CN110177821A - Wholly aromatic polyester and polyester and resin composition - Google Patents
Wholly aromatic polyester and polyester and resin composition Download PDFInfo
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- CN110177821A CN110177821A CN201880006958.8A CN201880006958A CN110177821A CN 110177821 A CN110177821 A CN 110177821A CN 201880006958 A CN201880006958 A CN 201880006958A CN 110177821 A CN110177821 A CN 110177821A
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- Prior art keywords
- wholly aromatic
- aromatic polyester
- polyester
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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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
- H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
- H01B3/42—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes polyesters; polyethers; polyacetals
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
- H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
- H01B3/42—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes polyesters; polyethers; polyacetals
- H01B3/421—Polyesters
Abstract
[project] provides high thermal stability, the good Wholly aromatic polyester of hydrolytic resistance and its polyester and resin composition.[solution] by using be 60~85 moles of % by 6-Hydroxy-2-naphthoic acid, 4-HBA is 12~40 moles of %, 1,4- benzene dicarboxylic acid or 4,4 '-dihydroxybiphenyls are the Wholly aromatic polyester that 0.1~3 mole of % is formed, to solve the above subject.
Description
Technical field
The present invention relates to thermal stability height, the good Wholly aromatic polyester of hydrolytic resistance and its polyester and resin compositions.
Background technique
There is excellent mobility, machinery well by the liquid-crystalline polymer harmony of representative of liquid crystalline polyester resin
Therefore intensity, heat resistance, chemical resistance, electrical property etc. are compatibly widely used as high function engineering plastics.
A kind of improvement autofrettage of the thermal stability thermotropic liquid crystal polyester of regulation chain length is disclosed in patent document 1.It should
In document, by making containing a small amount of Isosorbide-5-Nitrae-benzene dicarboxylic acid in liquid crystalline polyester, so that thermal stability be made to improve.However, the liquid
The thermal stability of crystalline substance polyester may not be abundant.
A kind of autofrettage of the thermal stability thermotropic liquid crystal polyester of regulation chain length is also disclosed in patent document 2.This article
In offering, by making in liquid crystalline polyester containing a small amount of 2,6- dihydroxy naphthlene or 4,4 '-dihydroxybiphenyls, to make thermal stability
It improves.However, the thermal stability of the liquid crystalline polyester also may not be abundant.
Insulating materials liquid crystal liquid crystal property aromatic polyester and its resin combination are disclosed in patent document 3.In the document, lead to
Crossing makes containing a large amount of 6-Hydroxy-2-naphthoic acid in liquid crystal liquid crystal property aromatic polyester, to reach low dielectric loss angle tangent.So
And the composition of the liquid crystal liquid crystal property aromatic polyester is only hydroxycarboxylic acid with high reactivity, that there are thermal stability is poor, decomposes more than gas
Problem.
In addition, these liquid crystalline polyesters may not be abundant in terms of hydrolytic resistance, under the inferior hygrothermal environment of high temperature and humidity
Using when polyester molded product, there are hydrolysis to be promoted obtained from forming polyester and resin composition, heat resistance, mechanical strength are bright
The problem of aobvious reduction etc.
Existing technical literature
Patent document
Patent document 1: Japanese Unexamined Patent Application 60-040127 bulletin
Patent document 2: Japanese Unexamined Patent Application 60-245631 bulletin
Patent document 3: Japanese Unexamined Patent Publication 2004-250620 bulletin
Summary of the invention
Problems to be solved by the invention
The present invention makes to solve the above-mentioned problems, and project is, provides: thermal stability height, hydrolytic resistance
Good Wholly aromatic polyester and its polyester and resin composition.
The solution to the problem
The inventors of the present invention further investigate repeatedly, as a result, it has been found that: it rubs by using by 6-Hydroxy-2-naphthoic acid for 60~85
That %, 4-HBA is 12~40 moles of %, 1,4- benzene dicarboxylic acids or 4,4 '-dihydroxybiphenyls are 0.1~3 mole of % shape
At Wholly aromatic polyester, so as to solve the above subject, the inventors of the present invention so far complete the present invention.More specifically,
The present invention provides scheme below.
