CN109824875A - A kind of liquid crystal polyester - Google Patents
A kind of liquid crystal polyester Download PDFInfo
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- CN109824875A CN109824875A CN201811617502.3A CN201811617502A CN109824875A CN 109824875 A CN109824875 A CN 109824875A CN 201811617502 A CN201811617502 A CN 201811617502A CN 109824875 A CN109824875 A CN 109824875A
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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
- C08G63/02—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
- C08G63/78—Preparation processes
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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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/098—Metal salts of carboxylic acids
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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
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/38—Polymers
- C09K19/3804—Polymers with mesogenic groups in the main chain
- C09K19/3809—Polyesters; Polyester derivatives, e.g. polyamides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
Abstract
The invention discloses a kind of liquid crystal polyesters, are made of formula [I]-[IV] constitutional repeating unit；Wherein differential scanning calorimetry DSC is used to test, which meets the double enthalpys defined by following formula (1) and be more than or equal to 0.1 than Δ H, is less than or equal to 0.9, preferably greater than or equal to 0.2 to less than equal to 0.7.(1) Δ H=H(melting enthalpy)/H(crystallization enthalpy).The bis- enthalpys of the DSC of liquid crystal polyester of the invention are more than or equal to 0.1 than Δ H, are less than or equal to 0.9, and liquid crystal polyester mobility with higher, melting characteristic is excellent, and the forming stability of small-sized thin molded article is high, particularly suitable in thin-walled electronic articles.
Description
The application is Patent No. 201610068348.3, and applying date 2016.02.01, invention and created name is " a kind of
The divisional application of liquid crystal polyester and the moulding compound being made from it and its application ".
Technical field
The present invention relates to polymeric material field, in particular to a kind of liquid crystal polyester.
Background technique
Thermotropic liquid crystal polymer (TLCP) is used as a kind of high-performance special engineering plastics, has excellent mechanical performance,
Good mobility, heat resistance is resistant to chemical etching, fire-retardant and electrical insulation capability, at present in electronic apparatus and miniature precision thin-walled
The fields such as components are widely used.It is high-temperature fusion polymerization that it, which prepares generally use, but due to the autohemagglutination of the monomers such as HBA or
The branching cross-linking reaction of strand, causes the melt processable of final liquid crystal product and physical property poor, especially resin
Mobility be severely impacted, cause liquid crystal polyester moulding compound to occur the feelings such as mold filling is discontented in forming process
Condition has seriously affected application of the liquid crystal polymer in electronic apparatus thin wall parts.
For inhibiting the autohemagglutination of HBA, and in high temperature polymerization process, the research of the side reactions generation such as control crosslinking is always
Key subjects in scientific research and industry, such as patent CN1673249A, CN104004170 A, CN104098760A,
It is mentioned in CN104098761A by the way that 4- toluenesulfonic acid, the autohemagglutination of the method inhibition decarboxylic reaction and HBA of water or acetic acid is added
Reaction etc., the above method has some improvement to the inherent viscosity of liquid crystal polymer.
Such as above-mentioned patent, the inherent viscosity of liquid crystal polyester has become one general means of the industry at present, to table
Levy the relative molecular mass and molecular chain movement characteristic of liquid crystal polyester, the indirect reaction mobility of final liquid crystal polyester.However
The difference of inherent viscosity is not the single factor for influencing polymer flowability.The difference of starting monomer structure or ratio, monomer
The size of autohemagglutination degree, the variation of molecular weight and strand sequential structure, whether molecule segment is uniform, the entanglement or branch of strand
The height of change degree, the locomitivity and crystalline texture of strand and the speed of speed, preparation process etc. all can be to polymerizations
The mobility of object has an impact.
Differential scanning calorimetric analysis (DSC) is one of most common thermal-analysis instrumentation, for characterizing polymer melting crystallization
Process, reacted molecular chain structure and crystallization between relationship, the variation of molecular chain structure, directly determine DSC heating or
Melting or crystallization behavior during cooling.The applicant constantly studies it has further been found that particular melt crystallization enthalpy ratio is
Double enthalpys are shown excellent than the liquid crystal polyester in range due to structure and crystalline state with specific strand
Processing fluidity and mechanical performance.
