CN105907058B - A kind of liquid-crystalline polyester composition - Google Patents
A kind of liquid-crystalline polyester composition Download PDFInfo
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- CN105907058B CN105907058B CN201610226651.1A CN201610226651A CN105907058B CN 105907058 B CN105907058 B CN 105907058B CN 201610226651 A CN201610226651 A CN 201610226651A CN 105907058 B CN105907058 B CN 105907058B
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/04—Ingredients characterised by their shape and organic or inorganic ingredients
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- 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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- 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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- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
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- 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
- C08K3/2279—Oxides; Hydroxides of metals of antimony
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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
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
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- C08K5/00—Use of organic ingredients
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- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/098—Metal salts of carboxylic acids
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- 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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- 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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- C08G2250/00—Compositions for preparing crystalline polymers
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- 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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- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
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- C08L2201/00—Properties
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Abstract
The invention discloses a kind of liquid-crystalline polyester composition, the total weight based on liquid-crystalline polyester composition, the weight content of metal strontium element is 0.1ppm 300ppm.The test method of the weight content of the metal strontium element：Liquid-crystalline polyester composition is 4 hours dry at 120 DEG C, the pending samples of 1g are taken, add in nitric acid and hydrogen peroxide, heats 2 hours, is during which continuously added nitric acid and hydrogen peroxide；After the completion of the resolution of sample, cancel the sample after solution, Agilent company models is used to analyze the weight content of Gold Samples category strontium element for the full-automatic inductively coupled plasma atomic emission spectrometer of 720ES.The present invention is by the way that when total weight of the weight content based on liquid-crystalline polyester composition of the addition metal strontium element in liquid-crystalline polyester composition formula being selected to be 0.1ppm 300ppm, obtained liquid-crystalline polyester composition has improved heat-resistant stable and proper alignment foaming characteristic.
Description
Technical field
The present invention relates to polymeric material field, more 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, there is higher fusing point and height
Heat-resistant stability, however thermal decomposition or the strand when by external force hot shearing when liquid crystal polyester remains processing at high temperature
Chain rupture, the phenomenon that various aspects of performance is caused to decline.On the other hand, liquid crystal polyester is commonly used to fabricate thin wall parts, and to carry out
Reflow Soldering is processed, and also has high requirement to foaming characteristic.In order to improve the heat-resistant stability of liquid crystal polyester, this field professional people
Member has done many trials.
US5397502 discloses the liquid-crystalline polymer composition that a kind of heat-resistant stability improves, and composition includes 15 ~
The alkali metal of 3000ppm or the magnesium of 50 ~ 3000ppm or calcium；Liquid crystal polymer contains P-hydroxybenzoic acid, hydroquinone, biphenyl
Diphenol, terephthalic acid (TPA), 2,6-naphthalenedicarboxylic acid and biphenyl dicarboxylic acid repetitive unit.The introducing of metallics improves composition
Fusing point and heat distortion temperature, are improved heat resistance.However being mentioned in patent makes liquid crystal polymer exist with functional compound
It is contacted under high temperature and long enough so that its melt viscosity declines at least 10%.Professional and technical personnel in the field institute is public
Know, liquid crystalline resin is handled under higher than its melting temperature for a long time, since thermal decomposition can lead to melt viscosity and molecular weight
It reduces, that thus brings also has the generation of decline and the side reaction of mechanical property, this may increase the wind of resin blistering
Danger.
CN1234749 discloses a kind of liquid-crystal polyester resin, wherein containing 4 hydroxyisophthalic acid and/or salicylic acid and
The repetitive unit come is as copolymer composition, and the alkali metal compound containing 10 ~ 5000ppm, and claims the coloring of resin excellent
It is good, heat resistance is high, and mechanicalness is good.The improvement of invention main sides weight liquid crystal polyester degree of staining and impact property, not in reality
It applies other parts in example or patent and illustrates whether heat resistance changes.And whether the patent and undeclared invention are suitable for liquid crystal
Polymer blend.
US6755991 discloses a kind of liquid-crystalline polyester composition, and comprising at least one aromatic dicarboxylic acid, at least one contains naphthalene
Ring carboxylic acid and 1 ~ 1000ppm at least one alkali metal and 0 ~ 3000ppm at least one transition metal.Liquid crystal prepared by the invention
Polymer blend has improved whiteness and impact strength, does not refer to whether high-temperature heat-resistance stability changes.
Up to the present, it is high to the liquid-crystalline polyester composition about metal strontium element is added in liquid-crystalline polyester composition
The influence of warm heat-resistant stability and proper alignment foaming characteristic has not been reported.
