CN105860465A - Liquid crystal polyester composition - Google Patents
Liquid crystal polyester composition Download PDFInfo
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- CN105860465A CN105860465A CN201610226657.9A CN201610226657A CN105860465A CN 105860465 A CN105860465 A CN 105860465A CN 201610226657 A CN201610226657 A CN 201610226657A CN 105860465 A CN105860465 A CN 105860465A
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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
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
- C08G63/065—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids the hydroxy and carboxylic ester groups being bound to aromatic rings
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/60—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from the reaction of a mixture of hydroxy carboxylic acids, polycarboxylic acids and polyhydroxy compounds
- C08G63/605—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from the reaction of a mixture of hydroxy carboxylic acids, polycarboxylic acids and polyhydroxy compounds the hydroxy and carboxylic groups being bound to aromatic rings
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/10—Metal compounds
- C08K3/14—Carbides
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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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
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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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08K5/00—Use of organic ingredients
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/098—Metal salts of carboxylic acids
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- 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
- 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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2231—Oxides; Hydroxides of metals of tin
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
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- C—CHEMISTRY; METALLURGY
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- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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Abstract
The invention discloses a liquid crystal polyester composition. The content of the metal barium element in the liquid crystal polyester composition is 0.1-500ppm. A test method of the weight content of the metal barium element comprises the following steps: drying the liquid crystal polyester composition at 120DEG C for 4h, taking 1g of a sample to be processed, adding nitric acid and hydrogen peroxide, heating the obtained mixture for 2h, and continuously adding nitric acid and hydrogen peroxide in the heating process; taking the obtained digested sample after digestion of the sample is completed, and analyzing the weight content of the metal barium element in the sample through adopting a fully-automatic inductively coupled plasma atomic emission spectrometer 720ES from Agilent Technologies. 0.1-500Ppm of the metal barium element is added to the formula of the liquid crystal polyester composition, so the high temperature resisting stability of the obtained liquid crystal polyester composition is unexpectedly substantially improved.
Description
Technical field
The present invention relates to polymeric material field, particularly to a kind of liquid-crystalline polyester composition.
Background technology
Liquid crystal polyester (LCP), as a kind of special engineered class material, compared with resins for universal use, has higher fusing point and height
Heat-resistant stability, but thermally decompose or because of the strand by external force hot shearing when liquid crystal polyester remains at high temperature processing
Chain rupture, causes the phenomenon that various aspects of performance declines.In order to improve the heat-resistant stability of liquid crystal polyester, those skilled in the art do
Many trials.
US5397502 discloses the liquid-crystalline polymer composition that a kind of heat-resistant stability improves, and compositions comprises 15 ~
The alkali metal of 3000ppm or the magnesium of 50 ~ 3000ppm or calcium；Liquid crystal polymer contains P-hydroxybenzoic acid, hydroquinone, biphenyl
Diphenol, p-phthalic acid, NDA and biphenyl dicarboxylic acid repetitive.The introducing of metallics improves compositions
Fusing point and heat distortion temperature, make thermostability be improved.But patent is mentioned and makes liquid crystal polymer and functional compound exist
Under high temperature contact and long enough make its melt viscosity decline at least 10%.Professional and technical personnel in the field institute is public
Knowing, liquid crystalline resin processes for a long time under higher than its melt temperature, owing to thermal decomposition can cause melt viscosity and molecular weight
Reducing, the decline also having mechanical property thus brought, and the generation of side reaction, this may increase the wind that resin bubbles
Danger.
CN1234749 discloses a kind of liquid-crystal polyester resin, wherein contain 4 hydroxyisophthalic acid and/or salicylic acid and
The repetitive come is as copolymer composition, and the alkali metal compound containing 10 ~ 5000ppm, and claims the coloring of resin excellent
Good, thermostability is high, and mechanicalness is good.This invention mainly stresses the improvement of liquid crystal polyester degree of staining and impact property, not in reality
Execute other parts in example or patent and illustrate whether heat resistance changes.And whether this patent undeclared invention are applicable to liquid crystal
Polymer blend.
US6755991 discloses a kind of liquid-crystalline polyester composition, comprises at least one aromatic dicarboxylic acid, and at least one contains naphthalene
Ring carboxylic acid and at least one alkali metal of 1 ~ 1000ppm and at least one transition metal of 0 ~ 3000ppm.Liquid crystal prepared by this invention
Polymer blend has whiteness and the impact strength of improvement, and whether not mentioned high-temperature heat-resistance stability changes.
Up to the present, high to described liquid-crystalline polyester composition about adding barium metal element in liquid-crystalline polyester composition
The impact of temperature heat-resistant stability has no report.
The present inventor through great many of experiments surprisingly it has been found that, select in liquid-crystalline polyester composition formula add barium metal unit
When the weight content gross weight based on liquid-crystalline polyester composition of element is 0.1ppm-500ppm, the liquid-crystalline polyester composition obtained
High-temperature heat-resistance stability obtain beyond thought significantly improving.
Summary of the invention
In order to overcome the shortcoming of prior art with not enough, the primary and foremost purpose of the present invention is to provide a kind of high-temperature heat-resistance stable
The liquid-crystalline polyester composition that property significantly improves.
The present invention is achieved through the following technical solutions:
A kind of liquid-crystalline polyester composition, gross weight based on liquid-crystalline polyester composition, the weight content of barium metal element is
0.1ppm-500ppm。
Being preferably based on the gross weight of liquid-crystalline polyester composition, the weight content of barium metal element is preferably 0.5ppm-
300ppm, more preferably 1ppm-100ppm.
Wherein, the method for testing of the weight content of barium metal element: liquid-crystalline polyester composition is dried 4 hours at 120 DEG C,
Taking the pending sample of 1g, add nitric acid and hydrogen peroxide, heat 2 hours, period is continuously added nitric acid and hydrogen peroxide；Clearing up of sample
After completing, cancel the sample after solution, the full-automatic inductance coupled plasma-atomic using Agilent company model to be 720ES
Emission spectrometer is analyzed Gold Samples and is belonged to the weight content of barium element.
