224 A CN 111073224A
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- 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
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- C09K19/38—Polymers
- C09K19/3804—Polymers with mesogenic groups in the main chain
- C09K19/3809—Polyesters; Polyester derivatives, e.g. polyamides
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Abstract
The invention provides a low-warpage liquid crystal polymer, which comprises the following components in parts by weight: 50-70 parts of wholly aromatic liquid crystal polyester resin; 5-40 parts of chopped glass fiber; 5-40 parts of a filler; wherein the diameter of the chopped glass fiber is 6-9 μm. The chopped glass fibers with the diameter of 6-9 mu m are used for modifying the wholly aromatic liquid crystal polyester resin, and the chopped glass fibers with the smaller diameter can be fused with the wholly aromatic liquid crystal polyester resin and are uniformly arranged, so that the arrangement direction of the chopped glass fibers is consistent with the flow direction of the wholly aromatic liquid crystal polyester resin, the support force of the wholly aromatic liquid crystal polyester resin in the longitudinal direction is improved, the contraction difference of the liquid crystal polyester compound in the longitudinal direction and the flow direction is reduced, the warping rate of the liquid crystal polyester compound is greatly reduced, the mechanical performance of the liquid crystal polyester compound is improved, and the application range of the liquid crystal polyester compound is effectively improved.
Description
Technical Field
The invention relates to the technical field of high-molecular composite materials, in particular to a low-warpage 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 common thermotropic liquid crystal polymer has better fluidity and is easy to process and mold. The formed product has the skin-core structure peculiar to the liquid crystal polymer, and the resin has fiber property and high orientation in a molten state, so that the fiber reinforcement effect can be achieved. However, due to the specific skin-core structure, when the precision electronic part is injection molded, the longitudinal direction and the flow direction of the precision electronic part shrink in different directions, so that shrinkage difference exists, the plastic part can be warped due to internal stress, and the precision of the electronic part is seriously affected.
Disclosure of Invention
The invention aims to provide a low-warpage liquid crystal polymer, and aims to solve the problem of severe warpage caused by strong shrinkage force of the liquid crystal polymer in the prior art.
In order to achieve the purpose, the invention adopts the following technical scheme:
a low-warpage liquid crystal polymer comprises the following components in parts by weight:
50-70 parts of wholly aromatic liquid crystal polyester resin;
5-40 parts of chopped glass fiber;
5-40 parts of a filler;
wherein the diameter of the chopped glass fiber is 6-9 μm.
And, a method for preparing a low-warpage liquid crystal polymer, the method comprising the steps of:
weighing the components according to the low-warpage liquid crystal polymer;
drying the wholly aromatic liquid crystal polyester resin, the chopped glass fibers and the filler;
mixing the dried wholly aromatic liquid crystal polyester resin, the chopped glass fibers and the filler to obtain a first mixture;
and melting and mixing the first mixture, extruding, bracing, cooling and granulating to obtain the low-warpage liquid crystal polymer.
The low-warpage liquid crystal polyester compound provided by the invention takes wholly aromatic liquid crystal polyester resin as a parent material, modifying the wholly aromatic liquid crystalline polyester resin by adding chopped glass fibers having a diameter of 6 to 9 μm and using the chopped glass fibers having a diameter of 6 to 9 μm, because the chopped glass fiber has smaller diameter, the chopped glass fiber can be fused with the wholly aromatic liquid crystal polyester resin and is uniformly distributed, the arrangement direction of the liquid crystal polyester resin is consistent with the flowing direction of the wholly aromatic liquid crystal polyester resin, the supporting force of the wholly aromatic liquid crystal polyester resin in the longitudinal direction is improved, the contraction difference of the liquid crystal polyester compound in the longitudinal direction and the flowing direction is reduced, the warping rate of the liquid crystal polyester compound is greatly reduced, meanwhile, the mechanical property of the liquid crystal polyester composite is improved, and the application range of the liquid crystal polyester composite in the fields of preparation of precise electronic devices and the like is effectively enlarged.
