CN105585828A - LCP (liquid crystal polyester) composition - Google Patents
LCP (liquid crystal polyester) composition Download PDFInfo
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- CN105585828A CN105585828A CN201511015758.3A CN201511015758A CN105585828A CN 105585828 A CN105585828 A CN 105585828A CN 201511015758 A CN201511015758 A CN 201511015758A CN 105585828 A CN105585828 A CN 105585828A
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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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
- C08G63/065—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids the hydroxy and carboxylic ester groups being bound to aromatic rings
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/60—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from the reaction of a mixture of hydroxy carboxylic acids, polycarboxylic acids and polyhydroxy compounds
- C08G63/605—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from the reaction of a mixture of hydroxy carboxylic acids, polycarboxylic acids and polyhydroxy compounds the hydroxy and carboxylic groups being bound to aromatic rings
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- 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
- C08K3/34—Silicon-containing compounds
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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
- C08K5/13—Phenols; Phenolates
- C08K5/132—Phenols containing keto groups, e.g. benzophenones
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
- C08L67/03—Polyesters derived from dicarboxylic acids and dihydroxy compounds the dicarboxylic acids and dihydroxy compounds having the carboxyl- and the hydroxy groups directly linked to aromatic rings
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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
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
Abstract
The invention discloses LCP (liquid crystal polyester) composition. The content of 4-hydroxyacetophenone by weight is 0.1-500 ppm on the basis of the total weight of the LCP composition. When the content of 4-hydroxyacetophenone added to an LCP composition formula is 0.1-500 ppm on the basis of the total weight of the LCP composition, the high-temperature heat-resistant stability of the obtained LCP composition is significantly improved unexpectedly, and the liquidity is also improved.
Description
Technical field
The present invention relates to polymeric material field, particularly 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 heightHeat-resistant stability, but liquid crystal polyester still exists and at high temperature adds thermal decomposition in man-hour or because being subject to external force hot shearing strandChain rupture, the phenomenon that causes various aspects of performance to decline. In order to improve the heat-resistant stability of liquid crystal polyester, those skilled in the art have doneMany trials.
US5397502 discloses the liquid-crystalline polymer composition that a kind of heat-resistant stability improves, and composition comprises 15 ~The alkali metal of 3000ppm or the magnesium of 50 ~ 3000ppm or calcium; Liquid crystal polymer contains P-hydroxybenzoic acid, hydroquinones, biphenylDiphenol, terephthalic acid (TPA), NDA and biphenyl dicarboxylic acid repetitive. The introducing of metallics has improved compositionFusing point and heat distortion temperature, improve heat resistance. But mention in patent, liquid crystal polymer and functional compound are existedUnder high temperature, contact long enough its melt viscosity that makes decline at least 10%. Professional and technical personnel in the field institute is publicKnow, liquid crystalline resin is processed for a long time under higher than its melt temperature, because thermal decomposition meeting meeting causes melt viscosity and molecular weightReduce, the decline that also has mechanical property bringing thus, and the generation of side reaction, this may increase the wind that resin bubblesDanger.
CN1408816 discloses the liquid-crystal polyester resin group that does not produce bubble in a kind of heat endurance improvement and welding processCompound, it by adding 0.01-0.2 weight portion bi-ester of phosphite to realize in 100 weight portion liquid crystal polyesters. ButWhether this patent not mentioned its mobility are improved.
Up to the present, about adding 4-hydroxyacetophenone to described liquid-crystalline polyester composition in liquid-crystalline polyester compositionMobility, the impact of high-temperature heat-resistance stability have no report.
The inventor surprisingly finds through great many of experiments, selects and in liquid-crystalline polyester composition formula, add 4-hydroxy benzenesWhen the gross weight of the content of ethyl ketone based on liquid-crystalline polyester composition is 0.1ppm-500ppm, the liquid-crystalline polyester composition obtainingHigh-temperature heat-resistance stability obtains beyond thought remarkable improvement, and mobility is also improved.
Summary of the invention
In order to overcome the shortcoming and deficiency of prior art, primary and foremost purpose of the present invention is to provide a kind of high-temperature heat-resistance stableProperty significantly improves, and mobility improves, and does not affect the liquid-crystalline polyester composition of other side performance.