Summary of the invention
The primary purpose of the present invention is that providing a kind of liquid crystal polyester of high fluidity, double enthalpys of the liquid crystal polyester are than Δ H
In particular range, there is the processing fluidity being obviously improved.
The present invention is achieved by the following technical solutions:
A kind of liquid crystal polyester is made of following formula [I]-[IV] constitutional repeating unit:
In terms of repetitive unit total amount 100mol%, the amount of the structural unit [I] derived from P-hydroxybenzoic acid is more than or equal to
40mol% is less than or equal to 80mol%；The amount of structural unit [II] derived from 4,4 '-'-biphenyl diphenols is more than or equal to 10mol%, small
In equal to 30mol%；Structural unit [III] derived from terephthalic acid (TPA) and the structural unit [IV] derived from M-phthalic acid
Total amount is more than or equal to 10mol%, is less than or equal to 32mol%；The amount and structural unit [III] and structural unit of structural unit [II]
[IV] the ratio between moles total number is 1:1, wherein being derived from the structural unit [IV] of M-phthalic acid and being derived from terephthalic acid (TPA)
Structural unit [III] molar ratio preferably 0.1 to 0.49, the mole percent of structural unit [I], [II], [III] and [IV] is total
Be 100%；
It is wherein tested using differential scanning calorimetry DSC, is warming up to+30 DEG C of fusing point from room temperature with the heating rate of 20 DEG C/min
Maximum temperature is down to room temperature again after stopping 3min at this temperature with the rate of 20 DEG C/min, and the crystallization for obtaining liquid crystal polyester is bent
Line, the crystallization onset temperature and crystallization for choosing peak crystallization terminate temperature, and calculating crystallization peak area is H(crystallization enthalpy)；It surveys
Test agent is stopped after 3min at room temperature and is warming up to+30 DEG C of fusing point of maximum temperature with the heating rate of 20 DEG C/min again, is obtained
To second of melting curve of liquid crystal polyester, the melt initiation temperature degree and melting for choosing melting peak terminate temperature, and calculate molten
Melting peak area is H(melting enthalpy), which meets the double enthalpys defined by following formula (1) and is more than or equal to 0.1 than Δ H, is less than
Equal to 0.9, preferably greater than or equal to 0.2 to less than be equal to 0.7；
(1) Δ H=H(melting enthalpy)/H(crystallization enthalpy).
The bis- enthalpys of DSC are the ratio of liquid crystal polyester crystal melt enthalpy and crystallization enthalpy than Δ H, and the physical significance of real reaction is
It is the complexity of the destruction of liquid crystal polyester crystal structure and strand crystallization and the relationship of liquid crystal polyester molecular chain structure.Crystallization row
For there are close ties with the structure feature of crystal melt behavior and strand, for ideal molecule interchain without interaction,
The resistances such as molecular chain structure is regular, and interior rotatory power is big, and flexibility is high, and the movement of strand at this time does not rub, strand
Freedom of motion shows perfect mobility, therefore strand crystallization ability is high, and crystalline texture is piled up fine and close regular.But it is practical
Liquid crystal polyester is synthesized due to starting monomer structure or the difference of ratio, the size of monomer autohemagglutination degree, molecular weight and strand sequence
The variation of array structure, whether uniform and strand is regular for molecule segment, the entanglement of strand or the height of degree of branching, point
The height of rotatory power in subchain, the locomitivity of strand, the influence of the factors such as preparation process, to affect
There are larger difference, strands to arrange crystallization behavior and crystal structure for the molecular chain structure for the liquid crystal polyester being finally prepared
Destruction vary widely, show in the melting enthalpy and crystallization enthalpy change of DSC that there is certain fluctuation, and this enthalpy change
Fluctuation exactly reacted the structure feature of strand, and mobility variations of the liquid crystal polyester macroscopic view resulted from.
The present invention passes through the study found that the bis- enthalpys of DSC when liquid crystal polyester are more than or equal to 0.1 than Δ H, less than or equal to 0.9, especially
It is shown higher being more than or equal to 0.2 to less than being equal to 0.7, HBA autohemagglutination segment or the obvious decrease of molecule chain branching crosslinking
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 molecule
The variation of chain structure and crystallization behavior causes its processing fluidity poor.
