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

Definitions

• the present invention relates to a wholly aromatic polyester and a method for producing the same.
• wholly aromatic polyesters using 1,4-phenylenedicarboxylic acid, 1,4-dihydroxybenzene, 4,4'-dihydroxybiphenyl, etc. as copolymerization components are known.
• the melting point of this wholly aromatic polyester is 350 ° C. or higher, which is too high for melt processing with a general-purpose apparatus.
• Patent Document 1 discloses a copolymer obtained by combining 4-hydroxybenzoic acid with 1,4-phenylenedicarboxylic acid, 1,3-phenylenedicarboxylic acid, and 4,4′-dihydroxybiphenyl. Polyester has been proposed.
• an object of the present invention is to provide a wholly aromatic polyester that is sufficiently compatible with low melting point and heat resistance and excellent in hue, and a method for producing the same.
• the inventors of the present invention have made extensive studies to solve the above problems. As a result, it has been found that the above-mentioned problems can be solved by a wholly aromatic polyester composed of specific structural units, the content of each structural unit being in a specific range, and the amount of ketone bond being in a specific range. It came to be completed. More specifically, the present invention provides the following.
• the content of the structural unit (I) is 61 to 68 mol% with respect to all the structural units
• the content of the structural unit (II) is 7 to 14 mol% with respect to all the structural units
• the content of the structural unit (III) with respect to all the structural units is 5.5 to 9 mol%
• the content of the structural unit (IV) is 16 to 19.5 mol% with respect to all the structural units
• the ratio of the structural unit (III) to the total of the structural unit (II) and the structural unit (III) is 0.30 to 0.48
• It has an ester bond or a combination of an ester bond and a ketone bond in the molecule, and the amount of the ketone bond with respect to the total of the ester bond and the ketone bond is 0 to 0.18 mol%.
• the deflection temperature under load is obtained by melt-kneading 60% by mass of the wholly aromatic polyester and 40% by mass of milled fiber having an average fiber diameter of 11 ⁇ m and an average fiber length of 75 ⁇ m at the melting point of the wholly aromatic polyester + 20 ° C.
• a method for producing a wholly aromatic polyester exhibiting optical anisotropy when melted In the method, 4-hydroxybenzoic acid and 4,4′-dihydroxybiphenyl are acylated with a fatty acid anhydride in the presence of a fatty acid metal salt, and ester with 1,4-phenylenedicarboxylic acid and 1,3-phenylenedicarboxylic acid.
• the amount of 4-hydroxybenzoic acid used is 61 to 68 mol%
• the amount of 1,4-phenylene dicarboxylic acid used is 7 to 14 mol%
• the amount of 1,3-phenylenedicarboxylic acid used is 5.5-9 mol%
• the amount of 4,4′-dihydroxybiphenyl used is 16 to 19.5 mol%
• the ratio of the amount of 1,3-phenylenedicarboxylic acid used to the total amount of 1,4-phenylenedicarboxylic acid and 1,3-phenylenedicarboxylic acid used is 0.30 to 0.48,
• a method in which the amount of the fatty acid anhydride used is 1.02 to 1.04 times the total hydroxyl equivalent of 4-hydroxybenzoic acid and 4,4′-dihydroxy
• the wholly aromatic polyester of the present invention which is composed of specific structural units and exhibits optical anisotropy when melted, has both a low melting point and sufficient heat resistance, and is excellent in hue. .
• the molding temperature of the wholly aromatic polyester of the present invention is not so high, injection molding, extrusion molding, compression molding and the like are possible without using a molding machine having a special structure.
• the wholly aromatic polyester of the present invention is excellent in moldability and can be molded using various molding machines. As a result, it can be easily processed into various three-dimensional molded products, fibers, films and the like. For this reason, molded products such as connectors, CPU sockets, relay switch parts, bobbins, actuators, noise reduction filter cases, or heat fixing rolls for OA equipment, which are suitable uses of the wholly aromatic polyester of the present invention, can be easily obtained. .
• the wholly aromatic polyester of the present invention comprises the following structural unit (I), the following structural unit (II), the following structural unit (III), and the following structural unit (IV).
• the structural unit (I) is derived from 4-hydroxybenzoic acid (hereinafter also referred to as “HBA”).