Document is not yet had to be reported in liquid-crystalline polyester composition the introducing barium metal element impact on composition properties at present,
Present inventors have unexpectedly found that and introduce appropriate barium element in liquid-crystalline polyester composition, liquid-crystalline polyester composition shows in high temperature environments
Reveal surprising heat-resistant stability.And when in liquid-crystalline polyester composition, the weight content of barium metal element exceedes particular value, liquid
Crystal composite contains higher metal residuals, will certainly affect its dielectric properties as electronic apparatus type component, significantly
Reduce its range, and mobility there will be significantly decline.
Introducing typically by adding what containing barium compound realized of barium metal element, containing barium compound can be selected from titanium
Acid barium, barium nitrate, barium hydroxide, barium zirconate, barium cerate, hafnium acid barium, chloroboric acid barium, barium sulfate, Barium monoxide, Barium acetate, sulfuration
Barium, barium nitrite, barium metaphosphate, barium fluoride, barium chloride, Barium hyposulfite., Barium sulfocyanate, barium iodide, barium tungstate, barium molybdate,
The inorganic compound such as barium chromate, Manganese green, barium perchlorate, barium periodate, trifluoromethanesulfonic acid barium, brium carbonate, it is also possible to selected from 2-
Thylhexoic acid barium, acetylacetone barium, 2,4-lithium barium pentane, tert-butyl alcohol barium, barium isopropoxide, two (6,6,7,7,8,8,8-
Seven fluoro-2,2-dimethyl-3,5-acetyl caproyls) barium, diphenylamines-4-barium sulfonate, double (DPM dpm,dipivalomethanes acid)
The organic compound such as barium, cyclohexane butyric acid barium.The source of the barium metal element pointed by the present invention is not limited only to the example above, nothing
Opinion uses the containing barium compound of which kind of form, and atomic emission spectrometry can be used to detect.The weight of barium metal element contains
Amount is by barium metal element itself rather than on the basis of the containing barium compound adding barium metal element.The gold represented with ppm
The weight content belonging to barium element is to calculate on the basis of the gross weight of liquid-crystalline polyester composition.
The liquid-crystalline polyester composition of the present invention can also include crome metal element, gross weight based on liquid-crystalline polyester composition
Amount, the weight content of crome metal element is 0.1ppm-500ppm, preferably 1ppm-200ppm.
Wherein, the method for testing of the weight content of crome metal element: liquid-crystalline polyester composition is dried 4 hours at 120 DEG C,
Taking the pending sample of 1g, add nitric acid and hydrogen peroxide, heat 2 hours, period is continuously added nitric acid and hydrogen peroxide；Clearing up of sample
After completing, cancel the sample after solution, the full-automatic inductance coupled plasma-atomic using Agilent company model to be 720ES
Emission spectrometer is analyzed Gold Samples and is belonged to the weight content of chromium element.
Introducing of crome metal element contains what chromium compound realized typically by adding, and can be selected from chromium containing chromium compound
The chromate such as acid sodium, barium chromate, plumbous chromate, caesium chromate, ammonium chromate, siliver chromate, the bichromate such as potassium dichromate, Ammonium bichromate.,
Can also be chromium dioxychloride., chromium acetate (III) hydroxide, chromic sulfate, chromic nitrate, chromium phosphate, chromium acetate, chromium carbide, chromium+oxalic acid
The inorganic compound such as potassium, chromium trifluoride, chromic oxide, Chlorizate chromium, chromium chloride hexahydrate, it is also possible to be the double (triphen of chromic acid
Base silicyl) ester, chloro-chromic acid TBuA, pyridinium dichromate, dichromic acid imidazoles, dichromic acid quinoline, 2,2 '-bipyridyl chlorine
Chromic acid, 3-carboxyl pyridine bichromate, 4-carboxyl pyridine bichromate, three carbonyls (N-toluidines) chromium, chromium acetylacetonate, six carbonyls
Base chromium, benzene tricarbonyl chromium, (ethyl benzoate) tricarbonyl chromium (0), three (DPM dpm,dipivalomethane) chromium (III),
Three (acetonitrile) tricarbonyl chromium (0), dicarbapentaborane (pentamethylcyclopentadiene base) chromium dimer, (essence of Niobe) tricarbonyl chromium, double
The organic compound such as (ethyl cyclopentadiene) chromium (II).The source of the crome metal element pointed by the present invention is not limited only to above-mentioned act
Example, no matter use which kind of form containing chromium compound, atomic emission spectrometry can be used to detect.The weight of crome metal element
Amount content be by crome metal element itself rather than by interpolation crome metal element containing chromium compound on the basis of.Represent with ppm
The weight content of crome metal element be to calculate on the basis of the gross weight of liquid-crystalline polyester composition.
The liquid-crystalline polyester composition of the present invention can also include metallic tin element, gross weight based on liquid-crystalline polyester composition
Amount, the weight content of metallic tin element is 0.1ppm-500ppm, preferably 1ppm-200ppm.
Wherein, the method for testing of the weight content of metallic tin element: liquid-crystalline polyester composition is dried 4 hours at 120 DEG C,
Taking the pending sample of 1g, add nitric acid and hydrogen peroxide, heat 2 hours, period is continuously added nitric acid and hydrogen peroxide；Clearing up of sample
After completing, cancel the sample after solution, the full-automatic inductance coupled plasma-atomic using Agilent company model to be 720ES
Emission spectrometer is analyzed Gold Samples and is belonged to the weight content of tin element.
