CN111117170B - High-fluidity liquid crystal polymer and preparation method thereof - Google Patents
High-fluidity liquid crystal polymer and preparation method thereof Download PDFInfo
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- CN111117170B CN111117170B CN201911363992.3A CN201911363992A CN111117170B CN 111117170 B CN111117170 B CN 111117170B CN 201911363992 A CN201911363992 A CN 201911363992A CN 111117170 B CN111117170 B CN 111117170B
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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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- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/38—Polymers
- C09K19/3804—Polymers with mesogenic groups in the main chain
- C09K19/3809—Polyesters; Polyester derivatives, e.g. polyamides
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/38—Polymers
- C09K19/3833—Polymers with mesogenic groups in the side chain
- C09K19/3838—Polyesters; Polyester derivatives
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
- C09K2019/521—Inorganic solid particles
Abstract
The invention provides a high-fluidity liquid crystal polymer, which comprises the following components in parts by weight: 50 to 70 parts of wholly aromatic liquid crystal polyester resin; 5-40 parts of ground glass fiber; 5-40 parts of a filler; wherein the milled glass fibers have a diameter of 6 to 9 μm. The ground glass fibers with the diameter of 6-9 mu m are used for modifying the wholly aromatic liquid crystal polyester resin, and the ground glass fibers are of uniform rod-shaped structures, so that the smoothness of the structures is better, the ground glass fibers can be fused with the wholly aromatic liquid crystal polyester resin, the linearity of the wholly aromatic liquid crystal polyester resin is further improved, the order of the wholly aromatic liquid crystal polyester resin is improved, and the flowing performance of a liquid crystal polymer is enhanced.
Description
Technical Field
The invention relates to the technical field of high-molecular composite materials, in particular to a high-fluidity liquid crystal polymer and a preparation method thereof.
Background
A Liquid Crystal Polymer (LCP) is an intermediate state polymer between a solid crystalline and a liquid, the molecular arrangement of which, although not three-dimensionally ordered as in the solid crystalline state, is not disordered as in the liquid, but rather has a certain (one-dimensional or two-dimensional) order. It is a novel polymeric material which generally exhibits liquid crystallinity in the 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 affected 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. However, when a precise electronic component is processed, the mold flow channel is narrow and long, the mold is cooled too fast in the injection molding process, and the poor flowability of the thermotropic liquid crystal polymer is easy to occur, so that the mold is not filled fully, and the precision of the electronic component is seriously affected.
Disclosure of Invention
The invention aims to provide a high-fluidity liquid crystal polymer and a preparation method thereof, and aims to solve the problem of low fluidity of the liquid crystal polymer in the prior art.
In order to achieve the purpose, the invention adopts the following technical scheme:
a high-fluidity 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 ground glass fiber;
5-40 parts of a filler;
wherein the milled glass fibers have a diameter of 6 to 9 μm.
And, a method for preparing a high-fluidity liquid crystal polymer, the method comprising the steps of:
weighing the components according to the high-fluidity liquid crystal polymer;
drying the wholly aromatic liquid crystalline polyester resin, the milled glass fiber, and the filler;
mixing the dried wholly aromatic liquid crystal polyester resin, the ground glass fiber and the filler to obtain a first mixture;
and melting and mixing the first mixture, extruding, bracing, cooling and granulating to obtain the high-fluidity liquid crystal polymer.
The high-fluidity liquid crystal polymer provided by the invention takes wholly aromatic liquid crystal polyester resin as a matrix material, and is modified by adding the milled glass fiber with the diameter of 6-9 mu m, and the milled glass fiber with the diameter of 6-9 mu m is a uniform rod-shaped structure, so that the milled glass fiber has good fluency of the structure of the milled glass fiber and can be fused with the wholly aromatic liquid crystal polyester resin, the linearity of the wholly aromatic liquid crystal polyester resin is further improved, the orderliness of the wholly aromatic liquid crystal polyester resin is improved, the fluidity of the liquid crystal polymer is enhanced, and the mechanical property of the liquid crystal polymer is improved at the same time, so that the prepared liquid crystal polyester compound has excellent mechanical strength and high fluidity, 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.
