CN105542408A - Modified wholly aromatic liquid crystal polyester resin composition and preparation method thereof - Google Patents
Modified wholly aromatic liquid crystal polyester resin composition and preparation method thereof Download PDFInfo
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- CN105542408A CN105542408A CN201511010425.1A CN201511010425A CN105542408A CN 105542408 A CN105542408 A CN 105542408A CN 201511010425 A CN201511010425 A CN 201511010425A CN 105542408 A CN105542408 A CN 105542408A
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- polyester resin
- liquid crystal
- wholly aromatic
- crystal polyester
- aromatic liquid
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- 125000003118 aryl group Chemical group 0.000 title claims abstract description 86
- 239000004645 polyester resin Substances 0.000 title claims abstract description 83
- 229920001225 polyester resin Polymers 0.000 title claims abstract description 83
- 239000004973 liquid crystal related substance Substances 0.000 title claims abstract description 63
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000000203 mixture Substances 0.000 title abstract description 9
- 239000000945 filler Substances 0.000 claims abstract description 36
- 239000000654 additive Substances 0.000 claims abstract description 17
- 230000000996 additive effect Effects 0.000 claims abstract description 14
- 150000001875 compounds Chemical class 0.000 claims description 48
- 239000007788 liquid Substances 0.000 claims description 25
- 239000000463 material Substances 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 15
- -1 aromatic diol Chemical class 0.000 claims description 14
- 239000003365 glass fiber Substances 0.000 claims description 11
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 9
- 238000006068 polycondensation reaction Methods 0.000 claims description 9
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 8
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 7
- 150000001491 aromatic compounds Chemical class 0.000 claims description 6
- 239000000178 monomer Substances 0.000 claims description 6
- 229920000728 polyester Polymers 0.000 claims description 6
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 4
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical compound NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 claims description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 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
- 150000004984 aromatic diamines Chemical class 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
- 125000002529 biphenylenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C12)* 0.000 claims description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims description 4
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 2
- 239000006229 carbon black Substances 0.000 claims description 2
- 239000004917 carbon fiber Substances 0.000 claims description 2
- 239000004927 clay Substances 0.000 claims description 2
- 229910052570 clay Inorganic materials 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 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
- 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
- 238000002844 melting Methods 0.000 claims 1
- 230000008018 melting Effects 0.000 claims 1
- 238000012643 polycondensation polymerization Methods 0.000 claims 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims 1
- 239000004810 polytetrafluoroethylene Substances 0.000 claims 1
- 235000012239 silicon dioxide Nutrition 0.000 claims 1
- 239000002131 composite material Substances 0.000 abstract description 13
- 238000012545 processing Methods 0.000 abstract description 4
- 230000000052 comparative effect Effects 0.000 description 7
- 239000002994 raw material Substances 0.000 description 6
- 239000007790 solid phase Substances 0.000 description 4
- 238000011161 development Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000008054 signal transmission Effects 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000012345 acetylating agent Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000000805 composite resin Substances 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 125000005504 styryl group Chemical group 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 235000012222 talc Nutrition 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 238000010407 vacuum cleaning Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 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
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
- C08L67/03—Polyesters derived from dicarboxylic acids and dihydroxy compounds the dicarboxylic acids and dihydroxy compounds having the carboxyl- and the hydroxy groups directly linked to aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention belongs to the technical field of high-molecular composite materials, and particularly discloses a modified wholly aromatic liquid crystal polyester resin composition and a preparation method thereof. The composition is prepared from the following components in parts by weight: 50-70 parts of liquid crystal polyester resin, 0.5-5 parts of additive, 0-40 parts of filler I and 0-30 parts of filler II. The wholly aromatic liquid crystal polyester resin composition has the most prominent performance of low dielectric constant, and is excellent in other performances, such as mechanical performance, heat resistance and the like, has low melt viscosity, and finally shows excellent processing performance. Therefore, the modified wholly aromatic liquid crystal polyester resin composition can be widely applied to the field of high-frequency electronic parts.
Description
Technical Field
The invention relates to the technical field of polymer composite materials, in particular to a modified wholly aromatic liquid crystal polyester resin compound and a preparation method thereof.
Background
Because wholly aromatic liquid crystalline polyester resin (LCP) has excellent heat resistance, dimensional stability and melt flowability, it is very suitable for use as a material for precision instrument parts. Especially, the material has excellent electrical insulation property, so the material can be widely applied to high-end electronic material films and substrate raw materials, and the application prospect is very optimistic.
