WO2023002877A1 - ポリアリーレンスルフィドの分離方法およびポリアリーレンスルフィド樹脂組成物の製造方法 - Google Patents
ポリアリーレンスルフィドの分離方法およびポリアリーレンスルフィド樹脂組成物の製造方法 Download PDFInfo
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- WO2023002877A1 WO2023002877A1 PCT/JP2022/027197 JP2022027197W WO2023002877A1 WO 2023002877 A1 WO2023002877 A1 WO 2023002877A1 JP 2022027197 W JP2022027197 W JP 2022027197W WO 2023002877 A1 WO2023002877 A1 WO 2023002877A1
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- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 125000005647 linker group Chemical group 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000013541 low molecular weight contaminant 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
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 150000002903 organophosphorus compounds Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 238000009428 plumbing Methods 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920001601 polyetherimide Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920002959 polymer blend Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 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
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- ZOCLAPYLSUCOGI-UHFFFAOYSA-M potassium hydrosulfide Chemical compound [SH-].[K+] ZOCLAPYLSUCOGI-UHFFFAOYSA-M 0.000 description 1
- DPLVEEXVKBWGHE-UHFFFAOYSA-N potassium sulfide Chemical compound [S-2].[K+].[K+] DPLVEEXVKBWGHE-UHFFFAOYSA-N 0.000 description 1
- 229910052903 pyrophyllite Inorganic materials 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 238000001226 reprecipitation Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- LXOXXUIVMOYGST-UHFFFAOYSA-M rubidium(1+);sulfanide Chemical compound [SH-].[Rb+] LXOXXUIVMOYGST-UHFFFAOYSA-M 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
- 239000000377 silicon dioxide Substances 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000004071 soot Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- ISXOBTBCNRIIQO-UHFFFAOYSA-N tetrahydrothiophene 1-oxide Chemical compound O=S1CCCC1 ISXOBTBCNRIIQO-UHFFFAOYSA-N 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 150000007944 thiolates Chemical group 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 239000003799 water insoluble solvent Substances 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 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
- C08J11/00—Recovery or working-up of waste materials
- C08J11/04—Recovery or working-up of waste materials of polymers
- C08J11/06—Recovery or working-up of waste materials of polymers without chemical reactions
- C08J11/08—Recovery or working-up of waste materials of polymers without chemical reactions using selective solvents for polymer components
-
- 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
- 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 separating polyarylene sulfide from a polyarylene sulfide resin composition or a molded article thereof and a method for producing a polyarylene sulfide resin composition.
- Polyphenylene sulfide (hereinafter sometimes abbreviated as PPS) resin is an engineering plastic with excellent heat resistance, chemical resistance, flame retardancy, and electrical properties.
- PPS Polyphenylene sulfide
- thermoplastic resins collected after being used in the market is accelerating.
- PPS is suitable for material recycling due to its excellent durability, most of it is distributed in the market as a glass fiber reinforced PPS resin composition, and there is a problem that it cannot be used as a highly versatile recycling resource.
- Patent Document 1 As a method for recovering and reusing resins and fibers from a resin composition, a method of hydrolyzing fiber-reinforced plastics using supercritical water or subcritical water to separate and recover resins and fibers has been disclosed.
- Patent Document 2 a method is disclosed in which polyarylene thioether is depolymerized by reacting it with an alkali metal sulfide, and then the resin and fiber are separated and recovered.
- Patent Document 2 Further, a method of recovering PAS by reprecipitating in a liquid medium after dissolving a polymer blend containing PAS and glass fibers in a solvent is disclosed (for example, Patent Document 3).
- the method for separating polyarylene sulfide of the present invention has the following constitution. i.e. A method for separating polyarylene sulfide (hereinafter referred to as PAS) by performing the following steps 1 to 4.
- PAS A method for separating polyarylene sulfide
- Step 1 A step of heating a PAS resin composition or a molded article thereof in an organic polar solvent to 200°C or higher and lower than 400°C to dissolve PAS to obtain a PAS solution (A);
- Step 2 A step of solid-liquid separation of the PAS solution (A) to separate the solid and the PAS solution (B);
- Step 3 A step of cooling the PAS solution (B) obtained in Step 2 to 20° C. or more and 200° C. or less to precipitate PAS;
- Step 4 A step of solid-liquid separation of the mixture obtained in Step 3 to separate PAS.
- the PAS resin composition or the molded article thereof in step 1 contains at least one selected from inorganic fillers and organic fillers.
- the molded article of the PAS resin composition in step 1 is preferably a molded article collected after being used as a product.
- the organic polar solvent in step 1 is preferably NMP.
- the precipitation in step 3 is preferably carried out at 50°C or higher and 150°C or lower.
- the weight average molecular weight (hereinafter referred to as Mw) of PAS contained in the PAS resin composition or its molded product before dissolution in Step 1 is 10,000 or more and 60,000 or less. is preferred.
- the Mw of PAS contained in the PAS resin composition or its molded product before dissolution in Step 1 is preferably reduced to 10,000 or more and 60,000 or less in Step 1. .
- the sulfur compound is preferably at least one compound selected from alkali metal sulfides, alkali metal hydrosulfides, and hydrogen sulfide.
- the separated PAS is preferably washed and recovered after step 4.
- the manufacturing method of the polyarylene sulfide resin composition of the present invention has the following configurations. i.e. A method for producing a PAS resin composition, wherein the PAS obtained by the separation method of washing and recovering the separated PAS after the step 4 is used as a raw material.
- PAS can be recovered rationally from the PAS resin composition or its molded product from the viewpoint of LCA.
- the PAS contained in the PAS resin composition or molded article thereof used in the present invention is a homopolymer or copolymer having repeating units of the formula -(Ar-S)- as main structural units.
- "considered as a main structural unit” means that the repeating unit is contained in an amount of 80 mol% or more of all the structural units constituting the PAS.
- Ar is exemplified by any one of the units represented by the following formulas (A) to (K), among which the unit represented by formula (A) is particularly preferred.
- R1 and R2 are substituents selected from hydrogen, alkyl groups, alkoxy groups, halogen groups and carboxyl groups, and R1 and R2 may be the same or different.
- this repeating unit is the main structural unit, it can contain a small amount of branching units or cross-linking units represented by the following formulas (L) to (N).
- the amount of copolymerization of these branching units or cross-linking units is preferably in the range of 0 to 1 mol % with respect to 1 mol of —(Ar—S)— units.
- the p-arylene sulfide unit of formula (A) preferably contains 90 mol% or more, more preferably 95 mol% or more, and still more preferably 98 mol% or more. If the p-arylene sulfide unit is less than 90 mol %, that is, if the o-arylene sulfide unit or the m-arylene sulfide unit is large, the high melting point inherent to PAS tends to decrease and the mechanical properties also tend to decrease.
