CN105838386A - Liquid crystalline polyester composition - Google Patents
Liquid crystalline polyester composition Download PDFInfo
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- CN105838386A CN105838386A CN201610226654.5A CN201610226654A CN105838386A CN 105838386 A CN105838386 A CN 105838386A CN 201610226654 A CN201610226654 A CN 201610226654A CN 105838386 A CN105838386 A CN 105838386A
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- crystalline polyester
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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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Abstract
The invention discloses a liquid crystalline polyester composition. The weight content of the metallic sodium element is 1ppm-800ppm based on the total weight of the liquid crystalline polyester composition. The test method of the weight content of the metallic sodium element includes: drying the liquid crystalline polyester composition for 4h at 120 DEG C, taking out 1g sample to be treated, adding nitric acid and hydrogen peroxide, heating the mixture for 2h, adding nitric acid and hydrogen peroxide continuously during the reaction, taking the digested sample after the digestion of the sample completed, and analyzing the weight content of the metallic sodium element of the sample by using an automatic inductively coupled plasma atomic emission spectrometer with model of 720 ES of Agilent company. The tensile strength of the obtained liquid crystalline polyester composition is improved obviously by using the formula of the liquid crystalline polyester composition adding the metallic sodium element with weight content of 1ppm-800ppm based on the total weight of the liquid crystalline polyester composition, and the heat-resistant stability at high temperature is obviously improved unexpectedly.
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) is as a kind of special engineered class material, compared with resins for universal use, there is higher fusing point and high heat-resistant stability, but thermally decompose or because of the strand chain rupture by external force hot shearing when liquid crystal polyester remains at high temperature processing, cause 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 have done many trials.
US5397502 discloses the liquid-crystalline polymer composition that a kind of heat-resistant stability improves, and compositions comprises the alkali metal of 15 ~ 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 fusing point and the heat distortion temperature of compositions, makes thermostability be improved.But patent is mentioned make liquid crystal polymer at high temperature contact with functional compound and long enough make its melt viscosity decline at least 10%.Well known to professional and technical personnel in the field, liquid crystalline resin processes for a long time under higher than its melt temperature, owing to thermal decomposition can cause the reduction of melt viscosity and molecular weight, and the decline also having mechanical property thus brought, and the generation of side reaction, this may increase the risk that resin bubbles.
CN1234749 discloses a kind of liquid-crystal polyester resin, the repetitive wherein containing 4 hydroxyisophthalic acid and/or salicylic acid and come is as copolymer composition, and containing the alkali metal compound of 10 ~ 5000ppm, and claim that the coloring of resin is excellent, thermostability is high, and mechanicalness is good.This invention mainly stresses the improvement of liquid crystal polyester degree of staining and impact property, and in embodiment or patent, other parts do not illustrate whether heat resistance changes.And whether this patent undeclared invention are applicable to liquid-crystalline polyester composition.
US6755991 discloses a kind of liquid-crystalline polyester composition, comprises at least one aromatic dicarboxylic acid, and at least one contains naphthalene nucleus carboxylic acid and at least one alkali metal of 1 ~ 1000ppm and at least one transition metal of 0 ~ 3000ppm.Liquid-crystalline polyester composition prepared by this invention has whiteness and the impact strength of improvement, and whether not mentioned high-temperature heat-resistance stability changes.
Up to the present, about interpolation metallic sodium element in liquid-crystalline polyester composition, the impact of described liquid-crystalline polyester composition hot strength and high-temperature heat-resistance stability is had no report.
The present inventor through great many of experiments surprisingly it has been found that, select the weight content gross weight based on liquid-crystalline polyester composition adding metallic sodium element in liquid-crystalline polyester composition formula when being 1ppm-800ppm, the hot strength of the liquid-crystalline polyester composition obtained is obviously improved, 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 hot strength to be obviously improved, and the liquid-crystalline polyester composition that high-temperature heat-resistance stability 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 metallic sodium element is 1ppm-800ppm.