With the rapid development of the electronic information industry, the trend of electronic devices toward high frequency development is more and more obvious, and especially with the rapid development of electronic products, communication products and satellite transmission, information products gradually move toward high speed and high frequency, which requires materials with more excellent performance as a basis. Therefore, this also puts higher demands on the performance of LCP as a raw material of electronic parts. The high frequency resistance of a material is determined by its dielectric properties, and since the signal transmission rate is inversely proportional to the square root of the dielectric constant of the material, a high dielectric constant tends to cause a delay in signal transmission, and thus, in future electronic components, the dielectric constant (Dk) of the LCP material must be small and stable. However, the dielectric properties of the existing LCP composite are not good, and when the LCP composite is used in the field of high-frequency electronic components, the delay is long, the signal loss is large, and the final signal distortion is often caused.
Based on the existing defects, the patent aims to solve the problems by optimizing the formula of the LCP compound and providing the LCP compound with greatly reduced dielectric constant.
Disclosure of Invention
The invention provides a modified wholly aromatic liquid crystal polyester resin compound and a preparation method thereof, aiming at solving the problem of large dielectric constant of the existing wholly aromatic liquid crystal polyester resin compound.
In order to achieve the purpose of the invention, the embodiment of the invention adopts the following technical scheme:
a modified wholly aromatic liquid crystal polyester resin compound comprises the following components in parts by weight:
and a method for preparing a modified wholly aromatic liquid crystalline polyester resin compound, comprising at least the steps of:
s01, weighing the liquid crystal polyester resin, the additive, the first filler and the second filler according to the proportion;
s02, drying the weighed liquid crystal polyester resin, additive, filler I and filler II respectively;
s03, mixing the liquid crystal polyester resin processed by the S02, the additive, the first filler and the second filler;
and S04, carrying out melt mixing, extruding, drawing, cooling and granulating on the mixed material obtained in the S03.
In the embodiment of the invention, only two pairs of liquid crystal polyester resins, namely the additive, the filler I and the filler, are adopted for modification, so that the modified wholly aromatic liquid crystal polyester resin compound with excellent mechanical property and heat resistance, reduced melt viscosity and obviously reduced dielectric constant can be obtained, and meanwhile, the modified wholly aromatic liquid crystal polyester resin compound also has good processing performance.
According to the preparation method of the modified wholly aromatic liquid crystal polyester resin compound provided by the embodiment of the invention, the production raw materials are simple, excessive addition agents are not required, the liquid crystal polyester resin, the additive and two fillers are mixed and then melted and extruded, the fillers can be uniformly dispersed in the liquid crystal polyester resin, and the compound with more excellent performance is finally obtained.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The embodiment of the invention provides a modified wholly aromatic liquid crystal polyester resin compound which comprises the following components in parts by weight:
wherein,
in any one of the embodiments, the liquid crystal polyester resin refers to a wholly aromatic liquid crystal polyester resin. The wholly aromatic liquid crystalline polyester resin is prepared by the following steps:
carrying out polycondensation reaction by adopting at least two monomers to synthesize a wholly aromatic liquid crystal polyester prepolymer; and then carrying out solid-phase polycondensation on the obtained wholly aromatic liquid crystal polyester prepolymer to finally obtain the wholly aromatic liquid crystal polyester resin.
The monomer referred to herein includes aromatic dicarboxylic acid and at least one of a free aromatic diol, an aromatic diamine and an aromatic hydroxylamine. Further, the monomer may further include at least one of an aromatic hydroxycarboxylic acid and an aromatic aminocarboxylic acid.
The wholly aromatic liquid crystalline polyester resin according to any one of the examples has a repeating unit.
Wherein the free aromatic diol comprises repeating units of: -O-Ar-O-;
the aromatic diamine comprises repeating units of:
aromatic hydroxylamines comprise repeating units of:
the aromatic dicarboxylic acid comprises repeating units of:
the aromatic hydroxycarboxylic acid comprises repeating units of:
the aromatic aminocarboxylic acid comprises the repeating unit:
in the above repeating units, Ar represents phenylene, biphenylene, naphthalene, or an aromatic compound in which two phenylenes are bonded by an element of carbon or non-carbon; or an aromatic compound in which at least one hydrogen element in phenylene, biphenylene, naphthalene, or an aromatic compound in which two phenylenes are bonded by an element other than carbon is substituted with another element.
