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
  • C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
  • C08G75/02—Polythioethers
  • C08G75/0204—Polyarylenethioethers
• • 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
  • C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
  • C08G75/20—Polysulfones
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L81/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen or carbon only; Compositions of polysulfones; Compositions of derivatives of such polymers

Definitions

• the present invention relates to aromatic thioether sulfone polymers, compositions, molded articles, and methods for producing them.
• resin materials have been widely used for optical materials such as optical lenses, prism sheets, and parts for organic light emitting diode devices (OLED) due to their excellent processability and productivity. Furthermore, due to the trend toward smaller and lighter optical members, resin materials with a high refractive index are required. Conventional resins generally have a refractive index of 1.30 to 1.70, and there are almost no general-purpose materials with a refractive index exceeding 1.70.
• a common approach to increasing the refractive index of resins is to introduce substituents with high molar refraction, small molar volume, and high specific gravity into molecules according to the Lorentz-Lorentz equation. That is, introduction of halogen atoms and sulfur atoms is said to be effective. Since sulfur atoms have high polarizability, stability, and ease of introduction into polymers, sulfur-containing resins for various optical materials have been reported. For example, a compound having a thiourethane skeleton is disclosed as a sulfur-containing resin. However, this compound has low heat resistance and has problems in use under high temperature conditions (Patent Document 1, Patent Document 2, Patent Document 3).
• aromatic polythioethers have a high sulfur content in the resin skeleton and a very high density, so they are promising high refractive materials.
• aromatic thioether sulfone polymers are highly transparent because they are amorphous resins, and they also have excellent heat resistance due to their high glass transition temperature of about 220°C, making them optical materials that can be used even under high-temperature conditions. It is expected that However, in the conventionally reported production methods of aromatic thioether sulfone polymers, the resulting resins are colored and lack transparency, so their use as optical materials has been avoided (Patent Document 4, Patent Document 5).
• the problem to be solved by the present invention is to provide an aromatic thioether sulfone polymer, a composition, a molded article, and a method for producing the same, which has a high refractive index, little coloring, and high transparency. .
• the present inventors conducted intensive studies and found that in the presence of a carbamide solvent, a dihaloaromatic compound and (i) an alkali metal sulfide, or (ii) an alkali metal hydrosulfide and It has been found that by polymerizing with an alkali metal hydroxide, it is possible to provide an aromatic thioether sulfone polymer that has a high refractive index, little coloration, and high transparency. It has also been found that an aromatic thioether sulfone polymer with excellent thermal stability can be provided when the oligomer content is within a specific value range.
• the present disclosure provides an aromatic thioether sulfone polymer having a refractive index of 1.65 or more, a brightness of 85 or more, a transmittance of 70% or more, and an oligomer content of 3.5 parts by mass or less. Regarding.
• the present disclosure also provides a method for polymerizing a dihaloaromatic compound and (i) an alkali metal sulfide, or (ii) an alkali metal hydrosulfide and an alkali metal hydroxide in a water-containing organic carbamide solvent.
• the present invention relates to a method for producing an aromatic thioether sulfone polymer.
• oligomer a polymer having 2 to 40 repeating units (a mixture of dimers to 40-mers) may be referred to as an "oligomer.”
• an aromatic thioether sulfone polymer that has a high refractive index, little coloring, and high transparency, and a method for producing the same.
• this embodiment an embodiment of the present invention (hereinafter referred to as “this embodiment”) will be described in detail, but the present invention is not limited to the following description, and can be modified in various ways within the scope of the gist. It can be implemented by
• the aromatic thioether sulfone polymer has the following general formula (1) (wherein R 1 to R 4 are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a nitro group, an amino group, It represents a phenyl group, a methoxy group, an ethoxy group, and X represents -O-, -SO 2 -, -SO- or -CO-) as a repeating unit.
• R 1 to R 4 in the formula are preferably hydrogen atoms from the viewpoint of mechanical strength of the aromatic thioethersulfone polymer.