Being preferably based on the gross weight of liquid-crystalline polyester composition, the weight content of metallic sodium element is preferably 5ppm-500ppm, more preferably 10ppm-300ppm.
Wherein, the method for testing of the weight content of metallic sodium element: liquid-crystalline polyester composition is dried 4 hours at 120 DEG C, take the pending sample of 1g, add nitric acid and hydrogen peroxide, heat 2 hours, period is continuously added nitric acid and hydrogen peroxide；After having cleared up of sample, cancelling the sample after solution, the full-automatic inductively coupled plasma atomic emission spectrometer using Agilent company model to be 720ES is analyzed Gold Samples and is belonged to the weight content of sodium element.
Document is not yet had to be reported in liquid-crystalline polyester composition the introducing metallic sodium element impact on composition properties at present, present inventors have unexpectedly found that in liquid-crystalline polyester composition, introduce appropriate sodium element, liquid-crystalline polyester composition hot strength is obviously improved, and shows surprising heat-resistant stability in high temperature environments.And when in liquid-crystalline polyester composition, the weight content of metallic sodium element exceedes particular value, liquid-crystal composition contains higher metal residuals, its dielectric properties as electronic apparatus type component will certainly be affected, be substantially reduced its range, and mobility there will be significantly decline.
nullIntroducing typically by adding what compounds containing sodium realized of metallic sodium element，Compounds containing sodium can be selected from D-ALPHA-Hydroxypropionic acid sodium、Pfansteihl sodium、Sodium acetate、Sodium sulfite、Sodium oxide、Sodamide.、Sodium nitrate、Sodium sulfide、Sodium sulfate、Sodium phosphate、Disodium oxalate.、Sodium tartrate binary dihydrate、Sodium chlorite、Sodium selenite、Sodium metasilicate、Sodium metabisulfite、Sodium hexafluorisilicate、The inorganic compound such as sodium diacetate，It can also be sodium acrylate、Sodium acetylide、Sodium ethylate、Sodium citrate、Enuatrol、Sodium salicylate、Feldalat NM、Biphenyl sodium、Sodium phenate、1-sodium butane sulfonate、1-propane sodium mercaptides、1-dodecane sulfonic acid sodium、1-sodium nonanesulfonate、1-sodium heptanesulfonate、1-decane sulfonate、2-propane sodium mercaptides、2-sodium naphthalene sulfonate、Disodium succinate、Sodium succinate、Sodium Pyruvate、Sodium propionate、Sodium xylene sulfonate、Sodium lauryl sulphate、The organic compound such as sodium tert-butoxide.The source of the metallic sodium element pointed by the present invention is not limited only to the example above, no matter uses the compounds containing sodium of which kind of form, and atomic emission spectrometry can be used to detect.The weight content of metallic sodium element is by metallic sodium element itself rather than on the basis of the compounds containing sodium adding metallic sodium element.The weight content of the metallic sodium element represented by ppm 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 Titanium element, gross weight based on liquid-crystalline polyester composition, and the weight content of Titanium element is 1ppm-800ppm, preferably 10ppm-500ppm.
Wherein, the method for testing of the weight content of Titanium element: liquid-crystalline polyester composition is dried 4 hours at 120 DEG C, take the pending sample of 1g, add nitric acid and hydrogen peroxide, heat 2 hours, period is continuously added nitric acid and hydrogen peroxide；After having cleared up of sample, cancelling the sample after solution, the full-automatic inductively coupled plasma atomic emission spectrometer using Agilent company model to be 720ES is analyzed Gold Samples and is belonged to the weight content of titanium elements.
