WO2012070335A1 - ポリアリーレンスルフィドの製造方法、及びポリアリーレンスルフィド - Google Patents
ポリアリーレンスルフィドの製造方法、及びポリアリーレンスルフィド Download PDFInfo
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- WO2012070335A1 WO2012070335A1 PCT/JP2011/073939 JP2011073939W WO2012070335A1 WO 2012070335 A1 WO2012070335 A1 WO 2012070335A1 JP 2011073939 W JP2011073939 W JP 2011073939W WO 2012070335 A1 WO2012070335 A1 WO 2012070335A1
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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
- C08G75/14—Polysulfides
- C08G75/16—Polysulfides by polycondensation of organic compounds with inorganic polysulfides
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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
Definitions
- the present invention when producing polyarylene sulfide, by contacting the produced polymer separated and recovered from the reaction solution after the polymerization reaction with an oxidizing aqueous solution, or after separating the produced polymer from the polymerization reaction solution Of Polyarylene Sulfide with Less Odor Generation During Manufacturing and Molding Process by Treating Washed Drainage After Washing Liquid or Product Polymer Containing Organic Amide Solvent with Organic Solvent or Water with Oxidizing Aqueous Solution About.
- PAS Polyarylene sulfide
- PPS polyphenylene sulfide
- a sulfur source and a dihaloaromatic compound are heated under an organic amide solvent such as N-methyl-2-pyrrolidone (hereinafter sometimes abbreviated as “NMP”).
- NMP N-methyl-2-pyrrolidone
- the method of making it react below is known.
- an alkali metal sulfide, an alkali metal hydrosulfide, or a mixture thereof is used as the sulfur source.
- the alkali metal hydrosulfide is used in combination with an alkali metal hydroxide.
- the PAS produced by the polymerization is separated from the reaction solution containing the produced polymer, it is purified by washing with water, an organic solvent, or a mixed solution of water and an organic solvent.
- these washing treatments did not completely suppress the generation of odors during the production of PAS and during the molding process.
- the dihaloaromatic compound is reacted in excess of 1.00 mol with respect to 1 mol of the sulfur source, the unreacted dihaloaromatic compound is encapsulated in the PAS particles or generated during the dehydration process or the polymerization process reaction.
- the liquid containing the organic amide solvent after the separation of PAS from the reaction liquid containing the polymer produced as described above, and the washing drainage liquid after washing the PAS using the organic solvent mentioned above Because it contains decomposition products such as unreacted raw materials used as raw materials and by-product sulfur compounds from raw material sources, organic amide solvents as reaction solvents, and organic solvents used for washing It took a lot of time and hindered the recycling of organic amide solvents.
- Patent Document 1 discloses that heating is performed by adding 1,3-dihalobenzene and reacting after the reaction between sulfide and 1,4-dihalobenzene is substantially completed. There has been proposed a method for producing a PAS in which the amount of sulfur-based gas generated during melting is reduced and corrosion of the mold during molding hardly occurs.
- JP 2004-182840 A Patent Document 2; corresponding to US Patent Application Publication No. 2006/0052578) describes that the NMP solution of PAS after the polymerization reaction is maintained at 230 to 290 ° C. and washed in a molten state. Thereafter, a method for producing PAS has been proposed in which a silane coupling agent is added and melt-kneaded to reduce disulfide structures and thiol structures in the resin.
- Patent Document 3 JP-A-2005-194212
- Patent Document 4 discloses a hydrophilic organic solvent such as acetone containing PAS obtained by polymerization and containing 1 to 30% by mass of water.
- the PAS manufacturing method has been proposed in which the nitrogen content is 50 ppm or less based on the polymer mass standard, and the deposits on the mold and the die are significantly reduced during melt molding.
- Patent Document 4 discloses that a polymer produced in the polymerization step is a washing solution comprising a hydrophilic organic solvent such as water, acetone, or a mixture thereof.
- the organic amide solvent, alkali metal halide, oligomer, decomposition product adhering to the PAS after separation treatment is controlled by controlling the pH by washing with water or a mixed solution in the final stage.
- a method for producing PAS with high whiteness and excellent melt stability has been proposed.