• the aromatic thioether sulfone polymer has not only a structural moiety represented by the general formula (1) but also a substituted phenyl group, a ketone group, an aliphatic group, etc., represented by the general formula (1). It may be contained in an amount of 30 mol% or less of the total amount of structural moieties. Regarding their bonding mode, either a random copolymer or a block copolymer may be used. Further, it may contain a trifunctional structural moiety represented by the following general formula (2). In that case, the amount is preferably in the range of 0.001 to 10 mol%, particularly preferably in the range of 0.01 to 1 mol%, based on the total number of moles with other structural parts.
• the aromatic thioether sulfone polymer has the following general formula (3) (wherein, ring Z is an aromatic hydrocarbon ring, and R 5 and R 6 may be any substituent, for example, an alkyl group, a cycloalkyl group, aryl group, aralkyl group, or alkoxy group.
• Y is -O-, -S-, -SO 2 -, -SO- or -CO-
• k is an integer from 0 to 4
• m is 0 or more.
• p is an integer of 1 or more).
• ring Z may be a benzene ring or a naphthalene ring.
• the amount is preferably in the range of 0.001 to 10 mol%, particularly preferably in the range of 0.01 to 1 mol%, based on the total number of moles with other structural parts.
• ring Z may be an aromatic hydrocarbon ring, and R 5 to R 7 may be any substituent
• examples include alkyl groups, cycloalkyl groups, aryl groups, aralkyl groups, and alkoxy groups.
• Y is -O-, -S-, -SO 2 -, -SO- or -CO-, and k is an integer of 0 to 4.
• m is an integer of 0 or more
• p is an integer of 1 or more
• ring Z may be a benzene ring or a naphthalene ring.
• the amount is preferably in the range of 0.001 to 10 mol%, particularly preferably in the range of 0.01 to 1 mol%, based on the total number of moles with other structural parts.
• the aromatic thioether sulfone polymer according to this embodiment has an excellent refractive index.
• the refractive index is preferably 1.65 or more, more preferably 1.70 or more.
• the refractive index is a value measured at room temperature (23° C.) and 589 nm using a test piece of an aromatic thioether sulfone polymer molded to a thickness of 40 ⁇ m using a method based on JIS K 7142.
• the aromatic thioether sulfone polymer according to this embodiment has excellent transparency.
• the brightness is preferably 85 or more, more preferably 90 or more
• the transmittance is preferably 70% or more, more preferably 80% or more.
• brightness is obtained by reflection measurement using a colorimetric colorimeter using an aromatic thioether sulfone polymer molded to a thickness of 40 ⁇ m as a test piece and using a white plate as a background in accordance with JIS Z 8781-4.
• the transmittance is the transmittance of the same test piece measured at a wavelength of 450 nm using an ultraviolet-visible spectrophotometer.
• the aromatic thioether sulfone polymer according to this embodiment has an oligomer content of 3.5 parts by mass or less per 100 parts by mass. In this range, the amount of gas generated when the polymer is heated and melted can be reduced, resulting in a polymer with excellent thermal stability. Note that the oligomer content of the polymer in the present disclosure can be measured by the method described in the Examples.
• the rate of viscosity change during retention is small.
• the viscosity change rate is preferably 10% or less, more preferably 8% or less. Note that the viscosity change rate in the present disclosure can be measured by the method described in Examples.
• the method for producing the aromatic thioether sulfone polymer is not particularly limited, but examples include the method for producing the aromatic thioether sulfone polymer described below.
• the method for producing an aromatic thioether sulfone polymer according to the first embodiment of the present disclosure includes combining a dihaloaromatic compound and (i) an alkali metal sulfide, or (ii) an alkali metal sulfide in a water-containing organic carbamide solvent. It is characterized by polymerizing a metal hydrosulfide and an alkali metal hydroxide.
• the method for producing an aromatic thioether sulfone polymer according to the second embodiment of the present disclosure includes: A step of polymerizing a dihaloaromatic compound and (i) an alkali metal sulfide, or (ii) an alkali metal hydrosulfide and an alkali metal hydroxide in a water-containing organic carbamide solvent to obtain a crude reaction mixture.
• the solid phase component (A) is brought into contact with an organic solvent and then subjected to solid-liquid separation to obtain a solid phase component (B) (4).
• the water-containing organic carbamide solvent used in this embodiment is a mixture of water and an organic carbamide solvent.
