CN105860037A - Liquid crystal polyester, molding composition composed of liquid crystal polyester and application of molding composition - Google Patents
Liquid crystal polyester, molding composition composed of liquid crystal polyester and application of molding composition Download PDFInfo
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- CN105860037A CN105860037A CN201610068349.8A CN201610068349A CN105860037A CN 105860037 A CN105860037 A CN 105860037A CN 201610068349 A CN201610068349 A CN 201610068349A CN 105860037 A CN105860037 A CN 105860037A
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- 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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- 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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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
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- 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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Abstract
The invention discloses liquid crystal polyester, a molding composition composed of the liquid crystal polyester and an application of the molding composition. The liquid crystal polyester is composed of repetitive structural units represented by the formula [I] and the formula [II]; according to 100 mol% of the total amount of the repetitive units, the amount of the structural unit [I] derived from p-hydroxybenzoic acid is greater than or equal to 50 mol%, preferably greater than or equal to 66 mol% and less than or equal to 85 mol%; the amount of the structural unit [II] derived from 6-hydroxy-2-naphthoic acid is less than or equal to 50 mol%, preferably greater than or equal to 15 mol% and less than or equal to 34 mol%. Through differential scanning calorimetry DSC testing, the liquid crystal polyester meets a condition that the double enthalpy ratio [delta]H defined by the following formula (1) is greater than or equal to 0.05 and less than or equal to 0.9, preferably greater than or equal to 0.1 and less than or equal to 0.6, wherein the formula (1) is [delta]H=H(melting enthalpy)/H(crystallization enthalpy). The liquid crystal polyester and the molding composition prepared by the liquid crystal polyester have the advantages of relatively high liquidity, excellent melting characteristics, and high forming stability of small thin-wall molding products, and are particularly suitable for use in thin-wall electronic preparation parts.
Description
Technical field
The present invention relates to polymeric material field, particularly to a kind of liquid crystal polyester and consisting of moulding compound and its apply.
Background technology
TLCP (TLCP), as a kind of high-performance special engineering plastics, has excellent mechanical performance, good mobility, heat resistance, resistance to chemical attack, fire-retardant and electrical insulation capability, it is widely used in fields such as electronic apparatus and miniature precision thin-wall part at present.Its preparation generally uses high-temperature fusion polymerization, but due to HBA, the autohemagglutination of the monomers such as HNA or the branched cross-linking reaction of strand, the melt processable and the physical property that cause final LCD product are poor, the particularly mobility of resin is severely impacted, the situations such as discontented filled by mould to cause liquid crystal polyester moulding compound to occur in forming process, 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 key subjects studied in always scientific research and industry that the side reactions such as crosslinking occur, such as patent
CN1673249A, CN104004170 A, CN104098760A, CN104098761A mention by adding 4-toluene sulfonic acide, water, or the method suppression decarboxylic reaction and the self-polymeric reaction etc. of HBA of acetic acid, the inherent viscosity of liquid crystal polymer is had some improvement by said method.
Such as above-mentioned patent, the inherent viscosity of current liquid crystal polyester has become as one general means of the industry, in order to characterize relative molecular mass and the molecular chain movement characteristic of liquid crystal polyester, and the indirect reaction mobility of final liquid crystal polyester.But the difference of inherent viscosity is not to affect the single factor of polymer flowability.Starting monomer structure or the difference of ratio, the size of monomer autohemagglutination degree, molecular weight and the change of strand sequential structure, molecule segment is the most uniform, the entanglement of strand or the height of degree of branching, the locomitivity of strand and crystalline texture and the speed of speed, preparation process etc. all can produce impact to the mobility of polymer.
Differential scanning calorimetric analysis (DSC) is one of the most frequently used thermal-analysis instrumentation, for characterizing polymer melting crystallization process, react the relation between molecular chain structure and crystallization, the change of molecular chain structure, directly determined DSC and heating up or melted or crystallization behavior during cooling.The applicant constantly studies it has further been found that liquid crystal polyester in the range of the i.e. double enthalpy ratio of particular melt crystallization enthalpy ratio, owing to having structure and the crystalline state of specific strand, 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, and double enthalpys of this liquid crystal polyester in particular range, have the processing fluidity being obviously improved than Δ H.
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] and [II]:
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 50mol%, is preferably greater than equal to 66mol%, less than or equal to 85mol%；Amount derived from the construction unit [II] of 6-Hydroxy-2-naphthoic acid is less than or equal to 50mol%, is preferably greater than equal to 15mol%, less than or equal to 34mol%；
Wherein use means of differential scanning calorimetry DSC test, it is warmed up to the maximum temperature of fusing point+30 DEG C with the heating rate of 20 DEG C/min from room temperature, it is down to room temperature with the speed of 20 DEG C/min again after stopping 3min at this temperature, obtain the crystallization curve of liquid crystal polyester, choose crystallization onset temperature and the crystallization end temp of peak crystallization, and calculate peak crystallization area and be H(crystallization enthalpy)；Test sample is warmed up to the maximum temperature of fusing point+30 DEG C again with the heating rate of 20 DEG C/min after at room temperature stopping 3min, obtain the second time melting curve of liquid crystal polyester, choose the melt initiation temperature degree of melting peak and melted end temp, and calculate melting peak area and be H(melting enthalpy), this liquid crystal polyester meets the double enthalpys defined by following formula (1) than Δ H more than or equal to 0.05, less than or equal to 0.9, preferably greater than or equal to 0.1 to less than or equal to 0.6；
(1) Δ H=H(melting enthalpy)/H(crystallization enthalpy).
