CN106633859A - Wholly aromatic liquid crystal polyester resin as well as preparation method and application thereof - Google Patents
Wholly aromatic liquid crystal polyester resin as well as preparation method and application thereof Download PDFInfo
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- CN106633859A CN106633859A CN201611243723.XA CN201611243723A CN106633859A CN 106633859 A CN106633859 A CN 106633859A CN 201611243723 A CN201611243723 A CN 201611243723A CN 106633859 A CN106633859 A CN 106633859A
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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
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/44—Polyester-amides
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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
- 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
- C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
- C09K19/54—Additives having no specific mesophase characterised by their chemical composition
- C09K19/542—Macromolecular compounds
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Abstract
The invention provides wholly aromatic liquid crystal polyester resin which is prepared from the following components in parts by mole: 1 to 10 parts of a first monomer, 40 to 60 parts of a second monomer, 20 to 30 parts of a third monomer, 20 to 30 parts of a fourth monomer and 1 to 10 parts of a fifth monomer, wherein each of the first monomer, the second monomer, the third monomer, the fourth monomer and the fifth monomer is independently selected from at least one of the following structural units: aromatic hydroxylamine: -HN-Ar-O-; aromatic diamine: -HN-Ar-NH-; aromatic amino carboxylic acid: -HN-Ar-CO-; aromatic diol: -O-Ar-O-; aromatic hydroxy carboxylic acid: -O-Ar-CO-; aromatic dicarboxylic acid: -OC-Ar-CO-; Ar is one of phenylene and a derivative thereof, biphenylene and a derivative thereof, naphthalene and a derivative thereof, and an aromatic compound formed by bonding two phenylenes through a carbon or non-carbon element and a derivative thereof.
Description
Technical field
The invention belongs to field of polymer composite material, more particularly to a kind of all aromatic liquid crystal polyester resin, its preparation
Side and application.
Background technology
Aromatic liquid crystal polyester resin (LCP), its molecular backbone is firm, in the molten state in liquid crystal state, and its molecule
Between without wrapping phenomena.Additionally, aromatic liquid crystal polyester resin mobility and excellent heat resistance, according to shearing force and can divide during shaping
Subchain to flow direction is orientated.Due to such characteristic, aromatic liquid crystal polyester resin can be widely applied for automobile, space flight,
It is electric to wait industry field.With the notable development of industry, the purposes of liquid-crystal polyester resin has higher degree and particularization
Tendency.Wholly aromatic liquid crystal polyester good fluidity, can effectively carry out injection mo(u)lding；Meanwhile, under its heat resistance, high temperature
Hydrolytic resistance and excellent in dimensional stability, and the mechanical strength of its bending strength, tensile strength and impact strength etc,
Therefore in available the precise electronic connector of fusion weld, various electronic route plates at high temperature.But due to some special products
During product such as precise electronic connector material production and use, need that there is higher heat distortion temperature and mechanical strength,
Simultaneously again melt temperature easy to process is needed, therefore, conventional aromatic liquid crystal polyester resin can not meet it using will
Ask.Therefore it provides a kind of such as precise electronic connection of product that can just produce high heat distortion temperature at the relatively low melting temperature
The aromatic liquid crystal polyester resin of device, it appears particularly necessary.
The content of the invention
It is an object of the invention to provide a kind of all aromatic liquid crystal polyester resin and its its preparation side, it is intended to solve existing
All aromatic liquid crystal polyester resin can not meet the problem at the relatively low melting temperature simultaneously with high heat distortion temperature.
Another object of the present invention is to provide a kind of all aromatic liquid containing above-mentioned all aromatic liquid crystal polyester resin
Brilliant polyester resin compound and preparation method thereof.
The present invention is achieved in that a kind of all aromatic liquid crystal polyester resin, by the following component of following molfraction
Composition：
First monomer, second comonomer, Third monomer, the 4th monomer, the 5th monomer are independently chosen from following construction units
In at least one：
Aromatic series azanol：-HN-Ar-O-；
Aromatic diamine：-HN-Ar-NH-；
Aromatic amine yl carboxylic acid：-HN-Ar-CO-；
Aromatic diol：-O-Ar-O-；
Aromatic hydroxy-carboxylic：-O-Ar-CO-；
Aromatic dicarboxylic acid：-OC-Ar-CO-；
Wherein, the Ar be penylene and its derivative, biphenylene and its derivative, naphthalene and its derivative, two penylenes by
One kind in aromatic compound that the element of carbon or non-carbon is bonded and its derivative；
And when first monomer, second comonomer, Third monomer, the 4th monomer, the 5th monomer are all aromatic series azanol, virtue
During a kind of in fragrant race's diamines, aromatic amine yl carboxylic acid, aromatic diol, aromatic hydroxy-carboxylic or aromatic dicarboxylic acid, institute
It is different structures alones to state the first monomer, second comonomer, Third monomer, the 4th monomer, the 5th monomer.
