CN105504714A - Liquid crystal polyester composition - Google Patents
Liquid crystal polyester composition Download PDFInfo
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- CN105504714A CN105504714A CN201511015738.6A CN201511015738A CN105504714A CN 105504714 A CN105504714 A CN 105504714A CN 201511015738 A CN201511015738 A CN 201511015738A CN 105504714 A CN105504714 A CN 105504714A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/14—Glass
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
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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
- 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
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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Abstract
The invention discloses a liquid crystal polyester composition. Based on the total weight of the liquid crystal polyester composition, the weight content of 4-hydroxyacetophenone is 0.1ppm to 500ppm, and the weight of benzoic acid compound with a structural formula defined as formula I is 0.1ppm to 500ppm; in formula I of the description, R represents hydrogen atom or methyl. According to the liquid crystal polyester composition disclosed by the invention, when the content of the 4-hydroxyacetophenone added in the liquid crystal polyester composition formula is 0.1ppm to 500ppm based on the total weight of the liquid crystal polyester composition, and the content of the benzoic acid compound added in the liquid crystal polyester composition and defined as structural formula I is 0.1ppm to 500ppm based on the total weight of the liquid crystal polyester composition, the high temperature resistant stability of the obtained liquid crystal polyester composition is remarkably improved beyond thought, and the liquidity of the liquid crystal polyester composition 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) 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 liquid crystal polyester still also exists and at high temperature adds thermolysis in man-hour or because by external force hot shearing and molecular chain chain rupture, 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 composition comprises the basic metal of 15 ~ 3000ppm or the magnesium of 50 ~ 3000ppm or calcium; Liquid crystalline polymers contains P-hydroxybenzoic acid, Resorcinol, '-biphenyl diphenol, terephthalic acid, NDA and biphenyl dicarboxylic acid repeating unit.The introducing of metallics improves fusing point and the heat-drawn wire of composition, and thermotolerance is improved.But mention in patent and liquid crystalline polymers and functional compound are at high temperature contacted and long enough its melt viscosity that makes declines at least 10%.Professional and technical personnel in the field are known, liquid crystalline resin processes for a long time under higher than its melt temperature, because thermolysis can cause the reduction of melt viscosity and molecular weight, and the decline also having mechanical property brought thus, and the generation of side reaction, this may increase the risk that resin bubbles.
CN1408816 discloses a kind of thermostability to be improved and the liquid crystal polyester resin compositions not producing bubble in welding process, and it realizes by adding 0.01-0.2 weight part bi-ester of phosphite in 100 weight part liquid crystal polyesters.But whether this patent its mobility not mentioned are improved.
And for example CN101967270 discloses a kind of liquid crystal polyester resin mixture, comprises 100 weight part one liquid crystal polyesters, a lipid acid ammonium of 10 to 150 weight part weighting materials and 0.001 to 5 weight part.This patent finds that this liquid-crystalline polyester composition has stable fusion time, and it can be molded in fixing cycling time, thus produces the mouldings with better mechanical characteristics and thermostability.But composition described herein is all through the mould plastics processing of specified time, whether its raising not pointing out thermostability just must reaches special processing process is shaping afterwards.
Up to the present, about adding the benzoic acid compounds that 4-hydroxyacetophenone and structural formula define such as formula I in liquid-crystalline polyester composition simultaneously, report is had no on the mobility of described liquid-crystalline polyester composition, the impact of high-temperature heat-resistance stability.
The present inventor surprisingly finds through great many of experiments, the content that adds 4-hydroxyacetophenone in liquid-crystalline polyester composition formula is selected to be 0.1ppm-500ppm based on the gross weight of liquid-crystalline polyester composition, when to add the content of benzoic acid compounds that structural formula defines such as formula I be 0.1ppm-500ppm based on the gross weight of liquid-crystalline polyester composition simultaneously, the high-temperature heat-resistance stability of the liquid-crystalline polyester composition obtained obtains beyond thought remarkable improvement, and mobility have also been obtained raising.