The present inventor pass through many experiments surprisingly it has been found that, select liquid-crystalline polyester composition formula in addition Preparation of Metallic Strontium member
When total weight of the weight content based on liquid-crystalline polyester composition of element is 0.1ppm-300ppm, obtained liquid-crystalline polyester composition
Heat-resistant stable and proper alignment foaming characteristic obtain unexpected significantly improve.
Invention content
The shortcomings that in order to overcome the prior art, primary and foremost purpose of the invention was that providing a kind of high-temperature heat-resistance stablizes with insufficient
The liquid-crystalline polyester composition that property and proper alignment foaming characteristic significantly improve.
The present invention is achieved through the following technical solutions：
A kind of liquid-crystalline polyester composition, the total weight based on liquid-crystalline polyester composition, the weight content of metal strontium element are
0.1ppm-300ppm。
The total weight of liquid-crystalline polyester composition is preferably based on, the weight content of metal strontium element is preferably 0.5ppm-
100ppm, more preferably 1ppm-50ppm.
Wherein, the test method of the weight content of metal strontium element：Liquid-crystalline polyester composition is 4 hours dry at 120 DEG C,
The pending samples of 1g are taken, add in nitric acid and hydrogen peroxide, heats 2 hours, is during which continuously added nitric acid and hydrogen peroxide；The resolution of sample
After the completion, cancel the sample after solution, use full-automatic inductance coupled plasma-atomic of the Agilent company models for 720ES
Emission spectrometer analyzes the weight content of Gold Samples category strontium element.
Introduce influence of the metal strontium element to composition properties in liquid-crystalline polyester composition there has been no document report at present,
Present inventors have unexpectedly found that introducing suitable strontium element in liquid-crystalline polyester composition, the high-temperature heat-resistance of liquid-crystalline polyester composition is stablized
Property and proper alignment foaming characteristic are significantly improved.And when the weight content of metal strontium element in liquid-crystalline polyester composition is more than specific
During value, liquid-crystal composition contains higher metal residuals, will certainly influence its dielectricity as electronic apparatus type component
Can, its use scope is substantially reduced, and mobility will appear significant decline, influences its mouldability.
The introducing of metal strontium element is typically by adding containing strontium compound come what is realized, second can be selected from containing strontium compound
Sour strontium, strontium oxide strontia, strontium nitrate, strontium sulfide, strontium sulfate, strontium carbonate, strontium phosphate, strontium oxalate, strontium fluoride, hydroxide
The inorganic chemicals such as strontium, strontium chloride, strontium bromide, selenizing strontium, strontium monophosphate, strontium peroxide, strontium titanates, strontium tungstate, strontium zirconate
Object or isopropanol strontium, bis- (2,2,6,6- tetramethyl -3,5- heptadione acid) strontium dihydrates, dipivaloylmethane
The organic compounds such as sour strontium.The source of metal strontium element pointed by the present invention is not limited only to the example above, no matter which kind of uses
Form contains strontium compound, can be detected using atomic emission spectrometry.The weight content of metal strontium element is with metal
Strontium element in itself rather than by add metal strontium element containing strontium compound on the basis of.With the ppm metal strontium elements represented
Weight content is calculated on the basis of the total weight of liquid-crystalline polyester composition.
The liquid-crystalline polyester composition of the present invention can also include metal antimony element, the gross weight based on liquid-crystalline polyester composition
Amount, the weight content of metal antimony element is 0.1ppm-300ppm, preferably 1ppm-50ppm.
Wherein, the test method of the weight content of metal antimony element：Liquid-crystalline polyester composition is 4 hours dry at 120 DEG C,
The pending samples of 1g are taken, add in nitric acid and hydrogen peroxide, heats 2 hours, is during which continuously added nitric acid and hydrogen peroxide；The resolution of sample
After the completion, cancel the sample after solution, use full-automatic inductance coupled plasma-atomic of the Agilent company models for 720ES
Emission spectrometer analyzes the weight content of Gold Samples category antimony element.
