CN111087765A - Low-density liquid crystal polymer and preparation method thereof - Google Patents
Low-density liquid crystal polymer and preparation method thereof Download PDFInfo
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- CN111087765A CN111087765A CN201911375568.0A CN201911375568A CN111087765A CN 111087765 A CN111087765 A CN 111087765A CN 201911375568 A CN201911375568 A CN 201911375568A CN 111087765 A CN111087765 A CN 111087765A
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- 229920000106 Liquid crystal polymer Polymers 0.000 title claims abstract description 119
- 239000004977 Liquid-crystal polymers (LCPs) Substances 0.000 title claims abstract description 97
- 238000002360 preparation method Methods 0.000 title description 18
- 239000011521 glass Substances 0.000 claims abstract description 94
- 239000011324 bead Substances 0.000 claims abstract description 88
- 125000003118 aryl group Chemical group 0.000 claims abstract description 86
- 229920001225 polyester resin Polymers 0.000 claims abstract description 68
- 239000004645 polyester resin Substances 0.000 claims abstract description 68
- 239000004973 liquid crystal related substance Substances 0.000 claims abstract description 64
- 239000000945 filler Substances 0.000 claims abstract description 27
- 239000004005 microsphere Substances 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims description 26
- 239000007788 liquid Substances 0.000 claims description 24
- 238000002156 mixing Methods 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 21
- 239000000203 mixture Substances 0.000 claims description 21
- 238000006068 polycondensation reaction Methods 0.000 claims description 17
- 229920000728 polyester Polymers 0.000 claims description 13
- 238000001816 cooling Methods 0.000 claims description 12
- 239000000178 monomer Substances 0.000 claims description 12
- 238000005303 weighing Methods 0.000 claims description 9
- -1 whiskers Substances 0.000 claims description 8
- 238000002844 melting Methods 0.000 claims description 5
- 230000008018 melting Effects 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 4
- 229920001577 copolymer Polymers 0.000 claims description 4
- 239000007790 solid phase Substances 0.000 claims description 4
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 2
- 239000006229 carbon black Substances 0.000 claims description 2
- 239000004927 clay Substances 0.000 claims description 2
- 229910052570 clay Inorganic materials 0.000 claims description 2
- 239000010445 mica Substances 0.000 claims description 2
- 229910052618 mica group Inorganic materials 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 239000000454 talc Substances 0.000 claims description 2
- 229910052623 talc Inorganic materials 0.000 claims description 2
- 239000004408 titanium dioxide Substances 0.000 claims description 2
- 239000010456 wollastonite Substances 0.000 claims description 2
- 229910052882 wollastonite Inorganic materials 0.000 claims description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims 1
- 230000002195 synergetic effect Effects 0.000 abstract description 10
- 239000011159 matrix material Substances 0.000 abstract description 6
- 239000011825 aerospace material Substances 0.000 abstract description 5
- 230000000052 comparative effect Effects 0.000 description 9
- 239000002131 composite material Substances 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 239000007789 gas Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 230000004927 fusion Effects 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 3
- 150000004984 aromatic diamines Chemical class 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000001746 injection moulding Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical compound NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 239000004974 Thermotropic liquid crystal Substances 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- 239000004976 Lyotropic liquid crystal Substances 0.000 description 1
- 239000012345 acetylating agent Substances 0.000 description 1
- 230000000397 acetylating effect Effects 0.000 description 1
- 230000010933 acylation Effects 0.000 description 1
- 238000005917 acylation reaction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 125000002529 biphenylenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C12)* 0.000 description 1
- 238000009529 body temperature measurement Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000001739 density measurement Methods 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- 239000007777 multifunctional material Substances 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
-
- 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
-
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention provides a low-density liquid crystal polymer which comprises the following components in parts by weight: 60-90 parts of wholly aromatic liquid crystal polyester resin; 10-30 parts of hollow glass beads; 1-3 parts of a compatilizer; 1-30 parts of a filler; wherein the diameter of the hollow glass bead is 10-50 μm. The low-density liquid crystal polymer takes wholly aromatic liquid crystal polyester resin as a matrix material, and the wholly aromatic liquid crystal polyester resin is modified by utilizing the synergistic effect of the hollow glass microspheres with the diameter of 10-50 mu m and the compatilizer, so that the overall density of the prepared liquid crystal polymer is reduced, the density of the prepared liquid crystal polymer is greatly reduced, and the low-density liquid crystal polymer has good thermal performance and can be widely applied to the fields of electronic and electrical, aerospace materials and the like.