Summary of the invention
In order to overcome the shortcoming of prior art with not enough, primary and foremost purpose of the present invention is to provide a kind of high-temperature heat-resistance stability to significantly improve, 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 is 0.1ppm-500ppm; And the weight content of the benzoic acid compounds that structural formula defines such as formula I is 0.1ppm-500ppm;
formula I
Wherein, R represents hydrogen atom or methyl.
Preferably, based on the gross weight of liquid-crystalline polyester composition, the weight content of 4-hydroxyacetophenone is preferably 0.5ppm-300ppm, is more preferably 1ppm-100ppm.
Preferably, based on the gross weight of liquid-crystalline polyester composition, structural formula is preferably 0.5ppm-300ppm such as formula the weight content of the benzoic acid compounds that I defines, and is more preferably 1ppm-100ppm.
Wherein, the testing method of the weight content of the benzoic acid compounds that 4-hydroxyacetophenone and structural formula define such as formula I: get 500mg liquid-crystalline polyester composition sample and add in 25ml volumetric flask, add the NaOH/CH that 2.5ml concentration is 5mol/L
3oH mixing solutions, and add 10ml and to dewater dimethyl sulfoxide (DMSO); Nitrogen atmosphere is kept at the temperature of 60 DEG C, more than concussion 24h is carried out to volumetric flask, after the liquid crystalline resin hydrolysis completely in sample, the aromatic monomer salt that the hydrolysis that is dissolved in water is formed, and with in hydrochloric acid and excessive alkali, lyophilize gained sample, this sample is the mixture of mineral filler in liquid crystal polyester complete hydrolysis thing and composition; Sample after hydrolysis is dissolved in acetone, adopts Agilent company 1260 of U.S. type high performance liquid chromatograph, the content of the benzoic acid compounds that the 4-hydroxyacetophenone in test sample and structural formula define such as formula I; And adopt external standard method to carry out quantitatively the benzoic acid compounds that the 4-hydroxyacetophenone in hydrolyzation sample and structural formula define such as formula I.
And when adding the weight content of 4-hydroxyacetophenone more than 500ppm in liquid-crystalline polyester composition formula, the mechanical properties decrease of liquid-crystalline polyester composition can be made.Similarly, when adding the weight content of the benzoic acid compounds that structural formula defines such as formula I more than 500ppm in liquid-crystalline polyester composition formula, the mechanical properties decrease of liquid-crystalline polyester composition can be made.
Wherein, described liquid-crystalline polyester composition, by weight, comprises following component:
Liquid crystal polyester 100 parts;
Weighting agent 5 parts-100 parts.
Wherein, the fusing point of described liquid-crystalline polyester composition is 150 DEG C-400 DEG C; The testing method of described fusing point is: by NETZSCH company DSC200F3 type differential scanning calorimeter DSC, testing with the Elevated Temperature Conditions of 20 DEG C/min from room temperature, observes endotherm peak temperature T
m1after, than T
m1keep 5 minutes at the temperature of high 20 DEG C, then under the cooling conditions of 20 DEG C/min, be cooled to room temperature, and then measure with the Elevated Temperature Conditions of 20 DEG C/min, the endotherm peak temperature T now observed
m2be the fusing point of liquid-crystalline polyester composition.
Wherein, described liquid crystal polyester, by mole% meter, comprises following repeating unit:
Derived from the repeating unit 30mol%-100mol% of aromatic hydroxy-carboxylic;
Derived from the repeating unit 0mol%-35mol% of aromatic diol;
Derived from the repeating unit 0mol%-35mol% of aromatic dicarboxylic acid.
Preferably, described liquid crystal polyester, by mole% meter, comprises following repeating unit:
Derived from the repeating unit 50mol%-100mol% of aromatic hydroxy-carboxylic;
Derived from the repeating unit 0mol%-25mol% of aromatic diol;
Derived from the repeating unit 0mol%-25mol% of aromatic dicarboxylic acid.