The preparation method of the high-fluidity liquid crystal polymer provided by the invention comprises the steps of drying the wholly aromatic liquid crystal polyester resin, the ground glass fiber and the filler, mixing, melting and mixing the mixture, extruding, drawing into strips, cooling and granulating to obtain the high-fluidity liquid crystal polymer. The preparation method can ensure that all components are fully dispersed and mutually act, so that the prepared high-fluidity liquid crystal polymer has stronger fluidity. 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 high-fluidity 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 ground glass fiber;
5-40 parts of a filler;
wherein the milled glass fibers have a diameter of 6 to 9 μm.
The high-fluidity liquid crystal polymer provided by the invention takes wholly aromatic liquid crystal polyester resin as a parent material, ground glass fiber with the diameter of 6-9 mu m is added, and the wholly aromatic liquid crystal polyester resin is modified by utilizing the ground glass fiber with the diameter of 6-9 mu m, and as the ground glass fiber is of a uniform rod-shaped structure, the ground glass fiber has better fluency of the structure of the liquid crystal polymer, and can be fused with the wholly aromatic liquid crystal polyester resin, the linearity of the wholly aromatic liquid crystal polyester resin is further improved, the orderliness of the wholly aromatic liquid crystal polyester resin is improved, the fluidity of the liquid crystal polymer is enhanced, and the mechanical performance of the liquid crystal polymer is improved at the same time, so that the prepared liquid crystal polyester compound has excellent mechanical strength and high fluidity, and the application range of the liquid crystal polyester compound in the fields of preparation of precision electronic devices and the like is effectively improved.
Specifically, the high-fluidity liquid crystal polymer includes 50 to 70 parts of a wholly aromatic liquid crystal polyester resin formed by polymerization of 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 crystalline polyester resin is composed of the monomers, so that the prepared wholly aromatic liquid crystalline polyester resin has better performance, and the high-fluidity liquid crystalline 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 crystalline polyester resin contains the repeating unit as a matrix material of the high-fluidity liquid crystalline polymer, and can ensure high thermal stability and stable size of the prepared high-fluidity liquid crystalline polymer.
Specifically, the high-fluidity liquid crystal polymer comprises 50 to 70 parts of wholly aromatic liquid crystal polyester resin, and if the addition amount is too large, the addition of ground glass fibers is influenced, the synergistic effect of the ground glass fibers and the ground glass fibers is further influenced, the linearity degree of the wholly aromatic liquid crystal polyester resin cannot be improved well, the order of the wholly aromatic liquid crystal polyester resin cannot be improved, and the flow performance of the liquid crystal polymer cannot be enhanced; if the amount is too small, the high-fluidity liquid crystal polymer matrix material is too small, and the heat resistance, dimensional stability and mechanical properties of the high-fluidity 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, 53 parts, 55 parts, 58 parts, 60 parts, 63 parts, 65 parts, 68 parts and 70 parts.
Specifically, the high-fluidity liquid crystal polymer comprises 5 to 40 parts of milled glass fiber; and the milled glass fibers have a diameter of 6 to 9 μm. The ground glass fibers with the diameter of 6-9 mu m are used for modifying the wholly aromatic liquid crystal polyester resin, and the ground glass fibers are of uniform rod-shaped structures, so that the smoothness of the structures is better, the ground glass fibers can be fused with the wholly aromatic liquid crystal polyester resin, the linearity of the wholly aromatic liquid crystal polyester resin is further improved, the order of the wholly aromatic liquid crystal polyester resin is improved, and the flowing performance of a liquid crystal polymer is enhanced. In a specific application, for example, when the liquid crystal polymer is subjected to injection molding to obtain a precise electronic part, the high-fluidity liquid crystal polymer obtained by modifying the wholly aromatic liquid crystal polyester resin by using the milled glass fiber is subjected to injection molding, and in the process of the obtained precise electronic part, the high-fluidity liquid crystal polymer has the advantages of better linearity, enhanced order and further improved fluidity, so that a mold can be fully filled, the precision of the electronic part is not affected, and the application is wider.
