CN110177821B - Wholly aromatic polyester and polyester resin composition - Google Patents
Wholly aromatic polyester and polyester resin composition Download PDFInfo
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- CN110177821B CN110177821B CN201880006958.8A CN201880006958A CN110177821B CN 110177821 B CN110177821 B CN 110177821B CN 201880006958 A CN201880006958 A CN 201880006958A CN 110177821 B CN110177821 B CN 110177821B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/60—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from the reaction of a mixture of hydroxy carboxylic acids, polycarboxylic acids and polyhydroxy compounds
- C08G63/605—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from the reaction of a mixture of hydroxy carboxylic acids, polycarboxylic acids and polyhydroxy compounds the hydroxy and carboxylic groups being bound to aromatic rings
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/60—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from the reaction of a mixture of hydroxy carboxylic acids, polycarboxylic acids and polyhydroxy compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
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- 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
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- 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
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
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- Spectroscopy & Molecular Physics (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
A wholly aromatic polyester having high thermal stability and good hydrolysis resistance, and a polyester resin composition thereof are provided. The problem is solved by using a wholly aromatic polyester comprising 60 to 85 mol% of 6-hydroxy-2-naphthoic acid, 12 to 40 mol% of 4-hydroxybenzoic acid, and 0.1 to 3 mol% of 1, 4-benzenedicarboxylic acid or 4, 4' -dihydroxybiphenyl.
Description
Technical Field
The present invention relates to a wholly aromatic polyester having high thermal stability and good hydrolysis resistance, and a polyester resin composition thereof.
Background
Liquid crystalline polymers represented by liquid crystalline polyester resins are widely used as high-performance engineering plastics because they have excellent flowability, mechanical strength, heat resistance, chemical resistance, electrical properties, and the like in a well-balanced manner.
Patent document 1 discloses an improved process for producing a thermotropic liquid crystalline polyester having a predetermined chain length and a thermal stability. In this document, the thermal stability is improved by incorporating a small amount of 1, 4-benzenedicarboxylic acid into the liquid crystalline polyester. However, the thermal stability of the liquid crystalline polyester is not necessarily sufficient.
Patent document 2 also discloses a method for producing a thermally stable thermotropic liquid crystalline polyester having a predetermined chain length. In this document, the thermal stability is improved by incorporating a small amount of 2, 6-dihydroxynaphthalene or 4, 4' -dihydroxybiphenyl into the liquid crystalline polyester. However, the thermal stability of the liquid crystalline polyester is not necessarily sufficient.
Patent document 3 discloses a liquid crystalline aromatic polyester for an insulating material and a resin composition thereof. In this document, a liquid crystalline aromatic polyester contains a large amount of 6-hydroxy-2-naphthoic acid, thereby achieving a low dielectric loss tangent. However, the composition of the liquid crystalline aromatic polyester is only a highly reactive hydroxycarboxylic acid, and has problems of poor thermal stability and a large amount of decomposition gas.
Further, these liquid crystalline polyesters are not necessarily sufficient in hydrolysis resistance, and when a polyester molded article obtained by molding a polyester resin composition is used in a humid and hot environment such as a high-temperature and high-humidity environment, hydrolysis is accelerated, and there is a problem that heat resistance and mechanical strength are remarkably reduced.
Documents of the prior art
Patent document
Patent document 1: japanese laid-open patent publication No. 60-040127
Patent document 2: japanese laid-open patent publication No. 60-245631
Patent document 3: japanese patent laid-open publication No. 2004-250620
Disclosure of Invention
Problems to be solved by the invention
The present invention has been made to solve the above problems, and an object of the present invention is to provide: a wholly aromatic polyester having high thermal stability and good hydrolysis resistance, and a polyester resin composition thereof.
