CN105837803A - Liquid crystal polyester and its molded composition and use - Google Patents
Liquid crystal polyester and its molded composition and use Download PDFInfo
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- CN105837803A CN105837803A CN201610068342.6A CN201610068342A CN105837803A CN 105837803 A CN105837803 A CN 105837803A CN 201610068342 A CN201610068342 A CN 201610068342A CN 105837803 A CN105837803 A CN 105837803A
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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
- C08G63/60—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from the reaction of a mixture of hydroxy carboxylic acids, polycarboxylic acids and polyhydroxy compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/80—Solid-state polycondensation
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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
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/04—Ingredients characterised by their shape and organic or inorganic ingredients
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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
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/38—Polymers
- C09K19/3804—Polymers with mesogenic groups in the main chain
- C09K19/3809—Polyesters; Polyester derivatives, e.g. polyamides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/004—Additives being defined by their length
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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
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
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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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Polymers & Plastics (AREA)
- Polyesters Or Polycarbonates (AREA)
- Crystallography & Structural Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a liquid crystal polyester and its molded composition and use. The liquid crystal polyester comprises repeated structural units [I]-[IV]. A dynamic thermomechanical analysis (DMA) test proves that the liquid crystal polyester has a storage modulus release rate delta G greater than or equal to 95.0% and less than or equal to 99.4% defined in the formula (1) of delta G=[G(-50)-G(melting point)]/G(-50)*100%. The liquid crystal polyester has a storage modulus release rate delta G greater than or equal to 95.0% and less than or equal to 99.4%. The liquid crystal polyester and the liquid crystal polyester molded composition have good fluidity and excellent melting characteristics. A small thin wall molded product has high stability and is especially suitable for a thin wall electronic product.
Description
Technical field
The present invention relates to polymeric material field, particularly to a kind of liquid crystal polyester and consisting of moulding compound
Apply with it.
Background technology
TLCP (TLCP), as a kind of high-performance special engineering plastics, has excellent mechanical performance,
Good mobility, thermostability, resistance to chemical attack, fire-retardant and electrical insulation capability, at present at electronic apparatus and miniature precision thin-walled
The fields such as parts are widely used.Its preparation generally uses high-temperature fusion polymerization, but due to the monomers such as HBA, HNA from
Gather or the branched cross-linking reaction of strand, cause the melt processable of final LCD product and physical property poor, particularly
The mobility of resin is severely impacted, and mould filling is discontented with to cause liquid crystal polyester moulding compound to occur in forming process
Situation, has had a strong impact on liquid crystal polymer application in electronic apparatus thin wall parts.
For suppressing the autohemagglutination of HBA, and in high temperature polymerization process, control the research of the side reaction generations such as crosslinking always
Key subjects in scientific research and industry, such as patent CN1673249A, CN104004170 A, CN104098760A,
CN104098761A mentions the method suppression decarboxylic reaction by adding 4-toluene sulfonic acide, water, or acetic acid and the autohemagglutination of HBA
Reactions etc., the intrinsic viscosity of liquid crystal polymer is had some improvement by said method.
Such as above-mentioned patent, the intrinsic viscosity of current liquid crystal polyester has become as one general means of the industry, in order to table
Levy relative molecular mass and the molecular chain movement characteristic of liquid crystal polyester, the indirect reaction mobility of final liquid crystal polyester.But
The difference of intrinsic viscosity is not to affect the single factor of polymer flowability.Starting monomer structure or the difference of ratio, monomer
The size of autohemagglutination degree, molecular weight and the change of strand sequential structure, whether molecule segment uniform, the entanglement of strand or
The height of change degree, the motor capacity of strand and crystalline texture and the speed of speed, preparation process etc. all can be to polymerization
The mobility of thing produces impact.
Dynamic thermomechanical analyzes (DMA), is generally used for characterizing the modulus variation with temperature situation of plastic, reacts
The motor capacity size of strand, along with autohemagglutination product and molecular entanglement degree and the degree of branching are the biggest, branched crosslinking points is the most, point
The motor capacity of subchain weakens, and causes high storage modulus.The applicant constantly studies and is further discovered that the energy storage when liquid crystal polyester
When modulus release rate Δ G is in particular range, this liquid crystal polyester substantially weakens due to autohemagglutination segment or the branched crosslinking of strand, point
Subchain ordered arrangement, therefore shows excellent processing fluidity and mechanical performance.
Summary of the invention
The primary and foremost purpose of the present invention is to provide the liquid crystal polyester of a kind of high fluidity, the storage modulus of this liquid crystal polyester to release
Put rate Δ G in particular range, there is the processing fluidity being obviously improved.
Another object of the present invention is to provide a kind of moulding compound comprising above-mentioned liquid crystal polyester.
The present invention is achieved by the following technical solutions:
A kind of liquid crystal polyester, is made up of the constitutional repeating unit of following formula [I]-[IV]:
In terms of repetitive total amount 100mol%, the amount derived from the construction unit [I] of P-hydroxybenzoic acid is more than or equal to
30mol%, less than or equal to 72mol%;Amount derived from the construction unit [II] of 6-Hydroxy-2-naphthoic acid is more than or equal to 1mol%, little
In equal to 7.5mol%;Construction unit [III] derived from p-phthalic acid and the construction unit [IV] derived from M-phthalic acid
Total amount be that less than or equal to 38mol%, the amount derived from the construction unit [V] of 4,4 '-'-biphenyl diphenol is big more than or equal to 10mol%
In equal to 10mol%, less than or equal to 31mol%;Described construction unit [I], [II], [III], [IV] and the Mole percent of [V]
Number summation is 100;
Wherein use dynamic thermomechanical to analyze DMA test, by liquid crystal polyester from initial temperature-50 DEG C, with heating rate be 3 DEG C/
Min, amplitude is 30um, and when frequency is to be warmed up to fusing point under conditions of 1Hz, the storage modulus of initial temperature-50 DEG C is designated as G(-
50), the storage modulus at fusing point is designated as G(fusing point), this liquid crystal polyester meets the storage modulus release rate Δ defined by following formula (1)
G more than or equal to 95.0% to less than or equal to 99.4%,
(1) Δ G=[G(-50)-G(fusing point)]/G(-50) * 100%.