nullIntroducing typically by adding what titanium-containing compound realized of Titanium element，Titanium-containing compound can be selected from Barium metatitanate.、Iron titanate (II)、Aluminium titanates、Lithium titanate、Zinc titanate、Metatitanic acid sodium salt、Titanium oxide (II)、Titanium oxide (IV)、Silicon titanium oxide、Titanium carbide (IV)、Titanium disulfide、Ammonium hexa-fluorotitanate、Ten dichloro Tritanium/Trititanium aluminum、Titanium tetrafluoride、Titanium fluoride (III)、Titanium carbonitride、The inorganic compound such as ammonium titanyl oxalate monohydrate，Titanium ethanolate can also be selected、Titanyl phthalocyanine、Poly(tributoxy titanium)、2-ethyl-1-hexanol titanium、Trichlorine one cyclopentadienyl titanium、Acetylacetone,2,4-pentanedione oxygen titanium (IV)、Double (levulinic ketone group) diisopropyl titanate esters、Double (cyclopentadienyl group) titanium chloride (IV)、Tert-butyl alcohol titanium、Four (dimethyl amido) titanium (IV)、Titanium tetraisopropylate、Four methanol titaniums (IV)、Normal propyl alcohol titanium、Three isopropoxy titanium chlorides、Dichloro two indenyl titanium、Butyl titanate、Four (ethyl-methyl amido) titanium (IV)、The organic compound such as four (diethyl amido) titanium (IV).The source of the Titanium element pointed by the present invention is not limited only to the example above, no matter uses the titanium-containing compound of which kind of form, and atomic emission spectrometry can be used to detect.The weight content of Titanium element is by Titanium element itself rather than on the basis of the titanium-containing compound adding Titanium element.The weight content of the Titanium element represented by ppm is to calculate on the basis of the gross weight of liquid-crystalline polyester composition.
Wherein, described liquid-crystalline polyester composition, by weight, including following component:
Liquid crystal polyester
100 parts；
Filler
5 parts-100 parts.
Wherein, the fusing point of described liquid-crystalline polyester composition is 150 DEG C-400 DEG C；The method of testing of described fusing point is: by NETZSCH company DSC
200 F3 type differential scanning calorimeter DSC, are starting to test with the Elevated Temperature Conditions of 20 DEG C/min from room temperature, are 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, be the most again measured with the Elevated Temperature Conditions of 20 DEG C/min, the endotherm peak temperature T now observedm2It is the fusing point of liquid-crystalline polyester composition.
Wherein, described liquid crystal polyester, by mole meter, comprise following repetitive:
Repetitive derived from aromatic hydroxy-carboxylic
30mol%-100mol%；
Repetitive derived from aromatic diol
0mol%-35mol%；
Repetitive derived from aromatic dicarboxylic acid
0mol%-35mol%。
Preferably, described liquid crystal polyester, by mole meter, including following repetitive:
Repetitive derived from aromatic hydroxy-carboxylic
50mol%-100mol%；
Repetitive derived from aromatic diol
0mol%-25mol%；
Repetitive derived from aromatic dicarboxylic acid
0mol%-25mol%。
Wherein, the described repetitive derived from aromatic hydroxy-carboxylic 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 repetitive of 4,4 '-dihydroxybiphenyl of hydroquinone；The described repetitive derived from aromatic dicarboxylic acid is selected from the repetitive of the repetitive of p-phthalic acid, the repetitive of M-phthalic acid, 2,6-naphthalenedicarboxylic acid 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:
In the reactor being equipped with agitator, thermometer, nitrogen ingress pipe and reflux condensate device, it is separately added into the repetitive derived from aromatic hydroxy-carboxylic, the repetitive derived from aromatic diol and the repetitive derived from aromatic dicarboxylic acid according to proportioning, and to add a certain proportion of acetic anhydride be acylating agent；Then nitrogen is passed through in reactor and replaces；Start stirring, in nitrogen stream, reactant mixture is heated to 140 DEG C-160 DEG C by room temperature, 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 unreacted acetic anhydride and side reaction product acetic acid in the process；Whole polycondensation phase, reduces pressure to reaction system, and the endpoint terminated as reaction by observing moment of torsion to raise；Now the prepolymer of melt state is discharged through drain hole, and be cooled to room temperature；Prepolymer being transferred to solid phase device further, through 5 hours-7 hours, temperature from ambient is increased to 260 DEG C-280 DEG C, insulation carries out solid-phase polymerization in 9 hours-11 hours at this temperature；Product is derived after terminating by reaction, thus obtains liquid crystal polyester.