In order to complete a kind of high fluidity liquid crystal polyester for preparing of the invention, the melting viscosity of liquid crystal polyester is 10Pa.s-
35Pa.s, preferably 15Pa.s -30Pa.s, melting viscosity are tested using capillary rheometer, and test temperature is greater than fusing point 0-
30 DEG C, 1000 S of shear rate-1, using internal diameter 1mm, the mouth mold of length 40mm is measured.
From the viewpoint of heat resistance, the fusing point of liquid crystal polyester should be high as far as possible, but in view of polymer melting is processed
When molding equipment 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 is measured using DSC, is warming up to+30 DEG C of fusing point of highest under the ramp rate conditions of 20 DEG C/min from room temperature
Temperature is cooled to room temperature again after stopping 3min at this temperature with the rate of 20 DEG C/min, and test sample stops at room temperature
It is warming up to+30 DEG C of fusing point of maximum temperature after 3min with the heating rate of 20 DEG C/min again, obtains second of liquid crystal polyester
Melting curve, choosing this curve peak melting is fusing point.
The content of each structural unit of the present invention can be calculated by the following method: by 500mg liquid crystal polyester or its mould
Molding composition is measured into 25ml volumetric flask, and the NaOH/CH that 2.5ml concentration is 5mol/L is added3OH solution adds 10ml and removes
Water dimethyl sulfoxide.60 DEG C at a temperature of, nitrogen atmosphere, thoroughly hydrolysis shake up 18h or more, be dissolved in water and be acidified with hydrochloric acid
After be freeze-dried.Take appropriate hydrolysate to NMR(nuclear magnetic resonance) in test tube, 1H-NMR measurement is carried out, is had 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, includes the following steps:
A, under nitrogen pressurized conditions, with P-hydroxybenzoic acid, 4,4 '-'-biphenyl diphenols, terephthalic acid (TPA) and M-phthalic acid are
Raw material, carries out acylation reaction under the action of acylating agent, and the pressure is maintained at 0.2MPa-0.6MPa；
B, after acylation reaction, reacting kettle inner pressure is carried out to be decompressed to 10KPa-30KPa, acetic acid is discharged rapidly from rectifying column
And unreacted acetic anhydride molecule is rapidly heated when acetic acid reception amount reaches 50% or more of theoretical value to 200 DEG C or more,
It keeps this reduced pressure and by reaction system temperature programming to reaction maximum temperature, is then further decompressed to 50Kpa-100
Kpa, melt polycondensation obtain prepolymer；
C, prepolymer is cooled and solidified and is granulated, solid phase is carried out in solid phase container and obtains liquid crystal polyester particle.
Phenolic hydroxyl group contained in above-mentioned raw materials monomer is acylated with fatty acid anhydride preferably before melt polycondensation.For fatty acid
Acid anhydride is not particularly limited, and acetic anhydride, propionic andydride, butyric anhydride, valeric anhydride, 2 ethyl hexanoic acid acid anhydride, dichloroacetic acid acid anhydride, dibromo can be used
Any one of acetic anhydride, difluoroacetic acid acid anhydride, maleic anhydride and succinic anhydride can also be used with two or more mixtures.
Consider from production cost angle, preferably acetic anhydride, propionic andydride or butyric anhydride, more preferable acetic anhydride.The amount of fatty acid anhydride used with
The molar ratio of phenolic hydroxyl group is (1~1.2): 1, consider from lower degassing and proper alignment foaming characteristic angle is generated, the use of fatty acid anhydride
Measure preferably 1.02~1.10 times of equivalents.