Corresponding, a kind of preparation method of all aromatic liquid crystal polyester resin is comprised the following steps：
Metallic catalyst, acid anhydrides or acid esters catalyst are provided, are claimed according to the formula of above-mentioned all aromatic liquid crystal polyester resin
Take each component；
First monomer, second comonomer, Third monomer, the 4th monomer, the 5th monomer and the metallic catalyst are fed
Material process, obtains mixed material, and the mixed material and the acid anhydrides or acid esters catalyst are put into Liquid-phase reactor,
Acetylization reaction is carried out under the conditions of 150-350 DEG C, Wholly aromatic liquid crystal polyester prepolyer is obtained；
The Wholly aromatic liquid crystal polyester prepolyer is carried out into cooling treatment, aromatic liquid-crystal polyester prepolymer solids are obtained
Material；
The aromatic liquid-crystal polyester prepolymer solids material is carried out into solid phase reaction, Jing powder under the conditions of 250-350 DEG C
Broken process obtains all aromatic liquid crystal polyester resin.
And, a kind of all aromatic liquid crystal polyester resin compound, with all aromatic liquid crystal polyester resin compound
Gross weight be 100%, including the following component of following weight percentage：
All aromatic liquid crystal polyester resin 50-75%；
First filler 10-30%；
Second filler 5-30%；
Wherein, all aromatic liquid crystal polyester resin is above-mentioned all aromatic liquid crystal polyester resin.
Corresponding, a kind of preparation method of all aromatic liquid crystal polyester resin compound is comprised the following steps：
All aromatic liquid crystal polyester resin is prepared according to the method described above；
By all aromatic liquid crystal polyester resin with first filler, the second filler according to above-mentioned Wholly aromatic liquid crystal
The recipe ingredient of polyester resin compound is weighed after mixing, feeding process, extruding pelletization.
The all aromatic liquid crystal polyester resin that the present invention is provided, is polymerized by the relative monomer for determining of five kinds of structures, its
With heat resistance, excellent mechanical performance and workability.Therefore all aromatic liquid crystal polyester resin that the present invention is provided, can use
In electronic units such as the precise electronic connectors for making high temperature resistant and good mechanical property.
The preparation method of all aromatic liquid crystal polyester resin that the present invention is provided, can be effectively prevented in system as secondary
The organic acid of product drastically outflows the bumping phenomenon for causing, and not only can obtain the resin of uniform physical property, and can fully go
Except accessory substance, there is no the deterioration of synthesized resin, gas is reduced in extrusion or injection and is produced, it is to avoid the presence shadow of bubble
The quality of resin is rung, the resin of the high and excellent heat resistance of the degree of polymerization is finally given.All aromatic liquid prepared by the inventive method
Brilliant polyester resin, can be used to make the electronic unit such as high temperature resistant and the precise electronic connector of good mechanical property.
The all aromatic liquid crystal polyester resin compound that the present invention is provided, containing above-mentioned all aromatic liquid crystal polyester resin,
Therefore, it meets high heat distortion temperature and mechanical strength simultaneously in relatively low melt temperature, disclosure satisfy that and " produces and used
Cheng Zhong, the specialities for having melt temperature easy to process while needs with high heat distortion temperature and mechanical strength again
The requirement of such as precise electronic connector " material.
The preparation method of all aromatic liquid crystal polyester resin compound that the present invention is provided, method is simple and easy to control, is capable of achieving
Batch production.
Specific embodiment
In order that the technical problem to be solved in the present invention, technical scheme and beneficial effect become more apparent, below in conjunction with
Embodiment, the present invention will be described in further detail.It should be appreciated that specific embodiment described herein is only to explain
The present invention, is not intended to limit the present invention.
