CN106750198B - Thermotropic liquid crystal polyester with stable monomer composition ratio, preparation method and application thereof - Google Patents
Thermotropic liquid crystal polyester with stable monomer composition ratio, preparation method and application thereof Download PDFInfo
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- CN106750198B CN106750198B CN201611141234.3A CN201611141234A CN106750198B CN 106750198 B CN106750198 B CN 106750198B CN 201611141234 A CN201611141234 A CN 201611141234A CN 106750198 B CN106750198 B CN 106750198B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
- C08G63/065—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids the hydroxy and carboxylic ester groups being bound to aromatic rings
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
- 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
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Abstract
本发明提供了一种单体组成比例稳定的热致性液晶聚酯及其制备方法和应用。该制备方法将单体在保压的条件下熔融缩聚制备得到预聚物，预聚物经固相聚合后得到液晶聚酯。本制备方法降低了单体在聚合过程中的损失，获得单体组成比例稳定的热致性液晶聚酯。所述热致性液晶聚酯经元素分析测定，元素含量与理论含量基本保持一致，单体组成比例基本保持不变。The invention provides a thermotropic liquid crystal polyester with stable monomer composition ratio and a preparation method and application thereof. In the preparation method, a prepolymer is prepared by melt polycondensation of the monomer under the condition of maintaining pressure, and the liquid crystal polyester is obtained after the solid phase polymerization of the prepolymer. The preparation method reduces the loss of monomers in the polymerization process, and obtains a thermotropic liquid crystal polyester with stable monomer composition ratio. The thermotropic liquid crystal polyester is determined by elemental analysis, the element content is basically the same as the theoretical content, and the monomer composition ratio is basically unchanged.
Description
Technical field
The present invention relates to the technical field of liquid crystal polyester, in particular to a kind of liquid crystal polyester that monomer ratio is stable and
Preparation method and application.
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, answers at present in fields such as electronic apparatus components
With extensive.
The method for preparing liquid crystal polyester generally comprises following steps: (1) in the reaction vessel by reaction monomers in acetylation
Acetylation is carried out under the action of reagent.(2) heat up condensation polymerization monomer, by polymer produced with molten state from reaction vessel
Middle discharge, and make its solidification；(3) so that cured polymer is carried out solid phase, and then increase the molecular weight of polymer.But upper
It states in preparation process, with the extraction of acetic acid and other by-products, partial monosomy or oligomer can not be returned to therewith being carried over
In reaction system.Due to the loss of monomer, cause the product structure (monomer ratio) of final liquid crystal polyester unstable, property
It can differ greatly.
Summary of the invention
The present invention is to overcome the defect of the above-mentioned prior art, and it is poly- to provide a kind of thermotropic liquid crystal that monomer ratio is stable
The preparation method of ester.
Another object of the present invention is to provide the thermotropic liquid crystalline polyester that above-mentioned preparation method is prepared.
Another object of the present invention is to provide application of the above-mentioned thermotropic liquid crystalline polyester in electronic apparatus.
In order to solve the above technical problems, the technical solution adopted by the present invention is that:
A kind of preparation method of thermotropic liquid crystalline polyester, comprising the following steps:
S1. acylation reaction is carried out to the monomer for being used to prepare thermotropic liquid crystalline polyester；
S2. melt polycondensation is carried out to the monomer after acylation, prepares performed polymer:
Monomer after acylation is placed in reaction vessel, in the case where pressure is the inert gas atmosphere of 0.5 ~ 1.5MPa, heating
To 270 ~ 300 DEG C, 1 ~ 3h is reacted in pressure maintaining, is decompressed to normal pressure later, after being heated to 320 DEG C, reaction vessel is discharged, obtains pre-polymerization
Body；
S3. the performed polymer is cooled down, is crushed after solidification, carried out solid phase, obtain thermotropic liquid crystalline polyester.
By using pressure maintaining to react when preparing performed polymer, the monomer after being acylated reacts under dwell condition at low the present invention
Polymers makes its later period be difficult to volatilize reaction system, to reduce the loss of monomer, obtains stable thermotropic of monomer ratio
Liquid crystal polyester.