• HBA 4-hydroxybenzoic acid
• the wholly aromatic polyester of the present invention contains 61 to 68 mol% of the structural unit (I) with respect to the total structural units. When the content of the structural unit (I) is less than 61 mol% or exceeds 68 mol%, at least one of lowering the melting point and heat resistance tends to be insufficient.
• the structural unit (II) is derived from 1,4-phenylenedicarboxylic acid (hereinafter also referred to as “TA”).
• the wholly aromatic polyester of the present invention contains 7 to 14 mol%, preferably 9.5 to 11.5 mol% of the structural unit (II) with respect to all the structural units. If the content of the structural unit (II) is less than 7 mol% or exceeds 14 mol%, at least one of lowering the melting point and heat resistance tends to be insufficient.
• the structural unit (III) is derived from 1,3-phenylenedicarboxylic acid (hereinafter also referred to as “IA”).
• the wholly aromatic polyester of the present invention contains 5.5 to 9 mol%, preferably 6.5 to 8 mol% of the structural unit (III) based on all the structural units. When the content of the structural unit (III) is less than 5.5 mol% or exceeds 9 mol%, at least one of lowering the melting point and heat resistance tends to be insufficient.
• the structural unit (IV) is derived from 4,4′-dihydroxybiphenyl (hereinafter also referred to as “BP”).
• BP 4,4′-dihydroxybiphenyl
• the wholly aromatic polyester of the present invention contains 16 to 19.5 mol% of the structural unit (IV) with respect to all the structural units. When the content of the structural unit (IV) is less than 16 mol% or exceeds 19.5 mol%, at least one of lowering the melting point and heat resistance tends to be insufficient.
• the ratio of the structural unit (III) to the total of the structural unit (II) and the structural unit (III) is 0.30 to 0.48 mol%.
• the ratio is less than 0.30 mol% or exceeds 0.48 mol%, at least one of lowering the melting point and heat resistance tends to be insufficient.
• the amount of the ketone bond relative to the total of the ester bond and the ketone bond is 0 to 0.18 mol%.
• the hue tends to be lowered.
• the wholly aromatic polyester of the present invention contains a specific amount of each of the specific structural units (I) to (IV) with respect to all the structural units, and the structural unit (II) and the structural units. Since the ratio of the structural unit (III) to the total of (III) is adjusted to a specific range, and the amount of ketone bond is adjusted to a specific range, both low melting point and heat resistance are compatible. Is sufficient and has excellent hue.
• DTUL a difference between a melting point and a deflection temperature under load
• this difference is 85 ° C. or less, the heat resistance tends to increase, which is preferable.
• DTUL is a polyester resin obtained by melt-kneading 60% by mass of the wholly aromatic polyester and 40% by mass of milled fiber having an average fiber diameter of 11 ⁇ m and an average fiber length of 75 ⁇ m at the melting point of the wholly aromatic polyester + 20 ° C. It is a value measured in the state of the composition, and can be measured in accordance with ISO75-1,2.
• the wholly aromatic polyester of the present invention is polymerized using a direct polymerization method or a transesterification method.
• a melt polymerization method a solution polymerization method, a slurry polymerization method, a solid phase polymerization method, or the like is used.
• an acylating agent for the polymerization monomer or a monomer having an activated terminal as an acid chloride derivative can be used.
• the acylating agent include fatty acid anhydrides such as acetic anhydride.
• various catalysts can be used. Typical examples include dialkyl tin oxide, diaryl tin oxide, titanium dioxide, alkoxy titanium silicates, titanium alcoholates, fatty acid metal salts, BF 3 Lewis acid salts such as are mentioned, and fatty acid metal salts are preferred.
• the amount of the catalyst used is generally about 0.001 to 1% by weight, particularly about 0.003 to 0.2% by weight, based on the total weight of the monomers.
• liquid paraffin high heat resistant synthetic oil, inert mineral oil, or the like is used as a solvent.
• the reaction conditions are, for example, a reaction temperature of 200 to 380 ° C. and a final ultimate pressure of 0.1 to 760 Torr (that is, 13 to 101,080 Pa). Particularly in a melt reaction, for example, a reaction temperature of 260 to 380 ° C., preferably 300 to 360 ° C., a final ultimate pressure of 1 to 100 Torr (ie, 133 to 13,300 Pa), preferably 1 to 50 Torr (ie, 133 to 6,670 Pa). ).