Introducing typically by adding what sn-containing compound realized of metallic tin element, sn-containing compound can be selected from stannum
Acid sodium, potassium stannate, tin acetate (IV), stannum oxide (II), stannum oxide (IV), Tin disulfide (II), STANNOUS SULPHATE CRYSTALLINE (II), tin oxalate, vinegar
The inorganic compound such as acid stannum, tin bifluoride, tin tetrafluoride, stannous iso caprylate, stannic chloride, Tin tetrabromide., Tin tetraiodide., it is also possible to be
Fentin acetate, plictran, 1-methyl-2-(tributyl tinbase) pyrroles, 1-methyl-2-(tributyl tinbase) imidazoles, 1-
Methyl-4-(tributyl tinbase)-1H-pyrazoles, 1-methyl-5-(tributyl tinbase) imidazoles, 2-(tributyl tin alkyl) furan, 2-
(tri-n-butyl tin base) azoles, 2-tributylstamlyl thiazole, 3-(tri-n-butyl tin) pyridine, N-methyl-2-(tributyl
Tinbase) indole, N-methyl-4-(tributyl tinbase) imidazoles, butyl stannonic acid, tributylvinyl tin, tri-butyl tin hydride, three
Butyl stannum oxide, tributyl tin isocyanates, trimethyl (tributyl tin alkyl) silane, trimethyltin chloride, acetenyl three
Normal-butyl stannum, hexa methyl ditin, hexaphenyl two stannum, tetrabutyltin, tetraethyl tin, tetravinyl stannum, fenbutatin oxide, tributyl
The organic compound such as (1-ethoxy ethylene) stannum.The source of the metallic tin element pointed by the present invention is not limited only to the example above,
No matter use the sn-containing compound of which kind of form, atomic emission spectrometry can be used to detect.The weight of metallic tin element
Content is by metallic tin element itself rather than on the basis of the sn-containing compound adding metallic tin element.Represent with ppm
The weight content of metallic tin element is to calculate on the basis of the gross weight of liquid-crystalline polyester composition.
Wherein, described liquid-crystalline polyester composition, by weight, including following component:
Liquid crystal polyester 100 parts；
Filler 5 parts-100 parts.
Wherein, the fusing point of described liquid-crystalline polyester composition is 150 DEG C-400 DEG C；The method of testing of described fusing point is: pass through
NETZSCH company DSC 200 F3 type differential scanning calorimeter DSC, is starting to survey with the Elevated Temperature Conditions of 20 DEG C/min from room temperature
Examination, observes endotherm peak temperature Tm1After, than Tm1Keep 5 minutes at a temperature of high 20 DEG C, then the cooling of 20 DEG C/min
Under the conditions of be cooled to room temperature, be the most again measured with the Elevated Temperature Conditions of 20 DEG C/min, the endotherm peak temperature now observed
Tm2It is the fusing point of liquid-crystalline polyester composition.
Wherein, described liquid crystal polyester, by mole meter, comprise following repetitive:
Repetitive 30mol%-100mol% derived from aromatic hydroxy-carboxylic；
Repetitive 0mol%-35mol% derived from aromatic diol；
Repetitive 0mol%-35mol% derived from aromatic dicarboxylic acid.
Preferably, described liquid crystal polyester, by mole meter, including following repetitive:
Repetitive 50mol%-100mol% derived from aromatic hydroxy-carboxylic；
Repetitive 0mol%-25mol% derived from aromatic diol；
Repetitive 0mol%-25mol% derived from aromatic dicarboxylic acid.
Wherein, the described repetitive derived from aromatic hydroxy-carboxylic is selected from the repetition list derived from 4-HBA
Unit and/or the repetitive of 2-hydroxyl-6-naphthoic acid；The described repetitive derived from aromatic diol is selected from hydroquinone
Repetitive and/or the repetitive of 4,4 '-dihydroxybiphenyl；The described repetitive derived from aromatic dicarboxylic acid is selected from right
The repetitive of phthalic acid, the repetitive of M-phthalic acid, 2,6-naphthalenedicarboxylic acid repetitive in one or more.
The preparation method of above-mentioned liquid crystal polyester, can use standard polycondensation techniques method well known to those skilled in the art,
Comprise the steps:
The reactor being equipped with agitator, thermometer, nitrogen ingress pipe and reflux condensate device is separately added into according to proportioning
Repetitive derived from aromatic hydroxy-carboxylic, the repetitive derived from aromatic diol and derived from aromatic dicarboxylic acid
Repetitive, and to add a certain proportion of acetic anhydride be acylating agent；Then nitrogen is passed through in reactor and replaces；Start
Stirring, is heated to 140 DEG C-160 DEG C by reactant mixture by room temperature in nitrogen stream, at this temperature backflow 1 hour-3 hours；
Hereafter continue to heat up, mixture was heated to 300 DEG C-350 DEG C through 2 hours-4 hours from 140 DEG C-160 DEG C, steams in the process
Go out unreacted acetic anhydride and side reaction product acetic acid；Whole polycondensation phase, reduces pressure to reaction system, and by observing moment of torsion
Raise the endpoint terminated as reaction；Now the prepolymer of melt state is discharged through drain hole, and be cooled to room temperature；Enter
Prepolymer is transferred to solid phase device by one step, through 5 hours-7 hours, temperature from ambient is increased to 260 DEG C-280 DEG C,
At a temperature of this, insulation carries out solid-phase polymerization in 9 hours-11 hours；Product is derived after terminating by reaction, thus obtains liquid crystal and gather
Ester.
Wherein, described filler is selected from fibrous filler and/or tabular filler；Described fibrous filler is selected from glass
Glass fiber, asbestos fibre, silicon dioxide fibre, silica-alumina fiber, potassium titanate fibre, carbon or graphite fibre, metal
One or more in fiber；It is preferably glass fibre；Described tabular filler is in Talcum, Muscovitum, graphite, Kaolin
One or more；It is preferably Muscovitum.
Preferably, the equal fibre diameter of number of described glass fibre is 3 microns-30 microns, and the equal draw ratio of number is more than or equal to 5,
Number average fiber length is 50 microns-3000 microns；The mean diameter of described Muscovitum is 0.5 micron-200 microns.
When adding filler, relative to liquid crystal polyester 100 weight portion, adding the filler more than more than 100 parts, liquid crystal gathers
The mechanical strength of ester compositions may reduce.The method adding filler is not particularly limited, and can enumerate in the art
Known method.