The present invention is achieved through the following technical solutions:
A kind of liquid-crystalline polyester composition, based on the gross weight of liquid-crystalline polyester composition, the weight content of 4-hydroxyacetophenone is0.1ppm-500ppm。
Preferably, based on the gross weight of liquid-crystalline polyester composition, the weight content of 4-hydroxyacetophenone is preferably 0.5ppm-300ppm, more preferably 1ppm-100ppm.
Wherein, the method for testing of the weight content of 4-hydroxyacetophenone: get 500mg liquid-crystalline polyester composition sample and addIn 25ml volumetric flask, adding 2.5ml concentration is the NaOH/CH of 5mol/L3OH mixed solution, and add the 10ml dimethyl Asia that dewatersSulfone; At the temperature of 60 DEG C, keep nitrogen atmosphere, more than volumetric flask is shaken to 24h, treat the liquid crystalline resin hydrolysis in sampleCompletely, the aromatic monomer salt that the hydrolysis that is dissolved in water forms, and with in hydrochloric acid and excessive alkali, freeze drying gained sample, is somebody's turn to doSample is the mixture of inorganic filler in liquid crystal polyester complete hydrolysis thing and composition; Sample after hydrolysis is dissolved in acetone,Adopt Agilent company of the U.S. 1260 type high performance liquid chromatographs, the 4-hydroxyacetophenone in test sample; And adopt external standard method4-hydroxyacetophenone in hydrolyzation sample is carried out quantitatively.
And the weight content that ought add 4-hydroxyacetophenone in liquid-crystalline polyester composition formula exceedes 500ppm, can makeThe mechanical properties decrease of liquid-crystalline polyester composition.
Wherein, described liquid-crystalline polyester composition, by weight, comprises following component:
100 parts of liquid crystal polyesters;
5 parts-100 parts of fillers.
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 throughThe DSC200F3 of NETZSCH company type differential scanning calorimeter DSC, surveys at the Elevated Temperature Conditions starting from room temperature with 20 DEG C/minExamination, observes endotherm peak temperature Tm1After, than Tm1At the temperature of high 20 DEG C, keep 5 minutes, then the cooling of 20 DEG C/minUnder condition, be cooled to room temperature, and then measure with the Elevated Temperature Conditions of 20 DEG C/min, the endotherm peak temperature now observingTm2Be the fusing point of liquid-crystalline polyester composition.
Wherein, described liquid crystal polyester, by mole% meter, comprises following repetitive:
Derived from the repetitive 30mol%-100mol% of aromatic hydroxy-carboxylic;
Derived from the repetitive 0mol%-35mol% of aromatic diol;
Derived from the repetitive 0mol%-35mol% of aromatic dicarboxylic acid.
Preferably, described liquid crystal polyester, by mole% meter, comprises following repetitive:
Derived from the repetitive 50mol%-100mol% of aromatic hydroxy-carboxylic;
Derived from the repetitive 0mol%-25mol% of aromatic diol;
Derived from the repetitive 0mol%-25mol% of aromatic dicarboxylic acid.
Wherein, the described repetitive derived from aromatic hydroxy-carboxylic is selected from the repetition list derived from 4-HBAThe repetitive of unit and/or 2-hydroxyl-6-naphthoic acid; The described repetitive derived from aromatic diol is selected from hydroquinonesRepetitive and/or 4, the repetitive of 4 '-dihydroxybiphenyl; It is right that the described repetitive derived from aromatic dicarboxylic acid is selected fromIn the repetitive of the repetitive of phthalic acid, the repetitive of M-phthalic acid, NDA one or more.
The preparation method of above-mentioned liquid crystal polyester, can adopt standard polycondensation technical method well known to those skilled in the art,Comprise the steps:
In the reactor that is equipped with agitator, thermometer, nitrogen ingress pipe and reflux condensate device, add respectively according to proportioningDerived from the repetitive of aromatic hydroxy-carboxylic, derived from the repetitive of aromatic diol with derived from aromatic dicarboxylic acidRepetitive, and to add a certain proportion of acetic anhydride be acylating agent; Then nitrogen is passed in reactor and replaced; StartStir, in nitrogen stream, reactant mixture is heated to 140 DEG C-160 DEG C by room temperature, at this temperature, reflux 1 hour-3 hours;After this 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, in this process, steamGo out unreacted acetic anhydride and side reaction product acetic acid; Whole polycondensation phase, reduces pressure to reaction system, and by observing moment of torsionThe endpoint finishing as reaction raises; Now the prepolymer of melt state is discharged through drain hole, and be cooled to room temperature; EnterPrepolymer is transferred to solid phase device by one step, through 5 hours-7 hours, temperature is increased to 260 DEG C-280 DEG C by room temperature,At this temperature, be incubated 9 hours and within-11 hours, carry out solid-phase polymerization; After reaction finishes, product is derived, thereby it is poly-to obtain liquid crystalEster.