- Patent Document 5 Patent Document 5; corresponding to US Patent Application Publication No. 2006/0086374.
- a polymer separated from a reaction solution is washed with an organic solvent such as acetone, and then the recovered organic solvent is treated with hydrochloric acid.
- An inorganic acid such as distillate and distilling has been proposed.
- Patent Documents 1 to 5 were able to completely suppress the generation of odor during the production and processing of PAS.
- an organic solvent is used for washing, it is impossible to avoid the odor during production and the odor during molding, which may be caused by hydrogen sulfides generated during the polymerization reaction and the reaction product from the organic solvent. It was.
- the liquid containing the organic amide solvent after the separation of PAS from the reaction liquid the remaining used raw material contained in the washing effluent after washing the PAS with the organic solvent, the raw material source causing odor generation It was not possible to avoid a great amount of labor required for the deodorization treatment of the by-product sulfur compound from the organic solvent, the organic amide solvent as the reaction solvent, and the decomposition product of the organic solvent used for washing.
- Patent Document 6 Japanese Patent Laid-Open No. 11-228696
- Patent Document 7 Japanese Patent Laid-Open No. 11-228696
- JP 2009-79317 A Patent Document 7
- PPS fine powder and PPS short fibers are dispersed in water to make a paper stock solution, and then selected from inorganic salt peroxide and hydrogen peroxide solution.
- Patent Document 8 discloses that a solid polymer in a suspension medium is oxidized using ozone, and the resulting reaction product is mixed with acetic acid.
- a two-stage oxidation process of PAS has been proposed in which it is reacted with hydrogen peroxide used in the form of a 30% strength aqueous solution in the presence of a catalytic amount of concentrated sulfuric acid.
- Patent Documents 6 to 8 are methods for producing polyarylene sulfoxide and PPSO by oxidizing and modifying PAS, and are not methods for producing PAS. Therefore, it is an engineering plastic excellent in heat resistance, chemical resistance, flame resistance, mechanical strength, electrical properties, dimensional stability, etc., and by general melt processing methods such as extrusion molding, injection molding, compression molding, By using the characteristic of PAS that it can be molded into various molded products, films, sheets, fibers, etc., PAS that can be used in a wide range of technical fields such as electrical equipment, electronic equipment, automotive equipment, packaging materials, etc. It could not be manufactured. In addition, since high-concentration hydrogen peroxide or the like is used to oxidize and denature PAS, the treatment step and post-treatment for detoxifying the hydrogen peroxide remaining in the waste liquid after the treatment are great. There were problems such as high costs.
- JP-A-8-134216 JP 2004-182840 A Japanese Patent Laid-Open No. 2005-19412 Japanese Patent Laying-Open No. 2005-225931 International Publication No. 2004/060973 JP-A-11-228696 JP 2009-79317 A Japanese Patent Laid-Open No. 7-3024
- An object of the present invention is to provide a method for producing PAS in which the odor during production is reduced and the generation of odor during processing is reduced, and the PAS obtained by the production method.
- the object of the present invention is to further remove residual or generated by-products during the production of PAS and after washing the polymer separated and recovered from the reaction liquid with an organic solvent after the PAS polymerization step. It is to reduce the odor generated from the polymer during the molding process.
- Another object of the present invention is to reduce the odor of the liquid after the PAS is separated from the reaction liquid and the cleaning effluent after the PAS is washed with an organic solvent.
- the present inventors treated residual or generated odor-causing substances in contact with an oxidizing aqueous solution during the production of PAS or during cleaning and recovery with an organic solvent. It was found that the odor during the production of PAS and the molding process at high temperature can be reduced. In addition, the present inventors have found that an effect is obtained particularly when an organic solvent such as acetone is used as a cleaning solvent for PAS after polymerization.
- steps (a), (b) and (d) or steps (a) to (d) are provided.
- A) a polymerization step for producing a polymer by polymerizing at least one sulfur source selected from the group consisting of alkali metal sulfides and alkali metal hydrosulfides and a dihaloaromatic compound in an organic amide solvent (B) a separation step of separating and recovering the polymer from the reaction solution containing the produced polymer after the polymerization step; (C) A washing step of washing the collected polymer with at least one washing liquid selected from the group consisting of water, an organic solvent, and a mixed solution of water and an organic solvent, and then separating and collecting the polymer; as well as, (D) an oxidizing aqueous solution treatment step for contacting the recovered polymer with an oxidizing aqueous solution;
- a process for producing a polyarylene sulfide containing is provided.
