WO2022070696A1 - 架橋ポリアリーレンスルフィド、組成物および成形品の製造方法 - Google Patents
架橋ポリアリーレンスルフィド、組成物および成形品の製造方法 Download PDFInfo
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- WO2022070696A1 WO2022070696A1 PCT/JP2021/031292 JP2021031292W WO2022070696A1 WO 2022070696 A1 WO2022070696 A1 WO 2022070696A1 JP 2021031292 W JP2021031292 W JP 2021031292W WO 2022070696 A1 WO2022070696 A1 WO 2022070696A1
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- GLNWILHOFOBOFD-UHFFFAOYSA-N lithium sulfide Chemical compound [Li+].[Li+].[S-2] GLNWILHOFOBOFD-UHFFFAOYSA-N 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 238000010128 melt processing Methods 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- DADSZOFTIIETSV-UHFFFAOYSA-N n,n-dichloroaniline Chemical compound ClN(Cl)C1=CC=CC=C1 DADSZOFTIIETSV-UHFFFAOYSA-N 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920001643 poly(ether ketone) Polymers 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920002530 polyetherether ketone Polymers 0.000 description 1
- 229920001601 polyetherimide Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000002954 polymerization reaction product Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920006124 polyolefin elastomer Polymers 0.000 description 1
- 229920001955 polyphenylene ether Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- AHKSSQDILPRNLA-UHFFFAOYSA-N rubidium(1+);sulfide Chemical compound [S-2].[Rb+].[Rb+] AHKSSQDILPRNLA-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 229910052979 sodium sulfide Inorganic materials 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000000326 ultraviolet stabilizing agent Substances 0.000 description 1
- 239000010456 wollastonite Substances 0.000 description 1
- 229910052882 wollastonite Inorganic materials 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C43/00—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
- B29C43/32—Component parts, details or accessories; Auxiliary operations
- B29C43/34—Feeding the material to the mould or the compression means
-
- 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
- C08G75/02—Polythioethers
- C08G75/0204—Polyarylenethioethers
- C08G75/0209—Polyarylenethioethers derived from monomers containing one aromatic ring
-
- 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
- C08G75/0231—Polyarylenethioethers containing chain-terminating or chain-branching agents
-
- 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
- C08G75/0286—Chemical after-treatment
- C08G75/0295—Modification with inorganic compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/12—Powdering or granulating
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/203—Solid polymers with solid and/or liquid additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
- C08J3/247—Heating methods
-
- 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
- C08L81/02—Polythioethers; Polythioether-ethers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D181/00—Coating compositions based on 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; Coating compositions based on polysulfones; Coating compositions based on derivatives of such polymers
- C09D181/02—Polythioethers; Polythioether-ethers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J181/00—Adhesives based on 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; Adhesives based on polysulfones; Adhesives based on derivatives of such polymers
- C09J181/02—Polythioethers; Polythioether-ethers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2381/00—Characterised by the use 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; Polysulfones; Derivatives of such polymers
- C08J2381/02—Polythioethers; Polythioether-ethers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/62—Plastics recycling; Rubber recycling
Definitions
- the present invention relates to a method for producing crosslinked polyarylene sulfide, a method for producing a composition containing the crosslinked polyarylene sulfide, and a method for producing a molded product in which the composition is melt-molded.
- PAS polyphenylene sulfides
- PPS polyphenylene sulfide
- MFR desired melt flow rate
- This oxidative cross-linking generally proceeds by heating PAS in a solid phase state below the melting point in an oxygen-containing atmosphere, or by heating it in a molten state above the melting point.
- Patent Document 1 As a method of oxidative cross-linking, a method of using a forced heating air circulation type dryer (Patent Document 1), a method of using a container-fixed heating / mixing device having a double spiral stirring blade (Patent Document 2), and a fluidized bed are used.
- Patent Document 3 a method of using a fluidized bed with a cyclone, a method of using a fluidized bed with a built-in bag filter, and the like.
- an object to be solved by the present invention is to provide a method for producing a crosslinked PAS having excellent quality stability by suppressing fluctuations in melt viscosity between lots.
- Another object of the present invention is to provide a method for producing a composition containing the crosslinked PAS and a method for producing a molded product by melt-molding the composition.
- the conventional method is a method of oxidatively cross-linking an uncrosslinked granulated product whose bulk density is adjusted to be within a specific range, and therefore, even if the bulk density is the same.
- the true specific gravity may differ due to the difference in the particle shape of the granulated product, and as a result, the melt viscosity between lots may fluctuate, and the true specific gravity of the uncrosslinked granulated product shall be within a certain range.
- a crosslinked PAS having excellent quality stability can be obtained by suppressing the fluctuation of the melt viscosity between lots, and the present invention has been solved.
- the present invention comprises a step of compression-molding a powdery unbridged polyarylene fide to obtain a compression-molded product, a step of measuring the true specific gravity of the compression-molded product, and a specific true specific gravity of the compression-molded product. It is characterized by having a step of crushing a product in the above range to obtain a crushed product, a step of sizing the crushed product to obtain a granulated product, and a step of oxidatively cross-linking the granulated product obtained in the previous step.