Wherein, described filler is selected from tabular filler; Described tabular filler is selected from talcum, mica, graphite, kaolinIn one or more; Be preferably mica.
Preferably, the average grain diameter of described mica is 0.5 micron-200 microns.
When adding filler, with respect to liquid crystal polyester 100 weight portions, add and exceed 100 parts of above fillers, liquid crystal is poly-The mechanical strength of ester composition may reduce. Add the not restriction especially of method of filler, and can enumerate in the artKnown method.
In addition, except said components, can be with the amount of not damaging the object of the invention to the liquid crystal using in the present inventionIn polymer blend, add known various additive; Various additives can be selected from filler, plasticizer, stabilizing agent, colouring agent,One or more in lubricant, releasing agent, antioxidant.
In order to improve mechanical strength, can in liquid-crystalline polyester composition according to the present invention, sneak into the shape such as particle, thin sliceInorganic or the organic filler of formula.
The example of granulated filler comprises that silicate is as calcium silicates, alumina silicate, clay, diatomite, wollastonite, various metalPowder is as iron oxide, titanium oxide, zinc oxide, antimony trioxide, aluminium oxide and calcium sulfate, carbon black, silica, quartz sand, glassThe hollow glass bead of pearl, grinding and glass powder.
The example of flake stuffing comprises glass flake and various metal forming. Other organic fillers comprise for example fragrant adoptionThe heat-resistant high-strength fiber that ester, aromatic polyimide, polyamide etc. are made.
As required, these fillers can carry out surface treatment with common known surface conditioning agent.
Suitable plasticizer is phthalic acid ester.
Suitable stabilizing agent comprises organic phosphite, as triphenyl phosphite, and tricresyl phosphite-(2,6-3,5-dimethylphenyl)Ester, tricresyl phosphite-nonyl phenylester, dimethyl benzene phosphonate ester, trimethyl phosphate etc., organic phosphite, alkylating monobasicPhenol or polyhydric phenols, the alkylation reaction product of polyhydric phenols and diene, the butylation reaction of paracresol or bicyclopentadiene is producedThing, alkylating hydroquinones, hydroxylated sulfo-diphenylether, alkylidene-bis-phenol, benzyl compounds, polyol ester class, benzeneAnd triazole type, one or more combinations of benzophenone.
Suitable releasing agent comprises Metallic stearates class, stearic acid alkyl esters, stearic acid pentaerythritol esters, stoneWax, montan wax etc.
Suitable colouring agent comprises various pigment, and dyestuff, as the metal oxide of inorganic pigment and mixed-metal oxidesZinc oxide, titanium oxide, iron oxide, sulfide is as zinc sulphide etc.; Aluminate, silicate, chromate, ferrite etc., carbon black, groupBlue or green; Organic pigment is as azo, diazonium class, Anthraquinones, phthalocyanine, quinolines, naphthalene, ketone, piperazine class etc.
Proper lubrication agent comprises the slaine of higher fatty acids, high-grade fatty ester, higher fatty acids etc.
Suitable antioxidant comprises organic phosphite, alkylating monohydric phenol or polyhydric phenols, polyhydric phenols and dieneAlkylation reaction product, the butylation product of paracresol or bicyclopentadiene, alkylating hydroquinones, hydroxylated sulphurFor diphenylether, alkylidene-bis-phenol, benzyl compounds, polyol ester class etc.