- PAS polyphenylene sulfide
- PPS polyphenylene sulfide
- a particularly preferred PAS is polyphenylene sulfide (PPS) containing 90 mol% or more, preferably 95 mol% or more, more preferably 98 mol% or more of the p-phenylene sulfide unit shown below as a main structural unit of the polymer. mentioned.
- the method for producing PAS is a known method such as a method of desalting polycondensation with a dihalogenated aromatic compound and a sulfidating agent in an organic polar solvent, or a method of synthesizing under melting conditions using diiodobenzene and sulfur. can be used.
- the PAS resin composition is used as a molded product, excellent heat resistance and chemical resistance are required. Therefore, the melting point of the PAS contained in the PAS resin composition or its molded product is 230° C. or more and less than 320° C.
- the lower limit of the general melting point of PPS in which the arylene unit is a phenylene unit is 250°C or higher and the upper limit is less than 300°C.
- the weight average molecular weight of PAS is preferably 10,000 or more, more preferably 15,000 or more, from the viewpoint of strength and toughness. In particular, it is more preferably 20,000 or more from the viewpoint of lowering the solubility in organic polar solvents and enhancing the separability from low-molecular-weight components such as stains.
- step 1 of dissolving the PAS resin composition of the present invention or a molded product thereof in an organic polar solvent if the molecular weight of PAS is too high, it will be difficult to dissolve in the organic polar solvent and the recovery efficiency will decrease.
- the weight average molecular weight of PAS contained in the molded product is preferably less than 200,000, more preferably less than 100,000. In particular, by increasing the solubility in organic polar solvents, it is more preferably less than 80,000, particularly preferably less than 60,000, from the viewpoint of lowering the heating temperature and reducing the energy load.
- PAS resin composition The PAS resin composition is obtained by blending PAS with additives such as fillers, heating to a temperature above the melting point of PAS, and melt-kneading. and organic fillers are generally used.
- Inorganic fillers include glass fiber, milled glass fiber, carbon fiber, potassium titanate whisker, zinc oxide whisker, calcium carbonate whisker, wollastonite whisker, aluminum borate whisker, alumina fiber, silicon carbide fiber, ceramic fiber, gypsum fiber.
- talc wollastonite, zeolite, sericite, mica, kaolin, clay, mica, ferrite, pyrophyllite, bentonite, alumina silicate, silicon oxide, magnesium oxide, alumina , zirconium oxide, titanium oxide, iron oxide, magnesium oxide, calcium carbonate, magnesium carbonate, dolomite, calcium sulfate, barium sulfate, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, glass beads, glass flakes, glass powder, ceramic beads , boron nitride, silicon nitride, silicon carbide, aluminum silicate, calcium silicate, silica, graphite, carbon black, and graphite.
- Organic fillers include polyethylene fiber, polypropylene fiber, polyester fiber, polyamide fiber, polyaramid fiber, fluororesin fiber, thermosetting resin fiber, epoxy resin fiber, polyvinylidene chloride fiber, polyvinylidene fluoride fiber, cellulose fiber, etc. fibrous organic fillers; and non-fibrous organic fillers such as ebonite powder, cork powder, and wood flour.
- fillers may be pretreated with a coupling agent such as an isocyanate-based compound, an organic silane-based compound, an organic titanate-based compound, an organic borane-based compound, and an epoxy compound before use.
- a coupling agent such as an isocyanate-based compound, an organic silane-based compound, an organic titanate-based compound, an organic borane-based compound, and an epoxy compound before use.
- a sizing agent may also be used.
- the PAS resin composition generally uses an olefin copolymer resin for the purpose of improving toughness, etc., and is selected from the group consisting of epoxy groups, carboxyl groups, acid anhydride groups, amino groups, hydroxyl groups and mercapto groups. and olefinic copolymer resins having at least one type of functional group, and olefinic copolymers not having the above functional groups.
- PAS resin composition other than olefinic copolymers such as polyamide, polyethersulfone, polysulfone, polyarylsulfone, polyetherimide, polyphenylene ether, fluorine resin, and polyetheretherketone, are used for the purpose of modifying other properties.
- resins epoxy-based compounds, amine-based compounds, isocyanate-based compounds, coupling agents such as anhydride-based compounds, phenol-based and phosphorus-based antioxidants, anti-coloring agents such as hypophosphite, Crystal nucleating agents such as talc, kaolin, organic phosphorus compounds, and polyether ether ketones, release agents such as ethylenediamine/stearic acid/sebacic acid polycondensates, silicone compounds, and phosphorous, bromine, and silicone compounds.
- a flame retardant, a blackening agent such as carbon, or the like may be used as an additive.
- PAS resin compositions are molded into desired shapes by injection molding, extrusion molding, compression molding, or the like, and used in various parts for automobiles, electrical/electronics, housing equipment, and the like.
- various molding methods are employed, such as molding with resin alone, insert molding that combines resin and metals, and two-color molding that combines with other resins, and the molding used in the present invention
- There are no particular restrictions on the molding method for the product it is also possible to use a molded product employing various bonding methods such as welding bonding such as laser welding, hot plate welding, IR welding, vibration welding, and bonding with an adhesive.
- welding bonding such as laser welding, hot plate welding, IR welding, vibration welding, and bonding with an adhesive.
- the molded product used in the present invention may be a defective molded product generated during molding, a non-standard molded product, or a remnant molded product such as a sprue or runner. It may be mixed. Furthermore, from the viewpoint of realizing a circular economy, it is preferable that the molded article is collected after being used in the market as a product. It is also a preferred embodiment that the molded articles collected from the market are appropriately sorted and washed. Molded articles collected from the market are often found to be contaminated with oil stains, but the present invention makes it possible to rationally separate them from contaminants and the like from the viewpoint of LCA.
- the method for forming small pieces include compression pulverization, impact pulverization, shear pulverization, cutter pulverization, mill pulverization, and cutting, and there are no particular limitations as long as the object of the present invention can be achieved.
- the size of the small pieces is preferably 50 mm or less, more preferably 20 mm or less from the viewpoint of solubility. It is also possible to melt-knead the molded product into small pieces using a known method, such as an extruder, and repelletize the product.
- organic polar solvents for dissolving the PAS resin composition or molded articles thereof include N-alkylpyrrolidones such as N-methyl-2-pyrrolidone and N-ethyl-2-pyrrolidone; caprolactams such as N-methyl- ⁇ -caprolactam.
- aprotic organic solvents typified by 1,3-dimethyl-2-imidazolidinone, N,N-dimethylacetamide, N,N-dimethylformamide, hexamethylphosphoric triamide, dimethylsulfone, tetramethylene sulfoxide and the like; and A mixture of these is preferably used.