- a method for producing a crosslinked polyarylene sulfide is provided.
- the present invention provides a method for producing a resin composition, which comprises a step of producing crosslinked polyarylene sulfide by the above-mentioned production method and a step of melt-kneading the obtained crosslinked polyarylene sulfide with other components.
- the present invention provides a method for producing a molded product, which comprises a step of producing a resin composition by the above-mentioned production method and a step of melt-molding the obtained resin composition.
- the present invention it is possible to provide a method for producing a crosslinked PAS having excellent quality stability by suppressing fluctuations in melt viscosity between lots. Further, according to the present invention, it is possible to provide a method for producing a composition containing the crosslinked PAS and a method for producing a molded product in which the composition is melt-molded.
- the method for producing a crosslinked polyarylene sulfide of the present invention is: A step of compression-molding a powdery unbridged polyarylene fide to obtain a compression-molded product, a step of measuring the true specific gravity of the compression-molded product, and a process of crushing a compression-molded product in a specific true specific gravity range. It is characterized by having a step of obtaining a crushed product, a step of sizing the crushed product to obtain a granulated product, and a step of oxidatively cross-linking the granulated product obtained in the previous step.
- the powdery uncrosslinked PAS is usually prepared with at least one polyhaloaromatic compound and at least one sulfidating agent in an organic polar solvent typified by, for example, N-methyl-2-pyrrolidone. Is synthesized by reacting under appropriate polymerization conditions.
- the polyhalo aromatic compound used in the present invention is, for example, a halogenated aromatic compound having two or more halogen atoms directly bonded to an aromatic ring, and specifically, p-dichlorobenzene, o-.
- Dihalo-aromatic compounds such as dibrombenzophenone, dichlordiphenyl ether, dibromdiphenyl ether, dichlordiphenylsulfide, dibromdiphenylsulfide, dichlorbiphenyl, dibromubiphenyl and mixtures thereof, and blocks these
- a polyhaloaromatic compound having three or more halogen substituents in one molecule may be used as a branching agent, if desired.
- polyhalo aromatic compounds include 1,2,4-trichlorobenzene, 1,3,5-trichlorobenzene, 1,4,6-trichlornaphthalene and the like.
- polyhaloaromatic compounds having a functional group having an active hydrogen such as an amino group, a thiol group, and a hydroxyl group
- a functional group having an active hydrogen such as an amino group, a thiol group, and a hydroxyl group
- 2,6-dichloroaniline and 2,5-dichloroaniline 2,6-dichloroaniline.
- 2,4-Dichloroaniline, 2,3-dichloroaniline and other dihaloanilines 2,3,4-trichloraniline, 2,3,5-trichloraniline, 2,4,6-trichloraniline, 3, Trihaloanilines such as 4,5-trichloroaniline; dihaloaminodiphenyl ethers such as 2,2'-diamino-4,4'-dichlorodiphenyl ether, 2,4'-diamino-2', 4-dichlorodiphenyl ether
- compounds in which the amino group is replaced with a thiol group or a hydroxyl group in these mixtures are exemplified.
- the hydrogen atom bonded to the carbon atom forming the aromatic ring in these active hydrogen-containing polyhaloaromatic compounds is replaced with another inactive group, for example, a hydrocarbon group such as an alkyl group.
- Aromatic compounds can also be used.
- the active hydrogen-containing dihaloaromatic compound is preferable, and dichloraniline is particularly preferable.
- Examples of the polyhaloaromatic compound having a nitro group include mono or dihalonitrobenzenes such as 2,4-dinitrochlorobenzene and 2,5-dichloronitrobenzene; 2-nitro-4,4'-dichlorodiphenyl ether and the like.
- the sulfidizing agent used in the present invention includes alkali metals sulfide such as lithium sulfide, sodium sulfide, rubidium sulfide, cesium sulfide and mixtures thereof.
- alkali metals sulfide such as lithium sulfide, sodium sulfide, rubidium sulfide, cesium sulfide and mixtures thereof.
- alkali metal sulfide can be used as a hydrate, an aqueous mixture or an anhydrate.
- the alkali metal sulfide can also be derived by the reaction between the alkali metal hydroxide and the alkali metal hydroxide.
- alkali metal hydroxide may be added in order to react with the alkali metal hydrosulfide and the alkali metal thiosulfate which are usually present in a trace amount in the alkali metal sulfide.
- organic polar solvent used in the present invention examples include amides such as N-methyl-2-pyrrolidone, formamide, acetamide, N-methylformamide, N, N-dimethylacetamide, N-methyl- ⁇ -caprolactam and ⁇ -.