A kind of all aromatic liquid crystal polyester resin is embodiments provided, by the following component group of following molfraction
Into：
First monomer, second comonomer, Third monomer, the 4th monomer, the 5th monomer are independently chosen from following construction units
In at least one：
Aromatic series azanol：-HN-Ar-O-；
Aromatic diamine：-HN-Ar-NH-；
Aromatic amine yl carboxylic acid：-HN-Ar-CO-；
Aromatic diol：-O-Ar-O-；
Aromatic hydroxy-carboxylic：-O-Ar-CO-；
Aromatic dicarboxylic acid：-OC-Ar-CO-；
Wherein, the Ar be penylene and its derivative, biphenylene and its derivative, naphthalene and its derivative, two penylenes by
One kind in aromatic compound that the element of carbon or non-carbon is bonded and its derivative；
And when first monomer, second comonomer, Third monomer, the 4th monomer, the 5th monomer are all aromatic series azanol, virtue
During a kind of in fragrant race's diamines, aromatic amine yl carboxylic acid, aromatic diol, aromatic hydroxy-carboxylic or aromatic dicarboxylic acid, institute
It is different structures alones to state the first monomer, second comonomer, Third monomer, the 4th monomer, the 5th monomer.
The all aromatic liquid crystal polyester resin being made up of the above-mentioned monomer of the embodiment of the present invention and its content, in relatively low melting
Temperature meets high heat distortion temperature and mechanical strength simultaneously, and disclosure satisfy that " during production and use, needs with high heat
There is specialities such as precise electronic connector etc. of melt temperature easy to process while deformation temperature and mechanical strength again "
The requirement of material.
Preferably, first monomer is P-hydroxybenzoic acid, and the second comonomer is m-hydroxybenzoic acid, the described 3rd
Monomer is '-biphenyl diphenol, and the 4th monomer is terephthalic acid (TPA), and the 5th monomer is M-phthalic acid.Preferred full fragrance
Race's liquid-crystal polyester resin, its above-mentioned performance is more preferably.
Preferably, all aromatic liquid crystal polyester resin molecular weight is 30000-60000, all aromatic under high polymerization
Liquid-crystal polyester resin has high thermal stability, excellent mechanical performance.
All aromatic liquid crystal polyester resin provided in an embodiment of the present invention, by five kinds of structures with respect to the monomer polymerization for determining
Into it has heat resistance, excellent mechanical performance and workability.Wholly aromatic liquid crystal polyester tree provided in an embodiment of the present invention
Fat, can be used to make the electronic unit such as high temperature resistant and the precise electronic connector of good mechanical property.
All aromatic liquid crystal polyester resin provided in an embodiment of the present invention, can be prepared by following methods.
It is corresponding, a kind of preparation method of all aromatic liquid crystal polyester resin is embodiments provided, including it is following
Step：
S01. metallic catalyst, acid anhydrides or acid esters catalyst are provided, according to matching somebody with somebody for above-mentioned all aromatic liquid crystal polyester resin
Side weighs each component；
S02. by first monomer, second comonomer, Third monomer, the 4th monomer, the 5th monomer and the metal catalytic
The process of agent feeding, obtains mixed material, and the mixed material and the acid anhydrides or acid esters catalyst are put into Liquid-phase reactor,
Acetylization reaction is carried out under the conditions of 150-350 DEG C, Wholly aromatic liquid crystal polyester prepolyer is obtained；
S03. the Wholly aromatic liquid crystal polyester prepolyer is carried out into cooling treatment, obtains aromatic liquid-crystal polyester prepolymer
Solid material；
S04. the aromatic liquid-crystal polyester prepolymer solids material is carried out into solid phase reaction under the conditions of 250-350 DEG C,
Size-reduced process obtains all aromatic liquid crystal polyester resin.
Specifically, in above-mentioned steps S01, the formula of all aromatic liquid crystal polyester resin as described above, in order to save
About length, here is omitted.
In the embodiment of the present invention, the acid anhydrides or acid esters catalyst catalyzing acetylization reaction in following step S02 is sent out
It is raw.Preferably, the acid anhydrides or acid esters catalyst are at least one in acetic anhydride, diphenyl carbonate, benzyl acetate, so as to more
The carrying out of catalyzing acetylization reaction well, and improve the reaction rate of the acetylization reaction.
Preferably, the metallic catalyst is at least one in potassium acetate, magnesium acetate, calcium acetate, zinc acetate.Preferably
The metallic catalyst, can more effectively promote the carrying out reacted.