The double enthalpy of DSC is the ratio of liquid crystal polyester crystal melt enthalpy and crystallization enthalpy than Δ H, and the physical significance of its real reaction is i.e. the relation that liquid crystal polyester crystal structure destroys the complexity with strand crystallization and liquid crystal polyester molecular chain structure.Crystallization behavior has close ties with the architectural feature of crystal melt behavior and strand, for preferable molecule interchain without interacting, molecular chain structure is regular, the resistances such as interior rotatory power is big, and compliance is high, the motion of strand now not friction, molecular chain movement is freely, showing perfect mobility, therefore strand crystallization ability is high, and crystalline texture is piled up fine and close regular.But actual synthesis liquid crystal polyester is due to starting monomer structure or the difference of ratio, the size of monomer autohemagglutination degree, molecular weight and the change of strand sequential structure, molecule segment is the most uniformly and strand is the most regular, the entanglement of strand or the height of degree of branching, the height of rotatory power in strand, the locomitivity of strand, the impact of the factors such as preparation process, thus there is bigger difference in the molecular chain structure that have impact on the liquid crystal polyester finally prepared, its strand arrangement crystallization behavior and the destruction generation large change of crystal structure, show that the melting enthalpy of DSC has certain fluctuation in crystallization enthalpy change, and the architectural feature of strand has been reacted in the fluctuation of this enthalpy change just, and the mobility variations of the liquid crystal polyester macroscopic view resulted from.
The present invention is found by research, when the double enthalpy of the DSC of liquid crystal polyester than Δ H more than or equal to 0.05, less than or equal to 0.9, especially more than or equal to 0.1 to during less than or equal to 0.6, HBA or HNA autohemagglutination segment or strand crosslinking substantially weaken, show higher mobility, melting characteristic is excellent, and the forming stability of small-sized thin molded article is high, when Δ H is higher than 0.9, then due to molecular chain structure and the change of crystallization behavior, cause its processing fluidity poor.
In order to complete the preparation one high fluidity liquid crystal polyester of the present invention, the melting viscosity of liquid crystal polyester is 10Pa.s-35Pa.s, preferably 15Pa.s-25Pa.s, and melting viscosity uses capillary rheometer test, 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 heat resistance, the fusing point of liquid crystal polyester should be the highest, but add the heating efficiency of former in man-hour in view of polymer melting, and the fusing point of liquid crystal polymer of the present invention is 250 DEG C-340 DEG C, preferably 270 DEG C-330 DEG C.Fusing point uses DSC to record, to be warmed up to the maximum temperature of fusing point+30 DEG C under the ramp rate conditions of 20 DEG C/min from room temperature, it is cooled to room temperature with the speed of 20 DEG C/min again after stopping 3min at this temperature, test sample is warmed up to the maximum temperature of fusing point+30 DEG C again with the heating rate of 20 DEG C/min after at room temperature stopping 3min, obtain the second time melting curve of liquid crystal polyester, choose this curve peak melting and be fusing point.
The content of each construction unit of the present invention can calculate by the following method: 500mg liquid crystal polyester or its moulding compound is measured to 25ml volumetric flask, and adding 2.5ml concentration is the NaOH/CH of 5mol/L3OH solution, adds 10ml except water dimethyl sulfoxide (DMSO).At a temperature of 60 DEG C, nitrogen atmosphere, thoroughly hydrolysis shakes up more than 18h, is dissolved in water and is acidified postlyophilization with hydrochloric acid.Take suitable quantity of water hydrolysis products to NMR(nuclear magnetic resonance) in test tube, carry out 1H-NMR mensuration, have the peak area ratio deriving from each construction unit to be 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 and 6-Hydroxy-2-naphthoic acid as raw material, under the effect of acylating agent, carry out acylation reaction, 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; acetic acid and unreacted acetic anhydride molecule is discharged rapidly from rectifying column; 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 granulation, solid phase container carries out solid phase and obtains liquid crystal polyester particle.
Phenolic hydroxyl group contained in above-mentioned raw materials monomer is preferably acylated with fatty acid anhydride before melt polycondensation.Fatty acid anhydride is not particularly limited, any one in acetic anhydride, propionic andydride, butyric anhydride, valeric anhydride, 2 ethyl hexanoic acid acid anhydride, dichloroacetic acid acid anhydride, dibromoacetic acid acid anhydride, difluoroacetic acid acid anhydride, maleic anhydride and succinyl oxide can be used, it is also possible to use with two or more mixture.Consider from production cost angle, preferably acetic anhydride, propionic andydride or butyric anhydride, more preferably acetic anhydride.The amount of fatty acid anhydride used is (1～1.2) with the mol ratio of phenolic hydroxyl group: 1, from producing relatively low degassing and the consideration of proper alignment foaming characteristic angle, preferably 1.02～1.10 times equivalents of the consumption of fatty acid anhydride.