The monomer for being used to prepare thermotropic liquid crystalline polyester is in any shown structural compounds in the following Expression 1 ~ 2
It is at least one:
1 HO-Ar1-COOH of formula；
2 HOOC-Ar2-COOH of formula；
Wherein, Ar1 is Isosorbide-5-Nitrae-phenylene or 2,6- naphthylene；Ar2 is 1,3- phenylene, 1,4- phenylene, the Asia 2,6- naphthalene
Base or 4,4 '-biphenylenes.
Preferably, the monomer is 4-HBA, 2- hydroxyl -6- naphthoic acid, resorcinol, hydroquinone, 4,4-
At least one of xenol, terephthalic acid (TPA), M-phthalic acid, 2,6- naphthalenedicarboxylic acid and 4,4- biphenyl dicarboxylic acid.
Preferably, the condition of the acylation reaction are as follows: under the action of acylating reagent, 100~180 DEG C react 30 minutes ~
20 hours.It is highly preferred that 120~160 DEG C are reacted 40 minutes ~ 5 hours.
The acylating reagent is fatty acid anhydride.Preferably, the fatty acid anhydride is acetic anhydride, propionic andydride, butyric anhydride, valeric acid
One of acid anhydride, 2 ethyl hexanoic acid acid anhydride, dichloroacetic acid acid anhydride, dibromoacetic acid acid anhydride, difluoroacetic acid acid anhydride, maleic anhydride and succinic anhydride
Or more than one combination.
Consider from production cost angle, it is preferred to use acetic anhydride, propionic andydride and butyric anhydride, more preferable acetic anhydride.It is used
The molar ratio of phenolic hydroxyl group in the amount of fatty acid anhydride and the monomer is 1~1.2:1, from the lower degassing of generation and proper alignment blistering
Property angle consider, preferably 1.02~1.10: 1.
In step s 2, the melt polycondensation can carry out under the effect of the catalyst, and catalyst is using conventionally known
Polymerization catalyst for polyester can be metallic salt catalyst, such as potassium acetate, sodium acetate, magnesium acetate, zinc acetate, three oxidations two
Antimony, butyl titanate etc..The melt polycondensation can carry out in intermittently or serially mode or combination.
The reaction vessel can be existing polyplant, preferably vertical polymerization tank, the agitating paddle in reaction vessel
It can be turbine impellers, double helix blade, multistage paddle blade, preferably turbine impellers.
Preferably, in step s 2, the pressure is 1.5MPa.
Preferably, in step s 2, the heating rate of the heating is 1 DEG C/min.
Preferably, after melt polycondensation, the discharge is to carry out under inert gas atmosphere.Add into the reaction vessel
Enter inert gas and increase pressure, the generation of side reaction can be inhibited in this way, while the increase of prepolymer molecular weight being inhibited (to inhibit
The melting viscosity of prepolymer).
In order to be easy that the prepolymer of molten condition is discharged from reaction vessel, the melting viscosity of the prepolymer preferably exists
10Pas or less.Valve, extruder and gear pump may be selected in the equipment of the discharge.
The molten monomer polycondensation is corresponding repetitive unit such as 3~4 institute of formula in obtained polymer derivative after performed polymer
Show:
3-O-Ar1-CO- of formula；
4-OC-Ar2-CO- of formula；
Wherein, Ar1 is Isosorbide-5-Nitrae-phenylene or 2,6- naphthylene；Ar2 be 1,3- phenylene, 1,4- phenylene, 2,
6- naphthylene or 4,4 '-biphenylenes.
Preferably, in the prepolymer, in terms of repetitive unit total amount 100mol%, containing with Isosorbide-5-Nitrae-phenylene structure
Amount >=50mol% of repetitive unit.
In step s3, prepolymer can continuously be transmitted with a direction while solidifying the prepolymer,
It can be cut or be crushed using wire cutter, sheet material cutting machine or pulverizer in direction of transfer downstream.To cutting or it is crushed
There is no particular restriction for the granular size of the prepolyer granule or powder that obtain afterwards, it is preferable that granular size is in 0.1~5mm.
Preferably, in step s3, the reaction condition of the solid phase are as follows: vacuum degree be 0.1Pa~50KPa it is lazy
Property gas atmosphere under, 20~340 DEG C react 0.5~40 hour.The solid phase can be in stirring or stationary state without mixing
Lower progress.It is highly preferred that being heated to 250 DEG C by room temperature in 10 hours, and herein under conditions of vacuum degree is less than 200Pa
At a temperature of maintain 2 hours.
