Classifications

• • 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
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
  • C08G63/78—Preparation processes
• • 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
• • 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
  • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
  • C08L67/03—Polyesters derived from dicarboxylic acids and dihydroxy compounds the dicarboxylic acids and dihydroxy compounds having the carboxyl- and the hydroxy groups directly linked to aromatic rings

Definitions

• the present invention relates to a total aromatic polyester in which sublimation substances are less generated during the polymerization reaction and foreign substances are reduced, and this polyester resin composition.
• Liquid crystal resins such as all-aromatic polyester have excellent fluidity, mechanical strength, heat resistance, chemical resistance, electrical properties, etc. in a well-balanced manner, and are therefore suitably widely used as high-performance engineering plastics.
• Patent Document 1 a totally aromatic polyester having a specific structure containing 6-hydroxy-2-naphthoic acid as a main component has been proposed.
• the sublimated product generated during the polymerization reaction of all aromatic polyesters is a monomer component, which causes a deviation in the terminal balance and hinders the increase in molecular weight.
• the present inventors consist of the following constituent units (I), (II), (III) and (IV) as essential constituents, and the content of the constituent unit (I) is 40 to 40 for all the constituent units. It is 75 mol%, the content of the constituent unit (II) is 0.5 to 7.5 mol% with respect to all the constituent units, and the content of the constituent unit (III) with respect to all the constituent units is 8.
• the content of the constituent unit (IV) is 8.5 to 30 mol% with respect to all the constituent units, and the constituent units (I), (II), ( A total aromatic polyester characterized in that the total content of III) and (IV) is 100 mol%, which is the content of the structural unit (III) and the content of the structural unit (IV).
• the essential constituents consist of the following constituent units (I), (II), (III) and (IV).
• the content of the constituent unit (I) is 40 to 75 mol% with respect to all the constituent units.
• the content of the constituent unit (II) is 0.5 to 7.5 mol% with respect to all the constituent units.
• the content of the constituent unit (III) is 8.5 to 30 mol% with respect to all the constituent units.
• the content of the constituent unit (IV) is 8.5 to 30 mol% with respect to all the constituent units.
• the total content of the constituent units (I), (II), (III) and (IV) with respect to all the constituent units is 100 mol%.
• All aromatic polyester A total aromatic polyester in which the difference between the content of the structural unit (III) and the content of the structural unit (IV) is 0.150 mol% or less.
• a method for producing an all-aromatic polyester comprises the steps of acylating 6-hydroxy-2-naphthoic acid, 4-hydroxybenzoic acid, and 4,4'-dihydroxybiphenyl with fatty acid anhydride and transesterifying with 1,4-phenylenedicarboxylic acid.
• acylating 6-hydroxy-2-naphthoic acid, 4-hydroxybenzoic acid, and 4,4'-dihydroxybiphenyl with fatty acid anhydride and transesterifying with 1,4-phenylenedicarboxylic acid.
• monomers consisting of 6-hydroxy-2-naphthoic acid, 4-hydroxybenzoic acid, 1,4-phenylenedicarboxylic acid, and 4,4'-dihydroxybiphenyl.
• the amount of 6-hydroxy-2-naphthoic acid used is 40-75 mol%
• the amount of 4-hydroxybenzoic acid used is 0.5 to 7.5 mol%
• the amount of 1,4-phenylenedicarboxylic acid used is 8.5 to 30 mol%
• the amount of 4,4'-dihydroxybiphenyl used is 8.5 to 30 mol%
• the total amount of 6-hydroxy-2-naphthoic acid, 4-hydroxybenzoic acid, 1,4-phenylenedicarboxylic acid, and 4,4'-dihydroxybiphenyl used is 100 mol%.
• a method for producing a totally aromatic polyester which comprises gradually raising the temperature from 140 ° C. to 360 ° C. in a stepwise manner.
• the total aromatic polyester according to the present invention comprises the following constituent units (I), (II), (III) and (IV) as essential constituents, and the constituent units (I) are contained in all the constituent units.
• the amount is 40 to 75 mol%
• the content of the constituent unit (II) is 0.5 to 7.5 mol% with respect to all the constituent units
• the content of the constituent unit (III) is contained with respect to all the constituent units.
