CN105801824A - Liquid crystal polyester composition - Google Patents
Liquid crystal polyester composition Download PDFInfo
- Publication number
- CN105801824A CN105801824A CN201610226653.0A CN201610226653A CN105801824A CN 105801824 A CN105801824 A CN 105801824A CN 201610226653 A CN201610226653 A CN 201610226653A CN 105801824 A CN105801824 A CN 105801824A
- Authority
- CN
- China
- Prior art keywords
- liquid
- polyester composition
- crystalline polyester
- repetitive
- weight content
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
-
- 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
- C08K3/38—Boron-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/098—Metal salts of carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/14—Glass
-
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2293—Oxides; Hydroxides of metals of nickel
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
- C08K2003/3009—Sulfides
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention discloses liquid crystal polyester composition. The weight content of metal nickel elements is 0.1 ppm-300 ppm in terms of the total weight of the liquid crystal polyester composition. A method for testing the weight content of the metal nickel elements comprises steps as follows: the liquid crystal polyester composition is dried at the temperature of 120 DEG C for 4 hours, 1 g of a to-be-treated sample is taken and mixed with nitric acid and hydrogen peroxide, the mixture is heated for 2 hours, and meanwhile, nitric acid and hydrogen peroxide are added constantly; after the sample is dissolved, the dissolved sample is taken, and the weight content of the metal nickel elements in the sample is analyzed with a full-automatic inductive coupled plasma atomic emission spectrometer in the model of 720ES in the Agilent company. When the weight content of the metal nickel elements added in the formula of the liquid crystal polyester composition reaches 0.1 ppm-300 ppm in terms of the total weight of the liquid crystal polyester composition, the melting point of the liquid crystal polyester composition is high, and the high-temperature heat-resistant stability is unexpectedly remarkably improved.
Description
Technical field
The present invention relates to polymeric material field, particularly to a kind of liquid-crystalline polyester composition.
Background technology
Liquid crystal polyester (LCP) 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 nickel element in liquid-crystalline polyester composition, the impact of described liquid-crystalline polyester composition 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 nickel element in liquid-crystalline polyester composition formula when being 0.1ppm-300ppm, the fusing point of the liquid-crystalline polyester composition obtained improves, 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 the liquid-crystalline polyester composition providing a kind of high-temperature heat-resistance stability to significantly improve.
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 nickel element is 0.1ppm-300ppm.
Being preferably based on the gross weight of liquid-crystalline polyester composition, the weight content of metallic nickel element is preferably 0.5ppm-100ppm, more preferably 1ppm-50ppm.
Wherein, the method for testing of the weight content of metallic nickel element: liquid-crystalline polyester composition is dried 4 hours at 120 DEG C, 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 nickel element.
Document is not yet had to be reported in liquid-crystalline polyester composition the introducing metallic nickel element impact on composition properties at present, present inventors have unexpectedly found that in liquid-crystalline polyester composition, introduce appropriate nickel element, the fusing point of liquid-crystalline polyester composition improves, and shows the heat-resistant stability of excellence in high temperature environments.And when in liquid-crystalline polyester composition, the weight content of metallic nickel 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 nickel compound containing realized of metallic nickel element，Nickel compound containing can be selected from nickel acetate (II) tetrahydrate、Nickel oxide (II)、Nickel nitrate (II) hexahydrate、Nickel sulfide、Nickel sulfate (II)、Nickel sulfate (II) ammonium hexahydrate、Nickel oxalate (II) dihydrate、Hexafluoro nickel (IV) acid potassium、Nickel difluoride (II)、Nickel hydroxide (II)、Nickel dichloride. (II)、Nickelous bromide (II)、Nickel borides、Basic nickel carbonate hydrate、Nickel phosphide、Nickel peroxide、The inorganic compound such as nickelous perchlorate (II) hexahydrate，Nickel octoate hydrate can also be selected from、2 ethyl hexanoic acid nickel、Nickel acetylacetonate、Etioporphyrin (ETIO) nickel、Double (cyclopentadiene) nickel (II)、Nickel Phthalocyanine、[1,Double (diphenylphosphine) propane of 3-] Nickel Chloride (II)、5,10,15,20-tetraphenyl-21H,23H-porphin nickel (II)、Glycol dimethyl ether nickelous bromide、Dichloro two (tributylphosphine) nickel (II)、Dichloro two (trimethyl-phosphine) nickel (II)、Double (1,5-cyclo-octadiene) nickel (O)、Double (tributylphosphine) Nickel Bromide、Double (tricyclohexyl phosphine) Nickel Chloride (II)、Double (triphenylphosphine) Nickel Bromide、Double (ethyl cyclopentadiene) nickel (II)、Four (triphenyl phosphite) nickel、The organic compound such as cyclohexane butyric acid nickel.The source of the metallic nickel element pointed by the present invention is not limited only to the example above, no matter uses the nickel compound containing of which kind of form, and atomic emission spectrometry can be used to detect.The weight content of metallic nickel element is by metallic nickel element itself rather than on the basis of the nickel compound containing adding metallic nickel element.The weight content of the metallic nickel 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 manganese metal element, gross weight based on liquid-crystalline polyester composition, and the weight content of manganese metal element is 0.1ppm-300ppm, preferably 1ppm-100ppm.
