CN105885370A - Liquid crystal polyester composition - Google Patents
Liquid crystal polyester composition Download PDFInfo
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- CN105885370A CN105885370A CN201610226666.8A CN201610226666A CN105885370A CN 105885370 A CN105885370 A CN 105885370A CN 201610226666 A CN201610226666 A CN 201610226666A CN 105885370 A CN105885370 A CN 105885370A
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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
- C08G63/60—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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- 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
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
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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
- C08K5/07—Aldehydes; Ketones
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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
- 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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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/38—Polymers
- C09K19/3804—Polymers with mesogenic groups in the main chain
- C09K19/3809—Polyesters; Polyester derivatives, e.g. polyamides
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- C—CHEMISTRY; METALLURGY
- 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
- C08K2003/2262—Oxides; Hydroxides of metals of manganese
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- 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
- C08K2003/2293—Oxides; Hydroxides of metals of nickel
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- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
- C08K2003/3045—Sulfates
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- 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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- C08K2201/004—Additives being defined by their length
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08K2201/00—Specific properties of additives
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Abstract
The invention discloses liquid crystal polyester composition. In terms of the total weight of the liquid crystal polyester composition, the weight content of metal manganese elements is 0.1 ppm-300 ppm. A method for testing the weight content of the metal manganese elements comprises steps as follows: the liquid crystal polyester composition is dried at the temperature of 120 DEG C for 4 hours, 1 g of to-be-treated samples are taken and mixed with nitric acid and hydrogen peroxide, the mixture is heated for 2 hours, and nitric acid and hydrogen peroxide are added constantly during heating; after the samples are completely dissolved, the dissolved samples are taken, and the weight content of the metal manganese elements in the samples is analyzed with a full-automatic inductively coupled plasma-atomic emission spectrometry with the model 720 ES in the Agilent company. When the weight content of the metal manganese elements added to the formula of the liquid crystal polyester composition is 0.1 ppm-300 ppm in terms of the total weight of the liquid crystal polyester composition, the melting point of the liquid crystal polyester composition is increased, and the high-temperature heat resistance and stability are unexpectedly and remarkably 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 the fall of melt viscosity and molecular weight
The decline also having mechanical property that is low, that thus bring, and the generation of side reaction, this may increase the risk that resin bubbles.
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 manganese 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 manganese metal unit
When the weight content gross weight based on liquid-crystalline polyester composition of element is 0.1ppm-300ppm, the liquid-crystalline polyester composition obtained
Fusing point improve, and high-temperature heat-resistance stability obtains 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 manganese metal element is
0.1ppm-300ppm。
Being preferably based on the gross weight of liquid-crystalline polyester composition, the weight content of manganese metal element is preferably 0.5ppm-
100ppm, more preferably 1ppm-50ppm.
Wherein, the method for testing of the weight content of manganese 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 manganese element.
Document is not yet had to be reported in liquid-crystalline polyester composition the introducing manganese metal element impact on composition properties at present,
Present inventors have unexpectedly found that and introduce appropriate manganese element in liquid-crystalline polyester composition, the fusing point of liquid-crystalline polyester composition improves, and
Show the heat-resistant stability of excellence in high temperature environments.And work as the weight content of manganese metal element in liquid-crystalline polyester composition and surpass
When crossing particular value, liquid-crystal composition contains higher metal residuals, will certainly affect it as electronic apparatus type component
Dielectric properties, are substantially reduced its range, and mobility there will be significantly decline.