• the organic carbamide solvent is not particularly limited as long as it is a compound having one or more carbamide groups, and any known organic solvent can be used. Examples include dimethylimidazolidinone (DMI), dimethylpropylene urea (DMPU), hexamethylphosphate triamide (HMPA), and tetramethylurea (TMU).
• DMI dimethylimidazolidinone
• DMPU dimethylpropylene urea
• HMPA hexamethylphosphate triamide
• TNU tetramethylurea
• DMI is preferred from the viewpoints of thermal stability, smoothness of polymerization reaction, economic efficiency, and the like.
• the water content of the water-containing organic carbamide solvent is preferably 1 mol/kg or more, more preferably 5 mol/kg or more, even more preferably 7 mol/kg or more, and preferably 30 mol/kg or less, based on the organic carbamide solvent. More preferably, it is 20 mol/kg or less. If it is below this range, there is a high possibility that a decomposition reaction will occur, and if it is above this range, there is a high possibility that the polymerization reaction will be significantly delayed or the granulation rate of the produced copolymer will be significantly reduced.
• the dihaloaromatic compound used in this embodiment is, for example, a halogenated aromatic compound having two halogen atoms directly bonded to an aromatic ring, and specifically, p-dichlorodiphenylsulfone, o- Dichlordiphenylsulfone, m-dichlordiphenylsulfone, p-dibromodiphenylsulfone, o-dibromodiphenylsulfone, m-dibromodiphenylsulfone, p-diiododiphenylsulfone, o-diiododiphenylsulfone, m-diiododiphenylsulfone , p-dichlorobenzene, o-dichlorobenzene, m-dichlorobenzene, dibromobenzene, diiodobenzene, tribromobenzene, dibrom
• dihaloaromatic compounds having functional groups with active hydrogen such as amino groups, thiol groups, and hydroxyl groups
• functional groups with active hydrogen such as amino groups, thiol groups, and hydroxyl groups
• specific examples include 2,6-dichloroaniline and 2,5-dichloroaniline.
• 2,2'-diamino-4,4'-dichlorodiphenyl ether 2,4'-diamino-2',4-di
• dihaloaminodiphenyl ethers such as chlordiphenyl ether, and compounds in which the amino group is replaced with a thiol group or a hydroxyl group in a mixture thereof.
• active hydrogen-containing dihaloaromatic compounds in which the hydrogen atom bonded to the carbon atom forming the aromatic ring in these active hydrogen-containing dihaloaromatic compounds are substituted with other inert groups, such as hydrocarbon groups such as alkyl groups.
• Aromatic compounds can also be used.
• active hydrogen-containing dihaloaromatic compounds are preferred, and dichloroaniline is particularly preferred.
• dihaloaromatic compounds having a nitro group examples include dihalonitrobenzenes such as 2,4-dinitrochlorobenzene and 2,5-dichloronitrobenzene; Halonitro diphenyl ethers; Dihalonitro diphenyl sulfones such as 3,3'-dinitro-4,4'-dichloro diphenyl sulfone; 2,5-dichloro-3-nitropyridine, 2-chloro-3,5-dinitro Mono- or dihalonitropyridines such as pyridine; or various dihalonitronaphthalenes; 9,9-bis(4-chlorophenyl)fluorene, 9,9-bis(4-bromophenyl)fluorene, 9,9-bis( 4-iodophenyl)fluorene, 9,9-bis(4-chloro-3-methylphenyl)fluorene, 9,9-bis(4-bromo-3-methylphenyl)fluoren
• an alkali metal sulfide, or an alkali hydrosulfide and an alkali metal hydroxide (hereinafter sometimes referred to as a sulfidating agent) are used as raw materials.
• the alkali metal sulfide includes lithium sulfide, sodium sulfide, rubidium sulfide, cesium sulfide, and mixtures thereof.
• Such alkali metal sulfides can be used as hydrates or aqueous mixtures or as anhydrides.
• an alkali metal sulfide can also be derived by a reaction between an alkali metal hydrosulfide and an alkali metal hydroxide. Note that a small amount of alkali metal hydroxide may be added in order to react with alkali metal hydrosulfide and alkali metal thiosulfate, which are usually present in a small amount in the alkali metal sulfide.