The introducing of metal antimony element is typically what is realized by adding antimony containing compounds, and antimony containing compounds can be selected from oxygen
Change antimony（III）, antimony oxide（V）, antimony trisulfide（III）, antimony trisulfide（V）, antimony sulfate, antimony acetate, antimony selenide (III), antimony iodide
(III) etc. inorganic compounds, can also be selected from propyl alcohol antimony（III）, antimony triphenyl (III), ethyoxyl antimony, isopropoxy antimony,
Methoxyl group antimony, 1- butyl -3- methylimidazoles hexafluoro antimonate, three (4- bromophenyls) chlordene ammonium antimonates, triphenyl oxalic acid antimony
(V), the organic compounds such as triphenyl antimony butter (V), tetraphenylphosphonibromide bromide antimony (V).Metal antimony element pointed by the present invention
Source is not limited only to the example above, no matter using which kind of form antimony containing compounds, can be examined using atomic emission spectrometry
It measures.The weight content of metal antimony element is with antimony containing compounds of the metal antimony element rather than to add metal antimony element in itself
On the basis of.The weight content of metal antimony element represented by ppm is calculated on the basis of the total weight of liquid-crystalline polyester composition
's.
Wherein, the liquid-crystalline polyester composition, by weight, including following component：
100 parts of liquid crystal polyester；
5 parts -100 parts of filler.
Wherein, the fusing point of the liquid-crystalline polyester composition is 150 DEG C -400 DEG C；The test method of the fusing point is：Pass through
200 F3 type differential scanning calorimeter DSC of NETZSCH companies DSC are being surveyed since room temperature with 20 DEG C/min of Elevated Temperature Conditions
Examination, observes endotherm peak temperature Tm1Afterwards, than Tm1It is kept for 5 minutes at a temperature of high 20 DEG C, then in 20 DEG C/min of cooling
Under the conditions of be cooled to room temperature, be then measured again with 20 DEG C/min of Elevated Temperature Conditions, the endotherm peak temperature observed at this time
Tm2The as fusing point of liquid-crystalline polyester composition.
Wherein, the liquid crystal polyester by mole meter, includes following repetitive unit：
Repetitive unit 30mol%-100mol% derived from aromatic hydroxy-carboxylic；
Repetitive unit 0mol%-35mol% derived from aromatic diol；
Repetitive unit 0mol%-35mol% derived from aromatic dicarboxylic acid.
Preferably, the liquid crystal polyester, by mole meter, including following repetitive unit：
Repetitive unit 50mol%-100mol% derived from aromatic hydroxy-carboxylic；
Repetitive unit 0mol%-25mol% derived from aromatic diol；
Repetitive unit 0mol%-25mol% derived from aromatic dicarboxylic acid.
Wherein, the repetitive unit derived from aromatic hydroxy-carboxylic is selected from the repetition list derived from 4-HBA
The repetitive unit of member and/or 2- hydroxyl -6- naphthoic acids；The repetitive unit derived from aromatic diol is selected from hydroquinone
The repetitive unit of repetitive unit and/or 4,4 '-dihydroxybiphenyl；The repetitive unit derived from aromatic dicarboxylic acid be selected from pair
The repetitive unit of phthalic acid, the repetitive unit of M-phthalic acid, 2,6- naphthalenedicarboxylic acids repetitive unit in it is one or more of.
Standard polycondensation techniques method well known to those skilled in the art may be used in the preparation method of above-mentioned liquid crystal polyester,
Include the following steps：
Distinguish in the reaction kettle for being equipped with blender, thermometer, nitrogen ingress pipe and reflux condensate device according to proportioning
Add in the repetitive unit derived from aromatic hydroxy-carboxylic, the repetitive unit derived from aromatic diol and derived from aromatic series two
The repetitive unit of carboxylic acid, and a certain proportion of acetic anhydride is added in as acylating agent；Then nitrogen is passed through in reaction kettle into line replacement；
Stirring is started, reaction mixture is heated to 140 DEG C -160 DEG C by room temperature in nitrogen stream, is flowed back 1 hour -3 at this temperature
Hour；Hereafter continue to heat up, mixture was heated to 300 DEG C -350 DEG C through -4 hours 2 hours from 140 DEG C -160 DEG C, herein mistake
Unreacted acetic anhydride and side reaction product acetic acid are steamed in journey；Whole polycondensation phase, depressurizes reaction system, and passes through sight
Examine the endpoint that torque raising terminates as reaction；The prepolymer of melt state through drain hole is discharged at this time, and is cooled to
Room temperature；Prepolymer is further transferred to solid phase device, through -7 hours 5 hours by temperature by room temperature be increased to 260 DEG C -
It 280 DEG C, keeps the temperature -11 hours 9 hours at this temperature and carries out solid-phase polymerization；Product is exported after reaction, so as to
To liquid crystal polyester.
Wherein, the filler is selected from fibrous filler and/or plate filler；The 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 of fiber；Preferably glass fibre；The plate filler is in talcum, mica, graphite, kaolin
It is one or more of；Preferably mica.