• the reaction can be started by charging all the raw material monomers (HBA, TA, IA, and BP), the acylating agent, and the catalyst in the same reaction vessel (one-stage system), or the hydroxyl groups of the raw material monomers HBA and BP. Can be acylated with an acylating agent and then reacted with carboxyl groups of TA and IA (two-stage system).
• the melt polymerization is performed after the inside of the reaction system reaches a predetermined temperature, and then the pressure reduction is started to a predetermined degree of pressure reduction. After the torque of the stirrer reaches a predetermined value, an inert gas is introduced, and the total aromatic polyester is discharged from the reaction system by changing from a reduced pressure state to a normal pressure to a predetermined pressure state.
• the molecular weight of the wholly aromatic polyester produced by the above polymerization method can be further increased by solid-phase polymerization which is heated at normal pressure or reduced pressure in an inert gas.
• Preferred conditions for the solid phase polymerization reaction are a reaction temperature of 230 to 330 ° C., preferably 250 to 320 ° C., and a final ultimate pressure of 10 to 760 Torr (ie 1,330 to 101,080 Pa).
• the process for producing a wholly aromatic polyester of the present invention comprises acylating 4-hydroxybenzoic acid and 4,4′-dihydroxybiphenyl with a fatty acid anhydride in the presence of a fatty acid metal salt to produce 1,4-phenylenedicarboxylic acid and 1 Preferably comprising a step of transesterification with 3,3-phenylenedicarboxylic acid,
• the amount of 4-hydroxybenzoic acid used is 61 to 68 mol%
• the amount of 1,4-phenylene dicarboxylic acid used is 7 to 14 mol%
• the amount of 1,3-phenylenedicarboxylic acid used is 5.5-9 mol%
• the amount of 4,4′-dihydroxybiphenyl used is 16 to 19.5 mol% It is preferable that The ratio of
• the fatty acid metal salt is an acetic acid metal salt and the fatty acid anhydride is acetic anhydride.
• the total number of moles of 1,4-phenylene dicarboxylic acid and 1,3-phenylene dicarboxylic acid is 1 to 1.06 times the number of moles of 4,4′-dihydroxybiphenyl, or 4,4
• the number of moles of '-dihydroxybiphenyl is preferably 1 to 1.06 times the total number of moles of 1,4-phenylenedicarboxylic acid and 1,3-phenylenedicarboxylic acid.
• the wholly aromatic polyester of the present invention exhibits optical anisotropy when melted.
• An optical anisotropy when melted means that the wholly aromatic polyester of the present invention is a liquid crystalline polymer.
• the fact that the wholly aromatic polyester is a liquid crystalline polymer is an indispensable element when the wholly aromatic polyester has both thermal stability and easy processability.
• the wholly aromatic polyester composed of the structural units (I) to (IV) may not form an anisotropic melt phase depending on the constituent components and the sequence distribution in the polymer. Limited to wholly 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 melting anisotropy can be confirmed by melting a sample placed on a hot stage manufactured by Linkham Co., Ltd. using a polarizing microscope manufactured by Olympus and observing it at a magnification of 150 times in a nitrogen atmosphere.
• the liquid crystalline polymer is optically anisotropic and transmits light when inserted between crossed polarizers. If the sample is optically anisotropic, for example, polarized light is transmitted even in a molten stationary liquid state.
• the melting point (liquid crystallinity expression temperature) is preferably as high as possible from the viewpoint of heat resistance, but it is 320 to 340 ° C. in consideration of thermal degradation during polymer melt processing and the heating capability of the molding machine. Is a preferred guideline. More preferably, the temperature is 325 to 335 ° C.
• ⁇ Polyester resin composition Various fibrous, granular, and plate-like inorganic and organic fillers can be blended in the wholly aromatic polyester of the present invention according to 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 ones.
• Silica such as 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 as fibrous inorganic filler
• Inorganic fibrous materials such as fibers, magnesium sulfate fibers, aluminum borate fibers, and metal fibrous materials such as stainless steel, aluminum, titanium, copper, and brass.
• a particularly typical fibrous filler is glass fiber.