Wherein, the described repeating unit derived from aromatic hydroxy-carboxylic is selected from the repeating unit of repeating unit derived from 4-HBA and/or 2-hydroxyl-6-naphthoic acid; The described repeating unit derived from aromatic diol is selected from the repeating unit and/or 4 of Resorcinol, the repeating unit of 4 '-dihydroxybiphenyl; The described repeating unit derived from aromatic dicarboxylic acid is selected from one or more in the repeating unit of the repeating unit of terephthalic acid, the repeating unit of m-phthalic acid, NDA.
The preparation method of above-mentioned liquid crystal polyester, can adopt 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, add the repeating unit derived from aromatic hydroxy-carboxylic, the repeating unit derived from aromatic diol and the repeating unit derived from aromatic dicarboxylic acid respectively according to proportioning, and to add a certain proportion of acetic anhydride be acylating agent; Then nitrogen is passed in reactor and replace; Start stirring, in nitrogen gas stream, reaction mixture is heated to 140 DEG C-160 DEG C by room temperature, reflux 1 hour-3 hours at this temperature; 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, steams unreacted acetic anhydride and side reaction product acetic acid in the process; Whole polycondensation phase, reduces pressure to reaction system, and raises by observing moment of torsion the endpoint terminated as reaction; Now the prepolymer of melt state is discharged through drain hole, and be cooled to room temperature; Further prepolymer is transferred to solid state polymerization device, 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; After reaction terminates, product is derived, thus obtain liquid crystal polyester.
Wherein, described weighting agent is selected from fibrous filler and/or tabular weighting agent; Described fibrous filler is selected from one or more in glass fibre, fibrous magnesium silicate, silica fiber, silica-alumina fiber, potassium titanate fiber, carbon or graphite fibre, steel fiber; Be preferably glass fibre; Described tabular weighting agent is selected from one or more in talcum, mica, graphite, kaolin; Be preferably mica.
Preferably, the fiber diameter of described glass fibre is 3 microns-30 microns, and average aspect ratio is more than or equal to 5, and average fiber length is 50 microns-1500 microns; The median size of described mica is 0.5 micron-200 microns.
Work as absorb fillers, relative to liquid crystal polyester 100 weight part, add the weighting agent more than more than 100 parts, the physical strength of liquid-crystalline polyester composition may reduce.The method of absorb fillers is not particularly limited, and can be set forth in method as known in the art.
In addition, in addition to the foregoing, known various additive is added in the liquid-crystalline polyester composition that can use in the present invention with the amount not damaging the object of the invention; Various additive can be selected from one or more in filler, softening agent, stablizer, tinting material, lubricant, releasing agent, oxidation inhibitor.
In order to improve physical strength, the inorganic of the form such as particle, thin slice or organic filler can be mixed in liquid-crystalline polyester composition according to the present invention.
The example of granulated filler comprises silicate if Calucium Silicate powder, pure aluminium silicate, clay, diatomite, wollastonite, various metal-powder are as the hollow glass bead of ferric oxide, titanium oxide, zinc oxide, ANTIMONY TRIOXIDE SB 203 99.8 PCT, aluminum oxide and calcium sulfate, carbon black, silicon-dioxide, quartz sand, granulated glass sphere, grinding and glass powder.
The example of flake stuffing comprises glass flake and various tinsel.Other organic fillers comprise the heat-resistant high-strength fiber that such as aromatic polyester, aromatic polyimide, polymeric amide etc. are made.
As required, these fillers can carry out surface treatment with usually known surface treatment agent.
Suitable softening agent is phthalic ester.
Suitable stablizer comprises organophosphite, as triphenyl phosphite, tricresyl phosphite-(2, 6-3,5-dimethylphenyl) ester, tricresyl phosphite-nonyl phenylester, dimethylbenene phosphonate, trimethyl phosphite 99 etc., organophosphite, alkylating monohydric phenol or polyphenol, the alkylation reaction product of polyphenol and diene, the butylation reaction product of p-cresol or Dicyclopentadiene (DCPD), alkylating hydroquinones, hydroxylated thiodiphenvl ethers, alkylidene group-bis-phenol, benzyl compounds, polyol ester class, benzotriazole category, one or more combinations of benzophenone.
Suitable releasing agent comprises metallic stearic salt, allcyl stearate class, stearic acid pentaerythritol esters, paraffin, montanin wax etc.