• the amount is 8.5 to 30 mol%, and the content of the constituent unit (IV) is 8.5 to 30 mol% with respect to all the constituent units, and the constituent units (I), ( A total aromatic polyester characterized in that the total content of II), (III) and (IV) is 100 mol%, and the content of the constituent unit (III) and the constituent unit (IV). It is a total aromatic polyester having a difference from the content of 0.150 mol% or less.
• the structural unit (I) is derived from 6-hydroxy-2-naphthoic acid (hereinafter, also referred to as "HNA").
• the total aromatic polyester of the present invention contains 40 to 75 mol% of the structural unit (I) with respect to all the structural units. If the content of the structural unit (I) is less than 40 mol%, the melting point is lowered and the heat resistance is insufficient. If the content of the structural unit (I) exceeds 75 mol%, solidification occurs during polymerization and a polymer cannot be obtained. From the viewpoint of heat resistance and polymerizable property, the content of the structural unit (I) is preferably 40 to 70 mol%, more preferably 40 to 65 mol%, and further preferably 40 to 63 mol%. , Even more preferably 40 to 62 mol%, and particularly preferably 40 to 60 mol%.
• the structural unit (II) is derived from 4-hydroxybenzoic acid (hereinafter, also referred to as "HBA").
• the total aromatic polyester of the present invention contains 0.5 to 7.5 mol% of the constituent unit (II) with respect to all the constituent units. If the content of the structural unit (II) is less than 0.5 mol%, solidification occurs during polymerization and a polymer cannot be obtained. If the content of the structural unit (II) exceeds 7.5 mol%, the melting point is lowered and the heat resistance is insufficient. From the viewpoint of heat resistance and polymerizable property, the content of the structural unit (II) is preferably 0.5 to 7.0 mol%, more preferably 1.0 to 7.0 mol%, and even more preferably. Is 1.2 to 7.0 mol%, more preferably 1.5 to 6.5 mol%, and particularly preferably 2.0 to 6.0 mol%.
• the structural unit (III) is derived from 1,4-phenylenedicarboxylic acid (hereinafter, also referred to as "TA").
• the total aromatic polyester of the present invention contains 8.5 to 30 mol% of the constituent unit (III) with respect to all the constituent units. If the content of the structural unit (III) is less than 8.5 mol% or more than 30 mol%, at least one of lower melting point and heat resistance tends to be insufficient. From the viewpoint of achieving both a low melting point and heat resistance, the content of the structural unit (III) is preferably 10 to 30 mol%, more preferably 12 to 28 mol%, and further preferably 14 to 28. It is mol%, more preferably 15 to 28 mol%, and particularly preferably 17 to 27 mol%.
• the structural unit (IV) is derived from 4,4'-dihydroxybiphenyl (hereinafter, also referred to as "BP").
• the total aromatic polyester of the present invention contains 8.5 to 30 mol% of structural units (IV) with respect to all structural units. If the content of the structural unit (IV) is less than 8.5 mol% or more than 30 mol%, at least one of lower melting point and heat resistance tends to be insufficient. From the viewpoint of achieving both a low melting point and heat resistance, the content of the structural unit (IV) is preferably 10 to 30 mol%, more preferably 12 to 28 mol%, and further preferably 14 to 28 mol%. It is mol%, more preferably 15 to 28 mol%, and particularly preferably 17 to 27 mol%.
• the total aromatic polyester of the present invention contains specific structural units (I) to (IV) in a specific amount with respect to all the structural units, and the content and composition of the structural unit (III). Since the difference from the content of the unit (IV) is 0.150 mol% or less, the generation of sublimated substances during the polymerization reaction is small, and foreign substances are reduced.
• the difference between the content of the structural unit (III) and the content of the structural unit (IV) is preferably 0.145 mol% or less, preferably 0.140 mol% or less. It is more preferably 0.135 mol% or less, further preferably 0.130 mol% or less, and particularly preferably 0.125 mol% or less.
• the total aromatic polyester of the present invention contains 100 mol% of the constituent units (I) to (IV) in total with respect to all the constituent units.
• the total aromatic polyester of the present invention exhibits optical anisotropy when melted. Exhibiting optical anisotropy when melted means that the all-aromatic polyester of the present invention is a liquid crystal polymer.
• the fact that the total aromatic polyester is a liquid crystal polymer is an indispensable element for the total aromatic polyester to have both thermal stability and easy workability.