The preparation method of the low-warpage liquid crystal polyester compound provided by the invention comprises the steps of drying the wholly aromatic liquid crystal polyester resin, the chopped glass fibers and the filler, mixing, melting and mixing the mixture, extruding, drawing into strips, cooling and granulating to obtain the low-warpage liquid crystal polymer. The preparation method can ensure that all components are fully dispersed and mutually act, so that the prepared low-warpage liquid crystal polyester compound has low warpage. 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-warpage liquid crystal polymer, which comprises the following components in parts by weight:
50-70 parts of wholly aromatic liquid crystal polyester resin;
5-40 parts of chopped glass fiber;
5-40 parts of a filler;
wherein the diameter of the chopped glass fiber is 6-9 μm.
The low-warpage liquid crystal polyester compound provided by the invention takes wholly aromatic liquid crystal polyester resin as a parent material, modifying the wholly aromatic liquid crystalline polyester resin by adding chopped glass fibers having a diameter of 6 to 9 μm and using the chopped glass fibers having a diameter of 6 to 9 μm, because the chopped glass fiber has smaller diameter, the chopped glass fiber can be fused with the wholly aromatic liquid crystal polyester resin and is uniformly distributed, the arrangement direction of the liquid crystal polyester resin is consistent with the flowing direction of the wholly aromatic liquid crystal polyester resin, the supporting force of the wholly aromatic liquid crystal polyester resin in the longitudinal direction is improved, the contraction difference of the liquid crystal polyester compound in the longitudinal direction and the flowing direction is reduced, the warping rate of the liquid crystal polyester compound is greatly reduced, meanwhile, the mechanical property of the liquid crystal polyester composite is improved, and the application range of the liquid crystal polyester composite in the fields of preparation of precise electronic devices and the like is effectively enlarged. In a specific application, for example, when the liquid crystal polymer is subjected to injection molding to obtain a precise electronic part, the low-warpage liquid crystal polymer obtained by modifying the wholly aromatic liquid crystal polyester resin with the chopped glass fibers is subjected to injection molding, so that in the process of obtaining the precise electronic part, the shrinkage difference of shrinkage generated in the longitudinal direction and the flow direction is not obvious, the plastic part is not warped, the precision of the electronic part is not affected, and the application is wider.
Specifically, the low warpage liquid crystal polymer includes 50 to 70 parts of a wholly aromatic liquid crystal polyester resin formed by polymerization of a monomer, 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-warpage 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 contains the repeating unit as a matrix material of the low warpage liquid crystal polymer, and can ensure high thermal stability and stable size of the prepared low warpage liquid crystal polymer.
Specifically, the low-warpage liquid crystal polymer comprises 50-70 parts of wholly aromatic liquid crystal polyester resin, and if the addition amount is too large, the addition of the chopped glass fiber is influenced, so that the synergistic effect of the chopped glass fiber and the liquid crystal polyester resin is further influenced, the shrinkage difference of the liquid crystal polyester compound in the longitudinal direction and the flow direction cannot be reduced well, and the performance of enabling the liquid crystal polyester compound to resist warpage deformation cannot be improved; if the amount is too small, the matrix material of the low-warpage liquid crystal polymer is too small, and the heat resistance, dimensional stability and mechanical properties of the low-warpage liquid crystal polymer are affected. 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 and 70 parts.