- a process for producing a polyarylene sulfide further comprising a step of treating the separated liquid to be contacted with an oxidizing aqueous solution.
- the mesityl oxide content produced by the production method is 65 ppm or less
- the diacetone alcohol content is 35 ppm or less
- the dihaloaromatic compound content is 110 ppm or less
- a polyarylene sulfide having a total content of mesityl oxide and diacetone alcohol of 100 ppm or less is provided.
- the method for producing polyarylene sulfide of the present invention According to the method for producing polyarylene sulfide of the present invention, residual or generated odor-causing substances are removed at the time of separation / recovery of PAS from the reaction solution containing the produced polymer and at the time of washing / recovery of PAS after separation. Therefore, the odor at the time of manufacture of PAS and the shaping
- the PAS obtained by the production method of the present invention is suitable for the application of general melt processing methods such as extrusion molding, injection molding, compression molding, and the like, including sealants and coating agents for electronic components. It can be suitably used in a wide range of fields such as electrical / electronic equipment and automobile equipment.
- the odor of the waste liquid discharged after the separation of PAS from the reaction liquid containing the produced polymer and the washing of PAS with an organic solvent or water is obtained. Since it can be reduced, the deodorizing process does not require much labor, and recycling use of organic amide solvent, organic solvent, etc. is promoted, and it can contribute to the solution of resource environment problems.
- 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 used in the present invention may contain a small amount of alkali metal hydrosulfide.
- the total molar amount of the alkali metal sulfide and the alkali metal hydrosulfide becomes the sulfur source after the dehydration step, that is, the “charged sulfur source”.
- the alkali metal hydrosulfide used in the present invention may contain a small amount of alkali metal sulfide. In this case, the total molar amount of the alkali metal hydrosulfide and the alkali metal sulfide becomes a charged sulfur source after the dehydration step. When 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, aqueous medium of water, water produced as a by-product due to reaction of alkali metal hydrosulfide and alkali metal hydroxide, or the like. is there.
- the dihaloaromatic compound used in the present invention is a dihalogenated aromatic compound having two halogen atoms directly bonded to an aromatic ring.
- Specific examples of the dihaloaromatic compound 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, m-dihalobenzene, and a mixture of both are preferable, and p-dihalobenzene is more preferable.
- the halogen atom refers to each atom of fluorine, chlorine, bromine and iodine, and in the same dihaloaromatic compound, the two halogen atoms may be the same or different.
- These dihaloaromatic compounds can be used alone or in combination of two or more.
- the charged amount of the dihaloaromatic compound is usually 0.90 to 1.50 mol, preferably 1 mol to 1 mol of the sulfur source (alkali metal sulfide and / or alkali metal hydrosulfide) remaining in the system after the dehydration step.
- the amount is from 1.00 to 1.10 mol, more preferably from 1.00 to 1.09 mol, particularly preferably more than 1.00 mol and not more than 1.09 mol. In many cases, good results can be obtained when the charged amount of the dihaloaromatic compound is in the range of 1.01 to 1.09 mol. 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.
- 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.
- Organic Amide Solvent in the present invention, an organic amide solvent that is an aprotic polar organic solvent is used as a solvent for the dehydration reaction and the polymerization reaction.
- the organic amide solvent is preferably stable to alkali at high temperatures.
- organic amide solvent examples 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 be used alone or in combination of two or more.
- N-alkylpyrrolidone compounds N-cycloalkylpyrrolidone compounds, N-alkylcaprolactam compounds, and N, N-dialkylimidazolidinone compounds are preferable, and in particular, N-methyl-2-pyrrolidone, N-methyl- ⁇ -caprolactam and 1,3-dialkyl-2-imidazolidinone are preferably used.
- the amount of the organic amide solvent used in the polymerization reaction of the present invention is usually in the range of 0.1 to 10 kg per mole of sulfur source.