In above-mentioned steps S02, by first monomer, second comonomer, Third monomer, the 4th monomer, the 5th monomer and institute
State the process of metallic catalyst feeding.In order to improve the degree of crystallinity of reaction, product purity is improved, when weighing each component, preferably in nothing
Feed intake mixing after weighing in dirt closing space, discharges Jing after dust and filter are processed.It is further preferred that raw material is in input
During, put into feeding machine via dustless material feeding room, still more preferably, there is the equipment that powder puts into be connected with and be equipped with cloth
Bag dust collector.
By in the mixed material and the acid anhydrides or acid esters catalyst input Liquid-phase reactor, it is preferred that use inertia
Gas is pushed into acetic anhydride in Liquid-phase reactor, and the mixed material is put into Liquid-phase reactor, heats.It is described to add
Heat treatment is carried out under the conditions of 150-350 DEG C, now, esterification occurs and obtains Wholly aromatic liquid crystal polyester prepolyer, is reacted
Time is preferably 2-10 hours.
Preferably, before the heating, also including polycondensation reaction activation, the polycondensation reaction activation
Method is：The mixed material is heated into 140-160 DEG C, keeping temperature backflow 1.5-2.5 hours, so that polycondensation reaction
Activation.It is concrete preferred, the mixed material is heated into 150 DEG C, keeping temperature 2 hours of backflow.Then condense
The acetic acid as accessory substance is removed, intensification heating is carried out.By first polycondensation reaction activation, the rear side heated
Method, can cause while higher production of resins rate is ensured, fully to carry out monomer polycondensation reaction, reduce unreacted monomer
Residual.Thus all aromatic liquid crystal polyester resin of high polymerization degree is obtained, and is suppressed in the rear working process such as extrusion or injection
The unreacted monomer distillation of remaining produces gas or carbonization generates carbide impurity.It is further preferred that above-mentioned stirring can be monitored
The torque value of device terminates when reaching 5-6Nm, now, all aromatic liquid crystal polyester resin of synthesis with suitable polymerization
Degree.If terminating above-mentioned steps in the case where the torque value reaches 5-6Nm, not only can obtain higher with the degree of polymerization
Resin, and the fluoropolymer resin for obtaining and do not solidify, so as to the discharge of resin becomes easy.
In the step, the acid waste gas of generation such as acetic acid, carbonic acid Jing after absorption column of gas, using NaOH neutralisation treatment
After discharge.Wherein, acetic acid is collected in acetic acid holding vessel after heat exchanger, is condensed together with the water generated with side reaction
Into acetum.
In above-mentioned steps S03, the Wholly aromatic liquid crystal polyester prepolyer is carried out into cooling treatment and obtains solid material.Institute
Stating cooling can be cooled down using recirculated cooling water, further, be pushed in solids breaker by pipeline.
In above-mentioned steps S04, to reach predetermined molecular weight scope, the embodiment of the present invention is anti-using solid phase reactor solid phase
Should, this process is only strand connection, therefore, contamination-free is produced.
Further, after the size-reduced machine of solid product is crushed, all aromatic liquid crystal polyester resin powder is obtained, now can be produced
The a small amount of dust of life, discharges Jing after dust and filter are processed.Preferably, the grain of all aromatic liquid crystal polyester resin powder
Footpath is 0.2-1.0mm, is particularly preferred as 0.6mm.
The preparation method of all aromatic liquid crystal polyester resin provided in an embodiment of the present invention, can be effectively prevented in system
Drastically outflow the bumping phenomenon that causes as the organic acid of accessory substance, not only can obtain the resin of uniform physical property, and can be with
Accessory substance is fully removed, the deterioration of synthesized resin does not occur, gas is reduced in extrusion or injection and is produced, it is to avoid bubble
Existing affects the quality of resin, finally gives the resin of the high and excellent heat resistance of the degree of polymerization.It is prepared by present invention method
All aromatic liquid crystal polyester resin, can be used to make the ministry of electronics industry such as high temperature resistant and the precise electronic connector of good mechanical property
Part.
And, the embodiment of the present invention additionally provides a kind of all aromatic liquid crystal polyester resin compound, with the full fragrance
The gross weight of race's liquid-crystal polyester resin compound is 100%, including the following component of following weight percentage：
All aromatic liquid crystal polyester resin 60-75%；
First filler 10-30%；
Second filler 5-30%；
Wherein, all aromatic liquid crystal polyester resin is above-mentioned all aromatic liquid crystal polyester resin.