Suitable tinting material comprises various pigment, dyestuff, as the metal oxide of mineral dye and the zinc oxide of mixed metal oxide, and titanium oxide, ferric oxide, sulfide is as zinc sulphide etc.; Aluminate, silicate, chromic salt, wustite etc., carbon black, ultramarine; Pigment dyestuff as azo, diazonium class, Anthraquinones, phthalocyanine, quinoline, naphthalene, ketone, piperazine class etc.
Proper lubrication agent comprises the metal-salt etc. of higher fatty acid, high-grade fatty ester, higher fatty acid.
Suitable oxidation inhibitor comprises organophosphite, alkylating monohydric phenol or polyphenol, the alkylation reaction product of polyphenol and diene, the butylation reaction product of p-cresol or Dicyclopentadiene (DCPD), alkylating hydroquinones, hydroxylated thiodiphenvl ethers, alkylidene group-bis-phenol, benzyl compounds, polyol ester class etc.
Various additive is not limited to above-mentioned several, can optionally containing to other material common in the thermostability of liquid crystal polyester and harmless other species components of physical properties and thermoplastic compounds, as one or more polypropylene, polymeric amide, polyester, polyphenylene sulfide, polyetherketone, polycarbonate, polyethersulfone, polyphenylene ether and modified material thereof, thermoplastic resin is as polyetherimide, and thermosetting resin is as resol, epoxy resin, polyimide resin and prussiate resin.
Liquid crystal polyester according to the present invention all can be processed into liquid-crystalline polyester composition through melt molding forming method well known in the art such as extrusion moulding, injection molding, compression moulding and blow molding.
Wherein, by the liquid-crystalline polyester composition that extruding-out process obtains, concrete steps are as follows: after benzoic acid compounds liquid crystal polyester, weighting agent, 4-hydroxyacetophenone, structural formula defined such as formula I according to proportioning and/or various additive high-speed mixer mix, add twin screw extruder, 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 0.1ppm-500ppm by selecting the content that adds 4-hydroxyacetophenone in liquid-crystalline polyester composition formula based on the gross weight of liquid-crystalline polyester composition, when to add the content of benzoic acid compounds that structural formula defines such as formula I be 0.1ppm-500ppm based on the gross weight of liquid-crystalline polyester composition simultaneously, the high-temperature heat-resistance stability of the liquid-crystalline polyester composition obtained obtains beyond thought remarkable improvement, and mobility have also been obtained raising.
Accompanying drawing explanation
Fig. 1 is use wide 5mm, thick 1mm spirrillum forming mould, by the products formed schematic diagram of liquid crystal polyester filling molding.
Embodiment
Further illustrate the present invention below by embodiment, following examples are the present invention's preferably embodiment, but embodiments of the present invention are not by the restriction of following embodiment.
The testing method of the weight content of the benzoic acid compounds that described 4-hydroxyacetophenone and structural formula define such as formula I: get 500mg liquid-crystalline polyester composition sample and add in 25ml volumetric flask, add the NaOH/CH that 2.5ml concentration is 5mol/L
3oH mixing solutions, and add 10ml and to dewater dimethyl sulfoxide (DMSO); Nitrogen atmosphere is kept at the temperature of 60 DEG C, more than concussion 24h is carried out to volumetric flask, after the liquid crystalline resin hydrolysis completely in sample, the aromatic monomer salt that the hydrolysis that is dissolved in water is formed, and with in hydrochloric acid and excessive alkali, lyophilize gained sample, this sample is the mixture of mineral filler in liquid crystal polyester complete hydrolysis thing and composition; Sample after hydrolysis is dissolved in acetone, adopts Agilent company 1260 of U.S. type high performance liquid chromatograph, the content of the benzoic acid compounds that the 4-hydroxyacetophenone in test sample and structural formula define such as formula I; And adopt external standard method to carry out quantitatively the benzoic acid compounds that the 4-hydroxyacetophenone in hydrolyzation sample and structural formula define such as formula I.