• the alkali metal hydrosulfide includes lithium hydrogen sulfide, sodium hydrogen sulfide, rubidium hydrogen sulfide, cesium hydrogen sulfide, and mixtures thereof.
• Such alkali metal hydrosulfides can be used as hydrates or aqueous mixtures or as anhydrides.
• the alkali metal hydrosulfide is used together with an alkali metal hydroxide.
• the alkali metal hydroxide include lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide, etc. Each of these may be used alone, or two or more types may be used in combination. It may also be used as Among these, lithium hydroxide, sodium hydroxide, and potassium hydroxide are preferred because they are easily available, and sodium hydroxide is particularly preferred.
• the amount of the sulfidating agent used in this step is preferably 0.1 mol/kg, more preferably 0.3 mol/kg, preferably 20 mol/kg or less, and 10 mol/kg based on the organic carbamide solvent.
• the following are more preferable.
• it is less than 0.1 mol/kg, the productivity of the polymer decreases, which is disadvantageous from an economical point of view.
• it is greater than 20 mol/kg, the viscosity of the system during the reaction will become high, making stirring difficult and potentially reducing the yield.
• the molar ratio of the dihaloaromatic compound to the sulfidating agent is preferably in the range of 0.95 to 1.2 (mol/mol), more preferably 1.00 to 1.10 (mol/mol). ) is within the range. If it is smaller than 0.95 (mol/mol), a decomposition reaction may occur or the resulting aromatic copolymer may have poor thermal stability; if it is larger than 1.2 (mol/mol), polymerization may The reaction may be difficult to proceed and it may be difficult to increase the molecular weight.
• the polymerization conditions for the above sulfidating agent and the dihaloaromatic compound in the presence of the above organic carbamide solvent are generally at a temperature of 150 to 330°C, and a pressure that substantially eliminates the polymerization solvent and the dihaloaromatic compound as the polymerization monomer.
• the pressure should be within a range such that the pressure is maintained in the liquid phase, and is generally selected from the range of 0.1 to 20 MPa, preferably 0.1 to 2 MPa.
• the reaction time varies depending on temperature and pressure, but is generally in the range of 10 minutes to 72 hours, preferably in the range of 1 hour to 10 hours.
• reaction temperature profile of two or more stages.
• the residual rate of the dihaloaromatic compound in the polymerization reaction system is preferably 1 mol% or more because it is easy to finally obtain a high molecular weight aromatic thioether sulfone polymer, and the residual rate of the dihaloaromatic compound in the polymerization reaction system is preferably 1 mol% or more.
• the content is preferably 40 mol% or less since side reactions such as the like are less likely to occur. It is preferable that the temperature is then raised and the final stage reaction is carried out at 180 to 300°C for 1 to 50 hours.
• the above temperature range is preferably a reaction temperature of 180°C or higher because it is easy to obtain an aromatic thioether sulfone polymer with a sufficiently high molecular weight, and side reactions such as depolymerization are difficult to occur, and a high molecular weight product can be stably produced. It is preferable to carry out the reaction at 300° C. or lower because it is easy to obtain.
• an aromatic thioether sulfone polymer is obtained as a product, but in addition to that, oligomers are also produced as a secondary product. be born.
• Substances contained in the crude reaction mixture after the reaction may also include, for example, by-products such as an alkali metal-containing inorganic salt and a terminal SH group-containing compound, and unreacted raw materials.
• Step (2) is a step of washing the crude reaction mixture obtained in step (1).
• the solvent used for washing the crude reaction mixture in this step is not particularly limited as long as it is compatible with the organic carbamide solvent and the unreacted monomer below the boiling point, but the organic carbamide solvent used in step (1) It is preferable to use a similar solvent from the viewpoint of affinity.
• preferable solvents other than organic carbamide-based solvents include amide-based, ester-based, and ether-based solvents, and specifically, N-methyl-2-pyrrolidone (NMP), dimethylformamide (DMF), and dimethylacetamide. (DMAc) and the like.
• the temperature at which the washing solvent is added is not particularly limited, but is preferably in the range of 10°C or higher, more preferably 20°C or higher, and preferably 200°C or lower, more preferably 150°C or lower.