The physical significance of DMA storage modulus release rate Δ G real reaction be i.e. from low temperature through temperature programming to fusing point time, liquid
Brilliant polyester molecule chain stores the change of the ability of energy in motor process.For preferable molecule interchain without interacting, point
Subchain is without tangling or branched liquid crystal polyester is when temperature arrives fusing point, and energy stored in molecular chain movement should be released completely
The resistances such as put, i.e. storage modulus release rate reaches 100%, the now motion not friction of preferable strand, show perfect
Mobility.But actual synthesis liquid crystal polyester is due to starting monomer structure or the difference of ratio, the size of monomer autohemagglutination degree, molecule
Amount and the change of strand sequential structure, molecule segment is the most uniform, the entanglement of strand or the height of degree of branching, strand
Motor capacity and crystalline texture and the speed of speed, the impact of the factors such as preparation process, thus have impact on final
There is bigger difference in the molecular chain structure of the liquid crystal polyester prepared, the energy therefore produced in its motor process cannot be complete
It is released, causes mobility to decline.
The present invention is found by research, when liquid crystal polyester DMA storage modulus release rate Δ G more than or equal to 95.0% to
Less than or equal to 99.4%, HBA or HNA autohemagglutination segment or the branched crosslinking of strand substantially weaken, and show higher mobility, molten
Melting excellent, the forming stability of small-sized thin molded article is high, and when Δ G is less than 95.0%, then the branched crosslinking of strand increases
Many, processing fluidity is poor.
In order to complete the preparation one high fluidity liquid crystal polyester of the present invention, the melting viscosity of liquid crystal polyester be 9Pa.s-
35Pa.s, preferably 15Pa.s-30Pa.s, melting viscosity uses capillary rheometer test, and test temperature is more than fusing point 0-
30 DEG C, shear rate 1000 S-1, using internal diameter 1mm, the mouth die of length 40mm is measured.
From the viewpoint of thermostability, the fusing point of liquid crystal polyester should be the highest, but processes in view of polymer melt
Time former heating efficiency, the fusing point of liquid crystal polymer of the present invention is 310 DEG C-390 DEG C, preferably 330 DEG C-
380℃.Fusing point uses DSC to record, to be warmed up to the highest of fusing point+30 DEG C under the ramp rate conditions of 20 DEG C/min from room temperature
Temperature, is cooled to room temperature with the speed of 20 DEG C/min after stopping 3min at this temperature again, and test sample at room temperature stops
Again it is warmed up to the maximum temperature of fusing point+30 DEG C after 3min with the heating rate of 20 DEG C/min, obtains the second time of liquid crystal polyester
Melting curve, chooses this curve peak melting and is fusing point.
The content of each construction unit of the present invention can calculate by the following method: by 500mg liquid crystal polyester or its mould
Molding composition measures to 25ml volumetric flask, and adding 2.5ml concentration is the NaOH/CH of 5mol/L3OH solution, adds 10ml and removes
Water dimethyl sulfoxide.At a temperature of 60 DEG C, nitrogen atmosphere, thoroughly hydrolysis shakes up more than 18h, is dissolved in water and is acidified with hydrochloric acid
Postlyophilization.Take suitable quantity of water hydrolysis products to NMR(nuclear magnetic resonance, NMR) in test tube, carry out 1H-NMR mensuration, derive from each structure
The peak area ratio of unit is calculated.
The preparation method of the above-mentioned liquid crystal polyester of the present invention, comprises the steps:
A, under nitrogen pressurized conditions, with P-hydroxybenzoic acid, 6-Hydroxy-2-naphthoic acid, 4,4 '-'-biphenyl diphenol, terephthaldehyde
Acid and M-phthalic acid are raw material, carry out acylation reaction under the effect of acylating agent, and described pressure is maintained at 0.2MPa-
0.6MPa;
After b, acylation reaction terminate, carry out being decompressed to 10KPa-30KPa by reacting kettle inner pressure, discharge rapidly acetic acid from rectifying column
And unreacted acetic anhydride molecule, when acetic acid reception amount arrives more than the 50% of theoretical value, be rapidly heated to 200 DEG C or more than,
Keep this reduced pressure and by reaction system temperature programming to reaction maximum temperature, be decompressed to 50Kpa-100 the most further
Kpa, melt polycondensation obtains prepolymer;
C, by prepolymer cooling and solidifying and pelletize, solid phase container carries out solid phase and obtains liquid crystal polyester granule.
Phenolic hydroxyl group contained in above-mentioned raw materials monomer is preferably acylated with fatty acid anhydride before melt polycondensation.For fatty acid
Acid anhydride is not particularly limited, and can use acetic anhydride, propionic andydride, butyryl oxide., valeric anhydride, 2 ethyl hexanoic acid acid anhydride, dichloroacetic acid acid anhydride, dibromo
Any one in acetic anhydride, difluoroacetic acid acid anhydride, maleic anhydride and succinic anhydrides, it is also possible to use with two or more mixture.
Consider from production cost angle, preferably acetic anhydride, propionic andydride or butyryl oxide., more preferably acetic anhydride.The amount of fatty acid anhydride used with
The mol ratio of phenolic hydroxyl group is (1~1.2): 1, from producing relatively low degassing and the consideration of proper alignment foaming characteristic angle, the use of fatty acid anhydride
Measure preferably 1.02~1.10 times equivalents.