- phase separation agent polymerization aid
- phase separation agent polymerization aid
- 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 generally known compounds can be used as polymerization assistants or phase separation agents for PAS.
- phase separation agents include water, organic carboxylic acid metal salts such as alkali metal carboxylates, organic sulfonic acid metal salts, alkali metal halides such as lithium halides, alkaline earth metal halides, and aromatic carboxylic acids.
- Alkaline earth metal salts, alkali metal phosphates, alcohols, paraffinic hydrocarbons and the like can be mentioned.
- water and organic carboxylic acid metal salts are preferable because they are inexpensive, and water is particularly preferable.
- the amount of the phase separation agent (polymerization aid) used varies depending on the type of compound used, but is usually in the range of 0.01 to 10 moles with respect to 1 mole of the charged sulfur source.
- water is allowed to be present in the polymerization reaction system as a phase separation agent at a ratio of more than 2.0 mol and not more than 10 mol with respect to 1 mol of the charged sulfur source.
- the phase separation agent other than water such as an organic carboxylic acid metal salt, is preferably 0.01 to 3 mol, more preferably 0.02 to 2 mol, particularly preferably 0. It is used within the range of 03 to 1 mol. Even when water is used as the phase separation agent, another phase separation agent can be used in combination as a polymerization aid from the viewpoint of efficiently performing the phase separation polymerization.
- Dehydration process As a pre-process of the polymerization process, it is preferable to arrange a dehydration process to adjust the amount of water in the reaction system.
- the dehydration step is preferably carried out by 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.
- water consisting of hydrated water (crystal water), aqueous medium, by-product water, etc. is dehydrated until it falls within the required range.
- the amount of coexisting water in the polymerization reaction system is usually 0.02 to 2.0 mol, preferably 0.05 to 2.0 mol, more preferably 0.5 to 2.0 mol with respect to 1 mol of the charged sulfur source. Dehydrate to 2.0 moles.
- the sulfur source after the dehydration step is referred to as “prepared sulfur source”.
- water may be added to the desired amount of water before the polymerization step.
- an organic amide solvent an alkali metal hydrosulfide, and 0.95 to 1.05 mole of alkali metal hydroxide per mole of the alkali metal hydrosulfide It is preferable to heat and react the mixture containing water and to discharge at least a part of the distillate containing water from the system containing the mixture to the outside of the system.
- the preferred molar ratio of alkali metal hydroxide per mole of alkali metal hydrosulfide in the dehydration step is 0.97 to 1.04, more preferably 0.98 to 1.03.
- Alkali metal hydrosulfides often contain a small amount of alkali metal sulfide, and the amount of sulfur source is the total amount of alkali metal hydrosulfide and 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 process may be the same as or different from the reaction tank (reaction can) used in the subsequent polymerization process.
- the material of the device is preferably a corrosion resistant material such as titanium.
- part of the organic amide solvent is usually discharged with the water out of the reaction vessel. At that time, hydrogen sulfide is discharged out of the system as a gas.
- an alkali metal hydroxide and water can be added to the mixture remaining in the system after the dehydration step, if necessary.
- alkali metal hydrosulfide used as the sulfur source
- the total number of moles of alkali metal hydroxide to be added later is 1.00 to 1.09 moles per mole of sulfur source present in the system after the dehydration step, more preferably 1.00 exceeds 1.09 moles.
- the number of moles of water is 0.02 to 2.0 moles, preferably 0.05 to 2.0 moles, more preferably 0.5 to 2.0 moles per mole of the charged sulfur source. it is desirable to adjust to.
- the molar ratio of the alkali metal hydroxide per mol of the charged sulfur source is preferably 1.005 to 1.085 mol, more preferably 1.01 to 1.08 mol, and particularly preferably 1.015 to 1.075. Is a mole. 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 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 sulfur source introduced into the reaction vessel in the dehydration process varies in the dehydration process.
- 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.
- Polymerization process The polymerization process is performed by charging the mixture after completion of the dehydration process with a dihaloaromatic compound and heating the sulfur source and the dihaloaromatic compound in an organic amide solvent.
- a polymerization tank different from the reaction tank used in the dehydration step the mixture after the dehydration step and the dihaloaromatic compound are charged into the polymerization tank.