Wherein, the method for testing of the weight content of manganese metal element: liquid-crystalline polyester composition is dried 4 hours at 120 DEG C, 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 manganese element.
nullIntroducing of manganese metal element contains what manganese compound realized typically by adding，Manganese oxide (II) can be selected from containing manganese compound、Manganese oxide (III)、Manganese oxide (IV)、Manganese acetate (II)、Manganese nitrate、Manganese monosulfide.、Manganese sulfate、Manganese carbonate、Manganese acetate、Potassium permanganate、High manganese lithium、Sodium permanganate、Magnesium permanganate、Mangano-manganic oxide、Manganous fluoride、Protochloride manganese、Manganese iodide、Manganese molybdate、Double (trifluoromethanesulfonic acid) manganese inorganic compound，It can also be manganese carbonyl、Manganese acetylacetonate (II)、Manganese acetylacetonate (III)、Pentacarbonyl Manganese dibromide.、Maneb、Six itrile group manganese potassium、Manganese phthalocyanine (II)、2-methyl cyclopentyl-dialkyl-tricarbon manganium、Three (2,2,6,6-tetramethyl-3,5-heptenoic acid) manganese、Three carbonyls cyclopentadiene manganese (I)、Double (pentamethylcyclopentadiene) manganese (II)、Double (tetramethyl-ring pentadiene) manganese (II)、Double (isopropylcyclopentadiene) manganese、Cyclohexyl butyric acid manganese、The organic compound such as hydroxyisopropyl cyclopentadienyl tricarbonyl manganese.The source of the manganese metal element pointed by the present invention is not limited only to the example above, no matter use which kind of form containing manganese compound, atomic emission spectrometry can be used to detect.The weight content of manganese metal element be by manganese metal element itself rather than by add manganese metal element containing manganese compound on the basis of.The weight content of the manganese metal element represented by ppm is to calculate on the basis of the gross weight of liquid-crystalline polyester composition.
The liquid-crystalline polyester composition of the present invention can also include metallic copper element, gross weight based on liquid-crystalline polyester composition, and the weight content of metallic copper element is 0.1ppm-300ppm, preferably 1ppm-100ppm.
Wherein, the method for testing of the weight content of metallic copper element: liquid-crystalline polyester composition is dried 4 hours at 120 DEG C, 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 copper.