Preferably, the number average fiber diameter of the 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 average grain diameter of the mica is 0.5 micron -200 microns.
When addition filler, relative to 100 parts by weight of liquid crystal polyester, the filler more than 100 parts or more is added, liquid crystal gathers
The mechanical strength of ester composition may be decreased.The method of addition filler is not particularly limited, and can enumerate in the art
Well known method.
It, can be not damage the liquid crystal that the amount of the object of the invention is used into the present invention in addition, in addition to the foregoing
Various additives well known to being added in polymer blend；Various additives can be selected from plasticizer, stabilizer, colorant, lubrication
One or more of agent, releasing agent, antioxidant.
Suitable plasticizer is phthalic acid ester.
Suitable stabilizer includes organic phosphite, such as triphenyl phosphite, and phosphorous acid three-（2,6- 3,5-dimethylphenyls）
Ester, phosphorous acid three-nonyl phenylester, dimethylbenene phosphonate, trimethyl phosphate etc., organic phosphite, alkylated unitary
The butylation reaction production of the alkylation reaction product of phenol or polyphenol, polyphenol and diene, paracresol or bicyclopentadiene
Object, alkylated hydroquinones, hydroxylated thiodiphenvl ethers, alkylidene-bis-phenol, benzyl compounds, polyalcohol esters, benzene
And triazole type, one or more kinds of combinations of benzophenone.
Suitable releasing agent includes metallic stearic salt, allcyl stearate class, stearic acid pentaerythritol esters, stone
Wax, lignite wax etc..
Suitable colorant includes various pigment, dyestuff, such as the metal oxide and mixed-metal oxides of inorganic pigment
Zinc oxide, titanium oxide, iron oxide, sulfide such as zinc sulphide etc.；Aluminate, silicate, ferrite etc., carbon black, ultramarine；It is organic
Pigment such as azo, diazonium class, Anthraquinones, phthalocyanine, quinolines, naphthalene, ketone, piperazine class etc..
Suitable lubricant includes metal salt of higher fatty acids, high-grade fatty ester, higher fatty acids etc..
Suitable antioxidant includes organic phosphite, alkylated monohydric phenol or polyphenol, polyphenol and diene
The butylation product of alkylation reaction product, paracresol or bicyclopentadiene, alkylated hydroquinones, hydroxylated sulphur
For diphenylether, alkylidene-bis-phenol, benzyl compounds, polyalcohol esters etc..
Various additives be not limited to it is above-mentioned several, can be optionally containing harmless to the thermal stability and physical property of liquid crystal polyester
Other species components and thermoplastic compounds in common other materials, such as one or more polypropylene, polyamide, poly-
Ester, polyphenylene sulfide, polyether-ketone, makrolon, polyether sulfone, polyphenyl ether and its modified material, thermoplastic resin such as polyetherimide
Amine, thermosetting resin such as phenolic resin, epoxy resin, polyimide resin and cyaniding resin.
Coordinate the method for filler, various additives etc. in the liquid crystal polyester of embodiments of the present invention, without specific
It limits, it is addition, melting mixing etc. that can use dry type blending, the polymerization of solution mixing method, liquid crystal polyester, wherein preferably molten
Melt mixing.Such as kneader, uniaxially or biaxially extruder, rubber-roller machine etc., wherein it is preferable to use biaxial extruders.The temperature of melting mixing
It spends more than the fusing point for liquid crystal polyester, below+50 DEG C of fusing point.
As mixing method, it can use from rear dress charger and put into liquid crystal polyester, filler, various additives together
The method being kneaded；Liquid crystal polyester and various additives can also be penetrated from rear dress charger, add and fill from side charger
The method that agent is kneaded can also prepare the liquid-crystalline polyester composition mother that high concentration includes liquid crystal polyester and various additives
Liquid-crystalline polyester composition master batch and filler are then kneaded with any side of the method for concentration as defined in becoming etc. by grain
Method.
By being injection moulded, injection compression molding is compressed into the liquid-crystalline polyester composition of embodiments of the present invention
Melt molding product well known to type, extrusion molding, blow molding, compression moulding spinning etc..Molded product described here can be note
It is each to penetrate molded product, extrusion molding article, compression moulding product, piece, pipe, non-stretched film, single axle drawn membrane, biaxially oriented film etc.
Various filaments such as kind membrane product, undrawn yarn, super drawing silk etc..In the case of extrusion molding, the present invention can be significantly obtained
Effect, therefore preferably.