The preparation method of liquid crystal polyester described above, first stage are the acylation reaction stage, and acylating agent is by principal monomer
The phenolic hydroxyl group of ingredient carries out acylation reaction, and acylation process is mainly characterized by, will in such a way that nitrogen pressurizes in acylation process
The pressure of reaction kettle is maintained at 0.2MPa-0.6MPa, wherein keeping the size of pressure without specific limitation, but must be by acylation reaction
Temperature controls in the acylation temperature range that technique requires, and the purpose is to make acetic anhydride and acetic acid product acute by way of pressurization
Strong boiling increases acetic gas volume since the self-polymeric reaction of P-hydroxybenzoic acid acylate generates acetic acid, and pressure increase is drawn
The direction that chemically reactive reduces towards gas volume carries out, therefore the self-polymeric reaction is by moderate inhibition, while the acetic acid to boil
Acid anhydride increases the probability with monomer collision, ensure that the balance of the acylation reaction of phenolic hydroxyl group.Second stage is ester interchange polymerization rank
Section, this stage entire reaction process are Depressor response, vacuumize and are decompressed to 10KPa-30KPa, wherein decompression passes through vacuum pumping
Gas realizes that the size of pressure is not particularly limited, but must satisfy the requirement of programmed rate.After acylation,
Acetic acid molecule is asked to be discharged rapidly, to meet the requirement being rapidly heated, due to the nitrogen pressurization in acylated stage, so that acetic acid molecule
A large amount of gasification mist formations, are evacuated by vacuum pump and depressurize, so that a large amount of acetic acid and unreacted acetic anhydride are discharged from reaction kettle, row
Acetic acid out flows into acetic acid receiving tank through heat exchanger cooling effect, when acetic acid reception amount reaches 50% or more of theoretical value, this
Shi Jia great heating rate is brought rapidly up the reaction temperature of reaction kettle to 200 DEG C or more, into phenolic hydroxyl group acylate group with
The condensation reaction of carboxylic acid group, to inhibit the autohemagglutination of monomer.In the ester interchange polymerization stage, by the way of decompression, and when reaction
After temperature reaches reaction maximum temperature, increases the vacuum degree of reaction kettle, be then further decompressed to 50Kpa-100 Kpa, so that
The by-product such as phenol small molecule that reaction generates persistently is discharged from reaction kettle under the action of decompression, reduces strand and resets
Or the probability of branching, to reduce the branching cross-linking reaction of strand.Acylation reaction usually reacts 30 points at 100 DEG C~180 DEG C
Clock~20 hour can preferably react 40 minutes~5 hours at 120 DEG C~160 DEG C.The melt polycondensation can be in the work of catalyst
It being carried out under, catalyst uses conventionally known polymerization catalyst for polyester, it can be metallic salt catalyst, such as potassium acetate,
Sodium acetate, magnesium acetate, zinc acetate, antimony oxide, butyl titanate etc..
The melt polycondensation can carry out under inert gas atmosphere；Polycondensation can be in intermittently or serially mode or combination side
Formula carries out.After acylation reaction, with the heating of 0.1 DEG C/min~150 DEG C/min rate, reaction kettle is made to be rapidly heated to 200
DEG C or more, into the melt polycondensation stage；Melt polycondensation carries out under 130 DEG C~400 DEG C temperature ranges, preferably 160 DEG C~
It is carried out under 370 DEG C of temperature ranges, wherein maximum temperature is more preferably+30 DEG C of fusing point of temperature of liquid crystal polyester.
Aggregation container used in the melt polycondensation can be the aggregation container with known form.It is preferable to use vertical
Formula polymerization tank, agitating paddle can be turbine impellers, double helix blade, multistage paddle blade, preferably turbine impellers.
After the melt polycondensation, for the easy prepolymer by molten condition from the viewpoint of being discharged in polymerization tank,
The melting viscosity of prepolymer is preferably below 10Pa s.Melting viscosity is surveyed using Dynisco LCR7000 type capillary rheometer
Examination, test temperature are 1000 S of shear rate greater than 30 DEG C of fusing point-1, using internal diameter 1mm, the mouth mold of length 40mm is measured.
After the melt polycondensation, the discharge of prepolymer is preferably carried out under inert atmosphere such as nitrogen atmosphere, i.e., to polymerization
Inert gas is added in container and increases pressure, the generation of side reaction can be inhibited, while inhibiting the increase of prepolymer molecular weight
(melting viscosity for inhibiting prepolymer).Valve, extruder and gear pump may be selected in the equipment that prepolymer is discharged in the molten state,
Solidify the prepolymer, while it continuously transmitted with a direction, direction of transfer downstream can using wire cutter,
Sheet material cutting machine or pulverizer are cut or are crushed.The prepolyer granule or powder for cutting or obtaining after broken have no special limit
System, preferably in 0.1mm~5mm.
In addition, acylation reaction can be carried out continuously with ester interchange polymerization in same reactor, it can also be in differential responses
It is carried out in container.