Specifically, the diameter of the milled glass fiber is 6 to 9 μm. If the milled glass fibers having the above diameters are too small, the degree of linearity of the wholly aromatic liquid crystalline polyester resin cannot be increased, the order of the product cannot be enhanced, and thus it is not ensured that a high-fluidity liquid crystalline polymer is obtained. Further preferably, the milled glass fibers have a diameter of 7 μm. The ground glass fiber with the diameter of 7 μm is selected for modification, so that the order of the wholly aromatic liquid crystal polyester resin can be improved to the maximum extent, and the liquid crystal polymer with high flow property can be obtained. More preferably, the milled glass fibers have a length of 10 to 100 μm, and the degree of order of the wholly aromatic liquid crystalline polyester resin can be enhanced and the fluidity of the wholly aromatic liquid crystalline polyester resin can be increased by selecting milled glass fibers having the above length.
Preferably, the structure of the milled glass fibers is a needle-like structure. The rod-shaped ground glass fiber is adopted to modify the wholly aromatic liquid crystal polyester resin, so that the fusion with the wholly aromatic liquid crystal polyester resin can be facilitated, and meanwhile, as the structure of the added ground glass fiber is the rod-shaped structure, the arrangement direction of the ground glass fiber can be ensured to be consistent with the flowing direction of the wholly aromatic liquid crystal polyester resin, and the ground glass fiber is uniformly arranged, so that the linearity degree of the wholly aromatic liquid crystal polyester resin is improved, the order of the wholly aromatic liquid crystal polyester resin is improved, and the flowing performance of a liquid crystal polymer is enhanced.
Preferably, the milled glass fibers are of a type selected from any one of EMG7-70, SUNGJIN 75W-NL, SUNGJIN 150, MGFP-200C, XGFT 91000. In a preferred embodiment of the invention, the milled glass fibers are of a type selected from EMG7-70, and the producer is taishan. Selecting the ground glass fiber with the Mount Taishan model of EMG7-70, wherein the EMG7-70 ground glass fiber is a white needle-shaped product, the diameter of a monofilament is 7 microns, and the length of the monofilament is 10-20 microns; the use of the milled glass fiber can improve the linearity of the wholly aromatic liquid crystalline polyester resin, and further improve the order of the wholly aromatic liquid crystalline polyester resin, thereby improving the flowability of the liquid crystalline polymer.
Specifically, the high-fluidity liquid crystal polymer comprises 5 to 40 parts of milled glass fiber; if the addition amount is too large, the addition amount of the wholly aromatic liquid crystalline polyester resin is affected, and further, the synergistic effect between the both is affected, the mechanical properties and the heat resistance of the wholly aromatic liquid crystalline polyester resin are affected, the linearity of the wholly aromatic liquid crystalline polyester resin cannot be improved well, the order of the wholly aromatic liquid crystalline polyester resin cannot be improved, and the liquid crystal polymer flowability cannot be improved; if the amount of the liquid crystal polymer is too small, the degree of linearity of the wholly aromatic liquid crystal polyester resin cannot be improved, the order of the wholly aromatic liquid crystal polyester resin cannot be improved, the fluidity of the liquid crystal polymer cannot be improved, and a substantial effect of improving the above performance is not provided. Preferably, the high-fluidity liquid crystal polymer includes 20 to 35 parts of milled glass fiber; controlling the addition amount of the milled glass fibers can ensure the synergistic effect of the milled glass fibers and the wholly aromatic liquid crystalline polyester resin, and can improve the linearity of the wholly aromatic liquid crystalline polyester resin, thereby improving the order of the wholly aromatic liquid crystalline polyester resin and improving the flowability of the liquid crystalline polymer. In a specific embodiment of the present invention, the specific addition parts of the milled glass fibers may be: 10 parts, 15 parts, 20 parts, 25 parts, 30 parts, 35 parts, 40 parts, 45 parts and 50 parts.