Various additives are not limited to above-mentioned several, can optionally contain heat endurance and physical property to liquid crystal polyester harmlessOther kind component and thermoplastic compounds in other common material, as one or more polypropylene, polyamide, poly-Ester, polyphenylene sulfide, polyether-ketone, Merlon, polyether sulfone, polyphenylene ether and modified material thereof, thermoplastic resin is as polyetherimideAmine, thermosetting resin is as phenolic resins, epoxy resin, polyimide resin and cyanide resin.
Liquid crystal polyester according to the present invention is through for example extrusion molding of melt molding forming method well known in the art, injectionMoulding, compressing and blow molding all can be processed into liquid-crystalline polyester composition.
Wherein, the liquid-crystalline polyester composition obtaining by extruding-out process, concrete steps are as follows: according to proportioning by liquid crystalPolyester, filler, 4-hydroxyacetophenone and/or various additive add twin-screw extrusion after mixing with high-speed mixerMachine, melting mixing under the screw speed of 280RPM-320RPM, barrel temperature is 290 DEG C-355 DEG C, extrudes, cooling, pelletizing,Obtain liquid-crystalline polyester composition.
The present invention compared with prior art, has following beneficial effect:
The present invention is by selecting the content that adds 4-hydroxyacetophenone in liquid-crystalline polyester composition formula based on liquid crystal polyester groupWhen the gross weight of compound is 0.1ppm-500ppm, the high-temperature heat-resistance stability of the liquid-crystalline polyester composition obtaining obtains expecting notThe remarkable improvement of arriving, mobility is also improved.
Brief description of the drawings
Fig. 1 is for using wide 5mm, thick 1mm helical form mould, by the products formed schematic diagram of liquid crystal polyester filling molding.
Detailed description of the invention
Further illustrate the present invention below by detailed description of the invention, following examples are the preferably side of enforcement of the present inventionFormula, but embodiments of the present invention are not subject to the restriction of following embodiment.
The method of testing of the weight content of described 4-hydroxyacetophenone: get 500mg liquid-crystalline polyester composition sample and addIn 25ml volumetric flask, adding 2.5ml concentration is the NaOH/CH of 5mol/L3OH mixed solution, and add the 10ml dimethyl Asia that dewatersSulfone; At the temperature of 60 DEG C, keep nitrogen atmosphere, more than volumetric flask is shaken to 24h, treat the liquid crystalline resin hydrolysis in sampleCompletely, the aromatic monomer salt that the hydrolysis that is dissolved in water forms, and with in hydrochloric acid and excessive alkali, freeze drying gained sample, is somebody's turn to doSample is the mixture of inorganic filler in liquid crystal polyester complete hydrolysis thing and composition; Sample after hydrolysis is dissolved in acetone,Adopt Agilent company of the U.S. 1260 type high performance liquid chromatographs, the 4-hydroxyacetophenone in test sample; And adopt external standard method4-hydroxyacetophenone in hydrolyzation sample is carried out quantitatively.
The method of testing of the melt viscosity of described liquid-crystalline polyester composition: adopt DyniscoLCR7000 type capillary flowBecome instrument liquid-crystalline polyester composition is tested, probe temperature is liquid-crystalline polyester composition fusing point+20 DEG C, and shear rate is 1000Second-1, using internal diameter 1mm, the mouth mould of length 40mm is measured.
The method of testing of the fusing point of described liquid-crystalline polyester composition: sweep by the differential of the DSC200F3 of NETZSCH company typeRetouch calorimeter (DSC), in the Elevated Temperature Conditions test starting from room temperature with 20 DEG C/min, observe endotherm peak temperature Tm1After, thanTm1At the temperature of high 20 DEG C, keep 5 minutes, then under the cooling conditions of 20 DEG C/min, be cooled to room temperature, and then with 20DEG C/min Elevated Temperature Conditions measure, the endotherm peak temperature T now observingm2For the fusing point of liquid-crystalline polyester composition.
The method of testing of the specific volume logarithm viscosity of described liquid-crystalline polyester composition: liquid-crystalline polyester composition is dissolved in to five fluorineIn phenol, make the solution that concentration is 0.01g/mL, probe temperature is 60 DEG C, adopts the Ubbelohde viscometer that internal diameter is 0.7mmMeasure; And by formula: specific volume logarithm viscosity=[ln (η r)]/C calculates, and wherein η r is relative viscosity (t solution/t solvent), CFor solution concentration.