Wherein, described filler is selected from fibrous filler and/or tabular filler；One or more in glass fibre, asbestos fibre, silicon dioxide fibre, silica-alumina fiber, potassium titanate fibre, carbon or graphite fibre, metallic fiber of described fibrous filler；It is preferably glass fibre；One or more in Talcum, Muscovitum, graphite, Kaolin of described tabular filler；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, and 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, the mechanical strength of liquid-crystalline polyester composition may reduce.The method adding filler is not particularly limited, and can be set forth in method as known in the art.
Additionally, in addition to the foregoing, not damage, the liquid-crystalline polyester composition that the amount of the object of the invention uses in the present invention can add known various additives；Various additives can be selected from one or more in plasticizer, stabilizer, coloring agent, lubricant, 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 monohydric phenol or polyhydric phenols, polyhydric phenols and the alkylation reaction product of diene, the butylation product of paracresol or bicyclopentadiene, alkylating hydroquinones, hydroxylated thiodiphenvl ethers, alkylidene-bis-phenol, benzyl compounds, polyhydric alcohol esters, benzotriazole, one or more combinations of benzophenone.
Suitably releasing agent includes metallic stearic salt, allcyl stearate class, stearic acid pentaerythritol esters, paraffin, lignite wax etc..
Suitably coloring agent includes various pigment, and dyestuff, such as metal-oxide and the zinc oxide of mixed-metal oxides of inorganic pigment, 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 the alkylation reaction product of diene, the butylation product of paracresol or bicyclopentadiene, alkylating hydroquinones, hydroxylated thiodiphenvl ethers, alkylidene-bis-phenol, benzyl compounds, polyhydric alcohol esters etc..
Various additives are not limited to above-mentioned several, can optionally contain other material common in the heat stability to liquid crystal polyester and harmless other species components of physical property and thermoplastic compounds, polypropylene, polyamide, polyester, polyphenylene sulfide, polyether-ketone, Merlon, polyether sulfone, polyphenyl ether and modified material thereof such as one or more, thermoplastic resin such as Polyetherimide, 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 specifically limits, it is possible to use dry type blending, solution mixing method, the polymerization of liquid crystal polyester are interpolation, melting mixing etc., the most preferably melting mixing.Such as kneader, uniaxially or biaxially extruder, rubber-roller machine etc., biaxial extruder is wherein preferably used.The temperature of melting mixing is more than the fusing point of 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 to carry out mixing method from rear dress charger；Liquid crystal polyester and various additive can also be penetrated from rear dress charger, add filler from side charger and carry out mixing method, the liquid-crystalline polyester composition master batch that high concentration comprises liquid crystal polyester and various additive can also be prepared, then liquid-crystalline polyester composition master batch and filler are carried out any one method of the method etc. of the mixing concentration to become regulation.
The liquid-crystalline polyester composition of embodiments of the present invention by carrying out injection moulding, the known melt molding product such as injection compression molding, compression forming, extrusion molding, blow molding, compressing spinning.Products formed described here, can be the various cellosilks etc. such as the various membrane products such as injection-molded article, extrusion molding article, compressing product, sheet, pipe, non-stretched film, single axle drawn membrane, biaxially oriented film, undrawn yarn, super drawing silk.In the case of extrusion molding, can significantly obtain the effect of the present invention, the most preferably.