Wherein, the liquid-crystalline polyester composition obtained by extruding-out process, is as follows：According to proportioning by liquid crystal
Polyester, filler, containing strontium compound and/or antimony containing compounds, and/or various additives with high-speed mixer after mixing,
Double screw extruder, the melting mixing under the screw speed of 280RPM-320RPM are added in, barrel temperature is 290 DEG C -355 DEG C, is squeezed
Go out, cooling, pelletizing are to get liquid-crystalline polyester composition.
Strontium acetate, strontium oxide strontia, strontium nitrate, strontium sulfide, strontium sulfate, strontium carbonate, phosphoric acid can be selected from containing strontium compound
Strontium, strontium oxalate, strontium fluoride, strontium hydroxide, strontium chloride, strontium bromide, selenizing strontium, strontium monophosphate, strontium peroxide, metatitanic acid
The inorganic compounds such as strontium, strontium tungstate, strontium zirconate or isopropanol strontium, bis- (2,2,6,6- tetramethyl -3,5- heptadione
Acid) organic compounds such as strontium dihydrate, dipivaloylmethane acid strontium.The source of metal strontium element pointed by the present invention is not
Be only limitted to the example above, no matter using which kind of form containing strontium compound, can be detected using atomic emission spectrometry.Gold
The weight content for belonging to strontium element be by metal strontium element in itself rather than by add metal strontium element containing on the basis of strontium compound
's.The weight content of metal strontium element represented by ppm is calculated on the basis of the total weight of liquid-crystalline polyester composition.
Antimony containing compounds can be selected from antimony oxide（III）, antimony oxide（V）, antimony trisulfide（III）, antimony trisulfide（V）, antimony sulfate,
The inorganic compounds such as antimony acetate, antimony selenide (III), antimony iodide (III) can also be selected from propyl alcohol antimony（III）, antimony triphenyl
(III), ethyoxyl antimony, isopropoxy antimony, methoxyl group antimony, 1- butyl -3- methylimidazoles hexafluoro antimonate, three (4- bromobenzenes
Base) organic compounds such as chlordene ammonium antimonate, triphenyl oxalic acid antimony (V), triphenyl antimony butter (V), tetraphenylphosphonibromide bromide antimony (V)
Object.The source of metal antimony element pointed by the present invention is not limited only to the example above, no matter using which kind of form chemical combination containing antimony
Object can be detected using atomic emission spectrometry.The weight content of metal antimony element be with metal antimony element in itself without
It is on the basis of adding the antimony containing compounds of metal antimony element.The weight content of metal antimony element represented with ppm is with liquid
It is calculated on the basis of the total weight of brilliant polymer blend.
The molded product 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 lamps, connector, socket, resistor, casing of relay, relay base, relay roll,
Switch, coil axis, capacitor, variable condenser housing, optical pickup unit, resonator, various terminal boards, transformer, plug, printing
Wiring plate, loud speaker, microphone, head type headphones, miniature motor, magnetic head pedestal, power module, shell, is partly led at tuner
Body, liquid crystal display component, FDD brackets, FDD chassis, HDD components, motor brush holder, parabola antenna, computer are related
Component etc. is the electrical and electronic parts of representative, with VTR components, TV part, flatiron, hair dryer, electric cooker component, micro-wave oven
The speech ciphering equipments such as component, sound part, audio, laser disk, CD component, parts of refrigerator, air supply rate, is beaten illuminace component
Word machine component, word processor component etc. are the family of representative, enterprise's electric product component, office computer associated components,
Telephone set associated components, facsimile machine associated components, duplicator associated components, washing fixture, oilless bearing, stern bearing, water
The various bearings such as middle (center) bearing, motor component, with igniter, typewriter etc. for the mechanical associated components of representative, with microscope, double
Tube telescope, camera, clock and watch etc. are optical device, the precision machinery associated components of representative；Alternating current generator terminal, exchange hair
The various valves such as motor connectors, IC adjusters, light modulator potentiometer pedestal, exhaust air valve, fuel association, exhaust system, air-breathing
The various pipes of system, inlet jet snorkel, inlet manifold, petrolift, engine cool water swivel, vaporizer main body, vaporization
Device spacer, exhaust gas sensor, cooling water sensor, oil temperature sensor, throttle position sensor, crank position sensing
Device, air flow meter, Brake pad abrasion sensor, idle call thermostat pedestal, air conditioning electricity motivation insulator, motorized window etc.