The preparation method of liquid crystal polyester described above, the first stage is the acylation reaction stage, and acylating agent is by principal monomer
The phenolic hydroxyl group of composition carries out acylation reaction, and acylation process is mainly characterized by, will by the way of nitrogen pressurizes in acylation process
The pressure of reactor is maintained at 0.2MPa-0.6MPa, wherein keep the size of pressure without specific restriction, but must be by acylation reaction
Temperature controls in the acylated temperature range of technological requirement, its objective is to make acetic anhydride and acetic acid product acute by the way of pressurization
Strong boiling, owing to the self-polymeric reaction of P-hydroxybenzoic acid acylate produces acetic acid, increases acetic gas volume, and pressure increase is drawn
Chemically reactive is carried out towards the direction that gas volume reduces, and therefore this self-polymeric reaction is by moderate inhibition, the acetic acid seethed with excitement simultaneously
Acid anhydride adds and the probability of monomer collision, it is ensured that the balance of the acylation reaction of phenolic hydroxyl group.Second stage is ester interchange polymerization rank
Section, this stage whole course of reaction is Depressor response, and evacuation is decompressed to 10KPa-30KPa, wherein reduces pressure by vacuum pumping
QI excess is existing, and the size of its pressure is not particularly limited, but must is fulfilled for the requirement of programmed rate.After acylation terminates,
Acetic acid molecule is asked to discharge rapidly, to meet the requirement being rapidly heated, owing to the nitrogen in acylated stage pressurizes so that acetic acid molecule
Gasify mist formation in a large number, bleeds decompression by vacuum pump so that substantial amounts of acetic acid and unreacted acetic anhydride are discharged from reactor, row
The acetic acid gone out flows into acetic acid through heat exchanger cooling effect and receives in tank, when acetic acid reception amount arrives more than the 50% of theoretical value, this
Shi Jia great heating rate, make the reaction temperature of reactor be brought rapidly up to 200 DEG C or more than, enter phenolic hydroxyl group acylate group with
The condensation reaction of hydroxy-acid group, to suppress the autohemagglutination of monomer.In the ester interchange polymerization stage, use the mode of decompression, and when reaction
After temperature arrives reaction maximum temperature, increase the vacuum of reactor, be decompressed to 50Kpa-100Kpa the most further so that be anti-
The by-product that should produce the such as little molecules such as phenol decompression effect under persistently discharge from reactor, reduce strand reset or
Branched probability, thus reduce the branched cross-linking reaction of strand.
Acylation reaction is generally reacted 30 minutes~20 hours at 100 DEG C~180 DEG C, preferably can be 120 DEG C~160 DEG C reactions
40 minutes~5 hours.Described melt polycondensation can be carried out under the effect of catalyst, and catalyst uses conventionally known polyester to gather
Catalysts, can be metallic salt catalyst, such as potassium acetate, sodium acetate, magnesium acetate, zinc acetate, antimony oxide, metatitanic acid
Four butyl esters etc..
Described melt polycondensation can be carried out under inert gas atmosphere;Polycondensation can be in intermittently or serially mode or combination side
Formula is carried out.After acylation reaction terminates, with 0.1 DEG C/min~the ramp of 150 DEG C/min, reactor is made to be rapidly heated 200
DEG C or more than, enter the melt polycondensation stage;Melt polycondensation is carried out under 130 DEG C~400 DEG C of temperature ranges, preferably at 160 DEG C~
Carrying out under 370 DEG C of temperature ranges, wherein maximum temperature is more preferably the temperature of fusing point+30 DEG C of liquid crystal polyester.
The aggregation container that described melt polycondensation is used can be the aggregation container with known form.It is preferably used vertical
Formula polymerization tank, stirring paddle can be turbine impellers, Double helix blade, multistage paddle blade, preferably turbine impellers.
After described melt polycondensation, from the viewpoint of easily the prepolymer of molten condition being discharged from polymerization tank,
The melting viscosity of prepolymer is preferably at below 10Pa s.Melting viscosity uses Dynisco LCR7000 type capillary rheometer to survey
Examination, test temperature is more than fusing point 30 DEG C, shear rate 1000 S-1, using internal diameter 1mm, the mouth die of length 40mm is measured.
After described melt polycondensation, the discharge of prepolymer is preferably carried out under inert atmosphere such as nitrogen atmosphere, i.e. to polymerization
Container add noble gas and increases pressure, the generation of side reaction can be suppressed, suppress the increase of prepolymer molecular weight simultaneously
(melting viscosity of suppression prepolymer).The equipment discharging prepolymer in the molten state may select valve, extruder and gear pump,
Solidify described prepolymer, with a direction, it transmitted continuously simultaneously, may utilize in direction of transfer downstream wire cutter,
Sheet material cutting machine or pulverizer cut or pulverize.The prepolyer granule obtained after cutting or being broken or powder there is no limit especially
System, preferably at 0.1mm~5mm.
It addition, acylation reaction can be carried out continuously with ester interchange polymerization in same reactor, it is also possible in differential responses
Container is carried out.
Described solid phase is preferably at vacuum 0.1Pa~50KPa, or the inert protective gas condition such as logical nitrogen
Under carry out, polymerization temperature about 0~340 DEG C, 0.5 hour response time~40 hours.Solid phase can be in stirring or without stirring
Carry out under resting state.
Lot of experimental data according to the present invention shows, monomer autohemagglutination occurs mainly under cryogenic conditions, such as less than 200 DEG C
Temperature, the reaction such as the branched crosslinking of strand is then concentrated mainly under hot conditions, such as more than 300 DEG C;Therefore use excellent
The preparation technology of choosing, controls the reaction of these two temperature sections well, is the key controlling the arrangement of strand sequential structure, is also to ensure that
The liquid crystal polyester of preparation has the key of preferable processing fluidity.The present invention uses the preparation technology after improvement, effectively controls
The reaction of each temperature section, it is to avoid the processing fluidity problem that caused due to monomer autohemagglutination or the branched crosslinking of strand.And it is right
Interpretation finds, uses the liquid crystal polyester prepared of present invention process and moulding compound thereof through DMA to storage modulus
Test, when DMA storage modulus release rate Δ G is in a preferred range, all shows higher mobility, but when DMA energy storage
When modulus release rate Δ G is less than the preferred scope of the present invention, then the branched crosslinking of strand increases, and processing fluidity is deteriorated.
Polymerization technique after adjustment is mainly characterized by being divided into reaction two stages, the acylated rank of first stage i.e. monomer
Section, for pressurization pressurize reaction in acylation process, its pressure is maintained at 0.2 MPa-0.6MPa;Second stage is ester interchange polymerization
In the stage, the whole process of this elementary reaction is Depressor response, and evacuation is decompressed to 10KPa-30KPa.This pressurization decompression is used to tie mutually
The purpose of the technique closed seeks to effectively resolve the problem of a series of side reactions that two reaction temperature sections produce, thus prepares
Go out to have liquid crystal polyester and the moulding compound thereof of excellent processing fluidity.