• the amount of the solvent used for one washing is preferably 20 parts by mass or more, more preferably 50 parts by mass or more, even more preferably
• the content ranges from 100 parts by weight or more, preferably 5000 parts by weight or less, more preferably 1800 parts by weight or less, even more preferably 600 parts by weight or less.
• Step (3) is a step of subjecting the crude reaction mixture that has passed through step (2) to solid-liquid separation to obtain a solid phase component (A) containing at least an aromatic thioether sulfone polymer.
• the method for solid-liquid separation is not particularly limited, and known devices and methods can be used.
• an appropriate method can be selected, such as a vacuum distillation method, a centrifugation method, a screw decanter method, a vacuum filtration method, and a pressure filtration method.
• these methods can be combined or repeated.
• step (2) and step (3) can be repeated.
• the degree of separation and removal of the liquid phase component containing the organic carbamide solvent is not particularly limited, but if the proportion of solid content (solid content concentration) in the solid phase component (A) is 100 parts by mass of the solid phase component (A).
• the amount is preferably 40 parts by mass or more, more preferably 50 parts by mass or more, still more preferably 55 parts by mass or more.
• the upper limit is not limited, it is preferably 100 parts by mass or less, more preferably less than 100 parts by mass, and even more preferably 99 parts by mass or less.
• Step (4) is a step of contacting the solid phase component (A) obtained in step (3) with an organic solvent and then performing solid-liquid separation to obtain the solid phase component (B).
• the organic solvent that can be used in this step is not particularly limited, and any known organic solvent can be used.
• any known organic solvent can be used.
• Amides, ureas and lactams such as amides, N-dimethylpropylene urea and 1,3-dimethyl-2-imidazolidinonic acid; Sulfolanes such as sulfolane and dimethylsulfolane; Nitriles such as benzonitrile; Methyl alcohol, ethyl alcohol , n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, t-butyl alcohol, ethylene glycol, propylene glycol, trimethylolpropane, benzyl alcohol, and other alcohols with 10 or less carbon atoms; 2-methoxyethyl alcohol , 2-ethoxyethyl alcohol, 1-methoxy-2-propyl alcohol, 1-ethoxy-2-propyl alcohol, 3-methoxy-1-butyl alcohol, 2-isopropoxyethyl alcohol, etc.
• ketones such as ketones and mixtures thereof, and among these, alcohols and ketones are preferred.
• a mixture of two or more of the above organic solvents may be used.
• the organic solvent may contain water.
• the polar organic solvent it is preferable to use an organic solvent such as an alcohol or a ketone, since impurities such as residual oligomers can be efficiently removed.
• a hydrous alcohol is more preferable because the salt generated during polymerization can be efficiently removed.
• the concentration of the alcohol solvent in the aqueous solution is not particularly limited, but the amount of the alcohol solvent is preferably in the range of 1000 parts by mass or less, more preferably 500 parts by mass or less, relative to 100 parts by mass of water. The amount is preferably 25 parts by mass or more, more preferably 45 parts by mass or more.
• the conditions for bringing the solid phase component (A) into contact with the organic solvent in this step range from preferably 10°C or higher, more preferably 20°C or higher, to preferably 100°C or lower, more preferably 70°C or lower. and the pressure (gauge pressure) is less than 0.1 MPa, preferably in the range of 0.05 MPa or less, and more preferably under atmospheric pressure.
• the amount of organic solvent used in this step is preferably 50 parts by mass or more, more preferably 100 parts by mass, based on 100 parts by mass of the aromatic thioethersulfone polymer.
• the amount ranges from 10000 parts or more, more preferably 2000 parts or more, more preferably 10000 parts or less, even more preferably 2000 parts or less.
• step (3) After washing, the same method as step (3) can be used to obtain the solid phase component (B) through solid-liquid separation.
• the filtered aromatic thioethersulfone polymer may be dried as it is and used as an aromatic thioethersulfone polymer powder, or it may be further washed with warm water or hot water, separated into solid and liquid, and dried. It is also possible to prepare a powdery or granular aromatic thioether sulfone polymer by performing this step. Furthermore, the obtained powdery or granular aromatic thioethersulfone polymer can be heat-treated to form a crosslinked aromatic thioethersulfone polymer.