On-vehicle motor insulator, heater warm wind flow control valve, radiator fan motor brush carrier, water pump vane, turbo blade,
Wiper motor associated components, ignition distributor, starter switch, starter relay, transmission device harness, window cleaning device
Nozzle, air-conditioning panel switch substrate, fuel association solenoid valve coil, fuse connector, loudspeaker terminal, parts of electric are exhausted
Listrium, stepping motor rotor, lamp ring, lamp holder, lamp reflector, lamp housing, brake piston, solenoid spool, engine oil strain
The automobiles such as device, ignition housings, vehicle associated components etc. especially have in printed wiring board, small-sized thin-walled electronic device etc.
With.
Compared with prior art, the present invention it has the advantages that：
The present invention is by selecting the weight content of the addition metal strontium element in liquid-crystalline polyester composition formula to be based on liquid crystal
When the total weight of polymer blend is 0.1ppm-300ppm, the heat-resistant stable of obtained liquid-crystalline polyester composition and resistance to weldering
It connects foaming characteristic and obtains unexpected significantly improve.
Specific embodiment
It is further illustrated the present invention below by specific embodiment, following embodiment is the preferable embodiment party of the present invention
Formula, but embodiments of the present invention are not limited by following embodiments.
The test method of the weight content of the metal strontium element：Liquid-crystalline polyester composition is 4 hours dry at 120 DEG C,
The pending samples of 1g are taken, add in nitric acid and hydrogen peroxide, heats 2 hours, is during which continuously added nitric acid and hydrogen peroxide；The resolution of sample
After the completion, cancel the sample after solution, use full-automatic inductance coupled plasma-atomic of the Agilent company models for 720ES
Emission spectrometer analyzes the weight content of Gold Samples category strontium element.
The test method of the weight content of the metal antimony element：Liquid-crystalline polyester composition is 4 hours dry at 120 DEG C,
The pending samples of 1g are taken, add in nitric acid and hydrogen peroxide, heats 2 hours, is during which continuously added nitric acid and hydrogen peroxide；The resolution of sample
After the completion, cancel the sample after solution, use full-automatic inductance coupled plasma-atomic of the Agilent company models for 720ES
Emission spectrometer analyzes the weight content of Gold Samples category antimony element.
The test method of the fusing point of the liquid-crystalline polyester composition：It is swept by 200 F3 type differentials of NETZSCH companies DSC
Retouch calorimeter（DSC）, tested since room temperature with 20 DEG C/min of Elevated Temperature Conditions, observing endotherm peak temperature Tm1Afterwards, than
Tm1It is kept for 5 minutes, is then cooled to room temperature under 20 DEG C/min of cooling conditions, then again with 20 at a temperature of high 20 DEG C
DEG C/min Elevated Temperature Conditions be measured, the endotherm peak temperature T observed at this timem2Fusing point for liquid-crystalline polyester composition.
Deflection temperature under the liquid-crystalline polyester composition load（HDT）Test method：Liquid-crystalline polyester composition is molded
Long 127 mm are made, then the sample of 6.4 mm of wide 12.7 mm and thickness is surveyed according to ASTM D648 under the load of 1.82MPa
It is fixed.
The test method of the maximum resistant blister temperature of the liquid-crystalline polyester composition：Liquid-crystalline polyester composition injection is made
40 mm of length, 40 mm of width, the model of thickness 0.8mm are used as blistering evaluation.By model in the silicone oil bath of arbitrary temp
Dipping after five minutes, observes its surface.The maximum temperature that surface is not occurred to blister is set as maximum resistant blister temperature, this temperature
It is higher to illustrate that heat resistance and proper alignment foaming characteristic are better.
The title for the corresponding monomer of repetitive unit that the liquid crystal polyester used in the present invention contains and abbreviation are as follows respectively：
4-HBA（HBA）；
4,4 '-dihydroxybiphenyl（BP）；
Terephthalic acid (TPA)（TA）；
M-phthalic acid（IA）；
2- hydroxyl -6- naphthoic acids（HNA）；
Hydroquinone（HQ）；
2,6- naphthalenedicarboxylic acids（NDA）；
What is used in the present invention contains strontium compound：
Strontium acetate：Sigma-Aldrich（Shanghai）Trade Co., Ltd；
Strontium oxide strontia：Sigma-Aldrich（Shanghai）Trade Co., Ltd；
Strontium carbonate：Sigma-Aldrich（Shanghai）Trade Co., Ltd；
Strontium sulfate：Sigma-Aldrich（Shanghai）Trade Co., Ltd；
The antimony containing compounds used in the present invention：
Antimony oxide（III）：Sigma-Aldrich（Shanghai）Trade Co., Ltd；
The glass fibre used in the present invention：Trade mark CS03JAPX-1,10 microns of number average fiber diameter, the equal draw ratio of number
300,3000 microns of number average fiber length, Asahi Fiber Glass Co., Ltd.