In the preparation process of the wholly aromatic liquid crystalline polyester resin, a solution polycondensation method or a bulk polycondensation method may be used. In order to accelerate the polycondensation reaction, the raw material may be pretreated with an acylating agent or the like, particularly an acetylating agent, in the process of synthesizing the wholly aromatic liquid crystalline polyester prepolymer.
In the solid phase polycondensation (solid phase polycondensation), it is necessary to supply an appropriate amount of heat to the wholly aromatic liquid crystalline polyester prepolymer, and specifically, the heat supply may be performed by a heating plate, hot air, high temperature fluid, or the like, and in order to remove the by-product of the solid phase polycondensation, purging with an inert gas or vacuum cleaning may be used.
In any of the examples, the additive is a polyhedral oligomeric silsesquioxane (POSS).
Specifically, the POSS has a physical size of 0.7-3nm and a molecular formula of (RSiO)1.5) Σ n, where Σ n is a multiple of 2 and the minimum value is 6.
In the above formula, R represents any of a hydrogen atom, an alkyl group, a phenyl group, a cycloalkyl group, a carboxyl group, an epoxy group, a hydrocarbon group, a vinyl group, and a styryl group. Additives of this type can lower the dielectric constant of the composite.
In any embodiment, the first filler is at least one of glass fiber, whisker, carbon fiber and tetrafluoroethylene. The addition of the first filler can enhance the mechanical property and the heat resistance of the compound.
In any embodiment, the second filler is at least one of wollastonite, talc, mica, titanium dioxide, carbon black, calcium carbonate, clay, barium sulfate, and silica. The addition of the second filler can enhance the heat resistance and the electrical property of the compound.
According to the modified wholly aromatic liquid crystal polyester resin compound provided by the embodiment of the invention, the wholly aromatic liquid crystal polyester resin and the polyhedral oligomeric silsesquioxane have good compatibility, other compatilizers are not required to be added, and the prepared modified wholly aromatic liquid crystal polyester resin compound has good mechanical property and heat resistance, low melt viscosity and dielectric constant and good processing property.
Accordingly, the present invention further provides a preparation method of the modified wholly aromatic liquid crystalline polyester resin compound according to the embodiment of the present invention on the basis of the above embodiment. In one embodiment, the method for preparing the modified wholly aromatic liquid crystalline polyester resin compound at least comprises the following steps:
s01, weighing the liquid crystal polyester resin, the additive, the first filler and the second filler according to the proportion;
s02, drying the weighed liquid crystal polyester resin, additive, filler I and filler II respectively;
s03, mixing the liquid crystal polyester resin processed by the S02, the additive, the first filler and the second filler;
and S04, carrying out melt mixing, extruding, drawing, cooling and granulating on the mixed material obtained in the S03.
In step S02, the drying temperature is 130-160 ℃, and the processing time is 4-6 h. The purpose of the drying treatment is mainly to fully dry the raw materials and avoid the influence of moisture on the performance of the final product.
In step S03, the liquid crystal polyester resin, the polyhedral oligomeric silsesquioxane, the filler one and the filler two are mixed to more uniformly disperse the filler in the composite so as to improve the performance of the composite, and an automatic mixer can be used for mixing. Of course, it is not limited to an automatic mixer.
In step S04, a twin-screw extruder is preferably used for melt kneading. Fusing at the screw rotation speed of 300RPM-600RPM, the temperature of the screw barrel is 320-370 ℃, and the vacuum degree is controlled at 0.5 MPa-0.8 MPa.
According to the preparation method of the modified wholly aromatic liquid crystal polyester resin compound provided by the embodiment of the invention, the production raw materials are simple, excessive addition of additives are not needed, and the liquid crystal polyester resin, the additives and the two fillers are mixed and then subjected to melt extrusion, so that the fillers can be uniformly dispersed in the resin, and the compound with more excellent performance is obtained.
The modified wholly aromatic liquid crystalline polyester resin compound provided above or the modified wholly aromatic liquid crystalline polyester resin compound prepared by the above preparation method can be applied to the field of high frequency electronic components. Of course, the application to high-frequency electronic components is only one application field of the modified wholly aromatic liquid crystal polyester resin compound provided by the embodiment of the present invention, and the modified wholly aromatic liquid crystal polyester resin compound provided by the embodiment of the present invention has the advantages of excellent mechanical properties and heat resistance, low melt viscosity and the like in addition to low dielectric constant, so the application field is not limited to high-frequency electronic components.
In order to better explain the modified wholly aromatic liquid crystalline polyester resin compound and the method for preparing the same according to the embodiments of the present invention, examples are given below.