Means for solving the problems
The present inventors have conducted extensive studies and, as a result, have found that: the above object can be achieved by using a wholly aromatic polyester comprising 60 to 85 mol% of 6-hydroxy-2-naphthoic acid, 12 to 40 mol% of 4-hydroxybenzoic acid, and 0.1 to 3 mol% of 1, 4-benzenedicarboxylic acid or 4, 4' -dihydroxybiphenyl, and the present inventors have completed the present invention. More specifically, the present invention provides the following.
(1) A wholly aromatic polyester comprising the following structural units (I), (II), and (III) or (IV) as essential constituent components,
the content of the structural unit (I) is 60 to 85 mol% relative to the total structural units,
the content of the structural unit (II) is 12 to 40 mol% relative to the total structural units,
the content of the structural unit (III) or (IV) is 0.1 to 3 mol% based on the total structural units,
the total content of the structural units (I), (II), and (III) or (IV) is 100 mol% with respect to the total structural units.
(2) The wholly aromatic polyester according to the item (1), which has a melt viscosity of 1000 pas or less at a temperature higher by 10to 30 ℃ than the melting point of the wholly aromatic polyester.
(3) The wholly aromatic polyester according to the item (1) or (2), which has a melt viscosity of 3 to 500 pas at a temperature higher by 10to 30 ℃ than the melting point of the wholly aromatic polyester.
(4) The wholly aromatic polyester according to any one of (1) to (3), which has a melting point of 380 ℃ or lower.
(5) The wholly aromatic polyester according to any one of (1) to (4), which has a melting point of 250 to 370 ℃.
(6) The wholly aromatic polyester according to any one of (1) to (5), wherein the heat of crystallization is 2.5J/g or more.
(7) The wholly aromatic polyester according to any one of (1) to (6), wherein the value of [ melting point-crystallization temperature ] is 20 ℃ or more.
(8) A polyester resin composition comprising the wholly aromatic polyester according to any one of (1) to (7).
(9) A polyester molded article obtained by molding the wholly aromatic polyester or polyester resin composition according to any one of (1) to (8).
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present invention, there can be provided: a wholly aromatic polyester having high thermal stability and good hydrolysis resistance, and a polyester resin composition thereof.
Detailed Description
Hereinafter, an embodiment of the present invention will be described in detail. The present invention is not limited to the following embodiments, and can be carried out by appropriately changing the embodiments within a range not to impair the effects of the present invention.
[ wholly aromatic polyester ]
The wholly aromatic polyester of the present invention contains the following structural units (I), (II), and (III) or (IV) as essential components, and the content of the structural unit (I) is 60 to 85 mol% with respect to the total structural units, the content of the structural unit (II) is 12 to 40 mol% with respect to the total structural units, the content of the structural unit (III) or (IV) is 0.1 to 3 mol% with respect to the total structural units, and the total content of the structural units (I), (II), and (III) or (IV) is 100 mol% with respect to the total structural units.
The structural unit (I) is derived from 6-hydroxy-2-naphthoic acid (hereinafter, also referred to as "HNA"). The wholly aromatic polyester of the present invention contains 60 to 85 mol% of the structural unit (I) with respect to the total structural units. When the content of the structural unit (I) is less than 60 mol%, the melting point decreases and the heat resistance is insufficient. When the content of the structural unit (I) exceeds 85 mol%, curing occurs during polymerization, and a polymer cannot be obtained. The content of the structural unit (I) is preferably 63 to 85 mol%, more preferably 63 to 83 mol%, even more preferably 65 to 80 mol%, and most preferably 68 to 80 mol%.
The structural unit (II) is derived from 4-hydroxybenzoic acid (hereinafter, also referred to as "HBA"). The wholly aromatic polyester of the present invention contains 12 to 40 mol% of the structural unit (II) with respect to the total structural units. When the content of the structural unit (II) is less than 12 mol%, the polymer is solidified in the polymerization vessel during production, and the polymer cannot be discharged. When the content of the structural unit (II) exceeds 40 mol%, the melting point decreases and the heat resistance becomes insufficient. The content of the structural unit (II) is preferably 15 to 40 mol%, more preferably 15 to 35 mol%, further preferably 18 to 30 mol%, most preferably 20 to 30 mol%, from the viewpoint of melting point and polymerizability.