Present invention also offers a kind of liquid crystal polyester moulding compound, the liquid crystal including 30 weight portion-99.9 weight portions gathers
Ester, the reinforcer of 1 weight portion-70 weight portion and other auxiliary agents of 0-20 weight portion and/or other polymer;Wherein,
Described liquid crystal polyester is made up of the constitutional repeating unit of following formula [I]-[IV]:
In terms of repetitive total amount 100mol%, the amount derived from the construction unit [I] of P-hydroxybenzoic acid is more than or equal to
30mol%, less than or equal to 72mol%;Amount derived from the construction unit [II] of 6-Hydroxy-2-naphthoic acid is more than or equal to 1mol%, little
In equal to 7.5mol%;Construction unit [III] derived from p-phthalic acid and the construction unit [IV] derived from M-phthalic acid
Total amount be that less than or equal to 38mol%, the amount derived from the construction unit [V] of 4,4 '-'-biphenyl diphenol is big more than or equal to 10mol%
In equal to 10mol%, less than or equal to 31mol%, described construction unit [I], [II], [III], [IV] and the Mole percent of [V]
Number summation is 100;
Wherein use dynamic thermomechanical to analyze DMA test, by liquid crystal polyester from initial temperature-50 DEG C, with heating rate be 3 DEG C/
Min, amplitude is 30um, and when frequency is to be warmed up to fusing point under conditions of 1Hz, the storage modulus of initial temperature-50 DEG C is designated as G(-
50), the storage modulus at fusing point is designated as G(fusing point), this liquid crystal polyester meets the storage modulus release rate Δ defined by following formula (1)
G more than or equal to 95.0% to less than or equal to 99.4%,
(1) Δ G=[G(-50)-G(fusing point)]/G(-50) * 100%.
Liquid crystal polyester moulding compound of the present invention is owing to adding various fillers, and its mobility is also by the shadow of filler
Ring the mobility showing slightly below resin, cause the storage modulus release rate Δ G of moulding compound somewhat to reduce, but contrast
Test data finds, when the storage modulus release rate Δ G of moulding compound more than or equal to 91.0% to during less than or equal to 99.0%, its
Processing fluidity is still better than the liquid-crystalline polyester composition in contrast test.
Liquid crystal polyester moulding compound of the present invention, uses dynamic thermomechanical to analyze DMA test, by liquid crystal polyester mould
Molding composition, from initial temperature-50 DEG C, is 3 DEG C/min with heating rate, and amplitude is 30um, and frequency is intensification under conditions of 1Hz
During to fusing point, the storage modulus of initial temperature-50 DEG C is designated as G(-50), the storage modulus at fusing point is designated as G(fusing point), this liquid crystal
Polyester molding compounds meets the storage modulus release rate Δ G defined by following formula (1) more than or equal to 91.0% to being less than or equal to
99.0%,
(1) Δ G=[G(-50)-G(fusing point)]/G(-50) * 100%.
Wherein, described reinforcer be shaped as threadiness, its average length is 0.01mm-20mm, preferably 0.1mm ~
6mm;Its draw ratio is 5:1 ~ 2000:1, preferably 30:1 ~ 600:1;When selected fibrous reinforced filler size is in above-mentioned scope
Time interior, liquid-crystalline polyester composition not only shows preferable melt-processed mobility, and shows high heat distortion temperature and Gao Gang
Property.
Reinforcer content is too low, causes liquid crystal polyester moulding compound mechanical property poor;Reinforcer too high levels,
Liquid crystal polyester moulding compound product surface is floating fine serious, affects product appearance.The content of described reinforcer is preferably 10 weights
Amount part-50 weight portion, more preferably 15 weight portion-40 weight portions;
Described reinforcer is inorganic reinforcing filler or organic reinforcing fillers.
Described inorganic reinforcing filler include but are not limited to glass fibre, potassium titanate fibre, metalclad glass fibre,
Ceramic fibre, wollastonite fibre, metallic carbide fibres, metal-cured fiber, asbestos fibre, alumina fibre, carborundum are fine
One or more of dimension, gypsum fiber or boron fibre, preferably glass fibre.Use glass fibre not only can improve liquid crystal polyester
The mouldability of compositions, and mechanical property such as hot strength, bending strength or bending modulus can be improved, and improve heat-resisting
Property such as thermoplastic resin composition carry out molding the heat distortion temperature being.
Described organic reinforcing fillers includes but are not limited to liquid crystalline polyester fiber and/or carbon fiber.
Described reinforcer be shaped as Non-fibrous, its mean diameter is 0.001 μm-50 μm, flat when reinforcer
All particle diameters will cause the melt processable of liquid-crystal polyester resin difference less than 0.001 μm;When the mean diameter of reinforcer is more than 50 μ
M, will cause bad injection-molded article appearance.It is selected from potassium titanate crystal whisker, ZnOw, aluminium borate whisker, Talcum
Powder, white carbon black, Gypsum Fibrosum, asbestos, zeolite, sericite, Kaolin, montmorillonite, clay, lithium montmorillonite, synthetic mica, aluminosilicate,
Silicon dioxide, titanium oxide, aluminium oxide, zinc oxide, zirconium oxide, ferrum oxide, calcium carbonate, magnesium titanate, dolomite, aluminum sulfate, sulphuric acid
Barium, magnesium sulfate, calcium carbonate, Muscovitum, silica flour, magnesium hydroxide, calcium hydroxide, aluminium hydroxide, bead, ceramic bead, boron nitride
Or one or more of carborundum.
In the liquid-crystalline polyester composition of embodiments of the present invention, in the range of the effect not damaging the present invention, also may be used
To coordinate selected from antioxidant, heat stabilizer, UV absorbent, lubricant, releasing agent, to comprise the coloring of dyestuff or pigment
Common processing aid in agent, plasticizer, antistatic additive.Maybe can coordinate liquid crystalline polyester or the liquid crystal polyester of other structures
Polymer in addition, other described polymer can be all aromatic or semi-aromatic TLCP, aromatic series
Or semiaromatic polyamide composition, polyether-ether-ketone, polyether sulfone, one or more of polyolefin homopolymer or copolymer etc..By so
Cooperation, the characteristic of regulation can be given further.