Specifically, the high-fluidity liquid crystal polymer comprises 5-40 parts of filler, and if the addition amount is too large, the synergistic effect between the milled glass fiber and the wholly aromatic liquid crystal polyester resin is influenced, and the performance of the prepared high-fluidity 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 having high fluidity is increased, and the liquid crystal polyester compound 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 amount of the filler may be 5 parts, 10 parts, 15 parts, 20 parts, 25 parts, 30 parts, 35 parts, or 40 parts.
The high-fluidity liquid crystal polymer is prepared by the following preparation method of the high-fluidity liquid crystal polymer.
Correspondingly, the embodiment of the invention also provides a preparation method of the high-fluidity liquid crystal polymer. The method comprises the following steps:
s01, weighing the components according to the high-fluidity liquid crystal polymer;
s02, drying the wholly aromatic liquid crystal polyester resin, the ground glass fibers and the filler;
s03, mixing the dried wholly aromatic liquid crystal polyester resin, the ground glass fiber and the filler to obtain a first mixture;
and S04, melting and mixing the first mixture, extruding, bracing, cooling and granulating to obtain the high-fluidity liquid crystal polymer.
The preparation method of the high-fluidity liquid crystal polymer provided by the invention comprises the steps of drying the wholly aromatic liquid crystal polyester resin, the ground glass fiber and the filler, mixing, melting and mixing the mixture, extruding, drawing into strips, cooling and granulating to obtain the high-fluidity liquid crystal polymer. The preparation method can ensure that all components are fully dispersed and mutually act, so that the prepared high-fluidity liquid crystal polymer has stronger fluidity. 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 crystalline polyester resin, the milled glass fiber and the filler are weighed according to the high-fluidity liquid crystalline 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 crystalline polyester resin is composed of the monomers, so that the prepared wholly aromatic liquid crystalline polyester resin has better performance, and the high-fluidity liquid crystalline 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 quickly, and is beneficial to subsequent reaction.
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 ground glass fiber and the filler are subjected to a drying process; the drying treatment is carried out for removing moisture and ensuring that each component is dried; if the drying treatment is not carried out, the product can generate bubbles in the subsequent process of preparing the high-fluidity 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 ensured to be better. More 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 above step S03, the wholly aromatic liquid crystalline polyester resin, the ground glass fiber, 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 melted and mixed, and then extruded, pulled into a strand, cooled, and granulated to obtain the high-fluidity 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 high-fluidity liquid crystal polyester compound is prepared through extrusion, bracing, cooling and granulation.
Further, specific examples are described.
Example 1
High-fluidity liquid crystal polymer
The high-fluidity liquid crystal polymer comprises 60 parts of wholly aromatic liquid crystal polyester resin; 10 parts of milled glass fibers; 30 parts of talcum powder; wherein the diameter of the milled glass fiber is 7 μm, and the model is Mount Taishan EMG7-70.
The preparation method of the high-fluidity liquid crystal polymer comprises the following steps: weighing the components according to the high-fluidity liquid crystal polymer; drying the wholly aromatic liquid crystalline polyester resin, the milled glass fiber and the filler at 140 ℃ for 6 hours; putting the wholly aromatic liquid crystal polyester resin after drying treatment, the ground glass fiber and the filler 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 high-fluidity liquid crystal polymer.
Example 2
High-fluidity liquid crystal polymer
The high-fluidity liquid crystal polymer comprises 60 parts of wholly aromatic liquid crystal polyester resin; 30 parts of milled glass fibers; 10 parts of talcum powder; wherein the milled glass fiber has a diameter of 7 μm and a model of Mount Taishan EMG of 7-70.
The preparation method of the high-fluidity liquid crystal polymer comprises the following steps: weighing the components according to the high-fluidity liquid crystal polymer; drying the wholly aromatic liquid crystalline polyester resin, the milled glass fiber and the filler at 140 ℃ for 6 hours; putting the wholly aromatic liquid crystal polyester resin after drying treatment, the ground glass fiber and the filler 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 high-fluidity liquid crystal polymer.