nullThe preparation method of liquid crystal polyester described above，First stage is the acylation reaction stage，The phenolic hydroxyl group of main monomer component is carried out acylation reaction by acylating agent，Acylation process is mainly characterized by，In acylation process, by the way of nitrogen pressurizes, the pressure of reactor is maintained at 0.2MPa-0.6MPa，Wherein keep the size of pressure without specific restriction，But acylation reaction temperature must be controlled in the acylated temperature range of technological requirement，Its objective is to make acetic anhydride and acetic acid product acutely seethe with excitement by the way of pressurization，Owing to the self-polymeric reaction of P-hydroxybenzoic acid acylate produces acetic acid，Increase acetic gas volume，And pressure increase causes chemical reaction to carry out towards the direction that gas volume reduces，Therefore this self-polymeric reaction is by moderate inhibition，The acetic anhydride simultaneously seethed with excitement adds and the probability of monomer collision，Ensure that the balance of the acylation reaction of phenolic hydroxyl group.Second stage is the ester interchange polymerization stage, and this stage, whole course of reaction was Depressor response, vacuumizes and is decompressed to 10KPa-30KPa, wherein reduces pressure and is bled realization by vavuum pump, and the size of its pressure is not particularly limited, but must is fulfilled for the requirement of programmed rate.After acylation terminates, require that acetic acid molecule to be discharged rapidly, to meet the requirement being rapidly heated, owing to the nitrogen in acylated stage pressurizes, acetic acid molecule is gasified mist formation in a large number, bleed decompression by vavuum pump, substantial amounts of acetic acid and unreacted acetic anhydride are discharged from reactor, the acetic acid discharged 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, now strengthen heating rate, the reaction temperature making reactor be brought rapidly up to 200 DEG C or more than, enter the acylate group of phenolic hydroxyl group and 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 after reaction temperature arrives reaction maximum temperature, increase the vacuum of reactor, be decompressed to 50Kpa-100 the most further
Kpa so that the accessory substance such as little molecules such as phenol that reaction produces persistently is discharged under the effect of decompression from reactor, reduces strand rearrangement or branched probability, thus reduces the cross-linking reaction of strand.Acylation reaction is generally reacted 30 minutes～20 hours at 100 DEG C～180 DEG C, preferably can react 40 minutes～5 hours at 120 DEG C～160 DEG C.Described melt polycondensation can be carried out under the effect of catalyst, and catalyst uses conventionally known polymerization catalyst for polyester, can be metallic salt catalyst, such as potassium acetate, sodium acetate, magnesium acetate, zinc acetate, antimony oxide, butyl titanate etc..
Described melt polycondensation can be carried out under inert gas atmosphere；Polycondensation can be carried out in intermittently or serially mode or combination.After acylation reaction terminates, 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 the melt polycondensation stage；Melt polycondensation is carried out under 130 DEG C～400 DEG C of temperature ranges, preferably carries out under 160 DEG C～370 DEG C of temperature ranges, and 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.Vertical polymerization tank is preferably used, and paddle can be turbine impellers, double helix blade, multistage paddle blade, preferably turbine impellers.
After described melt polycondensation, from the viewpoint of easily being discharged from polymerization tank by the prepolymer of molten condition, the melting viscosity of prepolymer is preferably at below 10Pa s.Melting viscosity uses the test of Dynisco LCR7000 type capillary rheometer, and 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, in aggregation container, i.e. add inert gas and increase pressure, the generation of side reaction can be suppressed, suppressing the increase (melting viscosity of suppression prepolymer) of prepolymer molecular weight simultaneously.The equipment discharging prepolymer in the molten state may select valve, extruder and gear pump, solidify described prepolymer, with a direction, it is transmitted continuously simultaneously, may utilize wire cutter, sheet material cutting machine or pulverizer in direction of transfer downstream and cut or pulverize.There is no particular restriction, preferably at 0.1mm～5mm for the prepolyer granule obtained after cutting or being broken or powder.
It addition, acylation reaction can be carried out continuously with ester interchange polymerization in same reactor, it is also possible to carry out in differential responses container.
Described solid phase is preferably at vacuum 0.1Pa～50KPa, or carries out under the conditions of the inert protective gas such as logical nitrogen, polymerization temperature about 0～340 DEG C, 0.5 hour reaction time～40 hours.Solid phase can be carried out under stirring or the inactive state without stirring.
Lot of experimental data according to the present invention shows, monomer autohemagglutination occurs mainly under cryogenic conditions, and such as the temperature below 200 DEG C, the crosslinking of strand etc. is reacted and is then concentrated mainly under hot conditions, such as more than 300 DEG C；Therefore use preferred preparation technology, control the reaction of these two temperature sections well, be the key controlling the arrangement of strand sequential structure, be 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 control the reaction of each temperature section, it is to avoid owing to monomer autohemagglutination or strand cross-link the processing fluidity problem caused.And interpretation is found, use the liquid crystal polyester prepared of present invention process and moulding compound thereof through DSC to crystallization enthalpy and the test of melting enthalpy, when double enthalpys are in a preferred range than Δ H, all show higher mobility, but when double enthalpys are higher than the preferred scope of the present invention than Δ H, then due to molecular chain structure and the change of crystalline texture, processing fluidity is deteriorated.
Polymerization technique after adjustment is mainly characterized by being divided into reaction two stages, the acylated stage of first stage i.e. monomer, and for pressurization pressurize reaction in acylation process, its pressure is maintained at 0.2
MPa-0.6MPa；Second stage is the ester interchange polymerization stage, and the whole process of this elementary reaction is Depressor response, vacuumizes and is decompressed to 10KPa-30KPa.The purpose of technique using this pressurization decompression to combine seeks to effectively resolve the problem of a series of side reactions that two reaction temperature sections produce, thus prepares liquid crystal polyester and the moulding compound thereof with excellent processing fluidity.