Wherein, the liquid-crystalline polyester composition obtained by extruding-out process, specifically comprise the following steps that after liquid crystal polyester, filler, compounds containing sodium and/or titanium-containing compound and/or various additive high-speed mixer mix homogeneously according to proportioning, add double screw extruder, melting mixing under the screw speed of 280RPM-320RPM, barrel temperature is 290 DEG C-355 DEG C, extrusion, cooling, pelletizing, obtain liquid-crystalline polyester composition.
nullWherein compounds containing sodium can be selected from D-ALPHA-Hydroxypropionic acid sodium、Pfansteihl sodium、Sodium acetate、Sodium sulfite、Sodium oxide、Sodamide.、Sodium nitrate、Sodium sulfide、Sodium sulfate、Sodium phosphate、Disodium oxalate.、Sodium tartrate binary dihydrate、Sodium chlorite、Sodium selenite、Sodium metasilicate、Sodium metabisulfite、Sodium hexafluorisilicate、The inorganic compound such as sodium diacetate，It can also be sodium acrylate、Sodium acetylide、Sodium ethylate、Sodium citrate、Enuatrol、Sodium salicylate、Feldalat NM、Biphenyl sodium、Sodium phenate、1-sodium butane sulfonate、1-propane sodium mercaptides、1-dodecane sulfonic acid sodium、1-sodium nonanesulfonate、1-sodium heptanesulfonate、1-decane sulfonate、2-propane sodium mercaptides、2-sodium naphthalene sulfonate、Disodium succinate、Sodium succinate、Sodium Pyruvate、Sodium propionate、Sodium xylene sulfonate、Sodium lauryl sulphate、The organic compound such as sodium tert-butoxide.The source of the metallic sodium element pointed by the present invention is not limited only to the example above, no matter uses the compounds containing sodium of which kind of form, and atomic emission spectrometry can be used to detect.The weight content of metallic sodium element is by metallic sodium element itself rather than on the basis of the compounds containing sodium adding metallic sodium element.The weight content of the metallic sodium element represented by ppm is to calculate on the basis of the gross weight of liquid-crystalline polyester composition.
nullWherein titanium-containing compound can be selected from Barium metatitanate.、Iron titanate (II)、Aluminium titanates、Lithium titanate、Zinc titanate、Metatitanic acid sodium salt、Titanium oxide (II)、Titanium oxide (IV)、Silicon titanium oxide、Titanium carbide (IV)、Titanium disulfide、Ammonium hexa-fluorotitanate、Ten dichloro Tritanium/Trititanium aluminum、Titanium tetrafluoride、Titanium fluoride (III)、Titanium carbonitride、The inorganic compound such as ammonium titanyl oxalate monohydrate，Titanium ethanolate can also be selected、Titanyl phthalocyanine、Poly(tributoxy titanium)、2-ethyl-1-hexanol titanium、Trichlorine one cyclopentadienyl titanium、Acetylacetone,2,4-pentanedione oxygen titanium (IV)、Double (levulinic ketone group) diisopropyl titanate esters、Double (cyclopentadienyl group) titanium chloride (IV)、Tert-butyl alcohol titanium、Four (dimethyl amido) titanium (IV)、Titanium tetraisopropylate、Four methanol titaniums (IV)、Normal propyl alcohol titanium、Three isopropoxy titanium chlorides、Dichloro two indenyl titanium、Butyl titanate、Four (ethyl-methyl amido) titanium (IV)、The organic compound such as four (diethyl amido) titanium (IV).The source of the Titanium element pointed by the present invention is not limited only to the example above, no matter uses the titanium-containing compound of which kind of form, and atomic emission spectrometry can be used to detect.The weight content of Titanium element is by Titanium element itself rather than on the basis of the titanium-containing compound adding Titanium element.The weight content of the Titanium element represented by ppm is to calculate on the basis of the gross weight of liquid-crystalline polyester composition.