- Amidoureas such as caprolactam, hexamethylphosphoramide, tetramethylurea, N-dimethylpropyleneurea, 1,3-dimethyl-2-imidazolidinone acid, and lactams; sulfolanes such as sulfolane, dimethylsulfolane; benzonitrile And other nitriles; ketones such as methylphenylketone and mixtures thereof can be mentioned.
- the polymerization conditions of the above-mentioned sulfidating agent and the polyhalo aromatic compound are generally a temperature of 200 to 330 ° C., and the pressure is substantially the same as that of the polymerization solvent and the polyhalo aromatic compound which is the polymerization monomer.
- the range should be such that it is retained 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 the temperature and pressure, but is generally in the range of 10 minutes to 72 hours, preferably 1 hour to 48 hours.
- the particulate uncrosslinked PAS used in the present invention is obtained by reacting a polyhalo aromatic compound and an organic polar solvent in the presence of a sulfidizing agent and an organic polar solvent while continuously or intermittently adding them.
- the morphology also includes the morphology obtained by reacting the sulfidating agent in the presence of a polyhaloaromatic compound and an organic polar solvent with continuous or intermittent addition of a sulfidizing agent.
- the particulate uncrosslinked PAS used in the present invention can be produced, for example, by further post-treating the PAS obtained by the polymerization method or a reaction mixture containing the PAS.
- the method for post-treating the reaction mixture containing PAS obtained by the above polymerization method is not particularly limited, but for example, after polymerizing PAS, a by-product contained in the polymerization reaction product (polymerization of PAS).
- the following methods (1) to (6) can be exemplified as a step of washing the reaction-derived unavoidable component (hereinafter, also simply referred to as “washing step”).
- reaction mixture is used as it is, or an acid or a base is added, and then the solvent is distilled off under reduced pressure or normal pressure. Wash once or twice or more with a solvent such as (organic solvent having equivalent solubility for low molecular weight polymer), acetone, methyl ethyl ketone, alcohols, and further neutralize, wash with water and filter, and if necessary, a dispersion medium. To make a dispersion.
- a solvent such as (organic solvent having equivalent solubility for low molecular weight polymer), acetone, methyl ethyl ketone, alcohols, and further neutralize, wash with water and filter, and if necessary, a dispersion medium.
- the reaction mixture is soluble in a solvent such as water, acetone, methyl ethyl ketone, alcohols, ethers, halogenated hydrocarbons, aromatic hydrocarbons, and aliphatic hydrocarbons (soluble in the polymerization solvent used).
- a solvent such as water, acetone, methyl ethyl ketone, alcohols, ethers, halogenated hydrocarbons, aromatic hydrocarbons, and aliphatic hydrocarbons (soluble in the polymerization solvent used).
- a solvent that is poor for PAS as a precipitant to precipitate solid products such as PAS and inorganic salts, which are washed and filtered, and if necessary, a dispersion medium.
- reaction solvent or an organic solvent having the same solubility as that of a low molecular weight polymer
- a reaction solvent or an organic solvent having the same solubility as that of a low molecular weight polymer
- reaction mixture is filtered, washed once or twice or more with a reaction solvent as needed, further washed with water and filtered, and if necessary, a dispersion medium is added to prepare the dispersion. how to.
- the reaction mixture is desolved to obtain a slurry containing PAS, and the slurry containing PAS is contacted with water and an oxygen atom-containing solvent having 1 to 10 carbon atoms.
- the oxygen atom-containing solvent having 1 to 10 carbon atoms include at least one selected from the group consisting of alcohols and ketones.
- alcohols also referred to as alcohol-based solvents or alcohol solvents
- examples of alcohols include methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, t-butyl alcohol, ethylene glycol, and propylene glycol.
- Alcohols with 10 or less carbon atoms such as trimethylolpropane and benzyl alcohol; 2-methoxyethyl alcohol, 2-ethoxyethyl alcohol, 1-methoxy-2-propyl alcohol, 1-ethoxy-2-propyl alcohol, 3-methoxy Alcohols with 10 or less carbon atoms containing ether bonds such as -1-butyl alcohol and 2-isopropoxyethyl alcohol; alcohols having 10 or less carbon atoms including ketone groups such as 3-hydroxy-2-butanone; hydroxy Examples thereof include alcohols containing an ester group such as methyl isobutyrate and having 10 or less carbon atoms.
- ketones also referred to as a ketone solvent or a ketone solvent
- examples of the ketones include acetone, methyl ethyl ketone, cyclohexanone, ⁇ -butyl lactone and N-methylpyrrolidinone.
- the melt viscosity of the powdery uncrosslinked PAS used in the present invention is not particularly limited, but the melt viscosity (V6) measured at 300 ° C. is preferably 1 [Pa ⁇ s] or more, more preferably 3 [Pa ⁇ s] or more, more preferably 5 [Pa ⁇ s] or more, preferably 800 [Pa ⁇ s] or less, more preferably 500 [Pa ⁇ s] or less, still more preferably 200 [Pa ⁇ s] or less.
- the range is up to.