The testing method of the melt viscosity of described liquid-crystalline polyester composition: adopt DyniscoLCR7000 type capillary rheometer to test liquid-crystalline polyester composition, probe temperature is liquid-crystalline polyester composition fusing point+20 DEG C, and shearing rate is 1000 seconds
-1, use internal diameter 1mm, the mouth mould of length 40mm is measured.
The testing method of the fusing point of described liquid-crystalline polyester composition: by NETZSCH company DSC200F3 type differential scanning calorimeter (DSC), testing with the Elevated Temperature Conditions of 20 DEG C/min from room temperature, observes endotherm peak temperature T
m1after, than T
m1keep 5 minutes at the temperature of high 20 DEG C, then under the cooling conditions of 20 DEG C/min, be cooled to room temperature, and then measure with the Elevated Temperature Conditions of 20 DEG C/min, the endotherm peak temperature T now observed
m2for the fusing point of liquid-crystalline polyester composition.
The testing method of the specific volume log viscosities of described liquid-crystalline polyester composition: be dissolved in by liquid-crystalline polyester composition in Pentafluorophenol, makes the solution that concentration is 0.01g/mL, and probe temperature is 60 DEG C, and employing internal diameter is that the Ubbelohde viscometer of 0.7mm is measured; And by formula: specific volume log viscosities=[ln (η r)]/C calculates, and wherein η r is relative viscosity (t solution/t solvent), and C is strength of solution.
The testing method of the mobility of described liquid-crystalline polyester composition: by liquid-crystalline polyester composition 120 DEG C of dryings after 4 hours, add injection moulding machine, barrel temperature is set as higher than the fusing point of liquid-crystalline polyester composition 20 DEG C, die temperature is set to 120 DEG C, under the injection rate of 3MPa injection pressure and 50mm/s, use wide 5mm, thick 1mm spirrillum forming mould, by liquid-crystalline polyester composition filling molding, as shown in Figure 1; Measure the length of products formed, be melt flow length, length of flow is longer, illustrates that the mobility of liquid-crystalline polyester composition is more excellent.
The testing method of the high-temperature heat-resistance stability of described liquid-crystalline polyester composition: by liquid-crystalline polyester composition 120 DEG C of dryings after 4 hours, add HAAKEPolylabOS type banburying instrument and carry out banburying, banburying temperature is higher than the fusing point of liquid-crystalline polyester composition 20 DEG C, the rotating speed of rotor is 50rpm, and the banburying time is 1 hour; After banburying completes, the liquid-crystalline polyester composition of melting is taken out in Banbury mixer, and cool to room temperature; Same sample all samples the test carrying out melt viscosity and specific volume log viscosities before banburying with after banburying, and carries out comparative analysis; Because banburying carries out on liquid-crystalline polyester composition melt temperature, pyrolysis now will be had to occur; And the molecular chain of rotation to polymer melt of banburying instrument rotor has shearing action, usually can with the reduction of molecular weight.Therefore the change of melt viscosity and specific volume log viscosities before and after banburying is compared, can reflecting liquid crystal polymer blend high-temperature heat-resistance stability at high temperature more intuitively, viscosity drop low value is less, represents high-temperature heat-resistance stability better.
Title and the abbreviation of the monomer that the repeating unit that the liquid crystal polyester used in the present invention contains is corresponding are as follows respectively:
P-hydroxybenzoic acid (HBA);
4,4 '-dihydroxybiphenyl (BP);
Terephthalic acid (TA);
M-phthalic acid (IA);
2-hydroxyl-6-naphthoic acid (HNA);
Resorcinol (HQ);
NDA (NDA);
The 4-hydroxyacetophenone used in the present invention: Aladdin reagent (Shanghai) Co., Ltd.;
The benzoic acid compounds that the structural formula used in the present invention defines such as formula I:
Phenylformic acid: purity 98%, Sigma-Aldrich (Shanghai) trade Co., Ltd;
O-toluic acid: purity 98%, Sigma-Aldrich (Shanghai) trade Co., Ltd;
M-methyl benzoic acid: purity 99%, Sigma-Aldrich (Shanghai) trade Co., Ltd;
P-methylbenzoic acid: purity 98%, Sigma-Aldrich (Shanghai) trade Co., Ltd;
The glass fibre used in the present invention: trade mark ECS309A-3, Chongqing Polycomp International Co., Ltd.