Description
Technical Field
The invention relates to the field of high-molecular composite materials, in particular to a low-density 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. However, the liquid crystal polymer has a large molecular weight and a high density, and cannot meet the requirements of certain fields on light materials in the using process, so that the application range of the liquid crystal polymer is influenced.
Disclosure of Invention
The invention aims to provide a low-density liquid crystal polymer and a preparation method thereof, and aims to solve the problem that the application of the liquid crystal polymer in the field of light materials is limited due to the high density of the liquid crystal polymer in the prior art.
In order to achieve the purpose, the invention adopts the following technical scheme:
a low-density liquid crystal polymer comprises the following components in parts by weight:
wherein the diameter of the hollow glass bead is 10-50 μm.
And, a method for preparing a low-density liquid crystalline polymer, the method comprising the steps of:
weighing the components according to the low-density liquid crystal polymer;
drying the wholly aromatic liquid crystal polyester resin, the hollow glass beads, the compatibilizer, and the filler;
mixing the dried wholly aromatic liquid crystal polyester resin, the hollow glass bead compatilizer and the filler to obtain a first mixture;
and melting and mixing the first mixture, extruding, bracing, cooling and granulating to obtain the low-density liquid crystal polymer.
The low-density liquid crystal polymer takes wholly aromatic liquid crystal polyester resin as a matrix material, the wholly aromatic liquid crystal polyester resin is modified by adding hollow glass beads and a compatilizer with the diameter of 10-50 mu m and utilizing the synergistic effect of the hollow glass beads and the compatilizer with the diameter of 10-50 mu m, the hollow glass beads are hollow structures and have hard shells, the shells are filled with thin gas, the density of air is low, the hollow glass beads with the hollow structures are added, the hollow glass beads are mixed with the wholly aromatic liquid crystal polyester resin, the compatilizer is added and has the synergistic effect with the hollow glass beads, the hollow glass beads are uniformly dispersed and are better fused with the wholly aromatic liquid crystal polyester resin, the overall density of the prepared liquid crystal polymer is further reduced, and the density of the prepared liquid crystal polymer is greatly reduced, meanwhile, the composite material has good thermal performance and can be widely applied to the fields of electronics, electrics, aerospace materials and the like.
The preparation method of the low-density liquid crystal polymer provided by the invention comprises the steps of drying the wholly aromatic liquid crystal polyester resin, the hollow glass beads, the compatilizer and the filler, mixing, melting and mixing the mixture, extruding, drawing into strips, cooling and granulating to obtain the low-density liquid crystal polymer. The preparation method can ensure that all components are fully dispersed and mutually act, so that the prepared low-density liquid crystal polymer has low-density 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-density liquid crystal polymer, which comprises the following components in parts by weight:
wherein the diameter of the hollow glass bead is 10-50 μm.
The low-density liquid crystal polymer takes wholly aromatic liquid crystal polyester resin as a matrix material, the wholly aromatic liquid crystal polyester resin is modified by adding hollow glass beads and a compatilizer with the diameter of 10-50 mu m and utilizing the synergistic effect of the hollow glass beads and the compatilizer with the diameter of 10-50 mu m, the hollow glass beads are hollow structures and have hard shells, the shells are filled with thin gas, the density of air is low, the hollow glass beads with the hollow structures are added, the hollow glass beads are mixed with the wholly aromatic liquid crystal polyester resin, the compatilizer is added and has the synergistic effect with the hollow glass beads, the hollow glass beads are uniformly dispersed and are better fused with the wholly aromatic liquid crystal polyester resin, the overall density of the prepared liquid crystal polymer is further reduced, and the density of the prepared liquid crystal polymer is greatly reduced, meanwhile, the composite material has good thermal performance and can be widely applied to the fields of electronics, electrics, aerospace materials and the like.
Specifically, the dense liquid crystal polymer includes 50 to 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 crystalline polyester resin is composed of the monomers, so that the prepared wholly aromatic liquid crystalline polyester resin has better performance, and the low-density 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 low-density liquid crystalline polymer, and can ensure high thermal stability and stable size of the prepared low-density liquid crystalline polymer.