- the non-Newtonian index of the powdery uncrosslinked PAS used in the present invention is not particularly limited, but is preferably 0.90 or more, more preferably 0.95 or more, preferably 1.25 or less, more preferably. Is in the range up to 1.20 or less.
- the melt viscosity (V6) measured at 300 ° C. is an orifice in which the ratio of the former / the latter is 10/1 at a temperature of 300 ° C., a load of 1.96 MPa, and an orifice length and an orifice diameter using a flow tester. Represents the melt viscosity after holding for 6 minutes using.
- N value non-Newtonian index
- SR indicates the shear rate (sec -1 )
- SS indicates the shear stress (dyne / cm 2 )
- K indicates a constant.
- the particle size of the powdery uncrosslinked PAS used in the present invention is not particularly limited, but the average particle size as observed by SEM is preferably 1 [ ⁇ m] or more, more preferably 5 [ ⁇ m] or more, and further.
- the range is preferably from 20 [ ⁇ m] to preferably 500 [ ⁇ m] or less, more preferably 400 [ ⁇ m] or less, still more preferably 300 [ ⁇ m] or less.
- the present invention includes a step of compression-molding the powdery uncrosslinked polyarylene fide thus obtained to obtain a compression-molded product, and a step of measuring the true specific gravity of the compression-molded product.
- the compression molding include a method of mechanically compression molding a powdery uncrosslinked PAS in a non-melted state.
- Various methods can be adopted for the compression molding process, and the process is not particularly limited. Specifically, from the viewpoint of stability of the production of the compressed product, it is in the form of powder between two press rolls that rotate so as to mesh with each other. It is particularly desirable that the powdery uncrosslinked PAS is sandwiched between them and sent out and compressed at a high density to form a plate by the method of pushing the uncrosslinked PAS.
- the method for measuring the true specific gravity of the obtained compression molded product is not particularly limited, but it can be measured by the Archimedes method, and for example, the method described in Examples can be used.
- the present invention has a step of crushing a compression molded product in a specific true specific gravity range to obtain a crushed product. That is, this step is a step of selecting a compression molded product having a specific true specific gravity range from the compression molded products measured in the previous step and pulverizing the product to obtain a crushed product.
- the range of the specific true specific gravity is not particularly limited, but for example, the true specific gravity is preferably 1.00 or more, and more preferably 1.10 or more from the viewpoint of suppressing the amount of fine powder. , It is preferably 1.30 or less, more preferably 1.20 or less, and from the viewpoint of being able to efficiently promote the crosslinking reaction and being excellent in productivity, it is more preferable to select one in the range of 1.15 or less. Just do it.
- the step of obtaining the compression molded product, the step of measuring the true specific gravity, and the step of obtaining the crushed product can be continuously performed, and in that case, the step of obtaining the compression molded product can be performed while adjusting the true specific gravity.
- the true specific gravity of the compression molded product can be adjusted by adjusting the compression pressure during compression molding.
- the true specific density of the plate-shaped compression molded product can be adjusted by adjusting the distance between the two press rolls.
- various methods can be adopted for crushing the compression molded product, and the method is not particularly limited, but at least two rolls are rotated so as to mesh with each other, and the compression molded product is mainly compressed between them.
- Some are the roll crusher method, which crushes by shearing force, the cutter mill method, which crushes the compression molded product while rotating the rotor with a cutter, etc., and the mortar-shaped impact rod is dropped and the compression molded product is crushed by the impact.
- Examples thereof include a stamp mill method and a stone mill type method in which a compression molded product is crushed by a shearing force generated when passing through a gap between two upper and lower grindstones.
- the shape of the crushed product is not particularly limited, and examples thereof include amorphous flakes and chips.
- the present invention has a step of sizing the crushed product thus obtained to obtain a granulated product.
- various methods can be adopted for sizing the crushed material, and the method is not particularly limited, but it passes through physical pores such as a sieve, a filter, a punching metal, etc. There is a method of making it.
- the true specific gravity of the granulated product thus obtained is the same as the true specific gravity of the compression molded product before crushing, and the granulated product does not easily collapse and can be allowed to proceed without inhibiting the oxygen supply during crosslinking. Therefore, the true specific gravity is preferably 1.00 or more, more preferably in the range of 1.10 or more, and preferably 1.30 or less, from the viewpoint of suppressing the amount of fine powder. It is preferably 1.20 or less, and more preferably 1.15 or less from the viewpoint of being able to efficiently promote the crosslinking reaction and being excellent in productivity.
- the shape of the granulated product may be irregular from the viewpoint of being suitable for oxidative cross-linking and subsequent melt extrusion.
- the irregular shape may be in any shape such as a particle shape, a plate shape, a bale shape, a needle shape, etc.
- the present invention has a step of oxidatively cross-linking the granulated product thus obtained.
- the oxidative crosslinking is not particularly limited as long as it is a known method, and examples thereof include a method of heat-treating the granulated product in an oxidizing atmosphere such as in air or oxygen-enriched air.