Embodiment A1-A4:The preparation of liquid crystal polyester
Distinguish in the reaction kettle for being equipped with blender, thermometer, nitrogen ingress pipe and reflux condensate device according to proportioning
Add in the repetitive unit derived from aromatic hydroxy-carboxylic, the repetitive unit derived from aromatic diol and derived from aromatic series two
The repetitive unit of carboxylic acid, and a certain proportion of acetic anhydride is added in as acylating agent；Then nitrogen is passed through in reaction kettle into line replacement；
Stirring is started, reaction mixture is heated to 140 DEG C -160 DEG C by room temperature in nitrogen stream, is flowed back 1 hour -3 at this temperature
Hour；Hereafter continue to heat up, mixture was heated to 300 DEG C -350 DEG C through -4 hours 2 hours from 140 DEG C -160 DEG C, herein mistake
Unreacted acetic anhydride and side reaction product acetic acid are steamed in journey；Whole polycondensation phase, depressurizes reaction system, and passes through sight
Examine the endpoint that torque raising terminates as reaction；The prepolymer of melt state through drain hole is discharged at this time, and is cooled to
Room temperature；Prepolymer is further transferred to solid phase device, through -7 hours 5 hours by temperature by room temperature be increased to 260 DEG C -
It 280 DEG C, keeps the temperature -11 hours 9 hours at this temperature and carries out solid-phase polymerization；Product is exported after reaction, so as to
To liquid crystal polyester.
The specific proportioning and its test performance result of 1 embodiment A1-A4 of table
Embodiment 1-14 and comparative example 1-6：The preparation of liquid-crystalline polyester composition
Gained liquid crystal polyester, filler will be prepared by embodiment A1-A4, containing strontium compound and/or containing antimony by the proportioning of table 2
Compound, and/or various additives after mixing, add in double screw extruder, in 280RPM-320RPM with high-speed mixer
Screw speed under melting mixing, barrel temperature is 290 DEG C -355 DEG C, is squeezed out, cooling, pelletizing is to get liquid-crystalline polyester composition.
The fusing point of gained liquid-crystalline polyester composition, maximum resistant blister temperature and HDT are listed in Table 2 below；
Wherein, the metal strontium element in liquid-crystalline polyester composition, metallic antimony constituent content are in liquid-crystalline polyester composition
It is adjusted and measures by the actual interpolation amount containing strontium compound, antimony containing compounds in preparation process.
Table 2
Continued 2
Continued 2
The present invention is can be seen that by selecting in liquid crystal polyester group from the comparison of the embodiment 1-14 and comparative example 1-6 of table 2
Total weight of the weight content based on liquid-crystalline polyester composition for closing addition metal strontium element in composition formula is 0.1ppm-300ppm
When, the high-temperature heat-resistance stability and proper alignment foaming characteristic of obtained liquid-crystalline polyester composition obtain unexpected significantly improve.
Claims (17)
1. a kind of liquid-crystalline polyester composition, which is characterized in that the total weight based on liquid-crystalline polyester composition, the weight of metal strontium element
Amount content is 0.1ppm-300ppm；
Metal antimony element is further included, the total weight based on liquid-crystalline polyester composition, the weight content of metal antimony element is 0.1ppm-
300ppm。
2. liquid-crystalline polyester composition according to claim 1, which is characterized in that the test of the weight content of metal strontium element
Method：Liquid-crystalline polyester composition is 4 hours dry at 120 DEG C, the pending samples of 1g are taken, add in nitric acid and hydrogen peroxide, heating 2 is small
When, during which it is continuously added nitric acid and hydrogen peroxide；After the completion of the resolution of sample, cancel the sample after solution, using Agilent company types
Number for 720ES full-automatic inductively coupled plasma atomic emission spectrometer analyze Gold Samples category strontium element weight contain
Amount.
3. liquid-crystalline polyester composition according to claim 1, which is characterized in that the gross weight based on liquid-crystalline polyester composition
Amount, the weight content of metal strontium element is 0.5ppm-100ppm.
4. liquid-crystalline polyester composition according to claim 3, which is characterized in that the gross weight based on liquid-crystalline polyester composition
Amount, the weight content of metal strontium element is 1ppm-50ppm.