- NMP N-methyl-2-pyrrolidone
- NMP is preferably used from the viewpoint of easy control of the solubility by the weight average molecular weight of PAS and the viewpoint of miscibility with water.
- a PAS solution (A) is obtained by heating a PAS resin composition or a molded article thereof in an organic polar solvent to a temperature of 200° C. or more and less than 400° C. to dissolve PAS.
- the temperature is preferably 220°C or higher, more preferably 240°C or higher.
- the temperature is preferably less than 300°C, and more preferably less than 270°C, which is the melting point of PAS or less.
- the weight ratio of the PAS resin composition or its molded product to the organic polar solvent in step 1 cannot be generalized because it depends on the type of the organic polar solvent and the weight average molecular weight of the PAS, but the PAS resin composition per 1 kg of the organic polar solvent
- the weight of PPS contained in the product or its molded product is preferably 20 g or more, more preferably 50 g or more, and further preferably 100 g or more from the viewpoint of efficiency of production.
- the upper limit is preferably 500 g or less, more preferably 300 g or less, still more preferably 200 g or less, particularly preferably 150 g or less, from the viewpoint of sufficiently dissolving PAS.
- the heating time for dissolving the PAS resin composition or its molded article in step 1 is not particularly limited as long as the PAS resin composition or its molded article is dissolved, and can be exemplified from 5 minutes to 5 hours. From the viewpoint of productivity and LCA, the upper limit is preferably 3 hours or less, more preferably 2 hours or less, and even more preferably 1 hour or less.
- step 1 various known reaction methods such as batch and continuous methods can be adopted.
- batch-type reactors include autoclaves, vertical/horizontal reactors, etc., each of which is equipped with a stirrer and a heating function.
- Continuous type extruders, flow reactors (e.g., flow reactors described in WO 2019/031435, etc.), tubular reactors, line mixers, and vertical/horizontal reactors are all equipped with a heating function. , towers, etc.
- a batch system it is preferable to adopt a continuous system from the viewpoint of productivity and LCA, since a heating time is required in addition to the heating time described above.
- the weight-average molecular weight of PAS is preferably within an appropriate range, and the lower limit thereof is preferably 10,000 or more, more preferably 20,000 or more, and even more preferably 30,000 or more.
- the upper limit is preferably 60,000 or less.
- the weight average molecular weight of the PAS is appropriately reduced to the above preferred range when the PAS resin composition or its molded article is dissolved in the organic polar solvent in Step 1. It is also a preferred embodiment to allow
- a sulfur compound As a method for lowering the molecular weight of the PAS, it is preferable to add a sulfur compound to a solution in which the PAS resin composition or its molded article is dissolved.
- the sulfur compound it is preferable to use at least one compound selected from alkali metal sulfides, alkali metal hydrosulfides and hydrogen sulfide.
- alkali metal sulfides include lithium sulfide, sodium sulfide, potassium sulfide, rubidium sulfide, cesium sulfide, and mixtures of two or more of these. Among them, lithium sulfide and/or sodium sulfide are preferred. Sodium sulfide is more preferably used.
- These alkali metal sulfides can be used as hydrates or aqueous mixtures, or in anhydrous form.
- An aqueous mixture refers to an aqueous solution, a mixture of an aqueous solution and a solid component, or a mixture of water and a solid component. Since commonly available and inexpensive alkali metal sulfides are hydrates or aqueous mixtures, it is preferred to use such forms of alkali metal sulfides.
- alkali metal hydrosulfides include lithium hydrosulfide, sodium hydrosulfide, potassium hydrosulfide, lithium hydrosulfide, rubidium hydrosulfide, cesium hydrosulfide, and mixtures of two or more of these. Lithium hydrosulfide and/or sodium hydrosulfide are preferred, and sodium hydrosulfide is more preferably used.
- alkali metal sulfide prepared in a reaction system from an alkali metal hydrosulfide and an alkali metal hydroxide can also be used.
- Alkali metal sulfides prepared by contacting alkali metal hydrosulfides and alkali metal hydroxides in advance can also be used.
- These alkali metal hydrosulfides and alkali metal hydroxides can be used in the form of hydrates, aqueous mixtures, or anhydrous forms, and hydrates or aqueous mixtures are readily available and cost-effective. preferable.
- alkali metal sulfides prepared in a reaction system from alkali metal hydroxides such as lithium hydroxide and sodium hydroxide and hydrogen sulfide can also be used.
- an alkali metal sulfide prepared by contacting an alkali metal hydroxide such as lithium hydroxide or sodium hydroxide with hydrogen sulfide in advance can also be used.
- the amount of the sulfur compound used is preferably 0.01 mol% or more, more preferably 0.1 mol% or more, and even more preferably 1.0 mol% or more per 1.0 mol of PAS.
- the upper limit is preferably 50 mol % or less, more preferably 10 mol % or less.
- the amount of the alkali metal hydroxide to be used is such that the hydroxide ion of the alkali metal hydroxide is 0.00 per mole of the sulfur component of the alkali metal hydrosulfide.
- the range of 95 mol or more and 2.5 mol or less is preferable. Within this preferable range, thermally unstable low-molecular-weight PAS is less likely to occur, while low-molecular-weight PAS containing many impurities is less likely to occur.
- the lower limit is preferably 1.0 mol or more, more preferably 1.1 mol or more, of the hydroxide ion of the alkali metal hydroxide per 1 mol of the sulfur component of the alkali metal hydrosulfide.
- the upper limit is preferably 2.0 mol or less, more preferably 1.8 mol or less.
- the crystallinity of the PAS resin composition or its molded product in step 1 is preferably 30% or less, and preferably 20% or less, from the viewpoint of improving solubility in organic polar solvents and increasing productivity. is more preferable, and 10% or less is even more preferable.
- the strand obtained by melt-kneading the PAS resin composition or its molded product with an extruder or the like is rapidly cooled or annealed. This is a specific example.
- the crystallinity here is a cold crystal from the heat of fusion (J / g) of PAS detected when the temperature is raised from 0 ° C. to 340 ° C.
- step 2 of the present invention the PAS solution (A) obtained in step 1 is subjected to solid-liquid separation into solids, which are insoluble components, and PAS solution (B).
- the method of performing solid-liquid separation is not particularly limited, and a known method can be adopted.
- Pressure filtration or vacuum filtration which is filtration using a filter
- sedimentation which is separation based on the difference in specific gravity between the solid content and the solution, or centrifugation. , and further a method combining these can be adopted.
- a decanter separation method in which sedimentation is separated before the filtration operation is also a preferred method.