- the heating conditions are preferably in a temperature range of 180 ° C. or higher, which is 20 ° C. lower than the melting point of PAS, from the viewpoint of the time required for the heat treatment and the good thermal stability when the PAS is melted after the heat treatment.
- the melting point here refers to the one measured in accordance with JIS K7121 using a differential scanning calorimeter (PerkinElmer DSC device Pyris Diamond).
- the oxygen concentration in the case of heat treatment in an oxidizing atmosphere such as air or oxygen-enriched air is preferably 5% by volume or more, more preferably 10% by volume or more from the viewpoint of high oxidation rate and quick treatment. It may be in the range of 30% by volume or less, more preferably 25% by volume or less, from the viewpoint of suppressing the increase in the amount of radical generation, suppressing the thickening during the heat treatment, and having a good hue. It may be a range.
- the non-Newtonian index of the crosslinked PAS of the present invention thus obtained is not particularly limited, but for example, the non-Newtonian index is preferably 1.26 or more, more preferably 1.30 or more, still more preferably 1. It may be in the range of 35 or more, preferably 2.00 or less, more preferably 1.95 or less, still more preferably 1.90 or less.
- the melt viscosity of the crosslinked PAS of the present invention is not particularly limited, but for example, the melt viscosity (V6) measured at 300 ° C. is preferably 20 [Pa ⁇ s] or more, more preferably 100 [Pa ⁇ s] or more. It may be in the range of 5,000 [Pa ⁇ s] or less, and more preferably 2,000 [Pa ⁇ s] or less.
- the crosslinked PAS of the present invention described in detail above is processed into a molded product having excellent heat resistance, molding processability, dimensional stability, etc. by various melt processing methods such as injection molding, extrusion molding, compression molding, and blow molding. Can be done.
- the crosslinked PAS of the present invention can be used as a PAS resin composition containing various fillers in order to further improve the performance such as strength, heat resistance and dimensional stability.
- the filler is not particularly limited, and examples thereof include a fibrous filler and an inorganic filler.
- the fibrous filler include glass fiber, carbon fiber, silane glass fiber, ceramic fiber, aramid fiber, metal fiber, potassium titanate, silicon carbide, calcium sulfate, calcium silicate and other fibers, and natural fiber such as wollastonite. Can be used.
- the inorganic filler examples include barium sulfate, calcium sulfate, clay, biloferrite, bentonite, sericite, zeolite, mica, mica, talc, attalpargit, ferrite, calcium silicate, calcium carbonate, magnesium carbonate, glass beads and the like. Can be used. Further, various additives such as a mold release agent, a colorant, a heat-resistant stabilizer, an ultraviolet stabilizer, a foaming agent, a rust preventive, a flame retardant, and a lubricant can be contained as additives in the molding process.
- the crosslinked PAS obtained by the present invention may be made of polyester, polyamide, polyimide, polyetherimide, polycarbonate, polyphenylene ether, polysulphon, polyethersulphon, polyether ether ketone, polyether ketone, as appropriate, depending on the intended use.
- the crosslinked PAS obtained by the manufacturing method of the present invention also has various performances such as heat resistance and dimensional stability inherent in the PAS resin.
- Injection molding or compression molding of automobile parts such as electronic parts, lamp reflectors and various electrical components, interior materials such as various buildings, aircraft and automobiles, or precision parts such as OA equipment parts, camera parts and watch parts.
- it is widely useful as a material for various molding processes such as extrusion molding of composites, sheets, pipes, etc., or pultrusion molding, or as a material for fibers or films.
- the crosslinked PAS resin of the present invention has a short crystallization time, is useful when used as a material for injection molding, improves mold releasability, and can further shorten the molding cycle. Can be improved.
- the mixed steam of water and p-DCB discharged from the rectification tower is condensed with a condenser, and the water and p-DCB are separated by a decanter. I put it back.
- the p-DCB distilled by azeotropic boiling during dehydration was separated by a decanter and returned to the kettle at any time, and after the dehydration was completed, the anhydrous sodium sulfide composition was dispersed in the p-DCB. Further, the internal temperature was cooled to 160 ° C., NMP 47.492 kg (479 mol) was charged, and the temperature was raised to 185 ° C.
- the valve connected to the rectification column was opened, and the temperature was raised to an internal temperature of 200 ° C. over 1 hour. At this time, cooling and valve opening were controlled so that the rectification tower outlet temperature was 110 ° C. or lower.
- the distilled p-DCB and the mixed steam of water were condensed by a condenser, separated by a decanter, and the p-DCB was returned to the kettle. The amount of distillate was 179 G.
- the temperature was raised from 200 ° C. to 230 ° C. over 3 hours and stirred for 1 hour, then the temperature was raised to 250 ° C.