A kind of thermotropic liquid crystalline polyester is prepared using above-mentioned preparation method, preparation-obtained thermotropic liquid crystalline polyester
Through determination of elemental analysis, constituent content is consistent substantially with theoretical content, and monomer ratio is held essentially constant.
Under the premise of not influencing the purpose of the present invention, inorganic fill out can be added in thermotropic liquid crystalline polyester as needed
Material.Such as glass fibre, carbon fiber, asbestos fibre, talcum powder, carbon black, gypsum, montmorillonite, silica, titanium oxide, oxidation
Aluminium, zinc oxide, aluminum sulfate, barium sulfate, magnesium sulfate, calcium carbonate, mica, silica flour and the glass fibre of crushing.
The thermotropic liquid crystalline polyester can be applicable in electronic apparatus.
Compared with prior art, the beneficial effects of the present invention are:
The present invention provides a kind of preparation methods of liquid crystal polyester that monomer ratio is stable, by preparing performed polymer
Shi Caiyong pressure maintaining reaction, the monomer after being acylated reacts under dwell condition generates oligomer, its later period is made to be difficult to volatilize reaction
System obtains the stable thermotropic liquid crystalline polyester of monomer ratio to reduce the loss of monomer in the course of the polymerization process.
Specific embodiment
Below with reference to embodiment, the present invention is described in further detail, and embodiments of the present invention are not limited thereto.
It is important to point out that following embodiment cannot be construed to the limitation to invention protection scope, person skilled in the art's root in the field
According to some nonessential modifications and adaptations that foregoing invention content makes the present invention, should belong to the scope of protection of the present invention.
It is evaluated using performance of the following method to thermotropic liquid crystalline polyester of the present invention:
(1) melt viscosity
It is tested using Dynisco LCR7000 type capillary rheometer, 380 DEG C of test temperature, shear rate 1000S-1,
It is measured using the mouth mold of internal diameter 1mm, length 40mm.
(2) logarithmic viscosity number
Using Pentafluorophenol as solvent, the solution that concentration is 0.1wt% is made in liquid crystal polyester, measuring temperature is 60 DEG C,
Internal diameter is used to measure for the Ubbelohde viscometer of 0.7mm.And by formula: logarithmic viscosity number=[ln (η r)]/C is calculated,
Wherein η r is relative viscosity (t solution/t solvent), and C is solution concentration.
(3) elemental analysis
German Elementar company Vario EL cube elemental analyser, it is dry in 60 DEG C of vacuum ovens before sample test
Dry overnight, moment burns under the action of micro-example is placed in quartz ampoule quantitative oxygen, and the mixed gas of generation completes quantitative turn
Enter chromatographic column after change to be separated, and signal is detected by detector, is obtained according to the calculated by peak area of example weight and signal
The mass percentage of each element in sample.
Embodiment 1
To equipped with the anti-of blender, monomeric charge mouth, reflux condenser, thermometer, nitrogen inlet and torque sensor
It answers in container, following raw material monomer, acylating agent, catalyst is added.
4-HBA (HBA) 10.08kg(73mmol),
6-Hydroxy-2-naphthoic acid (HNA) 5.08kg(27mmol),
Catalyst: 150 milli of magnesium acetate,
After the completion of feeding intake, the atmosphere in reaction vessel is thoroughly replaced with nitrogen, is led to the temperature of reaction system under nitrogen protection
Degree is increased to 120 DEG C, maintains 3 hours progress acetylization reactions of this temperature reflux.After acetylization reaction, nitrogen is increased
Reaction system pressure maintaining is warming up to 270 DEG C by pressure under the conditions of 1.5MPa, and pressure release is discharged simultaneously to normal pressure after sustained response 1h
The acetic acid generated, unreacted acetic anhydride are reacted, is further heated up to 320 DEG C, at this time by the discharge of the reacted container of performed polymer
Mouth is discharged with molten state, is cooled to room temperature, is obtained solid performed polymer.