- the solids separated in step 2 include, for example, inorganic fillers, organic fillers, olefinic copolymer resins, PAS, etc. that are insolubilized due to oxidative cross-linking, metals, dust, rust, and the like.
- the solid-liquid separation temperature in step 2 is preferably 200° C. or higher and lower than 400° C., as in step 1. From the viewpoint of productivity, it is preferably the same temperature as or higher than the heating temperature in step 1, and the PAS is sufficiently dissolved. From the viewpoint of increasing the PAS recovery rate, the temperature is more preferably 220°C or higher, and even more preferably 240°C or higher. From the viewpoint of energy saving, the temperature is more preferably less than 300°C, and more preferably less than 270°C, which is the melting point of PAS or less.
- the temperature is preferably 100° C. or higher, and more preferably 150° C. or higher in terms of balance with solubility.
- the solid-liquid separation in step 2 is preferably carried out in a non-oxidizing atmosphere from the viewpoint of suppressing oxidative cross-linking and degeneration of PAS, and the non-oxidizing atmosphere is preferably an inert gas such as nitrogen, helium, or argon. mentioned.
- the non-oxidizing atmosphere is preferably an inert gas such as nitrogen, helium, or argon. mentioned.
- the terminal of PAS becomes a thiolate structure that is susceptible to oxidation. Solid-liquid separation in a non-oxidizing atmosphere is effective.
- a filter is placed in the middle of a continuous dissolving device such as a flow reactor, and a process in which a decanter-type continuous centrifuge is installed after the continuous dissolving device to perform sedimentation and filtration separation. mentioned. Residues such as filler deposited on these filters can be recovered in a batch or continuous manner.
- Inorganic fillers and organic fillers recovered by solid-liquid separation in step 2 have a solution containing PAS and an organic solvent attached to the surface of the fillers.
- a method of recovering the filler by heating to a high temperature of about ° C. and volatilizing and burning the organic matter, and a method of recovering the filler by washing with a solvent compatible with the organic polar solvent used in step 1 can be exemplified.
- the washing conditions are not particularly limited, and the amount of washing, the number of washings, and the washing temperature that can remove the PAS and organic polar solvent from the inorganic filler and the organic filler may be appropriately set. Further, after washing with an organic polar solvent, the organic polar solvent may be appropriately substituted with water or the like.
- step 3 of the present invention the PAS solution (B) obtained in step 2 is cooled to 20° C. or higher and 200° C. or lower to precipitate PAS.
- the PPS resin composition or its molded article containing dirt etc. can be rationally removed from the viewpoint of LCA. Recovery of PAS becomes possible.
- the precipitation temperature in step 3 is preferably adjusted by the components other than PAS contained in the PAS solution (B).
- the higher the precipitation temperature the more components that dissolve in the organic polar solvent, so that the separation of PAS improves, but the recovery rate decreases because low-molecular-weight PAS cannot be recovered.
- the precipitation temperature is preferably 50° C. or higher from the viewpoint of separating dirt components and low molecular weight components derived from olefinic copolymer resins, and more preferably 100° C. or higher from the viewpoint of separating PAS-derived oligomers.
- the generation of gas during melt processing of recovered PAS can be suppressed, for example, the quality of films and fibers can be improved, and mold contamination during molding can be suppressed.
- the upper limit of the precipitation temperature is more preferably 150° C. or less from the viewpoint of increasing the recovery rate of PAS.
- Step 3 is a method of cooling at a constant temperature, a method of gradually lowering the temperature, or a method of continuously lowering the temperature so as to achieve both recovery and separation of PAS within the above temperature range. may be employed, and the particle size of PAS particles obtained by controlling the cooling rate may be adjusted.
- step 3 if the temperature is within the above range, a substance that improves the efficiency of PAS precipitation may be added in order to achieve both PAS recovery and separability, and water is preferable from the viewpoint of LCA and cost.
- the precipitation time in step 3 is not particularly limited as long as PAS is precipitated from the PAS solution (B), and can be 5 minutes or more and 24 hours or less. From the viewpoint of productivity and LCA, the upper limit is preferably 12 hours or less, more preferably 6 hours or less.
- step 3 various known reaction methods such as batch and continuous methods can be adopted.
- batch-type reactors include autoclaves, vertical/horizontal reactors, tanks, etc., all of which are equipped with a stirrer and a heating function.
- continuous systems include extruders, flow reactors, tubular reactors, line mixers, vertical/horizontal reactors, towers, and the like, all of which are equipped with a heating function.
- step 4 of the present invention the mixture containing the precipitated PAS obtained in step 3 is subjected to solid-liquid separation into PAS and an organic polar solvent containing dirt and the like.
- the method of performing solid-liquid separation is not particularly limited, and a known method can be adopted.
- Pressure filtration or vacuum filtration which is filtration using a filter
- sedimentation which is separation based on the difference in specific gravity between the solid content and the solution, or centrifugation.
- a decanter separation method in which sedimentation is separated before the filtration operation is also a preferred method.
- the solid-liquid separation temperature in step 4 is preferably 20°C or higher and 200°C or lower as in step 3, and from the viewpoint of productivity, it is preferably the same temperature as the precipitation temperature in step 3. On the other hand, it is also possible to perform solid-liquid separation at the precipitation temperature of step 3 or lower while suppressing precipitation of components other than PAS from the mixture obtained in step 3 by using a supercooled state.
- step 4 it is preferable to add a washing solvent as appropriate in order to improve the handleability of the mixture and wash the PAS.
- the washing solvent is not particularly limited, washing with an organic solvent has the problem of lowering the yield of recovered PAS because the oligomer components contained in the PAS are removed. is preferred.
- the weight average molecular weight of PAS is adjusted by developing a sulfur compound in step 1, it is preferable to wash with water from the viewpoint of washing reaction products such as salts.
- the timing of adding the washing solvent may be before or after solid-liquid separation of the mixture obtained in step 3.
- the PAS recovered in the present invention can be reused without inputting new resources such as repolymerization or consuming a large amount of energy.
- new resources such as repolymerization or consuming a large amount of energy.
- the recovered PAS preferably has a weight average molecular weight of 10,000 or more and 60,000 or less, more preferably 20,000 or more.
- the PAS recovered in the present invention can be recovered as high-molecular-weight PAS by polymerizing again using a dihalogenated aromatic compound or a sulfide compound as a raw material together with the recovered low-molecular-weight PAS. is.
- inorganic fillers and organic fillers separated and recovered in step 2 of the present invention can also be reused as fillers for various resin compositions.
- Example 1 A 1 L autoclave equipped with a bottom plug valve and an apparatus directly connected with a nitrogen-pressurizable high-temperature filter (using a PTFE filter with a pore size of 1 ⁇ m) were prepared below the bottom plug valve. 10 g of PPS-2 and 300 g of NMP (PPS weight per 1 kg of organic polar solvent is 20 g) were charged into an autoclave, and after purging with nitrogen, the temperature was raised to 250 ° C. over 60 minutes, and then held for 60 minutes to obtain a PPS solution (A). was obtained (Step 1).