• the total aromatic polyester composed of the constituent units (I) to (IV) may not form an anisotropic molten phase depending on the constituent components and the sequence distribution in the polymer, but the polymer of the present invention has. Limited to all aromatic polyesters that exhibit optical anisotropy when melted.
• melt anisotropy can be confirmed by a conventional polarization inspection method using an orthogonal polarizer. More specifically, the confirmation of melt anisotropy can be carried out by melting a sample placed on a hot stage manufactured by Linkham Co., Ltd. using a polarizing microscope manufactured by Olympus Corporation and observing it at a magnification of 150 times in a nitrogen atmosphere. Liquid crystal polymers are optically anisotropic and transmit light when inserted between orthogonal polarizers. If the sample is optically anisotropic, polarized light is transmitted even in a molten static liquid state, for example.
• a nematic liquid crystal polymer causes a significant decrease in viscosity above the melting point, it is generally an index of processability to exhibit liquid crystallinity at a temperature above the melting point.
• the melting point is preferably as high as possible from the viewpoint of heat resistance, but it is preferably 380 ° C. or lower in consideration of thermal deterioration during melt processing of the polymer and the heating capacity of the molding machine. It should be noted that the temperature is more preferably 260 to 370 ° C, even more preferably 270 to 370 ° C, and particularly preferably 280 to 360 ° C.
• the melt viscosity of the total aromatic polyester at a temperature 10 to 40 ° C. higher than the melting point of the total aromatic polyester of the present invention and a shear rate of 1000 / sec is preferably 1000 Pa ⁇ s or less, more preferably 4 to 500 Pa. It is s, more preferably 4 to 250 Pa ⁇ s, and particularly preferably 5 to 100 Pa ⁇ s.
• the melt viscosity means the melt viscosity measured according to ISO11443.
• the total aromatic polyester of the present embodiment is polymerized by using a direct polymerization method, a transesterification method, or the like.
• a melt polymerization method, a solution polymerization method, a slurry polymerization method, a solid phase polymerization method, etc., or a combination of two or more of these is used, and a melt polymerization method or a combination of the melt polymerization method and the solid phase polymerization method is used. Is preferably used.
• an acylating agent for the polymerized monomer or a monomer having an activated terminal can be used as an acid chloride derivative.
• the acylating agent include fatty acid anhydrides such as acetic anhydride.
• the total amount of fatty acid anhydride used is 6-hydroxy-2-naphthoic acid, 4-hydroxybenzoic acid, and 4,4'-dihydroxybiphenyl from the viewpoint of hue. It is preferably less than 1.08 times the hydroxyl group equivalent of, more preferably 1.00 to 1.07 times, further preferably 1.01 to 1.07 times, and 1.01 to 1 It is more preferably .06 times, and particularly preferably 1.02 to 1.06 times.
• catalysts can be used for these polymerizations, and typical ones are potassium acetate, magnesium acetate, stannous acetate, tetrabutyl titanate, lead acetate, sodium acetate, antimony trioxide, and tris (2).
• 4-Pentandionato) Examples include metal salt-based catalysts such as cobalt (III) and organic compound-based catalysts such as 1-methylimidazole and 4-dimethylaminopyridine.
• melt polymerization is carried out by starting depressurization to a predetermined decompression degree.
• an inert gas is introduced, and the pressure is changed from a reduced pressure state to a normal pressure state to a predetermined pressure state, and the total aromatic polyester is discharged from the reaction system.
• the total aromatic polyester produced by the above polymerization method can be further increased in molecular weight by solid phase polymerization of normal pressure, reduced pressure, or heating in an inert gas.
• 6-hydroxy-2-naphthoic acid, 4-hydroxybenzoic acid, and 4,4'-dihydroxybiphenyl are acylated with a fatty acid anhydride to form 1,4-phenylene. It is preferable to include a step of transesterifying with a dicarboxylic acid. For all monomers consisting of 6-hydroxy-2-naphthoic acid, 4-hydroxybenzoic acid, 1,4-phenylenedicarboxylic acid, and 4,4'-dihydroxybiphenyl.