Solid performed polymer is crushed to the particle of 0.1~3mm with pulverizer, and particle is imported in solid phase container
Carry out solid phase.Solid phase container is heated to 250 by room temperature in 10 hours under conditions of vacuum degree is less than 200Pa
DEG C, and maintain 2 hours at this temperature.Then, product is discharged from the outlet of solid phase container, it is poly- obtains liquid crystal
Ester.
By the obtained product of the polarized light microscope observing above method, find its for can molten state show optics respectively to
Anisotropic liquid crystal polymer.The melting viscosity of liquid crystal polyester obtained by the above method, logarithmic viscosity number and elemental analysis result column
In table 1.
Embodiment 2
To equipped with the anti-of blender, monomeric charge mouth, reflux condenser, thermometer, nitrogen inlet and torque sensor
It answers in container, following raw material monomer, acylating agent, catalyst is added.
4-HBA (HBA) 10.08kg(73mmol),
6-Hydroxy-2-naphthoic acid (HNA) 5.08kg(27mmol),
Catalyst: 150 milli of magnesium acetate,
After the completion of feeding intake, the atmosphere in reaction vessel is thoroughly replaced with nitrogen, is led to the temperature of reaction system under nitrogen protection
Degree is increased to 120 DEG C, maintains 3 hours progress acetylization reactions of this temperature reflux.After acetylization reaction, nitrogen is increased
Reaction system pressure maintaining is warming up to 280 DEG C by pressure under the conditions of 1.5MPa, and pressure release is discharged simultaneously to normal pressure after sustained response 1h
The acetic acid generated, unreacted acetic anhydride are reacted, is further heated up to 320 DEG C, at this time by the discharge of the reacted container of performed polymer
Mouth is discharged with molten state, is cooled to room temperature, is obtained solid performed polymer.
Solid performed polymer is crushed to the particle of 0.1~3mm with pulverizer, and particle is imported in solid phase container
Carry out solid phase.Solid phase container is heated to 250 by room temperature in 10 hours under conditions of vacuum degree is less than 200Pa
DEG C, and maintain 2 hours at this temperature.Then, product is discharged from the outlet of solid phase container, it is poly- obtains liquid crystal
Ester.
By the obtained product of the polarized light microscope observing above method, find its for can molten state show optics respectively to
Anisotropic liquid crystal polymer.The melting viscosity of liquid crystal polyester obtained by the above method, logarithmic viscosity number and elemental analysis result column
In table 1.
Embodiment 3
To equipped with the anti-of blender, monomeric charge mouth, reflux condenser, thermometer, nitrogen inlet and torque sensor
It answers in container, following raw material monomer, acylating agent, catalyst is added.
4-HBA (HBA) 10.08kg(73mmol),
6-Hydroxy-2-naphthoic acid (HNA) 5.08kg(27mmol),
Catalyst: 150 milli of magnesium acetate,
After the completion of feeding intake, the atmosphere in reaction vessel is thoroughly replaced with nitrogen, is led to the temperature of reaction system under nitrogen protection
Degree is increased to 120 DEG C, maintains 3 hours progress acetylization reactions of this temperature reflux.After acetylization reaction, nitrogen is increased
Reaction system pressure maintaining is warming up to 290 DEG C by pressure under the conditions of 1.5MPa, and pressure release is discharged simultaneously to normal pressure after sustained response 1h
The acetic acid generated, unreacted acetic anhydride are reacted, is further heated up to 320 DEG C, at this time by the discharge of the reacted container of performed polymer
Mouth is discharged with molten state, is cooled to room temperature, is obtained solid performed polymer.
Solid performed polymer is crushed to the particle of 0.1~3mm with pulverizer, and particle is imported in solid phase container
Carry out solid phase.Solid phase container is heated to 250 by room temperature in 10 hours under conditions of vacuum degree is less than 200Pa
DEG C, and maintain 2 hours at this temperature.Then, product is discharged from the outlet of solid phase container, it is poly- obtains liquid crystal
Ester.
By the obtained product of the polarized light microscope observing above method, find its for can molten state show optics respectively to
Anisotropic liquid crystal polymer.The melting viscosity of liquid crystal polyester obtained by the above method, logarithmic viscosity number and elemental analysis result column
In table 1.
Embodiment 4
To equipped with the anti-of blender, monomeric charge mouth, reflux condenser, thermometer, nitrogen inlet and torque sensor
It answers in container, following raw material monomer, acylating agent, catalyst is added.