- the bottom plug valve of the autoclave is opened, and the PPS solution is transferred to a high-temperature filter at 250°C, pressurized with nitrogen to 0.2 MPa, and filtered under pressure in a non-oxidizing atmosphere at 250°C. (B) and the glass fiber were separated (step 2).
- the resulting PAS solution (B) was cooled to 75° C. to precipitate PPS (step 3). After that, it was put into 5 L of ion-exchanged water and filtered through a filter with an opening of 10 to 16 ⁇ m.
- the resulting cake was washed with water at 75° C. and filtered in the same manner three times, and dried at 120° C. to obtain recovered PPS.
- the recovery rate was determined from the weight of the recovered PPS obtained and the PPS weight in the charged PPS-2. Also, the weight-average molecular weight of the recovered PPS and the amount of generated gas were determined by the above methods.
- Examples 2 to 9 Recovered PPS was obtained in the same manner as in Example 1, except that the PPS weight per 1 kg of the organic polar solvent and the precipitation temperature in step 3 were changed.
- Table 1 shows the conditions and characteristics of recovered PPS in Examples and Comparative Examples.
- Example 1 it can be seen that PAS with the same Mw as before dissolution can be recovered by dissolving the PPS resin composition in NMP, which is an organic polar solvent, and filtering at high temperature.
- NMP organic polar solvent
- PAS can be easily recovered with little loss during recovery, so that PAS can be obtained at a high recovery rate.
- Comparative Example 1 when PAS is dissolved in a water-insoluble solvent such as 1-chloronaphthalene, which is not an organic polar solvent, 1-chloronaphthalene is dissolved in an organic solvent such as acetone when PAS is recovered. It can be seen that the recovery rate of PAS decreases due to the partial dissolution and removal of PAS. Moreover, the amount of the organic solvent used is larger than in Example 1, which is obviously disadvantageous from the viewpoint of LCA.
- the amount of water remaining in the system per 1 mol of the charged alkali metal sulfide was 1.06 mol including the water consumed for hydrolysis of NMP.
- the amount of hydrogen sulfide scattered was 0.02 mol per 1 mol of the charged alkali metal sulfide.
- the content was diluted with about 35 L of NMP and stirred at 85° C. for 30 minutes to form a slurry, and then filtered through an 80-mesh wire mesh (opening 0.175 mm) to obtain a solid.
- the obtained solid matter was similarly washed with about 35 L of NMP and separated by filtration.
- the obtained solid matter was diluted with 70 L of ion-exchanged water, stirred at 70° C. for 30 minutes, filtered through an 80-mesh wire mesh to recover the solid matter, and the operation was repeated three times in total.
- the obtained solid and 32 g of acetic acid were diluted with 70 L of ion-exchanged water, stirred at 70° C.
- Example 10 A 1 L autoclave equipped with a bottom plug valve and an apparatus directly connected with a nitrogen-pressurizable high-temperature filter (using a PTFE filter with a pore size of 1 ⁇ m) were prepared below the bottom plug valve. 50 g of PPS-4 and 300 g of NMP (PPS weight per 1 kg of organic polar solvent is 100 g) were charged into an autoclave, and after purging with nitrogen, the temperature was raised to 250 ° C. and held for 1 hour to obtain a PPS solution (A) (step 1).
- PPS-4 and 300 g of NMP PPS weight per 1 kg of organic polar solvent is 100 g
- the bottom plug valve of the autoclave is opened, and the PPS solution is transferred to a high-temperature filter at 250°C, pressurized with nitrogen to 0.2 MPa, and filtered under pressure in a non-oxidizing atmosphere at 250°C. (B) and the glass fiber were separated (step 2).
- the obtained PAS solution (B) was cooled to 150° C. to precipitate PPS (step 3). After that, it was put into 5 L of ion-exchanged water and filtered through a filter with an opening of 10 to 16 ⁇ m. The resulting cake was washed with water at 75° C. and filtered in the same manner three times, and dried at 120° C. to obtain recovered PPS.
- the recovery rate was determined from the weight of the recovered PPS obtained and the PPS weight in the charged PPS-2. Also, the weight average molecular weight and the weight reduction rate of the recovered PPS were obtained by the above method. In addition, in order to analyze the weight average molecular weight of PPS after step 1, the weight average of the PAS solution (A) transferred without solid-liquid separation in step 2 was obtained by not using a PTFE filter in the high-temperature filter. Molecular weight was determined. [Example 11] Recovered PPS was obtained in the same manner as in Example 10, except that the heating temperature in step 1 was changed to 280°C.
- Example 13 In addition to PPS-4 and NMP, 114.0 g of 48% by weight sodium hydrosulfide (NaSH), 39.8 g of NaOH and 163.6 g of NMP are heated and reacted at 120 ° C. or higher to prepare in advance. Recovered PPS was obtained by the same operation as in Example 10, except that 0.73 g of the compound obtained in the reaction was charged.
- NaSH sodium hydrosulfide
- Table 2 shows the conditions in the example and the characteristics of the recovered PPS.
- Example 8 A comparison of Examples 8 and 10 shows that the PPS weight average molecular weight of the PPS resin composition or molded article increases, and the recovery rate of the recovered PPS decreases. However, it can be seen that there is a high molecular weight PPS separated as a solid in step 2. In order to improve the recovery rate, the heating temperature in step 1 is increased as shown in Example 11, the crystallinity of PPS is lowered as shown in Example 12, and the sulfur compound is added as shown in Example 13. It can be seen that adding to lower the molecular weight of PPS in step 1 is effective.
- Example 14 33.5 kg of PPS-2 and 200 kg of NMP (weight of PPS per 1 kg of organic polar solvent is 100 g) were charged into a 300 L pressure vessel (I) equipped with a circulation line (I) equipped with a pump and a stirrer, and the mixture was purged with nitrogen.
- a branch line (I) is connected to the circulation line (I) via a valve, and the pressure vessel (I) and the pressure vessel (II) are connected to the tip of the branch.
- a branch line (II) is connected to the circulation line (II) via a valve, and a pressure vessel (II) and a high-temperature filter (using a PTFE filter with a pore size of 1 ⁇ m) are connected to the tip of the branch.
- a branch line (III) is installed at the inlet of the hot filter to enable supply to the filter and withdrawal to another container.
- a container (III) is connected to the outlet of the filter.
- the temperature of the pressure-resistant container (I) was adjusted to 50°C, and the temperature of the pressure-resistant container (II) was adjusted to 250°C.