Additionally, in addition to the foregoing, can be not damage the liquid crystal that the amount of the object of the invention uses in the present invention
Polymer blend adds known various additives；Various additives can be selected from plasticizer, stabilizer, coloring agent, lubrication
One or more in agent, releasing agent, antioxidant.
Suitably plasticizer is phthalic acid ester.
Suitably stabilizer includes organic phosphite, such as triphenyl phosphite, tricresyl phosphite-(2,6-3,5-dimethylphenyl)
Ester, tricresyl phosphite-nonyl phenylester, dimethylbenene phosphonate, trimethyl phosphate etc., organic phosphite, alkylating unitary
The butylation reaction of the alkylation reaction product of phenol or polyhydric phenols, polyhydric phenols and diene, paracresol or bicyclopentadiene is produced
Thing, alkylating hydroquinones, hydroxylated thiodiphenvl ethers, alkylidene-bis-phenol, benzyl compounds, polyhydric alcohol esters, benzene
And triazole type, one or more combinations of benzophenone.
Suitably releasing agent includes metallic stearic salt, allcyl stearate class, stearic acid pentaerythritol esters, stone
Wax, lignite wax etc..
Suitably coloring agent includes various pigment, and dyestuff, such as metal-oxide and the mixed-metal oxides of inorganic pigment
Zinc oxide, titanium oxide, ferrum oxide, sulfide such as zinc sulfide etc.；Aluminate, silicate, ferrite etc., white carbon black, ultramarine；Organic
Pigment such as azo, diazonium class, Anthraquinones, phthalocyanine, quinolines, naphthalene, ketone, piperazine class etc..
Proper lubrication agent includes the slaine etc. of higher fatty acids, high-grade fatty ester, higher fatty acids.
Suitably antioxidant includes organic phosphite, alkylating monohydric phenol or polyhydric phenols, polyhydric phenols and diene
The butylation product of alkylation reaction product, paracresol or bicyclopentadiene, alkylating hydroquinones, hydroxylated sulfur
For diphenylether, alkylidene-bis-phenol, benzyl compounds, polyhydric alcohol esters etc..
Various additives are not limited to above-mentioned several, can optionally contain the heat stability to liquid crystal polyester and physical property is harmless
Other species components and thermoplastic compounds in common other material, such as the polypropylene, polyamide, poly-of one or more
Ester, polyphenylene sulfide, polyether-ketone, Merlon, polyether sulfone, polyphenyl ether and modified material thereof, thermoplastic resin such as polyetherimide
Amine, thermosetting resin such as phenolic resin, epoxy resin, polyimide resin and cyanide resin.
The method coordinating filler, various additives etc. in the liquid crystal polyester of embodiments of the present invention, the most specific
Limit, it is possible to use dry type blending, solution mixing method, the polymerization of liquid crystal polyester are interpolation, melting mixing etc., be wherein preferably molten
Melt mixing.Such as kneader, uniaxially or biaxially extruder, rubber-roller machine etc., biaxial extruder is wherein preferably used.The temperature of melting mixing
More than the degree fusing point for liquid crystal polyester, fusing point less than+50 DEG C.
As compounding process, it is possible to use put into liquid crystal polyester, filler, various additive in the lump from rear dress charger
Carry out mixing method；Liquid crystal polyester and various additive can also be penetrated from rear dress charger, add from side charger and fill
Agent carries out mixing method, can also prepare the liquid-crystalline polyester composition mother that high concentration comprises liquid crystal polyester and various additive
Grain, then carries out any one side of the method etc. of the mixing concentration to become regulation by liquid-crystalline polyester composition master batch and filler
Method.
The liquid-crystalline polyester composition of embodiments of the present invention, by carrying out injection moulding, injection compression molding, is compressed into
The known melt molding product such as type, extrusion molding, blow molding, compressing spinning.Products formed described here, can be note
Penetrate products formed, extrusion molding article, compressing product, sheet, pipe, non-stretched film, single axle drawn membrane, biaxially oriented film etc. each
Plant the various cellosilks etc. such as membrane product, undrawn yarn, super drawing silk.In the case of extrusion molding, can significantly obtain the present invention
Effect, the most preferably.
Wherein, the liquid-crystalline polyester composition obtained by extruding-out process, specifically comprise the following steps that liquid crystal according to proportioning
Polyester, filler, containing barium compound and/or mix at a high speed containing chromium compound and/or sn-containing compound and/or various additive
After conjunction machine mix homogeneously, add double screw extruder, melting mixing under the screw speed of 280RPM-320RPM, barrel temperature
It is 290 DEG C-355 DEG C, extrusion, cooling, pelletizing, obtain liquid-crystalline polyester composition.
Wherein containing barium compound can be selected from Barium metatitanate., barium nitrate, barium hydroxide, barium zirconate, barium cerate, hafnium acid barium, chlorine
Barium borate, barium sulfate, Barium monoxide, Barium acetate, barium sulfide, barium nitrite, barium metaphosphate, barium fluoride, barium chloride, thiosulfuric acid
Barium, Barium sulfocyanate, barium iodide, barium tungstate, barium molybdate, barium chromate, Manganese green, barium perchlorate, barium periodate, trifluoromethanesulfonic acid
The inorganic compound such as barium, brium carbonate, it is also possible to selected from 2 ethyl hexanoic acid barium, acetylacetone barium, 2,4-lithium barium pentane, tertiary fourth
Alcohol barium, barium isopropoxide, two (6,6,7,7,8,8,8-seven fluoro-2,2-dimethyl-3,5-acetyl caproyl) barium, diphenylamines-4-sulfonic acid
Barium, double (DPM dpm,dipivalomethane acid) organic compound such as barium, cyclohexane butyric acid barium.Pointed by the present invention
The source of barium metal element is not limited only to the example above, no matter uses the containing barium compound of which kind of form, can use atom
Emission spectrometry detects.The weight content of barium metal element is with barium metal element itself rather than to add barium metal element
Containing barium compound on the basis of.The weight content of the barium metal element represented with ppm is the gross weight with liquid-crystalline polyester composition
Calculate on the basis of amount.