Present invention also offers a kind of liquid crystal polyester moulding compound, including liquid crystal polyester, the reinforcer of 1 weight portion-70 weight portion and other auxiliary agents of 0-20 weight portion and/or other polymer of 30 weight portion-99.9 weight portions；Wherein,
Described liquid crystal polyester is made up of the constitutional repeating unit of following formula [I] and [II]:
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 50mol%, is preferably greater than equal to 66mol%, less than or equal to 85mol%；Amount derived from the construction unit [II] of 6-Hydroxy-2-naphthoic acid is less than or equal to 50mol%, is preferably greater than equal to 15mol%, less than or equal to 34mol%；
Wherein use means of differential scanning calorimetry DSC test, it is warmed up to the maximum temperature of fusing point+30 DEG C with the heating rate of 20 DEG C/min from room temperature, it is down to room temperature with the speed of 20 DEG C/min again after stopping 3min at this temperature, obtain the crystallization curve of liquid crystal polyester, choose crystallization onset temperature and the crystallization end temp of peak crystallization, and calculate peak crystallization area and be H(crystallization enthalpy)；Test sample is warmed up to the maximum temperature of fusing point+30 DEG C again with the heating rate of 20 DEG C/min after at room temperature stopping 3min, obtain the second time melting curve of liquid crystal polyester, choose the melt initiation temperature degree of melting peak and melted end temp, and calculate melting peak area and be H(melting enthalpy), this liquid crystal polyester meets the double enthalpys defined by following formula (1) than Δ H more than or equal to 0.05, less than or equal to 0.9, preferably greater than or equal to 0.1 to less than or equal to 0.6；
(1) Δ H=H(melting enthalpy)/H(crystallization enthalpy).
Liquid crystal polyester moulding compound of the present invention is owing to adding various fillers, its mobility is also affected the mobility showing slightly below resin by filler, the double enthalpys causing moulding compound can somewhat improve than Δ H, but contrast test data find, when double enthalpys of moulding compound are less than 1.0 than Δ H, its processing fluidity is still better than the liquid-crystalline polyester composition in contrast test.
Liquid crystal polyester moulding compound of the present invention, use means of differential scanning calorimetry DSC test, it is warmed up to the maximum temperature of fusing point+30 DEG C with the heating rate of 20 DEG C/min from room temperature, it is down to room temperature with the speed of 20 DEG C/min again after stopping 3min at this temperature, obtain the crystallization curve of liquid crystal polyester moulding compound, choose crystallization onset temperature and the crystallization end temp of peak crystallization, and calculate peak crystallization area and be H(crystallization enthalpy)；Test sample is warmed up to the maximum temperature of fusing point+30 DEG C again with the heating rate of 20 DEG C/min after at room temperature stopping 3min, obtain the second time melting curve of liquid crystal polyester moulding compound, choose the melt initiation temperature degree of melting peak and melted end temp, and calculate melting peak area and be H(melting enthalpy), this liquid crystal polyester moulding compound meets the double enthalpys defined by following formula (1) than Δ H more than or equal to 0.1, less than 1.0, preferably greater than or equal to 0.2 to less than or equal to 0.9；
(1) Δ H=H(melting enthalpy)/H(crystallization enthalpy).
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 within the above range time, liquid-crystalline polyester composition not only shows preferable melt-processed mobility, and shows high heat distortion temperature and high rigidity.
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 weight portion-50 weight portions, more preferably 15 weight portion-40 weight portions；
Described reinforcer is inorganic reinforcing filler or organic reinforcing fillers.
Described inorganic reinforcing filler includes but are not limited to one or more of glass fibre, potassium titanate fibre, metalclad glass fibre, ceramic fibre, wollastonite fibre, metallic carbide fibres, metal-cured fiber, asbestos fibre, alumina fibre, silicon carbide fibre, gypsum fiber or boron fibre, preferably glass fibre.Use glass fibre not only can improve the mouldability of liquid-crystalline polyester composition, and can improve mechanical property such as hot strength, bending strength or bending modulus, and raising heat resistance such as thermoplastic resin composition carries 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 average grain diameter is 0.001 μm-50 μm, when reinforcer average grain diameter less than 0.001 μm will cause liquid-crystal polyester resin difference melt processable；When the average grain diameter of reinforcer is more than 50 μm, bad injection-molded article appearance will be caused.It is selected from potassium titanate crystal whisker, ZnOw, aluminium borate whisker, talcum powder, carbon black, gypsum, asbestos, zeolite, sericite, kaolin, montmorillonite, clay, lithium montmorillonite, synthetic mica, alumino-silicate, silica, titanium oxide, aluminum oxide, zinc oxide, zirconium oxide, iron oxide, calcium carbonate, magnesium titanate, dolomite, aluminum sulfate, barium sulfate, magnesium sulfate, calcium carbonate, mica, silica flour, magnesium hydroxide, calcium hydroxide, aluminium hydroxide, bead, ceramic bead, one or more of boron nitride or carborundum.
In the liquid-crystalline polyester composition of embodiments of the present invention, in the range of the effect not damaging the present invention, it is also possible to coordinate selected from antioxidant, heat stabilizer, ultra-violet absorber, lubricant, releasing agent, the common processing aid that comprises in dyestuff or the colouring agent of pigment, plasticizer, antistatic additive.Maybe can coordinate the polymer beyond the liquid crystalline polyester of other structures or liquid crystal polyester, 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 such 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, the most specifically limit, can use dry type blending, solution mixing method, the polymerization of liquid crystalline polyester is interpolation, melting mixing etc., the most preferably melting mixing.Such as kneader, uniaxially or biaxially extruder, rubber-roller machine etc., biaxial extruder is wherein preferably used.The temperature of melting mixing is more than the fusing point of liquid crystal polyester, fusing point less than+50 DEG C.