• the amount of 6-hydroxy-2-naphthoic acid used is 40 to 75 mol%, preferably 40 to 70 mol%, more preferably 40 to 65 mol%, still more preferably 40 to 63, from the viewpoint of heat resistance and polymerizable property. Mol%, even more preferably 40-62 mol%, particularly preferably 40-60 mol%, The amount of 4-hydroxybenzoic acid used is 0.5 to 7.5 mol%, preferably 0.5 to 7.0 mol%, more preferably 1.0 to 7.0 from the viewpoint of heat resistance and polymerizable property.
• the amount of 1,4-phenylenedicarboxylic acid used is 8.5 to 30 mol%, preferably 10 to 30 mol%, more preferably 12 to 28 mol%, and further, from the viewpoint of achieving both a low melting point and heat resistance.
• the amount of 4,4'-dihydroxybiphenyl used is 8.5 to 30 mol%, preferably 10 to 30 mol%, more preferably 12 to 28 mol%, and further, from the viewpoint of achieving both a low melting point and heat resistance.
• 14-28 mol%, even more preferably 15-28 mol%, particularly preferably 17-27 mol% The total amount of 6-hydroxy-2-naphthoic acid, 4-hydroxybenzoic acid, 1,4-phenylenedicarboxylic acid, and 4,4'-dihydroxybiphenyl is preferably 100 mol%. It is preferable to raise the temperature in steps from 140 ° C. to 360 ° C.
• the temperature rise divided in stages is 140 ° C to 200 ° C, 200 ° C to 270 ° C, 270 ° C to 360 ° C. preferable.
• the rate of temperature rise from 140 ° C. to 200 ° C. is preferably 0.4 ° C./min or more and less than 0.8 ° C./min, and 0.5 ° C./min. More preferably, it is at least 0.7 ° C./min.
• the rate of temperature rise from 200 ° C. to 270 ° C. is preferably 0.8 ° C./min or more and 1.2 ° C./min or less, and 0.9 ° C./min. More preferably, it is at least 1.1 ° C./min.
• the rate of temperature rise from 270 ° C. to 360 ° C. is preferably 0.4 ° C./min or more and 1.2 ° C./min or less, and 0.5 ° C./min. More preferably, it is at least 1.1 ° C./min.
• the amount of 1,4-phenylenedicarboxylic acid used (mol%) and the amount of 4,4'-dihydroxybiphenyl used (mol%) are determined from the viewpoint of increasing the molecular weight. It is preferable that they are equal. It should be noted that the generation of sublimated products during the production of the total aromatic polyester of the present embodiment causes a difference in their contents.
• polyester resin composition Various fibrous, powdery, plate-like inorganic and organic fillers can be blended in the above-mentioned all-aromatic polyester of the present invention depending on the purpose of use.
• the inorganic filler blended in the polyester resin composition of the present invention includes fibrous, powdery, and plate-like fillers.
• fibrous inorganic filler glass fiber, milled glass fiber, asbestos fiber, silica fiber, silica / alumina fiber, alumina fiber, zirconia fiber, boron nitride fiber, silicon nitride fiber, boron fiber, potassium titanate fiber, wollastonite
• silicate fibers such as magnesium sulfate fibers, aluminum borate fibers
• inorganic fibrous substances such as metal fibrous materials such as stainless steel, aluminum, titanium, copper and brass.
• a particularly typical fibrous filler is glass fiber.
• the powdery granular inorganic filler carbon black, graphite, silica, quartz powder, glass beads, glass balloon, glass powder, calcium silicate, aluminum silicate, kaolin, clay, diatomaceous earth, wollastonite and the like.
• Acid salts iron oxide, titanium oxide, zinc oxide, antimony trioxide, metal oxides such as alumina, carbonates of metals such as calcium carbonate and magnesium carbonate, sulfates of metals such as calcium sulfate and barium sulfate, and other ferrites.
• examples of the plate-shaped inorganic filler include mica, glass flakes, talc, and various metal foils.
• organic fillers examples include aromatic polyester fibers, liquid crystal polymer fibers, aromatic polyamides, and heat-resistant high-strength synthetic fibers such as polyimide fibers.
• inorganic and organic fillers can be used alone or in combination of two or more.
• the combined use of the fibrous inorganic filler and the granular or plate-like inorganic filler is a preferable combination in terms of combining mechanical strength, dimensional accuracy, electrical properties, and the like.
• glass fiber is used as the fibrous filler
• mica and talc are used as the plate-shaped filler, and the blending amount thereof is 120 parts by mass or less, preferably 20 to 80 parts by mass with respect to 100 parts by mass of the total aromatic polyester. Is.