(1) a kind of Wholly aromatic polyester, it includes following structural units (I), (II) and (III) or (IV) as necessary
Constituent,
Relative to entire infrastructure unit, the content of structural unit (I) is 60~85 moles of %,
Relative to entire infrastructure unit, the content of structural unit (II) is 12~40 moles of %,
Relative to entire infrastructure unit, the content of structural unit (III) or (IV) are 0.1~3 mole of %,
Relative to entire infrastructure unit, structural unit (I), (II) and (III) or (IV) the content of total be 100 to rub
You are %.
(2) Wholly aromatic polyester according to (1), in high 10~30 DEG C of the temperature of fusing point than Wholly aromatic polyester
Under melt viscosity be 1000Pas or less.
(3) Wholly aromatic polyester according to (1) or (2) is 10~30 DEG C high in the fusing point than Wholly aromatic polyester
At a temperature of melt viscosity be 3~500Pas.
(4) Wholly aromatic polyester according to any one of (1)~(3), fusing point are 380 DEG C or less.
(5) Wholly aromatic polyester according to any one of (1)~(4), fusing point are 250~370 DEG C.
(6) Wholly aromatic polyester according to any one of (1)~(5), crystallization heat are 2.5J/g or more.
(7) Wholly aromatic polyester according to any one of (1)~(6), the value of [fusing point-crystallization temperature] are 20 DEG C
More than.
(8) a kind of polyester and resin composition contains Wholly aromatic polyester described in any one of (1)~(7).
(9) a kind of polyester molded product is by Wholly aromatic polyester or polyester resin described in any one of (1)~(8)
Obtained from composition molding.
The effect of invention
According to the present invention it is possible to provide: thermal stability height, the good Wholly aromatic polyester of hydrolytic resistance and its polyester tree
Oil/fat composition.
Specific embodiment
Hereinafter, one embodiment of the present invention is described in detail.The present invention is not limited to the following embodiments and the accompanying drawings, can
To be suitable for being changed and being implemented in the range of not interfering effect of the invention.
[Wholly aromatic polyester]
Wholly aromatic polyester of the invention includes following structural units (I), (II) and (III) or (IV) as necessary
Constituent, relative to entire infrastructure unit, the content of structural unit (I) is 60~85 moles of %, relative to entire infrastructure list
Member, the content of structural unit (II) is 12~40 moles of %, relative to entire infrastructure unit, structural unit (III) or (IV's)
Content is 0.1~3 mole of %, relative to entire infrastructure unit, the total of structural unit (I), (II) and (III) or (IV)
Content is 100 moles of %.
Structural unit (I) is derived from 6-Hydroxy-2-naphthoic acid (hereinafter also referred to as " HNA ").All aromatic of the invention is poly-
Ester includes the structural unit (I) for being 60~85 moles of % relative to entire infrastructure unit.The content of structural unit (I) is rubbed lower than 60
When your %, fusing point is reduced, and heat resistance is insufficient.When the content of structural unit (I) is more than 85 moles of %, when polymerization, is cured, nothing
Method obtains polymer.The content of structural unit (I) preferably 63~85 moles of %, more preferable 63~83 moles of %, further preferably
The %, most preferably 68~80 moles of 65~83 moles of %, still more preferably 65~80 moles %.
Structural unit (II) is derived from 4-HBA (hereinafter also referred to as " HBA ").Wholly aromatic polyester of the invention
Include the structural unit (II) for being 12~40 moles of % relative to entire infrastructure unit.The content of structural unit (II) is rubbed lower than 12
When your %, polymer solidifies in aggregation container when manufacture, and polymer can not be discharged.The content of structural unit (II) is more than 40 to rub
When your %, fusing point is reduced, and heat resistance is insufficient.From the viewpoint of fusing point and polymerism, the content preferably 15 of structural unit (II)
~40 moles of %, more preferable 15~35 moles of %, further preferred 18~35 moles of %, still more preferably 18~30 are rubbed
You are the % of %, most preferably 20~30 moles.