Specifically, the low-density 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 density of the liquid crystal polymer cannot be reduced well; if the amount is too small, the low-density liquid-crystalline polymer matrix material will be too small, affecting the heat resistance, dimensional stability and mechanical properties of the low-density liquid-crystalline 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-density liquid crystal polymer comprises 10-30 parts of hollow glass beads, and the diameter of each hollow glass bead is 10-50 microns. The method comprises the steps of modifying the wholly aromatic liquid crystal polyester resin by using hollow glass beads with the diameter of 10-50 mu m, wherein the hollow glass beads are of hollow structures and have hard shells, the shells are thin gases, the density of air is low, and the hollow glass beads with the hollow structures are added to mix with the wholly aromatic liquid crystal polyester resin, so that the density of the prepared liquid crystal polymer is reduced. In specific applications, for example, the low-density liquid crystal polymer is interacted with an aerospace material, so that the prepared material has low density and is beneficial to use.
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 distribution is uneven, the density of the liquid crystal polymer cannot be reduced, and other properties such as mechanical property and the like of the prepared low-density 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 distribution of the hollow glass beads is uneven, the density of the liquid crystal polymer cannot be reduced, and other properties such as mechanical properties of the prepared low-density liquid crystal polymer are affected. 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 prepared liquid crystal composite is low in density, and the preparation method is favorable for being applied to the fields of electronics, aerospace 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, thin gas is filled in the shell, the density of air is low, the hollow glass beads are favorably and uniformly mixed with the wholly aromatic liquid crystal polyester resin, and the density of the prepared liquid crystal compound is low.
Preferably, the type of the hollow glass bead is any one selected from 3M iM16K, 3M S60, 3M VS5500, 3M K20 and SHENNA K110. 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 shells are thin gas, the air density is low, 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 density 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-density liquid crystal polymer comprises 10-30 parts of hollow glass microspheres; if the addition amount is too much, the hollow glass beads are easy to agglomerate, so that the distribution is uneven, the density of the liquid crystal polymer cannot be reduced, and other properties such as mechanical property and the like of the prepared low-density liquid crystal polymer are influenced; if the amount of the additive is too small, fusion between the hollow glass beads and the wholly aromatic liquid crystalline polyester resin is incomplete, resulting in uneven distribution of the hollow glass beads, and the density of the liquid crystalline polymer cannot be reduced. In the specific embodiment of the present invention, the specific addition parts of the hollow glass beads may be: 5 parts, 10 parts, 15 parts, 20 parts, 25 parts and 30 parts.
Specifically, the low-density liquid crystal polymer comprises 1-3 parts of a compatilizer; the purpose of adding the compatilizer is to enable the glass beads to be dispersed more uniformly, and the fusion degree of the glass beads and the wholly aromatic liquid crystal polyester resin can be improved, so that the overall density of the glass beads and the wholly aromatic liquid crystal polyester resin is reduced. Preferably, the compatibilizer is selected from a methacrylate copolymer or an ethacrylate copolymer; further preferably, the type of the compatilizer is any one selected from GMA Lotader AX8840, PET-1010, SAG-002 and HS 3-310A. In a preferred embodiment of the invention, the compatilizer is GMA Lotader AX8840, and the compatilizer can generate a synergistic effect with the wholly aromatic liquid crystal polyester resin and the hollow glass beads, so that the compatibility between the wholly aromatic liquid crystal polyester resin and the hollow glass beads is promoted, and the prepared liquid crystal polymer is low in density.
Preferably, the low-density liquid crystal polymer comprises 1-3 parts of a compatilizer, and if the addition amount of the compatilizer is too small, the fusion effect of the glass beads and the wholly aromatic liquid crystal polyester resin is poor; if the addition amount of the compatibilizer is too large, the mechanical properties of the liquid crystal polymer prepared are affected.
Specifically, the low-density liquid crystal polymer also comprises 1-30 parts of filler. If the amount of the hollow glass microspheres is too large, the synergistic effect between the hollow glass microspheres and the wholly aromatic liquid crystalline polyester resin is affected, and the density 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 embodiment of the present invention, the specific addition parts of the filler may be 5 parts, 10 parts, 15 parts, 20 parts, 25 parts, and 30 parts.
The low-density liquid crystal polymer is prepared by the following preparation method of the low-density liquid crystal polymer.
Correspondingly, the embodiment of the invention also provides a preparation method of the low-density liquid crystal polymer. The method comprises the following steps:
s01, weighing each component according to the low-density liquid crystal polymer;
s02, drying the wholly aromatic liquid crystal polyester resin, the hollow glass beads, the compatilizer and the filler;
s03, mixing the dried wholly aromatic liquid crystal polyester resin, the hollow glass bead compatilizer 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-density liquid crystal polymer.