As compounding process, it is possible to use put into liquid crystal polyester, reinforcer, other processing aids in the lump to carry out mixing method from rear dress charger；Liquid crystal polyester and other processing aid agent can also be penetrated from rear dress charger, add reinforcer from side charger and carry out mixing method, high concentration can also be prepared and comprise the liquid crystalline polyester composition mother particle of liquid crystalline polyester and other processing aids, then by master batch and liquid crystal polyester, reinforcer carries out any one method of the method etc. of the mixing concentration to become regulation.
The liquid-crystalline polyester composition of embodiments of the present invention by carrying out injection moulding, the known melt molding product such as injection compression molding, compression forming, extrusion molding, blow molding, compressing spinning.Products formed described here, can be the various filaments etc. such as the various membrane products such as injection-molded article, extrusion molding article, compressing product, sheet, pipe, non-stretched film, single axle drawn membrane, biaxially oriented film, undrawn yarn, super drawing silk.In the case of injection molding, the effect of the present invention can significantly be obtained, the most preferably.
nullLiquid crystalline polyester or the products formed of liquid crystal polyester moulding compound formation that the present invention is obtained can have following application，With various gears、Various housings、Sensor、LED lamp、Connector、Socket、Resistor、Casing of relay、Relay base、Relay roll、Switch、Coil axle、Capacitor、Variable condenser housing、Optical pickup unit、Resonator、Various terminal boards、Transformer、Plug、Printed wiring board、Tuner、Loudspeaker、Microphone、Head type headphones、Miniature motor、Magnetic head base、Power model、Shell、Semiconductor、Liquid crystal display component、FDD bracket、FDD chassis、HDD parts、Motor brush holder、Parabola antenna、The electrical and electronic parts that computer associated components etc. are representative、With VTR parts、TV part、Flatiron、Hair dryer、Electric cooker parts、Microwave oven component、Sound part、Audio frequency、Laser disk、The speech ciphering equipment parts such as CD、Illuminace component、Parts of refrigerator、Air supply rate、Typewriter parts、The family that word processor parts etc. are representative、Enterprise's electric product parts、Office computer associated components、Telephone set associated components、Facsimile machine associated components、Duplicator associated components、Washing fixture、Oilless bearing、Stern bearing、The various bearings such as water middle (center) bearing、Motor component、With igniter、The mechanical associated components that typewriter etc. are representative、With microscope、Binoculars、Camera、The optical device that clock and watch etc. are representative、Precision optical machinery associated components；nullAlternating current generator terminal、Alternating current generator connector、IC adjuster、Light modulator potentiometer base、The various valves such as exhaust air valve、Fuel associates、Exhaust system、The various pipes of air-breathing system、Inlet jet breather pipe、Inlet manifold、Petrolift、Engine cool water swivel、Vaporizer main body、Vaporizer spacer、Exhaust gas sensor、Cooling water sensor、Oil temperature sensor、TPS、Crankshaft position sensor、Mass air flow sensor、Brake pad abrasion sensor、Idle call thermostat base、Air conditioning electricity motivation insulator、The on-vehicle motor insulators such as motorized window、Warmer heated airflow control valve、Radiator fan motor brush carrier、Water pump vane、Turbo blade、Wiper motor associated components、Ignition distributor、Starter switch、Starter relay、Transmission device wire harness、Window cleaning device nozzle、Air-conditioning panel switch substrate、Fuel association magnetic valve coil、Fuse connector、Loudspeaker terminal、Parts of electric insulation board、Stepping motor rotor、Lamp ring、Lamp socket、Lamp reflector、Lamp housing、Brake piston、Solenoid bobbin、Engine oil filter、The automobiles such as ignition housings、Vehicle associated components etc.，At printed wiring board，In small-sized thin-walled electronic device etc. particularly useful.
The present invention compared with prior art, has the advantages that
(1) present invention is found by research, the double enthalpy of the DSC of the liquid crystal polyester of the present invention is more than or equal to 0.05 than Δ H, less than or equal to 0.9, the structure that there is specific strand due to it and crystalline state, therefore there is higher mobility, melting characteristic is excellent, and the forming stability of small-sized thin molded article is high.
(2) present invention is in whole building-up process; in conjunction with pressurization and the polymerization technique of decompression; can effectively control the acylated efficiency of hydroxyl; and effectively stop monomer autohemagglutination in the process being polymerized; the entanglement of strand; the generation of the side reactions such as branched crosslinking, controls the ordered arrangement of the strand of liquid crystal polyester, prepares liquid crystal polyester and the moulding compound thereof with higher mobility.
(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
Other auxiliary agents such as each raw material, acylating agent, catalyst, glass fibre, mica and the calcium stearate that the embodiment of the present invention is used derive from commercial.
Performance characterization necessary in the present invention and method of testing thereof:
(1) fusing point and melting enthalpy, crystallization enthalpy test: use NETZSCH
Company DSC 200 F3 records, it is warmed up to the maximum temperature of fusing point+30 DEG C with the heating rate of 20 DEG C/min from room temperature, it is cooled to room temperature with the speed of 20 DEG C/min again after stopping 3min at this temperature, obtain crystallization curve, choose crystallization onset temperature and the crystallization end temp of peak crystallization, and calculate peak crystallization area and be H(crystallization enthalpy)；Test sample is warmed up to the maximum temperature of fusing point+30 DEG C again with the heating rate of 20 DEG C/min after at room temperature stopping 3min, obtain the second time melting curve of polyester, choose this curve peak melting and be fusing point, choose the melt initiation temperature degree of melting peak and melted end temp, and calculate melting peak area and be H(melting enthalpy), double enthalpys are calculated as follows than Δ H:
Δ H=H(melting enthalpy)/H(crystallization enthalpy).
