WO2016159234A1 - 微粉ポリアリーレンスルフィドを製造する方法及び微粉ポリアリーレンスルフィド - Google Patents
微粉ポリアリーレンスルフィドを製造する方法及び微粉ポリアリーレンスルフィド Download PDFInfo
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- WO2016159234A1 WO2016159234A1 PCT/JP2016/060656 JP2016060656W WO2016159234A1 WO 2016159234 A1 WO2016159234 A1 WO 2016159234A1 JP 2016060656 W JP2016060656 W JP 2016060656W WO 2016159234 A1 WO2016159234 A1 WO 2016159234A1
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- 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
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- 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
- C08G75/0277—Post-polymerisation treatment
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- 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
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- 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
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- 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
- C08G75/0213—Polyarylenethioethers derived from monomers containing one aromatic ring containing elements other than carbon, hydrogen or sulfur
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- 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
- C08G75/025—Preparatory processes
- C08G75/0254—Preparatory processes using metal sulfides
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- 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
- C08G75/025—Preparatory processes
- C08G75/0259—Preparatory processes metal hydrogensulfides
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- 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
- C08G75/0277—Post-polymerisation treatment
- C08G75/0281—Recovery or purification
Definitions
- the present invention relates to a production method for producing finely divided polyarylene sulfide from a dispersion containing granular polyarylene sulfide and a finely divided polyarylene sulfide.
- PAS Polyarylene sulfide
- PPS polyphenylene sulfide
- PPS polyphenylene sulfide
- PAS can be molded into various molded products, films, sheets, fibers, etc. by general melt processing methods such as extrusion molding, injection molding, compression molding, etc., so electrical equipment, electronic equipment, automotive equipment, packaging materials, etc. Widely used in a wide range of technical fields.
- pDCB paradichlorobenzene
- NMP N-methyl-2-pyrrolidone
- DHA dihaloaromatic compound
- S sulfur compound
- a method is well known in which PAS is separated from a PAS-containing reaction solution obtained by a polymerization reaction under reduced conditions, and recovered through washing and drying.
- This polymerization reaction is a desalting polycondensation reaction.
- by-product alkali metal salts such as alkali metal halides (for example, NaCl)
- low polymer such as dimers and trimers
- Impurities volatile substances, high-boiling substances, etc.
- these organic amide solvents, by-product alkali metal salts, low polymerization products, impurities, and the like are present between the PAS particles after the polymerization reaction, in the particles, or in the reaction solution.
- the PAS separated from the PAS-containing reaction solution is thoroughly washed to remove the organic amide solvent, by-product alkali metal salt, low polymer, impurities, etc., and then recovered to obtain the quality of PAS as a product. To maintain and improve
- the separated liquid obtained by separating PAS from the PAS-containing reaction liquid by solid-liquid separation contains fine particulate PAS (hereinafter sometimes abbreviated as “raw material fine powder PAS”).
- raw material fine powder PAS is inferior in quality (molecular weight, color tone, odor, gas generation, etc.) compared to the PAS of the product, it is discarded without being recovered as a product.
- raw material fine powder PAS is recovered from the separated liquid by solid-liquid separation such as by filtration, and then, if necessary, The organic amide solvent, by-product alkali metal salt, low polymer, impurities, etc. that are present between and within the fine powder PAS are removed by washing, and after confirming conformity with environmental standards (for example, landfill or It is currently incinerated.
- the raw material fine powder PAS was commercialized, so it was not industrially useful and there were few problems even if discarded (hereinafter, the raw material fine powder PAS was recovered and commercialized. In some cases, the amount is abbreviated as “product rate”).
- Patent Document 1 discloses a PAS oligomer obtained by performing polymerization at a reaction temperature of 260 ° C. for 3.0 hours, separating a granular polymer with a 60 mesh screen, and removing NaCl from the separated liquid. It has been proposed that water is added to a mixed solution containing water and a solvent to aggregate the oligomers, and then the PAS oligomers are separated by centrifugation.
- an oligomer having a particle size of 250 ⁇ m or less is selected. That is, in Patent Document 1, a PAS polymer having a particle diameter of 250 ⁇ m or more is produced from a polymerization method, and a PAS oligomer having a particle diameter of 250 ⁇ m or less is separated.
- Patent Document 2 proposes to perform polymerization using a phase separation agent to separate the PAS oligomer from the slurry containing granular PAS, PAS oligomer, organic polar solvent, water, and alkali metal halide salt.
- a phase separation agent to separate the PAS oligomer from the slurry containing granular PAS, PAS oligomer, organic polar solvent, water, and alkali metal halide salt.
- the PAS oligomer is further separated by a glass filter having an opening of 10 to 16 ⁇ m.
- the obtained PAS oligomer is a PAS oligomer having a particle size distribution having a lower limit of 10 to 16 ⁇ m and an upper limit of 175 ⁇ m.
- Patent Document 3 proposes a method for producing a PAS resin in which the PAS oligomer obtained by the method of Patent Document 2 is thermally oxidized at 150 to 260 ° C. in a gas-phase oxidizing atmosphere in order to reduce volatile components. Yes.
- the present inventors have recovered raw materials recovered as solids by solid-liquid separation such as filtration from a separated liquid produced by solid-liquid separation of a PAS-containing reaction liquid. Fine powder PAS was intended to be commercialized.
- the inventors of the present invention are that the main factor that inhibits the recovery of the raw fine powder PAS as a product is that (i) the ratio of the low polymer that is easily thermally decomposed is higher than that of the granular PAS of the product. (Iii) a fine particulate matter (hereinafter sometimes abbreviated as “fine powder”), and (iii) a heat treatment performed for the purpose of reforming such as volatile content reduction. I thought it was not working as expected.
- the PAS polymer is known to have different thermal stability depending on the molecular weight, and among them, the lower polymer tends to be thermally decomposed more easily than the higher molecular weight one, There is a problem that the raw fine powder PAS contains many such low polymers.
- the low polymer contained in the raw material fine powder PAS is not easily removed by washing because it forms a part of the fine powder that is a fine particulate matter, and because it is fine powder.
- organic amide solvents, by-product alkali metal salts, impurities (volatile substances, high-boiling substances), etc. remain between the fine powders and in the fine powders. In commercialization, the impact on quality is expected to increase.
- the present inventors in the production of fine powder PAS, solid-liquid separation such as filtration from a separated liquid obtained by separating a granular PAS-containing dispersion into granular PAS and separated liquid.
- solid-liquid separation such as filtration from a separated liquid obtained by separating a granular PAS-containing dispersion into granular PAS and separated liquid.
- the object of the present invention is to maintain the wettability of the fine powder PAS in the solid powder containing fine powder PAS after the solid-liquid separation from the separated liquid obtained by separating the granular PAS into the granular PAS and the separated liquid. It is to provide a method for producing finely divided PAS with reduced impurities such as alkali metal salts and / or PAS oligomers, and finely divided PAS.
- a method for producing a finely divided polyarylene sulfide comprising the following steps: (A) a separation step of separating the granular polyarylene sulfide and the separated liquid from the dispersion containing the granular polyarylene sulfide by solid-liquid separation using at least one screen having an opening diameter of 75 to 180 ⁇ m; (B) a solid-liquid separation step for solid-liquid separation of the separated liquid to obtain a finely divided polyarylene sulfide-containing solid; (C) a heating step of heating the fine polyarylene sulfide-containing solid to reduce the amount of organic solvent to obtain a wet cake; (D) a washing step of washing the wet cake with an aqueous solvent; Including A method is provided in which the moisture content of the wet cake after the heating step is 30% by weight or more.
- a method for producing finely divided polyarylene sulfide comprising the following steps: (A) a separation step of separating the granular polyarylene sulfide and the separated liquid from the dispersion containing the granular polyarylene sulfide by solid-liquid separation using at least one screen having an opening diameter of 75 to 180 ⁇ m; (B) a solid-liquid separation step for solid-liquid separation of the separated liquid to obtain a finely divided polyarylene sulfide-containing solid; (C) a heating step of heating the fine polyarylene sulfide-containing solid to reduce the amount of organic solvent to obtain a wet cake; (D) a washing step of washing the wet cake with an aqueous solvent; Including There is provided a method further comprising a water addition step of adding water to the separation liquid after the separation step and before the heating step.
- a method for producing finely divided polyarylene sulfide comprising the following steps: (A) a separation step of separating the granular polyarylene sulfide and the separated liquid from the dispersion containing the granular polyarylene sulfide by solid-liquid separation using at least one screen having an opening diameter of 75 to 180 ⁇ m; (B) a solid-liquid separation step for solid-liquid separation of the separated liquid to obtain a finely divided polyarylene sulfide-containing solid; (C) a heating step of heating the fine polyarylene sulfide-containing solid to reduce the amount of organic solvent to obtain a wet cake; (D) a washing step of washing the wet cake with an aqueous solvent; Including Specific surface area retention ratio A2 / specific surface area A2 of the finely divided polyarylene sulfide contained in the wet cake after the heating step relative to the specific surface area A1 of the finely divided polyarylene sul
- a method for producing finely divided polyarylene sulfide comprising the following steps: (A) a separation step of separating the granular polyarylene sulfide and the separated liquid from the dispersion containing the granular polyarylene sulfide by solid-liquid separation using at least one screen having an opening diameter of 75 to 180 ⁇ m; (B) a solid-liquid separation step for solid-liquid separation of the separated liquid to obtain a finely divided polyarylene sulfide-containing solid; (C) a heating step of heating the fine polyarylene sulfide-containing solid to reduce the amount of organic solvent to obtain a wet cake; (D) a washing step of washing the wet cake with an aqueous solvent; Including A method is provided in which the heating temperature in the heating step is 85 ° C. or lower on average.
- finely divided polyarylene sulfide has an average particle size of 1 to 200 ⁇ m
- a finely divided polyarylene sulfide in which the melt viscosity of the finely divided polyarylene sulfide is 1 Pa ⁇ s or more.
- the present invention while maintaining the wettability of the fine powder PAS in the fine powder PAS-containing solid after the solid-liquid separation from the separated liquid obtained by separating the granular PAS into the granular PAS and the separated liquid.
- the method for producing a finely divided polyarylene sulfide according to the present invention includes the following steps: (A) a separation step of separating the granular polyarylene sulfide and the separated liquid from the dispersion containing the granular polyarylene sulfide by solid-liquid separation using at least one screen having an opening diameter of 75 to 180 ⁇ m; (B) a solid-liquid separation step for solid-liquid separation of the separated liquid to obtain a finely divided polyarylene sulfide-containing solid; (C) a heating step of heating the fine polyarylene sulfide-containing solid to reduce the amount of organic solvent to obtain a wet cake; (D) a washing step of washing the wet cake with an aqueous solvent; Including The moisture content of the wet cake after the heating step is 30% by weight or more.
- the method for producing a finely divided polyarylene sulfide according to the present invention includes the following steps: (A) a separation step of separating the granular polyarylene sulfide and the separated liquid from the dispersion containing the granular polyarylene sulfide by solid-liquid separation using at least one screen having an opening diameter of 75 to 180 ⁇ m; (B) a solid-liquid separation step for solid-liquid separation of the separated liquid to obtain a finely divided polyarylene sulfide-containing solid; (C) a heating step of heating the fine polyarylene sulfide-containing solid to reduce the amount of organic solvent to obtain a wet cake; (D) a washing step of washing the wet cake with an aqueous solvent; Including The method further includes a water addition step of adding water to the separation liquid after the separation step and before the heating step.