The method of testing of the mobility of described liquid-crystalline polyester composition: liquid-crystalline polyester composition is dried to 4 hours at 120 DEG CAfter, adding injection (mo(u)lding) machine, barrel temperature is set as higher 20 DEG C than the fusing point of liquid-crystalline polyester composition, and mold temperature is made as 120DEG C, under the injection rate of 3MPa injection pressure and 50mm/s, use wide 5mm, thick 1mm helical form mould, liquid crystal is poly-Ester composition filling molding, as shown in Figure 1; The length of measuring products formed, is melt flows length, and length of flow is longer to be saidThe mobility of bright liquid-crystalline polyester composition is more excellent.
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 CBe dried after 4 hours, add HAAKEPolylabOS type banburying instrument to carry out banburying, banburying temperature is more molten than liquid-crystalline polyester compositionPoint is high 20 DEG C, and the rotating speed of rotor is 50rpm, and the banburying time is 1 hour; After banburying completes, by the liquid-crystalline polyester composition of meltingIn banbury, take out, and cool to room temperature; Same sample all samples and carries out melt viscosity and specific volume before banburying with after banburyingThe test of logarithm viscosity, and carry out comparative analysis; Because banburying is to carry out on liquid-crystalline polyester composition melt temperature, nowTo there is pyrolysis to occur; And the rotation of banburying instrument rotor has shear action to the strand of polymer melt, conventionally can accompanyWith the reduction of molecular weight. Therefore the relatively variation of banburying front and back melt viscosity and specific volume logarithm viscosity, can reflect more intuitivelyLiquid-crystalline polyester composition high-temperature heat-resistance stability at high temperature, reduced viscosity value is less, represents that high-temperature heat-resistance stability is better.
The title of the monomer that repetitive that the liquid crystal polyester using in the present invention contains is corresponding and abbreviation are as follows respectively:
P-hydroxybenzoic acid (HBA);
4,4 '-dihydroxybiphenyl (BP);
Terephthalic acid (TPA) (TA);
M-phthalic acid (IA);
2-hydroxyl-6-naphthoic acid (HNA);
Hydroquinones (HQ);
NDA (NDA);
The 4-hydroxyacetophenone using in the present invention: Aladdin reagent (Shanghai) Co., Ltd.;
The mica using in the present invention: the trade mark: Y150422, Chuzhou Grea Minerals Co., Ltd..
Embodiment A 1-A4: the preparation of liquid crystal polyester
In the reactor that is equipped with agitator, thermometer, nitrogen ingress pipe and reflux condensate device, add respectively according to proportioningDerived from the repetitive of aromatic hydroxy-carboxylic,, derived from the repetitive of aromatic diol with derived from aromatic series dicarboxylThe repetitive of acid, and to add a certain proportion of acetic anhydride be acylating agent; Then nitrogen is passed in reactor and replaced; OpenMoving stirring is heated to 140 DEG C-160 DEG C by reactant mixture by room temperature in nitrogen stream, at this temperature, reflux 1 hour-3 littleTime; After this 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, in this processIn steam unreacted acetic anhydride and side reaction product acetic acid; Whole polycondensation phase, reduces pressure to reaction system, and by observingMoment of torsion raises as the endpoint of reaction end; Now the prepolymer of melt state is discharged through drain hole, and be cooled to chamberTemperature; Further prepolymer is transferred to solid phase device, through 5 hours-7 hours, temperature is increased to 260 DEG C-280 by room temperatureDEG C, at this temperature, be incubated 9 hours and within-11 hours, carry out solid-phase polymerization; After reaction finishes, product is derived, thereby obtain liquidBrilliant polyester.
The concrete proportioning of table 1 embodiment A 1-A4 and test performance result thereof
Embodiment 1-12 and comparative example 1-6: the preparation of liquid-crystalline polyester composition
To prepare gained liquid crystal polyester, filler, 4-hydroxyacetophenone and/or various adding by embodiment A 1-A4 by the proportioning of table 2After adding agent high-speed mixer and mixing, add double screw extruder, under the screw speed of 280RPM-320RPM, melting is mixedClose, barrel temperature is 290 DEG C-355 DEG C, extrudes, and cooling, pelletizing, obtains liquid-crystalline polyester composition. Gained liquid-crystalline polyester compositionFusing point, length of flow, melt viscosity and specific volume logarithm viscosity list in table 2.