- the amount of organic amide solvent and the amount of coexisting water may be adjusted as necessary.
- the mixture obtained after the dehydration step and the dihaloaromatic compound are usually mixed within a temperature range of 100 to 350 ° C., preferably 120 to 330 ° C.
- the charging order is not particularly limited, and is carried out by charging both components partially or at a time.
- the polymerization reaction is preferably carried out in a two-step process of a pre-stage polymerization process and a post-stage polymerization process, generally in the range of 170 to 290 ° C.
- 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 organic amide solvent used in the polymerization step is usually 0.1 to 10 kg, preferably 0.15 to 5 kg per mole of the charged sulfur source present in the polymerization step. Within this range, the amount may be changed during the polymerization reaction.
- the amount of coexisting water at the start of the polymerization reaction is usually 0.02 to 2.0 mol, preferably 0.05 to 2.0 mol, more preferably 0.5 to 2.0 mol, relative to 1 mol of the charged sulfur source. It is desirable to be within the molar range.
- the amount of coexisting water can also be increased during the polymerization reaction.
- the polymerization step In the production method of the present invention, in the polymerization step, in an organic amide solvent, at least one sulfur source selected from the group consisting of alkali metal sulfides and alkali metal hydrosulfides is polymerized with a dihaloaromatic compound, so that the conversion of the dihaloaromatic compound is 80 to 80%.
- At least one sulfur source selected from the group consisting of alkali metal sulfides and alkali metal hydrosulfides and a dihaloaromatic compound are added in an amount of 0.02 to 2.0 mol per mol of the charged sulfur source.
- the polymerization reaction system is adjusted by adjusting the amount of water in the polymerization reaction system so that water exceeding 2.0 moles and 10 moles or less per mole of the charged sulfur source is present, and heating to a temperature of 245 to 290 ° C.
- a subsequent polymerization step in which the polymerization reaction is continued in a phase-separated state in which the produced polymer rich phase and the produced polymer dilute phase are mixed; More preferably, the polymerization reaction is carried out by at least two stages of polymerization processes including
- 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. And when it is a manufacturing method including a phase-separation polymerization process, the stage before the liquid phase of a polymerization process will be in a phase-separation state is said. In the pre-stage polymerization step, no phase separation state appears.
- the conversion rate of the dihaloaromatic compound in the former polymerization step is a value calculated by the following formula.
- DHA dihaloaromatic compound
- Conversion [[DHA charge (mol) ⁇ DHA remaining amount (mol)] / [DHA charge] Amount (mole) -DHA excess (mole)]] ⁇ 100
- 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 former polymerization step is usually 0.02 to 2.0 mol, preferably 0.05 to 2.0 mol, more preferably 0.5 to 2.0 mol per mol of the charged sulfur source. Mol, particularly preferably in the range of 1.0 to 1.9 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.
- 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.
- pre-stage polymerization step it is desirable to produce a polymer (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 in the present invention is not a simple fractionation / granulation step of the polymer produced in the pre-polymerization step, but is for raising the polymerization degree of the polymer.
- the phase separation agent is 0.01 to 10 mol, preferably 0.01 to 9.5 mol, more preferably 0.02 to 9 mol, relative to 1 mol of the charged sulfur source. It is a range.
- the phase separation agent is less than 0.01 mol or more than 10 mol with respect to 1 mol of the charged sulfur source, the phase separation state cannot be sufficiently caused and a high degree of polymerization PAS cannot be obtained.
- the phase separation agent it is particularly preferable to use water, and in the production method using water alone, the amount exceeding 2.0 mol is less than 10 mol, preferably 2.0 mol, relative to 1 mol of the charged sulfur source. It is preferable to adjust the amount of water in the reaction system so that an excess of 9 mol or less, more preferably 2.1 to 8 mol, particularly preferably 2.2 to 7 mol of water is present.
- the degree of polymerization of the produced PAS decreases.
- water and a phase separation agent other than water can be used in combination as the phase separation agent.
- the amount of water in the reaction system is adjusted to an excess of 2.0 moles per mole of charged sulfur source to 10 moles or less, and other phase separation agents other than water are added to 0 mole per mole of charged sulfur source. It is preferably present in the range of 0.01 to 3 mol.