Embodiment A 1-A4: the preparation of liquid crystal polyester
In the reactor being equipped with agitator, thermometer, nitrogen ingress pipe and reflux condensate device, add the repeating unit derived from aromatic hydroxy-carboxylic, the repeating unit derived from aromatic diol and the repeating unit derived from aromatic dicarboxylic acid respectively according to proportioning, and to add a certain proportion of acetic anhydride be acylating agent; Then nitrogen is passed in reactor and replace; Start stirring, in nitrogen gas stream, reaction mixture is heated to 140 DEG C-160 DEG C by room temperature, reflux 1 hour-3 hours at this temperature; 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, steams unreacted acetic anhydride and side reaction product acetic acid in the process; Whole polycondensation phase, reduces pressure to reaction system, and raises by observing moment of torsion the endpoint terminated as reaction; Now the prepolymer of melt state is discharged through drain hole, and be cooled to room temperature; Further prepolymer is transferred to solid state polymerization device, 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; After reaction terminates, product is derived, thus obtain liquid crystal polyester.
The concrete proportioning of table 1 embodiment A 1-A4 and test performance result thereof
Embodiment 1-12 and comparative example 1-8: the preparation of liquid-crystalline polyester composition
To be prepared after benzoic acid compounds that gained liquid crystal polyester, weighting agent, 4-hydroxyacetophenone, structural formula define such as formula I and/or various additive high-speed mixer mix by embodiment A 1-A4 by the proportioning of table 2, add twin screw extruder, melting mixing under the screw speed of 280RPM-320RPM, barrel temperature is 290 DEG C-355 DEG C, extrude, cooling, pelletizing, obtain liquid-crystalline polyester composition.The fusing point of gained liquid-crystalline polyester composition, length of flow, melt viscosity and specific volume log viscosities are listed in table 2.
Table 2
Continued 2
As can be seen from the embodiment 1-12 of table 2 and comparative example 1-8 relatively, the present invention is 0.1ppm-500ppm by selecting the content that adds 4-hydroxyacetophenone in liquid-crystalline polyester composition formula based on the gross weight of liquid-crystalline polyester composition, when to add the content of benzoic acid compounds that structural formula defines such as formula I be 0.1ppm-500ppm based on the gross weight of liquid-crystalline polyester composition simultaneously, the high-temperature heat-resistance stability of the liquid-crystalline polyester composition obtained obtains beyond thought remarkable improvement, and mobility have also been obtained raising.
Claims (11)
1. a liquid-crystalline polyester composition, is characterized in that, based on the gross weight of liquid-crystalline polyester composition, the weight content of 4-hydroxyacetophenone is 0.1ppm-500ppm; And the weight content of the benzoic acid compounds that structural formula defines such as formula I is 0.1ppm-500ppm;
formula I
Wherein, R represents hydrogen atom or methyl.
2. liquid-crystalline polyester composition according to claim 1, it is characterized in that, the testing method of the weight content of the benzoic acid compounds that 4-hydroxyacetophenone and structural formula define such as formula I: get 500mg liquid-crystalline polyester composition sample and add in 25ml volumetric flask, add the NaOH/CH that 2.5ml concentration is 5mol/L
3oH mixing solutions, and add 10ml and to dewater dimethyl sulfoxide (DMSO); Nitrogen atmosphere is kept at the temperature of 60 DEG C, more than concussion 24h is carried out to volumetric flask, after the liquid crystalline resin hydrolysis completely in sample, the aromatic monomer salt that the hydrolysis that is dissolved in water is formed, and with in hydrochloric acid and excessive alkali, lyophilize gained sample, this sample is the mixture of mineral filler in liquid crystal polyester complete hydrolysis thing and composition; Sample after hydrolysis is dissolved in acetone, adopts Agilent company 1260 of U.S. type high performance liquid chromatograph, the content of the benzoic acid compounds that the 4-hydroxyacetophenone in test sample and structural formula define such as formula I; And adopt external standard method to carry out quantitatively the benzoic acid compounds that the 4-hydroxyacetophenone in hydrolyzation sample and structural formula define such as formula I.