Introducing of manganese metal element contains what manganese compound realized typically by adding, and can be selected from oxygen containing manganese compound
Change manganese (II), manganese oxide (III), manganese oxide (IV), manganese acetate (II), manganese nitrate, Manganese monosulfide., manganese sulfate, manganese carbonate, acetic acid
Manganese, potassium permanganate, high manganese lithium, sodium permanganate, magnesium permanganate, mangano-manganic oxide, manganous fluoride, protochloride manganese, manganese iodide, molybdic acid
Manganese, double (trifluoromethanesulfonic acid) manganese inorganic compound, it is also possible to be manganese carbonyl, manganese acetylacetonate (II), manganese acetylacetonate (III),
Pentacarbonyl Manganese dibromide., maneb, six itrile group manganese potassium, manganese phthalocyanine (II), 2-methyl cyclopentyl-dialkyl-tricarbon manganium, three (2,2,6,6-
Tetramethyl-3,5-heptenoic acid) manganese, three carbonyls cyclopentadiene manganese (I), double (pentamethylcyclopentadiene) manganese (II), double (tetramethyl
Cyclopentadiene) manganese (II), double (isopropylcyclopentadiene) manganese, cyclohexyl butyric acid manganese, hydroxyisopropyl cyclopentadienyl group three carbonyl
The organic compound such as manganese.The source of the manganese metal element pointed by the present invention is not limited only to the example above, no matter uses which kind of shape
Formula containing manganese compound, atomic emission spectrometry can be used to detect.The weight content of manganese metal element is with manganese metal
Element itself rather than by add manganese metal element containing manganese compound on the basis of.Weight with the manganese metal element that ppm represents
Amount content 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 metallic nickel element, gross weight based on liquid-crystalline polyester composition
Amount, the weight content of metallic nickel element is 0.1ppm-300ppm, preferably 1ppm-100ppm.
Wherein, the method for testing of the weight content of metallic nickel 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 nickel element.
Introducing typically by adding what nickel compound containing realized of metallic nickel element, nickel compound containing can be selected from second
Acid nickel (II) tetrahydrate, nickel oxide (II), nickel nitrate (II) hexahydrate, nickel sulfide, nickel sulfate (II), nickel sulfate (II) ammonium
Hexahydrate, nickel oxalate (II) dihydrate, hexafluoro nickel (IV) acid potassium, Nickel difluoride (II), nickel hydroxide (II), Nickel dichloride.
(II), nickelous bromide (II), nickel borides, basic nickel carbonate hydrate, nickel phosphide, nickel peroxide, nickelous perchlorate (II) hexahydrate
Deng inorganic compound, it is also possible to selected from nickel octoate hydrate, 2 ethyl hexanoic acid nickel, nickel acetylacetonate, etioporphyrin (ETIO) nickel, double (ring penta
Diene) nickel (II), Nickel Phthalocyanine, [1,3-double (diphenylphosphine) propane] Nickel Chloride (II), 5,10,15,20-tetraphenyl-21H,
23H-porphin nickel (II), glycol dimethyl ether nickelous bromide, dichloro two (tributylphosphine) nickel (II), dichloro two (trimethyl-phosphine)
Nickel (II), double (1,5-cyclo-octadiene) nickel (O), double (tributylphosphine) Nickel Bromide, double (tricyclohexyl phosphine) Nickel Chloride
(II), double (triphenylphosphine) Nickel Bromides, double (ethyl cyclopentadiene) nickel (II), four (triphenyl phosphite) nickel, hexamethylene
The organic compound such as butanoic acid nickel.The source of the metallic nickel element pointed by the present invention is not limited only to the example above, no matter which uses
The nickel compound containing of the form of kind, can use atomic emission spectrometry to detect.The weight content of metallic nickel element is with gold
Belong to nickel element itself rather than on the basis of the nickel compound containing adding metallic nickel element.The metallic nickel element represented with ppm
Weight content be on the basis of the gross weight of liquid-crystalline polyester composition calculate.
The liquid-crystalline polyester composition of the present invention can also include metallic copper element, gross weight based on liquid-crystalline polyester composition
Amount, the weight content of metallic copper element is 0.1ppm-300ppm, preferably 1ppm-100ppm.
Wherein, the method for testing of the weight content of metallic copper 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 copper.