Wherein can be selected from the chromic acid such as sodium chromate, barium chromate, plumbous chromate, caesium chromate, ammonium chromate, siliver chromate containing chromium compound
Salt, the bichromate such as potassium dichromate, Ammonium bichromate., it is also possible to be chromium dioxychloride., chromium acetate (III) hydroxide, chromic sulfate, nitric acid
Chromium, chromium phosphate, chromium acetate, chromium carbide, potassium trioxalatochromate(III), chromium trifluoride, chromic oxide, Chlorizate chromium, chromium chloride hexahydrate etc.
Inorganic compound, it is also possible to be double (triphenyl-silyl) ester of chromic acid, chloro-chromic acid TBuA, pyridinium dichromate, weight chromium
Imidazole acid, dichromic acid quinoline, 2,2 '-bipyridyl chloro-chromic acid, 3-carboxyl pyridine bichromate, 4-carboxyl pyridine bichromate, three
Carbonyl (N-toluidines) chromium, chromium acetylacetonate, Chromium hexacarbonyl., benzene tricarbonyl chromium, (ethyl benzoate) tricarbonyl chromium (0), three (2,
2,6,6-tetramethyl-3,5-heptadione) chromium (III), three (acetonitrile) tricarbonyl chromium (0), dicarbapentaborane (pentamethylcyclopentadiene base)
The organic compound such as chromium dimer, (essence of Niobe) tricarbonyl chromium, double (ethyl cyclopentadiene) chromium (II).Pointed by the present invention
The source of crome metal element be not limited only to the example above, no matter use which kind of form containing chromium compound, can use former
Sub-emission spectrometry detects.The weight content of crome metal element is with crome metal element itself rather than to add crome metal unit
Element containing chromium compound on the basis of.The weight content of the crome metal element represented with ppm is total with liquid-crystalline polyester composition
Calculate on the basis of weight.
Wherein sn-containing compound can be selected from sodium stannate, potassium stannate, tin acetate (IV), stannum oxide (II), stannum oxide (IV),
Tin disulfide (II), STANNOUS SULPHATE CRYSTALLINE (II), tin oxalate, tin acetate, tin bifluoride, tin tetrafluoride, stannous iso caprylate, stannic chloride, bromination
The inorganic compound such as stannum, Tin tetraiodide., it is also possible to be fentin acetate, plictran, 1-methyl-2-(tributyl tinbase) pyrroles,
1-methyl-2-(tributyl tinbase) imidazoles, 1-methyl-4-(tributyl tinbase)-1H-pyrazoles, 1-methyl-5-(tributyl tin
Base) imidazoles, 2-(tributyl tin alkyl) furan, 2-(tri-n-butyl tin base) azoles, 2-tributylstamlyl thiazole, 3-(three
Normal-butyl stannum) pyridine, N-methyl-2-(tributyl tinbase) indole, N-methyl-4-(tributyl tinbase) imidazoles, butyl stannonic acid,
Tributylvinyl tin, tri-butyl tin hydride, tributyltin oxide, tributyl tin isocyanates, trimethyl (tributyl stannane
Base) silane, trimethyltin chloride, acetenyl tri-n-butyl tin, hexa methyl ditin, hexaphenyl two stannum, tetrabutyltin, tetraethyl
The organic compound such as stannum, tetravinyl stannum, fenbutatin oxide, tributyl (1-ethoxy ethylene) stannum.Metal pointed by the present invention
The source of tin element is not limited only to the example above, no matter use which kind of form containing chromium compound, atomic emissions can be used
Spectrographic method detects.The weight content of metallic tin element is with metallic tin element itself rather than to add containing of metallic tin element
On the basis of tin compound.The weight content of the metallic tin element represented with ppm is to be with the gross weight of liquid-crystalline polyester composition
Benchmark.
The products formed that the liquid-crystalline polyester composition that the present invention is obtained is formed can have following application, with various gears, respectively
Kind of housing, sensor, LED lamp, adapter, socket, resistor, casing of relay, relay base, relay roll,
Switch, coil axle, capacitor, variable condenser housing, optical pickup unit, resonator, various terminal board, transformator, plug, printing
Wiring plate, tuner, speaker, microphone, head type headphones, miniature motor, magnetic head base, power model, shell, partly lead
Body, liquid crystal display component, FDD bracket, FDD chassis, HDD parts, motor brush holder, parabola antenna, computer are correlated with
Electrical and electronic parts that parts etc. are representative, with VTR parts, TV part, flatiron, hair dryer, electric cooker parts, microwave oven
Speech ciphering equipment parts, illuminace component, parts of refrigerator, the air supply rates such as parts, sound part, audio frequency, laser disk, CD, beat
Family that word machine parts, word processor parts etc. are representative, enterprise's electric product parts, office computer associated components,
Telephone set associated components, facsimile machine associated components, photocopier associated components, washing fixture, oilless bearing, stern bearing, water
The various bearing such as middle (center) bearing, motor component, mechanical associated components with lighter, typewriter etc. as representative, with microscope, double
Optical device that tube telescope, photographing unit, clock and watch etc. are representative, precision optical machinery associated components；Alternating current generator terminal, exchange are sent out
Various valves, fuel association, exhaust system, the air-breathings such as motor connectors, IC actuator, dimmer potentiometer base, aerofluxus air valve
The various pipes of system, inlet jet breather, inlet manifold, petrolift, engine cool water swivel, carburator main body, vaporization
Device spacer, exhaust gas sensor, cooling water sensor, oil temperature sensor, TPS, crank position sensing
Device, mass air flow sensor, Brake pad abrasion sensor, idle call thermostat base, air conditioning electricity motivation insulator, motorized window etc.