nullIntroducing typically by adding what copper-containing compound realized of metallic copper element，Copper-containing compound can be selected from copper acetate、Copper oxide、Copper sulfide、Copper nitrate (II) hydrate、Cupric tartrate (II)、1-butanethiol copper、Bifluoride copper (II)、Cupric chromate(III).、Copper hydrate (II)、Red copper oxide、Cu-lyt.、Copper chloride (II)、Cuprous sulfide、Copper diiodide (I)、Basic copper carbonate、Copper sulfate、Sulfurous acid copper、The inorganic compound such as Copper pyrophosphate.，It can also be bathocuproine、2,3-naphthalene CuPc、2 ethyl hexanoic acid copper (II)、2-pyrazine carboxylic acid copper (II)、3-cresotic acid copper (I)、Cupric acetylacetonate、Perfluor CuPc、Poly-CuPc、Phenylmercaptan. copper (I)、CuPc (II)、3,5-diisopropyl copper salicylate hydrate、Trifluoroacetylacetone (TFA) copper、Trifluoromethayl sulfonic acid copper (II)、Hexafluorophosphoric acid tetrem cyanogen copper、Double (2,2,6,6-tetramethyl-3,The acid of 5-heptadione) copper、Double (triphenylphosphine) hydroboration copper (I)、Thiophene-2-carboxylic acid is cuprous、The organic compound such as bromine three (triphenylphosphine) copper (I).The source of the metallic copper element pointed by the present invention is not limited only to the example above, no matter uses the copper-containing compound of which kind of form, and atomic emission spectrometry can be used to detect.The weight content of metallic copper element is by metallic copper element itself rather than on the basis of the copper-containing compound adding metallic copper element.The weight content of the metallic copper 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, 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.
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, titanium oxide, ferrum oxide, sulfide such as zinc sulfide etc.；Aluminate, silicate, ferrite etc., white carbon black, ultramarine；Organic pigment such as azo, diazonium class, Anthraquinones, phthalocyanine, quinolines, naphthalene, ketone, piperazine class etc..
Proper lubrication agent includes the slaine etc. of higher fatty acids, high-grade fatty ester, higher fatty acids.
Suitably antioxidant includes organic phosphite, alkylating monohydric phenol or polyhydric phenols, polyhydric phenols and 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 according to proportioning by liquid crystal polyester, filler, nickel compound containing and/or containing manganese compound and/or copper-containing compound and/or various additive high-speed mixer mix homogeneously after, 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.
nullNickel compound containing can be selected from nickel acetate (II) tetrahydrate、Nickel oxide (II)、Nickel nitrate (II) hexahydrate、Nickel sulfide、Nickel sulfate (II)、Nickel sulfate (II) ammonium hexahydrate、Nickel oxalate (II) dihydrate、Hexafluoro nickel (IV) acid potassium、Nickel difluoride (II)、Nickel hydroxide (II)、Nickel dichloride. (II)、Nickelous bromide (II)、Nickel borides、Basic nickel carbonate hydrate、Nickel phosphide、Nickel peroxide、The inorganic compound such as nickelous perchlorate (II) hexahydrate，Nickel octoate hydrate can also be selected from、2 ethyl hexanoic acid nickel、Nickel acetylacetonate、Etioporphyrin (ETIO) nickel、Double (cyclopentadiene) nickel (II)、Nickel Phthalocyanine、[1,Double (diphenylphosphine) propane of 3-] Nickel Chloride (II)、5,10,15,20-tetraphenyl-21H,23H-porphin nickel (II)、Glycol dimethyl ether nickelous bromide、Dichloro two (tributylphosphine) nickel (II)、Dichloro two (trimethyl-phosphine) nickel (II)、Double (1,5-cyclo-octadiene) nickel (O)、Double (tributylphosphine) Nickel Bromide、Double (tricyclohexyl phosphine) Nickel Chloride (II)、Double (triphenylphosphine) Nickel Bromide、Double (ethyl cyclopentadiene) nickel (II)、Four (triphenyl phosphite) nickel、The organic compound such as cyclohexane butyric acid nickel.The source of the metallic nickel element pointed by the present invention is not limited only to the example above, no matter uses the nickel compound containing of which kind of form, and atomic emission spectrometry can be used to detect.The weight content of metallic nickel element is by metallic nickel element itself rather than on the basis of the nickel compound containing adding metallic nickel element.The weight content of the metallic nickel element represented by ppm is to calculate on the basis of the gross weight of liquid-crystalline polyester composition.