Comparative example 1
High-fluidity liquid crystal polymer
The high-fluidity liquid crystal polymer comprises 60 parts of wholly aromatic liquid crystal polyester resin; 10 parts of milled glass fibers; 30 parts of talcum powder; wherein the milled glass fibers have a diameter of 10 μm.
The preparation method of the high-fluidity liquid crystal polymer comprises the following steps: weighing the components according to the high-fluidity liquid crystal polymer; drying the wholly aromatic liquid crystalline polyester resin, the milled glass fiber and the filler at 140 ℃ for 6 hours; putting the wholly aromatic liquid crystal polyester resin after drying treatment, the ground glass fiber and the filler 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 high-fluidity liquid crystal polymer.
Comparative example 2
High-fluidity liquid crystal polymer
The high-fluidity liquid crystal polymer comprises 60 parts of wholly aromatic liquid crystal polyester resin; 30 parts of milled glass fibers; 10 parts of talcum powder; wherein the milled glass fibers have a diameter of 10 μm.
The preparation method of the high-fluidity liquid crystal polymer comprises the following steps: weighing the components according to the high-fluidity liquid crystal polymer; drying the wholly aromatic liquid crystalline polyester resin, the milled glass fiber and the filler at 140 ℃ for 6 hours; putting the wholly aromatic liquid crystal polyester resin after drying treatment, the ground glass fiber and the filler 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 high-fluidity liquid crystal polymer.
In order to verify the properties of the high-fluidity liquid crystal polymers prepared in examples 1-2 and comparative examples 1-2 of the present invention, the high-fluidity liquid crystal polymers obtained in the above examples 1-2 and comparative examples 1-2, respectively, were used as injection molding materials, injection-molded using an injection molding machine, and the properties of the compounds in the examples and comparative examples were tested and evaluated by the following methods:
(1) Melt index
The melt index according to the examples of the present invention was measured at 280 ℃ and 10kgs using a capillary rheometer (RH 2000).
(2) Flexural strength, flexural modulus and flexural strain
The flexural strength measurements to which the examples of the invention relate follow ASTM D-790.
(3) Heat distortion temperature
The heat distortion temperature measurements referred to in the examples of the present invention were made according to ASTM D-648.
(4) Breaking strength
The fracture strength of the examples of the present invention was measured according to ASTM D-638 with a prototype standard of 80X 3X 0.2mm.
Results analysis is shown in Table 1 below, and it can be seen from Table 1 that the fluidity of the high-fluidity liquid crystal polymer is further characterized by the determination of the melt index, the melt index of the high-fluidity liquid crystal polymer prepared in example 1 is 24.3g/10min, the melt index of the high-fluidity liquid crystal polymer prepared in example 2 is 30.1g/10min, the melt index of the high-fluidity liquid crystal polymer prepared in comparative example 1 is 21.0g/10min, and the melt index of the high-fluidity liquid crystal polymer prepared in comparative example 2 is 26.6g/10min, and according to the data obtained by the determination, the melt index of the 7 micron milled glass fiber modified high-fluidity liquid crystal polymer prepared in example 1 is 3.3g/10min higher than the melt index of the 10 micron milled glass fiber modified high-fluidity liquid crystal polymer prepared in comparative example 1; the melt index of the high-fluidity liquid crystal polymer modified by adding 7-micron milled glass fiber prepared in example 2 was 3.5g/10min higher than that of the high-fluidity liquid crystal polymer modified by adding 10-micron milled glass fiber prepared in comparative example 2.
Meanwhile, the high-fluidity liquid crystal polymer prepared in the embodiment 1 and the embodiment 2 can keep better bending strength performance, bending strain performance, bending modulus performance, heat distortion temperature and breaking strength, the high-fluidity liquid crystal polymer provided by the invention takes wholly aromatic liquid crystal polyester resin as a parent material, ground glass fibers with the diameter of 6-9 microns are added, and the wholly aromatic liquid crystal polyester resin is modified by utilizing the ground glass fibers with the diameter of 6-9 microns.