The preparation method of the low-density liquid crystal polymer provided by the invention comprises the steps of drying the wholly aromatic liquid crystal polyester resin, the hollow glass beads, the compatilizer and the filler, mixing, melting and mixing the mixture, extruding, drawing into strips, cooling and granulating to obtain the low-density liquid crystal polymer. The preparation method can ensure that all components are fully dispersed and mutually act, so that the prepared low-density liquid crystal polymer has low-density 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, weighing the components of the wholly aromatic liquid crystal polyester resin, the hollow glass beads, the compatibilizer, and the filler according to the low-density liquid crystal polymer; the addition amount of the components is as described above, and is not described 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 crystalline polyester resin is composed of the monomers, so that the prepared wholly aromatic liquid crystalline polyester resin has better performance, and the low-density 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 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 hollow glass beads, the compatibilizer, and the filler are subjected to a drying treatment; 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-density 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 120 ℃, and the time of the drying process is 6 hours.
In the above step S03, the wholly aromatic liquid crystalline polyester resin, the hollow glass beads, the compatibilizer, 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 low-density liquid crystal polymer is obtained by melt-kneading the first mixture, extruding, drawing, cooling, and granulating. 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-density liquid crystal polyester compound is prepared through extrusion, drawing, cooling and granulation.
Further, specific examples are described.
Example 1
Low-density liquid crystal polymer
The low-density liquid crystal polymer comprises 73 parts of wholly aromatic liquid crystal polyester resin; 25 parts of hollow glass microspheres; 1 part of a compatilizer; 1 part of a filler; 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-density liquid crystal polymer comprises the following steps: weighing the components according to the low-density liquid crystal polymer; drying the wholly aromatic liquid crystalline polyester resin, the hollow glass beads, the compatibilizer, and the filler at 120 ℃ for 6 hours; putting the wholly aromatic liquid crystal polyester resin, the hollow glass beads, the compatilizer and the filler 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-density liquid crystal polymer.
Example 2
Low-density liquid crystal polymer
The low-density liquid crystal polymer includes, for example, 83 parts of wholly aromatic liquid crystal polyester resin; 15 parts of hollow glass beads; 1 part of a compatilizer; 1 part of a filler; 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-density liquid crystal polymer comprises the following steps: weighing the components according to the low-density liquid crystal polymer; drying the wholly aromatic liquid crystalline polyester resin, the hollow glass beads, the compatibilizer, and the filler at 120 ℃ for 6 hours; putting the wholly aromatic liquid crystal polyester resin, the hollow glass beads, the compatilizer and the filler 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-density liquid crystal polymer.
Example 3
Low-density liquid crystal polymer
The low-density liquid crystal polymer includes, for example, 69 parts of wholly aromatic liquid crystal polyester resin; 10 parts of hollow glass beads; 1 part of a compatilizer; 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-density liquid crystal polymer comprises the following steps: weighing the components according to the low-density liquid crystal polymer; drying the wholly aromatic liquid crystalline polyester resin, the hollow glass beads, the compatibilizer, and the filler at 120 ℃ for 6 hours; putting the wholly aromatic liquid crystal polyester resin, the hollow glass beads, the compatilizer and the filler 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-density liquid crystal polymer.
Comparative example 1
Low-density liquid crystal polymer
The low-density liquid crystal polymer includes, for example, 99 parts of wholly aromatic liquid crystal polyester resin; 1 part of compatilizer.
The preparation method of the low-density liquid crystal polymer comprises the following steps: weighing the components according to the low-density liquid crystal polymer; drying the wholly aromatic liquid crystal polyester resin and the compatilizer at 120 ℃ for 6 hours; putting the wholly aromatic liquid crystal polyester resin and the compatilizer 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-density liquid crystal polymer.
Comparative example 2
Low-density liquid crystal polymer
The low-density liquid crystal polymer includes, for example, 69 parts of wholly aromatic liquid crystal polyester resin; 1 part of a compatilizer; 30 parts of glass fiber.
The preparation method of the low-density liquid crystal polymer comprises the following steps: weighing the components according to the low-density liquid crystal polymer; drying the wholly aromatic liquid crystalline polyester resin, the compatibilizer, and the filler at 120 ℃ for 6 hours; putting the wholly aromatic liquid crystal polyester resin after drying treatment, the compatilizer 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 low-density 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) 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) Density of
The density measurements referred to in the examples of the present invention were in accordance with ASTM D-792.