The structural unit (III) is derived from 1, 4-benzenedicarboxylic acid (hereinafter, also referred to as "TA"), and the structural unit (IV) is derived from 4, 4' -dihydroxybiphenyl (hereinafter, also referred to as "BP"). The wholly aromatic polyester of the present invention contains 0.1 to 3 mol% of the structural unit (III) or the structural unit (IV) with respect to the total structural units. When the content of the structural unit (III) or the structural unit (IV) is less than 0.1 mol%, thermal stability is lowered. When the content of the structural unit (III) or the structural unit (IV) exceeds 3 mol%, the molecular weight (melt viscosity) does not increase. From the viewpoint of thermal stability and molecular weight, the content of the structural unit (III) or the structural unit (IV) is preferably 0.2 to 2.5 mol%, more preferably 0.2 to 2 mol%, further preferably 0.3 to 1.5 mol%, most preferably 0.4 to 1.5 mol%.
As described above, the wholly aromatic polyester of the present invention contains specific structural units (I) to (IV) in a specific amount relative to all the structural units, and therefore, it generates less gas, has high thermal stability, and has good hydrolysis resistance. The wholly aromatic polyester of the present invention contains the structural units (I) to (IV) in a total amount of 100 mol% based on the total structural units.
Next, the properties of the wholly aromatic polyester will be described. The wholly aromatic polyester of the present invention exhibits optical anisotropy when melted. The wholly aromatic polyester of the present invention is a liquid crystalline polymer exhibiting optical anisotropy when melted.
In the present invention, the wholly aromatic polyester is an essential element for the wholly aromatic polyester to be a liquid crystalline polymer, in terms of both thermal stability and easy processability. The wholly aromatic polyester composed of the structural units (I) to (IV) includes polymers not forming an anisotropic melt phase depending on the constituent components and the sequence distribution in the polymers, but the polymer of the present invention is limited to wholly aromatic polyesters exhibiting optical anisotropy at the time of melting.
The properties of melt anisotropy can be confirmed by a commonly used polarization inspection method using crossed polarizers. More specifically, the confirmation of the melt anisotropy can be performed as follows: the sample placed on the thermal stage of Linkham was melted using a polarizing microscope manufactured by Olympus Corporation, and observed at a magnification of 150 times under a nitrogen atmosphere. The liquid crystalline polymer is optically anisotropic and transmits light when inserted between crossed polarizers. When the sample is optically anisotropic, polarized light transmits even in a molten static liquid state, for example.
Since a nematic liquid crystalline polymer is significantly reduced in viscosity at a temperature not lower than the melting point, it generally exhibits liquid crystallinity at a temperature not lower than the melting point as an index of processability. From the viewpoint of heat resistance, the melting point is preferably as high as possible, and 380 ℃ or lower is a preferable target in consideration of thermal deterioration in melt processing of the polymer, heating capacity of a molding machine, and the like. The melting point is more preferably 250 to 370 ℃, still more preferably 270 to 350 ℃, and most preferably 290 to 350 ℃.
The melt viscosity of the wholly aromatic polyester at a temperature 10to 30 ℃ higher than the melting point of the wholly aromatic polyester of the present invention and a shear rate of 1000/sec is preferably 1000 pas or less, more preferably 3 to 500 pas, and still more preferably 3 to 250 pas. When the melt viscosity is within the above range, the wholly aromatic polyester itself or the composition containing the wholly aromatic polyester is likely to have fluidity during molding, and the filling pressure is unlikely to become excessive. In the present specification, the melt viscosity refers to a melt viscosity measured according to ISO 11443.