On-vehicle motor insulator, warmer heated airflow control valve, radiator fan motor brush carrier, water pump vane, turbo blade,
Wiper motor associated components, ignition distributor, starter switch, starter relay, actuating device wire harness, window cleaning device
Nozzle, air-conditioning panel switch substrate, fuel association electromagnetic valve coil, electric fuse adapter, loudspeaker terminal, parts of electric are exhausted
Listrium, stepping motor rotor, lamp ring, lamp socket, lamp reflector, lamp housing, brake piston, solenoid bobbin, electromotor oil strain
The automobile such as device, ignition housings, vehicle associated components etc., at printed wiring board, have in small-sized thin-walled electronic device etc. especially
With.
The present invention compared with prior art, has the advantages that
The present invention is by selecting the weight content adding barium metal element in liquid-crystalline polyester composition formula based on liquid crystal polyester
When the gross weight of compositions is 0.1ppm-500ppm, the high-temperature heat-resistance stability of the liquid-crystalline polyester composition obtained is expected
Less than significantly improve.
Detailed description of the invention
Further illustrating the present invention below by detailed description of the invention, following example are the present invention preferably embodiment party
Formula, but embodiments of the present invention are not limited by following embodiment.
The method of testing of the weight content of described barium metal element: liquid-crystalline polyester composition is dried 4 hours at 120 DEG C,
Taking the pending sample of 1g, add nitric acid and hydrogen peroxide, heat 2 hours, period is continuously added nitric acid and hydrogen peroxide；Clearing up of sample
After completing, cancel the sample after solution, the full-automatic inductance coupled plasma-atomic using Agilent company model to be 720ES
Emission spectrometer is analyzed Gold Samples and is belonged to the weight content of barium element.
The method of testing of the weight content of described crome metal element: liquid-crystalline polyester composition is dried 4 hours at 120 DEG C,
Taking the pending sample of 1g, add nitric acid and hydrogen peroxide, heat 2 hours, period is continuously added nitric acid and hydrogen peroxide；Clearing up of sample
After completing, cancel the sample after solution, the full-automatic inductance coupled plasma-atomic using Agilent company model to be 720ES
Emission spectrometer is analyzed Gold Samples and is belonged to the weight content of chromium element.
The method of testing of the weight content of described metallic tin element: liquid-crystalline polyester composition is dried 4 hours at 120 DEG C,
Taking the pending sample of 1g, add nitric acid and hydrogen peroxide, heat 2 hours, period is continuously added nitric acid and hydrogen peroxide；Clearing up of sample
After completing, cancel the sample after solution, the full-automatic inductance coupled plasma-atomic using Agilent company model to be 720ES
Emission spectrometer is analyzed Gold Samples and is belonged to the weight content of tin element.
The method of testing of the melt viscosity of described liquid-crystalline polyester composition: use Dynisco LCR7000 type capillary flow
Becoming instrument to test liquid-crystalline polyester composition, test temperature is liquid-crystalline polyester composition fusing point+20 DEG C, and shear rate is 1000
Second-1, using internal diameter 1mm, the mouth die of length 40mm is measured.
The method of testing of the fusing point of described liquid-crystalline polyester composition: swept by the DSC 200 F3 type differential of NETZSCH company
Retouch calorimeter (DSC), starting to test with the Elevated Temperature Conditions of 20 DEG C/min from room temperature, observing endotherm peak temperature Tm1After, than
Tm1Keep 5 minutes at a temperature of high 20 DEG C, then under the cooling conditions of 20 DEG C/min, be cooled to room temperature, the most again with 20
DEG C/min Elevated Temperature Conditions be measured, the endotherm peak temperature T now observedm2Fusing point for liquid-crystalline polyester composition.
The method of testing of the specific volume log viscosities of described liquid-crystalline polyester composition: liquid-crystalline polyester composition is dissolved in five fluorine
In phenol, being fallen by glass fiber filter, then make the solution that concentration is 0.01 g/mL, test temperature is 60 DEG C, and employing internal diameter is
The Ubbelohde viscometer of 0.7 mm is measured；And by formula: specific volume log viscosities=[ln (η r)]/C is calculated, and wherein η r is relative
Viscosity (t solution/t solvent), C is solution concentration.
The method of testing of the high-temperature heat-resistance stability of described liquid-crystalline polyester composition: by liquid-crystalline polyester composition at 120 DEG C
After being dried 4 hours, adding HAAKE Polylab OS type banburying instrument and carry out banburying, banburying temperature than liquid-crystalline polyester composition is molten
Point is high 20 DEG C, and the rotating speed of rotor is 50 rpm, and the banburying time is 1 hour；After banburying completes, by melted liquid-crystalline polyester composition
Take out in banbury, and be cooled to room temperature；Same sample before banburying with banburying after all sampling carry out melt viscosity and specific volume
The test of log viscosities, and carry out comparative analysis；Owing to banburying is to carry out, now on liquid-crystalline polyester composition melt temperature
Pyrolysis will be had to occur；And the strand to polymer melt that rotates of banburying instrument rotor has shear action, it will usually companion
Reduction with molecular weight.Therefore compare melt viscosity and the change of specific volume log viscosities before and after banburying, can reflect more intuitively
Liquid-crystalline polyester composition high-temperature heat-resistance stability at high temperature, melt viscosity and specific volume log viscosities decreasing value are less, represent
High-temperature heat-resistance stability is preferable.Generally, the filler (such as glass fibre, Talcum etc.) included in compositions is to liquid crystal polyester group
The thermostability of compound there is no impact, and at high temperature polymer can occur thermal decomposition to make molecular chain rupture, molecular weight and molecular weight.Liquid crystal gathers
The mechanism that in ester compositions, addition containing barium compound makes liquid-crystalline polyester composition thermostability improve is not fully understood, it may be possible to gold
Belong to ion and form complex with macromole, make structure more stable；Also it is likely to be metal ion strand growth is served
Catalytic action, at high temperature strand rate of rise is close with molecular chain rupture speed so that macromolecular structure entirety keeps steady
Fixed.