- the method for producing a finely divided polyarylene sulfide according to the present invention includes the following steps: (A) a separation step of separating the granular polyarylene sulfide and the separated liquid from the dispersion containing the granular polyarylene sulfide by solid-liquid separation using at least one screen having an opening diameter of 75 to 180 ⁇ m; (B) a solid-liquid separation step for solid-liquid separation of the separated liquid to obtain a finely divided polyarylene sulfide-containing solid; (C) a heating step of heating the fine polyarylene sulfide-containing solid to reduce the amount of organic solvent to obtain a wet cake; (D) a washing step of washing the wet cake with an aqueous solvent; Including Specific surface area retention ratio A2 / specific surface area A2 of the finely divided polyarylene sulfide contained in the wet cake after the heating step relative to the specific surface area A1 of the finely divided polyarylene sulf
- the method for producing finely divided polyarylene sulfide according to the present invention includes the following steps: (A) a separation step of separating the granular polyarylene sulfide and the separated liquid from the dispersion containing the granular polyarylene sulfide by solid-liquid separation using at least one screen having an opening diameter of 75 to 180 ⁇ m; (B) a solid-liquid separation step for solid-liquid separation of the separated liquid to obtain a finely divided polyarylene sulfide-containing solid; (C) a heating step of heating the fine polyarylene sulfide-containing solid to reduce the amount of organic solvent to obtain a wet cake; (D) a washing step of washing the wet cake with an aqueous solvent; Including The heating temperature in the heating step is 85 ° C. or lower on average.
- the production method for producing the fine powder PAS according to the present invention is a production method that necessarily includes the separation step (a), the solid-liquid separation step (b), and the liquid removal step (c), and other steps.
- a step of concentrating or diluting the reaction solution or the separation solution, a washing step, a drying step or the like may be additionally used, or the steps (a) to (c) described above, particularly (b) One or both of the steps (e) and (e) may be additionally used.
- the dispersion containing the granular PAS is not particularly limited, and may be any dispersion as long as it contains the granular PAS.
- the organic amide solvent from the group consisting of alkali metal sulfide and alkali metal hydrosulfide Examples thereof include a reaction liquid containing granular PAS produced in a polymerization process in which at least one selected sulfur source and a dihaloaromatic compound are subjected to a polymerization reaction.
- Sulfur source At least one sulfur source selected from the group consisting of alkali metal sulfides and alkali metal hydrosulfides is used as the sulfur source.
- alkali metal sulfide include lithium sulfide, sodium sulfide, potassium sulfide, rubidium sulfide, cesium sulfide, and a mixture of two or more thereof.
- alkali metal hydrosulfide include lithium hydrosulfide, sodium hydrosulfide, potassium hydrosulfide, rubidium hydrosulfide, cesium hydrosulfide, and a mixture of two or more thereof.
- the alkali metal sulfide any of an anhydride, a hydrate, and an aqueous solution may be used. Among these, sodium sulfide and lithium sulfide are preferable because they can be obtained industrially at low cost.
- the alkali metal sulfide is preferably used as an aqueous mixture such as an aqueous solution (that is, a mixture with fluid water) from the viewpoint of processing operation, measurement, and the like.
- the alkali metal hydrosulfide may be any of anhydride, hydrate, and aqueous solution. Among these, sodium hydrosulfide and lithium hydrosulfide are preferable because they can be obtained industrially at low cost.
- the alkali metal hydrosulfide is preferably used as an aqueous solution or an aqueous mixture (that is, a mixture with fluid water) from the viewpoint of processing operation, measurement, and the like.
- the alkali metal sulfide a small amount of alkali metal hydrosulfide may be contained.
- the total molar amount of the alkali metal sulfide and the alkali metal hydrosulfide becomes a sulfur source to be used for the polymerization reaction in the polymerization step after the dehydration step to be arranged as necessary, that is, the “charged sulfur source”.
- alkali metal hydrosulfide a small amount of alkali metal sulfide may be contained. In this case, the total molar amount of the alkali metal hydrosulfide and the alkali metal sulfide becomes the charged sulfur source.
- the alkali metal sulfide and the alkali metal hydrosulfide are mixed and used, naturally, a mixture of both becomes a charged sulfur source.
- an alkali metal hydroxide is used in combination.
- the alkali metal hydroxide include lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide, and a mixture of two or more thereof.
- sodium hydroxide and lithium hydroxide are preferable because they can be obtained industrially at low cost.
- the alkali metal hydroxide is preferably used as an aqueous solution or an aqueous mixture.
- the water to be dehydrated in the dehydration step is hydrated water, an aqueous medium of an aqueous solution, water produced as a by-product due to a reaction between an alkali metal hydrosulfide and an alkali metal hydroxide, or the like.
- a dihaloaromatic compound is a dihalogenated aromatic compound having two halogen atoms directly bonded to an aromatic ring.
- a halogen atom refers to each atom of fluorine, chlorine, bromine, and iodine. In the same dihaloaromatic compound, two halogen atoms may be the same or different. These dihaloaromatic compounds can be used alone or in combination of two or more.
- dihaloaromatic compound examples include, for example, o-dihalobenzene, m-dihalobenzene, p-dihalobenzene, dihalotoluene, dihalonaphthalene, methoxy-dihalobenzene, dihalobiphenyl, dihalobenzoic acid, dihalodiphenyl ether, dihalodiphenyl sulfone. , Dihalodiphenyl sulfoxide, dihalodiphenyl ketone and the like.
- p-dihalobenzene p-dihalobenzene, m-dihalobenzene, and a mixture of both are preferable, p-dihalobenzene is more preferable, and p-dichlorobenzene (pDCB) is particularly preferably used.
- pDCB p-dichlorobenzene
- Branching / crosslinking agent In order to introduce a branched or crosslinked structure into the produced PAS, a polyhalo compound (not necessarily an aromatic compound) having 3 or more halogen atoms bonded thereto, an active hydrogen-containing halogenated aromatic compound, halogen Aromatic nitro compounds can be used in combination.
- the polyhalo compound as the branching / crosslinking agent is preferably trihalobenzene.
- a monohalo compound can be used in combination in order to form a terminal with a specific structure in the produced PAS resin, or to adjust a polymerization reaction or a molecular weight.
- the monohalo compound not only a monohaloaromatic compound but also a monohaloaliphatic compound can be used.
- the branching / crosslinking agent is used in the range of 0.0001 to 0.01 mol, preferably 0.0002 to 0.008 mol, more preferably 0.0003 to 0.005 mol per mol of the charged sulfur source.
- Organic amide solvent An organic amide solvent which is an aprotic polar organic solvent is used as a solvent for the dehydration reaction and polymerization reaction.
- the organic amide solvent is preferably stable to alkali at high temperatures.
- Specific examples of the organic amide solvent include amide compounds such as N, N-dimethylformamide and N, N-dimethylacetamide; N-alkylcaprolactam compounds such as N-methyl- ⁇ -caprolactam; N-methyl-2-pyrrolidone, N-alkylpyrrolidone compounds or N-cycloalkylpyrrolidone compounds such as N-cyclohexyl-2-pyrrolidone; N, N-dialkylimidazolidinone compounds such as 1,3-dialkyl-2-imidazolidinone; tetramethylurea, etc. Tetraalkylurea compounds; hexaalkylphosphoric acid triamide compounds such as hexamethylphosphoric acid triamide. These organic amide solvents may
- N-alkylpyrrolidone compounds N-cycloalkylpyrrolidone compounds, N-alkylcaprolactam compounds, and N, N-dialkylimidazolidinone compounds are preferable, and in particular, N-methyl-2-pyrrolidone ( NMP), N-methyl- ⁇ -caprolactam, and 1,3-dialkyl-2-imidazolidinone are preferably used, and NMP is particularly preferred.
- NMP N-methyl-2-pyrrolidone
- NMP N-methyl- ⁇ -caprolactam
- 1,3-dialkyl-2-imidazolidinone 1,3-dialkyl-2-imidazolidinone
- polymerization aids Various polymerization aids can be used as necessary to promote the polymerization reaction.
- Specific examples of polymerization aids include water, organic carboxylic acid metal salts, organic sulfonic acid metal salts, alkali metal halides such as lithium halides, alkaline earth metal halides, and aromatic carboxylic acids that are generally known as polymerization aids for PAS. Examples include alkaline earth metal salts of acids, alkali metal phosphates, alcohols, paraffinic hydrocarbons, and mixtures of two or more thereof.
- the organic carboxylic acid metal salt an alkali metal carboxylate is preferable.
- alkali metal carboxylate examples include lithium acetate, sodium acetate, potassium acetate, sodium propionate, lithium valerate, lithium benzoate, sodium benzoate, sodium phenylacetate, potassium p-toluate, and two types thereof. The mixture of the above can be mentioned.
- sodium acetate is particularly preferable because it is inexpensive and easily available.
- the amount of the polymerization aid used varies depending on the type of the compound, but is usually 0.01 to 10 mol, preferably 0.1 to 2 mol, more preferably 0.2 to 1.8 mol per mol of the charged sulfur source. Mol, particularly preferably in the range of 0.3 to 1.7 mol.
- the polymerization assistant is an organic carboxylic acid metal salt, an organic sulfonate, and an alkali metal halide
- the upper limit of the amount used is preferably 1 mol or less, more preferably 1 mol with respect to 1 mol of the charged sulfur source. It is desirable that it is 0.8 mol or less.
- Phase Separation Agent Various phase separation agents are used in order to accelerate the polymerization reaction and obtain a high degree of polymerization PAS in a short time, or to cause phase separation and obtain granular PAS.
- a phase separation agent is a compound that dissolves in an organic amide solvent by itself or in the presence of a small amount of water and has an action of reducing the solubility of PAS in an organic amide solvent.
- the phase separation agent itself is a compound that is not a solvent for PAS.
- phase separation agent a compound known to function as a phase separation agent in the technical field of PAS can be used.
- the phase separation agent includes the compound used as the above-mentioned polymerization aid.
- the phase separation agent is a step of performing a polymerization reaction in a phase separation state, that is, as a phase separation agent in the phase separation polymerization step. It means a compound used in an amount ratio that can function, or in an amount ratio sufficient to cause phase separation in the presence of the polymer after the end of polymerization.
- phase separation agents include water, organic carboxylic acid metal salts, organic sulfonic acid metal salts, alkali metal halides such as lithium halides, alkaline earth metal halides, alkaline earth metal salts of aromatic carboxylic acids, phosphorus Examples include acid alkali metal salts, alcohols, and paraffinic hydrocarbons.
- organic carboxylic acid metal salts include alkali metal carboxylic acids such as lithium acetate, sodium acetate, potassium acetate, sodium propionate, lithium valerate, lithium benzoate, sodium benzoate, sodium phenylacetate, and potassium p-toluate. Salts are preferred.
- phase separation agents can be used alone or in combination of two or more. Among these phase separation agents, water that is inexpensive and easy to post-process, or a combination of water and an organic carboxylic acid metal salt such as an alkali metal carboxylate is particularly preferable.
- phase separation agent other than water can be used in combination as a polymerization aid from the viewpoint of efficiently performing the phase separation polymerization.
- the total amount may be an amount that can cause phase separation.
- the phase separation agent may coexist at least partially from the time when the polymerization reaction component is charged, but the phase separation agent may be added during the polymerization reaction or to form phase separation after the polymerization reaction. It is desirable to adjust to a sufficient amount.
- Polymerization Step PAS is produced by subjecting at least one sulfur source selected from the group consisting of an alkali metal sulfide and an alkali metal hydrosulfide to a polymerization reaction with a dihaloaromatic compound in an organic amide solvent to produce a granular PAS. Is done.