Wherein, the composition and its preferred situation of all aromatic liquid crystal polyester resin as described above, in order to save a piece
Width, here is omitted.
The mobility for being favorably improved compound, resistance to bond, the insulating properties of first filler.Preferably, described first
Filler is talcum powder.
Second filler can strengthen the mechanical performance of compound, hot property.Preferably, second filler is glass
Fiber.
All aromatic liquid crystal polyester resin compound provided in an embodiment of the present invention, containing above-mentioned Wholly aromatic liquid crystal polyester
Resin, therefore, it meets high heat distortion temperature and mechanical strength simultaneously in relatively low melt temperature, disclosure satisfy that " production and
During use, there is the spy of melt temperature easy to process while needs with high heat distortion temperature and mechanical strength again
The requirement of different product such as precise electronic connector etc. " material.
All aromatic liquid crystal polyester resin compound provided in an embodiment of the present invention can be prepared by following methods.
It is corresponding, a kind of preparation method of all aromatic liquid crystal polyester resin compound is embodiments provided, wrap
Include following steps：
Q01. all aromatic liquid crystal polyester resin is prepared according to the method described above；
Q02. by all aromatic liquid crystal polyester resin with first filler, the second filler according to above-mentioned all aromatic
The recipe ingredient of liquid-crystal polyester resin compound is weighed after mixing, feeding process, extruding pelletization.
Specifically, in above-mentioned steps Q01, the preparation of all aromatic liquid crystal polyester resin as described above, in order to save a piece
Width, here is omitted.
In above-mentioned steps Q02, all aromatic liquid crystal polyester resin and first filler, the content of the second filler,
Repeat in all aromatic liquid crystal polyester resin compound, no longer stated herein.Preferably, the Wholly aromatic liquid crystal gathers
Ester resin, first filler, the second filler carry out feeding from different spouts respectively, thus, it is possible to so that substantial amounts of powder
Body can be well mixed as far as possible, so as to put forward high performance stable homogeneous.
The preparation method of all aromatic liquid crystal polyester resin compound provided in an embodiment of the present invention, method is simple and easy to control,
It is capable of achieving batch production.
Illustrate with reference to specific embodiment.
Embodiment 1
A kind of all aromatic liquid crystal polyester resin compound, with the gross weight of all aromatic liquid crystal polyester resin compound
For 100%, including each component as shown in table 1 below weight percentage, wherein, all aromatic liquid crystal polyester resin is by under
The each group of each molar content is grouped into shown in table 2.
The preparation method of all aromatic liquid crystal polyester resin compound is comprised the following steps：
Mol ratio is put into the 10L reactors equipped with agitating device, nitrogen ingress pipe, thermometer and reflux cooler is
1:24:12.5:11.5:1 HBA, HNA, BP, TPA, IPA, and the potassium acetate as catalyst or magnesium acetate 2.5g (compare
In monomer total amount potassium ion or magnesium ion be 70wtppm).
The nitrogen injection in the reactor, makes above-mentioned reactor inner space become inactive state, then 30 minutes
Inside it is heated to 150 DEG C of keeping temperatures 2 hours of backflow；Condensation removes the acetic acid as accessory substance, while by reactor temperature
After degree is warming up to 250 DEG C with the speed of 1 DEG C/min, maintain 2 hours at 350 DEG C；By above-mentioned temperature of reactor again with 1 DEG C/min
Speed when being warming up to the torque value of above-mentioned agitator and reaching 6Nm, discharge Wholly aromatic liquid crystal to the outside of above-mentioned reactor and gather
Ester prepolymer.
Above-mentioned Wholly aromatic liquid crystal polyester prepolyer is reclaimed and cooled and solidified；Then, using pulverizer by above-mentioned pre-polymerization
Thing is ground into average grain diameter for 0.6mm.
Product 3000g with uniform particle size is put into the rotary kiln reactor of 10L capacity, by nitrogen with
1Nm3While the flow velocity of/hr is continued to flow into, the solid phase reaction of 8 hours is carried out at 300 DEG C and all aromatic liquid has been manufactured
Brilliant polyester resin.From the reactions above device has reclaimed Wholly aromatic liquid crystal after above-mentioned reactor is cooled to normal temperature by 1 hour
Polyester resin.
The all aromatic liquid crystal polyester resin of above-mentioned manufacture, the first filler and the second filler are entered using double screw extruder
Row melting mixing and manufactured all aromatic liquid crystal polyester resin compound.