As the method coordinating reinforcer, processing aid etc. in the liquid crystal polyester of embodiments of the present invention, do not have
Specific restriction, it is possible to use dry type blending, solution mixing method, the polymerization of liquid crystalline polyester are interpolation, melting mixing etc., wherein
It is preferably melting mixing.Such as kneader, uniaxially or biaxially extruder, rubber-roller machine etc., biaxial extruder is wherein preferably used.Melted
Mixing temperature 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 in the lump from rear dress charger, reinforcer, other processing help
Agent carries out mixing method;Liquid crystal polyester and other processing aid agent can also be penetrated, from side charger from rear dress charger
Add reinforcer and carry out mixing method, high concentration can also be prepared and comprise the liquid crystal of liquid crystalline polyester and other processing aids
Property polymer blend master batch, then by master batch and liquid crystal polyester, reinforcer carries out the method for the mixing concentration to become regulation
Deng any one method.
The liquid-crystalline polyester composition of embodiments of the present invention, by carrying out injection moulding, injection compression molding, is compressed into
The known melt molding product such as type, extrusion molding, blow molding, compressing spinning.Products formed described here, can be note
Penetrate products formed, extrusion molding article, compressing product, sheet, pipe, non-stretched film, single axle drawn membrane, biaxially oriented film etc. each
Plant the various cellosilks etc. such as membrane product, undrawn yarn, super drawing silk.In the case of injection molding, the present invention can significantly be obtained
Effect, the most preferably.
Liquid crystalline polyester or the products formed of liquid crystal polyester moulding compound formation that the present invention is obtained can have following answering
With, at the bottom of various gears, various housing, sensor, LED lamp, adapter, socket, resistor, casing of relay, relay
Seat, relay roll, switch, coil axle, capacitor, variable condenser housing, optical pickup unit, resonator, various terminal
At the bottom of plate, transformator, plug, printed wiring board, tuner, speaker, microphone, head type headphones, miniature motor, magnetic head
Seat, power model, shell, quasiconductor, liquid crystal display component, FDD bracket, FDD chassis, HDD parts, motor brush holder,
Electrical and electronic parts that parabola antenna, computer associated components etc. are representative, blow with VTR parts, TV part, flatiron, electricity
Speech ciphering equipment parts, illuminace component, the electricity such as wind, electric cooker parts, microwave oven component, sound part, audio frequency, laser disk, CD
Family, enterprise's electric product parts that refrigerator parts, air supply rate, typewriter parts, word processor parts etc. are representative, do
Public room computer associated components, telephone set associated components, facsimile machine associated components, photocopier associated components, washing fixture, nothing
The various bearings such as oil bearing, stern bearing, water middle (center) bearing, motor component, mechanical phase with lighter, typewriter etc. as representative
Close parts, the optical device with microscope, binoculars, photographing unit, clock and watch etc. as representative, precision optical machinery associated components;Hand over
The various valves such as stream generator terminal, alternating current generator adapter, IC actuator, dimmer potentiometer base, aerofluxus air valve,
Fuel association, exhaust system, the various pipes of air-breathing system, inlet jet breather, inlet manifold, petrolift, engine cooling water
Joint, carburator main body, carburator spacer, exhaust gas sensor, cooling water sensor, oil temperature sensor, air throttle position
Put sensor, crankshaft position sensor, mass air flow sensor, Brake pad abrasion sensor, idle call thermostat base, idle call
The on-vehicle motor insulators such as motor insulator, motorized window, warmer heated airflow control valve, radiator fan motor are brushed
Hold, water pump vane, turbo blade, wiper motor associated components, ignition distributor, starter switch, starter relay, transmission
Device wire harness, window cleaning device nozzle, air-conditioning panel switch substrate, fuel association electromagnetic valve coil, electric fuse connect
Device, loudspeaker terminal, parts of electric insulation board, stepping motor rotor, lamp ring, lamp socket, lamp reflector, lamp housing, brake piston,
The automobiles such as solenoid bobbin, engine oil filter, ignition housings, vehicle associated components etc. are at printed wiring board, small-sized thin
In wall electronic device etc. particularly useful.
The present invention compared with prior art, has the advantages that
(1) present invention is found by research, and the DMA storage modulus release rate Δ G of the liquid crystal polyester of the present invention is more than or equal to
95.0%, to less than or equal to 99.4%, has higher mobility, and melting characteristic is excellent, the forming stability of small-sized thin molded article
High.
(2) present invention is in whole building-up process, in conjunction with pressurization and the polymerization technique of decompression, it is possible to effectively control hydroxyl
Acylated efficiency, and effectively stop monomer autohemagglutination in the process of polymerization, the entanglement of strand, the generation of the side reaction such as branched crosslinking,
Control the ordered arrangement of the strand of liquid crystal polyester, prepare liquid crystal polyester and the molding group thereof with higher mobility
Compound.
(3) preparation method of the present invention is simple to operate, and product is easily obtained, and the production cycle is shorter, is suitable to industrialized production.
Detailed description of the invention
Each raw material, acylating agent, catalyst, glass fibre, Muscovitum and calcium stearate etc. that the embodiment of the present invention is used its
His auxiliary agent derives from commercial.
Performance characterization necessary in the present invention and method of testing thereof:
(1) fusing point: use NETZSCH company DSC 200 F3 to record, with the heating rate bar of 20 DEG C/min from room temperature
It is warmed up to the maximum temperature of fusing point+30 DEG C under part, after stopping 3min at this temperature, is cooled to room with the speed of 20 DEG C/min again
Temperature, test sample is warmed up to the highest temperature of fusing point+30 DEG C again with the heating rate of 20 DEG C/min after at room temperature stopping 3min
Degree, obtains the second time melting curve of polyester, chooses this curve peak melting and be fusing point.
(2) storage modulus release rate Δ G: using the Q800 type DMA test of Ta company of the U.S. to obtain, observation is from initial temperature
Spending-50 DEG C, be 3 DEG C/min with heating rate, amplitude is 30um, when frequency is to be warmed up to fusing point under conditions of 1Hz, and initial temperature
The storage modulus spending-50 DEG C is designated as G(-50), the storage modulus at fusing point is designated as G(fusing point), storage modulus release rate Δ G presses
Formula calculates:
Δ G=[G(-50)-G(fusing point)]/G(-50) * 100%.