Table 2
Continued 2
From the embodiment 1-12 of table 2 and relatively can finding out of comparative example 1-6, the present invention is by selecting at liquid-crystalline polyester compositionWhen the gross weight of the content that adds 4-hydroxyacetophenone in formula based on liquid-crystalline polyester composition is 0.1ppm-500ppm, obtainThe high-temperature heat-resistance stability of liquid-crystalline polyester composition obtain beyond thought remarkable improvement, mobility is also improved.
Claims (11)
1. a liquid-crystalline polyester composition, is characterized in that, based on the gross weight of liquid-crystalline polyester composition, 4-hydroxyacetophenoneWeight content is 0.1ppm-500ppm.
2. liquid-crystalline polyester composition according to claim 1, is characterized in that, the survey of the weight content of 4-hydroxyacetophenoneMethod for testing: get 500mg liquid-crystalline polyester composition sample and add in 25ml volumetric flask, adding 2.5ml concentration is the NaOH/ of 5mol/LCH3OH mixed solution, and add the 10ml dimethyl sulfoxide (DMSO) that dewaters; At the temperature of 60 DEG C, keep nitrogen atmosphere, volumetric flask is enteredMore than row concussion 24h, after the liquid crystalline resin hydrolysis completely in sample, the aromatic monomer salt that the hydrolysis that is dissolved in water forms, and useIn hydrochloric acid and excessive alkali, freeze drying gained sample, this sample is inorganic filling out in liquid crystal polyester complete hydrolysis thing and compositionThe mixture of material; Sample after hydrolysis is dissolved in acetone, adopts Agilent company of the U.S. 1260 type high performance liquid chromatographs, survey4-hydroxyacetophenone in test agent; And adopt external standard method to carry out quantitatively the 4-hydroxyacetophenone in hydrolyzation sample.
3. liquid-crystalline polyester composition according to claim 1, is characterized in that, based on the gross weight of liquid-crystalline polyester compositionAmount, the weight content of 4-hydroxyacetophenone is preferably 0.5ppm-300ppm, more preferably 1ppm-100ppm.
4. according to the liquid-crystalline polyester composition described in claim 1-3 any one, it is characterized in that described liquid crystal polyester combinationThing, by weight, comprises following component:
100 parts of liquid crystal polyesters;
5 parts-100 parts of fillers.
5. liquid-crystalline polyester composition according to claim 4, is characterized in that, the fusing point of described liquid-crystalline polyester composition is150 DEG C-400 DEG C; The method of testing of described fusing point is: by the DSC200F3 of NETZSCH company type differential scanning calorimeterDSC, in the Elevated Temperature Conditions test starting from room temperature with 20 DEG C/min, observes endotherm peak temperature Tm1After, than Tm1High 20 DEG CTemperature under keep 5 minutes, then under the cooling conditions of 20 DEG C/min, be cooled to room temperature, and then with 20 DEG C/minElevated Temperature Conditions is measured, the endotherm peak temperature T now observingm2Be the fusing point of liquid-crystalline polyester composition.
6. liquid-crystalline polyester composition according to claim 4, is characterized in that, described liquid crystal polyester, by mole%Meter, comprises following repetitive:
Derived from the repetitive 30mol%-100mol% of aromatic hydroxy-carboxylic;
Derived from the repetitive 0mol%-35mol% of aromatic diol;
Derived from the repetitive 0mol%-35mol% of aromatic dicarboxylic acid.
7. liquid-crystalline polyester composition according to claim 6, is characterized in that, described liquid crystal polyester, by mole%Meter, comprises following repetitive:
Derived from the repetitive 50mol%-100mol% of aromatic hydroxy-carboxylic;
Derived from the repetitive 0mol%-25mol% of aromatic diol;
Derived from the repetitive 0mol%-25mol% of aromatic dicarboxylic acid.
8. according to the liquid-crystalline polyester composition described in claim 6 or 7, it is characterized in that, described derived from aromatic hydroxyl carboxylicThe repetitive of acid is selected from derived from the repetitive of 4-HBA and/or the repetitive of 2-hydroxyl-6-naphthoic acid; InstituteState the repetitive and/or 4 that is selected from hydroquinones derived from the repetitive of aromatic diol, the repetition of 4 '-dihydroxybiphenylUnit; The described repetitive derived from aromatic dicarboxylic acid is selected from the repetitive of terephthalic acid (TPA), the weight of M-phthalic acidIn the repetitive of multiple unit, NDA one or more.