- the polymerization method for producing granular PAS may be any polymerization method as long as the present invention is not impaired.
- polymerization methods for producing granular PAS are broadly classified as follows: (i) the polymerization step includes a phase separation polymerization step, and after the phase separation polymerization, the method is gradually cooled; (ii) the phase separation agent is added after the polymerization reaction And (iii) a method using a polymerization aid such as lithium chloride, and (iv) a method of cooling the gas phase portion of the reaction vessel.
- phase-separation polymerization a polymerization reaction step
- phase-separation polymerization a polymerization reaction step
- a phase separation state in which a polymer-rich phase and a polymer-rich phase are mixed in the polymerization reaction system in the presence of a phase separation agent by controlling polymerization conditions.
- the granular PAS is produced by a polymerization method including a “step” in some cases, a granular PAS having a high degree of polymerization can be obtained, so that the opening diameter of the screen of the sieve can be reduced. Therefore, it is an advantageous polymerization method for increasing the recovery rate of granular PAS of products having a high degree of polymerization.
- the polymerization step in this case is performed by polymerizing at least one sulfur source selected from the group consisting of alkali metal sulfides and alkali metal hydrosulfides with a dihaloaromatic compound in an organic amide solvent to form granular PAS.
- This is a polymerization step including a polymerization reaction in a phase-separated state where a product polymer rich phase and a product polymer dilute phase coexist.
- the polymerization process in this case will be described in detail.
- the polymerization step can be carried out through the following preparation steps.
- the charging step the mixture remaining in the system and the dihaloaromatic compound are mixed in a dehydration step that is arranged as desired, and an alkali metal hydroxide and water are added as necessary to prepare an organic amide solvent, a sulfur source ( A charged mixture containing a charged sulfur source), an alkali metal hydroxide, moisture, and a dihaloaromatic compound is prepared.
- a sulfur source A charged mixture containing a charged sulfur source
- an alkali metal hydroxide moisture
- a dihaloaromatic compound is prepared.
- an organic amide solvent may be added in the preparation step.
- a sulfur source may be added in the charging step.
- adjustment of each component amount in the preparation step needs to be performed in consideration of the amount of each component in the mixture obtained in the dehydration step. .
- the amount of the dihaloaromatic compound used is usually 0.90 to 1.50 mol, preferably 0.92 to 1.10 mol, more preferably 0.95 to 1.05 mol with respect to 1 mol of the charged sulfur source. is there. If the charged molar ratio of the dihaloaromatic compound to the sulfur source becomes too large, it becomes difficult to produce a high molecular weight polymer. On the other hand, if the charged molar ratio of the dihaloaromatic compound to the sulfur source becomes too small, a decomposition reaction tends to occur, and it becomes difficult to carry out a stable polymerization reaction.
- alkali metal hydrosulfide when used as a sulfur source, when hydrogen sulfide is volatilized in the dehydration step, an alkali metal hydroxide is generated by an equilibrium reaction and remains in the system. Therefore, it is necessary to accurately grasp the volatilization amount and determine the molar ratio of the alkali metal hydroxide to the sulfur source in the preparation process.
- the total number of moles of alkali metal hydroxide produced during dehydration, the number of moles of alkali metal hydroxide added before dehydration, and the number of moles of alkali metal hydroxide added after dehydration is determined after the dehydration step.
- the sulfur source in the preparation process is referred to as “prepared sulfur source”.
- prepared sulfur source the sulfur source in the preparation process.
- the reason is that the amount of the sulfur source put into the reaction tank before the dehydration step varies in the dehydration step.
- the charged sulfur source is consumed by the reaction with the dihaloaromatic compound in the polymerization step, but the molar amount of the charged sulfur source is based on the molar amount in the charged step.
- the organic amide solvent is likely to be altered, and abnormal reactions and decomposition reactions during polymerization are likely to occur. In addition, the yield and quality of the produced PAS are often lowered. It is preferable to carry out the polymerization reaction with a small excess of alkali metal hydroxide in order to stably carry out the polymerization reaction and obtain a high-quality PAS.
- the amount of the organic amide solvent is usually 0.1 to 10 kg, preferably 0.13 to 5 kg, more preferably 0.15 to 2 kg per mol of the charged sulfur source.
- Polymerization step In the polymerization step, the charge mixture prepared in the charge step is heated to a temperature of usually 170 to 290 ° C, preferably 180 to 280 ° C, more preferably 190 to 275 ° C to start a polymerization reaction, Allow polymerization to proceed.
- a heating method a method of maintaining a constant temperature, a stepwise or continuous temperature raising method, or a combination of both methods is used.
- the polymerization reaction time is generally in the range of 10 minutes to 72 hours, preferably 30 minutes to 48 hours.
- the polymerization reaction is preferably performed in a two-stage process including a pre-stage polymerization process and a post-stage polymerization process. In this case, the polymerization time is the total time of the pre-stage polymerization process and the post-stage polymerization process.
- the polymerization process includes a polymerization step in which a polymerization reaction is performed in a phase-separated state in which a produced polymer rich phase and a produced polymer dilute phase coexist.
- a phase separation agent water described above, a compound known to function as a phase separation agent, or the like is preferably used.
- At least one sulfur source selected from the group consisting of alkali metal sulfides and alkali metal hydrosulfides and a dihaloaromatic compound are polymerized in an organic amide solvent at a temperature of 170 to 270 ° C.
- a phase separation agent is added to the polymerization reaction mixture so that the phase separation agent is present in the polymerization reaction system, and then the polymerization reaction is performed.
- the temperature of the mixture is increased, and the polymerization reaction can be continued at a temperature of 245 to 290 ° C. in a phase separation state in which the produced polymer rich phase and the produced polymer dilute phase are mixed in the polymerization reaction system in the presence of the phase separation agent. ,preferable.
- At least one sulfur source selected from the group consisting of alkali metal sulfides and alkali metal hydrosulfides is polymerized with a dihaloaromatic compound, and the dihaloaromatic compound is reacted.
- a pre-polymerization step for producing a polymer having a compound conversion rate of 30% or more, preferably 80 to 99%; and in the presence of a phase separation agent, a mixed polymer phase and a diluted polymer phase are mixed in the polymerization reaction system. It is preferable to carry out the polymerization reaction by at least two stages of polymerization processes including a subsequent polymerization process in which the polymerization reaction is continued in a phase separated state.
- At least one sulfur source selected from the group consisting of alkali metal sulfides and alkali metal hydrosulfides and a dihaloaromatic compound are added per mole of the charged sulfur source.
- a pre-stage polymerization step in which a polymerization reaction is carried out at a temperature of 170 to 270 ° C.
- polymerization is performed by heating to a temperature of 245 to 290 ° C.
- a post-stage polymerization step including a post-polymerization step in which the polymerization reaction is continued in a phase-separated state where the produced polymer rich phase and the produced polymer dilute phase coexist in the reaction system. It is more preferable to perform the focus reaction.
- the pre-stage polymerization process is a stage where the conversion rate of the dihaloaromatic compound reaches 80 to 99%, preferably 85 to 98%, more preferably 90 to 97% after the start of the polymerization reaction.
- the polymerization temperature is too high, side reactions and decomposition reactions tend to occur.
- the conversion rate of the dihaloaromatic compound is a value calculated by the following formula.
- DHA dihaloaromatic compound
- Conversion [[DHA charge (mol) ⁇ DHA remaining amount ( Mol)] / [DHA charge (mol) -DHA excess (mol)]] ⁇ 100 To calculate the conversion.
- Conversion [[DHA charge (mol) ⁇ DHA remaining amount (mol)] / [DHA charge (mol)]] ⁇ 100 To calculate the conversion.
- Conversion [[DHA charge (mol) ⁇ DHA remaining amount (mol)] / [DHA charge (mol)]] ⁇ 100 To calculate the conversion.
- the amount of coexisting water in the reaction system in the pre-stage polymerization step is usually 0.01 to 2.0 mol, preferably 0.05 to 1.8 mol, more preferably 0.5 to 1.6 mol, per mol of the charged sulfur source. Particularly preferred is the range of 0.8 to 1.5 mol.
- the amount of coexisting water in the pre-stage polymerization step may be small, but if it is too small, an undesirable reaction such as decomposition of the produced PAS may easily occur. If the amount of coexisting water exceeds 2.0 mol, the polymerization rate is remarkably reduced, and the organic amide solvent and the produced PAS are likely to be decomposed.
- the polymerization is carried out within a temperature range of 170 to 270 ° C., preferably 180 to 265 ° C. If the polymerization temperature is too low, the polymerization rate becomes too slow. Conversely, if the polymerization temperature is higher than 270 ° C., the produced PAS and the organic amide solvent are liable to decompose, and the degree of polymerization of the produced PAS becomes extremely low.
- prepolymer In the former polymerization step, it is desirable to produce a polymer (sometimes referred to as “prepolymer”) having a melt viscosity of usually 0.5 to 30 Pa ⁇ s measured at a temperature of 310 ° C. and a shear rate of 1,216 sec ⁇ 1 . .
- the post-polymerization step is not a simple fractionation / granulation step of the polymer (prepolymer) produced in the pre-polymerization step, but is for causing an increase in the degree of polymerization of the polymer.
- phase separation agent polymerization aid
- the subsequent polymerization step it is particularly preferable to use water as the phase separation agent, and more than 2.0 mol, more preferably less than 10 mol, more preferably more than 2.0 mol, more than 9 mol relative to 1 mol of the charged sulfur source It is preferable to adjust the amount of water in the polymerization reaction system so that 2.1 to 8 mol, particularly preferably 2.2 to 7 mol of water is present.
- the degree of polymerization of the produced PAS may decrease.
- water and another phase separation agent other than water can be used in combination.
- the amount of water in the polymerization reaction system is 0.1 to 10 mol, preferably 0.3 to 10 mol, more preferably 0.4 to 9 mol, particularly preferably 0. It is preferable to adjust the amount within the range of 5 to 8 mol, and to make the phase separation agent other than water exist within the range of 0.01 to 3 mol per mol of the charged sulfur source.
- phase separation agents that are particularly preferred to be used in combination with organic carboxylic acid metal salts, especially alkali metal carboxylates, in which case water is added in an amount of 0.5 to 1 mol per mol of the charged sulfur source. It is used within a range of 10 mol, preferably 0.6 to 7 mol, particularly preferably 0.8 to 5 mol, and alkali metal carboxylate is used in an amount of 0.001 to 0.7 mol, preferably 0.02 to It may be used within a range of 0.6 mol, particularly preferably 0.05 to 0.5 mol.
- the polymerization temperature in the subsequent polymerization step is in the range of 245 to 290 ° C. If the polymerization temperature is less than 245 ° C., it is difficult to obtain a granular PAS with a high degree of polymerization, and if it exceeds 290 ° C., the granular PAS and organic amide solvent There is a risk of disassembly. In particular, a temperature range of 250 to 270 ° C. is preferable because granular PAS having a high degree of polymerization can be easily obtained.
- water may be added late in the polymerization reaction or at the end to increase the water content. It can.
- the polymerization reaction system may be a batch system, a continuous system, or a combination of both systems. In the batch polymerization, for the purpose of shortening the polymerization cycle time, a system using two or more reaction vessels can be used as desired.
- a dehydration step may be arranged as desired before the preparation step in carrying out the polymerization step.
- the dehydration step is preferably carried out by a method of heating and reacting a mixture containing an organic amide solvent and an alkali metal sulfide in an inert gas atmosphere and discharging water out of the system by distillation.