The heat of crystallization of the wholly aromatic polyester of the present invention is preferably 2.5J/g or more, more preferably 2.5 to 4.4J/g. When the heat of crystallization indicating the crystalline state of the polymer as determined by differential thermal measurement is less than 2.5J/g, the crystallinity is low and the hydrolysis resistance is deteriorated. When the heat of crystallization exceeds 4.4J/g, toughness is lowered, which is not preferable.
The heat of crystallization is the heat quantity of an exothermic peak obtained from the peak of an exothermic peak temperature observed when a polymer is measured under a temperature rise condition of 20 ℃/min from room temperature after the observation of the endothermic peak temperature (Tm1) in the differential heat measurement and after being held at a temperature of (Tm1+40) ° c for 2 minutes, under a temperature drop condition of 20 ℃/min.
In addition, in the invention of the wholly aromatic polyester, from the melting point minus the crystallization temperature value, namely, [ melting point-crystallization temperature ] value is preferably 20 degrees C or more, more preferably 30 ~ 90 ℃. When the value of [ melting point-crystallization temperature ] is within the above range, the wholly aromatic polyester itself or a composition containing the wholly aromatic polyester is likely to have fluidity during molding, and the filling pressure is unlikely to become excessive.
Next, a method for producing the wholly aromatic polyester of the present invention will be described. The wholly aromatic polyester of the present invention can be polymerized by a direct polymerization method, an ester exchange method, or the like. In the polymerization, a melt polymerization method, a solution polymerization method, a slurry polymerization method, a solid phase polymerization method, or the like, or a combination of 2 or more of them may be used, and a melt polymerization method or a combination of a melt polymerization method and a solid phase polymerization method is preferably used.
In the present invention, in the polymerization, as the acylating agent or the acid chloride derivative to the monomer to be polymerized, a monomer having an activated terminal can be used. Examples of the acylating agent include fatty acid anhydrides such as acetic anhydride.
In the polymerization, various catalysts can be used, and typical examples thereof include metal salt catalysts such as potassium acetate, magnesium acetate, stannous acetate, tetrabutyl titanate, lead acetate, sodium acetate, antimony trioxide, tris (2, 4-pentanedionato) cobalt (III), and organic compound catalysts such as N-methylimidazole and 4-dimethylaminopyridine. The catalyst is generally used in an amount of about 0.001 to 1% by mass, preferably about 0.003 to 0.2% by mass, based on the total mass of the monomers.
[ polyester resin composition ]
The wholly aromatic polyester of the present invention may contain various inorganic and organic fillers in the form of fibers, powder particles, or plates depending on the purpose of use.
The inorganic filler to be blended in the polyester resin composition of the present invention includes fibrous, granular and plate-like inorganic fillers.
Examples of the fibrous inorganic filler include inorganic fibrous materials such as glass fibers, ground glass fibers, asbestos fibers, silica-alumina fibers, zirconia fibers, boron nitride fibers, silicon nitride fibers, boron fibers, potassium titanate fibers, and silicate fibers such as wollastonite, magnesium sulfate fibers, aluminum borate fibers, and further metallic fibrous materials such as stainless steel, aluminum, titanium, copper, and brass. A particularly representative fibrous filler is glass fiber.
Examples of the particulate inorganic filler include carbon black, graphite, silica, quartz powder, glass beads, glass spheres, glass powder, calcium silicate, aluminum silicate, kaolin, clay, diatomaceous earth, silicates such as wollastonite, iron oxides, titanium oxides, zinc oxides, antimony trioxide, metal oxides such as aluminum oxides, carbonates such as calcium carbonate and magnesium carbonate, sulfates such as calcium sulfate and barium sulfate, and ferrite, silicon carbide, silicon nitride, boron nitride, and various metal powders.
Examples of the plate-like inorganic filler include mica, glass flakes, talc, and various metal foils.