(3) mobility: the length of the bar-shaped thin slice injection molding body using the widest * thickness to be 5*0.45mm is gathered to characterize liquid crystal
The mobility of ester, injection temperature is near fusing point, by the length meansigma methods of 30 bar-shaped thin slice injection molding bodies as parameter measure
Liquid crystal polyester and the mobility of moulding compound thereof.Under conditions of injecting condition is identical, bar-shaped thin slice injection molding body length is the longest,
Show that its mobility is the best.
(4) melt viscosity: using DyniscoLCR7001 type capillary rheometer to test, port mould diameter is
1mm, a length of 40mm, described liquid crystal polyester more than its melt temperature 20 DEG C, shear rate is 1000s-1Under the conditions of viscous
Degree is melt viscosity.
Embodiment 1
Anti-to the polymerization equipped with agitator, reflux condenser, monomeric charge mouth, nitrogen inlet, thermometer and torque sensor
Answer in device, add following raw material monomer, acylating agent, catalyst.
(I) P-hydroxybenzoic acid 1298.4 grams (47 mol %) HBA
(II) 6-Hydroxy-2-naphthoic acid 112.9 grams (3mol %) HNA
(III) 731 grams of (22mol%) TA of p-phthalic acid
(IV) M-phthalic acid 99.7 grams (3 mol%) IA
(V) 4,4 '-'-biphenyl diphenol 931.1 grams (25mol %) BP
Acylating agent: acetic anhydride 2041 grams
Catalyst: magnesium acetate 103 milligrams
After having fed intake, by the atmosphere in nitrogen thorough displacement reaction container, by the temperature liter of reaction system under logical nitrogen protection
Up to 140 DEG C, and to keep nitrogen pressure be 0.2MPa, maintains this temperature reflux to carry out acylation reaction in 2 hours;Acylation reaction terminates
After, open vacuum pump and reacting kettle inner pressure is depressurized to 10KPa-30 KPa, discharge rapidly acetic acid and unreacted vinegar from rectifying column
Anhydride molecule, to meet the technological requirement being brought rapidly up, when acetic acid reception amount arrives more than the 50% of theoretical value, is brought rapidly up
To 200 DEG C, keeping this reduced pressure and reaction system was warming up in 6 hours maximum temperature 360 DEG C, period persistently discharges vinegar
Acid particularly phenol etc. causes strand to reset and branched small molecular by product, is then decompressed to 50KPa in 30 minutes;When
After stirring moment of torsion reaches predetermined value, it is believed that reaction terminates, now take out the product in reactor;After product is cooled to room temperature,
Pulverize with pulverizer, then under in vacuum less than 200Pa, in 10 hours, be heated to 300 DEG C by room temperature, and temperature at this
Degree is lower to be maintained 10 hours;By the product obtained by polarized light microscope observing said method, find that it is can to show in molten state
Show optically anisotropic liquid crystal polymer.The melt temperature of this liquid crystal polyester, melt viscosity, storage modulus release rate, bar-shaped
Injection molding body length, is listed in table 1.
Embodiment 2-5: according to the formula of table 1, after acylation reaction terminates, opens vacuum pump and is depressurized to by reacting kettle inner pressure
10KPa-30KPa, discharges rapidly acetic acid and unreacted acetic anhydride molecule from rectifying column, wants with the satisfied technique being brought rapidly up
Ask, when acetic acid reception amount arrives more than the 50% of theoretical value, be brought rapidly up to 210 DEG C, keep this reduced pressure and by reactant
Being warming up to maximum temperature 370 DEG C in tying up to 6 hours, period persistently discharges acetic acid particularly phenol etc. and causes strand to reset and prop up
The small molecular by product changed, was then decompressed to 60KPa in 30 minutes;Remaining is with embodiment 1;The fusing point of this liquid crystal polyester, molten
Melt-viscosity, storage modulus release rate, bar-shaped fluid length is shown in Table 1.
Embodiment 6-12: according to the formula of table 1, after acylation reaction terminates, opens vacuum pump and is depressurized to by reacting kettle inner pressure
10KPa-30KPa, discharges rapidly acetic acid and unreacted acetic anhydride molecule from rectifying column, wants with the satisfied technique being brought rapidly up
Ask, when acetic acid reception amount arrives more than the 50% of theoretical value, be brought rapidly up to 220 DEG C, keep this reduced pressure and by reactant
Being warming up to maximum temperature 380 DEG C in tying up to 6 hours, period persistently discharges acetic acid particularly phenol etc. and causes strand to reset and prop up
The small molecular by product changed, was then decompressed to 70KPa in 30 minutes;Remaining is with embodiment 1;The fusing point of this liquid crystal polyester, molten
Melt-viscosity, storage modulus release rate, bar-shaped fluid length is shown in Table 1.
Comparative example 1-3: after having fed intake, by the atmosphere in nitrogen thorough displacement reaction container, logical nitrogen protection is lower will be anti-
The temperature answering system is increased to 140 DEG C, maintains this temperature reflux to carry out acylation reaction in 2 hours;After acylation reaction terminates, from rectification
Post, while discharging acetic acid and unreacted acetic anhydride molecule, heats up and in 6 hours, reaction system is warming up to the highest temperature
Spending 360 DEG C, period persistently discharges acetic acid, is then decompressed to 30KPa in 30 minutes;After stirring moment of torsion reaches predetermined value, recognize
Terminate for reaction, now take out the product in reactor;After product is cooled to room temperature, pulverize with pulverizer, then very
Reciprocal of duty cycle was heated to 300 DEG C by room temperature less than under 200Pa in 10 hours, and maintained 10 hours at this temperature;By partially
Light microscope observes the product obtained by said method, finds that it is can to show optically anisotropic polymerizable mesogenic in molten state
Thing.The fusing point of this liquid crystal polyester, melt viscosity, storage modulus release rate, bar-shaped injection molding body length, it is listed in table 1.