- the contents of pressure vessel (I) were then continuously fed to pressure vessel (II) at 40 kg/h.
- the content was continuously extracted from the pressure vessel (II) at a rate of 40 kg/hour.
- a PAS solution (A) was obtained in the pressure vessel (II) (Step 1).
- the pressure in the pressure vessel (II) was constant at about 0.2 MPa. Since the amount of supply to and withdrawal from the pressure vessel (II) was constant, it can be said that the amount of content in the pressure vessel (II) was constant during this operation.
- the residence time of the PAS solution (A) was 30 minutes.
- the branch line (III) is supplied to the high-temperature filter, and the PPS solution (B) and the glass fiber are was separated (step 2) to obtain a PAS solution (B).
- the obtained PAS solution (B) was cooled to 150° C. to precipitate PPS (Step 3). After that, it was put into ion-exchanged water and filtered through a filter with an opening of 10 to 16 ⁇ m. The resulting cake was washed with water at 75° C. and filtered in the same manner three times, and dried at 120° C. to obtain recovered PPS.
- the recovery rate was determined from the weight of the recovered PPS obtained and the PPS weight in the charged PPS-2. Also, the weight-average molecular weight of the recovered PPS and the amount of generated gas were determined by the above methods.
- Table 3 shows the conditions in the example and the characteristics of the recovered PPS.
- Example 14 adopting a continuous system was comparable in recovery rate and generated gas amount to Example 8 using a batch system. Further, if the operation becomes steady state, it becomes possible to shorten the temperature rising time and the heating time in step 1, which is excellent from the viewpoint of LCA and productivity.
- Reference Example 5 After removing the resin part composed of the PPS resin composition from the automotive metal insert part collected after use in the market, it is roughly crushed with a crusher so that the long axis dimension is 100 mm or less, and washed with water. , to obtain a PPS resin composition molded article (PPS-5) to which oil stains adhered by pulverizing to a major axis dimension of 10 mm or less.
- PPS-5 was composed of 60% by weight of PPS and 40% by weight of GF, and the weight average molecular weight of PPS was 45,000.
- Reference Example 6 After removing the resin part composed of the PPS resin composition from the water-related parts of housing equipment collected after use in the market, it is pulverized so that the long axis dimension is 10 mm or less and washed with water to remove rust. A molded article (PPS-6) of the adhered PPS resin composition was obtained.
- PPS-6 was composed of 65% by weight of PPS, 30% by weight of GF, and 5% by weight of olefinic copolymer resin, and the weight average molecular weight of PPS was 50,000.
- Fibers composed of PPS were collected from bag filters collected after market use and washed with water. A PPS fiber (PPS-7) with soot and oil stains was obtained.
- PPS-7 was composed of about 100% PPS, and the weight average molecular weight of PPS was 55,000.
- Recovered PPS was obtained in the same manner as in Example 8, except that the type of PPS resin composition or molded product and the precipitation temperature in step 3 were as shown in Table 4.
- Table 4 shows the conditions in the example and the characteristics of the recovered PPS.
- Example 24 A molded product of ISO (1A) dumbbell was produced in the same manner as in Reference Example 2 except that the PPS (PPS-8) recovered in Example 8 was used instead of PPS-1. 2 mechanical properties.
- the PPS resin composition obtained using the recovered PPS obtained by the present invention has a sufficient weight-average molecular weight, the PPS resin obtained using virgin PPS without undergoing treatment such as repolymerization It can be seen that the properties similar to those of the composition are expressed.