(2) mobility: the length of the bar-shaped thin slice injection molding body using the widest * thickness to be 5*0.45mm is to characterize the mobility of liquid crystal polyester, injection temperature is near fusing point, by the length mean value 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, shows that its mobility is the best.
(3) melt viscosity: using DyniscoLCR7001 type capillary rheometer to test, port mould diameter is 1mm, a length of 40mm, and described liquid crystal polyester more than its melt temperature 20 DEG C, shear rate is 1000s-1Under the conditions of viscosity be melt viscosity.
Embodiment
1
In the polymerizing reactor equipped with agitator, reflux condenser, monomeric charge mouth, nitrogen inlet, thermometer and torque sensor, add following raw material monomer, acylating agent, catalyst.
(I) P-hydroxybenzoic acid 911.7 grams (66 mol %) HBA
(II) 6-Hydroxy-2-naphthoic acid 639.8 grams (34mol %) HNA
Acylating agent: acetic anhydride 1020 grams
Catalyst: magnesium acetate 95 milligrams
After having fed intake, by the atmosphere in nitrogen thorough displacement reaction container, under logical nitrogen protection, the temperature of reaction system is increased to 140 DEG C, and to keep nitrogen pressure be 0.2MPa, maintain this temperature reflux to carry out acylation reaction in 2 hours；After acylation reaction terminates; drive vavuum pump and reacting kettle inner pressure is depressurized to 10KPa-30KPa; acetic acid and unreacted acetic anhydride molecule is discharged rapidly from rectifying column; to meet the technological requirement being brought rapidly up; when acetic acid reception amount arrives more than the 50% of theoretical value; it is brought rapidly up to 200 DEG C; keep this reduced pressure and reaction system was warming up in 6 hours maximum temperature 325 DEG C; period persistently discharges acetic acid particularly phenol etc. and causes strand to reset and branched small molecular by product, is then decompressed to 50KPa in 30 minutes；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, be then less than 200Pa in vacuum
Under in 10 hours, be heated to 250 DEG C by room temperature, and at this temperature maintain 10 hours；By the product obtained by polarized light microscope observing said method, find that it is can to show optically anisotropic liquid crystal polymer in molten state.The fusing point of this liquid crystal polyester, melt viscosity, double enthalpy ratios, bar-shaped injection molding body length, it is listed in table 1.
Embodiment 2-5 :According to the formula of table 1, after acylation reaction terminates, drive vavuum pump and reacting kettle inner pressure is depressurized to 10KPa
-30KPa, acetic acid and unreacted acetic anhydride molecule is discharged rapidly from rectifying column, to meet the technological requirement being brought rapidly up, when acetic acid reception amount arrives more than the 50% of theoretical value, it is brought rapidly up to 210 DEG C, keeping this reduced pressure and reaction system was warming up in 6 hours maximum temperature 330 DEG C, period persistently discharges acetic acid particularly phenol etc. and causes strand to reset and branched small molecular by product, is then decompressed to 60KPa in 30 minutes；Remaining is with embodiment 1；The fusing point of this liquid crystal polyester, melt viscosity, double enthalpy ratios, bar-shaped injection molding body length is shown in Table 1.
Embodiment 6-12 :According to the formula of table 1, after acylation reaction terminates, drive vavuum pump and reacting kettle inner pressure is depressurized to 10KPa
-30KPa, acetic acid and unreacted acetic anhydride molecule is discharged rapidly from rectifying column, to meet the technological requirement being brought rapidly up, when acetic acid reception amount arrives more than the 50% of theoretical value, it is brought rapidly up to 220 DEG C, keeping this reduced pressure and reaction system was warming up in 6 hours maximum temperature 335 DEG C, period persistently discharges acetic acid particularly phenol etc. and causes strand to reset and branched small molecular by product, is then decompressed to 70KPa in 30 minutes；Remaining is with embodiment 1；The fusing point of this liquid crystal polyester, 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, under logical nitrogen protection, the temperature of reaction system is increased to 140 DEG C, maintains this temperature reflux to carry out acylation reaction in 2 hours；After acylation reaction terminates, discharging acetic acid and unreacted acetic anhydride molecule from rectifying column, while heating up and reaction system being warming up in 6 hours maximum temperature 325 DEG C, period persistently discharges acetic acid, was then decompressed to 30KPa in 30 minutes；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, be then less than 200Pa in vacuum
Under in 10 hours, be heated to 250 DEG C by room temperature, and at this temperature maintain 10 hours；By the product obtained by polarized light microscope observing said method, find that it is can to show optically anisotropic liquid crystal polymer in molten state.The fusing point of this liquid crystal polyester, melt viscosity, double enthalpy ratios, bar-shaped injection molding body length, it is listed in table 1.
Table 1
By the above results it can be seen that double enthalpys are than Δ H more than or equal to 0.05 in embodiment, the liquid crystal polyester less than or equal to 0.9, bar-shaped injection molding body length, apparently higher than comparative example, illustrates that the liquid crystal polyester in embodiment has high mobility.
Additionally, from embodiment and comparative example it is also seen that, even if it is identical in starting monomer structure, ratio, under conditions of melt viscosity is similar, liquid crystal polyester in the range of different double enthalpy ratios, due to its its molecular chain structure and the difference of crystal habit, bar-shaped injection molding body length has notable difference, and the liquid crystal polyester i.e. with different double enthalpy ratio can show different mobility.