Specifically, the low-warpage liquid crystal polymer comprises 5-40 parts of chopped glass fiber; and the diameter of the chopped glass fiber is 6-9 μm. The chopped glass fibers with the diameter of 6-9 mu m are used for modifying the wholly aromatic liquid crystal polyester resin, and the chopped glass fibers with the small diameter can be fused with the wholly aromatic liquid crystal polyester resin and are uniformly distributed, and the distribution direction of the chopped glass fibers is consistent with the flow direction of the wholly aromatic liquid crystal polyester resin, so that the supporting force of the wholly aromatic liquid crystal polyester resin in the longitudinal direction is improved, the contraction difference of the liquid crystal polyester compound in the longitudinal direction and the flow direction is reduced, the warping rate of the liquid crystal polyester compound is greatly reduced, the mechanical performance of the liquid crystal polyester compound is improved, and the application range of the liquid crystal polyester compound in the fields of preparation of precise electronic devices and the like is effectively improved. In a specific application, for example, when the liquid crystal polymer is subjected to injection molding to obtain a precise electronic part, the low-warpage liquid crystal polymer obtained by modifying the wholly aromatic liquid crystal polyester resin with the chopped glass fibers is subjected to injection molding, so that in the process of obtaining the precise electronic part, the shrinkage difference of shrinkage generated in the longitudinal direction and the flow direction is not obvious, the plastic part is not warped, the precision of the electronic part is not affected, and the application is wider.
Specifically, the diameter of the chopped glass fiber is 6-9 μm. Selecting the chopped glass fibers with the diameters for modification, wherein if the diameters of the chopped glass fibers are too small, the supporting force of the wholly aromatic liquid crystal polyester resin in the longitudinal direction cannot be improved, the shrinkage difference of the liquid crystal polyester compound in the longitudinal direction and the flowing direction cannot be reduced, and further the wholly aromatic liquid crystal polyester resin cannot be modified; if the diameter of the chopped glass fibers is too large, the flowability and heat resistance of the wholly aromatic liquid crystalline polyester resin are affected, and the performance of the low warpage liquid crystalline polyester compound produced is affected. More preferably, the chopped glass fibers have a diameter of 7 μm. The chopped glass fiber with the diameter of 7 mu m is selected for modification, so that the supporting force of the wholly aromatic liquid crystal polyester resin in the longitudinal direction can be improved to the maximum extent, the shrinkage difference of the liquid crystal polyester compound in the longitudinal direction and the flowing direction can be reduced to the maximum extent, and the liquid crystal polymer with low warping degree can be obtained.
Preferably, the chopped glass fibers have a sheet-like structure. The glass fiber with a flat sheet structure is adopted to modify the wholly aromatic liquid crystal polyester resin, so that the wholly aromatic liquid crystal polyester resin can be favorably fused with the wholly aromatic liquid crystal polyester resin, and meanwhile, the added chopped glass fiber has a sheet structure, so that the arrangement direction of the glass fiber is consistent with the flow direction of the wholly aromatic liquid crystal polyester resin and is uniformly arranged, the supporting force of the wholly aromatic liquid crystal polyester resin in the longitudinal direction is further improved, the shrinkage difference of the liquid crystal polyester compound in the longitudinal direction and the flow direction is reduced, and the liquid crystal polyester compound has excellent buckling deformation resistance.
Preferably, the type of the chopped glass fiber is selected from one of Owens Corning 7um E-glass, Taishan glass fiber T443 and Delhi glass fiber ECS-301. In a preferred embodiment of the invention, the type of the chopped glass fiber is selected from Owens Corning 7um E-glass, and the Owens Corning 7um E-glass added with the chopped glass fiber can greatly improve the supporting force of the wholly aromatic liquid crystal polyester resin in the longitudinal direction, furthest reduce the shrinkage difference of the liquid crystal polyester compound in the longitudinal direction and the flowing direction and obtain the liquid crystal polymer with low warpage.