Results analysis As shown in Table 1 below, the density of the low-density liquid-crystalline polymer prepared in example 1, which can be obtained from Table 1, was 1.09g/cm3(ii) a Example 2 the low density liquid crystalline polymer prepared had a density of 1.18g/cm3(ii) a Example 3 the low density liquid crystalline polymer prepared had a density of 1.37g/cm3(ii) a The density of the low-density liquid-crystalline polymer prepared in comparative example 1 was 1.09g/cm3(ii) a Comparative example 2 the low-density liquid-crystalline polymer prepared in this way had a density of 1.60g/cm3。
Further analysis shows that the density of the low-density liquid crystal polymer (such as examples 1-3) obtained by modifying with the hollow glass beads, the compatilizer and the filler is obviously reduced, and the density of the low-density liquid crystal polymer (such as comparative example 1 and comparative example 2) obtained by not adding the hollow glass beads is higher. The low-density liquid crystal polymer prepared in the embodiments 1 to 3 has excellent bending strength, bending modulus and heat distortion temperature, and is beneficial to wide application.
The low-density liquid crystal polymer takes wholly aromatic liquid crystal polyester resin as a matrix material, the wholly aromatic liquid crystal polyester resin is modified by adding hollow glass beads and a compatilizer with the diameter of 10-50 mu m and utilizing the synergistic effect of the hollow glass beads and the compatilizer with the diameter of 10-50 mu m, the hollow glass beads are hollow structures and have hard shells, the shells are filled with thin gas, the density of air is low, the hollow glass beads with the hollow structures are added, the hollow glass beads are mixed with the wholly aromatic liquid crystal polyester resin, the compatilizer is added and has the synergistic effect with the hollow glass beads, the hollow glass beads are uniformly dispersed and are better fused with the wholly aromatic liquid crystal polyester resin, the overall density of the prepared liquid crystal polymer is further reduced, and the density of the prepared liquid crystal polymer is greatly reduced, meanwhile, the composite material has good thermal performance and can be widely applied to the fields of electronics, electrics, aerospace materials and the like.
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-density liquid crystal polymer is characterized by comprising the following components in parts by weight:
wherein the diameter of the hollow glass bead is 10-50 μm.
2. The low density liquid crystalline polymer of claim 1, wherein the hollow glass microspheres have a wall thickness of 1 to 2 μm.
3. The low-density liquid crystal polymer according to claim 1, wherein the hollow glass beads have a size selected from any one of 3M iM16K, 3M S60, 3M VS5500, 3M K20, and shen K110.
4. A low density liquid crystalline polymer according to any of claims 1 to 3, wherein the compatibilizer is selected from a methacrylate copolymer or an ethyl acrylate copolymer.
5. The low-density liquid crystal polymer according to any one of claims 1 to 3, wherein the type of the compatibilizer is any one selected from GMA Lotader AX8840, PET-1010, SAG-002, HS 3-310A.
6. A low-density liquid-crystalline polymer according to any one of claims 1 to 3, wherein said filler is at least one selected from talc, whiskers, wollastonite, mica, titanium dioxide, carbon black, calcium carbonate, clay, barium sulfate and silica.
7. A method for preparing a low-density liquid crystal polymer, comprising the steps of:
weighing the components according to the low density liquid crystal polymer of any one of claims 1 to 6;
drying the wholly aromatic liquid crystal polyester resin, the hollow glass beads, the compatibilizer, and the filler;
mixing the dried wholly aromatic liquid crystal polyester resin, the hollow glass bead compatilizer and the filler to obtain a first mixture;
and melting and mixing the first mixture, extruding, bracing, cooling and granulating to obtain the low-density liquid crystal polymer.
8. The method for preparing a low-density liquid crystalline polymer according to claim 7, wherein the temperature of the drying treatment is 120 to 160 ℃.
9. The method of preparing a low density liquid crystalline polymer according to claim 7, wherein the method of preparing the wholly aromatic liquid crystalline 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.
10. The method of preparing a low-density liquid crystalline polymer according to claim 9, wherein the step of performing a polycondensation reaction to obtain the wholly aromatic liquid crystalline polyester prepolymer is a polycondensation reaction selected from a solution polycondensation method or a bulk polycondensation method.
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