Examples of the organic filler to be blended in the polyester resin composition of the present invention include heat-resistant high-strength synthetic fibers such as aromatic polyester fibers, liquid crystalline polymer fibers, aromatic polyamides, and polyimide fibers.
These inorganic and organic fillers may be used singly or in combination. The combination use of the fibrous inorganic filler and the particulate or plate-like inorganic filler is a preferable combination in view of both of mechanical strength, dimensional accuracy, electrical properties, and the like. The fibrous filler is particularly preferably glass fiber, and the plate-like filler is particularly preferably mica and talc, and the amount of the fibrous filler blended is 120 parts by mass or less, preferably 20 to 80 parts by mass, based on 100 parts by mass of the wholly aromatic polyester. The combination of the glass fiber with mica or talc significantly improves the heat distortion temperature, mechanical properties and the like of the polyester resin composition.
When these fillers are used, a sizing agent or a surface treatment agent may be used if necessary.
The polyester resin composition of the present invention contains the wholly aromatic polyester of the present invention and, if necessary, an inorganic or organic filler as essential components as described above, and may contain other components as long as the effects of the present invention are not impaired. The other component is an arbitrary component, and examples thereof include other resins, antioxidants, stabilizers, pigments, and additives such as crystal nucleating agents.
The method for producing the polyester resin composition of the present invention is not particularly limited, and the polyester resin composition can be produced by a conventionally known method.
[ polyester molded article ]
The polyester molded article of the present invention is obtained by molding the wholly aromatic polyester or the polyester resin composition of the present invention. The molding method is not particularly limited, and a general molding method can be employed. Typical molding methods include injection molding, extrusion molding, compression molding, blow molding, vacuum molding, foam molding, rotational molding, gas injection molding, inflation molding, and the like.
The polyester molded article obtained by molding the wholly aromatic polyester or the like of the present invention has excellent heat resistance. In addition, the polyester resin composition of the invention formed into polyester molded products excellent in heat resistance, and according to the need of containing inorganic or organic fillers, therefore, the mechanical strength and other further improved.
The wholly aromatic polyester and polyester resin composition of the present invention are excellent in moldability and can be processed into various three-dimensional molded articles, fibers, films, and the like.
Preferable applications of the polyester molded article of the present invention having the above properties include a connector, a CPU socket, a relay switch part, a bobbin (bobbin), a driver, a noise reduction filter housing, a heating and fixing roller of an electronic circuit board or an OA equipment.
Examples
The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.
< example 1 >
The following raw material monomers, fatty acid metal salt catalyst and acylating agent were charged into a polymerization vessel equipped with a stirrer, reflux column, monomer inlet, nitrogen gas inlet, and depressurization/outflow line, and nitrogen substitution was started.
(I) 1.44 mol (76 mol%) of 6-hydroxy-2-naphthoic acid (HNA)
(II) 4-hydroxybenzoic acid 0.44 mol (23.3 mol%) (HBA)
(III) terephthalic acid 0.1 mol (0.7 mol%) (TA)
Potassium acetate catalyst 22.5mg
196g of acetic anhydride (1.02 times the total hydroxyl equivalent of HNA and HBA)
After the charge of the raw materials, the temperature of the reaction system was raised to 140 ℃ and reacted at 140 ℃ for 2 hours. Then, the temperature was raised to 340 ℃ over a further 4.1 hours, and from this temperature, the pressure was reduced to 10Torr (1330 Pa) over a further 15 minutes, and polycondensation was carried out while distilling off acetic acid, excess acetic anhydride, and other low-boiling components. After the stirring torque reached a predetermined value, nitrogen gas was introduced, and the pressure was increased from a reduced pressure state to a normal pressure state, and the polymer was discharged from the bottom of the polymerization vessel.
< evaluation >
The wholly aromatic polyester of example 1 was evaluated for melting point, crystallization temperature, crystallization heat, melt viscosity, thermal stability and hydrolysis resistance by the following methods. The evaluation results are shown in table 1.