nullManganese oxide (II) can be selected from containing manganese compound、Manganese oxide (III)、Manganese oxide (IV)、Manganese acetate (II)、Manganese nitrate、Manganese monosulfide.、Manganese sulfate、Manganese carbonate、Manganese acetate、Potassium permanganate、High manganese lithium、Sodium permanganate、Magnesium permanganate、Mangano-manganic oxide、Manganous fluoride、Protochloride manganese、Manganese iodide、Manganese molybdate、Double (trifluoromethanesulfonic acid) manganese inorganic compound，It can also be manganese carbonyl、Manganese acetylacetonate (II)、Manganese acetylacetonate (III)、Pentacarbonyl Manganese dibromide.、Maneb、Six itrile group manganese potassium、Manganese phthalocyanine (II)、2-methyl cyclopentyl-dialkyl-tricarbon manganium、Three (2,2,6,6-tetramethyl-3,5-heptenoic acid) manganese、Three carbonyls cyclopentadiene manganese (I)、Double (pentamethylcyclopentadiene) manganese (II)、Double (tetramethyl-ring pentadiene) manganese (II)、Double (isopropylcyclopentadiene) manganese、Cyclohexyl butyric acid manganese、The organic compound such as hydroxyisopropyl cyclopentadienyl tricarbonyl manganese.The source of the manganese metal element pointed by the present invention is not limited only to the example above, no matter use which kind of form containing manganese compound, atomic emission spectrometry can be used to detect.The weight content of manganese metal element be by manganese metal element itself rather than by add manganese metal element containing manganese compound on the basis of.The weight content of the manganese metal element represented by ppm is to calculate on the basis of the gross weight of liquid-crystalline polyester composition.
nullCopper-containing compound can be selected from copper acetate、Copper oxide、Copper sulfide、Copper nitrate (II) hydrate、Cupric tartrate (II)、1-butanethiol copper、Bifluoride copper (II)、Cupric chromate(III).、Copper hydrate (II)、Red copper oxide、Cu-lyt.、Copper chloride (II)、Cuprous sulfide、Copper diiodide (I)、Basic copper carbonate、Copper sulfate、Sulfurous acid copper、The inorganic compound such as Copper pyrophosphate.，It can also be bathocuproine、2,3-naphthalene CuPc、2 ethyl hexanoic acid copper (II)、2-pyrazine carboxylic acid copper (II)、3-cresotic acid copper (I)、Cupric acetylacetonate、Perfluor CuPc、Poly-CuPc、Phenylmercaptan. copper (I)、CuPc (II)、3,5-diisopropyl copper salicylate hydrate、Trifluoroacetylacetone (TFA) copper、Trifluoromethayl sulfonic acid copper (II)、Hexafluorophosphoric acid tetrem cyanogen copper、Double (2,2,6,6-tetramethyl-3,The acid of 5-heptadione) copper、Double (triphenylphosphine) hydroboration copper (I)、Thiophene-2-carboxylic acid is cuprous、The organic compound such as bromine three (triphenylphosphine) copper (I).The source of the metallic copper element pointed by the present invention is not limited only to the example above, no matter uses the copper-containing compound of which kind of form, and atomic emission spectrometry can be used to detect.The weight content of metallic copper element is by metallic copper element itself rather than on the basis of the copper-containing compound adding metallic copper element.The weight content of the metallic copper 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 0.1ppm-300ppm by selecting the weight content gross weight based on liquid-crystalline polyester composition adding metallic nickel element in liquid-crystalline polyester composition formula, the fusing point of the liquid-crystalline polyester composition obtained improves, 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 nickel 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 nickel element.
The method of testing of the weight content of described manganese metal 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 manganese element.
The method of testing of the weight content of described metallic copper 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 copper.
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), starting to test with the Elevated Temperature Conditions of 20 DEG C/min from room temperature, observing endotherm peak temperature Tm1After, than Tm1Keep 5 minutes at a temperature of high 20 DEG C, then under the cooling conditions of 20 DEG C/min, be cooled to room temperature, 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 specific volume log viscosities of described liquid-crystalline polyester composition: liquid-crystalline polyester composition is dissolved in Pentafluorophenol, glass fiber filter is fallen, then making the solution that concentration is 0.01 g/mL, test temperature is 60 DEG C, and the Ubbelohde viscometer using internal diameter to be 0.7 mm is measured；And by formula: specific volume log viscosities=[ln (η r)]/C is calculated, and wherein η r is relative viscosity (t solution/t solvent), and C is solution concentration.