The solid phase is preferably in the inert protective gas condition such as vacuum degree 0.1Pa~50KPa or logical nitrogen
Lower progress, about 0~340 DEG C of polymerization temperature, the reaction time 0.5 hour~40 hours.Solid phase can stirring or it is without mixing
It is carried out under stationary state.
Lot of experimental data according to the present invention shows that monomer autohemagglutination occurs mainly under cryogenic conditions, such as 200 DEG C or less
Temperature, and the branching of strand crosslinking etc. reactions be then concentrated mainly under hot conditions, such as 300 DEG C or more；Therefore using excellent
The preparation process of choosing controls the reaction of this two temperature sections, is the key that control strand sequential structure arrangement, and guarantee
The liquid crystal polyester of preparation has the key of preferable processing fluidity.The present invention uses improved preparation process, effectively controls
The reaction of each temperature section, the processing fluidity problem caused by avoiding monomer autohemagglutination or the crosslinking of molecule chain branching.And it is right
Interpretation discovery to crystallization enthalpy and is melted using the liquid crystal polyester and its moulding compound of present invention process preparation through DSC
The test for melting enthalpy all shows higher mobility, but when double enthalpys are higher than than Δ H when double enthalpys are in a preferred range than Δ H
When preferred scope of the invention, then due to the variation of molecular weight structural and crystalline texture, processing fluidity is deteriorated.
Polymerization technique adjusted, which is mainly characterized by react, is divided into two stages, first stage, that is, monomer acylation rank
Section is pressurization pressure maintaining reaction in acylation process, and pressure is maintained at 0.2 MPa-0.6MPa；Second stage is ester interchange polymerization
Stage, this elementary reaction whole process are Depressor response, vacuumize and are decompressed to 10KPa-30KPa.It is mutually tied using this pressurization decompression
The purpose of the technique of conjunction seeks to the problem of effectively resolving a series of side reactions of two reaction temperature sections generation, to prepare
Provide the liquid crystal polyester and its moulding compound of excellent processing fluidity.
Compared with prior art, the present invention having the following beneficial effects:
(1) present invention pass through the study found that the bis- enthalpys of the DSC of liquid crystal polyester of the invention than Δ H more than or equal to 0.1, be less than or equal to
0.9, due to its structure and crystalline state with specific strand, mobility with higher, melting characteristic is excellent,
The forming stability of small-sized thin molded article is high.
(2) present invention, in conjunction with the polymerization technique of pressurization and decompression, can effectively control hydroxyl in entire synthesis process
Acylated efficiency, and effectively prevents monomer autohemagglutination, the entanglement of strand in the process of polymerization, the generation for the side reactions such as branching is crosslinked,
The liquid crystal polyester and its molding group of mobility with higher is prepared in the ordered arrangement for controlling the strand of liquid crystal polyester
Close object.
(3) preparation method of the invention is easy to operate, and product is easily obtained, and the production cycle is shorter, is suitable for industrialized production.
Specific embodiment
Each raw material, acylating agent, catalyst, glass fibre, mica and calcium stearate used by the embodiment of the present invention etc. its
His auxiliary agent derives from commercially available.
Necessary performance characterization and its test method in the present invention:
(1) fusing point and melting enthalpy, crystallization enthalpy test: being measured using 200 F3 of NETZSCH corporation DSC, from room temperature with
The heating rate of 20 DEG C/min is warming up to+30 DEG C of fusing point of maximum temperature, stops after 3min again with 20 DEG C/min at this temperature
Rate be cooled to room temperature, obtain crystallization curve, the crystallization onset temperature and crystallization for choosing peak crystallization terminate temperature, and calculate
Crystallizing peak area is H(crystallization enthalpy)；Test sample is stopped after 3min at room temperature again with the heating rate liter of 20 DEG C/min
Temperature arrives+30 DEG C of fusing point of maximum temperature, obtains second of melting curve of polyester, and choosing this curve peak melting is fusing point,
The melt initiation temperature degree and melting for choosing melting peak terminate temperature, and calculating melting peak area is H(melting enthalpy), double enthalpy ratios
Δ H is calculated as follows:
Δ H=H(melting enthalpy)/H(crystallization enthalpy).