9. liquid-crystalline polyester composition according to claim 4, is characterized in that, described filler is selected from tabular filler;Described tabular filler is selected from one or more in talcum, mica, graphite, kaolin; Be preferably mica.
10. liquid-crystalline polyester composition according to claim 9, is characterized in that, the average grain diameter of described mica is 0.5 micro--200 microns, rice.
11. liquid-crystalline polyester compositions according to claim 4, is characterized in that, also comprise various additives; Described variousAdditive is selected from one or more in filler, plasticizer, stabilizing agent, colouring agent, lubricant, releasing agent, antioxidant.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201511015758.3A CN105585828A (en) | 2015-12-30 | 2015-12-30 | LCP (liquid crystal polyester) composition |
| PCT/CN2016/109984 WO2017114161A1 (en) | 2015-12-30 | 2016-12-14 | Liquid crystal polyester composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201511015758.3A CN105585828A (en) | 2015-12-30 | 2015-12-30 | LCP (liquid crystal polyester) composition |
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| Publication Number | Publication Date |
|---|---|
| CN105585828A true CN105585828A (en) | 2016-05-18 |
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| CN201511015758.3A Pending CN105585828A (en) | 2015-12-30 | 2015-12-30 | LCP (liquid crystal polyester) composition |
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| Country | Link |
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| CN (1) | CN105585828A (en) |
| WO (1) | WO2017114161A1 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017114162A1 (en) * | 2015-12-30 | 2017-07-06 | 金发科技股份有限公司 | Liquid crystal polyester composition |
| WO2017114161A1 (en) * | 2015-12-30 | 2017-07-06 | 金发科技股份有限公司 | Liquid crystal polyester composition |
| WO2022099978A1 (en) * | 2020-11-16 | 2022-05-19 | 金发科技股份有限公司 | Liquid crystal polymer resin, preparation method therefor and application thereof |
| US11917753B2 (en) | 2019-09-23 | 2024-02-27 | Ticona Llc | Circuit board for use at 5G frequencies |
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| CN105504247A (en) * | 2015-12-30 | 2016-04-20 | 金发科技股份有限公司 | Liquid crystal polyester and liquid crystal polyester composition composed by liquid crystal polyester |
| CN105542136A (en) * | 2015-12-30 | 2016-05-04 | 金发科技股份有限公司 | Liquid crystal polyester and liquid crystal polyester composition consisting of same |
| CN105566868A (en) * | 2015-12-30 | 2016-05-11 | 金发科技股份有限公司 | Liquid crystal polyester composition |
| CN105585828A (en) * | 2015-12-30 | 2016-05-18 | 金发科技股份有限公司 | LCP (liquid crystal polyester) composition |
| CN105504714A (en) * | 2015-12-30 | 2016-04-20 | 金发科技股份有限公司 | Liquid crystal polyester composition |
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| CN103665354A (en) * | 2012-09-06 | 2014-03-26 | 金发科技股份有限公司 | Liquid crystal polyester, preparation method and composition thereof as well as application of composition thereof |
| CN104725619A (en) * | 2013-12-19 | 2015-06-24 | 金发科技股份有限公司 | Liquid crystal polyester, liquid crystal polyester composition composed of liquid crystal polyester, and applications of liquid crystal polyester composition |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017114162A1 (en) * | 2015-12-30 | 2017-07-06 | 金发科技股份有限公司 | Liquid crystal polyester composition |
| WO2017114161A1 (en) * | 2015-12-30 | 2017-07-06 | 金发科技股份有限公司 | Liquid crystal polyester composition |
| US11917753B2 (en) | 2019-09-23 | 2024-02-27 | Ticona Llc | Circuit board for use at 5G frequencies |
| WO2022099978A1 (en) * | 2020-11-16 | 2022-05-19 | 金发科技股份有限公司 | Liquid crystal polymer resin, preparation method therefor and application thereof |
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| WO2017114161A1 (en) | 2017-07-06 |
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