CN105542135A - Liquid crystal polyester and liquid crystal polyester composition consisting of same - Google Patents
Liquid crystal polyester and liquid crystal polyester composition consisting of same Download PDFInfo
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- CN105542135A CN105542135A CN201511015760.0A CN201511015760A CN105542135A CN 105542135 A CN105542135 A CN 105542135A CN 201511015760 A CN201511015760 A CN 201511015760A CN 105542135 A CN105542135 A CN 105542135A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/60—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from the reaction of a mixture of hydroxy carboxylic acids, polycarboxylic acids and polyhydroxy compounds
- C08G63/605—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from the reaction of a mixture of hydroxy carboxylic acids, polycarboxylic acids and polyhydroxy compounds the hydroxy and carboxylic groups being bound to aromatic rings
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
- C08G63/065—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids the hydroxy and carboxylic ester groups being bound to aromatic rings
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
- 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 liquid crystal polyester. Based on total weight of the liquid crystal polyester, the weight content of a benzoic acid compound with a structural formula defined by formula I shown in the specification is 0.1-500ppm, wherein in the formula I, R represents hydrogen atom or methyl. The invention also discloses a liquid crystal polyester composition comprising the liquid crystal polyester. When the weight content of the benzoic acid compound with a structural formula defined by formula I added into the liquid crystal polyester formula is 0.1-500ppm based on total weight of the liquid crystal polyester, the high-temperature heatproof stability of the obtained liquid crystal polyester is remarkably improved while the fluidity is also increased; and moreover, the liquid crystal polyester composition consisting of the liquid crystal polyester also has excellent high-temperature heatproof stability and fluidity.
Description
Technical field
The present invention relates to polymeric material field, particularly a kind of liquid crystal polyester and consisting 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.
CN1234749 discloses a kind of liquid-crystal polyester resin, the repeating unit wherein come containing 4 hydroxyisophthalic acid and/or Whitfield's ointment is as copolymer composition, and the alkali metal compound containing 10 ~ 5000ppm, the tint permanence of this resin is excellent and thermotolerance is high, and mechanicalness is good.But this resinoid is owing to the addition of metallic compound, the insulating power of difference must be caused.And this invention mainly stresses the improvement of liquid crystal polyester degree of staining and impact property, in embodiment or patent, other parts do not prove whether resistance toheat changes.
CN1760232 discloses a kind of method preparing liquid crystal polyester, first carries out acylations with acylting agent to principal monomer, then principal monomer is carried out polycondensation, and polycondensation is carried out under the existence of 1 ~ 5000ppm biphosphate metal-salt.The liquid crystal polyester of the method manufacture has the thermotolerance of good tone and raising, but whether this patent the mobility of not mentioned polyester improve.
CN100567363 discloses a kind of method preparing liquid crystal polyester, first utilizes fatty acid anhydride to carry out acidylate to principal monomer, and then carries out transesterify to principal monomer, and described acidylate and transesterify carry out under a kind of existence of glyoxaline compound.Liquid-crystal polyester resin prepared by the method has mechanical property and the tinting strength of improvement, but and not mentioned thermostability and mobility whether improve.
US5397502 discloses the composition that a kind of thermotolerance gets a promotion, and it contains the basic metal of 15 ~ 3000ppm, and after adding alkali metal compound, the heat-drawn wire (HDT) of composition is improved.The liquid-crystal composition that the method obtains contains metal residual material, will certainly affect the dielectric properties of liquid crystalline resin as electronic apparatus type component, reduce its use range.Whether the mobility of the not mentioned composition of this patent improves on the other hand.
Up to the present, about adding the mobility of benzoic acid compounds on described liquid crystal polyester in liquid crystal polyester, the impact of high-temperature heat-resistance stability has no report.
The present inventor surprisingly finds through great many of experiments, when selecting the weight content that adds the benzoic acid compounds that structural formula defines such as formula I in liquid crystal polyester formula to be 0.1ppm-500ppm based on the gross weight of liquid crystal polyester, the high-temperature heat-resistance stability of the liquid crystal polyester obtained obtains beyond thought remarkable improvement, and mobility have also been obtained raising; The liquid-crystalline polyester composition be made up of this liquid crystal polyester equally also has excellent high-temperature heat-resistance stability and mobility.