Structural unit (III) is derived from Isosorbide-5-Nitrae-benzene dicarboxylic acid (hereinafter also referred to as " TA "), and structural unit (IV) is derived from 4,
4 '-dihydroxybiphenyls (hereinafter also referred to as " BP ").Wholly aromatic polyester of the invention includes to be relative to entire infrastructure unit
The structural unit (III) or structural unit (IV) of 0.1~3 mole of %.The content of structural unit (III) or structural unit (IV) is low
When 0.1 mole of %, thermal stability is reduced.When the content of structural unit (III) or structural unit (IV) is more than 3 moles of %, point
Son amount (melt viscosity) does not rise.From the viewpoint of thermal stability and molecular weight, structural unit (III) or structural unit (IV)
Content preferably 0.2~2.5 mole of %, more preferable 0.2~2 mole of %, further preferred 0.3~2 mole of %, further it is excellent
Select the % of 0.3~1.5 mole of %, most preferably 0.4~1.5 mole.
As previously discussed, it is the specific of specific quantity that Wholly aromatic polyester of the invention, which contains relative to entire infrastructure unit,
Structural unit is (I)~(IV), and therefore, generation gas is few, and thermal stability is high, and hydrolytic resistance is good.It should be noted that
It is structural unit (I)~(IV) for amounting to 100 moles of % that Wholly aromatic polyester of the invention, which includes relative to entire infrastructure unit,.
Then, the property of Wholly aromatic polyester is illustrated.Wholly aromatic polyester of the invention embodies light in melting
Learn anisotropy.It embodies optical anisotropy in melting to refer to, Wholly aromatic polyester of the invention is liquid-crystalline polymer.
In the present invention, Wholly aromatic polyester is that liquid-crystalline polymer is to have both thermal stability and Yi Jia in Wholly aromatic polyester
Essential element in work.The Wholly aromatic polyester being made of above structure unit (I)~(IV) according to constituent and
Sequence in polymer is distributed and there is also the polymer for having not formed anisotropy melting behaviors, but polymer of the invention limits
In melting when embody optically anisotropic Wholly aromatic polyester.
Melting anisotropic property can be confirmed and the common polarisation inspection method using cross-polarization piece.More
Specifically, melting anisotropic confirmation can be implemented as follows: using Olympus Corporation petrographic microscope,
Make the sample melting for being placed in Linkham company heating microscope carrier, in a nitrogen atmosphere, is observed with 150 times of multiplying power, thus
It can be implemented.Liquid-crystalline polymer is optical anisotropy, penetrates light when between insertion cross-polarization piece.Sample be optics respectively to
When anisotropic, such as even if to melt static liquid status, polarisation is also penetrated.
Nematic crystal polymer obviously generates viscosity more than fusing point and reduces, therefore, generally more than fusing point or its
At a temperature of embody liquid crystal liquid crystal property become processability index.From the viewpoint of heat resistance, preferably fusing point is high as far as possible, if it is considered that
The heating efficiency etc. of heat deterioration, molding machine when the melt-processed of polymer then becomes preferred target for 380 DEG C or less.It needs
Illustrate, fusing point is 250~370 DEG C more preferable, it is 270~370 DEG C further preferred, still more preferably 270~350 DEG C, most
It is preferred that 290~350 DEG C.
10~30 DEG C of temperature higher than the fusing point of Wholly aromatic polyester of the invention and under shear velocity 1000/ second before
State the preferred 1000Pas or less of melt viscosity of Wholly aromatic polyester, more preferable 3~500Pas, even more preferably 3~
250Pa·s.When above-mentioned melt viscosity is in above range, aforementioned Wholly aromatic polyester itself or poly- containing aforementioned all aromatic
In its molding, it is easy to ensure that mobility, stuffing pressure is not easy to become over the composition of ester.It should be noted that this explanation
In book, melt viscosity refers to, the melt viscosity measured according to ISO11443.
The preferred 2.5J/g or more of the crystallization heat of Wholly aromatic polyester of the invention, more preferable 2.5~4.4J/g.Pass through differential thermal
When measuring the crystallization heat of the crystalline state of the embodiment polymer found out lower than 2.5J/g, crystallinity is low, and hydrolytic resistance deteriorates.Separately
Outside, when crystallization heat is more than 4.4J/g, toughness is lower, not preferably.