- an alkali metal hydrosulfide is used as the sulfur source
- the reaction is carried out by heating and reacting a mixture containing the alkali metal hydrosulfide and the alkali metal hydroxide, and discharging water out of the system by distillation.
- the dehydration step water consisting of hydrated water (crystal water), an aqueous medium, by-product water and the like is dehydrated until it falls within the required amount.
- water and the organic amide solvent are distilled as a vapor by heating. Therefore, the distillate contains water and an organic amide solvent.
- a part of the distillate may be circulated in the system in order to suppress the discharge of the organic amide solvent out of the system.
- at least one of the distillates containing water is used. The part is discharged out of the system.
- a small amount of organic amide solvent is discharged out of the system together with water.
- hydrogen sulfide is volatilized due to the sulfur source. As at least part of the distillate containing water is discharged out of the system, the volatilized hydrogen sulfide is also discharged out of the system.
- the amount of coexisting water in the polymerization reaction system is usually 0.01 to 2.0 mol, preferably 0.05 to 1.8 mol, more preferably 0.5 to 0.1 mol with respect to 1 mol of the charged sulfur source. Dehydrate to 1.6 moles.
- the sulfur source after the dehydration step and before the start of the polymerization step is referred to as “prepared sulfur source”.
- water may be added to the desired amount of water before the polymerization step.
- an alkali metal hydrosulfide When an alkali metal hydrosulfide is used as the sulfur source, 0.9 to 1.1 mol, preferably 0.91 per mol of the organic amide solvent, the alkali metal hydrosulfide, and the alkali metal hydrosulfide in the dehydration step.
- the mixture containing ⁇ 1.08 mol, more preferably 0.92 to 1.07 mol, particularly preferably 0.93 to 1.06 mol of alkali metal hydroxide is heated to react, and the mixture is reacted. It is preferable that at least a part of the distillate containing water is discharged out of the system.
- the alkali metal hydrosulfide contains a small amount of alkali metal sulfide, and the amount of the sulfur source is the total amount of the alkali metal hydrosulfide and the alkali metal sulfide. Further, even if a small amount of alkali metal sulfide is mixed, in the present invention, the molar ratio with the alkali metal hydroxide is calculated based on the content (analytical value) of the alkali metal hydrosulfide. Adjust the ratio.
- each raw material is generally charged into the reaction vessel in a temperature range from room temperature (5-35 ° C.) to 300 ° C., preferably from room temperature to 200 ° C.
- the order in which the raw materials are charged can be arbitrarily set, and further, the respective raw materials may be additionally charged during the dehydration operation.
- An organic amide solvent is used as a solvent used in the dehydration step. This solvent is preferably the same as the organic amide solvent used in the polymerization step, and NMP is particularly preferred.
- the amount of the organic amide solvent used is usually about 0.1 to 10 kg per mole of sulfur source charged into the reaction tank.
- the mixture after the raw materials are charged into the reaction vessel is usually heated at a temperature of 300 ° C. or lower, preferably 100 to 250 ° C., usually for 15 minutes to 24 hours, preferably 30 minutes to 10 hours. Done.
- a heating method there are a method for maintaining a constant temperature, a stepwise or continuous temperature raising method, or a method in which both are combined.
- the dehydration step is performed by a batch method, a continuous method, or a combination method of both methods.
- the apparatus for performing the dehydration step may be the same as or different from the reaction vessel (reaction can) used in the subsequent polymerization step.
- the material of the device is preferably a corrosion resistant material such as titanium.
- a method of adjusting to an amount sufficient to form phase separation after the completion of polymerization and slowly cooling is preferred.
- the separation step the granular PAS and the separation liquid are separated from the dispersion containing the granular PAS by solid-liquid separation using at least one screen having an opening diameter of 75 to 180 ⁇ m.
- the finely divided PAS of the present invention is obtained from a separated liquid obtained by solid-liquid separation in the above-described production method for producing finely divided PAS, while granular PAS is produced and recovered from the solid content after solid-liquid separation.
- recovered as a product is illustrated.
- the separation and recovery process of granular PAS can be performed, for example, by a separation process using sieving.
- the reaction liquid containing the granular PAS produced in the polymerization step is used as the dispersion containing the granular PAS
- the product slurry that is the reaction liquid containing the produced granular PAS after the polymerization reaction is used as the separation step.
- the product slurry is diluted with water or the like as necessary, and then sieved to separate and recover the granular PAS from the reaction solution.
- the opening diameter of the screen used for separation by sieving in the separation step is usually 75 ⁇ m (200 mesh) to 180 ⁇ m (80 mesh), preferably 90 ⁇ m (170 mesh) to 150 ⁇ m (100 mesh). It is. At least one screen in this range is used, but it may be used in multiple stages. Usually, a screen having an opening diameter of 150 ⁇ m (100 mesh) is often used.
- the recovery rate of the granular PAS recovered as a product is the PAS mass (theoretical amount) when it is assumed that all of the effective sulfur components in the charged sulfur source present in the reaction vessel after the dehydration step have been converted to PAS. Calculated as the total amount of PAS obtained.
- This recovery rate depends on the sieve opening of the screen, but in the case of at least one screen having an opening of 75 ⁇ m (200 mesh) to 180 ⁇ m (80 mesh), it is usually 80% by mass or more. Is 83% by mass or more, and in some cases, 85% by mass or more. The upper limit of the recovery rate is about 99.5% by mass.
- the average particle diameter of the obtained granular PAS depends on the mesh opening diameter of the screen, but in the case of at least one screen having an opening diameter of 75 ⁇ m (200 mesh) to 180 ⁇ m (80 mesh), Usually, it is 130 to 1,500 ⁇ m, preferably 150 to 1,500 ⁇ m, and more preferably 180 to 1,500 ⁇ m.
- the weight average molecular weight of the obtained granular PAS depends on the screen diameter of the sieve screen, but in the case of at least one screen having an opening diameter of 75 ⁇ m (200 mesh) to 180 ⁇ m (80 mesh), the granular PAS
- the weight average molecular weight is usually 30,000 or more, preferably 33,000 or more, more preferably 35,000 or more.
- the upper limit of the weight average molecular weight is about 90,000.
- the peak top molecular weight of the obtained granular PAS depends on the aperture diameter of the sieve screen, but in the case of at least one screen having an aperture diameter of 75 ⁇ m (200 mesh) to 180 ⁇ m (80 mesh), It is 35,000 or more, preferably 38,000 or more, more preferably 40,000 or more.
- the upper limit of the peak top molecular weight is about 100,000.
- the melt viscosity of the obtained granular PAS depends on the screen diameter of the sieve screen, but in the case of at least one screen having a mesh diameter of 75 ⁇ m (200 mesh) to 180 ⁇ m (80 mesh),
- the melt viscosity is usually 5 Pa ⁇ s or higher, preferably 10 Pa ⁇ s or higher, more preferably 15 Pa ⁇ s or higher.
- the upper limit of the melt viscosity is about 500 Pa ⁇ s.
- As the melt viscosity a 1 mm ⁇ ⁇ 10 mmL flat die was used as the capillary, and the set temperature was 310 ° C. A polymer sample is introduced into the apparatus and held for 5 minutes before measuring the melt viscosity at a shear rate of 1,216 sec ⁇ 1 .
- the separation liquid separated from the granular PAS produced in the above separation step includes raw material fine powder PAS, by-product alkali metal salts (such as NaCl), oligomers, volatile substances, high-boiling substances, etc. Containing impurities, organic amide solvents, phase separation agents (such as water), and the like.
- the fine powder PAS of the present invention is separated from the dispersion containing the granular PAS into the granular PAS and the separated liquid by solid-liquid separation using at least one screen having a mesh size of 75 to 180 ⁇ m. It is a fine powder PAS produced from the resulting separation liquid.
- the fine powder PAS of the present invention is subjected to a solid-liquid separation step for solid-liquid separation of the separated liquid to obtain a fine powder PAS-containing solid, and then the organic powder is heated to heat the fine powder PAS-containing solid. It is a fine powder PAS obtained by performing a heating process to obtain a wet cake, and then performing a washing process of washing the wet cake with an aqueous solvent, which is useful as a product.
- a solid-liquid separation step is immediately performed from the separated solution, or a preliminary solid-liquid separation step described later is performed on the separated solution.
- a solid-liquid separation process is performed later is included.
- a solid-liquid separation process, a heating process, and a washing process are performed in the following processes.
- the solid-liquid separation step is a step of solid-liquid separation of the separated liquid to obtain a fine powder PAS-containing solid.
- the solid-liquid separation is performed by filtration, centrifugation, sieving, sedimentation, or the like.
- filtration often uses a filtration device using a normal filter cloth for fine powder.
- a suction filtration device is advantageous in view of the processing time and the like.
- the solid-liquid separation step can be either a continuous type or a batch type. As a continuous type, there is a horizontal belt type filter. In the case of the batch type, when the raw material fine powder PAS concentration is low, it is preferable that the filtration apparatus is performed by a filter press in view of the processing amount.
- the weight average molecular weight of the raw material fine powder PAS in the obtained fine powder PAS-containing solid is at least 1 in the range of the opening diameter of 75 ⁇ m (200 mesh) to 180 ⁇ m (80 mesh), although it depends on the opening diameter of the screen of the sieve. In the case of one screen, it is preferably 15,000 or more, more preferably 18,000 or more, and even more preferably 20,000 or more. The upper limit of the weight average molecular weight is about 75,000.
- the peak top molecular weight of the raw fine powder PAS in the obtained fine powder PAS-containing solid depends on the opening diameter of the screen of the sieve, but the opening diameter is in the range of 75 ⁇ m (200 mesh) to 180 ⁇ m (80 mesh). In the case of at least one screen, it is preferably 30,000 or more, more preferably 33,000 or more, and even more preferably 35,000 or more. The upper limit of the peak top molecular weight is about 85,000.
- the average particle size of the raw material fine powder PAS in the obtained fine powder PAS-containing solid is a value measured by a laser diffraction particle size distribution measuring device, preferably 1 to 80 ⁇ m, more preferably 2 to 80 ⁇ m, and still more preferably. 3 to 80 ⁇ m.
- the melt viscosity of the raw fine powder PAS in the obtained fine powder PAS-containing solid is preferably 0.2 Pa ⁇ s or more, more preferably 0.6 Pa ⁇ s or more, and even more preferably 1.0 Pa ⁇ s or more.
- the upper limit of the melt viscosity is about 50 Pa ⁇ s.
- the method for measuring the melt viscosity is as described above.
- (Ii) Heating step In the heating step, the fine powder PAS-containing solid is heated to reduce the amount of organic solvent to obtain a wet cake.
- the concentration of the organic solvent contained in the waste liquid after the washing step can be effectively reduced.
- the origin of the organic solvent is not particularly limited.
- the organic solvent was included in an organic solvent added in an organic solvent washing step (described later) performed before the solid-liquid separation step or a dispersion containing granular PAS. An organic solvent etc. are mentioned.
- the heat treatment can be either a continuous type or a batch type.
- the heat treatment can be performed using a drier such as a normal tank drier, a tank rotation drier, an airflow drier, or a fluidized bed drier.
- the fine powder PAS-containing solid may be in a stationary state, but when a large amount of fine powder PAS-containing solid is uniformly heated, it is desirable to cause the fine powder PAS-containing solid to flow by some method. Examples of the method of heating the finely powdered PAS-containing solid while flowing include a method of using a dryer equipped with a fluidized bed, a stirring blade, a paddle, or a stirring screw.
- the heat treatment can be performed in air, a low oxygen concentration atmosphere, or an inert gas atmosphere such as nitrogen gas, carbon dioxide gas, or water vapor. Moreover, it can carry out in any state of normal pressure, pressure reduction, and pressurization.