Specifically, the low-warpage liquid crystal polymer comprises 5-40 parts of chopped glass fiber; if the amount of the liquid crystal polyester compound is too large, the amount of the liquid crystal polyester compound added is affected, and the synergistic effect between the two is further affected, so that the fluidity and the heat resistance of the wholly aromatic liquid crystal polyester resin are affected, the shrinkage difference in the longitudinal direction and the flow direction of the liquid crystal polyester compound cannot be reduced well, and the buckling deformation resistance of the liquid crystal polyester compound cannot be improved; if the amount of the additive is too small, the supporting force in the longitudinal direction of the wholly aromatic liquid crystalline polyester resin cannot be increased, the difference in shrinkage between the longitudinal direction and the flow direction of the liquid crystalline polyester composite cannot be reduced, and the wholly aromatic liquid crystalline polyester resin cannot be modified. Preferably, the low-warpage liquid crystal polymer comprises 20-35 parts of chopped glass fiber; the addition amount of the chopped glass fiber is controlled, so that the synergistic effect of the chopped glass fiber and the wholly aromatic liquid crystal polyester resin can be ensured, the shrinkage difference of the liquid crystal polyester compound in the longitudinal direction and the flowing direction can be better reduced, and the warping performance of the liquid crystal polyester compound is reduced. In a specific embodiment of the present invention, the chopped glass fibers may be added in the following specific parts: 10 parts, 15 parts, 20 parts, 25 parts, 30 parts, 35 parts, 40 parts, 45 parts and 50 parts.
Specifically, the low-warpage liquid crystal polymer comprises 5-40 parts of filler, and if the addition amount is too large, the synergistic effect between the chopped glass fiber and the wholly aromatic liquid crystal polyester resin is influenced, and the performance of the prepared low-warpage liquid crystal polyester compound is further influenced; if the amount of the liquid crystal polyester compound is too small, the cost of the liquid crystal polyester compound with low warpage will be increased, which is not suitable for wide application. 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 embodiment of the present invention, the specific addition parts of the filler may be 5 parts, 10 parts, 15 parts, 20 parts, 25 parts, 30 parts, 35 parts, and 40 parts.
The low-warpage liquid crystal polymer is prepared by the following preparation method of the low-warpage liquid crystal polymer.
Correspondingly, the embodiment of the invention also provides a preparation method of the low-warpage liquid crystal polymer. The method comprises the following steps:
s01, weighing the components according to the low-warpage liquid crystal polymer;
s02, drying the wholly aromatic liquid crystal polyester resin, the chopped glass fibers and the filler;
s03, mixing the dried wholly aromatic liquid crystal polyester resin, the dried chopped glass fibers and the filler to obtain a first mixture;
and S04, melting and mixing the first mixture, extruding, bracing, cooling and granulating to obtain the low-warpage liquid crystal polymer.
The preparation method of the low-warpage liquid crystal polyester compound provided by the invention comprises the steps of drying the wholly aromatic liquid crystal polyester resin, the chopped glass fibers and the filler, mixing, melting and mixing the mixture, extruding, drawing into strips, cooling and granulating to obtain the low-warpage liquid crystal polymer. The preparation method can ensure that all components are fully dispersed and mutually act, so that the prepared low-warpage liquid crystal polyester compound has low warpage. 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 wholly aromatic liquid crystal polyester resin, the chopped glass fiber and the filler are weighed according to the low warpage liquid crystal polymer, and the types of the components are added as described above, and are not repeated herein 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-warpage 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 crystalline polyester resin, the chopped glass fiber, and the filler are dried; the drying treatment is carried out for removing moisture and ensuring that each component is dried; if the drying treatment is not carried out, bubbles can be generated in the product in the subsequent process of preparing the low-warpage liquid crystal polyester compound, and the product performance is influenced.
Preferably, the temperature of the drying treatment is 120-160 ℃, 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, the chopped glass fibers, and the filler 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 warpage 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-warpage liquid crystal polyester compound is prepared through extrusion, drawing, cooling and granulation.
Further, specific examples are described.
Example 1
Low-warpage liquid crystal polymer
The low warpage liquid crystal polymer comprises 60 parts of wholly aromatic liquid crystal polyester resin; 10 parts of chopped glass fiber; 30 parts of talcum powder; wherein the diameter of the chopped glass fiber is 7 μm, and the model is Owens Corning 7um E-glass.