The method of testing of the high-temperature heat-resistance stability of described liquid-crystalline polyester composition: liquid-crystalline polyester composition is dried 4 hours at 120 DEG C, add in Dynisco LCR7000 type high pressure capillary rheometer, barrel temperature maintains on liquid-crystalline polyester composition fusing point 10 DEG C, using internal diameter 1mm, the mouth die of length 40mm is measured；After sample adds, set test program, keep constant temperature 5 min, with 1000 seconds-1Constant shear rate measure, obtain the shear viscosity of sample constant temperature 5 min, now can be extruded by some sample, remaining sample continue in barrel constant temperature, when 60min, still with 1000 seconds-1Constant shear rate measure, obtain the shear viscosity of constant temperature 60 min；Due to liquid-crystalline polyester composition sample constant temperature on its melt temperature, pyrolysis now will be had to occur, it will usually with the reduction of molecular weight；Therefore sample shear viscosity and reduction degree of specific volume log viscosities when constant temperature 5 min and constant temperature 60 min are compared, can reflecting liquid crystal polymer blend heat-resistant stability at high temperature more intuitively, melt viscosity and specific volume log viscosities decreasing value are less, represent high-temperature heat-resistance stability preferable.Generally, the filler (such as glass fibre, Talcum etc.) included in compositions there is no impact to the thermostability of liquid-crystalline polyester composition, and at high temperature polymer can occur thermal decomposition to make molecular chain rupture, molecular weight and molecular weight.The mechanism that in liquid-crystalline polyester composition, addition nickel compound containing makes liquid-crystalline polyester composition thermostability improve is not fully understood, it may be possible to metal ion forms complex with macromole, makes structure more stable；Also being likely to be metal ion and strand growth is served catalytic action, at high temperature strand rate of rise is close with molecular chain rupture speed so that macromolecular structure entirety keeps stable.
Title and the abbreviation of the monomer that the repetitive that contains of liquid crystal polyester that uses in the present invention is corresponding are as follows:
4-HBA (HBA)；
4,4 '-dihydroxybiphenyl (BP)；
P-phthalic acid (TA)；
M-phthalic acid (IA)；
2-hydroxyl-6-naphthoic acid (HNA)；
Hydroquinone (HQ)；
2,6-naphthalenedicarboxylic acid (NDA)；
The nickel compound containing used in the present invention:
Nickel oxide (II): Sigma-Aldrich (Shanghai) trade Co., Ltd；
Nickel borides: Sigma-Aldrich (Shanghai) trade Co., Ltd；
2 ethyl hexanoic acid nickel: Sigma-Aldrich (Shanghai) trade Co., Ltd；
Nickel sulfide: Sigma-Aldrich (Shanghai) trade Co., Ltd；
In the present invention use containing manganese compound:
Manganese oxide (IV): Sigma-Aldrich (Shanghai) trade Co., Ltd；
The copper-containing compound used in the present invention:
Copper acetate: Sigma-Aldrich (Shanghai) trade Co., Ltd；
The glass fibre used in the present invention: trade mark CS03JAPX-1, number equal fibre diameter 10 microns, the equal draw ratio 300 of number, number 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.
Table 1The concrete proportioning of embodiment A1-A4 and test performance result thereof
Embodiment
1-17
And comparative example
1-6
: the preparation of liquid-crystalline polyester composition
PressTable 2Proportioning will by embodiment A1-A4 prepare gained liquid crystal polyester, filler, nickel compound containing and/or containing manganese compound and/or copper-containing compound and/or various additive high-speed mixer mix homogeneously after, 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, melt viscosity and specific volume log viscosities are listed inTable 2In.
Wherein, the metallic nickel element in liquid-crystalline polyester composition, manganese metal element, metallic copper constituent content are that actual addition by nickel compound containing, containing manganese compound, copper-containing compound is adjusted and records in the preparation process of liquid-crystalline polyester composition.