- the average heating temperature is preferably 85 ° C. or lower, more preferably 80 ° C. to 25 ° C., and even more preferably 75 ° C. to 30 ° C.
- the heating temperature is an average temperature in the heating process.
- the heating temperature is 85 ° C. or less, the finely powdered PAS-containing solid does not dry too much, and is included in the wet cake after the heating step with respect to the specific surface area of the finely powdered PAS-containing solid before the heating step. Since the specific surface area retention ratio of the specific surface area of the fine powder PAS is less likely to be low, the wettability of the fine powder PAS is difficult to decrease. Moreover, the amount of organic solvents can be effectively reduced as heating temperature is more than the said minimum. In 4th embodiment of this invention, the heating temperature in a heating process is 85 degrees C or less.
- the heating time is preferably 0.3 to 10 hours, more preferably 0.5 to 6 hours, and even more preferably 1.0 to 4 hours.
- the degree of reduced pressure is in the range of 70 to 101 KPa.
- the moisture content of the wet cake after the heating step is preferably 30% by mass or more, more preferably 33 to 50% by mass, and even more preferably 35 to 45% by mass. If the moisture content of the wet cake after the heating step is 30% by mass or more, the wettability of the fine powder PAS is easily secured. Further, when the moisture content of the wet cake after the heating step is not more than the above upper limit, the handleability of the wet cake is likely to be improved.
- the method for keeping the moisture content of the wet cake after the heating step in the above range is not particularly limited. For example, a method of providing a water addition step (described later) for adding water to the separation liquid after the separation step and before the heating step. Is mentioned. Water is preferably added in the form of a water-containing organic solvent (described later). In 1st embodiment of this invention, the moisture content of the wet cake after a heating process is 30 mass% or more.
- the specific surface area retention ratio A2 / A1 of the specific surface area A2 of the fine powder PAS contained in the wet cake after the heating step with respect to the specific surface area A1 of the fine powder PAS contained in the solid material containing the fine powder PAS before the heating step is preferably 0.2. Or more (that is, 20% or more), more preferably 0.25 or more (that is, 25% or more), and even more preferably 0.3 or more (that is, 30% or more). If the specific surface area retention rate is 20% or more, the interior of the fine powder PAS contained in the wet cake after the heating step has a sufficient space communicating with the outside, and the aqueous solvent easily penetrates into the washing step.
- the upper limit of the specific surface area retention is 1 (that is, 100%).
- the method for maintaining the specific surface area retention within the above range is not particularly limited, and examples thereof include a method in which the heating temperature in the heating step is set lower than the glass transition point (Tg) of PAS.
- Tg glass transition point
- the specific surface area is measured by the BET method by nitrogen adsorption.
- the specific surface area retention A2 / A1 is 20% or more.
- Water addition step may be performed after the separation step and before the heating step.
- the water addition step is a step of adding water to the separation liquid.
- the organic solvent in the water-containing organic solvent include an organic solvent having a lower boiling point than water, preferably an organic solvent that dissolves an organic amide solvent in addition to a lower boiling point than water, and more preferably a ketone.
- a solvent, and even more preferably acetone The water content in the water-containing organic solvent is not particularly limited, and examples thereof include 20 to 70% by mass, preferably 25 to 50% by mass.
- the concentration of the organic solvent does not become too low, for example, it is easy to ensure the washing effect by the organic solvent, the removal effect of the organic amide solvent, etc., and even after the heating step, The wettability of fine powder PAS is difficult to decrease.
- the water addition step is performed after the separation step and before the heating step.
- washing step In the washing step, the wet cake is washed with an aqueous solvent.
- the purpose of this washing step is to reduce the alkali metal concentration (for example, Na concentration) derived from the by-product alkali metal salt in the fine powder PAS and to reduce the PAS oligomer concentration in the fine powder PAS.
- aqueous solvent for example, water; an aqueous solution of an acid such as acetic acid or hydrochloric acid, or an aqueous solution of a salt such as acetate is preferable.
- water is used.
- filtration may be performed. The same number of filtrations is performed according to the number of washings.
- a drying step After the washing step, a drying step may be performed.
- the drying process is a process of drying the wet cake washed in the washing process.
- the drying process can be either a continuous process or a batch process.
- the drying treatment can be performed using a heat treatment apparatus such as a normal hot air heat treatment machine, a heating device with a stirring blade, a fluidized bed heat treatment machine, a tank rotary heat treatment machine or the like.
- the dryer for the heating process and the heat treatment apparatus for the drying process may be performed using the same apparatus.
- the drying treatment may be in a stationary state, but when a large amount of wet cake is uniformly dried, it is desirable to cause the wet cake to flow by some method.
- Examples of the method for drying the wet cake while flowing include a method using a heat treatment apparatus equipped with a fluidized bed, stirring blades, paddles, or a stirring screw.
- the drying treatment can be performed in air or a low oxygen concentration atmosphere, or in an inert gas atmosphere such as nitrogen gas, carbon dioxide gas, or water vapor. Moreover, it can carry out in any state of normal pressure, pressure reduction, and pressurization.
- the degree of vacuum is sufficient if it is in the range of 70 to 101 KPa.
- the drying treatment can be performed up to a temperature lower than the melting point of the fine powder PAS, but is preferably performed at 100 to 260 ° C, more preferably 120 to 250 ° C, and further preferably 140 to 240 ° C.
- the drying treatment time is usually 0.5 to 10 hours, preferably 1 to 8 hours, more preferably 2 to 5 hours. You may perform a drying process in a pressure-reduced state.
- the preliminary solid-liquid separation step is a step in which the separated liquid is solid-liquid separated into the raw material fine powder PAS and the filtrate by a preliminary solid-liquid separation means such as filtration.
- Organic solvent washing process In the organic solvent washing step, acetone or the like is added to the raw fine powder PAS, the organic amide solvent contained in the raw fine powder PAS is washed, and the washed raw fine powder PAS is obtained again by separation means such as filtration. It is.
- the by-product alkali metal salt removing step is a step of washing the raw fine powder PAS after the preliminary solid-liquid separation step with water to dissolve and remove the by-product alkali metal salt.
- the liquid containing the raw fine powder PAS that has undergone the preliminary solid-liquid separation step, organic solvent washing step, and by-product alkali metal salt removal step thus obtained is preferably 0.1 to 15% by mass of the raw fine powder PAS, more preferably The liquid is about 0.15 to 10% by mass, more preferably about 0.2 to 5% by mass.
- the separation by filtration in the solid-liquid separation step is performed by centrifugal filtration or filtration using a filter press to obtain the raw material fine powder PAS.
- the solid content is recovered in the form of a wet cake.
- Fine powder PAS after the washing step is used as a product. Usually, the entire amount is recovered and used, but further separation by sieving may be performed, and fine powder PPS having a certain particle diameter or more may be used. For example, when granular PAS is sieved with a screen having an opening diameter of 150 ⁇ m (100 mesh), fine powder PAS obtained from the separated liquid is separated by sieving with a screen having an opening diameter of 75 ⁇ m (200 mesh), etc. It is to be. However, when the fine powder PAS is separated by sieving, the productization rate is lowered.
- the fine powder PAS of the present invention is a fine powder PAS produced by the production method according to the present invention.
- the fine powder PAS of the present invention is The fine particle PAS has an average particle size of 1 to 200 ⁇ m, The fine powder PAS has a melt viscosity of 1 Pa ⁇ s or more.
- the fine powder PAS of the present invention in the sixth embodiment is manufactured by, for example, the manufacturing method according to the present invention.
- the fine powder PAS of the present invention is reduced in impurities such as alkali metal salts and PAS oligomers.
- the fine powder PAS of the present invention can be used as a resin composition (compound) by mixing with a granular PAS obtained from a sieved product in a sieving in the above-described separation step, which is a conventional product.
- the weight average molecular weight of the fine powder PAS of the present invention is preferably 30,000 or more, more preferably 33,000 or more, and even more preferably 35,000 or more.
- the upper limit of the weight average molecular weight is about 90,000.
- the peak top molecular weight of the fine powder PAS of the present invention is preferably 32,000 or more, more preferably 34,000 or more, and even more preferably 36,000 or more.
- the upper limit of the peak top molecular weight is about 100,000.
- the melt viscosity of the fine powder PAS of the present invention is preferably 50% to 150%, more preferably 55% to 130%, and even more preferably the melt viscosity of the granular PAS compared to the melt viscosity of the granular PAS obtained in the separation step. It is preferably 58% to 120%, particularly preferably 65% to 110%. The melt viscosity is measured as described above.
- the melt viscosity is usually 1 Pa ⁇ s or more, preferably 3 Pa ⁇ s or more, more preferably 5 Pa ⁇ s, particularly preferably 10 Pa ⁇ s or more.
- the upper limit of the melt viscosity is about 500 Pa ⁇ s.
- the average particle size of the fine powder PAS of the present invention is usually 1 to 200 ⁇ m, preferably 2 to 100 ⁇ m, more preferably 3 to 80 ⁇ m as measured by a laser diffraction particle size distribution measuring apparatus.
- the generated gas may be a sulfur-containing benzene compound, a halogen-containing benzene compound, a nitrogen-containing halogen compound, an organic substance, a sulfur-containing low-boiling substance, or the like.
- the alkali metal content of the fine powder PAS of the present invention is preferably 1500 ppm or less, more preferably 1000 ppm or less, and even more preferably 500 ppm or less.
- the lower limit is 0 ppm, but is practically about 10 ppm.
- Recovery rate of granular PAS (% by mass)
- the granular PAS recovery rate is calculated by calculating the PAS mass (theoretical amount) as the total amount of PAS, assuming that all of the available sulfur components in the charged sulfur source present in the reaction vessel after the dehydration step have been converted to PAS. . That is, the recovery rate of granular PAS was calculated by the mass of recovered granular PAS / PAS mass (theoretical amount).
- the average particle diameter of the recovered granular PAS is mesh # 7 (mesh diameter 2,800 ⁇ m), # 12 (mesh diameter 1,410 ⁇ m), # 16 (mesh) Aperture diameter 1,000 ⁇ m), # 24 (aperture diameter 710 ⁇ m), # 32 (aperture diameter 500 ⁇ m), # 60 (aperture diameter 250 ⁇ m), # 100 (aperture diameter 150 ⁇ m), # 145 (aperture diameter 105 ⁇ m) ), # 200 (aperture diameter 75 ⁇ m), and measured by a sieving method.
- Average particle diameter of fine powder PAS The average particle diameter of fine powder PAS was measured with a laser diffraction particle size distribution measuring device (SALD, manufactured by Shimadzu Corporation).
- Weight average molecular weight and peak top molecular weight The weight average molecular weight (Mw) of PAS was measured using a high temperature gel permeation chromatograph (GPC) SSC-7101 manufactured by Senshu Kagaku Co., Ltd. under the following conditions. The weight average molecular weight and peak top molecular weight were calculated as polystyrene equivalent values.
- Solvent 1-chloronaphthalene, Temperature: 210 ° C Detector: UV detector (360 nm), Sample injection volume: 200 ⁇ l (concentration: 0.1% by mass), Flow rate: 0.7 ml / min, Standard polystyrene: Five standard polystyrenes of 616,000, 113,000, 26,000, 8,200, and 600.
- melt Viscosity Using about 20 g of a dry product of PAS, the melt viscosity was measured by Capillograph 1-C manufactured by Toyo Seiki. At this time, the capillary used a flat die of 1 mm ⁇ ⁇ 10 mmL, and the set temperature was 310 ° C. The PAS sample was introduced into the apparatus and held for 5 minutes, and then the melt viscosity at a shear rate of 1,216 sec ⁇ 1 was measured.