nullThe products formed that the liquid-crystalline polyester composition that the present invention is obtained is formed can have following application，With various gears、Various housings、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 boards、Transformator、Plug、Printed wiring board、Tuner、Speaker、Microphone、Head type headphones、Miniature motor、Magnetic head base、Power model、Shell、Quasiconductor、Liquid crystal display component、FDD bracket、FDD chassis、HDD parts、Motor brush holder、Parabola antenna、The electrical and electronic parts that computer associated components etc. are representative、With VTR parts、TV part、Flatiron、Hair dryer、Electric cooker parts、Microwave oven component、Sound part、Audio frequency、Laser disk、The speech ciphering equipment parts such as CD、Illuminace component、Parts of refrigerator、Air supply rate、Typewriter parts、The family that 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、The various bearings such as water middle (center) bearing、Motor component、With lighter、The mechanical associated components that typewriter etc. are representative、With microscope、Binoculars、Photographing unit、The optical device that clock and watch etc. are representative、Precision optical machinery associated components；nullAlternating current generator terminal、Alternating current generator adapter、IC actuator、Dimmer potentiometer base、The various valves such as aerofluxus air valve、Fuel associates、Exhaust system、The various pipes of air-breathing system、Inlet jet breather、Inlet manifold、Petrolift、Engine cool water swivel、Carburator main body、Carburator spacer、Exhaust gas sensor、Cooling water sensor、Oil temperature sensor、TPS、Crankshaft position sensor、Mass air flow sensor、Brake pad abrasion sensor、Idle call thermostat base、Air conditioning electricity motivation insulator、The on-vehicle motor insulators such as motorized window、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 insulation board、Stepping motor rotor、Lamp ring、Lamp socket、Lamp reflector、Lamp housing、Brake piston、Solenoid bobbin、Engine oil filter、The automobiles such as ignition housings、Vehicle associated components etc.，At printed wiring board，In small-sized thin-walled electronic device etc. particularly useful.
The present invention compared with prior art, has the advantages that
When the present invention is 1ppm-800ppm by selecting the weight content gross weight based on liquid-crystalline polyester composition adding metallic sodium element in liquid-crystalline polyester composition formula, the hot strength of the liquid-crystalline polyester composition obtained is obviously improved, and high-temperature heat-resistance stability 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, but embodiments of the present invention are not limited by following embodiment.
The method of testing of the weight content of described metallic sodium element: 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, heats 2 hours, and period is continuously added nitric acid and hydrogen peroxide；After having cleared up of sample, cancelling the sample after solution, the full-automatic inductively coupled plasma atomic emission spectrometer using Agilent company model to be 720ES is analyzed Gold Samples and is belonged to the weight content of sodium element.
The method of testing of the weight content of described Titanium element: 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, heats 2 hours, and period is continuously added nitric acid and hydrogen peroxide；After having cleared up of sample, cancelling the sample after solution, the full-automatic inductively coupled plasma atomic emission spectrometer using Agilent company model to be 720ES is analyzed Gold Samples and is belonged to the weight content of titanium elements.
The method of testing of the fusing point of described liquid-crystalline polyester composition: by NETZSCH company DSC
200 F3 type differential scanning calorimeter (DSC), are starting to test with the Elevated Temperature Conditions of 20 DEG C/min from room temperature, are 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, be the most again measured with the Elevated Temperature Conditions of 20 DEG C/min, the endotherm peak temperature T now observedm2Fusing point for liquid-crystalline polyester composition.
The method of testing of the hot strength of described liquid-crystalline polyester composition: liquid-crystal composition is molded into No. 4 dumbbell shape samples of ASTM, then according to the hot strength of ASTM D638 standard testing compositions.
Deflection temperature (HDT) method of testing under described liquid-crystalline polyester composition load: liquid-crystalline polyester composition injection is made long 127
Mm, wide 12.7 mm and thick 6.4
The sample of mm, then according to ASTM D648 measures under the load of 1.82MPa.