It should be noted that crystallization heat refers to, in differential thermal measurement, surveyed under Elevated Temperature Conditions of the room temperature at 20 DEG C/min
After the observation for determining the endotherm peak temperature (Tm1) observed when polymer, (Tm1+40) DEG C at a temperature of kept for 2 minutes after, by
The heat for the exothermic peak that the peak of the exothermic peak temperature observed when measuring under 20 DEG C/min of cooling conditions is found out.
In addition, for the Wholly aromatic polyester in the present invention, from subtracted in fusing point value obtained from crystallization temperature, i.e., it is [molten
Point-crystallization temperature] preferably 20 DEG C or more of value, 30~90 DEG C more preferable.The value of [fusing point-crystallization temperature] is in above range
When, aforementioned Wholly aromatic polyester itself or the composition containing aforementioned Wholly aromatic polyester are in its molding, it is easy to ensure that flowing
Property, stuffing pressure is not easy to become over.
Then, the manufacturing method of Wholly aromatic polyester of the invention is illustrated.Wholly aromatic polyester of the invention can
It is polymerize with using direct polymerization method, ester-interchange method etc..When polymerization, it is poly- that melt phase polycondensation, solution polymerization process, slurry can be used
Legal, solid phase polymerization method etc. or their combination of more than two kinds are, it is preferable to use melt phase polycondensation or melt phase polycondensation and solid phase
The combination of polymerization.
In the present invention, when polymerization, as acylating agent, the acyl chlorides compound derivative to polymerized monomer, can be used makes end
The monomer activated.As acylating agent, fatty acid anhydrides such as acetic anhydride etc. can be enumerated.
When they polymerize, various catalyst can be used, as representative catalyst, potassium acetate, acetic acid can be enumerated
The metals such as magnesium, stannous acetate, butyl titanate, lead acetate, sodium acetate, antimony trioxide, three (2,4- pentanedione acidic group) cobalts (III)
The organic compounds series catalysts such as salt series catalysts, N- methylimidazole, 4-dimethylaminopyridine.The general base of the dosage of catalyst
In the gross mass of monomer, preferably from about 0.001~1 mass %, particularly preferably about 0.003~0.2 mass %.
[polyester and resin composition]
In the Wholly aromatic polyester of aforementioned present invention, various threadinesss, granular, plate can be compounded according to purpose is used
The inorganic and organic filler of shape.
As the inorganic filler being compounded in polyester and resin composition of the invention, have fibrous, granular, plate inorganic
Filler.
As fibrous inorganic filler, glass fibre, milled glass fibre, asbestos fibre, silica can be enumerated
Fiber, silica alumina fiber, alumina fibre, Zirconium oxide fibre, boron nitride fiber, silicon nitride fiber, boron fibre,
The fiber of silicate as potassium titanate fibre, wollastonite, magnesium sulfate fiber, aluminum borate fiber, further stainless steel, aluminium, titanium,
The inorganic fibres shape substance such as fibrous material of the metals such as copper, brass.The fibrous filler of special representative's property is glass fibre.
In addition, as granular inorganic filler, can enumerate carbon black, graphite, silica, quartz powder, bead,
Silicate as glass marble, glass powder, calcium silicates, alumina silicate, kaolin, clay, diatomite, wollastonite, iron oxygen materialization,
Titanyl compound, the oxide of zinc, antimony trioxide, aluminium oxide as metal oxide, calcium carbonate, magnesium carbonate it is such
The carbonate of metal, calcium sulfate, the sulfate of metal as barium sulfate and ferrite, silicon carbide, silicon nitride, nitridation
Boron, various metal powders etc..
In addition, mica, glass flake, talcum, various metal foils etc. can be enumerated as plate like inorganic filler.
If showing example be compounded in polyester and resin composition of the invention, organic filler, for fragrant adoption
Heat resistances high strength synthetic fibres such as ester fiber, liquid-crystalline polymer fiber, aromatic polyamide, polyimide fiber etc..