Table
2
ContinuousTable 2
ContinuousTable 2
FromTable 2Embodiment 1-17 and comparative example 1-6 relatively can be seen that, when the present invention is 0.1ppm-300ppm by selecting the weight content gross weight based on liquid-crystalline polyester composition adding metallic nickel element in liquid-crystalline polyester composition formula, the fusing point of the liquid-crystalline polyester composition obtained improves, and high-temperature heat-resistance stability obtains beyond thought significantly improving.
Claims (15)
1. a liquid-crystalline polyester composition, it is characterised in that gross weight based on liquid-crystalline polyester composition, the weight content of metallic nickel element is 0.1ppm-300ppm.
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 nickel 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 nickel 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 nickel element is preferably 0.5ppm-100ppm, more preferably 1ppm-50ppm.
Liquid-crystalline polyester composition the most according to claim 1, it is characterised in that also include manganese metal element, gross weight based on liquid-crystalline polyester composition, the weight content of manganese metal element is 0.1ppm-300ppm, preferably 1ppm-100ppm.
Liquid-crystalline polyester composition the most according to claim 4, it is characterised in that the method for testing of the weight content of manganese metal 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 manganese element.
Liquid-crystalline polyester composition the most according to claim 1, it is characterised in that also include metallic copper element, gross weight based on liquid-crystalline polyester composition, the weight content of metallic copper element is 0.1ppm-300ppm, preferably 1ppm-100ppm.
Liquid-crystalline polyester composition the most according to claim 6, it is characterised in that the method for testing of the weight content of metallic copper 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 copper.
8. according to the liquid-crystalline polyester composition described in any one of claim 1-7, 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 8, 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 8, it is characterised in that described liquid crystal polyester, by mole meter, comprises following repetitive:
Repetitive 30mol%-100mol% derived from aromatic hydroxy-carboxylic；
Repetitive 0mol%-35mol% derived from aromatic diol；
Repetitive 0mol%-35mol% derived from aromatic dicarboxylic acid.
11. liquid-crystalline polyester compositions according to claim 10, it is characterised in that described liquid crystal polyester, by mole meter, including following repetitive:
Repetitive 50mol%-100mol% derived from aromatic hydroxy-carboxylic；
Repetitive 0mol%-25mol% derived from aromatic diol；
Repetitive 0mol%-25mol% derived from aromatic dicarboxylic acid.
12. according to the liquid-crystalline polyester composition described in claim 10 or 11, it is characterised in that 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.
13. liquid-crystalline polyester compositions according to claim 8, 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.
14. liquid-crystalline polyester compositions according to claim 13, 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.
15. liquid-crystalline polyester compositions according to claim 8, 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.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610226653.0A CN105801824A (en) | 2016-04-13 | 2016-04-13 | Liquid crystal polyester composition |
| PCT/CN2017/080251 WO2017177921A1 (en) | 2016-04-13 | 2017-04-12 | Liquid crystal polyester composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610226653.0A CN105801824A (en) | 2016-04-13 | 2016-04-13 | Liquid crystal polyester composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN105801824A true CN105801824A (en) | 2016-07-27 |
Family
ID=56459240
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610226653.0A Pending CN105801824A (en) | 2016-04-13 | 2016-04-13 | Liquid crystal polyester composition |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN105801824A (en) |