Title and the abbreviation of the monomer that the repetitive that contains of liquid crystal polyester that uses in the present invention is corresponding are as follows:
4-HBA (HBA)；
4,4 '-dihydroxybiphenyl (BP)；
P-phthalic acid (TA)；
M-phthalic acid (IA)；
2-hydroxyl-6-naphthoic acid (HNA)；
Hydroquinone (HQ)；
2,6-naphthalenedicarboxylic acid (NDA)；
The containing barium compound used in the present invention:
Barium acetate: Sigma-Aldrich (Shanghai) trade Co., Ltd；
Brium carbonate: Sigma-Aldrich (Shanghai) trade Co., Ltd；
Barium molybdate: Sigma-Aldrich (Shanghai) trade Co., Ltd；
Acetylacetone barium: Sigma-Aldrich (Shanghai) trade Co., Ltd；
In the present invention use containing chromium compound:
Chromium carbide: Sigma-Aldrich (Shanghai) trade Co., Ltd；
The sn-containing compound used in the present invention:
Stannum oxide (IV): Sigma-Aldrich (Shanghai) trade Co., Ltd；
The glass fibre used in the present invention: trade mark CS03JAPX-1, number equal fibre diameter 10 microns, the equal draw ratio 300 of number, number
All fibre length 3000 microns, Asahi Fiber Glass Co., Ltd.
Embodiment A1-A4: the preparation of liquid crystal polyester
The reactor being equipped with agitator, thermometer, nitrogen ingress pipe and reflux condensate device is separately added into according to proportioning
Repetitive derived from aromatic hydroxy-carboxylic, the repetitive derived from aromatic diol and derived from aromatic dicarboxylic acid
Repetitive, and to add a certain proportion of acetic anhydride be acylating agent；Then nitrogen is passed through in reactor and replaces；Start
Stirring, is heated to 140 DEG C-160 DEG C by reactant mixture by room temperature in nitrogen stream, at this temperature backflow 1 hour-3 hours；
Hereafter continue to heat up, mixture was heated to 300 DEG C-350 DEG C through 2 hours-4 hours from 140 DEG C-160 DEG C, steams in the process
Go out unreacted acetic anhydride and side reaction product acetic acid；Whole polycondensation phase, reduces pressure to reaction system, and by observing moment of torsion
Raise the endpoint terminated as reaction；Now the prepolymer of melt state is discharged through drain hole, and be cooled to room temperature；Enter
Prepolymer is transferred to solid phase device by one step, through 5 hours-7 hours, temperature from ambient is increased to 260 DEG C-280 DEG C,
At a temperature of this, insulation carries out solid-phase polymerization in 9 hours-11 hours；Product is derived after terminating by reaction, thus obtains liquid crystal and gather
Ester.
The concrete proportioning of table 1 embodiment A1-A4 and test performance result thereof
Embodiment 1-17 and comparative example 1-6: the preparation of liquid-crystalline polyester composition
Gained liquid crystal polyester, filler, containing barium compound will be prepared by embodiment A1-A4 by the proportioning of table 2 and/or close containing chromaking
After thing and/or sn-containing compound and/or various additive high-speed mixer mix homogeneously, add double screw extruder,
Melting mixing under the screw speed of 280RPM-320RPM, barrel temperature is 290 DEG C-355 DEG C, extrusion, and cooling, pelletizing obtain liquid
Brilliant polymer blend.The fusing point of gained liquid-crystalline polyester composition, melt viscosity and specific volume log viscosities are shown in Table 2；
Wherein, the barium metal element in liquid-crystalline polyester composition, crome metal element, metallic tin constituent content are in liquid crystal polyester group
In the preparation process of compound, the actual addition by containing barium compound, containing chromium compound, sn-containing compound is adjusted also
Record.
Table 2
Continued 2
Continued 2
From embodiment 1-17 of table 2 and the comparison of comparative example 1-6 it can be seen that the present invention is by selecting at liquid-crystalline polyester composition
When in formula, the weight content gross weight based on liquid-crystalline polyester composition of interpolation barium metal element is 0.1ppm-500ppm,
To the high-temperature heat-resistance stability of liquid-crystalline polyester composition obtain beyond thought significantly improving.
Claims (15)
1. a liquid-crystalline polyester composition, it is characterised in that gross weight based on liquid-crystalline polyester composition, the weight of barium metal element
Amount content is 0.1ppm-500ppm.
Liquid-crystalline polyester composition the most according to claim 1, it is characterised in that the test of the weight content of barium metal element
Method: be dried 4 hours at 120 DEG C by liquid-crystalline polyester composition, takes the pending sample of 1g, adds nitric acid and hydrogen peroxide, and heating 2 is little
Time, period is continuously added nitric acid and hydrogen peroxide；After having cleared up of sample, cancel the sample after solution, use Agilent company type
Number analyzing Gold Samples for the full-automatic inductively coupled plasma atomic emission spectrometer of 720ES belongs to the weight of barium element and contains
Amount.
Liquid-crystalline polyester composition the most according to claim 1, it is characterised in that gross weight based on liquid-crystalline polyester composition
Amount, the weight content of barium metal element is preferably 0.5ppm-300ppm, more preferably 1ppm-100ppm.
Liquid-crystalline polyester composition the most according to claim 1, it is characterised in that also include crome metal element, based on liquid crystal
The gross weight of polymer blend, the weight content of crome metal element is 0.1ppm-500ppm, preferably 1ppm-200ppm.
Liquid-crystalline polyester composition the most according to claim 4, it is characterised in that the test of the weight content of crome metal element
Method: be dried 4 hours at 120 DEG C by liquid-crystalline polyester composition, takes the pending sample of 1g, adds nitric acid and hydrogen peroxide, and heating 2 is little
Time, period is continuously added nitric acid and hydrogen peroxide；After having cleared up of sample, cancel the sample after solution, use Agilent company type
Number analyzing Gold Samples for the full-automatic inductively coupled plasma atomic emission spectrometer of 720ES belongs to the weight of chromium element and contains
Amount.