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 (8)
1. The high-fluidity liquid crystal polymer is characterized by being formed by melting and mixing the following components in parts by weight:
60 parts of wholly aromatic liquid crystal polyester resin;
grinding 30 parts of glass fiber;
10 parts of a filler;
wherein the milled glass fibers have a diameter of 7 μm;
the milled glass fibers have a length of 10 to 100 μm;
the model of the ground glass fiber is EMG7-70;
the filler is talcum powder.
2. The high flow liquid crystalline polymer of claim 1, wherein the milled glass fiber has a needle-like structure.
3. The high-fluidity liquid crystal polymer according to any one of claims 1 to 2, wherein the wholly aromatic liquid crystal polyester resin comprises 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 derived 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.
4. A preparation method of a high-fluidity liquid crystal polymer is characterized by comprising the following steps:
weighing the components according to the high-fluidity liquid crystal polymer of any one of claims 1 to 3;
drying the wholly aromatic liquid crystalline polyester resin, the milled glass fiber, and the filler;
mixing the wholly aromatic liquid crystal polyester resin, the ground glass fibers and the filler after drying treatment to obtain a first mixture;
and melting and mixing the first mixture, extruding, bracing, cooling and granulating to obtain the high-fluidity liquid crystal polymer.
5. The method for producing a high-fluidity liquid-crystalline polymer according to claim 4, wherein the temperature of the drying treatment is 120 to 160 ℃.
6. The method of preparing a high fluidity liquid crystal polymer according to claim 5, 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.
7. The method of claim 6, wherein the polycondensation reaction is selected from a solution polycondensation method and a bulk polycondensation method in the step of preparing the wholly aromatic liquid crystalline polyester prepolymer.
8. The method for preparing a high-fluidity liquid-crystalline polymer according to claim 6, wherein the monomeric substance is pretreated with an acylating agent.
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| CN113527844A (en) * | 2021-08-31 | 2021-10-22 | 重庆沃特智成新材料科技有限公司 | Low-surface-roughness liquid crystal polyester compound and preparation method thereof |
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Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002294038A (en) * | 2001-03-28 | 2002-10-09 | Sumitomo Chem Co Ltd | Liquid crystal ester resin composition |
| JP2009108179A (en) * | 2007-10-30 | 2009-05-21 | Sumitomo Chemical Co Ltd | Liquid crystalline polyester resin composition and connector comprising the resin composition |
| JP5325442B2 (en) * | 2008-03-28 | 2013-10-23 | Ｊｘ日鉱日石エネルギー株式会社 | Liquid crystalline polyester resin composition for camera modules |
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| KR20120052647A (en) * | 2010-11-16 | 2012-05-24 | 삼성정밀화학 주식회사 | Wholly aromatic liquid crystalline polyester resin compound with enhanced fluidity |
| WO2012117475A1 (en) * | 2011-02-28 | 2012-09-07 | 東レ株式会社 | Liquid crystal polyester resin composition and metal composite molded article using same |
| CN106633859A (en) * | 2016-12-29 | 2017-05-10 | 江苏沃特特种材料制造有限公司 | Wholly aromatic liquid crystal polyester resin as well as preparation method and application thereof |
| JP7032904B2 (en) * | 2017-10-18 | 2022-03-09 | 上野製薬株式会社 | Liquid crystal polyester resin composition |
-
2019
- 2019-12-26 CN CN201911363992.3A patent/CN111117170B/en active Active
Non-Patent Citations (2)
| Title |
|---|
| Dynamic mechanical properties of unfilled and glass fiber filled liquid crystal polyester;H. C. Kim，等;《Journal of Macromolecular Science, Part B: Physics》;第33卷(第1期);第11-20页 * |
| 不同无机物改性热致液晶聚合物材料的介电性能;周广亮，等;《工程塑料应用》;第47卷(第7期);第110-113页 * |
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