(2) it mobility: uses poly- to characterize liquid crystal for the length of the rodlike thin slice injection molding body of 5*0.45mm having a size of wide * thickness
The mobility of ester, injection temperature is near fusing point, by the length average value of 30 rodlike thin slice injection molding bodies as parameter measure
The mobility of liquid crystal polyester and its moulding compound.Injecting condition under the same conditions, rodlike thin slice injection molding body length is longer,
Show that its mobility is better.
(3) it melt viscosity: is tested using DyniscoLCR7001 type capillary rheometer, port mould diameter is
1mm, length 40mm, the liquid crystal polyester is 20 DEG C more than its melting temperature, shear rate 1000s-1Under the conditions of it is viscous
Degree is melt viscosity.
Embodiment 1
It is anti-to the polymerization equipped with blender, reflux condenser, monomeric charge mouth, nitrogen inlet, thermometer and torque sensor
It answers in device, following raw material monomer, acylating agent, catalyst is added.
(I) 1180 grams of P-hydroxybenzoic acid (60 mol %) HBA
(II) 530.1 grams of 4,4 '-'-biphenyl diphenol (20mol %) BP
(III) 402.1 grams of terephthalic acid (TPA) (17mol%) TA
(IV) 70.9 grams of M-phthalic acid (3 mol%) IA
Acylating agent: 1527 grams of acetic anhydride
Catalyst: 115 milligrams of magnesium acetate
After the completion of feeding intake, the atmosphere in reaction vessel is thoroughly replaced with nitrogen, is led to the temperature liter of reaction system under nitrogen protection
Up to 150 DEG C, and keeping nitrogen pressure is 0.2MPa, maintains 2 hours progress acylation reactions of this temperature reflux；Acylation reaction terminates
Afterwards, it opens vacuum pump and reacting kettle inner pressure is depressurized to 10KPa-30 KPa, acetic acid and unreacted vinegar is discharged rapidly from rectifying column
Anhydride molecule, when acetic acid reception amount reaches 50% or more of theoretical value, is brought rapidly up with meeting the technique being brought rapidly up requirement
To 200 DEG C, keeps this reduced pressure and reaction system is warming up to 360 DEG C of maximum temperature in 6 hours, vinegar is during which persistently discharged
Acid especially phenol etc. causes strand to be retaken and the small molecular by product of branching, is then decompressed to 50KPa in 30 minutes；When
After stirring torque reaches predetermined value, it is believed that reaction terminates, and takes out the product in reactor at this time；After product is cooled to room temperature,
It is crushed with pulverizer, is then being heated to 290 DEG C by room temperature in 10 hours in the case where vacuum degree is less than 200Pa, and warm herein
Degree is lower to be maintained 10 hours；By the obtained product of the polarized light microscope observing above method, it is found as that can show in molten state
Show optically anisotropic liquid crystal polymer.The melting temperature of the liquid crystal polyester, melt viscosity, storage modulus release rate are rodlike
It is molded body length, is listed in table 1.
Embodiment 2-5: it by according to the formula in table 1, after acylation reaction, opens vacuum pump and is depressurized to reacting kettle inner pressure
Acetic acid and unreacted acetic anhydride molecule are discharged rapidly from rectifying column by 10KPa -30KPa, are wanted with meeting the technique being brought rapidly up
It asks, when acetic acid reception amount reaches 50% or more of theoretical value, is brought rapidly up to 210 DEG C, keeps this reduced pressure and by reactant
It ties up in 6 hours and is warming up to 370 DEG C of maximum temperature, acetic acid especially phenol etc. is during which persistently discharged, strand is caused to reset and prop up
Then the small molecular by product of change is decompressed to 60KPa in 30 minutes；Remaining is the same as embodiment 1；The fusing point of the liquid crystal polyester melts
Melt-viscosity, double enthalpy ratios, rodlike injection molding body length are listed in Table 1 below.