4-HBA (HBA) 10.08kg(73mmol),
6-Hydroxy-2-naphthoic acid (HNA) 5.08kg(27mmol),
Catalyst: 150 milli of magnesium acetate,
After the completion of feeding intake, the atmosphere in reaction vessel is thoroughly replaced with nitrogen, is led to the temperature of reaction system under nitrogen protection
Degree is increased to 120 DEG C, maintains 3 hours progress acetylization reactions of this temperature reflux.After acetylization reaction, nitrogen is increased
Reaction system pressure maintaining is warming up to 300 DEG C by pressure under the conditions of 1.5MPa, and pressure release is discharged simultaneously to normal pressure after sustained response 1h
The acetic acid generated, unreacted acetic anhydride are reacted, is further heated up to 320 DEG C, at this time by the discharge of the reacted container of performed polymer
Mouth is discharged with molten state, is cooled to room temperature, is obtained solid performed polymer.
Solid performed polymer is crushed to the particle of 0.1~3mm with pulverizer, and particle is imported in solid phase container
Carry out solid phase.Solid phase container is heated to 250 by room temperature in 10 hours under conditions of vacuum degree is less than 200Pa
DEG C, and maintain 2 hours at this temperature.Then, product is discharged from the outlet of solid phase container, it is poly- obtains liquid crystal
Ester.
By the obtained product of the polarized light microscope observing above method, find its for can molten state show optics respectively to
Anisotropic liquid crystal polymer.The melting viscosity of liquid crystal polyester obtained by the above method, logarithmic viscosity number and elemental analysis result column
In table 1.
Comparative example 1
To equipped with the anti-of blender, monomeric charge mouth, reflux condenser, thermometer, nitrogen inlet and torque sensor
It answers in container, following raw material monomer, acylating agent, catalyst is added.
4-HBA (HBA) 10.08kg(73mmol),
6-Hydroxy-2-naphthoic acid (HNA) 5.08kg(27mmol),
Catalyst: 150 milli of magnesium acetate,
After the completion of feeding intake, the atmosphere in reaction vessel is thoroughly replaced with nitrogen, is led to the temperature of reaction system under nitrogen protection
Degree is increased to 120 DEG C, maintains 3 hours progress acetylization reactions of this temperature reflux.After acetylization reaction, with about 1 DEG C/
The heating rate of min is heated to 320 DEG C, while acetic acid, unreacted acetic anhydride that reaction generates is discharged, and vacuumizes further row
Other low boiling point components out, after about 30min after stirring torque and reaching predetermined value, polycondensation reaction terminates, and at this time passes through performed polymer
The outlet of reaction vessel is discharged with molten state, is cooled to room temperature, and solid performed polymer is obtained.
Solid performed polymer is crushed to the particle of 0.1~3mm with pulverizer, and particle is imported in solid phase container
Carry out solid phase.Solid phase container is heated to 250 by room temperature in 10 hours under conditions of vacuum degree is less than 200Pa
DEG C, and maintain 2 hours at this temperature.Then, product is discharged from the outlet of solid phase container, it is poly- obtains liquid crystal
Ester.
By the obtained product of the polarized light microscope observing above method, find its for can molten state show optics respectively to
Anisotropic liquid crystal polymer.The melting viscosity of liquid crystal polyester obtained by the above method, logarithmic viscosity number and elemental analysis result column
In table 1.
Comparative example 2
To equipped with the anti-of blender, monomeric charge mouth, reflux condenser, thermometer, nitrogen inlet and torque sensor
It answers in container, following raw material monomer, acylating agent, catalyst is added.
4-HBA (HBA) 10.08kg(73mmol),
6-Hydroxy-2-naphthoic acid (HNA) 5.08kg(27mmol),
Catalyst: 150 milli of magnesium acetate,
After the completion of feeding intake, the atmosphere in reaction vessel is thoroughly replaced with nitrogen, is led to the temperature of reaction system under nitrogen protection
Degree is increased to 120 DEG C, maintains 3 hours progress acetylization reactions of this temperature reflux.After acetylization reaction, by reactant
System is warming up to 280 DEG C with the rate of 1 DEG C/min, after reacting 1h, is continuously heating to 320 DEG C, at the same be discharged acetic acid that reaction generates,
Unreacted acetic anhydride vacuumizes and other low boiling point components is further discharged, when stirring torque reaches predetermined value after about 30min
Afterwards, polycondensation reaction terminates, and the outlet of the reacted container of performed polymer is discharged with molten state at this time, is cooled to room temperature, consolidate
Body performed polymer.