One or two or more kinds can be applied in combination in these inorganic and organic fillers.Fibrous inorganic filler with it is granular
Or plate like inorganic filler is combined in that have both be preferably to combine in mechanical strength and dimensional accuracy, electrical property etc..Make
It is compounded for fibrous filler, particularly preferably glass fibre as plate filler, particularly preferably mica and talcum
Amount is relative to 100 mass parts of Wholly aromatic polyester, below the mass for 120, preferably 20~80 mass parts.By glass fibre and cloud
Female or talcum combination, so that the raising of the heat distortion temperature of polyester and resin composition, mechanical properties etc. is particularly evident.
When using these fillers, if it is desired, sizing agent or surface treating agent then can be used.
Polyester and resin composition of the invention is for example above-mentioned, includes Wholly aromatic polyester of the invention and nothing as needed
Machine or organic filler are as essential component, as long as also may include other compositions for the range for not interfering effect of the invention.
Herein, other compositions refer to any ingredient, for example, other resins, antioxidant, stabilizer, pigment, crystallization nucleation
The additives such as agent.
In addition, the manufacturing method of polyester and resin composition of the invention is not particularly limited, known side can be used
Method prepares polyester and resin composition.
[polyester molded product]
Polyester molded product of the invention is to be molded with Wholly aromatic polyester or polyester and resin composition of the invention.
It as forming method, is not particularly limited, general forming method can be used.As general forming method, can enumerate
Injection moulding, extrusion molding, compression forming, blow molding, vacuum forming, foaming, rotational forming, STUDY ON AIR INJECTION MOLDING,
The methods of inflation molding.
The excellent heat resistance for the polyester molded product that Wholly aromatic polyester etc. of the invention is molded with.In addition, this is sent out
The excellent heat resistance for the polyester molded product that bright polyester and resin composition is molded with, and as needed comprising inorganic or organic fill out
Agent is filled, therefore, mechanical strength etc. is further improved.
In addition, the mouldability of Wholly aromatic polyester of the invention, polyester and resin composition is excellent, therefore, can be processed into
Various stereo shaping product, fiber, film etc..
As the preferable use of the polyester molded product of the invention with the above property, connector can be enumerated, CPU is inserted
Seat, relay switch component, bobbin (bobbin), driver, noise filter shell, electronic circuit board or OA equipment
Heat fixing roll etc..
Embodiment
Embodiment is shown the present invention is further concretely demonstrated in below, but the present invention is not by these embodiments
It limits.
1 > of < embodiment
Have blender, reflux column, monomer input port, nitrogen inlet, in decompression/outflow pipeline aggregation container,
Starting monomer below, fatty acid metal salt catalyst, acylating agent are put into, nitrogen displacement is started.
(I) 1.44 moles of 6-Hydroxy-2-naphthoic acid (76 moles of %) (HNA)
(II) 0.44 mole of 4-HBA (23.3 moles of %) (HBA)
(III) 0.1 mole of terephthalic acid (TPA) (0.7 mole of %) (TA)
Potassium acetate catalyst 22.5mg
Acetic anhydride 196g (1.02 times of the hydroxyl equivalent of the total of HNA and HBA)
After putting into raw material, the temperature of reaction system is increased to 140 DEG C, is reacted 2 hours with 140 DEG C.Later, it further uses
Be warming up to 340 DEG C within 4.1 hours, be decompressed to 10Torr (that is, 1330Pa) from it with 15 minutes, while make acetic acid, superfluous acetic anhydride,
Other low boilings carry out polycondensation at side is fractionated out.After stirring torque reaches defined value, nitrogen is imported, from the frequent swaging of decompression state
At pressurized state, polymer is discharged from the lower part of aggregation container.
< evaluates >
For the Wholly aromatic polyester of embodiment 1, fusing point, crystallization temperature, crystallization heat, melting have been carried out with the following method
The evaluation of viscosity, thermal stability and hydrolytic resistance.Show the results of the evaluation table 1.