Introducing typically by adding what copper-containing compound realized of metallic copper element, copper-containing compound can be selected from second
Acid copper, copper oxide, copper sulfide, copper nitrate (II) hydrate, cupric tartrate (II), 1-butanethiol copper, bifluoride copper
(II), Cupric chromate(III)., Copper hydrate (II), Red copper oxide, Cu-lyt., copper chloride (II), cuprous sulfide, Copper diiodide
(I), the inorganic compound such as basic copper carbonate, copper sulfate, sulfurous acid copper, Copper pyrophosphate., it is also possible to be bathocuproine, 2,3-naphthalene phthalein
Cyanines copper, 2 ethyl hexanoic acid copper (II), 2-pyrazine carboxylic acid copper (II), 3-cresotic acid copper (I), cupric acetylacetonate, complete
Fluorine CuPc, poly-CuPc, phenylmercaptan. copper (I), CuPc (II), 3,5-diisopropyl copper salicylate hydrate, trifluoro second
Acyl acetonation copper, trifluoromethayl sulfonic acid copper (II), hexafluorophosphoric acid tetrem cyanogen copper, double (DPM dpm,dipivalomethane
Acid) copper, double (triphenylphosphine) hydroboration copper (I), cuprous, bromine three (triphenylphosphine) copper (I) of thiophene-2-carboxylic acid etc. organises
Compound.The source of the metallic copper element pointed by the present invention is not limited only to the example above, no matter uses the cupric of which kind of form
Compound, can use atomic emission spectrometry to detect.The weight content of metallic copper element is with metallic copper element itself
On the basis of not being the copper-containing compound to add metallic copper element.The weight content of the metallic copper element represented with ppm be with
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, the most mixed containing manganese compound and/or nickel compound containing and/or copper-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.
Manganese oxide (II), manganese oxide (III), manganese oxide (IV), manganese acetate (II), nitric acid can be selected from containing manganese compound
Manganese, Manganese monosulfide., manganese sulfate, manganese carbonate, manganese acetate, potassium permanganate, high manganese lithium, sodium permanganate, magnesium permanganate, four oxidations three
Manganese, manganous fluoride, protochloride manganese, manganese iodide, manganese molybdate, double (trifluoromethanesulfonic acid) manganese inorganic compound, it is also possible to be manganese carbonyl,
Manganese acetylacetonate (II), manganese acetylacetonate (III), pentacarbonyl Manganese dibromide., maneb, six itrile group manganese potassium, manganese phthalocyanine (II), 2-first
Butylcyclopentadiene manganese tricarbonyl, three (2,2,6,6-tetramethyl-3,5-heptenoic acid) manganese, three carbonyls cyclopentadiene manganese (I), double
(pentamethylcyclopentadiene) manganese (II), double (tetramethyl-ring pentadiene) manganese (II), double (isopropylcyclopentadiene) manganese, cyclohexyl fourth
The acid organic compound such as manganese, hydroxyisopropyl cyclopentadienyl tricarbonyl manganese.The source of the manganese metal element pointed by the present invention
Be not limited only to the example above, no matter use which kind of form containing manganese compound, atomic emission spectrometry can be used to detect.
The weight content of manganese metal element be with manganese metal element itself rather than with add manganese metal element containing manganese compound as base
Accurate.The weight content of the manganese metal element represented by ppm is to calculate on the basis of the gross weight of liquid-crystalline polyester composition.
Nickel compound containing can be selected from nickel acetate (II) tetrahydrate, nickel oxide (II), nickel nitrate (II) hexahydrate, sulfur
Change nickel, nickel sulfate (II), nickel sulfate (II) ammonium hexahydrate, nickel oxalate (II) dihydrate, hexafluoro nickel (IV) acid potassium, Nickel difluoride
(II), nickel hydroxide (II), Nickel dichloride. (II), nickelous bromide (II), nickel borides, basic nickel carbonate hydrate, nickel phosphide, peroxidating
The inorganic compound such as nickel, nickelous perchlorate (II) hexahydrate, it is also possible to selected from nickel octoate hydrate, 2 ethyl hexanoic acid nickel, acetyl
Acetone nickel, etioporphyrin (ETIO) nickel, double (cyclopentadiene) nickel (II), Nickel Phthalocyanine, [double (diphenylphosphine) propane of 1,3-] Nickel Chloride (II)
, 5,10,15,20-tetraphenyl-21H, 23H-porphin nickel (II), glycol dimethyl ether nickelous bromide, dichloro two (tributylphosphine) nickel
(II), dichloro two (trimethyl-phosphine) nickel (II), double (1,5-cyclo-octadiene) nickel (O), double (tributylphosphine) Nickel Bromide, double
(tricyclohexyl phosphine) Nickel Chloride (II), double (triphenylphosphine) Nickel Bromide, double (ethyl cyclopentadiene) nickel (II), four (Asias
Triphenyl phosphate) organic compound such as nickel, cyclohexane butyric acid nickel.The source of the metallic nickel element pointed by the present invention not only limits
In the example above, no matter use the nickel compound containing of which kind of form, atomic emission spectrometry can be used to detect.Metallic nickel
The weight content of element is by metallic nickel element itself rather than on the basis of the nickel compound containing adding metallic nickel element.With
The weight content of the metallic nickel element that ppm represents is to calculate on the basis of the gross weight of liquid-crystalline polyester composition.