The preparation method of the low-warpage liquid crystal polymer comprises the following steps: weighing the components according to the low-warpage liquid crystal polymer; drying the wholly aromatic liquid crystalline polyester resin, the chopped glass fibers and the filler at 140 ℃ for 6 hours; putting the wholly aromatic liquid crystal polyester resin, the chopped glass fibers and the filler 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-warpage liquid crystal polymer.
Example 2
Low-warpage liquid crystal polymer
The low warpage liquid crystal polymer comprises 60 parts of wholly aromatic liquid crystal polyester resin; 30 parts of chopped glass fiber; 10 parts of talcum powder; wherein the diameter of the chopped glass fiber is 7 μm, and the model is Owens Corning 7um E-glass.
The preparation method of the low-warpage liquid crystal polymer comprises the following steps: weighing the components according to the low-warpage liquid crystal polymer; drying the wholly aromatic liquid crystalline polyester resin, the chopped glass fibers and the filler at 140 ℃ for 6 hours; putting the wholly aromatic liquid crystal polyester resin, the chopped glass fibers and the filler 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-warpage liquid crystal polymer.
Comparative example 1
Low-warpage liquid crystal polymer
The low warpage liquid crystal polymer comprises 60 parts of wholly aromatic liquid crystal polyester resin; 10 parts of chopped glass fiber; 30 parts of talcum powder; wherein the chopped glass fibers have a diameter of 10 μm.
The preparation method of the low-warpage liquid crystal polymer comprises the following steps: weighing the components according to the low-warpage liquid crystal polymer; drying the wholly aromatic liquid crystalline polyester resin, the chopped glass fibers and the filler at 140 ℃ for 6 hours; putting the wholly aromatic liquid crystal polyester resin, the chopped glass fibers and the filler 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-warpage liquid crystal polymer.
Comparative example 2
Low-warpage liquid crystal polymer
The low warpage liquid crystal polymer comprises 60 parts of wholly aromatic liquid crystal polyester resin; 30 parts of chopped glass fiber; 10 parts of talcum powder; wherein the chopped glass fibers have a diameter of 10 μm.
The preparation method of the low-warpage liquid crystal polymer comprises the following steps: weighing the components according to the low-warpage liquid crystal polymer; drying the wholly aromatic liquid crystalline polyester resin, the chopped glass fibers and the filler at 140 ℃ for 6 hours; putting the wholly aromatic liquid crystal polyester resin, the chopped glass fibers and the filler 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-warpage liquid crystal polymer.
In order to verify the properties of the low warpage liquid crystal polymers prepared in examples 1 to 2 and comparative examples 1 to 2 of the present invention, the low warpage liquid crystal polymers obtained in the above examples 1 to 2 and comparative examples 1 to 2, respectively, 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) flexural strength, flexural modulus and flexural strain
The flexural strength measurements to which the examples of the invention relate follow ASTM D-790.
(2) Heat distortion temperature
The heat distortion temperature measurements referred to in the examples of the present invention were made according to ASTM D-648.
(3) Degree of warping
The warpage measurement according to the present invention uses a connector sample having a length of 100mm as a test sample, and measures the height difference between the edge of the sample and the center of the sample with a vernier caliper.