[ melting Point ]
An endothermic peak temperature (Tm1) observed when the wholly aromatic polyester is measured from room temperature under a temperature rise condition of 20 ℃/min by a differential scanning calorimeter (DSC, Perkin Elmer Co., Ltd.), the obtained product is held at a temperature of (Tm1+40) ° C for 2 minutes, then cooled down to room temperature under a temperature rise condition of 20 ℃/min, and then the temperature of the endothermic peak observed when the temperature is measured again under a temperature rise condition of 20 ℃/min is measured.
[ crystallization temperature ]
An endothermic peak temperature (Tm1) observed when the wholly aromatic polyester is measured from room temperature under a temperature rise condition of 20 ℃/min by a differential scanning calorimeter (DSC, Perkin Elmer Co., Ltd.), and then the wholly aromatic polyester is held at a temperature of (Tm1+40) ° C for 2 minutes, and then an exothermic peak temperature observed when the wholly aromatic polyester is measured under a temperature drop condition of 20 ℃/min is measured.
[ Heat of crystallization ]
The endothermic peak temperature (Tm1) observed when the wholly aromatic polyester is measured from room temperature under a temperature rise condition of 20 ℃/min by a differential scanning calorimeter (DSC, Perkin Elmer Co., Ltd.), and after holding at a temperature of (Tm1+40) ° C for 2 minutes, the heat quantity of the exothermic peak obtained from the peak of the exothermic peak temperature observed when measured under a temperature drop condition of 20 ℃/min is measured.
[ melt viscosity ]
The melt viscosity of the wholly aromatic polyester was measured at a shear rate of 1000/sec according to ISO11443 using Capilograph manufactured by Toyo Seiki Seisaku-Sho K.K., using an orifice having an inner diameter of 0.5mm and a length of 30mm at a temperature of 10to 30 ℃ higher than the melting point of the wholly aromatic polyester.
[ thermal stability ]
The weight loss of the wholly aromatic polyester at 10mg held at 370 ℃ for 30 minutes under a nitrogen gas flow was measured as the amount of gas generated using a differential thermogravimetry simultaneous measurement apparatus (TG/DTA, manufactured by Seiko Instruments Inc.). It is to be noted that the generated gas amount is judged to be satisfactory if it is less than 15000 ppm.
[ hydrolysis resistance ]
The wholly aromatic polyester was subjected to a pressure cooker test at 121 ℃ and a humidity of 100% under 2 atmospheres for 100 hours, and the melt viscosity of the wholly aromatic polyester was measured to determine the retention ratio with respect to the initial value. The retention ratio with respect to the initial value was determined to be good if 90% or more.
< example 2 >
Polymers were obtained in the same manner as in example 1 except that the kinds and charge ratios (mol%) of the raw material monomers were as shown in table 1. The resulting polymer was heated from room temperature to 290 ℃ over 20 minutes under a nitrogen atmosphere, and after 3 hours, it was naturally cooled to obtain a further polymer. In addition, the same evaluation as in example 1 was performed. The evaluation results are shown in table 1.
< example 3 >
The following raw material monomers, fatty acid metal salt catalyst and acylating agent were charged into a polymerization vessel equipped with a stirrer, reflux column, monomer inlet, nitrogen gas inlet, and depressurization/outflow line, and nitrogen substitution was started.
(I) 1.51 mol (81 mol%) (HNA) of 6-hydroxy-2-naphthoic acid
(II) 4-hydroxybenzoic acid 0.34 mol (18 mol%) (HBA)
(IV)4, 4' -Dihydroxybiphenyl 0.02 mol (1 mol%) (BP)
Potassium acetate catalyst 22.5mg
196g of acetic anhydride (1.02 times the hydroxyl equivalent of the total of HNA, HBA and BP)
After the charge of the raw materials, the temperature of the reaction system was raised to 140 ℃ and reacted at 140 ℃ for 2 hours. Then, the temperature was raised to 370 ℃ over a further 4.7 hours, and from this temperature, the pressure was reduced to 10Torr (1330 Pa) over a further 15 minutes, and polycondensation was carried out while distilling off acetic acid, excess acetic anhydride, and other low-boiling components. After the stirring torque reached a predetermined value, nitrogen gas was introduced, and the pressure was increased from a reduced pressure state to a normal pressure state, and the polymer was discharged from the bottom of the polymerization vessel. In addition, the same evaluation as in example 1 was performed. The evaluation results are shown in table 1.