Copper-containing compound can be selected from copper acetate, copper oxide, copper sulfide, copper nitrate (II) hydrate, cupric tartrate
(II), 1-butanethiol copper, bifluoride copper (II), Cupric chromate(III)., Copper hydrate (II), Red copper oxide, Cu-lyt.
, copper chloride (II), cuprous sulfide, Copper diiodide (I), basic copper carbonate, copper sulfate, sulfurous acid copper, the inorganic chemical such as Copper pyrophosphate.
Thing, it is also possible to be bathocuproine, 2,3-naphthalene CuPc, 2 ethyl hexanoic acid copper (II), 2-pyrazine carboxylic acid copper (II), 3-methyl water
Poplar acid copper (I), cupric acetylacetonate, perfluor CuPc, poly-CuPc, phenylmercaptan. copper (I), CuPc (II), 3,5-bis-are different
Propyl group copper salicylate hydrate, trifluoroacetylacetone (TFA) copper, trifluoromethayl sulfonic acid copper (II), hexafluorophosphoric acid tetrem cyanogen copper, double
(DPM dpm,dipivalomethane acid) copper, double (triphenylphosphine) hydroboration copper (I), thiophene-2-carboxylic acid are cuprous, bromine
Organic compound such as three (triphenylphosphine) copper (I).The source of the metallic copper element pointed by the present invention is not limited only to above-mentioned act
No matter example, use the copper-containing compound of which kind of form, and atomic emission spectrometry can be used to detect.The weight of metallic copper element
Amount content is by metallic copper element itself rather than on the basis of the copper-containing compound adding metallic copper element.Represent with ppm
The weight content of metallic copper element be to calculate on the basis of the gross weight of liquid-crystalline polyester composition.
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 manganese metal element in liquid-crystalline polyester composition formula based on liquid crystal polyester
When the gross weight of compositions is 0.1ppm-300ppm, the fusing point of the liquid-crystalline polyester composition obtained improves, and high-temperature heat-resistance is stable
Property obtains beyond thought significantly improving.
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 manganese 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 manganese element.
The method of testing of the weight content of described metallic nickel 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 nickel element.
The method of testing of the weight content of described metallic copper 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 copper.
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
Being dried 4 hours, add in Dynisco LCR7000 type high pressure capillary rheometer, barrel temperature maintains liquid crystal polyester combination
On thing fusing point 10 DEG C, using internal diameter 1mm, the mouth die of length 40mm is measured；After sample adds, set test program, keep perseverance
Temperature 5 min, with 1000 seconds-1Constant shear rate measure, obtain the shear viscosity of sample constant temperature 5 min, now have
A part of sample is extruded, and remaining sample continues constant temperature in barrel, when 60min, still with 1000 seconds-1Constant shear speed
Rate measures, and obtains the shear viscosity of constant temperature 60 min；Due to liquid-crystalline polyester composition sample perseverance on its melt temperature
Temperature, now will have pyrolysis to occur, it will usually with the reduction of molecular weight；Therefore sample is compared in constant temperature 5 min and perseverance
Shear viscosity and the reduction degree of specific volume log viscosities during temperature 60 min, can more intuitively reflecting liquid crystal polymer blend at height
Heat-resistant stability under Wen, melt viscosity and specific volume log viscosities decreasing value are less, represent high-temperature heat-resistance stability preferable.Logical
Often, the filler (such as glass fibre, Talcum etc.) included in compositions there is no impact to the thermostability of liquid-crystalline polyester composition,
At high temperature polymer can occur thermal decomposition to make molecular chain rupture, molecular weight and molecular weight.Liquid-crystalline polyester composition adds containing manganese
The mechanism that compound makes liquid-crystalline polyester composition thermostability improve is not fully understood, it may be possible to metal ion forms network with macromole
Compound, makes structure more stable；Also it is likely to be metal ion and strand growth is served catalytic action, at high temperature molecule
Rate of chain growth is close with molecular chain rupture speed so that macromolecular structure entirety keeps stable.