• the aromatic thioether sulfone polymer obtained by the above production method has an excellent refractive index.
• the refractive index is preferably 1.65 or more, more preferably 1.7 or more, and preferably 1.8 or less.
• the refractive index is a value measured at room temperature (23° C.) and 589 nm using a test piece of an aromatic thioether sulfone polymer melt-molded to a thickness of 40 ⁇ m using a method based on JIS K 7142.
• the aromatic thioether sulfone polymer obtained by the above production method has excellent transparency.
• the brightness is preferably in the range of 85 or higher, more preferably 90 or higher, and preferably 99.9 or lower.
• the transmittance is preferably in the range of 70% or more, more preferably 80% or more, and preferably 99.9% or less.
• brightness is obtained by reflection measurement using a colorimeter with a test piece of an aromatic thioethersulfone polymer melt-molded to a thickness of 40 ⁇ m using a white plate as a background in accordance with JIS Z 8781-4.
• the transmittance is the transmittance of the same test piece measured at a wavelength of 450 nm using an ultraviolet-visible spectrophotometer.
• the aromatic thioether sulfone polymer obtained by the above production method has a low oligomer content.
• the oligomer content per 100 parts by mass is preferably 3.5 parts by mass or less, more preferably 2 parts by mass or less, and even more preferably 1.8 parts by mass or less. preferable. Within this range, the amount of gas generated when the polymer is heated and melted can be reduced. Note that the oligomer content of the polymer in the present disclosure can be measured by the method described in the Examples.
• the aromatic thioether sulfone polymer obtained by the above production method has excellent melt stability, so the rate of viscosity change during retention is small.
• the viscosity change rate is preferably 10% or less, more preferably 8% or less. Note that the viscosity change rate in the present disclosure can be measured by the method described in Examples.
• the aromatic thioethersulfone polymer composition according to this embodiment is formed by blending the aromatic thioethersulfone polymer according to this embodiment described above and other substances. Further, the method for producing a composition according to the present embodiment includes a step of blending the aromatic thioether sulfone polymer produced by the above method with another substance and melt-kneading the mixture.
• the aromatic thioether sulfone polymer according to this embodiment may contain other substances such as a mold release agent, a coloring agent, a heat stabilizer, an ultraviolet stabilizer, a foaming agent, a rust preventive agent, as long as the effects of the present invention are not impaired. It can be used as a composition by containing additives such as flame retardants, lubricants, coupling agents, and fillers. As the filler, known and commonly used materials can be used as long as they do not impair the effects of the present invention. Examples include inorganic fillers.
• fibrous fillers such as glass fiber, carbon fiber, silane glass fiber, ceramic fiber, aramid fiber, metal fiber, potassium titanate, silicon carbide, calcium silicate, wollastonite, natural fiber, etc. It can also be used for glass beads, glass flakes, barium sulfate, clay, pyrophyllite, bentonite, sericite, mica, talc, attapulgite, ferrite, calcium silicate, calcium carbonate, glass beads, zeolite, milled fiber, calcium sulfate, etc.
• Non-fibrous fillers can also be used.
• the aromatic thioether sulfone polymer according to the present embodiment may be used as a composition by mixing the following synthetic resins and elastomers as other substances within the range that does not impair the effects of the present invention.
• synthetic resins include polyester, polyamide, polyimide, polyetherimide, polycarbonate, polyphenylene ether, polysulfone, polyether sulfone, polyether ether ketone, polyether ketone, polyarylene, polyarylene sulfide, polyethylene, polypropylene, polytetra
• Examples include fluorinated ethylene, polydifluoroethylene, polystyrene, ABS resin, epoxy resin, silicone resin, phenol resin, urethane resin, liquid crystal polymer, etc.
• elastomers include polyolefin rubber, fluororubber, silicone rubber, etc. It will be done.
• the method of blending and kneading the above-mentioned components with the aromatic thioethersulfone polymer according to the present embodiment is not particularly limited, but the aromatic thioethersulfone polymer and optional components as needed are blended and melted.
• the kneading method more specifically, includes a method of uniformly dry-mixing the mixture using a tumbler or a Henschel mixer as necessary, and then charging the mixture into a twin-screw extruder and melt-kneading it.