- Example / Manufacturing example Molding, crushing and sizing were performed using a roll-type compression granulator (roller compactor). That is, the PPS mixture obtained in the synthesis example was charged into a hopper with a screw feeder of a roller compactor, the rotation speed of the screw feeder was 63.5 rpm, and the roll compression pressure was 1.0, 1.2, 1.5, 1. It was adjusted in 5 steps of 8 and 2.0 ton / cm, and a plate-shaped compression molded product was produced at a roll rotation speed of 15 rpm in an amount of 30 kg each.
- roll-type compression granulator roll compactor
- Example 1 (Oxidation cross-linking process) A box in which 5 kg of each of the granulated products 1, 2 and 3 is arbitrarily weighed and preheated to 150 ° C. so that the true specific gravity is constant from the granulated products thus obtained. It was charged in a mold shelf type dryer and heat-treated while sending 2 L / min of air. The temperature was controlled so that the internal temperature of the heat treatment machine was 250 ° C. After holding for 0, 2, 4, and 6 hours, each granulated product having been oxidatively crosslinked was obtained. The melt viscosities of each of these oxidatively crosslinked granules were measured, and the results are shown in Table 2.
- Example 2 Each granulated product having been oxidatively crosslinked was obtained in the same manner as in Example 1 except that "granulated products 4, 5, 6" were used instead of "granulated products 1, 2, 3" in Example 1. rice field. The melt viscosities of each of these oxidatively crosslinked granules were measured, and the results are shown in Table 2.
- Example 3 Each granulated product having been oxidatively crosslinked was obtained in the same manner as in Example 1 except that "granulated products 7, 8 and 9" were used instead of "granulated products 1, 2 and 3" in Example 1. rice field. The melt viscosities of each of these oxidatively crosslinked granules were measured, and the results are shown in Table 2.
- Example 4 Each granulated product having been oxidatively crosslinked was obtained in the same manner as in Example 1 except that "granulated products 10, 11, 12" were used instead of "granulated products 1, 2, 3" in Example 1. rice field. The melt viscosities of each of these oxidatively crosslinked granules were measured, and the results are shown in Table 2.
- Example 5 Each granulated product having been oxidatively crosslinked was obtained in the same manner as in Example 1 except that "granulated products 13, 14, 15" were used instead of "granulated products 1, 2, 3" in Example 1. rice field. The melt viscosities of each of these oxidatively crosslinked granules were measured, and the results are shown in Table 2.
- Comparative Example 2 In Comparative Example 1, each granulated product having been oxidatively crosslinked was obtained in the same manner as in Example 1 except that "Granulated products 2, 5, 8" were used instead of "Granulated products 1, 4, 7". rice field. The melt viscosities of each of these oxidatively crosslinked granules were measured, and the results are shown in Table 3.