Table 1
By the above results it can be seen that storage modulus release rate Δ G is more than or equal to 95.0% to less than or equal to 99.4% in embodiment
Liquid crystal polyester, bar-shaped injection molding body length, apparently higher than comparative example, illustrates that the liquid crystal polyester in embodiment has high mobility.
Even if it addition, from embodiment with comparative example it can also be seen that identical in starting monomer structure, ratio, melt viscosity
Under conditions of similar, the liquid crystal polyester in the range of different storage modulus release rates, due to the difference of its its molecular chain structure, bar-shaped
Injection molding body length has notable difference, and the liquid crystal polyester i.e. with different storage modulus release rate can show different flowings
Property.
Embodiment 13-24, comparative example 4-7: the preparation of liquid crystal polyester moulding compound
By the proportioning of table 2 by the liquid crystal polyester by embodiment 1-12 and comparative example, do in 150 DEG C of vacuum carrying out more than 12h
After dry, high-speed mixer is utilized to join extruder, proportionally by resin and auxiliary agent from twin-screw extrusion owner's spout
By glass fibre and Muscovitum, other auxiliary agents such as calcium stearate join extruder from twin-screw extrusion pusher side spout, through molten
Melting mixing, select suitable barrel temperature to extrude, pelletize, the ring-type cooling air cooling at sufficiently long air stream solidifies, and obtains
Liquid-crystalline polyester composition;Test the fusing point of liquid-crystalline polyester composition, melt viscosity, storage modulus release rate, bar-shaped injection respectively
Body length test result is listed in table 2.
Table 2
By the result of table 2 it can be seen that be more than or equal to 95.0% to being less than or equal to owing to have employed storage modulus release rate Δ G
The liquid-crystal polyester resin of 99.4%, its molecular chain structure there occurs large change, the flowing of embodiment liquid crystal polyester moulding compound
Property substantially relatively comparative example high, be particularly suitable in thin-walled electronic articles.
Claims (15)
1. a liquid crystal polyester, is made up of the constitutional repeating unit of following formula [I]-[IV]:
In terms of repetitive total amount 100mol%, the amount derived from the construction unit [I] of P-hydroxybenzoic acid is more than or equal to
30mol%, less than or equal to 72mol%;Amount derived from the construction unit [II] of 6-Hydroxy-2-naphthoic acid is more than or equal to 1mol%, little
In equal to 7.5mol%;Construction unit [III] derived from p-phthalic acid and the construction unit [IV] derived from M-phthalic acid
Total amount be that less than or equal to 38mol%, the amount derived from the construction unit [V] of 4,4 '-'-biphenyl diphenol is big more than or equal to 10mol%
In equal to 10mol%, less than or equal to 31mol%;Described construction unit [I], [II], [III], [IV] and the Mole percent of [V]
Number summation is 100;
Wherein use dynamic thermomechanical to analyze DMA test, by liquid crystal polyester from initial temperature-50 DEG C, with heating rate be 3 DEG C/
Min, amplitude is 30um, and when frequency is to be warmed up to fusing point under conditions of 1Hz, the storage modulus of initial temperature-50 DEG C is designated as G(-
50), the storage modulus at fusing point is designated as G(fusing point), this liquid crystal polyester meets the storage modulus release rate Δ defined by following formula (1)
G more than or equal to 95.0% to less than or equal to 99.4%,
(1) Δ G=[G(-50)-G(fusing point)]/G(-50) * 100%.
Liquid crystal polyester the most according to claim 1, it is characterised in that the melting viscosity of described liquid crystal polyester be 9Pa.s-
35Pa.s, preferably 15Pa.s-30Pa.s, melting viscosity uses capillary rheometer test, and test temperature is more than fusing point 0-
30 DEG C, shear rate 1000 S-1, using internal diameter 1mm, the mouth die of length 40mm is measured.
Liquid crystal polyester the most according to claim 1, it is characterised in that: the fusing point of described liquid crystal polyester is 310 DEG C-390 DEG C,
Being preferably 330 DEG C-380 DEG C, fusing point uses DSC to record, and is warmed up to melt from room temperature under ramp rate conditions with 20 DEG C/min
The maximum temperature of point+30 DEG C, is cooled to room temperature with the speed of 20 DEG C/min after stopping 3min at this temperature again, and test sample exists
Again it is warmed up to the maximum temperature of fusing point+30 DEG C after stopping 3min under room temperature with the heating rate of 20 DEG C/min, obtains liquid crystal and gather
The second time melting curve of ester, chooses this curve peak melting and is fusing point.
4. according to the preparation method of the liquid crystal polyester described in any one of claim 1-3, it is characterised in that comprise the steps:
A, under nitrogen pressurized conditions, with P-hydroxybenzoic acid, 6-Hydroxy-2-naphthoic acid, 4,4 '-'-biphenyl diphenol, terephthaldehyde
Acid and M-phthalic acid are raw material, carry out acylation reaction under the effect of acylating agent, and described pressure is maintained at 0.2MPa-
0.6MPa;
After b, acylation reaction terminate, carry out being decompressed to 10KPa-30KPa by reacting kettle inner pressure, discharge rapidly acetic acid from rectifying column
And unreacted acetic anhydride molecule, when acetic acid reception amount arrives more than the 50% of theoretical value, be rapidly heated to 200 DEG C or more than,
Keep this reduced pressure and by reaction system temperature programming to reaction maximum temperature, be decompressed to 50Kpa-100 the most further
Kpa, melt polycondensation obtains prepolymer;
C, by prepolymer cooling and solidifying and pelletize, solid phase container carries out solid phase and obtains liquid crystal polyester granule.
The preparation method of liquid crystal polyester the most according to claim 4, it is characterised in that in step a, described acylation reaction
Temperature is 100 DEG C~180 DEG C, preferably 120 DEG C~160 DEG C, and the response time is 30 minutes~20 hours, preferably 40 minutes~5 little
Time.
The preparation method of liquid crystal polyester the most according to claim 4, it is characterised in that in step b, acylation reaction terminates
After, with 0.1 DEG C/min~the ramp of 150 DEG C/min, make reactor be rapidly heated 200 DEG C or more than, enter melted contracting
In the poly-stage, the temperature of described melt polycondensation is 130 DEG C~400 DEG C, preferably 160 DEG C~370 DEG C.