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 present invention uses containing manganese compound: (four kinds of concrete kinds containing manganese compound please be given)
Manganese oxide (IV): Sigma-Aldrich (Shanghai) trade Co., Ltd；
Manganese acetate (II): Sigma-Aldrich (Shanghai) trade Co., Ltd；
Manganese sulfate: Sigma-Aldrich (Shanghai) trade Co., Ltd；
Manganese acetylacetonate (II): Sigma-Aldrich (Shanghai) trade Co., Ltd；
The nickel compound containing used in the present invention:
Nickel oxide (II): Sigma-Aldrich (Shanghai) trade Co., Ltd；
The copper-containing compound used in the present invention:
Copper acetate: 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
By the proportioning of table 2 will by embodiment A1-A4 prepare gained liquid crystal polyester, filler, containing manganese compound and/or nickeliferous chemical combination
After thing and/or copper-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 manganese metal element in liquid-crystalline polyester composition, metallic nickel element, metallic copper constituent content are in liquid crystal polyester group
By being adjusted also containing manganese compound, nickel compound containing, the actual addition of copper-containing compound in the preparation process of compound
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 manganese metal element is 0.1ppm-300ppm,
The fusing point of the liquid-crystalline polyester composition arrived improves, and high-temperature heat-resistance stability obtains 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 manganese metal element
Amount content is 0.1ppm-300ppm.
Liquid-crystalline polyester composition the most according to claim 1, it is characterised in that the test of the weight content of manganese 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 manganese 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 manganese metal element is preferably 0.5ppm-100ppm, more preferably 1ppm-50ppm.
Liquid-crystalline polyester composition the most according to claim 1, it is characterised in that also include metallic nickel element, based on liquid crystal
The gross weight of polymer blend, the weight content of metallic nickel element is 0.1ppm-300ppm, preferably 1ppm-100ppm.
Liquid-crystalline polyester composition the most according to claim 4, it is characterised in that the test of the weight content of metallic nickel 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 nickel element and contains
Amount.
Liquid-crystalline polyester composition the most according to claim 1, it is characterised in that also include metallic copper element, based on liquid crystal
The gross weight of polymer blend, the weight content of metallic copper element is 0.1ppm-300ppm, preferably 1ppm-100ppm.
Liquid-crystalline polyester composition the most according to claim 6, it is characterised in that the test of the weight content of metallic copper 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 copper 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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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017177921A1 (en) * | 2016-04-13 | 2017-10-19 | 金发科技股份有限公司 | Liquid crystal polyester composition |
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| US20020045728A1 (en) * | 2000-07-28 | 2002-04-18 | Kabushiki Kaisha Ueno Seiyaku Oyo Kenkyujo | Aromatic dicarboxylic acid composition and liquid crystalline polyester resin made from the same |
| CN103360730A (en) * | 2012-03-29 | 2013-10-23 | 住友化学株式会社 | A liquid crystal polyester composition and a molded body formed by the same |
| CN103540151A (en) * | 2012-07-13 | 2014-01-29 | 金发科技股份有限公司 | Modified resin composition for depositing metal film as well as preparation method and application of modified resin composition |
| CN103717672A (en) * | 2011-12-27 | 2014-04-09 | 东丽株式会社 | Thermoplastic resin composition and molded article thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20020045728A1 (en) * | 2000-07-28 | 2002-04-18 | Kabushiki Kaisha Ueno Seiyaku Oyo Kenkyujo | Aromatic dicarboxylic acid composition and liquid crystalline polyester resin made from the same |
| CN103717672A (en) * | 2011-12-27 | 2014-04-09 | 东丽株式会社 | Thermoplastic resin composition and molded article thereof |
| CN103360730A (en) * | 2012-03-29 | 2013-10-23 | 住友化学株式会社 | A liquid crystal polyester composition and a molded body formed by the same |
| CN103540151A (en) * | 2012-07-13 | 2014-01-29 | 金发科技股份有限公司 | Modified resin composition for depositing metal film as well as preparation method and application of modified resin composition |
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| WO2017177921A1 (en) * | 2016-04-13 | 2017-10-19 | 金发科技股份有限公司 | Liquid crystal polyester composition |
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Application publication date: 20160824 |