- Moisture content The moisture content of the wet cake was calculated from the mass difference before and after drying by drying the wet cake at 60 ° C. for 3 hours under reduced pressure (90 KPa) (the mass difference / the mass of the wet cake ⁇ 100 ( %)).
- the ratio (g / mol) of NMP / prepared sulfur source (hereinafter abbreviated as “prepared S”) in the can is 375, pDCB / added S (mol / mol) is 1.050, H 2 O / prepared. S (mol / mol) was 1.50. The conversion rate of pDCB in the former polymerization was 92%.
- the granular PPS on the sieve was subjected to a usual recovery process such as washing and drying to obtain a granular PPS as a product with a recovery rate of 88% by mass.
- the average particle size was 360 ⁇ m
- the weight average molecular weight was 42,800
- the peak top molecular weight was 51,200.
- the melt viscosity was 35 Pa ⁇ s.
- Example 1 The following treatment was performed on the sieving liquid in the separation process using the sieving of Production Example 1.
- the separated liquid was filtered and subjected to preliminary solid-liquid separation into the raw material fine powder PPS and the filtrate (preliminary solid-liquid separation step).
- the raw material fine powder PPS was washed twice with water-containing acetone having a water content of 50% by mass and filtered again to separate the raw material fine powder PPS and the filtrate (organic solvent washing step).
- the raw material fine powder PPS was heated at 70 ° C. in a normal pressure state for 5 hours (water content after heating: 35 mass%) (heating step).
- the specific surface area of the raw material fine powder PPS before heating was 115 m 2 / g, and the specific surface area of the raw material fine powder PPS after heating was 89 m 2 / g.
- the specific surface area retention was 0.77 (ie 77%).
- washing was performed several times with distilled water (water washing step), and solid-liquid separation was performed by filtration to obtain a wet cake.
- the obtained wet cake was dried under reduced pressure (90 KPa) at 60 ° C. for 3 hours to obtain fine powder PPS (drying step).
- the average particle diameter, melt viscosity, and Na ion amount of this fine powder PPS were measured. As a result, the average particle size was 95 ⁇ m, the melt viscosity was 25 Pa ⁇ s, and the amount of Na ions was 150 ppm.
- the melt viscosity of the raw material fine powder PPS sufficiently washed and dried was less than 2 Pa ⁇ s.
- Example 2 In the drying step, the measurement was performed in the same manner as in Example 1 except that the wet cake was dried under reduced pressure (90 KPa) at 30 ° C. for 12 hours to obtain fine powder PPS. As a result, the average particle size was 91 ⁇ m, the melt viscosity was 23 Pa ⁇ s, and the amount of Na ions was 185 ppm.
- Example 3 In the drying step, the measurement was performed in the same manner as in Example 1 except that the wet cake was dried at 120 ° C. for 5 hours under normal pressure to obtain fine powder PPS. As a result, the average particle size was 84 ⁇ m, the melt viscosity was 28 Pa ⁇ s, and the amount of Na ions was 198 ppm.
- Example 4 In the drying step, the measurement was performed in the same manner as in Example 1 except that the wet cake was dried at 120 ° C. for 5 hours in a nitrogen atmosphere at normal pressure to obtain fine powder PPS. As a result, the average particle size was 98 ⁇ m, the melt viscosity was 24 Pa ⁇ s, and the amount of Na ions was 170 ppm.
- Example 1 In the heating step, measurement was performed in the same manner as in Example 1 except that the raw material fine powder PPS was heated at 140 ° C. for 12 hours in a reduced pressure state (90 KPa). As a result, the average particle size was 88 ⁇ m, the melt viscosity was 3 Pa ⁇ s, and the amount of Na ions was 4,500 ppm.
- Example 2 In the organic solvent washing step, measurement was performed in the same manner as in Example 1 except that anhydrous acetone was used. As a result, the average particle size was 80 ⁇ m, the melt viscosity was 2 Pa ⁇ s, and the amount of Na ions was 4,000 ppm. The specific surface area was 13 m 2 / g, and the specific surface area retention was 11%.
- the fine powder PAS of the present invention can be reused as a component of a compound.
- the fine powder PAS of the present invention is produced from the raw fine powder PAS in the separation liquid that has not been discarded or used in the past, and it is very significant that it can be reused without polluting the work environment. It is.
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Abstract
Description
(a)粒状ポリアリーレンスルフィドを含有する分散液から、目開き径75~180μmの範囲の少なくとも1つのスクリーンを用いた固液分離により粒状ポリアリーレンスルフィドと分離液とに分離する分離工程;
(b)該分離液を固液分離し、微粉ポリアリーレンスルフィド含有固形物を得る固液分離工程;
(c)該微粉ポリアリーレンスルフィド含有固形物を加熱して有機溶媒量を減らし、ウエットケーキを得る加熱工程;
(d)水性溶媒により、該ウエットケーキを洗浄する洗浄工程;
を含み、
該加熱工程後のウエットケーキの含水率が30重量%以上である方法が提供される。
(a)粒状ポリアリーレンスルフィドを含有する分散液から、目開き径75~180μmの範囲の少なくとも1つのスクリーンを用いた固液分離により粒状ポリアリーレンスルフィドと分離液とに分離する分離工程;
(b)該分離液を固液分離し、微粉ポリアリーレンスルフィド含有固形物を得る固液分離工程;
(c)該微粉ポリアリーレンスルフィド含有固形物を加熱して有機溶媒量を減らし、ウエットケーキを得る加熱工程;
(d)水性溶媒により、該ウエットケーキを洗浄する洗浄工程;
を含み、
該分離工程後、該加熱工程前に、該分離液に水を添加する水添加工程を更に含む方法が提供される。
(a)粒状ポリアリーレンスルフィドを含有する分散液から、目開き径75~180μmの範囲の少なくとも1つのスクリーンを用いた固液分離により粒状ポリアリーレンスルフィドと分離液とに分離する分離工程;
(b)該分離液を固液分離し、微粉ポリアリーレンスルフィド含有固形物を得る固液分離工程;
(c)該微粉ポリアリーレンスルフィド含有固形物を加熱して有機溶媒量を減らし、ウエットケーキを得る加熱工程;
(d)水性溶媒により、該ウエットケーキを洗浄する洗浄工程;
を含み、
該加熱工程前の微粉ポリアリーレンスルフィド含有固形物に含まれる微粉ポリアリーレンスルフィドの比表面積A1に対する、該加熱工程後のウエットケーキに含まれる微粉ポリアリーレンスルフィドの比表面積A2の比表面積保持率A2/A1が20%以上である方法が提供される。
(a)粒状ポリアリーレンスルフィドを含有する分散液から、目開き径75~180μmの範囲の少なくとも1つのスクリーンを用いた固液分離により粒状ポリアリーレンスルフィドと分離液とに分離する分離工程;
(b)該分離液を固液分離し、微粉ポリアリーレンスルフィド含有固形物を得る固液分離工程;
(c)該微粉ポリアリーレンスルフィド含有固形物を加熱して有機溶媒量を減らし、ウエットケーキを得る加熱工程;
(d)水性溶媒により、該ウエットケーキを洗浄する洗浄工程;
を含み、
該加熱工程における加熱温度が平均して85℃以下である方法が提供される。
該微粉ポリアリーレンスルフィドの平均粒子径が1~200μmであり、
該微粉ポリアリーレンスルフィドの溶融粘度が1Pa・s以上である