Embodiment 6-12: it by according to the formula in table 1, after acylation reaction, opens vacuum pump and is depressurized to reacting kettle inner pressure
Acetic acid and unreacted acetic anhydride molecule are discharged rapidly from rectifying column by 10KPa -30KPa, are wanted with meeting the technique being brought rapidly up
It asks, when acetic acid reception amount reaches 50% or more of theoretical value, is brought rapidly up to 220 DEG C, keeps this reduced pressure and by reactant
It ties up in 6 hours and is warming up to 380 DEG C of maximum temperature, acetic acid especially phenol etc. is during which persistently discharged, strand is caused to reset and prop up
Then the small molecular by product of change is decompressed to 70KPa in 30 minutes；Remaining is the same as embodiment 1；The fusing point of the liquid crystal polyester melts
Melt-viscosity, storage modulus release rate, rodlike fluid length are listed in Table 1 below.
Comparative example 1-3: after the completion of feeding intake, the atmosphere in reaction vessel is thoroughly replaced with nitrogen, is led under nitrogen protection
The temperature of reaction system is increased to 140 DEG C, maintains 2 hours progress acylation reactions of this temperature reflux；After acylation reaction, from
Acetic acid and unreacted acetic anhydride molecule is discharged in rectifying column on one side, heats up on one side and is warming up to reaction system most in 6 hours
360 DEG C of high-temperature, acetic acid is during which persistently discharged, is then decompressed to 30KPa in 30 minutes；When stirring torque reaches predetermined value
Afterwards, it is believed that reaction terminates, and takes out the product in reactor at this time；It after product is cooled to room temperature, is crushed with pulverizer, is then existed
290 DEG C are heated to by room temperature in 10 hours in the case where vacuum degree is less than 200Pa, and is maintained 10 hours at this temperature；It is logical
The obtained product of the polarized light microscope observing above method is crossed, finds it as that can show optically anisotropic liquid crystal in molten state
Polymer.The fusing point of the liquid crystal polyester, melt viscosity, double enthalpy ratios, rodlike injection molding body length are listed in table 1.
Table 1
Double enthalpys are more than or equal to 0.1 than Δ H in embodiment it can be seen from the above results, poly- less than or equal to the liquid crystal in 0.9 range
Ester, rodlike injection molding body length are apparently higher than comparative example, illustrate that the liquid crystal polyester in embodiment has high mobility.
In addition, from embodiment and comparative example it can also be seen that even if identical in starting monomer structure, ratio, melt viscosity
Under the conditions of similar, different double enthalpys are than the liquid crystal polyester in range, due to the difference of its its molecular chain structure and crystal habit, stick
Shape, which is molded body length, has notable difference, that is, there is the liquid crystal polyester of different double enthalpy ratios can show different mobility.
Claims (7)
1. a kind of liquid crystal polyester is made of following formula [I]-[IV] constitutional repeating unit:
In terms of repetitive unit total amount 100mol%, the amount of the structural unit [I] derived from P-hydroxybenzoic acid is more than or equal to
40mol% is less than or equal to 80mol%；The amount of structural unit [II] derived from 4,4 '-'-biphenyl diphenols is more than or equal to 10mol%, small
In equal to 30mol%；Structural unit [III] derived from terephthalic acid (TPA) and the structural unit [IV] derived from M-phthalic acid
Total amount is more than or equal to 10mol%, is less than or equal to 32mol%；The amount and structural unit [III] and structural unit of structural unit [II]
[IV] the ratio between moles total number is 1:1, wherein being derived from the structural unit [IV] of M-phthalic acid and being derived from terephthalic acid (TPA)
Structural unit [III] molar ratio be 0.1 to 0.49, the mole percent summation of structural unit [I], [II], [III] and [IV]
It is 100%；
It is wherein tested using differential scanning calorimetry DSC, is warming up to+30 DEG C of fusing point from room temperature with the heating rate of 20 DEG C/min
Maximum temperature is down to room temperature again after stopping 3min at this temperature with the rate of 20 DEG C/min, and the crystallization for obtaining liquid crystal polyester is bent
Line, the crystallization onset temperature and crystallization for choosing peak crystallization terminate temperature, and calculating crystallization peak area is H(crystallization enthalpy)；It surveys
Test agent is stopped after 3min at room temperature and is warming up to+30 DEG C of fusing point of maximum temperature with the heating rate of 20 DEG C/min again, is obtained
To second of melting curve of liquid crystal polyester, the melt initiation temperature degree and melting for choosing melting peak terminate temperature, and calculate molten
Melting peak area is H(melting enthalpy), which meets the double enthalpys defined by following formula (1) and is more than or equal to 0.1 than Δ H, is less than
Equal to 0.9, preferably greater than or equal to 0.2 to less than be equal to 0.7；
(1) Δ H=H(melting enthalpy)/H(crystallization enthalpy).