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 crystal polyester of other side performance.
Another object of the present invention is to provide the liquid-crystalline polyester composition comprising above-mentioned liquid crystal polyester.
The present invention is achieved through the following technical solutions:
The invention provides a kind of liquid-crystal polyester resin, based on the gross weight of liquid crystal polyester, 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, 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, based on the gross weight of liquid crystal polyester, the testing method of the weight content of the benzoic acid compounds that described structural formula defines such as formula I: get 500mg liquid crystal polyester 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); At the temperature of 60 DEG C, keep nitrogen atmosphere, more than concussion 24h is carried out to volumetric flask, after sample hydrolysis completely, 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, obtains the product of liquid crystal polyester complete hydrolysis; Sample after hydrolysis is dissolved in acetone, adopts Agilent company 1260 of U.S. type high performance liquid chromatograph, the benzoic acid compounds that the structural formula in test sample defines such as formula I; And adopt external standard method to carry out quantitatively the benzoic acid compounds that the structural formula in hydrolyzation sample defines such as formula I.
Well known in the art, in the polymerization process of liquid crystal polyester, first need to carry out acidylate to the hydroxyl of aromatic monomer, generate acyloxy, for acylating agent diacetyl oxide, aromatic hydroxy changes acetoxyl group into after by acetic anhydride acylation; Acetoxyl group is unstable, and when temperature of reaction reaches about 200 DEG C, part acetoxyl group can start to decompose generation byproduct ethylene ketone, and temperature is higher, and side reaction Shaoxing opera is strong; Byproduct ethylene ketone has multiple harm, and as coloured product can be made to deepen, thermostability is deteriorated, mechanical properties decrease etc.
Similarly, well known in the art, aromatic dicarboxylic acid class material such as terephthalic acid has the solvability of extreme difference in reaction mixture system, even if temperature of reaction reaches 300 DEG C, it also only has small part to be dissolved in the mixing solutions of reaction system, therefore such monomer usually only just starts to participate in polyreaction at relatively high temperatures, which greatly limits the reactive behavior of itself and other monomer.
And the benzoic acid compounds that structural formula defines such as formula I is as a kind of benzoic acids Monofunctional reagents, be very easily dissolved in reaction system, it easily reacts with acetoxyl group and generates ester bond, thus the generation of ketene in minimizing reaction process.Therefore structural formula is controlled in the zone of reasonableness of 0.1ppm-500ppm such as formula the benzoic acid compounds addition that I defines, the acyloxy of liquid crystal polyester not only effectively can be avoided to decompose in advance and to produce byproduct ethylene ketone, thus significantly improve the high-temperature heat-resistance stablizer of liquid crystal polyester, and the change of end group kind changes the interaction between molecular chain simultaneously, the mobility of liquid crystal polyester is got a promotion.
And when the content adding the benzoic acid compounds that structural formula defines such as formula I in liquid crystal polyester formula is more than 500ppm, because benzoic acid compounds can excessively react with the acetoxyl group in molecular chain, and benzoic acid derivative is Monofunctional reagents, this can cause molecular chain end-blocking, makes the molecular weight and molecular weight of liquid crystal polyester.Therefore, the benzoic acid compounds content controlling proper ratio is very important to the performance impact of liquid crystalline polymers.
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:
The repeating unit derived from aromatic hydroxy-carboxylic, the repeating unit derived from aromatic diol and the repeating unit derived from aromatic dicarboxylic acid is added respectively according to proportioning in the reactor being equipped with agitator, thermometer, nitrogen ingress pipe and reflux condensate device, and to add a certain proportion of acetic anhydride be acylating agent, add the benzoic acid compounds that the structural formula based on liquid crystal polyester gross weight 0.1ppm-500ppm defines such as formula I simultaneously; 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, the fusing point of described liquid crystal polyester is 150 DEG C-400 DEG C, is preferably 260 DEG C-380 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 crystal polyester.
The invention also discloses a kind of liquid-crystalline polyester composition comprising above-mentioned liquid crystal polyester.