微粉ポリアリーレンスルフィドが提供される。
(a)粒状ポリアリーレンスルフィドを含有する分散液から、目開き径75~180μmの範囲の少なくとも1つのスクリーンを用いた固液分離により粒状ポリアリーレンスルフィドと分離液とに分離する分離工程;
(b)該分離液を固液分離し、微粉ポリアリーレンスルフィド含有固形物を得る固液分離工程;
(c)該微粉ポリアリーレンスルフィド含有固形物を加熱して有機溶媒量を減らし、ウエットケーキを得る加熱工程;
(d)水性溶媒により、該ウエットケーキを洗浄する洗浄工程;
を含み、
該加熱工程後のウエットケーキの含水率が30重量%以上である。
(a)粒状ポリアリーレンスルフィドを含有する分散液から、目開き径75~180μmの範囲の少なくとも1つのスクリーンを用いた固液分離により粒状ポリアリーレンスルフィドと分離液とに分離する分離工程;
(b)該分離液を固液分離し、微粉ポリアリーレンスルフィド含有固形物を得る固液分離工程;
(c)該微粉ポリアリーレンスルフィド含有固形物を加熱して有機溶媒量を減らし、ウエットケーキを得る加熱工程;
(d)水性溶媒により、該ウエットケーキを洗浄する洗浄工程;
を含み、
該分離工程後、該加熱工程前に、該分離液に水を添加する水添加工程を更に含む。
(a)粒状ポリアリーレンスルフィドを含有する分散液から、目開き径75~180μmの範囲の少なくとも1つのスクリーンを用いた固液分離により粒状ポリアリーレンスルフィドと分離液とに分離する分離工程;
(b)該分離液を固液分離し、微粉ポリアリーレンスルフィド含有固形物を得る固液分離工程;
(c)該微粉ポリアリーレンスルフィド含有固形物を加熱して有機溶媒量を減らし、ウエットケーキを得る加熱工程;
(d)水性溶媒により、該ウエットケーキを洗浄する洗浄工程;
を含み、
該加熱工程前の微粉ポリアリーレンスルフィド含有固形物に含まれる微粉ポリアリーレンスルフィドの比表面積A1に対する、該加熱工程後のウエットケーキに含まれる微粉ポリアリーレンスルフィドの比表面積A2の比表面積保持率A2/A1が20%以上である。
(a)粒状ポリアリーレンスルフィドを含有する分散液から、目開き径75~180μmの範囲の少なくとも1つのスクリーンを用いた固液分離により粒状ポリアリーレンスルフィドと分離液とに分離する分離工程;
(b)該分離液を固液分離し、微粉ポリアリーレンスルフィド含有固形物を得る固液分離工程;
(c)該微粉ポリアリーレンスルフィド含有固形物を加熱して有機溶媒量を減らし、ウエットケーキを得る加熱工程;
(d)水性溶媒により、該ウエットケーキを洗浄する洗浄工程;
を含み、
該加熱工程における加熱温度が平均して85℃以下である。
1.硫黄源
硫黄源としてアルカリ金属硫化物及びアルカリ金属水硫化物からなる群より選ばれる少なくとも一種の硫黄源を使用する。アルカリ金属硫化物としては、硫化リチウム、硫化ナトリウム、硫化カリウム、硫化ルビジウム、硫化セシウム、及びこれらの2種以上の混合物などを挙げることができる。アルカリ金属水硫化物としては、水硫化リチウム、水硫化ナトリウム、水硫化カリウム、水硫化ルビジウム、水硫化セシウム、及びこれらの2種以上の混合物などを挙げることができる。
ジハロ芳香族化合物(DHA)は、芳香環に直接結合した2個のハロゲン原子を有するジハロゲン化芳香族化合物である。ハロゲン原子とは、フッ素、塩素、臭素、及びヨウ素の各原子を指し、同一ジハロ芳香族化合物において、2つのハロゲン原子は、同じでも異なっていてもよい。これらのジハロ芳香族化合物は、それぞれ単独で、あるいは2種以上を組み合わせて用いることができる。ジハロ芳香族化合物の具体例としては、例えば、o-ジハロベンゼン、m-ジハロベンゼン、p-ジハロベンゼン、ジハロトルエン、ジハロナフタレン、メトキシ-ジハロベンゼン、ジハロビフェニル、ジハロ安息香酸、ジハロジフェニルエーテル、ジハロジフェニルスルホン、ジハロジフェニルスルホキシド、ジハロジフェニルケトン等が挙げられる。これらの中でも、p-ジハロベンゼン、m-ジハロベンゼン、及びこれら両者の混合物が好ましく、p-ジハロベンゼンがより好ましく、p-ジクロロベンゼン(pDCB)が、特に好ましく用いられる。
生成PASに分岐または架橋構造を導入するために、3個以上のハロゲン原子が結合したポリハロ化合物(必ずしも芳香族化合物でなくてもよい)、活性水素含有ハロゲン化芳香族化合物、ハロゲン化芳香族ニトロ化合物等を併用することができる。分岐・架橋剤としてのポリハロ化合物として、好ましくはトリハロベンゼンが挙げられる。また、生成PAS樹脂に特定構造の末端を形成したり、あるいは重合反応や分子量を調節したりするために、モノハロ化合物を併用することができる。モノハロ化合物は、モノハロ芳香族化合物だけではなく、モノハロ脂肪族化合物も使用することができる。
分岐・架橋剤は、仕込み硫黄源1モル当たり0.0001~0.01モル、好ましくは0.0002~0.008モル、より好ましくは、0.0003~0.005モルの範囲で用いられる。
脱水反応及び重合反応の溶媒として、非プロトン性極性有機溶媒である有機アミド溶媒を用いる。有機アミド溶媒は、高温でアルカリに対して安定なものが好ましい。有機アミド溶媒の具体例としては、N,N-ジメチルホルムアミド、N,N-ジメチルアセトアミド等のアミド化合物;N-メチル-ε-カプロラクタム等のN-アルキルカプロラクタム化合物;N-メチル-2-ピロリドン、N-シクロヘキシル-2-ピロリドン等のN-アルキルピロリドン化合物またはN-シクロアルキルピロリドン化合物;1,3-ジアルキル-2-イミダゾリジノン等のN,N-ジアルキルイミダゾリジノン化合物;テトラメチル尿素等のテトラアルキル尿素化合物;ヘキサメチルリン酸トリアミド等のヘキサアルキルリン酸トリアミド化合物等が挙げられる。これらの有機アミド溶媒は、それぞれ単独で用いてもよいし、2種類以上を組み合わせて用いてもよい。
重合反応を促進させるために、必要に応じて、各種重合助剤を用いることができる。重合助剤の具体例としては、一般にPASの重合助剤として公知の水、有機カルボン酸金属塩、有機スルホン酸金属塩、ハロゲン化リチウムなどのアルカリ金属ハライド、アルカリ土類金属ハライド、芳香族カルボン酸のアルカリ土類金属塩、リン酸アルカリ金属塩、アルコール類、パラフィン系炭化水素類、及びこれらの2種以上の混合物などが挙げられる。有機カルボン酸金属塩としては、アルカリ金属カルボン酸塩が好ましい。アルカリ金属カルボン酸塩としては、例えば、酢酸リチウム、酢酸ナトリウム、酢酸カリウム、プロピオン酸ナトリウム、吉草酸リチウム、安息香酸リチウム、安息香酸ナトリウム、フェニル酢酸ナトリウム、p-トルイル酸カリウム、及びこれらの2種以上の混合物を挙げることができる。アルカリ金属カルボン酸塩としては、安価で入手しやすいことから、酢酸ナトリウムが特に好ましい。重合助剤の使用量は、化合物の種類により異なるが、仕込み硫黄源1モルに対し、通常0.01~10モル、好ましくは0.1~2モル、より好ましくは0.2~1.8モル、特に好ましくは0.3~1.7モルの範囲である。
重合反応を促進させ、高重合度のPASを短時間で得るために、または相分離を生起し粒状PASを得るために、各種相分離剤を用いる。相分離剤とは、それ自身でまたは少量の水の共存下に、有機アミド溶媒に溶解し、PASの有機アミド溶媒に対する溶解性を低下させる作用を有する化合物である。相分離剤自体は、PASの溶媒ではない化合物である。
PASの製造は、有機アミド溶媒中で、アルカリ金属硫化物及びアルカリ金属水硫化物からなる群より選ばれる少なくとも一種の硫黄源とジハロ芳香族化合物とを重合反応させて粒状PASを生成させることで行われる。
この場合の重合工程を詳述する。
重合工程は、以下の仕込み工程を経て実施することができる。
仕込み工程は、所望により配置する脱水工程で系内に残存する混合物とジハロ芳香族化合物とを混合し、必要に応じてアルカリ金属水酸化物及び水を添加して、有機アミド溶媒、硫黄源(仕込み硫黄源)、アルカリ金属水酸化物、水分、及びジハロ芳香族化合物を含有する仕込み混合物を調製する。脱水工程で有機アミド溶媒の留出量が多すぎる場合は、仕込み工程で有機アミド溶媒を追加させてもよい。また、仕込み硫黄源を調整するために仕込み工程で硫黄源を追加させてもよい。一般に、脱水工程において各成分の含有量及び量比が変動するため、仕込み工程での各成分量の調整は、脱水工程で得られた混合物中の各成分の量を考慮して行う必要がある。
重合工程では、前記の仕込み工程により調整した仕込み混合物を、通常170~290℃、好ましくは180~280℃、より好ましくは190~275℃の温度に加熱して、重合反応を開始させ、重合を進行させる。加熱方法は、一定温度を保持する方法、段階的または連続的な昇温方法、または両方法の組み合わせが用いられる。重合反応時間は、一般に10分間~72時間の範囲であり、望ましくは30分間~48時間である。重合反応は、前段重合工程と後段重合工程の2段階工程で行うことが好ましく、その場合の重合時間は前段重合工程と後段重合工程との合計時間である。
転化率=〔〔DHA仕込み量(モル)-DHA残存量(モル)〕/〔DHA仕込み量(モル)-DHA過剰量(モル)〕〕×100
によって転化率を算出する。それ以外の場合には、下記式
転化率=〔〔DHA仕込み量(モル)-DHA残存量(モル)〕/〔DHA仕込み量(モル)〕〕×100
によって転化率を算出する。
本発明の熱処理微粉PASの製造において、重合工程を実施する際の仕込み工程前に、所望により脱水工程を配置してもよい。
また、脱水工程では、加熱により水及び有機アミド溶媒が蒸気となって留出する。したがって、留出物には、水と有機アミド溶媒とが含まれる。留出物の一部は、有機アミド溶媒の系外への排出を抑制するために、系内に環流してもよいが、水分量を調節するために、水を含む留出物の少なくとも一部は系外に排出する。留出物を系外に排出する際に、微量の有機アミド溶媒が水と同伴して系外に排出される。
分離工程では、粒状PASを含有する分散液から、目開き径75~180μmの範囲の少なくとも1つのスクリーンを用いた固液分離により粒状PASと分離液とに分離する。
以下に、製品として回収される好ましい粒状PASの性状について例示する。
また、粒状PASを含有する分散液として、上記重合工程において生成した粒状PASを含有する反応液を用いる場合、室温程度まで冷却することなく、生成物スラリーから高温状態で粒状PASを篩分けすることもできる。
(IV-1)上記分離工程で生ずる、粒状PASと分離された分離液には、多くの場合、原料微粉PAS、副生アルカリ金属塩(NaCl等)、オリゴマー、揮発性物質や高沸点物質等を含有する不純物、有機アミド溶媒、相分離剤(水等)等が含まれている。
固液分離工程、加熱工程、洗浄工程は、以下の工程で行う。
固液分離工程は、分離液を固液分離し、微粉PAS含有固形物を得る工程である。固液分離工程では、固液分離は、濾過、遠心分離、篩分、沈降等で行う。例えば濾過は、微粉用の通常の濾布を用いた濾過装置を用いることが多い。吸引濾過装置が、処理時間等からみて、有利である。固液分離工程は、連続式でもバッチ式のどちらの方法も可能である。連続式としては、水平ベルト型濾過機がある。バッチ式の場合、濾過装置としては、原料微粉PAS濃度が低い場合は、処理量からみて、フィルタープレスで行うことが好ましい。
加熱工程では、微粉PAS含有固形物を加熱して有機溶媒量を減らし、ウエットケーキを得る。加熱工程において微粉PAS含有固形物中の有機溶媒量を減らすことにより、洗浄工程後の廃液中に含まれる有機溶媒の濃度を効果的に低減することができる。有機溶媒の由来としては、特に限定されず、例えば、固液分離工程の前に行われる有機溶媒洗浄工程(後述)で添加される有機溶媒や、粒状PASを含有する分散液に含まれていた有機溶媒等が挙げられる。
また、常圧、減圧、加圧いずれの状態下でも行うことができる。
分離工程後、該加熱工程前には、水添加工程を行ってもよい。水添加工程は、分離液に水を添加する工程である。水添加工程において、含水有機溶媒の形態で分離液に水を添加するのが好ましい。含水有機溶媒における有機溶媒としては、例えば、水より沸点の低い有機溶媒が挙げられ、好ましくは、水より沸点の低いことに加え、有機アミド溶媒を溶解する有機溶媒が挙げられ、より好ましくはケトン系溶媒が挙げられ、更により好ましくはアセトンが挙げられる。含水有機溶媒における含水率としては、特に限定されず、例えば、20~70質量%が挙げられ、好ましくは25~50質量%である。この含水率が上記範囲内であると、有機溶媒の濃度が低くなりすぎず、例えば、有機溶媒による洗浄効果や有機アミド溶媒の除去効果等を確保しやすく、また、加熱工程を経た後でも、微粉PASの濡れ性が低下しにくい。水添加工程は、後述の有機溶媒洗浄工程として行ってもよい。本発明の第二の実施形態においては、分離工程後、該加熱工程前に、水添加工程を行う。
洗浄工程では、水性溶媒により、ウエットケーキを洗浄する。この洗浄工程の目的は、微粉PAS中の副生アルカリ金属塩由来のアルカリ金属濃度(例えば、Na濃度)低減及び微粉PAS中のPASオリゴマー濃度低減が目的である。
洗浄工程後には、乾燥工程を行ってもよい。乾燥工程は、洗浄工程で洗浄されたウエットケーキを乾燥させる工程である。乾燥処理は、連続式、バッチ式のどちらの方法も可能である。乾燥処理は、通常の熱風熱処理機、撹拌翼付の加熱装置、流動層熱処理機、槽回転式熱処理機等の熱処理装置を使って行うことができる。加熱工程の乾燥機と乾燥工程の熱処理装置を同じ装置を用いて行うこともできる。