< examples 4 to 8, comparative examples 1 to 8 >
Polymers were obtained in the same manner as in example 1, except that the kinds and charge ratios (mol%) of the raw material monomers were as shown in tables 1 and 2. In addition, the same evaluation as in example 1 was performed. The evaluation results are shown in tables 1 and 2. In comparative example 4, the polymer was solidified in the polymerization vessel during production, and the polymer could not be discharged.
[ Table 1]
[ Table 2]
Claims (9)
1. A wholly aromatic polyester comprising the following structural units (I), (II), and (III) or (IV) as essential constituent components,
the content of the structural unit (I) is 60 to 85 mol% relative to the total structural units,
the content of the structural unit (II) is 12 to 40 mol% relative to the total structural units,
the content of the structural unit (III) or (IV) is 0.1 to 3 mol% based on the total structural units,
the total content of the structural units (I), (II), and (III) or (IV) is 100 mol% based on the total structural units,
(I)
(II)
(III)
(IV)
2. the wholly aromatic polyester according to claim 1, having a melt viscosity of 1000Pa s or less at a temperature 10to 30 ℃ higher than the melting point of the wholly aromatic polyester.
3. The wholly aromatic polyester according to claim 1 or 2, having a melt viscosity of 3 to 500 pas at a temperature of 10to 30 ℃ higher than a melting point of the wholly aromatic polyester.
4. The wholly aromatic polyester according to claim 1 or 2, having a melting point of 380 ℃ or lower.
5. The wholly aromatic polyester according to claim 1 or 2, having a melting point of 250 to 370 ℃.
6. The wholly aromatic polyester according to claim 1 or 2, wherein the heat of crystallization is 2.5J/g or more.
7. The wholly aromatic polyester according to claim 1 or 2, wherein the value of [ melting point-crystallization temperature ] is 20 ℃ or more.
8. A polyester resin composition comprising the wholly aromatic polyester according to any one of claims 1 to 7.
9. A polyester molded article obtained by molding the wholly aromatic polyester or polyester resin composition according to any one of claims 1 to 8.
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 |
|---|---|
| CN110177821A CN110177821A (en) | 2019-08-27 |
| CN110177821B true CN110177821B (en) | 2020-03-24 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201880006958.8A Active CN110177821B (en) | 2017-01-26 | 2018-01-22 | Wholly aromatic polyester and polyester resin composition |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JP6412296B1 (en) |
| KR (1) | KR102120296B1 (en) |
| CN (1) | CN110177821B (en) |
| TW (1) | TWI730219B (en) |
| WO (1) | WO2018139393A1 (en) |
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| KR20210150422A (en) * | 2019-04-03 | 2021-12-10 | 포리프라스틱 가부시키가이샤 | Whole 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 |
| 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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- 2018-01-22 JP JP2018527815A patent/JP6412296B1/en active Active
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Also Published As
| Publication number | Publication date |
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| KR102120296B1 (en) | 2020-06-08 |
| TW201840638A (en) | 2018-11-16 |
| WO2018139393A1 (en) | 2018-08-02 |
| JP6412296B1 (en) | 2018-10-24 |
| TWI730219B (en) | 2021-06-11 |
| CN110177821A (en) | 2019-08-27 |
| KR20190103213A (en) | 2019-09-04 |
| JPWO2018139393A1 (en) | 2019-02-07 |
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