Preferably, described liquid-crystalline polyester composition, by weight, comprises following component:
Liquid crystal polyester 100 parts;
Weighting agent 5 parts-100 parts.
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, can be mixed into filler in liquid-crystalline polyester composition according to the present invention, this filler can be the inorganic of the form such as particle, thin slice or organic filler.
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 liquid crystal polyester, weighting agent and/or various additive high-speed mixer being mixed according to proportioning, 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:
When the present invention is by selecting the content that adds the benzoic acid compounds that structural formula defines such as formula I in liquid crystal polyester formula to be 0.1ppm-500ppm based on the gross weight of liquid crystal polyester, the high-temperature heat-resistance stability of the liquid crystal polyester obtained obtains beyond thought remarkable improvement, mobility have also been obtained raising, and does not affect the other side performance of liquid crystal polyester; The liquid-crystalline polyester composition be made up of this liquid crystal polyester equally also has excellent high-temperature heat-resistance stability and mobility.
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 structural formula defines such as formula I: get 500mg liquid crystal polyester 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); At the temperature of 60 DEG C, keep nitrogen atmosphere, more than concussion 24h is carried out to volumetric flask, after sample hydrolysis completely, 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, obtains the product of liquid crystal polyester complete hydrolysis; Sample after hydrolysis is dissolved in acetone, adopts Agilent company 1260 of U.S. type high performance liquid chromatograph, the benzoic acid compounds that the structural formula in test sample defines such as formula I; And adopt external standard method to carry out quantitatively the benzoic acid compounds that the structural formula in hydrolyzation sample defines such as formula I.
The testing method of the melt viscosity of described liquid crystal polyester: adopt DyniscoLCR7000 type capillary rheometer to test liquid crystal polyester, probe temperature is liquid crystal polyester 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 crystal polyester: 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 crystal polyester.
The testing method of the specific volume log viscosities of described liquid crystal polyester: be dissolved in by liquid crystal polyester 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, wherein η
rfor relative viscosity (t solution/t solvent), C is strength of solution.
The testing method of the mobility of described liquid crystal polyester: by liquid crystal polyester 120 DEG C of dryings after 4 hours, add injection moulding machine, barrel temperature is set as higher than the fusing point of liquid crystal polyester 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 crystal polyester 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 crystal polyester is more excellent.
The testing method of the high-temperature heat-resistance stability of described liquid crystal polyester: by liquid crystal polyester 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 crystal polyester 20 DEG C, and the rotating speed of rotor is 50rpm, and the banburying time is 1 hour; After banburying completes, the liquid crystal polyester 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 crystal polyester 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 polyester 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 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 1-12 and comparative example 1-6: the preparation of liquid crystal polyester
In the reactor being equipped with agitator, thermometer, nitrogen ingress pipe and reflux condensate device according to proportioning add respectively derived from aromatic hydroxy-carboxylic repeating unit, the repeating unit derived from aromatic diol and the repeating unit derived from aromatic dicarboxylic acid, and to add a certain proportion of acetic anhydride be acylating agent, add the benzoic acid compounds that the structural formula based on liquid crystal polyester gross weight 0.1ppm-500ppm defines such as formula I simultaneously; 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 fusing point of gained liquid crystal polyester, length of flow, melt viscosity and specific volume log viscosities are listed in table 1.
Table 1 embodiment 1
-12 and comparative example 1
-the concrete proportioning of 6 and test performance result thereof
Continued 1
embodiment 13-24 and comparative example 7-9: the preparation of liquid-crystalline polyester composition
To prepare after gained liquid crystal polyester, weighting agent and/or various additive high-speed mixer mix by embodiment 1-12 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
From the embodiment 1 of table 1
-12 and comparative example 1
-6 relatively can find out, when the present invention is by selecting the weight content that adds the benzoic acid compounds that structural formula defines such as formula I in liquid crystal polyester formula to be 0.1ppm-500ppm based on the gross weight of liquid crystal polyester, the high-temperature heat-resistance stability of the liquid crystal polyester obtained obtains beyond thought remarkable improvement, and mobility have also been obtained raising; The liquid-crystalline polyester composition be made up of this liquid crystal polyester equally also has excellent high-temperature heat-resistance stability and mobility.