Solid performed polymer is crushed to the particle of 0.1~3mm with pulverizer, and particle is imported in solid phase container
Carry out solid phase.Solid phase container is heated to 250 by room temperature in 10 hours under conditions of vacuum degree is less than 200Pa
DEG C, and maintain 2 hours at this temperature.Then, product is discharged from the outlet of solid phase container, it is poly- obtains liquid crystal
Ester.
By the obtained product of the polarized light microscope observing above method, find its for can molten state show optics respectively to
Anisotropic liquid crystal polymer.The melting viscosity of liquid crystal polyester obtained by the above method, logarithmic viscosity number and elemental analysis result column
In table 1.
Table 1
Obviously, the above embodiment of the present invention be only to clearly illustrate example of the present invention, and not be pair
The restriction of embodiments of the present invention.For those of ordinary skill in the art, may be used also on the basis of the above description
To make other variations or changes in different ways.There is no necessity and possibility to exhaust all the enbodiments.It is all this
Made any modifications, equivalent replacements, and improvements etc., should be included in the claims in the present invention within the spirit and principle of invention
Protection scope within.
Claims (8)
1. a kind of preparation method of thermotropic liquid crystalline polyester, which comprises the following steps:
S1. acylation reaction is carried out to the monomer for being used to prepare thermotropic liquid crystalline polyester；
S2. melt polycondensation is carried out to the monomer after acylation, prepares performed polymer:
Monomer after acylation is placed in reaction vessel, in the case where pressure is the inert gas atmosphere of 0.5 ~ 1.5MPa, is heated to 270
~ 300 DEG C, 1 ~ 3h is reacted in pressure maintaining, is decompressed to normal pressure later, after being heated to 320 DEG C, reaction vessel is discharged, obtains performed polymer；
S3. the performed polymer is cooled down, is crushed after solidification, carried out solid phase, obtain thermotropic liquid crystalline polyester.
2. preparation method according to claim 1, which is characterized in that the condition of the acylation reaction are as follows: in acylating reagent
Under the action of, 100~180 DEG C are reacted 30 minutes ~ 20 hours.
3. preparation method according to claim 2, which is characterized in that the acylating reagent is fatty acid anhydride.
4. preparation method according to claim 1, which is characterized in that in step s 2, the pressure is 1.5MPa.
5. preparation method according to claim 1, which is characterized in that in step s 2, after melt polycondensation, the discharge
To carry out under inert gas atmosphere.
6. preparation method according to claim 1, which is characterized in that in step s3, the reaction item of the solid phase
Part are as follows: in the case where vacuum degree is the inert gas atmosphere of 0.1Pa~50KPa, 20~340 DEG C are reacted 0.5~40 hour.
7. a kind of thermotropic liquid crystalline polyester, which is characterized in that made using the described in any item preparation methods of claim 1 ~ 6
At.
8. application of the thermotropic liquid crystalline polyester as claimed in claim 7 in electronic apparatus.
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| JP3988775B2 (en) * | 2005-05-17 | 2007-10-10 | 住友化学株式会社 | Liquid crystal polymer |
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| CN101649044A (en) * | 2009-09-04 | 2010-02-17 | 金发科技股份有限公司 | Wholly aromatic liquid crystal polymer and preparation method thereof |
| CN103342804A (en) * | 2013-07-23 | 2013-10-09 | 南通海迪化工有限公司 | Thermotropic liquid crystal polymer material and synthesis method thereof |
Cited By (3)
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| US12142820B2 (en) | 2019-09-10 | 2024-11-12 | Ticona Llc | 5G system containing a polymer composition |
| US12209164B2 (en) | 2019-09-10 | 2025-01-28 | Ticona Llc | Polymer composition and film for use in 5G applications |
| US12230865B2 (en) | 2021-02-18 | 2025-02-18 | Ticona Llc | Polymer composition for use in an antenna system |
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