Embodiment 2
Except HBA：HNA：BP：TPA：The mol ratio of IPA is 1:24:12.5:10:Outside 2.5, other are same as Example 1.
Embodiment 3
Except HBA：HNA：BP：TPA：The mol ratio of IPA is 1:24:12.5:9:Outside 3.5, other are same as Example 1.
Comparative example 1
Except HBA：HNA：BP：TPA：The mol ratio of IPA is 1:24:12.5:12.5:Outside 0, other are same as Example 1.
The all aromatic liquid crystal polyester resin compound manufactured in above-described embodiment 1-3, comparative example 1 is former as injection
Material, using injection moulding machine injection mo(u)lding, then tests by the following method and evaluates embodiment with composition in comparative example
Performance：
(1) bending strength：Described bending strength presses ASTM D-790 tests.
(2) heat distortion temperature：Described thermal denaturation temperature presses ASTM D-648 tests.
(2) melt temperature：Melt temperature is determined using differential scanning calorimeter (TA instrument companies, DSCQ20).Will tree
Fat sample from heated with the Elevated Temperature Conditions of 10 DEG C/min for 25 DEG C when, the temperature that the endothermic peak for being observed is shown is warm as melting
Degree (TM1)。
Test result is as shown in table 3 below.
Table 1
Table 2
Table 3
From upper table 3, make in all aromatic liquid crystal polyester resin compound manufactured in embodiment 1-3 and comparative example 1
The resin complexes made are compared, and in the case where high heat distortion temperature is kept, its melt temperature is substantially reduced, i.e. liquid crystal polyester tree
The processing temperature of fat is minimized.And the reduction with TPA contents and the increase of IPA content, keeping high heat distortion temperature
In the case of, its melt temperature is gradually lowered.Therefore, it is adapted to according to all aromatic liquid crystal polyester resin compound of present invention manufacture
In the electronic unit such as precise electronic connector for improving heat distortion temperature and keep compared with low melting glass, but it is not limited only to this.
Presently preferred embodiments of the present invention is the foregoing is only, not to limit the present invention, all essences in the present invention
Any modification, equivalent and improvement made within god and principle etc., should be included within the scope of the present invention.
Claims (10)
1. a kind of all aromatic liquid crystal polyester resin, it is characterised in that be made up of the following component of following molfraction：
First monomer, second comonomer, Third monomer, the 4th monomer, the 5th monomer are independently chosen from following construction units
It is at least one：
Aromatic series azanol：-HN-Ar-O-；
Aromatic diamine：-HN-Ar-NH-；
Aromatic amine yl carboxylic acid：-HN-Ar-CO-；
Aromatic diol：-O-Ar-O-；
Aromatic hydroxy-carboxylic：-O-Ar-CO-；
Aromatic dicarboxylic acid：-OC-Ar-CO-；
Wherein, the Ar be penylene and its derivative, biphenylene and its derivative, naphthalene and its derivative, two penylenes by carbon or
One kind in aromatic compound that the element of non-carbon is bonded and its derivative；
And when first monomer, second comonomer, Third monomer, the 4th monomer, the 5th monomer are all aromatic series azanol, aromatic series
During a kind of in diamines, aromatic amine yl carboxylic acid, aromatic diol, aromatic hydroxy-carboxylic or aromatic dicarboxylic acid, described
One monomer, second comonomer, Third monomer, the 4th monomer, the 5th monomer are different structures alones.
2. all aromatic liquid crystal polyester resin as claimed in claim 1, it is characterised in that first monomer is para hydroxybenzene
Formic acid, the second comonomer is m-hydroxybenzoic acid, and the Third monomer is '-biphenyl diphenol, and the 4th monomer is terephthaldehyde
Acid, the 5th monomer is M-phthalic acid.
3. a kind of preparation method of all aromatic liquid crystal polyester resin, comprises the following steps：
Metallic catalyst, acid anhydrides or acid esters catalyst are provided, according to all aromatic liquid crystal polyester resin described in claim 1 or 2
Formula weigh each component；
At first monomer, second comonomer, Third monomer, the 4th monomer, the 5th monomer and the metallic catalyst feeding
Reason, obtains mixed material, and the mixed material and the acid anhydrides or acid esters catalyst are put into Liquid-phase reactor, in 150-
Acetylization reaction is carried out under the conditions of 350 DEG C, Wholly aromatic liquid crystal polyester prepolyer is obtained；
The Wholly aromatic liquid crystal polyester prepolyer is carried out into cooling treatment, aromatic liquid-crystal polyester prepolymer solids thing is obtained
Material；
The aromatic liquid-crystal polyester prepolymer solids material is carried out into solid phase reaction, size-reduced place under the conditions of 250-350 DEG C
Reason obtains all aromatic liquid crystal polyester resin.