3. liquid-crystalline polyester composition according to claim 1, is characterized in that, based on the gross weight of liquid-crystalline polyester composition, the weight content of 4-hydroxyacetophenone is preferably 0.5ppm-300ppm, is more preferably 1ppm-100ppm; Based on the gross weight of liquid-crystalline polyester composition, structural formula is preferably 0.5ppm-300ppm such as formula the weight content of the benzoic acid compounds that I defines, and is more preferably 1ppm-100ppm.
4. the liquid-crystalline polyester composition according to any one of claim 1-3, is characterized in that, described liquid-crystalline polyester composition, by weight, comprises following component:
Liquid crystal polyester 100 parts;
Weighting agent 5 parts-100 parts.
5. liquid-crystalline polyester composition according to claim 4, is characterized in that, the fusing point of described liquid-crystalline polyester composition is 150 DEG C-400 DEG C; The testing method of described fusing point is: by NETZSCH company DSC200F3 type differential scanning calorimeter DSC, testing with the Elevated Temperature Conditions of 20 DEG C/min from room temperature, observes endotherm peak temperature T
m1after, than T
m1keep 5 minutes at the temperature of high 20 DEG C, then under the cooling conditions of 20 DEG C/min, be cooled to room temperature, and then measure with the Elevated Temperature Conditions of 20 DEG C/min, the endotherm peak temperature T now observed
m2be 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 repeating unit:
Derived from the repeating unit 30mol%-100mol% of aromatic hydroxy-carboxylic;
Derived from the repeating unit 0mol%-35mol% of aromatic diol;
Derived from the repeating unit 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 repeating unit:
Derived from the repeating unit 50mol%-100mol% of aromatic hydroxy-carboxylic;
Derived from the repeating unit 0mol%-25mol% of aromatic diol;
Derived from the repeating unit 0mol%-25mol% of aromatic dicarboxylic acid.
8. the liquid-crystalline polyester composition according to claim 6 or 7, is characterized in that, the described repeating unit derived from aromatic hydroxy-carboxylic is selected from the repeating unit of repeating unit derived from 4-HBA and/or 2-hydroxyl-6-naphthoic acid; The described repeating unit derived from aromatic diol is selected from the repeating unit and/or 4 of Resorcinol, the repeating unit of 4 '-dihydroxybiphenyl; The described repeating unit derived from aromatic dicarboxylic acid is selected from one or more in the repeating unit of the repeating unit of terephthalic acid, the repeating unit of m-phthalic acid, NDA.
9. liquid-crystalline polyester composition according to claim 4, is characterized in that, described weighting agent is selected from fibrous filler and/or tabular weighting agent; Described fibrous filler is selected from one or more in glass fibre, fibrous magnesium silicate, silica fiber, silica-alumina fiber, potassium titanate fiber, carbon or graphite fibre, steel fiber; Be preferably glass fibre; Described tabular weighting agent 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 fiber diameter of described glass fibre is 3 microns-30 microns, and average aspect ratio is more than or equal to 5, and average fiber length is 50 microns-1500 microns; The median size of described mica is 0.5 micron-200 microns.
11. liquid-crystalline polyester compositions according to claim 4, is characterized in that, also comprise various additive; Described various additive is selected from one or more in filler, softening agent, stablizer, tinting material, lubricant, releasing agent, oxidation inhibitor.
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| WO2017114161A1 (en) * | 2015-12-30 | 2017-07-06 | 金发科技股份有限公司 | Liquid crystal polyester composition |
| CN112409582A (en) * | 2020-11-16 | 2021-02-26 | 金发科技股份有限公司 | Liquid crystal polymer resin and preparation method and application thereof |
| CN114805769A (en) * | 2022-02-28 | 2022-07-29 | 珠海万通特种工程塑料有限公司 | Liquid crystal polyester, liquid crystal polyester composite material and application |
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