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 compounds containing sodium used in the present invention:
Sodium acetate: Sigma-Aldrich (Shanghai) trade Co., Ltd；
Sodium sulfate: Sigma-Aldrich (Shanghai) trade Co., Ltd；
Sodium tert-butoxide: Sigma-Aldrich (Shanghai) trade Co., Ltd；
Biphenyl sodium: Sigma-Aldrich (Shanghai) trade Co., Ltd；
The titanium-containing compound used in the present invention:
Titanium oxide (IV): Sigma-Aldrich (Shanghai) trade Co., Ltd；
The glass fibre used in the present invention: trade mark CS03JAPX-1, number equal fibre diameter 10 microns, the equal draw ratio 300 of number, number average fiber length 3000 microns, Asahi Fiber
Glass Co., Ltd。
Embodiment
A1-A4:
The preparation of liquid crystal polyester
In the reactor being equipped with agitator, thermometer, nitrogen ingress pipe and reflux condensate device, it is separately added into the repetitive derived from aromatic hydroxy-carboxylic, the repetitive derived from aromatic diol and the repetitive derived from aromatic dicarboxylic acid according to proportioning, and to add a certain proportion of acetic anhydride be acylating agent；Then nitrogen is passed through in reactor and replaces；Start stirring, in nitrogen stream, reactant mixture is heated to 140 DEG C-160 DEG C by room temperature, 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 unreacted acetic anhydride and side reaction product acetic acid in the process；Whole polycondensation phase, reduces pressure to reaction system, and the endpoint terminated as reaction by observing moment of torsion to raise；Now the prepolymer of melt state is discharged through drain hole, and be cooled to room temperature；Prepolymer being transferred to solid phase device further, through 5 hours-7 hours, temperature from ambient is increased to 260 DEG C-280 DEG C, insulation carries out solid-phase polymerization in 9 hours-11 hours at this temperature；Product is derived after terminating by reaction, thus obtains liquid crystal polyester.
The concrete proportioning of table 1 embodiment A1-A4 and test performance result thereof
Embodiment
1-14
And comparative example
1-6
: the preparation of liquid-crystalline polyester composition
After gained liquid crystal polyester, filler, compounds containing sodium and/or titanium-containing compound and/or various additive high-speed mixer mix homogeneously being prepared by embodiment A1-A4 by the proportioning of table 2, add double screw extruder, melting mixing under the screw speed of 280RPM-320RPM, barrel temperature is 290 DEG C-355 DEG C, extrusion, cooling, pelletizing, obtain liquid-crystalline polyester composition.The fusing point of gained liquid-crystalline polyester composition, hot strength and HDT are shown in Table 2；
Wherein, the metallic sodium element in liquid-crystalline polyester composition, Titanium constituent content are to be adjusted by the actual addition of compounds containing sodium, titanium-containing compound and recorded in the preparation process of liquid-crystalline polyester composition.
Table 2
Continued 2
Continued 2
From the embodiment 1 of table 2-14 and comparative example 1-6 relatively can be seen that, when the present invention is 1ppm-800ppm by selecting the weight content gross weight based on liquid-crystalline polyester composition adding metallic sodium element in liquid-crystalline polyester composition formula, the hot strength of the liquid-crystalline polyester composition obtained is obviously improved, and high-temperature heat-resistance stability obtains beyond thought significantly improving.
Claims (13)
1. a liquid-crystalline polyester composition, it is characterised in that gross weight based on liquid-crystalline polyester composition, the weight content of metallic sodium element is 1ppm-800ppm.
Liquid-crystalline polyester composition the most according to claim 1, it is characterised in that the method for testing of the weight content of metallic sodium element: liquid-crystalline polyester composition is dried 4 hours at 120 DEG C, take the pending sample of 1g, adding nitric acid and hydrogen peroxide, heat 2 hours, period is continuously added nitric acid and hydrogen peroxide；After having cleared up of sample, cancelling the sample after solution, the full-automatic inductively coupled plasma atomic emission spectrometer using Agilent company model to be 720ES is analyzed Gold Samples and is belonged to the weight content of sodium element.