- phase separation agents other than water include 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 It can be selected from acid alkali metal salts, alcohols, or paraffinic hydrocarbons.
- the polymerization temperature in the subsequent polymerization step is in the range of 245 to 290 ° C.
- the polymerization temperature is less than 245 ° C, it is difficult to obtain a high degree of polymerization PAS, and when it exceeds 290 ° C, the produced PAS and organic amide solvent are decomposed. There is a risk.
- a temperature range of 250 to 270 ° C. is preferable because a PAS having a high degree of polymerization can be easily obtained.
- water may be added at the end of the polymerization reaction or at the end to increase the water content.
- the polymerization reaction system may be a batch system, a continuous system, or a combination of both systems.
- a system using two or more reaction vessels can be used as desired.
- the separation and recovery treatment of the produced PAS polymer after the polymerization reaction can be performed by the same method as the separation and collection treatment step of the produced PAS polymer after the normal polymerization reaction.
- the separation step after completion of the polymerization reaction, after cooling the product slurry, which is a reaction solution containing the produced PAS polymer, the product slurry is diluted with water if necessary, and then filtered to obtain a reaction solution.
- the produced PAS can be separated and recovered from the.
- granular PAS can be generated.
- a sieving method using a screen By separating the granular PAS from the reaction solution by a sieving method using a screen, by-products and oligomers are obtained. It can be easily separated from the above.
- the PAS polymer can also be sieved from the product slurry at elevated temperatures without cooling to about room temperature.
- the recovered PAS can be directly subjected to a contact treatment with an oxidizing aqueous solution described below, but preferably, the recovered PAS is treated with water, an organic solvent, and water and organic prior to the contact treatment with the oxidizing aqueous solution. It is possible to provide a cleaning process for performing a cleaning process with at least one cleaning liquid selected from the group consisting of a mixed solution with a solvent, and to perform PAS cleaning in order to minimize by-product alkali metal salts and oligomers. It is more preferable for enhancing the effect of the contact treatment.
- the organic solvent used for the washing treatment is preferably washed with the same organic amide solvent as the polymerization solvent, or an organic solvent such as ketones (for example, acetone) or alcohols (for example, methanol).
- ketones for example, acetone
- alcohols for example, methanol
- Those containing acetone are preferred in that they are excellent in the effect of removing impurities (low molecular weight components) such as oligomers and decomposition products.
- Acetone is preferable from the viewpoints of economy and safety. It is more preferable to use it as a mixed solution of water and acetone.
- As the mixed solution it is preferable to use a mixed solution having a water ratio of preferably 1 to 60% by mass, more preferably 1 to 30% by mass, and particularly preferably 1 to 20% by mass. It is preferable for improving the removal efficiency of impurities.
- the cleaning treatment with the cleaning liquid is generally performed by mixing and stirring the PAS and the cleaning liquid, and is preferably performed not only once but multiple times.
- the amount of the cleaning solution used in each cleaning step is usually 1 to 15 times, preferably 2 to 10 times, more preferably the theoretical PPS polymer (the amount of PPS polymer from which water or organic solvent has been removed by drying). 3-8 times capacity.
- the washing time is usually 1 to 120 minutes, preferably 3 to 100 minutes, more preferably 5 to 60 minutes.
- Separate the cleaning solution using a screen or centrifuge When filtration is performed using a screen, a wet cake having a liquid content of usually 30 to 75% by mass, and often 40 to 65% by mass is obtained. It is good also as a wet cake with a low liquid content using a centrifuge.
- the cleaning treatment is generally performed at room temperature (10 to 40 ° C.), but may be performed at a lower or higher temperature as long as the cleaning liquid is in a liquid state.
- high temperature water can be used as the cleaning liquid in order to increase the cleaning power of water.
- inorganic acids for example, hydrochloric acid
- organic acids for example, acetic acid
- Acid washing for the end group treatment of PAS with an aqueous solution of these salts for example, ammonium chloride
- Oxidizing aqueous solution treatment step is carried out in which the recovered PAS is brought into contact with the oxidizing aqueous solution for treatment.