Example 1
A modified wholly aromatic liquid crystal polyester resin compound comprises the following components in parts by weight:
the preparation method of the modified wholly aromatic liquid crystalline polyester resin compound provided in example 1 is as follows:
step S01, drying 64.5 parts of wholly aromatic liquid crystal polyester resin (provided by Jiangsu Wott special material manufacturing company), 0.5 part of dodecylphenyl POSS, 25 parts of glass fiber and 10 parts of talcum powder for 4 hours at the temperature of 130 ℃;
step S02, putting the dried wholly aromatic liquid crystal polyester resin, the dodecylphenyl POSS, the glass fiber and the talcum powder into an automatic mixer, and uniformly mixing to obtain a mixed material;
and S03, putting the mixture obtained in the step S02 into a double-screw extruder for melt mixing, and then extruding, drawing, cooling and granulating to obtain the modified wholly aromatic liquid crystal polyester resin compound.
Example 2
A modified wholly aromatic liquid crystal polyester resin compound comprises the following components in parts by weight:
the preparation method of the modified wholly aromatic liquid crystalline polyester resin compound provided in example 2 is as follows:
step S01, drying 64 parts of wholly aromatic liquid crystal polyester resin (provided by Jiangsu Wott special material manufacturing Co., Ltd.), 1 parts of dodecylphenyl POSS, 25 parts of glass fiber and 10 parts of talcum powder at 130 ℃ for 4 hours;
step S02, putting the dried wholly aromatic liquid crystal polyester resin, the dodecylphenyl POSS, the glass fiber and the talcum powder into an automatic mixer, and uniformly mixing to obtain a mixed material;
and S03, putting the mixture obtained in the step S02 into a double-screw extruder for melt mixing, and then extruding, drawing, cooling and granulating to obtain the modified wholly aromatic liquid crystal polyester resin compound.
Example 3
A modified wholly aromatic liquid crystal polyester resin compound comprises the following components in parts by weight:
the preparation method of the modified wholly aromatic liquid crystalline polyester resin compound provided in example 1 is as follows:
step S01, drying 64 parts of wholly aromatic liquid crystal polyester resin (provided by Jiangsu Wott special material manufacturing Co., Ltd.), 5 parts of dodecylphenyl POSS, 25 parts of glass fiber and 6 parts of talcum powder at 130 ℃ for 4 hours;
step S02, putting the dried wholly aromatic liquid crystal polyester resin, the dodecylphenyl POSS, the glass fiber and the talcum powder into an automatic mixer, and uniformly mixing to obtain a mixed material;
and S03, putting the mixture obtained in the step S02 into a double-screw extruder for melt mixing, and then extruding, drawing, cooling and granulating to obtain the modified wholly aromatic liquid crystal polyester resin compound.
Comparative example 1
A modified wholly aromatic liquid crystal polyester resin compound comprises the following components in parts by weight:
wholly aromatic liquid crystal polyester resin 65;
glass fibers 25;
talc powder 10.
The preparation method of the modified wholly aromatic liquid crystalline polyester resin compound provided in comparative example 1 is as follows:
step S01, drying 65 parts of wholly aromatic liquid crystal polyester resin (provided by Jiangsu Wott special material manufacturing Co., Ltd.), 25 parts of glass fiber and 10 parts of talcum powder at 130 ℃ for 4 hours;
step S02, putting the dried wholly aromatic liquid crystal polyester resin, the glass fiber and the talcum powder into an automatic mixer to be uniformly mixed to obtain a mixed material;
and S03, putting the mixture obtained in the step S02 into a double-screw extruder for melt mixing, and then extruding, drawing, cooling and granulating to obtain the modified wholly aromatic liquid crystal polyester resin compound.
In order to verify the properties of the composites prepared in examples 1 to 3 and comparative example 1 of the present invention, the composites obtained in examples 1 to 3 and comparative example 1 were used as injection molding materials, injection-molded using an injection molding machine, and then the properties of the composites in examples and comparative example were tested and evaluated by the following methods:
(1) tensile strength
The tensile strength according to the examples of the present invention was measured according to ASTM D-638.
(2) Heat distortion temperature
The heat distortion temperature according to the present invention was measured according to ASTM D-648.
(3) Dielectric constant
The dielectric constant related to the embodiment of the invention is tested according to ASTM D-150, and the testing frequency is 1KHz and 1 MHz.
(4) Melt viscosity
The melt viscosity according to the examples of the present invention was measured at 330 ℃ and 1000/s using a capillary rheometer (RH 2000).