- Comparative Example 3 In Comparative Example 1, each granulated product having been oxidatively crosslinked was obtained in the same manner as in Example 1 except that "Granulated products 3, 6, 9" were used instead of "Granulated products 1, 4, 7". rice field. The melt viscosities of each of these oxidatively crosslinked granules were measured, and the results are shown in Table 3.
- the true specific gravity of the compression molded product is based on the principle of the Archimedes method using the obtained compression molded product (200 g) using an electronic hydrometer (“MDS-300” manufactured by Alpha Mirage Co., Ltd.). Measured based on.
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Abstract
Description
粉末状の未架橋ポリアリーレンスフィドを圧縮成形して圧縮成形物を得る工程と、圧縮成形物の真比重を測定する工程と、圧縮成形物の内、特定の真比重の範囲のものを粉砕して破砕物を得る工程と、破砕物を整粒して造粒物を得る工程と、前工程で得られた造粒物を酸化架橋する工程とを有することを特徴とする。
圧縮成形は、粉末状の未架橋のPASを非溶融状態で機械的に圧縮成形する方法が挙げられる。圧縮成形する工程には様々な方法が採用でき特に限定はされないが、具体的には、圧縮物の生産の安定性の面から、互いに噛合するように回転する2個のプレスロール間に粉末状の未架橋のPASを押し込む方法によって、粉末状の未架橋のPASはその間で挟み込まれ、かつ、送り出され高密度に圧縮されて、板状とすることが特に望ましい。
具体的には、破砕物を整粒する方法には様々な方法が採用でき特に限定はされないが、篩、フィルター、パンチングメタルなど、適した大きさや形に整えるための物理的な空孔を通過させる方法等が挙げられる。
このようにして得られた本発明の架橋PASの非ニュートン指数は特に限定されないが、例えば、その非ニュートン指数が、好ましくは1.26以上、より好ましくは1.30以上、さらに好ましくは1.35以上の範囲であってよく、そして、好ましくは2.00以下、より好ましくは1.95以下、さらに好ましくは1.90以下の範囲であって良い。
圧力計、温度計、コンデンサー、デカンター、精留塔を付けた撹拌翼付き150Lオートクレーブにp-ジクロロベンゼン(以下、p-DCBと略す)33.222kg(226mol)、N-メチル-2-ピロリドン(以下、NMPと略す)2.280kg(23mol)、47.23質量%水硫化ソーダ27.300kg(230mol)、及び49.21質量%苛性ソーダ18.533kg(228mol)を仕込み、次に、前記オートクレーブから蒸留装置へ通ずる配管のバルブを開き、脱水を開始するとともに、減圧装置へ通ずる配管のバルブを開き、-6.6〔kPa abs〕/minの割合で大気圧下から47〔kPa abs〕まで減圧すると伴に、液温を128℃から147℃まで0.1℃/minの割合で徐々に昇温し、最終的に47〔kPa abs〕、液温147℃で4時間、脱水した。精留塔から排出された水とp-DCBの混合蒸気をコンデンサーで凝縮し、水とp-DCBをデカンターで分離して、随時、水は系外へ留出し、p-DCBはオートクレーブ内に戻した。脱水時に共沸により留出したp-DCBはデカンターで分離して随時釜内に戻し、脱水終了後の釜内は無水硫化ナトリウム組成物がp-DCB中に分散した状態であった。更に、内温を160℃に冷却し、NMP47.492kg(479mol)を仕込み、185℃まで昇温した。圧力が0.00MPaに到達した時点で、精留塔を連結したバルブを開放し、内温200℃まで1時間掛けて昇温した。この際、精留塔出口温度が110℃以下になる様に冷却とバルブ開度で制御した。留出したp-DCBと水の混合蒸気はコンデンサーで凝縮し、デカンターで分離して、p-DCBは釜へ戻した。留出水量は179Gであった。次に、内温200℃から230℃まで3時間掛けて昇温し、1時間攪拌した後、250℃まで昇温し1時間攪拌して反応終了後、オートクレーブの内温を250℃から235℃に冷却し、到達後にオートクレープの底弁を開いて減圧状態のまま撹拌翼付き150L真空撹拌乾燥機(脱溶媒機ジャケット温度120℃)にフラッシュさせてNMPを抜き取り、室温まで冷却し、サンプリングした結果、不揮発分(N.V.)が55%のPPS混合物を得た。
(圧縮工程)
ロール式圧縮造粒機(ローラーコンパクター)を用いて成形、粉砕および整粒を行なった。すなわち、合成例で得られたPPS混合物をローラーコンパクターのスクリューフィーダー付ホッパーに仕込み、スクリューフィーダーの回転数を63.5 rpm、ロール圧縮圧を1.0、1.2、1.5、1.8、2.0ton/cmの5段階で調整し、ロール回転数を15rpmで板状の圧縮成形物を30kgずつ製造した。
次に、得られた各圧縮成形物の真比重を測定した。
続いて、各圧縮成形物を、それぞれ、848.4、732.3、654.7kg/hrの3段階で処理量を調整して、粗砕機により破砕して破砕物を10kgずつ製造した。
続いて、上述の破砕物に対して整粒機を用いて整粒した後、さらに、整粒機のスクリーン目開き(5.0 mmに調整)で篩分けして、それぞれ、造粒物を得た。
続いて、得られた各造粒物を10kgずつ秤量し、それぞれ嵩密度を測定した。
(酸化架橋工程)
このようにして得られた造粒物の中から真比重が一定となるよう、造粒物1、2、3の中からそれぞれ任意に5kgを秤量し、それぞれ150℃に予熱しておいた箱型棚段式乾燥機に仕込み、2L/minの空気を送り込みながら熱処理を行った。熱処理機の内温が250℃になるように温度をコントロールした。0、2、4、6時間保持後、酸化架橋済みの各造粒物を得た。これら酸化架橋済みの各造粒物の溶融粘度を測定し、結果を表2に示した。
実施例1において「造粒物1、2、3」の代わりに「造粒物4、5、6」を用いたこと以外は実施例1と同様にして酸化架橋済みの各造粒物を得た。これら酸化架橋済みの各造粒物の溶融粘度を測定し、結果を表2に示した。