5. liquid-crystalline polyester composition according to claim 1, which is characterized in that the gross weight based on liquid-crystalline polyester composition
Amount, the weight content of metal antimony element is 1ppm-50ppm.
6. liquid-crystalline polyester composition according to claim 1, which is characterized in that the test of the weight content of metal antimony element
Method：Liquid-crystalline polyester composition is 4 hours dry at 120 DEG C, the pending samples of 1g are taken, add in nitric acid and hydrogen peroxide, heating 2 is small
When, during which it is continuously added nitric acid and hydrogen peroxide；After the completion of the resolution of sample, cancel the sample after solution, using Agilent company types
Number for 720ES full-automatic inductively coupled plasma atomic emission spectrometer analyze Gold Samples category antimony element weight contain
Amount.
7. according to claim 1-6 any one of them liquid-crystalline polyester compositions, which is characterized in that the liquid crystal polyester combination
Object, by weight, including following component：
100 parts of liquid crystal polyester；
5 parts -100 parts of filler.
8. liquid-crystalline polyester composition according to claim 7, which is characterized in that the fusing point of the liquid-crystalline polyester composition is
150℃-400℃；The test method of the fusing point is：Pass through 200 F3 type differential scanning calorimeters of NETZSCH companies DSC
DSC is being tested with 20 DEG C/min of Elevated Temperature Conditions since room temperature, is observing endotherm peak temperature Tm1Afterwards, than Tm1It is 20 DEG C high
At a temperature of kept for 5 minutes, be then cooled to room temperature under 20 DEG C/min of cooling conditions, then again with 20 DEG C/min
Elevated Temperature Conditions are measured, the endotherm peak temperature T observed at this timem2The as fusing point of liquid-crystalline polyester composition.
9. liquid-crystalline polyester composition according to claim 7, which is characterized in that the liquid crystal polyester, by mole
Meter, includes following repetitive unit：
Repetitive unit 30mol%-100mol% derived from aromatic hydroxy-carboxylic；
Repetitive unit 0mol%-35mol% derived from aromatic diol；
Repetitive unit 0mol%-35mol% derived from aromatic dicarboxylic acid.
10. liquid-crystalline polyester composition according to claim 9, which is characterized in that the liquid crystal polyester, by mole
Meter, including following repetitive unit：
Repetitive unit 50mol%-100mol% derived from aromatic hydroxy-carboxylic；
Repetitive unit 0mol%-25mol% derived from aromatic diol；
Repetitive unit 0mol%-25mol% derived from aromatic dicarboxylic acid.
11. liquid-crystalline polyester composition according to claim 9 or 10, which is characterized in that described to be derived from aromatic hydroxyl
The repetitive unit of carboxylic acid is selected from the repetitive unit of repetitive unit and/or 2- hydroxyl -6- naphthoic acids derived from 4-HBA；
The repetitive unit derived from aromatic diol is selected from the repetitive unit of hydroquinone and/or the weight of 4,4 '-dihydroxybiphenyl
Multiple unit；The repetitive unit derived from aromatic dicarboxylic acid is selected from the repetitive unit of terephthalic acid (TPA), M-phthalic acid
Repetitive unit, 2,6- naphthalenedicarboxylic acids repetitive unit in it is one or more of.
12. liquid-crystalline polyester composition according to claim 7, which is characterized in that the filler is selected from fibrous filler
Agent and/or plate filler；The fibrous filler is selected from glass fibre, asbestos fibre, silicon dioxide fibre, titanium dioxide
One or more of silicon-alumina fibre, potassium titanate fibre, carbon or graphite fibre, metallic fiber；The plate filler choosing
From one or more of talcum, mica, graphite, kaolin.
13. liquid-crystalline polyester composition according to claim 12, which is characterized in that the fibrous filler is glass fibers
Dimension.
14. liquid-crystalline polyester composition according to claim 12, which is characterized in that the plate filler is mica.
15. liquid-crystalline polyester composition according to claim 13, which is characterized in that the equal fiber of number of the glass fibre is straight
Diameter 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.
16. liquid-crystalline polyester composition according to claim 14, which is characterized in that the average grain diameter of the mica is 0.5
- 200 microns of micron.
17. liquid-crystalline polyester composition according to claim 7, which is characterized in that also comprising various additives；It is described various
Additive is selected from one or more of plasticizer, stabilizer, colorant, lubricant, releasing agent, antioxidant.
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| JP2009155623A (en) * | 2007-12-03 | 2009-07-16 | Sumitomo Chemical Co Ltd | Liquid crystalline polyester resin composition and molded article thereof |
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