The results are analyzed in the following table 1, and it can be seen from table 1 that the low-warpage liquid crystal polymer prepared by adding 7-micron chopped glass fiber in the examples 1 and 2 has better modification effect, and the thermodynamic properties are represented by higher heat distortion temperature, higher bending strength and higher bending modulus. Under the condition of 20 ℃, the warpage of the low-warpage liquid crystal polymer prepared in example 1 is 0.058mm, the warpage of the low-warpage liquid crystal polymer prepared in example 2 is 0.096mm, the warpage of the low-warpage liquid crystal polymer prepared in comparative example 1 is 0.116mm, the warpage of the low-warpage liquid crystal polymer prepared in comparative example 2 is 0.193mm, and the warpage degree of the low-warpage liquid crystal polymer modified by adding 7 microns of chopped glass fibers prepared in examples 1 and 2 is only half of that of the low-warpage liquid crystal polymer prepared in comparative example 1 and 2 by adding 10 microns of chopped glass fibers. Further, when the test was carried out at a high temperature of 260 ℃, the warpage of the low warpage liquid crystal polymer prepared in example 1 was 0.120mm, the warpage of the low warpage liquid crystal polymer prepared in example 2 was 0.188mm, the warpage of the low warpage liquid crystal polymer prepared in comparative example 1 was 0.144mm, the warpage of the low warpage liquid crystal polymer prepared in comparative example 2 was 0.228mm, and the warpage of the low warpage liquid crystal polymers of examples 1 and 2 was still lower than that of the low warpage liquid crystal polymers prepared in comparative examples 1 and 2 by 15% or more. Meanwhile, the low-warpage liquid crystal polymer prepared in the embodiment 1 and the embodiment 2 can keep better bending strength performance, bending strain performance and bending modulus performance, the low-warpage liquid crystal polyester compound provided by the invention utilizes the chopped glass fiber with the diameter of 6-9 μm to modify the wholly aromatic liquid crystal polyester resin, because the chopped glass fiber has smaller diameter, the chopped glass fiber can be fused with the wholly aromatic liquid crystal polyester resin and is uniformly distributed, the arrangement direction of the liquid crystal polyester resin is consistent with the flowing direction of the wholly aromatic liquid crystal polyester resin, the supporting force of the wholly aromatic liquid crystal polyester resin in the longitudinal direction is improved, the contraction difference of the liquid crystal polyester compound in the longitudinal direction and the flowing direction is reduced, the warping rate of the liquid crystal polyester compound is greatly reduced, meanwhile, the mechanical property of the liquid crystal polyester composite is improved, and the application range of the liquid crystal polyester composite in the fields of preparation of precise electronic devices and the like is effectively enlarged.
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-warpage liquid crystal polymer is characterized by comprising the following components in parts by weight:
50-70 parts of wholly aromatic liquid crystal polyester resin;
5-40 parts of chopped glass fiber;
5-40 parts of a filler;
wherein the diameter of the chopped glass fiber is 6-9 μm.
2. The low warpage liquid crystal polymer of claim 1, wherein the structure of the chopped glass fibers is a sheet-like structure.
3. The low warpage liquid crystal polymer of claim 1, wherein the chopped glass fiber is selected from the group consisting of Owens Corning 7um E-glass, Taishan glass fiber T443, and Delhi glass fiber ECS-301.
4. The low warpage liquid crystal polymer according to any one of claims 1 to 3, wherein the wholly aromatic liquid crystal polyester resin contains the following repeating units:
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.
5. The low warpage liquid crystal polymer according to any one of claims 1 to 3, 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-warpage 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, the chopped glass fibers and the filler;
mixing the dried wholly aromatic liquid crystal polyester resin, the chopped glass fibers and the filler to obtain a first mixture;
and melting and mixing the first mixture, extruding, bracing, cooling and granulating to obtain the low-warpage liquid crystal polymer.
7. The method for preparing a low warpage liquid crystal polymer according to claim 6, wherein the temperature of the drying treatment is 120 to 160 ℃.
8. The method for preparing a low warpage liquid crystal polymer according to claim 6, wherein the method for 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 for producing a low warpage liquid crystal polymer according to claim 8, wherein in the step of producing the wholly aromatic liquid crystal polyester prepolymer by performing a polycondensation reaction, the polycondensation reaction is selected from a solution polycondensation method or a bulk polycondensation method.
10. The method for preparing a low warpage liquid crystal polymer according to claim 8, wherein the monomer material is pretreated with an acylating agent.
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Application publication date: 20200428 |