[fusing point]
With differential scanning calorimetry (DSC) (DSC, Perkin Elmer corporation), from room temperature with 20 DEG C/min of Elevated Temperature Conditions
After the observation of endotherm peak temperature (Tm1) observed when measuring Wholly aromatic polyester, (Tm1+40) DEG C at a temperature of kept for 2 points
Zhong Hou, after being temporarily cooled to room temperature with 20 DEG C/min of cooling conditions, measurement is measured again with 20 DEG C/min of Elevated Temperature Conditions
When the temperature of endothermic peak that observes.
[crystallization temperature]
With differential scanning calorimetry (DSC) (DSC, Perkin Elmer corporation), with 20 DEG C/min of Elevated Temperature Conditions from room temperature
After the observation of endotherm peak temperature (Tm1) observed when measuring Wholly aromatic polyester, (Tm1+40) DEG C at a temperature of kept for 2 points
Zhong Hou, the exothermic peak temperature that measurement observes when being measured with 20 DEG C/min of cooling conditions.
[crystallization heat]
With differential scanning calorimetry (DSC) (DSC, Perkin Elmer corporation), with 20 DEG C/min of Elevated Temperature Conditions from room temperature
After the observation of endotherm peak temperature (Tm1) observed when measuring Wholly aromatic polyester, (Tm1+40) DEG C at a temperature of kept for 2 points
Zhong Hou, the heat for the exothermic peak that the peak of the exothermic peak temperature observed when measurement with 20 DEG C/min of cooling conditions by being measured is found out
Amount.
[melt viscosity]
Make made Capilograph using Toyo Co., Ltd.'s essence mechanism, the fusing point than Wholly aromatic polyester it is high by 10~
At a temperature of 30 DEG C, with the aperture of internal diameter 0.5mm, length 30mm, with shear velocity 1000/ second, according to ISO11443, measurement was complete
The melt viscosity of aromatic polyester.
[thermal stability]
Using differential thermal thermogravimetric while measurement device (TG/DTA, Seiko Instruments Inc. system), measure in nitrogen
Weight when 30 minutes Wholly aromatic polyester 10mg is kept to reduce as generation gas flow under air-flow, using 370 DEG C.It needs to illustrate
It is, if generating gas flow is lower than 15000ppm, to be judged as good.
[hydrolytic resistance]
For Wholly aromatic polyester, under 100%, 2 121 DEG C, humidity air pressure conditions, it is small to carry out pressure cooker testing 100
When, for the Wholly aromatic polyester, the measurement of melt viscosity is carried out, finds out the conservation rate relative to initial value.It needs to illustrate
It is that the conservation rate relative to initial value is judged as good if it is 90% or more.
2 > of < embodiment
The type that makes starting monomer, output-input ratio (mole %) as shown in table 1, in addition to this, similarly to Example 1
To polymer.In a nitrogen atmosphere, resulting polymers were warming up to 290 DEG C with 20 minutes from room temperature, it is natural after being kept for 3 hours
It is cooling, obtain further polymer.In addition, carrying out evaluation similarly to Example 1.Show the results of the evaluation table 1.
3 > of < embodiment
Have blender, reflux column, monomer input port, nitrogen inlet, in decompression/outflow pipeline aggregation container,
Starting monomer below, fatty acid metal salt catalyst, acylating agent are put into, nitrogen displacement is started.
(I) 1.51 moles of 6-Hydroxy-2-naphthoic acid (81 moles of %) (HNA)
(II) 0.34 mole of 4-HBA (18 moles of %) (HBA)
(IV) 0.02 mole of 4,4 '-dihydroxybiphenyl (1 mole of %) (BP)
Potassium acetate catalyst 22.5mg
Acetic anhydride 196g (1.02 times of the hydroxyl equivalent of the total of HNA and HBA and BP)
After putting into raw material, the temperature of reaction system is increased to 140 DEG C, is reacted 2 hours with 140 DEG C.Later, it further uses
Be warming up to 370 DEG C within 4.7 hours, be decompressed to 10Torr (that is, 1330Pa) from it with 15 minutes, while make acetic acid, superfluous acetic anhydride,
Other low boilings carry out polycondensation at side is fractionated out.After stirring torque reaches defined value, nitrogen is imported, from the frequent swaging of decompression state
At pressurized state, polymer is discharged from the lower part of aggregation container.In addition, carrying out evaluation similarly to Example 1.By evaluation result
It is shown in table 1.