4. the preparation method of all aromatic liquid crystal polyester resin as claimed in claim 3, it is characterised in that the acid anhydrides or acid
Ester catalyst is at least one in acetic anhydride, diphenyl carbonate, benzyl acetate.
5. the preparation method of all aromatic liquid crystal polyester resin as claimed in claim 3, it is characterised in that the metal catalytic
Agent is at least one in potassium acetate, magnesium acetate, calcium acetate, zinc acetate.
6. a kind of all aromatic liquid crystal polyester resin compound, it is characterised in that multiple with all aromatic liquid crystal polyester resin
The gross weight of compound is 100%, including the following component of following weight percentage：
All aromatic liquid crystal polyester resin 50-75%；
First filler 10-30%；
Second filler 5-30%；
Wherein, all aromatic liquid crystal polyester resin is all aromatic liquid crystal polyester resin described in claim 1 or 2.
7. all aromatic liquid crystal polyester resin compound as claimed in claim 6, it is characterised in that first filler is to slide
Stone flour.
8. all aromatic liquid crystal polyester resin compound as claimed in claim 6, it is characterised in that second filler is glass
At least one in glass fiber, whisker, carbon fiber.
9. a kind of preparation method of all aromatic liquid crystal polyester resin compound, comprises the following steps：
All aromatic liquid crystal polyester resin is prepared according to the arbitrary methods described of claim 3-5；
The all aromatic liquid crystal polyester resin is arbitrary described according to claim 6-8 with first filler, the second filler
The recipe ingredient of all aromatic liquid crystal polyester resin compound is weighed after mixing, feeding process, extruding pelletization.
10. the preparation method of all aromatic liquid crystal polyester resin compound as claimed in claim 9, it is characterised in that described
All aromatic liquid crystal polyester resin, first filler, the second filler carry out feeding from different spouts respectively.
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111117170A (en) * | 2019-12-26 | 2020-05-08 | 江苏沃特特种材料制造有限公司 | High-fluidity liquid crystal polymer and preparation method thereof |
| CN111117169A (en) * | 2019-12-26 | 2020-05-08 | 江苏沃特特种材料制造有限公司 | High-dielectric-constant liquid crystal polymer and preparation method thereof |
| CN115449061A (en) * | 2022-09-30 | 2022-12-09 | 江苏沃特特种材料制造有限公司 | Wholly aromatic liquid crystal polyester resin and preparation method and application thereof |
| US11572438B2 (en) | 2019-07-02 | 2023-02-07 | Industrial Technology Research Institute | Liquid-crystal polymer, laminated material, liquid-crystal polymer solution, and method of forming liquid-crystal polymer film |
| US11866632B2 (en) | 2019-07-02 | 2024-01-09 | Industrial Technology Research Institute | Liquid-crystal polymer, laminated material, liquid-crystal polymer solution, and method of forming liquid-crystal polymer film |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US11572438B2 (en) | 2019-07-02 | 2023-02-07 | Industrial Technology Research Institute | Liquid-crystal polymer, laminated material, liquid-crystal polymer solution, and method of forming liquid-crystal polymer film |
| US11866632B2 (en) | 2019-07-02 | 2024-01-09 | Industrial Technology Research Institute | Liquid-crystal polymer, laminated material, liquid-crystal polymer solution, and method of forming liquid-crystal polymer film |
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| US12107617B2 (en) | 2019-09-23 | 2024-10-01 | Ticona Llc | RF filter for use at 5G frequencies |
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| US12035467B2 (en) | 2020-02-26 | 2024-07-09 | Ticona Llc | Circuit structure |
| US12104010B2 (en) | 2021-02-04 | 2024-10-01 | Ticona Llc | Polymer composition for an electric circuit protection device |
| CN115449061A (en) * | 2022-09-30 | 2022-12-09 | 江苏沃特特种材料制造有限公司 | Wholly aromatic liquid crystal polyester resin and preparation method and application thereof |
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