• the polyester resin composition is particularly remarkable in improving the thermal deformation temperature, mechanical properties and the like.
• a converging agent or a surface treatment agent can be used if necessary.
• the polyester resin composition of the present invention contains the all-aromatic polyester of the present invention as an essential component, and optionally contains an inorganic or organic filler, as long as it does not impair the effects of the present invention.
• other components may be contained.
• the other component may be any component, and examples thereof include additives such as other resins, antioxidants, stabilizers, pigments, and 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 prepared by a conventionally known method.
• the polyester molded product of the present invention can be obtained by molding the all-aromatic polyester or polyester resin composition of the present invention.
• the molding method is not particularly limited, and a general molding method can be adopted. Examples of general molding methods include injection molding, extrusion molding, compression molding, blow molding, vacuum molding, foam molding, rotary molding, gas injection molding, and inflation molding.
• the polyester molded product obtained by molding the all-aromatic polyester or the like of the present invention has excellent heat resistance. Further, the polyester molded product obtained by molding the polyester resin composition of the present invention has excellent heat resistance and contains an inorganic or organic filler as required, so that the mechanical strength and the like are further improved.
• the all-aromatic polyester and polyester resin composition of the present invention are excellent in moldability, they can be processed into various three-dimensional molded products, fibers, films and the like.
• Preferred applications of the polyester molded product of the present invention having the above properties include connectors, CPU sockets, relay switch parts, bobbins, actuators, noise reduction filter cases, electronic circuit boards, heating fixing rolls for OA equipment, and the like. Be done.
• Example 1 The following raw material monomers, fatty acid metal salt catalysts, and acylating agents were charged into a polymerization vessel equipped with a stirrer, a reflux column, a monomer inlet, a nitrogen inlet, and a depressurization / outflow line, and nitrogen substitution was started.
• the monomer composition was calculated by the pyrolysis gas chromatography method described in Polymer Degradation and Stability 76 (2002) 85-94. Specifically, using a pyrolysis device (“PY2020iD” manufactured by Frontier Lab Co., Ltd.), all aromatic polyester is heated in the presence of tetramethylammonium hydroxide (TMAH), and gas is pyrolyzed / methylated. Was generated. This gas was analyzed using gas chromatography (“GC-6890N” manufactured by Azilent Technology Co., Ltd.), and the peak area derived from 1,4-phenylenedicarboxylic acid and the peak derived from 4,4′-dihydroxybiphenyl were analyzed. From the ratio to the area, the difference between the content of the constituent unit derived from 1,4-phenylenedicarboxylic acid and the content of the constituent unit derived from 4,4'-dihydroxybiphenyl was calculated.
• TMAH tetramethylammonium hydroxide
• Examples 2 to 4 Comparative Examples 1 to 10> A polymer was obtained in the same manner as in Example 1 except that the type of raw material monomer, the amount used (mol%), and the rate of temperature rise were as shown in Tables 1 and 2. Further, the same evaluation as in Example 1 was performed (the melt viscosities of Example 4 and Comparative Example 4 were measured at a temperature of 350 ° C.). The evaluation results are shown in Tables 1 and 2.
• Comparative Example 8 in which the rate of temperature rise from 140 ° C. to 200 ° C. is 0.30 ° C./min and Comparative Example 9 in which the temperature rise rate is 0.89 ° C./min, foreign matter is generated. It was. Further, as shown in Tables 1 and 2, Comparative Example 2 in which the rate of temperature rise from 200 ° C. to 270 ° C. is 0.60 ° C./min, and Comparative Example 5, 1.30 ° C. in which the temperature rise rate is 0.69 ° C./min. In Comparative Example 6 at / min, foreign matter was generated. Further, as shown in Tables 1 and 2, Comparative Examples 1 to 4 in which the rate of temperature rise from 270 ° C. to 360 ° C. is 1.50 ° C./min, and Comparative Examples 7 and 1 in which 0.30 ° C./min. Foreign matter was also generated in Comparative Example 10 at 29 ° C./min.

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• Polyesters Or Polycarbonates (AREA)
• Compositions Of Macromolecular Compounds (AREA)

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• 2020
  • 2020-04-02 WO PCT/JP2020/015149 patent/WO2020204124A1/ja active Application Filing
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