- the PAS recovered by the separation method of the present invention is polymerized again using a dihalogenated aromatic compound or a sulfide compound as a raw material together with the recovered low-molecular-weight PAS, as long as there is no problem from the viewpoint of LCA, and recovered as high-molecular-weight PAS. is also possible.
- inorganic fillers and organic fillers separated and recovered in step 2 of the present invention can also be reused as fillers for various resin compositions.
- PAS and compounding materials can be recovered rationally from the viewpoint of LCA from the PAS resin composition or its molded product.
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Abstract
Description
下記の工程1~4を行うポリアリーレンスルフィド(以下、PAS)の分離方法、である。
工程1:有機極性溶媒中でPAS樹脂組成物またはその成形品を200℃以上400℃未満に加熱してPASを溶解させてPAS溶液(A)を得る工程、
工程2:PAS溶液(A)を固液分離して、固体とPAS溶液(B)に分離する工程、
工程3:工程2で得たPAS溶液(B)を20℃以上200℃以下に冷却してPASを析出させる工程、
工程4:工程3で得た混合物を固液分離してPASを分離する工程。
上記の、前記工程4の後に、分離したPASを洗浄して回収する分離方法により得られたPASを原料に用いる、PAS樹脂組成物の製造方法。
PAS樹脂組成物は、PASに充填材などの添加剤を配合し、PASの融点以上に加熱、溶融混練して得られるものであるが、優れた特性を発現させるために充填材として無機充填材や有機充填材を用いることが一般的である。
自動車、電気電子、住設などの各種部材では、PAS樹脂組成物を射出成形、押出成形、圧縮成形などで所望の形状に成形して用いられる。これら成形品を成形する際、樹脂単独での成形、樹脂と金属類を複合化するインサート成形、他樹脂と複合化する二色成形など様々な成形方法が採用されており、本発明で用いる成形品もこれら成形方法に特に制限はない。また、レーザー溶着、熱板溶着、IR溶着、振動溶着などの溶着接合や、接着剤での接合など、各種接合方法が採用された成形品を用いることも可能である。また、上記成形によって得られた成形品だけでなく、PASで構成される繊維やフィルムやそれらの複合体を用いることも可能である。
PAS樹脂組成物またはその成形品を溶解させる有機極性溶媒としては、N-メチル-2-ピロリドン、N-エチル-2-ピロリドンなどのN-アルキルピロリドン類;N-メチル-ε-カプロラクタムなどのカプロラクタム類;1,3-ジメチル-2-イミダゾリジノン、N,N-ジメチルアセトアミド、N,N-ジメチルホルムアミド、ヘキサメチルリン酸トリアミド、ジメチルスルホン、テトラメチレンスルホキシドなどに代表されるアプロチック有機溶媒;およびこれらの混合物が好ましく使用される。なかでも、PASの重量平均分子量によって溶解性が制御しやすい観点と、水との混和性の観点で、N-メチル-2-ピロリドン(以下、NMP)が好ましく用いられる。
工程1では、有機極性溶媒中でPAS樹脂組成物またはその成形品を200℃以上400℃未満に加熱してPASを溶解させてPAS溶液(A)を得る。PASを十分溶解させてPASの回収率を高める観点で220℃以上が好ましく、240℃以上がより好ましい。また、省エネルギーの観点で300℃未満が好ましく、PASの融点以下である270℃未満がより好ましい。
本発明の工程2では、工程1で得たPAS溶液(A)を不溶成分である固体とPAS溶液(B)へ固液分離を行う。固液分離を行う方法は特に制限されず公知の方法を採用可能であり、フィルターを用いるろ過である加圧ろ過や減圧濾過、固形分と溶液の比重差による分離である沈降分離や、遠心分離、さらにこれらを組み合わせた方法などを採用可能である。ろ過操作の前に沈殿分離を行うデカンタ分離方式も好ましい方法である。
本発明の工程3では、工程2で得たPAS溶液(B)を20℃以上200℃以下に冷却してPASを析出させる。工程1から工程3にかけて同一の有機極性溶媒中で、温度を段階的に変化させて固液分離を行うことで、LCAの観点で合理的に汚れ等を含むPPS樹脂組成物またはその成形品からPASの回収が可能となる。
本発明の工程4では、工程3で得た析出したPASを含む混合物をPASと、汚れ等を含む有機極性溶媒へ固液分離を行う。固液分離を行う方法は特に制限されず公知の方法を採用可能であり、フィルターを用いるろ過である加圧ろ過や減圧濾過、固形分と溶液の比重差による分離である沈降分離や、遠心分離さらにこれらを組み合わせた方法などを採用可能である。ろ過操作の前に沈殿分離を行うデカンタ分離方式も好ましい方法である。
本発明で回収したPASは、再重合等で新たに資源を投入したり、多大なエネルギーを消費することなく、再度利用することができ、PASをフィルム、繊維、樹脂に加工したり、PASと配合材を溶融混練することでPAS樹脂組成物やその成形品として再生可能であり、自動車、電気電子、住設など各種用途でのエコマテリアルとしての利用が期待できる。またこれら用途で十分な物性を発現させるため、回収したPASの重量平均分子量は10,000以上、60,000以下が好ましく、20,000以上がより好ましい。
重量平均分子量(Mw)は、ゲルパーミエーションクロマトグラフィー(GPC)により、ポリスチレン換算で算出した。GPCの測定条件を以下に示す。
装置:SSC-7100((株)センシュー科学)
カラム名:GPC3506((株)センシュー科学)
溶離液:1-クロロナフタレン
検出器:示差屈折率検出器
カラム温度、検出器温度:210℃
流量:1.0mL/min
サンプル濃度:0.2重量%(溶媒:1-クロロナフタレン)
(2)発生ガス量
各実施例および比較例により得られた回収PPSをアルミカップに10g秤量し、320℃に加熱したエスペック(株)製熱風乾燥機PHH202中にて2hr処理し、室温で放冷した。次いで、重量を測定し、乾燥処理前の重量に対する乾燥処理前後における重量変化の比である重量減少率(%)を求め、発生ガス量とした。
(3)機械特性
ISO(1A)ダンベル試験片について、23℃条件下、オートグラフ試験機AG-Xplus20kNを用い、ISO527-1(2012),ISO527-2(2012)に従い、支点間距離114mm、引張速度5mm/minの条件で引張特性を評価した。
撹拌機および底栓弁付きの70Lオートクレーブに、47.5%水硫化ナトリウム8.3kg(70.0モル)、96%水酸化ナトリウム2.9kg(69.8モル)、N-メチル-2-ピロリドン(NMP)11.5kg(115.5モル)、酢酸ナトリウム1.9kg(23.1モル)、及びイオン交換水10.5kgを仕込み、常圧で窒素を通じながら245℃まで約3時間かけて徐々に加熱し、水14.8kgおよびNMP0.3kgを留出した後、反応容器を200℃に冷却した。硫化水素の飛散量は、仕込みアルカリ金属硫化物1モル当たり0.02モルであった。
(株)日本製鋼所製TEX30α型二軸押出機(L/D=30)の元込め部にPPS-1を60重量部投入し、更に、該二軸押出機のサイドフィーダーからガラス繊維(日本電気硝子(株)製T-747H、平均繊維径10.5μm)を40重量部投入し、320℃、200rpmの条件で溶融混練を行った。ストランドカッターで10mm長以下にペレット化した後、120℃で乾燥してPPS樹脂組成物を得た。得られたPPS樹脂組成物を住友重機械工業(株)製射出成形機SE75DUZ-C250を用いて樹脂温度310℃、金型温度130℃で射出成形を行い、ISO(1A)ダンベルの成形品(PPS-2)を作製した。