Claims (12)
1. a liquid crystal polyester, is characterized in that, based on the gross weight of liquid crystal polyester, 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 crystal polyester according to claim 1, is characterized in that, the testing method of the weight content of the benzoic acid compounds that structural formula defines such as formula I: get 500mg liquid crystal polyester 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); At the temperature of 60 DEG C, keep nitrogen atmosphere, more than concussion 24h is carried out to volumetric flask, after sample hydrolysis completely, 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, obtains the product of liquid crystal polyester complete hydrolysis; Sample after hydrolysis is dissolved in acetone, adopts Agilent company 1260 of U.S. type high performance liquid chromatograph, the benzoic acid compounds that the structural formula in test sample defines such as formula I; And adopt external standard method to carry out quantitatively the benzoic acid compounds that the structural formula in hydrolyzation sample defines such as formula I.
3. liquid crystal polyester according to claim 1, is characterized in that, based on the gross weight of liquid crystal polyester, the weight content of benzoic acid compounds is preferably 0.5ppm-300ppm, is more preferably 1ppm-100ppm.
4. liquid crystal polyester according to claim 1, 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.
5. liquid crystal polyester according to claim 4, 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.
6. the liquid crystal polyester according to claim 4 or 5, 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.
7. liquid crystal polyester according to claim 1, is characterized in that, the fusing point of described liquid crystal polyester is 150 DEG C-400 DEG C, is preferably 260 DEG C-380 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 crystal polyester.
8. one kind comprises the liquid-crystalline polyester composition of the liquid crystal polyester described in any one of claim 1-7.
9. liquid-crystalline polyester composition according to claim 8, is characterized in that, by weight, comprises following component:
Liquid crystal polyester 100 parts;
Weighting agent 5 parts-100 parts.
10. liquid-crystalline polyester composition according to claim 9, 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.
11. liquid-crystalline polyester compositions according to claim 10, 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.
12. liquid-crystalline polyester compositions according to claim 9, 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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| CN201511015760.0A CN105542135A (en) | 2015-12-30 | 2015-12-30 | Liquid crystal polyester and liquid crystal polyester composition consisting of same |
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| WO2017114160A1 (en) * | 2015-12-30 | 2017-07-06 | 金发科技股份有限公司 | Liquid crystal polyester composition |
| CN109651607A (en) * | 2018-12-03 | 2019-04-19 | 成都博斐特新材料有限公司 | A kind of resinous polymeric material and its preparation method and application |
| CN110724367A (en) * | 2019-11-13 | 2020-01-24 | 上海普利特化工新材料有限公司 | Liquid crystal polymer/PET in-situ composite polyester material capable of being extruded into film and preparation method thereof |
| CN110746754A (en) * | 2019-09-25 | 2020-02-04 | 广东格瑞新材料股份有限公司 | Laser-engraved liquid crystal polymer composition and preparation method thereof |
| 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 |
| US11917753B2 (en) | 2019-09-23 | 2024-02-27 | Ticona Llc | Circuit board for use at 5G frequencies |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2017114160A1 (en) * | 2015-12-30 | 2017-07-06 | 金发科技股份有限公司 | Liquid crystal polyester composition |
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| CN110746754B (en) * | 2019-09-25 | 2021-06-29 | 广东格瑞新材料股份有限公司 | Laser-engraved liquid crystal polymer composition and preparation method thereof |
| CN110724367A (en) * | 2019-11-13 | 2020-01-24 | 上海普利特化工新材料有限公司 | Liquid crystal polymer/PET in-situ composite polyester material capable of being extruded into film and preparation method thereof |
| CN110724367B (en) * | 2019-11-13 | 2022-04-08 | 上海普利特化工新材料有限公司 | Liquid crystal polymer/PET in-situ composite polyester material capable of being extruded into film and preparation method thereof |
| 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 |
| WO2022099978A1 (en) * | 2020-11-16 | 2022-05-19 | 金发科技股份有限公司 | Liquid crystal polymer resin, preparation method therefor and application thereof |
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