2. liquid crystal polyester according to claim 1, which is characterized in that the melting viscosity of the liquid crystal polyester is 10Pa.s-
35Pa.s, preferably 15Pa.s -30Pa.s, melting viscosity are tested using capillary rheometer, and test temperature is greater than fusing point 0-
30 DEG C, 1000 S of shear rate-1, using internal diameter 1mm, the mouth mold of length 40mm is measured.
3. liquid crystal polyester according to claim 1, it is characterised in that: the fusing point of the liquid crystal polyester is 310 DEG C -390 DEG C,
Preferably 330 DEG C -380 DEG C, fusing point is measured using DSC, is warming up under the ramp rate conditions of 20 DEG C/min from room temperature molten
The maximum temperature of+30 DEG C of point is cooled to room temperature again after stopping 3min at this temperature with the rate of 20 DEG C/min, and test sample exists
It is warming up to+30 DEG C of fusing point of maximum temperature after stop 3min with the heating rate of 20 DEG C/min again at room temperature, it is poly- to obtain liquid crystal
Second of melting curve of ester, choosing this curve peak melting is fusing point.
4. the preparation method of liquid crystal polyester according to claim 1-3, which comprises the steps of:
A, under nitrogen pressurized conditions, with P-hydroxybenzoic acid, 4,4 '-'-biphenyl diphenols, terephthalic acid (TPA) and M-phthalic acid are
Raw material, carries out acylation reaction under the action of acylating agent, and the pressure is maintained at 0.2MPa-0.6MPa；
B, after acylation reaction, reacting kettle inner pressure is carried out to be decompressed to 10KPa-30KPa, acetic acid is discharged rapidly from rectifying column
And unreacted acetic anhydride molecule is rapidly heated when acetic acid reception amount reaches 50% or more of theoretical value to 200 DEG C or more,
It keeps this reduced pressure and by reaction system temperature programming to reaction maximum temperature, is then further decompressed to 50Kpa-100
Kpa, melt polycondensation obtain prepolymer；
C, prepolymer is cooled and solidified and is granulated, solid phase is carried out in solid phase container and obtains liquid crystal polyester particle.
5. the preparation method of liquid crystal polyester according to claim 4, which is characterized in that in step a, the acylation reaction
Temperature is 100 DEG C~180 DEG C, and preferably 120 DEG C~160 DEG C, the reaction time is 30 minutes~20 hours, and preferably 40 minutes~5 is small
When.
6. the preparation method of liquid crystal polyester according to claim 4, which is characterized in that in step b, acylation reaction terminates
Afterwards, with the heating of 0.1 DEG C/min~150 DEG C/min rate, reaction kettle is made to be rapidly heated to 200 DEG C or more, contracted into melting
Poly- stage, the temperature of the melt polycondensation are 130 DEG C~400 DEG C, preferably 160 DEG C~370 DEG C.
7. the preparation method of liquid crystal polyester according to claim 4, which is characterized in that in step c, the solid phase exists
It is carried out under the conditions of the inert protective gas such as vacuum degree 0.1Pa~50KPa or logical nitrogen, polymerization temperature is 0~340 DEG C, instead
It is 0.5 hour~40 hours between seasonable.
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| US20010014708A1 (en) * | 1999-03-30 | 2001-08-16 | Nippon Petrochemical Co., Ltd. | Method of producing thermotropic liquid crystalline copolyester, thermotropic liquid crystalline copolyester composition obtained by the same method, and molding made of the same composition |
| CN101875762A (en) * | 2008-12-25 | 2010-11-03 | 住友化学株式会社 | Liquid crystal polyester resin compositions and utilize its junctor |
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| US20010014708A1 (en) * | 1999-03-30 | 2001-08-16 | Nippon Petrochemical Co., Ltd. | Method of producing thermotropic liquid crystalline copolyester, thermotropic liquid crystalline copolyester composition obtained by the same method, and molding made of the same composition |
| CN101875762A (en) * | 2008-12-25 | 2010-11-03 | 住友化学株式会社 | Liquid crystal polyester resin compositions and utilize its junctor |
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