Liquid-crystalline polyester composition the most according to claim 1, it is characterised in that gross weight based on liquid-crystalline polyester composition, the weight content of metallic sodium element is preferably 5ppm-500ppm, more preferably 10ppm-300ppm.
Liquid-crystalline polyester composition the most according to claim 1, it is characterised in that also include Titanium element, gross weight based on liquid-crystalline polyester composition, the weight content of Titanium element is 1ppm-800ppm, preferably 10ppm-500ppm.
Liquid-crystalline polyester composition the most according to claim 4, it is characterised in that the method for testing of the weight content of Titanium element: liquid-crystalline polyester composition is dried 4 hours at 120 DEG C, take the pending sample of 1g, adding nitric acid and hydrogen peroxide, heat 2 hours, period is continuously added nitric acid and hydrogen peroxide；After having cleared up of sample, cancelling the sample after solution, the full-automatic inductively coupled plasma atomic emission spectrometer using Agilent company model to be 720ES is analyzed Gold Samples and is belonged to the weight content of titanium elements.
6. according to the liquid-crystalline polyester composition described in any one of claim 1-5, it is characterised in that described liquid-crystalline polyester composition, by weight, including following component:
Liquid crystal polyester 100 parts；
Filler 5 parts-100 parts.
Liquid-crystalline polyester composition the most according to claim 6, it is characterised in that 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: 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 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, be the most again measured with the Elevated Temperature Conditions of 20 DEG C/min, 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 6, it is characterised in that described liquid crystal polyester, by mole meter, comprises following repetitive:
Repetitive 30mol%-100mol% derived from aromatic hydroxy-carboxylic；
Repetitive derived from aromatic diol
0mol%-35mol%；
Repetitive 0mol%-35mol% derived from aromatic dicarboxylic acid.
Liquid-crystalline polyester composition the most according to claim 8, it is characterised in that 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.
Liquid-crystalline polyester composition the most according to claim 8 or claim 9, it is characterised in that the described repetitive derived from aromatic hydroxy-carboxylic 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 repetitive of 4,4 '-dihydroxybiphenyl of hydroquinone；The described repetitive derived from aromatic dicarboxylic acid is selected from the repetitive of the repetitive of p-phthalic acid, the repetitive of M-phthalic acid, 2,6-naphthalenedicarboxylic acid one or more.
11. liquid-crystalline polyester compositions according to claim 6, it is characterised in that described filler is selected from fibrous filler and/or tabular filler；One or more in glass fibre, asbestos fibre, silicon dioxide fibre, silica-alumina fiber, potassium titanate fibre, carbon or graphite fibre, metallic fiber of described fibrous filler；It is preferably glass fibre；One or more in Talcum, Muscovitum, graphite, Kaolin of described tabular filler；It is preferably Muscovitum.
12. liquid-crystalline polyester compositions according to claim 11, it is characterised in that the equal fibre diameter of number of described glass fibre is 3 microns-30 microns, the equal draw ratio of number is more than or equal to 5, and number average fiber length is 50 microns-3000 microns；The mean diameter of described Muscovitum is 0.5 micron-200 microns.
13. liquid-crystalline polyester compositions according to claim 6, it is characterised in that also comprise various additive；One or more in plasticizer, stabilizer, coloring agent, lubricant, releasing agent, antioxidant of described various additive.
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| CN201610226654.5A CN105838386A (en) | 2016-04-13 | 2016-04-13 | Liquid crystalline polyester composition |
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| CN201610226654.5A CN105838386A (en) | 2016-04-13 | 2016-04-13 | Liquid crystalline polyester composition |
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Application publication date: 20160810 |