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, after 150 DEG C of vacuum drying carrying out more than 12h, high-speed mixer is utilized to join extruder by resin and auxiliary agent from twin-screw extrusion owner's spout, proportionally by glass fibre and mica, other auxiliary agents such as calcium stearate join extruder from twin-screw extrusion pusher side spout, through melting mixing, suitable barrel temperature is selected to extrude, granulation, ring-type cooling air cooling at sufficiently long air stream solidifies, and obtains liquid-crystalline polyester composition；Testing the fusing point of liquid-crystalline polyester composition, melt viscosity, double enthalpy ratios respectively, bar-shaped injection molding body length testing result is listed in table 2.
Table 2
Be can be seen that by the result of table 2, owing to have employed double enthalpy than Δ H more than or equal to 0.05, liquid-crystal polyester resin less than or equal to 0.9, its molecular chain structure and crystal habit there occurs large change, the mobility of embodiment liquid crystal polyester moulding compound substantially relatively comparative example is high, is 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] and [II]:
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 50mol%, is preferably greater than equal to 66mol%, less than or equal to 85mol%；Amount derived from the construction unit [II] of 6-Hydroxy-2-naphthoic acid is less than or equal to 50mol%, is preferably greater than equal to 15mol%, less than or equal to 34mol%；
Wherein use means of differential scanning calorimetry DSC test, it is warmed up to the maximum temperature of fusing point+30 DEG C with the heating rate of 20 DEG C/min from room temperature, it is down to room temperature with the speed of 20 DEG C/min again after stopping 3min at this temperature, obtain the crystallization curve of liquid crystal polyester, choose crystallization onset temperature and the crystallization end temp of peak crystallization, and calculate peak crystallization area and be H(crystallization enthalpy)；Test sample is warmed up to the maximum temperature of fusing point+30 DEG C again with the heating rate of 20 DEG C/min after at room temperature stopping 3min, obtain the second time melting curve of liquid crystal polyester, choose the melt initiation temperature degree of melting peak and melted end temp, and calculate melting peak area and be H(melting enthalpy), this liquid crystal polyester meets the double enthalpys defined by following formula (1) than Δ H more than or equal to 0,05, less than or equal to 0.9, preferably greater than or equal to 0.1 to less than or equal to 0.6；
(1) Δ H=H(melting enthalpy)/H(crystallization enthalpy).
Liquid crystal polyester the most according to claim 1, it is characterised in that the melting viscosity of described liquid crystal polyester is 10Pa.s-35Pa.s, it is preferably 15Pa.s-25Pa.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 characterized in that: the fusing point of described liquid crystal polyester is 250 DEG C-340 DEG C, it is preferably 270 DEG C-330 DEG C, fusing point uses DSC to record, to be warmed up to the maximum temperature of fusing point+30 DEG C under the ramp rate conditions of 20 DEG C/min from room temperature, it is cooled to room temperature with the speed of 20 DEG C/min again after stopping 3min at this temperature, test sample is warmed up to the maximum temperature of fusing point+30 DEG C again with the heating rate of 20 DEG C/min after at room temperature stopping 3min, obtain the second time melting curve of liquid crystal polyester, choose this curve peak melting and be 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 and 6-Hydroxy-2-naphthoic acid as raw material, under the effect of acylating agent, carry out acylation reaction, 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; acetic acid and unreacted acetic anhydride molecule is discharged rapidly from rectifying column; when acetic acid reception amount arrives more than the 50% of theoretical value; be rapidly heated to 200 DEG C or more than; keeping this reduced pressure and by reaction system temperature programming to reaction maximum temperature, be decompressed to 50Kpa-100 Kpa the most further, melt polycondensation obtains prepolymer；
C, by prepolymer cooling and solidifying and granulation, solid phase container carries out solid phase and obtains liquid crystal polyester particle.
The preparation method of liquid crystal polyester the most according to claim 4, it is characterised in that in step a, the temperature of described acylation reaction is 100 DEG C～180 DEG C, preferably 120 DEG C～160 DEG C, and the reaction time is 30 minutes～20 hours, preferably 40 minutes～5 hours.
The preparation method of liquid crystal polyester the most according to claim 4; it is characterized in that; in step b; after acylation reaction terminates; 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 the melt polycondensation 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 is in vacuum
Carrying out under the conditions of 0.1Pa～50KPa, or the inert protective gas such as logical nitrogen, polymerization temperature is 0～340 DEG C, and the reaction time is 0.5 hour～40 hours.
8. comprise a liquid crystal polyester moulding compound for liquid crystal polyester described in any one of claim 1-3, including liquid crystal polyester, the reinforcer of 1 weight portion-70 weight portion and other auxiliary agents of 0-20 weight portion and/or other polymer of 30 weight portion-99.9 weight portions；Wherein,
Described liquid crystal polyester is made up of the constitutional repeating unit of following formula [I] and [II]:
In terms of repetitive total amount 100mol%, the amount of construction unit [I] is more than or equal to 50mol%, is preferably greater than equal to 66mol%, less than or equal to 85mol%；The amount of construction unit [II] is less than or equal to 50mol%, is preferably greater than equal to 15mol%, less than or equal to 34mol%；
Wherein use means of differential scanning calorimetry DSC test, it is warmed up to the maximum temperature of fusing point+30 DEG C with the heating rate of 20 DEG C/min from room temperature, it is down to room temperature with the speed of 20 DEG C/min again after stopping 3min at this temperature, obtain the crystallization curve of liquid crystal polyester, choose crystallization onset temperature and the crystallization end temp of peak crystallization, and calculate peak crystallization area and be H(crystallization enthalpy)；Test sample is warmed up to the maximum temperature of fusing point+30 DEG C again with the heating rate of 20 DEG C/min after at room temperature stopping 3min, obtain the second time melting curve of liquid crystal polyester, choose the melt initiation temperature degree of melting peak and melted end temp, and calculate melting peak area and be H(melting enthalpy), this liquid crystal polyester meets the double enthalpy ratios defined by following formula (1) more than or equal to 0,05, less than or equal to 0.9, preferably greater than or equal to 0.1 to less than or equal to 0.6；
(1) Δ H=H(melting enthalpy)/H(crystallization enthalpy).