また、常圧、減圧、加圧いずれの状態下でも行うことができる。減圧度は、70~101KPaの範囲であれば充分である。
[予備固液分離工程]
予備固液分離工程は、分離液を、濾過等の予備固液分離手段により、原料微粉PASと、濾液とに固液分離する工程である。
有機溶媒洗浄工程は、原料微粉PASに、アセトン等を添加し、原料微粉PASに含まれた有機アミド溶媒等を洗浄し、再度、濾過等の分離手段により、洗浄された原料微粉PASを得る工程である。
副生アルカリ金属塩除去工程は、予備固液分離工程後の、原料微粉PASを水で洗浄して、副生アルカリ金属塩を溶解させ除去する工程である。
第五の実施形態において、本発明の微粉PASは、本発明に係る製造方法により製造された微粉PASである。
第六の実施形態において、本発明の微粉PASは、
該微粉PASの平均粒子径が1~200μmであり、
該微粉PASの溶融粘度が1Pa・s以上である
微粉PASである。第六の実施形態における本発明の微粉PASは、例えば、本発明に係る製造方法により製造される。
本発明の微粉PASは、アルカリ金属塩、PASオリゴマー等の不純物が低減されている。
(1)粒状PASの回収率(質量%)
粒状PAS回収率は、脱水工程後の反応缶中に存在する仕込み硫黄源中の有効硫黄成分の全てがPASに転換したと仮定したときのPAS質量(理論量)を、PASの全量として算出する。
すなわち、粒状PASの回収率は、回収した粒状PASの質量/PAS質量(理論量)で算出した。
回収した粒状PASの平均粒子径は、使用篩として、メッシュ#7(目開き径2,800μm)、#12(目開き径1,410μm)、#16(目開き径1,000μm)、#24(目開き径710μm)、#32(目開き径500μm)、#60(目開き径250μm)、#100(目開き径150μm)、#145(目開き径105μm)、#200(目開き径75μm)を用いた篩分法により測定した。
微粉PASの平均粒子径は、レーザ回折式粒子径分布測定装置(SALD 株式会社島津製作所製)により、測定した。
PASの重量平均分子量(Mw)は、株式会社センシュー科学製の高温ゲルパーミエーションクロマトグラフ(GPC)SSC-7101を用いて、以下の条件で測定した。重量平均分子量、及びピークトップ分子量は、ポリスチレン換算値として算出した。
溶媒: 1-クロロナフタレン、
温度: 210℃、
検出器: UV検出器(360nm)、
サンプル注入量: 200μl(濃度:0.1質量%)、
流速: 0.7ml/分、
標準ポリスチレン: 616,000、113,000、26,000、8,200、及び600の5種類の標準ポリスチレン。
PASの乾燥品約20gを用いて、東洋精機製キャピログラフ1-Cにより溶融粘度を測定した。この際、キャピラリーは、1mmφ×10mmLのフラットダイを使用し、設定温度は、310℃とした。上記のPAS試料を装置に導入し、5分間保持した後、剪断速度1,216sec-1での溶融粘度を測定した。
加熱した濃硫酸中でPASを分解した後、得られた分解物を過酸化水素水で処理して試料溶液を調製し、この試料溶液について、イオンクロマト法によりNaイオンを定量した。
PASの比表面積は、以下の装置及び条件により測定した。なお、PAS中に水分等が残留しているときは、乾燥工程後に、更に真空乾燥機で室温にて24時間、PASを乾燥して、比表面積を測定した。
装置:株式会社島津製作所製フローソープII2300
測定:窒素吸着によるBET法により比表面積を決定
温度:液体窒素温度
ウエットケーキの含水率は、ウエットケーキを減圧状態(90KPa)で60℃、3時間乾燥させて、乾燥前後の質量差から算出した(該質量差/ウエットケーキの質量×100(%))。
(脱水工程)
20リットルのオートクレーブに、NMP6,001gと水硫化ナトリウム水溶液(NaSH:純度62質量%)2,000g、水酸化ナトリウム(NaOH:純度74.0質量%)1,171gを仕込んだ。
上記脱水工程後、オートクレーブの内容物を150℃まで冷却し、pDCB3,360g、NMP2,707g、水酸化ナトリウム19g、及び水167gを加え、撹拌しながら、220℃の温度で5時間反応させて、前段重合を行った。
前段重合のpDCBの転化率は、92%であった。
後段重合終了後、室温付近まで冷却してから、内容物を目開き径150μm(100メッシュ)のスクリーンで篩分けし、篩上に、粒状PPSのウエットケーキ、篩下に分離液を得た。
製造例1の篩分による分離工程での篩下の分離液に以下の処理を行った。
乾燥工程において、ウエットケーキを、減圧状態(90KPa)で、30℃、12時間乾燥し微粉PPSを得た以外は実施例1と同様に測定を行った。その結果、平均粒径は91μmであり、溶融粘度は23Pa・sであり、Naイオン量は185ppmあった。
乾燥工程において、ウエットケーキを、常圧状態で、120℃、5時間乾燥し微粉PPSを得た以外は実施例1と同様に測定を行った。その結果、平均粒径は84μmであり、溶融粘度は28Pa・sであり、Naイオン量は198ppmあった。
乾燥工程において、ウエットケーキを、常圧の窒素雰囲気状態で、120℃、5時間乾燥し微粉PPSを得た以外は実施例1と同様に測定を行った。その結果、平均粒径は98μmであり、溶融粘度は24Pa・sであり、Naイオン量は170ppmあった。
加熱工程において、原料微粉PPSを、減圧状態(90KPa)で、140℃、12時間加熱した以外は実施例1と同様に測定を行った。その結果、平均粒径は88μmであり、溶融粘度は3Pa・sであり、Naイオン量は4,500ppmあった。
有機溶媒洗浄工程において、無水アセトンを用いた以外は実施例1と同様に測定を行った。その結果、平均粒径は80μmであり、溶融粘度は2Pa・sであり、Naイオン量は4,000ppmあった。また、比表面積は13m2/gであり、比表面積保持率は11%であった。
Claims (9)
- 微粉ポリアリーレンスルフィドを製造する方法であって、下記の工程;
(a)粒状ポリアリーレンスルフィドを含有する分散液から、目開き径75~180μmの範囲の少なくとも1つのスクリーンを用いた固液分離により粒状ポリアリーレンスルフィドと分離液とに分離する分離工程;
(b)該分離液を固液分離し、微粉ポリアリーレンスルフィド含有固形物を得る固液分離工程;
(c)該微粉ポリアリーレンスルフィド含有固形物を加熱して有機溶媒量を減らし、ウエットケーキを得る加熱工程;
(d)水性溶媒により、該ウエットケーキを洗浄する洗浄工程;
を含み、
該加熱工程後のウエットケーキの含水率が30重量%以上である方法。 - 微粉ポリアリーレンスルフィドを製造する方法であって、下記の工程;
(a)粒状ポリアリーレンスルフィドを含有する分散液から、目開き径75~180μmの範囲の少なくとも1つのスクリーンを用いた固液分離により粒状ポリアリーレンスルフィドと分離液とに分離する分離工程;
(b)該分離液を固液分離し、微粉ポリアリーレンスルフィド含有固形物を得る固液分離工程;
(c)該微粉ポリアリーレンスルフィド含有固形物を加熱して有機溶媒量を減らし、ウエットケーキを得る加熱工程;
(d)水性溶媒により、該ウエットケーキを洗浄する洗浄工程;
を含み、
該分離工程後、該加熱工程前に、該分離液に水を添加する水添加工程を更に含む方法。 - 前記水添加工程において、含水有機溶媒の形態で前記分離液に水を添加する請求項2に記載の製造方法。
- 微粉ポリアリーレンスルフィドを製造する方法であって、下記の工程;
(a)粒状ポリアリーレンスルフィドを含有する分散液から、目開き径75~180μmの範囲の少なくとも1つのスクリーンを用いた固液分離により粒状ポリアリーレンスルフィドと分離液とに分離する分離工程;
(b)該分離液を固液分離し、微粉ポリアリーレンスルフィド含有固形物を得る固液分離工程;
(c)該微粉ポリアリーレンスルフィド含有固形物を加熱して有機溶媒量を減らし、ウエットケーキを得る加熱工程;
(d)水性溶媒により、該ウエットケーキを洗浄する洗浄工程;
を含み、
該加熱工程前の微粉ポリアリーレンスルフィド含有固形物に含まれる微粉ポリアリーレンスルフィドの比表面積A1に対する、該加熱工程後のウエットケーキに含まれる微粉ポリアリーレンスルフィドの比表面積A2の比表面積保持率A2/A1が20%以上である方法。 - 微粉ポリアリーレンスルフィドを製造する方法であって、下記の工程;
(a)粒状ポリアリーレンスルフィドを含有する分散液から、目開き径75~180μmの範囲の少なくとも1つのスクリーンを用いた固液分離により粒状ポリアリーレンスルフィドと分離液とに分離する分離工程;
(b)該分離液を固液分離し、微粉ポリアリーレンスルフィド含有固形物を得る固液分離工程;
(c)該微粉ポリアリーレンスルフィド含有固形物を加熱して有機溶媒量を減らし、ウエットケーキを得る加熱工程;
(d)水性溶媒により、該ウエットケーキを洗浄する洗浄工程;
を含み、
該加熱工程における加熱温度が平均して85℃以下である方法。 - 粒状ポリアリーレンスルフィドを含有する前記分散液が、有機アミド溶媒中で、アルカリ金属硫化物及びアルカリ金属水硫化物からなる群より選ばれる少なくとも一種の硫黄源とジハロ芳香族化合物とを重合反応させる重合工程において生成した粒状ポリアリーレンスルフィドを含有する反応液である請求項1乃至5のいずれか1項に記載の製造方法。
- 請求項1乃至6のいずれか1項に記載の製造方法により製造される微粉ポリアリーレンスルフィド。
- 微粉ポリアリーレンスルフィドであって、
該微粉ポリアリーレンスルフィドの平均粒子径が1~200μmであり、
該微粉ポリアリーレンスルフィドの溶融粘度が1Pa・s以上である
微粉ポリアリーレンスルフィド。 - 前記微粉ポリアリーレンスルフィドのアルカリ金属含有量が1500ppm以下である請求項8に記載の微粉ポリアリーレンスルフィド。
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US6201097B1 (en) * | 1998-12-31 | 2001-03-13 | Phillips Petroleum Company | Process for producing poly (arylene sulfide) |
JP4848688B2 (ja) | 2005-07-08 | 2011-12-28 | 東レ株式会社 | ポリフェニレンスルフィド樹脂の製造方法 |
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JPS63215728A (ja) * | 1987-01-23 | 1988-09-08 | フィリップス・ペトロリウム・カンパニー | ポリ(アリーレンスルフィド)反応混合物からのポリ(アリーレンスルフィド)オリゴマーの回収方法 |
JP2007002172A (ja) * | 2005-06-27 | 2007-01-11 | Toray Ind Inc | ポリフェニレンスルフィドオリゴマーの回収方法 |
JP2009227972A (ja) * | 2008-02-28 | 2009-10-08 | Toray Ind Inc | ポリアリーレンスルフィドとオリゴアリーレンスルフィドの分離方法 |
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JP2021521307A (ja) * | 2018-07-03 | 2021-08-26 | エルジー・ケム・リミテッド | ポリアリーレンスルフィドの製造方法 |
US11414521B2 (en) | 2018-07-03 | 2022-08-16 | Lg Chem, Ltd. | Preparation method of polyarylene sulfide |
JP7191344B2 (ja) | 2018-07-03 | 2022-12-19 | エルジー・ケム・リミテッド | ポリアリーレンスルフィドの製造方法 |
JP2021535952A (ja) * | 2018-10-19 | 2021-12-23 | エルジー・ケム・リミテッド | ポリアリーレンスルフィドの分離精製方法 |
JP7150385B2 (ja) | 2018-10-19 | 2022-10-11 | エルジー・ケム・リミテッド | ポリアリーレンスルフィドの分離精製方法 |
Also Published As
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CN107207743B (zh) | 2020-03-03 |
KR101984418B1 (ko) | 2019-05-30 |
US10280264B2 (en) | 2019-05-07 |
CN107207743A (zh) | 2017-09-26 |
US20180112042A1 (en) | 2018-04-26 |
KR20170103875A (ko) | 2017-09-13 |
JP6419311B2 (ja) | 2018-11-07 |
JPWO2016159234A1 (ja) | 2017-10-19 |
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