• the granular inorganic filler carbon black, graphite, silica, quartz powder, glass beads, milled glass fiber, glass balloon, glass powder, calcium oxalate, aluminum oxalate, kaolin, clay, diatomaceous earth, wollast Silicates such as knight, iron oxide, titanium oxide, zinc oxide, antimony trioxide, metal oxides such as alumina, metal carbonates such as calcium carbonate and magnesium carbonate, metal sulfates such as calcium sulfate and barium sulfate Examples thereof include salts, other ferrites, 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.
• organic fillers include heat-resistant high-strength synthetic fibers such as aromatic polyester fibers, liquid crystalline polymer fibers, aromatic polyamides, and polyimide fibers.
• the fibrous inorganic filler is glass fiber
• the platy filler is mica and talc.
• 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 wholly aromatic polyester. It is.
• the polyester resin composition is particularly prominent in improving the heat distortion temperature and mechanical properties.
• a sizing agent or a surface treatment agent can be used if necessary.
• the polyester resin composition of the present invention contains the wholly aromatic polyester of the present invention, an inorganic or organic filler as an essential component, but other components are included as long as the effects of the present invention are not impaired. It may be included.
• the other component may be any component, and examples thereof include other resins, antioxidants, stabilizers, pigments, crystal nucleating agents and the like.
• 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 article of the present invention is formed by molding the wholly aromatic polyester or polyester resin composition of the present invention.
• the molding method is not particularly limited, and a general molding method can be employed. Examples of general molding methods include injection molding, extrusion molding, compression molding, blow molding, vacuum molding, foam molding, rotational molding, gas injection molding, and the like.
• the polyester molded product formed by molding the wholly aromatic polyester of the present invention is excellent in heat resistance and toughness. Moreover, since the polyester molded article formed by shape
• the wholly aromatic polyester and polyester resin composition of the present invention are excellent in moldability, a polyester molded product having a desired shape can be easily obtained.
• polyester molded product of the present invention having the above properties include connectors, CPU sockets, relay switch parts, bobbins, actuators, noise reduction filter cases, heat fixing rolls for OA equipment, and the like.
• Example 1 A polymerization vessel equipped with a stirrer, a reflux column, a monomer inlet, a nitrogen inlet, and a decompression / outflow line was charged with the following raw material monomers, fatty acid metal salt catalyst, and acylating agent, and nitrogen substitution was started.
• polyester resin composition pellets 60% by mass of polymer and 40% by mass of glass fiber (manufactured by Central Glass Co., Ltd., milled fiber, average fiber diameter 11 ⁇ m, average fiber length 75 ⁇ m), a twin-screw extruder (TEX30 ⁇ type, manufactured by Nippon Steel) And melt-kneading at a cylinder temperature of the melting point of the polymer + 20 ° C. to obtain polyester resin composition pellets.
• the polyester resin composition pellets were molded under the following molding conditions using a molding machine (“SE100DU” manufactured by Sumitomo Heavy Industries, Ltd.) to obtain measurement specimens (4 mm ⁇ 10 mm ⁇ 80 mm).
• the L value of the polymer was measured using a spectral color difference meter (“SE6000” manufactured by Nippon Denshoku Industries Co., Ltd.).
• the ketone bond amount of the polymer was calculated by a pyrolysis gas chromatography method described in Polymer Degradation and Stability 76 (2002) 85-94. Specifically, the polymer is heated in the presence of tetramethylammonium hydroxide (TMAH) using a pyrolysis device ("PY2020iD” manufactured by Frontier Laboratories) to generate gas by pyrolysis / methylation. It was. This gas is analyzed using gas chromatography (“GC-6890N” manufactured by Agilent Technologies), and the amount of ketone bond is calculated from the ratio of the peak area derived from the ketone bond to the peak area derived from the ester bond. did.
• TMAH tetramethylammonium hydroxide
• Examples 2 to 7, Comparative Examples 1 to 12> A polymer was obtained in the same manner as in Example 1 except that the type of raw material monomer and the charging ratio (mol%) were as shown in Table 1 or 2. Moreover, the same evaluation as Example 1 was performed. However, when the polymer of Comparative Example 11 was obtained, the potassium acetate catalyst was not used, and the amount of acetic anhydride used was 1.10 times the total hydroxyl equivalent of HBA and BP. The evaluation results are shown in Tables 1 and 2.

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• 2016
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