< embodiment 4~8,1~8 > of comparative example
The type that makes starting monomer, output-input ratio (mole %) are as shown in Table 1 and Table 2, in addition to this, same with embodiment 1
Obtain polymer to sample.In addition, carrying out evaluation similarly to Example 1.Show the results of the evaluation Tables 1 and 2.It needs to illustrate
It is that, for comparative example 4, polymer solidifies in aggregation container when manufacture, polymer can not be discharged.
[table 1]
[table 2]
Claims (9)
1. a kind of Wholly aromatic polyester, it includes following structural units (I), (II) and (III) or (IV) to be used as necessary composition
Ingredient,
Relative to entire infrastructure unit, the content of structural unit (I) is 60~85 moles of %,
Relative to entire infrastructure unit, the content of structural unit (II) is 12~40 moles of %,
Relative to entire infrastructure unit, the content of structural unit (III) or (IV) are 0.1~3 mole of %,
Relative to entire infrastructure unit, structural unit (I), (II) and (III) or (IV) the content of total be 100 moles of %,
(I)
(II)
(III)
(IV)
2. Wholly aromatic polyester according to claim 1, in high 10~30 DEG C of the temperature of fusing point than Wholly aromatic polyester
Melt viscosity under degree is 1000Pas or less.
3. Wholly aromatic polyester according to claim 1 or 2, in high 10~30 DEG C of fusing point than Wholly aromatic polyester
At a temperature of melt viscosity be 3~500Pas.
4. Wholly aromatic polyester described in any one of claim 1 to 3, fusing point is 380 DEG C or less.
5. Wholly aromatic polyester according to any one of claims 1 to 4, fusing point is 250~370 DEG C.
6. Wholly aromatic polyester according to any one of claims 1 to 5, crystallization heat is 2.5J/g or more.
7. Wholly aromatic polyester described according to claim 1~any one of 6, the value of [fusing point-crystallization temperature] is 20 DEG C
More than.
8. a kind of polyester and resin composition contains Wholly aromatic polyester according to any one of claims 1 to 7.
9. a kind of polyester molded product is by Wholly aromatic polyester according to any one of claims 1 to 8 or polyester resin group
It closes obtained from object molding.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2017011860 | 2017-01-26 | ||
| JP2017-011860 | 2017-01-26 | ||
| PCT/JP2018/001718 WO2018139393A1 (en) | 2017-01-26 | 2018-01-22 | Wholly aromatic polyester and polyester resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
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| KR (1) | KR102120296B1 (en) |
| CN (1) | CN110177821B (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116134553A (en) * | 2020-07-16 | 2023-05-16 | 宝理塑料株式会社 | Resin composition and molded article thereof |
| US11912817B2 (en) | 2019-09-10 | 2024-02-27 | Ticona Llc | Polymer composition for laser direct structuring |
| US11917753B2 (en) | 2019-09-23 | 2024-02-27 | Ticona Llc | Circuit board for use at 5G frequencies |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP6837189B1 (en) * | 2019-04-03 | 2021-03-03 | ポリプラスチックス株式会社 | Total aromatic polyester and polyester resin composition |
| US20210070927A1 (en) * | 2019-09-10 | 2021-03-11 | Ticona Llc | Polymer Composition and Film for Use in 5G Applications |
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| US11917753B2 (en) | 2019-09-23 | 2024-02-27 | Ticona Llc | Circuit board for use at 5G frequencies |
| CN116134553A (en) * | 2020-07-16 | 2023-05-16 | 宝理塑料株式会社 | Resin composition and molded article thereof |
Also Published As
| Publication number | Publication date |
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| JPWO2018139393A1 (en) | 2019-02-07 |
| JP6412296B1 (en) | 2018-10-24 |
| TW201840638A (en) | 2018-11-16 |
| KR20190103213A (en) | 2019-09-04 |
| KR102120296B1 (en) | 2020-06-08 |
| WO2018139393A1 (en) | 2018-08-02 |
| TWI730219B (en) | 2021-06-11 |
| CN110177821B (en) | 2020-03-24 |
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