- the oxidizing aqueous solution treatment step may be performed once or multiple times after “9. Separation step”, or may be performed on the PAS separated and recovered in “9. Separation step”. You may perform with respect to PAS which isolate
- the oxidizing aqueous solution treatment step is performed by mixing and stirring the separated and recovered PAS and the oxidizing aqueous solution.
- the oxidizing aqueous solution in the present invention means a solution obtained by dissolving an oxidizing agent in water.
- the oxidizing agent used in the present invention include inorganic salts such as potassium persulfate, potassium permanganate, and sodium hypochlorite, organic peroxides such as peracetic acid and perbenzoic acid, hydrogen peroxide, and ozone. Can be mentioned. Particularly preferred is hydrogen peroxide because the by-product is water and no polymer purification is required.
- the amount of the oxidizing agent used is in the range of 0.005 to 50 parts by weight, preferably 0.01 to 35 parts by weight, more preferably 0.025 to 25 parts by weight, based on 100 parts by weight of the theoretical PAS polymer. It is a range. If the amount of the oxidizing agent used exceeds 50 parts by mass, PAS itself may be denatured. Moreover, if the usage-amount of an oxidizing agent is less than 0.005 mass part, an odor reduction effect will not be acquired. The amount of the oxidizing agent used can be appropriately adjusted so as to be within the above range by adjusting the concentration of the oxidizing agent in the oxidizing aqueous solution and the amount of the oxidizing aqueous solution added to PAS.
- the concentration of the oxidizing agent in the oxidizing aqueous solution is used in the form of an aqueous solution having a content of 10 to 100,000 mg / L, preferably an aqueous solution having a content of 20 to 70,000 mg / L. Even if the concentration of the oxidizing agent is too high, the effect of reducing the odor is not improved. On the other hand, if the concentration of the oxidizing agent is too low, the effect of reducing odor is insufficient.
- the concentration of the hydrogen peroxide solution is usually used in the form of an aqueous solution having a content of 50 to 50,000 mg / L. Even if the concentration of the hydrogen peroxide solution is too high, the odor reduction effect is not improved, and the PAS itself is undesirably modified. On the other hand, if the concentration of the hydrogen peroxide solution is too low, the effect of reducing odor is insufficient. Therefore, the concentration of the hydrogen peroxide solution is preferably 50 to 10,000 mg / L, more preferably 100 to 9,000 mg / L. In this case, it goes without saying that the amount of hydrogen peroxide used is in the above range with respect to 100 parts by mass of the theoretical PAS polymer.
- the amount of the oxidizing aqueous solution used for the treatment is adjusted according to the concentration of the oxidizing agent in the oxidizing aqueous solution to be used so that mixing or stirring with PAS is sufficient. If the amount of the oxidizing aqueous solution used for the treatment is too small, mixing or stirring with the PAS becomes insufficient, and sufficient contact with the PAS by the oxidizing aqueous solution or an oxidizing effect cannot be obtained, resulting in an effect of reducing odor. It will be enough. On the other hand, if the amount of the oxidizing aqueous solution used for the treatment is too large, there may be a disadvantage in the manufacturing process due to an increase in the size of the processing apparatus or a longer time for separation and recovery of the PAS after the processing.
- the temperature of the treatment with the oxidizing aqueous solution is not particularly limited, but is preferably room temperature (10 to 40 ° C.).
- the treatment conditions with the oxidizing aqueous solution are not particularly limited and are generally neutral, but may be weakly acidic such as hydrogen peroxide solution or alkaline.
- the treatment time with the oxidizing aqueous solution is sufficient from 1 minute to 3 hours. If the treatment time is too short, the effect of reducing odor is insufficient. On the other hand, if the treatment time is too long, the effect of reducing the odor is not improved, and the PAS itself may be denatured. Therefore, a treatment time of 3 minutes to 1 hour is preferable, and a treatment time of 5 to 30 minutes is particularly preferable.
- the separation liquid treatment step using an oxidizing aqueous solution is further selected from the group consisting of a liquid obtained by separating the polymer from the polymerization reaction liquid in the separation step, and a drainage of the washing liquid obtained by separating the polymer in the washing step.
- a separation liquid treatment process in which a kind of separation liquid is brought into contact with an oxidizing aqueous solution that is, a separation liquid treatment process using an oxidizing aqueous solution can be performed.