実施例1において「造粒物1、2、3」の代わりに「造粒物7、8、9」を用いたこと以外は実施例1と同様にして酸化架橋済みの各造粒物を得た。これら酸化架橋済みの各造粒物の溶融粘度を測定し、結果を表2に示した。
実施例1において「造粒物1、2、3」の代わりに「造粒物10、11、12」を用いたこと以外は実施例1と同様にして酸化架橋済みの各造粒物を得た。これら酸化架橋済みの各造粒物の溶融粘度を測定し、結果を表2に示した。
実施例1において「造粒物1、2、3」の代わりに「造粒物13、14、15」を用いたこと以外は実施例1と同様にして酸化架橋済みの各造粒物を得た。これら酸化架橋済みの各造粒物の溶融粘度を測定し、結果を表2に示した。
(酸化架橋工程)
このようにして得られた造粒物の中から嵩密度が一定となるよう、造粒物1、4、7の中からそれぞれ任意に5kgを秤量し、それぞれ150℃に予熱しておいた箱型棚段式乾燥機に仕込み、2L/minの空気を送り込みながら熱処理を行った。熱処理機の内温が250℃になるように温度をコントロールした。0、2、4、6時間保持後、酸化架橋済みの各造粒物を得た。これら酸化架橋済みの各造粒物の溶融粘度を測定し、結果を表3に示した。
比較例1において「造粒物1、4、7」の代わりに「造粒物2、5、8」を用いたこと以外は実施例1と同様にして酸化架橋済みの各造粒物を得た。これら酸化架橋済みの各造粒物の溶融粘度を測定し、結果を表3に示した。
比較例1において「造粒物1、4、7」の代わりに「造粒物3、6、9」を用いたこと以外は実施例1と同様にして酸化架橋済みの各造粒物を得た。これら酸化架橋済みの各造粒物の溶融粘度を測定し、結果を表3に示した。
圧縮成形物の真比重は、得られた圧縮成形物(200g)を、電子比重計(アルファーミラージュ株式会社製「MDS-300」)を用いてアルキメデス法の原理に基づき測定した。
造粒物を、体積一定の容器にすりきり一杯充填し、蓋をした上で、電子計量計を用いて重量を測定し、体積で除して、嵩密度〔g/cm3〕を算出した。
酸化架橋済みの造粒物PPSについて、フローテスターCFT-500D(株式会社島津製作所製)を用い、温度300℃、荷重1.96×106Pa、L/D=10(mm)/1(mm)の条件で、6分間保持した後に300℃における溶融粘度を測定した。
Claims (5)
- 粉末状の未架橋ポリアリーレンスフィドを圧縮成形して圧縮成形物を得る工程と、圧縮成形物の真比重を測定する工程と、圧縮成形物の内、特定の真比重の範囲のものを粉砕して破砕物を得る工程と、破砕物を整粒して造粒物を得る工程と、前工程で得られた造粒物を酸化架橋する工程とを有することを特徴とする、架橋ポリアリーレンスルフィドの製造方法。
- 造粒物の形状が、不定形である請求項1記載の架橋ポリアリーレンスルフィドの製造方法。
- 前記特定の真比重の範囲が、真比重1.10~1.30の範囲である、請求項1又は2に記載の架橋ポリアリーレンスルフィドの製造方法。
- 請求項1~3の何れか一項に記載の製造方法で架橋ポリアリーレンスルフィドを製造する工程と、得られた架橋ポリアリーレンスルフィドを他の成分と溶融混錬する工程を有する、樹脂組成物の製造方法。
- 請求項4に記載の製造方法で樹脂組成物を製造する工程と、得られた樹脂組成物を溶融成形する工程とを有する、成形品の製造方法。
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US3717620A (en) | 1971-07-20 | 1973-02-20 | Phillips Petroleum Co | Arylene sulfide resin oxidative curing process |
US3793256A (en) | 1972-08-30 | 1974-02-19 | Phillips Petroleum Co | Controlled curing pf poly(arylene sulfide)resins |
JPH07699B2 (ja) | 1986-01-29 | 1995-01-11 | 大日本インキ化学工業株式会社 | 架橋されたポリアリ−レンスルフイドポリマ−の製造法 |
-
2021
- 2021-08-26 WO PCT/JP2021/031292 patent/WO2022070696A1/ja active Application Filing
- 2021-08-26 JP JP2021568922A patent/JP7067680B1/ja active Active
- 2021-08-26 US US18/027,383 patent/US20240043621A1/en active Pending
- 2021-08-26 CN CN202180064714.7A patent/CN116234862A/zh active Pending
- 2021-08-26 KR KR1020237009801A patent/KR20230056033A/ko unknown
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JPH04128011A (ja) * | 1990-09-20 | 1992-04-28 | Dainippon Ink & Chem Inc | ポリアリーレンスルフィド樹脂造粒物の製造方法 |
JPH04129704A (ja) * | 1990-09-20 | 1992-04-30 | Dainippon Ink & Chem Inc | ポリアリーレンスルフィド樹脂ペレットの製造方法 |
JPH04248841A (ja) * | 1991-01-25 | 1992-09-04 | Dainippon Ink & Chem Inc | 架橋されたポリアリーレンスルフィドの製造方法 |
JPH061855A (ja) * | 1992-06-19 | 1994-01-11 | Toyobo Co Ltd | 顆粒状ポリフェニレンスルフィドの製造方法 |
JPH0665376A (ja) * | 1992-08-19 | 1994-03-08 | Dainippon Ink & Chem Inc | ポリアリーレンスルフィド樹脂の架橋方法 |
JP2020007387A (ja) * | 2018-07-03 | 2020-01-16 | ポリプラスチックス株式会社 | 多孔質成形体及びその製造方法 |
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CN116234862A (zh) | 2023-06-06 |
KR20230056033A (ko) | 2023-04-26 |
JP7067680B1 (ja) | 2022-05-16 |
US20240043621A1 (en) | 2024-02-08 |
JPWO2022070696A1 (ja) | 2022-04-07 |
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