The above test results are summarized in table 1.
Table 1 results of composite property test in examples and comparative examples
As can be seen from table 1 above, the dielectric constants of the modified wholly aromatic liquid crystalline polyester resin composites prepared in examples 1 to 3 at 1KHz and 1MHz were significantly reduced as compared with the resin composite prepared in comparative example 1, and other properties such as mechanical properties, heat resistance, and the like were excellent; at the same time, the melt viscosity is low, and good processability is exhibited. Thus, LCP composites prepared according to embodiments of the invention can be used in the field of high frequency electronic components.
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 or improvements made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (10)
1. A modified wholly aromatic liquid crystal polyester resin compound comprises the following components in parts by weight:
2. the modified wholly aromatic liquid crystalline polyester resin compound according to claim 1, wherein: the liquid crystal polyester resin is wholly aromatic liquid crystal polyester resin.
3. The modified wholly aromatic liquid crystalline polyester resin compound according to claim 2, wherein: the wholly aromatic liquid crystal polyester resin is prepared by the following steps:
A. carrying out condensation polymerization on at least two monomers to obtain a wholly aromatic liquid crystal polyester prepolymer;
B. carrying out solid-state polycondensation reaction on the wholly aromatic liquid crystal polyester prepolymer;
wherein the monomer is aromatic dicarboxylic acid and at least one of free aromatic diol, aromatic diamine and aromatic hydroxylamine.
4. The modified wholly aromatic liquid crystalline polyester resin compound according to claim 3, wherein: the monomer further includes at least one of an aromatic hydroxycarboxylic acid and an aromatic aminocarboxylic acid.
5. The modified wholly aromatic liquid crystalline polyester resin compound according to any one of claims 2 to 4, wherein: the free aromatic diol, the aromatic diamine, the aromatic hydroxylamine, the aromatic dicarboxylic acid, the aromatic hydroxycarboxylic acid, and the aromatic aminocarboxylic acid each contain a repeating unit represented by: -O-Ar-O-),
Wherein Ar is phenylene, biphenylene, naphthalene or an aromatic compound in which two phenylenes are bonded by carbon or non-carbon elements; or an aromatic compound in which a hydrogen element of at least one of phenylene, biphenylene, naphthalene, or an aromatic compound in which two phenylenes are bonded by a carbon or non-carbon element is substituted by another element.
6. The modified wholly aromatic liquid crystalline polyester resin compound according to claim 1, wherein: the additive is polyhedral oligomeric silsesquioxane.
7. The modified wholly aromatic liquid crystalline polyester resin compound according to any one of claims 1 to 2, wherein: the first filler is at least one of glass fiber, whisker, carbon fiber and polytetrafluoroethylene; and/or the second filler is at least one of wollastonite, talcum powder, mica, titanium dioxide, carbon black, calcium carbonate, clay, barium sulfate and silicon dioxide.
8. A preparation method of a modified wholly aromatic liquid crystal polyester resin compound at least comprises the following steps:
s01, weighing the liquid crystal polyester resin, the additive, the first filler and the second filler according to the proportion, wherein the first filler is the polyester resin as defined in any one of claims 1 to 7;
s02, drying the weighed liquid crystal polyester resin, additive, filler I and filler II respectively;
s03, mixing the liquid crystal polyester resin processed by the S02, the additive, the first filler and the second filler;
and S04, carrying out melt mixing, extruding, drawing, cooling and granulating on the mixed material obtained in the S03.
9. The method of preparing a modified wholly aromatic liquid crystalline polyester resin compound according to claim 8, wherein: the drying temperature is 130-160 ℃, and the treatment time is 4-6 h.
10. The method of preparing a modified wholly aromatic liquid crystalline polyester resin compound according to claim 8, wherein: the melting and mixing equipment is a double-screw extruder.
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| CN201511010425.1A CN105542408A (en) | 2015-12-29 | 2015-12-29 | Modified wholly aromatic liquid crystal polyester resin composition and preparation method thereof |
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| CN201511010425.1A CN105542408A (en) | 2015-12-29 | 2015-12-29 | Modified wholly aromatic liquid crystal polyester resin composition and preparation method thereof |
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Cited By (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106633680A (en) * | 2016-12-29 | 2017-05-10 | 江苏沃特特种材料制造有限公司 | Modified liquid crystal polyester resin composition, preparation method thereof and application of composition |
| CN109937230A (en) * | 2016-11-18 | 2019-06-25 | 住友化学株式会社 | Foam molding and method for producing foam molding |
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