• the melt-kneading machine is preferably a twin-screw kneading extruder from the viewpoint of dispersibility and productivity, for example, a discharge rate of the resin component in the range of 5 to 500 (kg/hr) and a screw rotation speed of 50 to 500 (rpm). It is preferable to melt and knead while appropriately adjusting the range, and melt and knead under conditions such that the ratio (discharge amount/screw rotation speed) is in the range of 0.02 to 5 (kg/hr/rpm). is even more preferable. Further, the addition and mixing of each component to the melt-kneading machine may be performed simultaneously or may be performed separately.
• the position of the side feeder is preferably such that the ratio of the distance from the extruder resin input part (top feeder) to the side feeder to the total screw length of the twin-screw kneading extruder is 0.1 or more, and 0. More preferably, it is .3 or more. Moreover, it is preferable that this ratio is 0.9 or less, and it is more preferable that it is 0.7 or less.
• the aromatic thioethersulfone polymer composition according to the present embodiment obtained by melt-kneading as described above has a morphology in which the aromatic thioethersulfone polymer forms a continuous phase and other essential components and optional components are dispersed.
• the aromatic thioethersulfone polymer composition according to the present embodiment can be produced by a known method, for example, by extruding the molten polymer composition into a strand shape, and then forming the composition into pellets, chips, granules, powder, etc. After processing into the form, it is preferable to perform preliminary drying at a temperature range of 100 to 150°C as necessary.
• the molded article according to this embodiment is obtained by melt-molding the aromatic thioether sulfone polymer composition according to this embodiment described above.
• the method for producing a molded article according to the present embodiment includes a step of melt-molding the aromatic thioethersulfone polymer composition obtained by the method for producing an aromatic thioethersulfone polymer composition according to the present embodiment described above. It is characterized by having the following.
• the aromatic thioether sulfone polymer composition can be molded by various molding methods such as injection molding, compression molding, extrusion molding of composites, sheets, pipes, etc., pultrusion molding, blow molding, and transfer molding.
• various molding conditions are not particularly limited, and molding can be performed by a general method.
• aromatic thioether sulfone polymer and polymer composition is not particularly limited, and can be used as various products.
• electrical/electronic parts such as connectors, printed circuit boards, and molded seals
• automotive parts such as lamp reflectors and various electrical components, interior materials for various buildings, aircraft, automobiles, etc., OA equipment parts, camera parts, etc.
• precision parts such as watch parts.
• optical materials such as plastic lenses such as eyeglass lenses, camera lenses, and prism lenses, hard coating agents, antireflection films, prism lenses, and LED sealing materials.
• Tg glass transition point
• Example 1-Step (1) In a 1L autoclave made of titanium, 4,4-dichlorodiphenylsulfone (0.52 mol, 147.88 g), sodium acetate (0.50 mol, 41.02 g), dimethylimidazolidinone (hereinafter referred to as DMI) (3.82 mol, 436 .54g), deionized water (2.22mol, 39.96g), sodium sulfide (47.6%, 0.50mol, 59.34g), sodium hydroxide (48.8%, 0.50mol, 41.08g) ), heated to 200°C, and heated under seal at 200°C for 3 hours.
• DMI dimethylimidazolidinone
• Example 1-Step (2) After the polymerization was completed, the crude reaction mixture slurry was collected in a container and DMI (300 mL) was added. This slurry was filtered using a 200 mesh wire gauze to obtain a solid phase component. DMI (300 mL) was further added to the obtained solid phase component, and the mixture was heated and stirred at 120° C. for 30 minutes. Thereafter, the slurry was cooled to 60°C.
• Example 1-Step (3) The cooled slurry was filtered through a 200 mesh wire gauze to remove liquid phase components.
• Example 1-Step (4) After cooling the obtained solid phase component to room temperature, an aqueous methanol solution was added, decantation was performed, and the liquid phase component was removed by filtration. The solid phase component was further washed with warm water (70° C.), decanted, and filtered to remove the liquid phase component. This process was repeated three times. The obtained solid phase component was dried at 120° C. for 2 hours under normal pressure, and then further dried under reduced pressure at 150° C. for 5 hours to obtain a polymer (1). Table 1 shows the properties of the obtained polymer (1).

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