The preparation method of liquid crystal polyester the most according to claim 4, it is characterised in that in step c, described solid phase exists
Carrying out under the conditions of vacuum 0.1Pa~50KPa, or the inert protective gas such as logical nitrogen, polymerization temperature is 0~340 DEG C, instead
It is 0.5 hour~40 hours between Ying Shi.
8. comprise a liquid crystal polyester moulding compound for liquid crystal polyester described in any one of claim 1-3, including 30 weight
Part liquid crystal polyester of-99.9 weight portions, the reinforcer of 1 weight portion-70 weight portion and other auxiliary agents of 0-20 weight portion and/or
Other polymer;Wherein,
Described liquid crystal polyester is made up of the constitutional repeating unit of following formula [I]-[IV]:
In terms of repetitive total amount 100mol%, the amount derived from the construction unit [I] of P-hydroxybenzoic acid is more than or equal to
30mol%, less than or equal to 72mol%;Amount derived from the construction unit [II] of 6-Hydroxy-2-naphthoic acid is more than or equal to 1mol%, little
In equal to 7.5mol%;Construction unit [III] derived from p-phthalic acid and the construction unit [IV] derived from M-phthalic acid
Total amount be that less than or equal to 38mol%, the amount derived from the construction unit [V] of 4,4 '-'-biphenyl diphenol is big more than or equal to 10mol%
In equal to 10mol%, less than or equal to 31mol%;Described construction unit [I], [II], [III], [IV] and the Mole percent of [V]
Number summation is 100;
Wherein use dynamic thermomechanical to analyze DMA test, by liquid crystal polyester from initial temperature-50 DEG C, with heating rate be 3 DEG C/
Min, amplitude is 30um, and when frequency is to be warmed up to fusing point under conditions of 1Hz, the storage modulus of initial temperature-50 DEG C is designated as G(-
50), the storage modulus at fusing point is designated as G(fusing point), this liquid crystal polyester meets the storage modulus release rate Δ defined by following formula (1)
G more than or equal to 95.0% to less than or equal to 99.4%,
(1) Δ G=[G(-50)-G(fusing point)]/G(-50) * 100%.
Liquid crystal polyester moulding compound the most according to claim 8, it is characterised in that the melting viscosity of described liquid crystal polyester
For 9Pa.s-35Pa.s, preferably 15Pa.s-30Pa.s, melting viscosity uses capillary rheometer test, tests temperature and is
More than fusing point 0-30 DEG C, shear rate 1000 S-1, using internal diameter 1mm, the mouth die of length 40mm is measured.
Liquid crystal polyester moulding compound the most according to claim 8, it is characterised in that: the fusing point of described liquid crystal polyester is
310 DEG C-390 DEG C, preferably 330 DEG C-380 DEG C, fusing point uses DSC to record, with the heating rate bar of 20 DEG C/min from room temperature
It is warmed up to the maximum temperature of fusing point+30 DEG C under part, after stopping 3min at this temperature, is cooled to room with the speed of 20 DEG C/min again
Temperature, test sample is warmed up to the highest temperature of fusing point+30 DEG C again with the heating rate of 20 DEG C/min after at room temperature stopping 3min
Degree, obtains the second time melting curve of liquid crystal polyester, chooses this curve peak melting and be fusing point.
11. liquid crystal polyester moulding compounds according to claim 8, it is characterised in that being shaped as of described reinforcer
Threadiness, its average length is 0.01mm-20mm, preferably 0.1mm ~ 6mm;Its draw ratio is 5:1 ~ 2000:1, preferably 30:
1~600:1;The content of described reinforcer is preferably 10 weight portion-50 weight portions, more preferably 15 weight portion-40 weight portions;
Described reinforcer is inorganic reinforcing filler or organic reinforcing fillers, and described inorganic reinforcing filler includes but are not limited to glass fibers
Dimension, potassium titanate fibre, metalclad glass fibre, ceramic fibre, wollastonite fibre, metallic carbide fibres, metal-cured
One or more of fiber, asbestos fibre, alumina fibre, silicon carbide fibre, gypsum fiber or boron fibre, preferably glass fibers
Dimension;Described organic reinforcing fillers includes but are not limited to liquid crystalline polyester fiber and/or carbon fiber.
12. liquid crystal polyester moulding compounds according to claim 8, it is characterised in that being shaped as of described reinforcer
Non-fibrous, its mean diameter is 0.001 μm-50 μm, selected from potassium titanate crystal whisker, ZnOw, aluminium borate whisker, Talcum
Powder, white carbon black, Gypsum Fibrosum, asbestos, zeolite, sericite, Kaolin, montmorillonite, clay, lithium montmorillonite, synthetic mica, aluminosilicate,
Silicon dioxide, titanium oxide, aluminium oxide, zinc oxide, zirconium oxide, ferrum oxide, calcium carbonate, magnesium titanate, dolomite, aluminum sulfate, sulphuric acid
Barium, magnesium sulfate, calcium carbonate, Muscovitum, silica flour, magnesium hydroxide, calcium hydroxide, aluminium hydroxide, bead, ceramic bead, boron nitride
Or one or more of carborundum.
13. liquid crystal polyester moulding compounds according to claim 8, it is characterised in that other auxiliary agents described are selected from antioxygen
One or several in agent, heat stabilizer, UV absorbent, lubricant, releasing agent, coloring agent, plasticizer or antistatic additive
Kind.
14. liquid crystal polyester moulding compounds described in-13 any one according to Claim 8, it is characterised in that use Dynamic mechanical
DMA test analyzed by tool, by liquid crystal polyester moulding compound from initial temperature-50 DEG C, is 3 DEG C/min with heating rate, and amplitude is
30um, when frequency is to be warmed up to fusing point under conditions of 1Hz, the storage modulus of initial temperature-50 DEG C is designated as G(-50), at fusing point
Storage modulus is designated as G(fusing point), this liquid crystal polyester moulding compound meets the storage modulus release rate Δ G defined by following formula (1)
More than or equal to 91.0% to less than or equal to 99.0%,
(1) Δ G=[G(-50)-G(fusing point)]/G(-50) * 100%.
15. liquid crystal polyester moulding compound described in-14 any one application in electric field according to Claim 8.
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