| WO (1) | WO2017177921A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017177921A1 (en) * | 2016-04-13 | 2017-10-19 | 金发科技股份有限公司 | Liquid crystal polyester composition |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114591602B (en) * | 2022-02-28 | 2023-06-20 | 珠海万通特种工程塑料有限公司 | High dielectric constant liquid crystal polyester composition and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6755991B2 (en) * | 2000-07-28 | 2004-06-29 | Kabushiki Kaisha Ueno Seiyaku Oyo Kenkyujo | Aromatic dicarboxylic acid composition and liquid crystalline polyester resin made from the same |
| CN103540151A (en) * | 2012-07-13 | 2014-01-29 | 金发科技股份有限公司 | Modified resin composition for depositing metal film as well as preparation method and application of modified resin composition |
| CN103717672A (en) * | 2011-12-27 | 2014-04-09 | 东丽株式会社 | Thermoplastic resin composition and molded article thereof |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0710976A (en) * | 1993-06-29 | 1995-01-13 | Mitsubishi Chem Corp | Production of melt-anisotropic copolyester |
| EP2280036B1 (en) * | 2008-05-21 | 2013-11-13 | Toray Industries, Inc. | Method for producing aliphatic polyester resin, and an aliphatic polyester resin composition |
| WO2010014630A2 (en) * | 2008-07-29 | 2010-02-04 | Polyone Corporation | Crystallized thermoplastic polyhydroxyalkanoate compounds |
| CN105801824A (en) * | 2016-04-13 | 2016-07-27 | 金发科技股份有限公司 | Liquid crystal polyester composition |
| CN105860445A (en) * | 2016-04-13 | 2016-08-17 | 金发科技股份有限公司 | Liquid crystal polyester composition |
| CN105885370A (en) * | 2016-04-13 | 2016-08-24 | 金发科技股份有限公司 | Liquid crystal polyester composition |
-
2016
- 2016-04-13 CN CN201610226653.0A patent/CN105801824A/en active Pending
-
2017
- 2017-04-12 WO PCT/CN2017/080251 patent/WO2017177921A1/en active Application Filing
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6755991B2 (en) * | 2000-07-28 | 2004-06-29 | Kabushiki Kaisha Ueno Seiyaku Oyo Kenkyujo | Aromatic dicarboxylic acid composition and liquid crystalline polyester resin made from the same |
| CN103717672A (en) * | 2011-12-27 | 2014-04-09 | 东丽株式会社 | Thermoplastic resin composition and molded article thereof |
| CN103540151A (en) * | 2012-07-13 | 2014-01-29 | 金发科技股份有限公司 | Modified resin composition for depositing metal film as well as preparation method and application of modified resin composition |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017177921A1 (en) * | 2016-04-13 | 2017-10-19 | 金发科技股份有限公司 | Liquid crystal polyester composition |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2017177921A1 (en) | 2017-10-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP6315152B1 (en) | Liquid crystalline polyester resin composition, molded article and method for producing molded article | |
| JP5240420B1 (en) | Thermoplastic resin composition and molded article thereof | |
| KR101305878B1 (en) | Liquid-crystalline polyester resin composition, method for producing same, and molded article made thereof | |
| TWI422627B (en) | Thermoplastic resin composition and article using thereof | |
| TW200914488A (en) | Liquid crystalline polyester composition | |
| KR20140043846A (en) | Polyphenylene sulfide resin composition, method for producing same, and molded product of same | |
| JP2008013702A (en) | Crystalline polyester composition | |
| CN105860445A (en) | Liquid crystal polyester composition | |
| CN105801824A (en) | Liquid crystal polyester composition | |
| CN105801823A (en) | Liquid crystal polyester composition | |
| CN105907058B (en) | A kind of liquid-crystalline polyester composition | |
| JP2015063641A (en) | Liquid crystalline polyester resin composition and molded article comprising the same | |
| CN105733219A (en) | Liquid crystal polyester composition | |
| JPH09291213A (en) | Polyphenylene sulfide resin composition | |
| CN105885370A (en) | Liquid crystal polyester composition | |
| JP6206174B2 (en) | Liquid crystalline polyester resin composition and molded product thereof | |
| JP2003301107A (en) | Resin composition | |
| WO2019093237A1 (en) | Polyphenylene sulfide resin composition, method for producing same, and molded article | |
| CN105860465A (en) | Liquid crystal polyester composition | |
| JP2013227366A (en) | Thermoplastic resin composition and its molding | |
| JP4834940B2 (en) | High dielectric resin composition | |
| CN105838386A (en) | Liquid crystalline polyester composition | |
| CN105885369A (en) | Liquid crystal polyester composition | |
| CN105801822A (en) | Liquid crystal polyester composition | |
| JPH05230371A (en) | Polyphenylene sulfide resin composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20160727 |