Liquid-crystalline polyester composition the most according to claim 1, it is characterised in that also include metallic tin element, based on liquid crystal
The gross weight of polymer blend, the weight content of metallic tin element is 0.1ppm-500ppm, preferably 1ppm-200ppm.
Liquid-crystalline polyester composition the most according to claim 6, it is characterised in that the test of the weight content of metallic tin element
Method: be dried 4 hours at 120 DEG C by liquid-crystalline polyester composition, takes the pending sample of 1g, adds nitric acid and hydrogen peroxide, and heating 2 is little
Time, period is continuously added nitric acid and hydrogen peroxide；After having cleared up of sample, cancel the sample after solution, use Agilent company type
Number analyzing Gold Samples for the full-automatic inductively coupled plasma atomic emission spectrometer of 720ES belongs to the weight of tin element and contains
Amount.
8. according to the liquid-crystalline polyester composition described in any one of claim 1-7, it is characterised in that described liquid crystal polyester combines
Thing, by weight, including following component:
Liquid crystal polyester 100 parts；
Filler 5 parts-100 parts.
Liquid-crystalline polyester composition the most according to claim 8, it is characterised in that the fusing point of described liquid-crystalline polyester composition is
150℃-400℃；The method of testing of described fusing point is: by NETZSCH company DSC 200 F3 type differential scanning calorimeter
DSC, is starting to test with the Elevated Temperature Conditions of 20 DEG C/min from room temperature, is observing endotherm peak temperature Tm1After, than Tm1High 20 DEG C
At a temperature of keep 5 minutes, then under the cooling conditions of 20 DEG C/min, be cooled to room temperature, the most again with 20 DEG C/min
Elevated Temperature Conditions is measured, the endotherm peak temperature T now observedm2It is the fusing point of liquid-crystalline polyester composition.
Liquid-crystalline polyester composition the most according to claim 8, it is characterised in that described liquid crystal polyester, by mole
Meter, comprises following repetitive:
Repetitive 30mol%-100mol% derived from aromatic hydroxy-carboxylic；
Repetitive 0mol%-35mol% derived from aromatic diol；
Repetitive 0mol%-35mol% derived from aromatic dicarboxylic acid.
11. liquid-crystalline polyester compositions according to claim 10, it is characterised in that described liquid crystal polyester, by Mole percent
Than meter, including following repetitive:
Repetitive 50mol%-100mol% derived from aromatic hydroxy-carboxylic；
Repetitive 0mol%-25mol% derived from aromatic diol；
Repetitive 0mol%-25mol% derived from aromatic dicarboxylic acid.
12. according to the liquid-crystalline polyester composition described in claim 10 or 11, it is characterised in that described derived from aromatic hydroxyl
The repetitive of carboxylic acid is selected from the repetitive derived from 4-HBA and/or the repetitive of 2-hydroxyl-6-naphthoic acid；
The described repetitive derived from aromatic diol is selected from repetitive and/or the weight of 4,4 '-dihydroxybiphenyl of hydroquinone
Multiple unit；The described repetitive derived from aromatic dicarboxylic acid is selected from the repetitive of p-phthalic acid, M-phthalic acid
Repetitive, 2,6-naphthalenedicarboxylic acid repetitive in one or more.
13. liquid-crystalline polyester compositions according to claim 8, it is characterised in that described filler is selected from fibrous filler
Agent and/or tabular filler；Described fibrous filler is selected from glass fibre, asbestos fibre, silicon dioxide fibre, titanium dioxide
One or more in silicon-alumina fibre, potassium titanate fibre, carbon or graphite fibre, metallic fiber；It is preferably glass fibre；
One or more in Talcum, Muscovitum, graphite, Kaolin of described tabular filler；It is preferably Muscovitum.
14. liquid-crystalline polyester compositions according to claim 13, it is characterised in that the equal fiber of number of described glass fibre is straight
Footpath is 3 microns-30 microns, and the equal draw ratio of number is more than or equal to 5, and number average fiber length is 50 microns-3000 microns；Described Muscovitum
Mean diameter is 0.5 micron-200 microns.
15. liquid-crystalline polyester compositions according to claim 8, it is characterised in that also comprise various additive；Described various
One or more in plasticizer, stabilizer, coloring agent, lubricant, releasing agent, antioxidant of additive.
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| CN201610226657.9A CN105860465A (en) | 2016-04-13 | 2016-04-13 | Liquid crystal polyester composition |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108570220A (en) * | 2017-03-14 | 2018-09-25 | 珠海万通特种工程塑料有限公司 | A kind of polyester and resin composition |
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| JP2003320592A (en) * | 2002-05-07 | 2003-11-11 | Kuraray Co Ltd | Method for manufacturing liquid crystal polymer film |
| CN103717672A (en) * | 2011-12-27 | 2014-04-09 | 东丽株式会社 | Thermoplastic resin composition and molded article thereof |
| JP2015063641A (en) * | 2013-09-26 | 2015-04-09 | 東レ株式会社 | Liquid crystalline polyester resin composition and molded article comprising the same |
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2016
- 2016-04-13 CN CN201610226657.9A patent/CN105860465A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5397502A (en) * | 1993-06-10 | 1995-03-14 | E. I. Du Pont De Nemours And Company | Heat resistant liquid crsytalline polymers |
| JP2003320592A (en) * | 2002-05-07 | 2003-11-11 | Kuraray Co Ltd | Method for manufacturing liquid crystal polymer film |
| CN103717672A (en) * | 2011-12-27 | 2014-04-09 | 东丽株式会社 | Thermoplastic resin composition and molded article thereof |
| JP2015063641A (en) * | 2013-09-26 | 2015-04-09 | 東レ株式会社 | Liquid crystalline polyester resin composition and molded article comprising the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108570220A (en) * | 2017-03-14 | 2018-09-25 | 珠海万通特种工程塑料有限公司 | A kind of polyester and resin composition |
| CN108570220B (en) * | 2017-03-14 | 2020-09-08 | 珠海万通特种工程塑料有限公司 | Polyester resin composition |
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