底栓弁を備えた1Lオートクレーブおよび底栓弁の下方に窒素加圧可能な高温濾過器(ポアサイズ1μmのPTFEフィルター使用)を直結した装置を用意した。PPS-2を10g、NMP300g(有機極性溶媒1kgあたりのPPS重量は20g)をオートクレーブに仕込み、窒素置換した後に60分かけて250℃まで昇温した後、60分保持してPPS溶液(A)を得た(工程1)。その後、オートクレーブの底栓弁を開放して250℃の高温濾過器に移送すると共に高温濾過器を窒素で0.2MPaに加圧し、250℃の非酸化性雰囲気化で加圧濾過してPPS溶液(B)とガラス繊維を分離した(工程2)。得られたPAS溶液(B)を75℃まで冷却してPPSを析出させた(工程3)。その後、5Lのイオン交換水中に投入して、目開き10~16μmの濾過器で濾過した。得られたケークは75℃で同様の水洗と濾過を3回繰り返し、120℃で乾燥して回収PPSを得た。得られた回収PPSの重量と、仕込んだPPS-2中のPPS重量から回収率を求めた。また、前記方法で回収PPSの重量平均分子量と、発生ガス量を求めた。
有機極性溶媒1kgあたりのPPS重量と、工程3の析出温度を変更した以外は、実施例1と同様の操作により回収PPSを得た。
有機極性溶媒に替えて1-クロロナフタレン(1-CN)300gを溶媒としてオートクレーブに仕込み、実施例1と同様に工程1および工程2を行った。得られた250℃のPPS溶液(B)を5Lのアセトン中に投入してPPSを析出させ、目開き10~16μmの濾過器で濾過した。得られたケークは30℃のアセトンで洗浄と濾過を3回繰り返し、120℃で乾燥して回収PPSを得た。
溶媒1kgあたりのPPS重量を変更した以外は比較例1と同様の操作により回収PPSを得た。
撹拌機および底栓弁付きの70Lオートクレーブに、47.5%水硫化ナトリウム8.27kg(70.00モル)、96%水酸化ナトリウム2.94kg(70.63モル)、N-メチル-2-ピロリドン(NMP)11.45kg(115.50モル)、酢酸ナトリウム2.24kg(27.3モル)、及びイオン交換水5.50kgを仕込み、常圧で窒素を通じながら245℃まで約3時間かけて徐々に加熱し、水9.77kgおよびNMP0.28kgを留出した後、反応容器を200℃に冷却した。仕込みアルカリ金属硫化物1モル当たりの系内残存水分量は、NMPの加水分解に消費された水分を含めて1.06モルであった。また、硫化水素の飛散量は、仕込みアルカリ金属硫化物1モル当たり0.02モルであった。
[参考例4]PPS樹脂組成物の成形品(PPS-4)
PPS-1の代わりにPPS-3を用いたこと以外はPPS-2と同様にASTM1号ダンベルの成形品(PPS-4)を作製した。
[実施例10]
底栓弁を備えた1Lオートクレーブおよび底栓弁の下方に窒素加圧可能な高温濾過器(ポアサイズ1μmのPTFEフィルター使用)を直結した装置を用意した。PPS-4を50g、NMP300g(有機極性溶媒1kgあたりのPPS重量は100g)をオートクレーブに仕込み、窒素置換した後に250℃まで昇温して1時間保持してPPS溶液(A)を得た(工程1)。その後、オートクレーブの底栓弁を開放して250℃の高温濾過器に移送すると共に高温濾過器を窒素で0.2MPaに加圧し、250℃の非酸化性雰囲気化で加圧濾過してPPS溶液(B)とガラス繊維を分離した(工程2)。得られたPAS溶液(B)を150℃まで冷却してPPSを析出させた(工程3)。その後、5Lのイオン交換水中に投入して、目開き10~16μmの濾過器で濾過した。得られたケークは75℃で同様の水洗と濾過を3回繰り返し、120℃で乾燥して回収PPSを得た。得られた回収PPSの重量と、仕込んだPPS-2中のPPS重量から回収率を求めた。また、前記方法で回収PPSの重量平均分子量と、重量減少率を求めた。また、工程1後のPPSの重量平均分子量を分析するために、高温濾過器にPTFEフィルターを使用しないことで、工程2で固液分離を行わずに移液したPAS溶液(A)の重量平均分子量を測定した。
[実施例11]
工程1の加熱温度を280℃に変更した以外実施例10と同様の操作により回収PPSを得た。
[実施例12]
工程1の前にPPS-4を(株)日本製鋼所製TEX30α型二軸押出機(L/D=30)に投入し、320℃、200rpmの条件で溶融混練を行って得たストランドを水冷バスで急冷した後、ストランドカッターで10mm長以下にペレット化したこと以外は、実施例10と同様の操作により回収PPSを得た。
[実施例13]
工程1に投入する原料に、PPS-4とNMPに加えて、48重量%水硫化ナトリウム(NaSH)を114.0g、NaOH39.8gとNMP163.6gを120℃以上に加熱・反応させて事前作製した化合物を0.73g仕込んだこと以外は、実施例10と同様の操作により回収PPSを得た。
[実施例14]
ポンプを具備した循環ライン(I)と撹拌機を具備した300L耐圧容器(I)にPPS-2を33.5kg、NMP200kg(有機極性溶媒1kgあたりのPPS重量は100g)を仕込み、窒素置換した。ポンプを具備した循環ライン(II)と撹拌ラインを具備した70L耐圧容器(II)にNMP20kgを仕込み、窒素置換した。
[参考例5]
市場での使用後に回収された自動車用金属インサート部品からPPS樹脂組成物で構成された樹脂部を取り外した後、長軸寸法が100mm以下になるよう破砕機で粗く破砕し、水で洗浄して、長軸寸法が10mm以下になるように粉砕して油汚れが付着したPPS樹脂組成物の成形品(PPS-5)を得た。
[参考例6]
市場での使用後に回収された住設水廻り部品からPPS樹脂組成物で構成された樹脂部を取り外した後、長軸寸法が10mm以下になるように粉砕して水で洗浄して、錆びが付着したPPS樹脂組成物の成形品(PPS-6)を得た。
[参考例7]
市場での使用後に回収されたバグフィルターからPPSで構成された繊維を回収し、水で洗浄した。煤や油汚れが付着したPPS繊維(PPS-7)を得た。
[実施例15~23]
PPS樹脂組成物または成形品の種類と、工程3の析出温度を表4に示す通りにした以外は、実施例8と同様の操作により回収PPSを得た。
[実施例24]
PPS-1の代わりに、実施例8により回収されたPPS(PPS-8)を用いたこと以外は、参考例2と同様の操作により、ISO(1A)ダンベルの成形品を作製し、PPS-2の機械特性と比較した。
Claims (12)
- 下記の工程1~4を行うポリアリーレンスルフィド(以下、PAS)の分離方法。
工程1:有機極性溶媒中でPAS樹脂組成物またはその成形品を200℃以上400℃未満に加熱してPASを溶解させてPAS溶液(A)を得る工程、
工程2:PAS溶液(A)を固液分離して、固体とPAS溶液(B)に分離する工程、
工程3:工程2で得たPAS溶液(B)を20℃以上200℃以下に冷却してPASを析出させる工程、
工程4:工程3で得た混合物を固液分離してPASを分離する工程 - 前記工程1のPAS樹脂組成物またはその成形品が、無機充填材および有機充填材から選ばれる少なくとも一種を含む請求項1記載のPASの分離方法。
- 前記工程1のPAS樹脂組成物の成形品が、製品として使用後に回収された成形品である請求項1または2記載のPASの分離方法。
- 前記工程1の有機極性溶媒がNMPである請求項1~3いずれか記載のPASの分離方法。
- 前記工程3の析出を、50℃以上150℃以下で行う請求項1~4いずれか記載のPASの分離方法。
- 前記工程1の溶解前におけるPAS樹脂組成物またはその成形品に含まれるPASの重量平均分子量(以下、Mw)が1万以上、6万以下である請求項1~5いずれか記載のPASの分離方法。
- 前記工程1~4の一部または全てを連続方式で行う請求項1~6いずれか記載のPASの分離方法。
- 前記工程1の溶解前におけるPAS樹脂組成物またはその成形品に含まれるPASのMwを、工程1において1万以上、6万以下まで低下させる請求項1~7いずれか記載のPASの分離方法。
- 前記工程1において、溶液に硫黄化合物を添加する請求項8記載のPASの分離方法。
- 前記硫黄化合物が、アルカリ金属硫化物、アルカリ金属水硫化物および硫化水素から選ばれる少なくとも一種の化合物である請求項9記載のPASの分離方法。
- 前記工程4の後に、分離したPASを洗浄して回収する請求項1~10いずれか記載のPASの分離方法。
- 請求項11の分離方法により得られたPASを原料に用いる、PAS樹脂組成物の製造方法。
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