Liquid crystal polyester moulding compound the most according to claim 8, it is characterized in that, the melting viscosity of described liquid crystal polyester is 10Pa.s-35Pa.s, it is preferably 15Pa.s-25Pa.s, melting viscosity uses capillary rheometer test, 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 moulding compound the most according to claim 8, it is characterized in that: the fusing point of described liquid crystal polyester is 250 DEG C-340 DEG C, it is preferably 270 DEG C-330 DEG C, fusing point uses DSC to record, to be warmed up to the maximum temperature of fusing point+30 DEG C under the ramp rate conditions of 20 DEG C/min from room temperature, it is cooled to room temperature with the speed of 20 DEG C/min again after stopping 3min at this temperature, test sample is warmed up to the maximum temperature of fusing point+30 DEG C again with the heating rate of 20 DEG C/min after at room temperature stopping 3min, obtain the second time melting curve of liquid crystal polyester, choose this curve peak melting and be fusing point.
11. liquid crystal polyester moulding compounds according to claim 8, it is characterised in that 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；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, described inorganic reinforcing filler includes but are not limited to one or more of glass fibre, potassium titanate fibre, metalclad glass fibre, ceramic fibre, wollastonite fibre, metallic carbide fibres, metal-cured fiber, asbestos fibre, alumina fibre, silicon carbide fibre, gypsum fiber or boron fibre, preferably glass fibre；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 characterized in that, described reinforcer be shaped as Non-fibrous, its average grain diameter is 0.001 μm-50 μm, selected from potassium titanate crystal whisker, ZnOw, aluminium borate whisker, talcum powder, carbon black, gypsum, asbestos, zeolite, sericite, kaolin, montmorillonite, clay, lithium montmorillonite, synthetic mica, alumino-silicate, silica, titanium oxide, aluminum oxide, zinc oxide, zirconium oxide, iron oxide, calcium carbonate, magnesium titanate, dolomite, aluminum sulfate, barium sulfate, magnesium sulfate, calcium carbonate, mica, silica flour, magnesium hydroxide, calcium hydroxide, aluminium hydroxide, bead, ceramic bead, one or more of boron nitride or carborundum.
13. liquid crystal polyester moulding compounds according to claim 8, it is characterised in that one or more in antioxidant, heat stabilizer, ultra-violet absorber, lubricant, releasing agent, colouring agent, plasticizer or antistatic additive of other auxiliary agents described.
14. liquid crystal polyester moulding compounds described in-13 any one according to Claim 8, it is characterized in that, use means of differential scanning calorimetry DSC test, it is warmed up to the maximum temperature of fusing point+30 DEG C with the heating rate of 20 DEG C/min from room temperature, it is down to room temperature with the speed of 20 DEG C/min again after stopping 3min at this temperature, obtain the crystallization curve of liquid crystal polyester moulding compound, choose crystallization onset temperature and the crystallization end temp of peak crystallization, and calculate peak crystallization area and be H(crystallization enthalpy)；Test sample is warmed up to the maximum temperature of fusing point+30 DEG C again with the heating rate of 20 DEG C/min after at room temperature stopping 3min, obtain the second time melting curve of liquid crystal polyester moulding compound, choose the melt initiation temperature degree of melting peak and melted end temp, and calculate melting peak area and be H(melting enthalpy), this liquid crystal polyester moulding compound meets the double enthalpy ratios defined by following formula (1) more than or equal to 0.1, less than 1.0, preferably greater than or equal to 0.2 to less than or equal to 0.9；
(1) Δ H=H(melting enthalpy)/H(crystallization enthalpy).
15. liquid crystal polyester moulding compound described in-14 any one application in electric field according to Claim 8.
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|---|---|---|---|---|
| US11917753B2 (en) | 2019-09-23 | 2024-02-27 | Ticona Llc | Circuit board for use at 5G frequencies |
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| US20060025561A1 (en) * | 2004-07-30 | 2006-02-02 | Polyplastics Co., Ltd. | Liquid crystalline polyester resin composition |
| CN104004170A (en) * | 2014-02-23 | 2014-08-27 | 华东理工大学 | Industrial preparation method for high-performance thermotropic liquid crystal polyester with homogeneous segmer structure |
| CN104098760A (en) * | 2013-04-12 | 2014-10-15 | 中国石油化工股份有限公司 | Method for inhibiting self-polymerization of PABA in preparation of thermally-induced PET-PHB liquid crystal polyester |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060025561A1 (en) * | 2004-07-30 | 2006-02-02 | Polyplastics Co., Ltd. | Liquid crystalline polyester resin composition |
| CN104098760A (en) * | 2013-04-12 | 2014-10-15 | 中国石油化工股份有限公司 | Method for inhibiting self-polymerization of PABA in preparation of thermally-induced PET-PHB liquid crystal polyester |
| CN104004170A (en) * | 2014-02-23 | 2014-08-27 | 华东理工大学 | Industrial preparation method for high-performance thermotropic liquid crystal polyester with homogeneous segmer structure |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US11917753B2 (en) | 2019-09-23 | 2024-02-27 | Ticona Llc | Circuit board for use at 5G frequencies |
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