- the separation liquid treatment process using an oxidizing aqueous solution is performed by adding an oxidizing aqueous solution to a separation liquid such as a liquid containing an organic amide solvent after separating the polymer produced from the polymerization reaction liquid or the above washing waste liquid, and mixing the mixture for a predetermined time. Stirring, allowing to stand for a predetermined time, or performing mixing and stirring for a predetermined time.
- the content of the odor component in the separation liquid can be reduced by passing through the treatment process of the separation liquid with the oxidizing aqueous solution.
- the content of mesityl oxide that is an odor component is 200 ppm or less, preferably 170 ppm or less, and the content of diacetone alcohol is 200 ppm or less, preferably with respect to the total amount of the mixture of the separation liquid and the oxidizing aqueous solution.
- the odor component contains mesityl oxide and diacetone alcohol
- the total content thereof is 400 ppm or less, preferably 350 ppm or less, based on the total amount of the mixed solution of the separation liquid and the oxidizing aqueous solution.
- it can be 300 ppm or less.
- the treatment of the separation solution with the oxidizing aqueous solution can be performed at any time as long as it is after “9. Separation step”.
- Separation step the liquid containing the organic amide solvent after the PAS is separated by filtration can be promptly treated with the oxidizing aqueous solution.
- Washing step the washing drainage of at least one kind of washing liquid selected from the group consisting of water, an organic solvent, and a mixed solution of water and an organic solvent used for the washing treatment is further washed with water.
- an oxidizing aqueous solution treatment of the separated liquid can be performed quickly on the washing waste liquid subjected to the washing treatment. it can. Also, store the liquid containing the organic amide solvent obtained in “9. Separation step” or the washing drainage liquid obtained in “10. Washing step” in a separately prepared container, etc. Collectively, the oxidizing solution treatment of the separated liquid can be performed.
- the oxidizing aqueous solution used for the treatment of the separated solution with the oxidizing aqueous solution is the same as that used for the oxidizing aqueous solution treatment of the recovered PAS detailed in “11. It is. Particularly preferred is hydrogen peroxide.
- the amount of the oxidizing aqueous solution used for the treatment of the separation solution with the oxidizing aqueous solution is the concentration of the oxidizing agent in the mixture of the separation solution and the oxidizing aqueous solution when the oxidizing aqueous solution is added to and mixed with the separation solution.
- concentration of the oxidizing aqueous solution is 10 to 100,000 mg / L, preferably 20 to 70,000 mg / L, more preferably 50 to 20,000 mg / L. May be adjusted as appropriate.
- the concentration of the oxidizing agent in the mixed solution is too low, sufficient contact treatment with the separated solution is not performed, and the effect of reducing odor cannot be obtained. On the other hand, if the concentration of the oxidizing agent in the mixed solution is too high, the effect of reducing odor is not improved, and problems such as generation of oxygen gas may occur.
- the concentration of the oxidizing agent in the oxidizing aqueous solution used for the treatment of the separation solution with the oxidizing aqueous solution is 100 to 900,000 mg / L content, preferably 1,000 to 600,000 mg / L content, more preferably 2, Used in the form of an aqueous solution having a content of 000 to 400,000 mg / L and a wide concentration range. If the concentration of the oxidizing agent is too low, the effect of reducing odor is insufficient, so that there is a problem that the amount of the oxidizing aqueous solution added to the separation liquid increases and a large container is required.
- the solubility of hydrogen peroxide in water is infinite, so the concentration of hydrogen peroxide is 1 to 60% by mass, preferably 2 to 40% by mass. %, More preferably 5 to 20% by mass of hydrogen peroxide water can be used.
- a commercially available hydrogen peroxide solution may be used as it is, or may be diluted to an appropriate concentration with water prior to addition to the separation liquid.
- the temperature of the separation liquid treated with the oxidizing aqueous solution is not particularly limited, but is preferably room temperature (10 to 40 ° C.).
- neutrality is generally preferable, but it may be weakly acidic such as hydrogen peroxide or alkaline.
- the treatment time of the separation solution with the oxidizing aqueous solution is sufficient from 1 minute to 3 hours. If the treatment time is too short, the effect of reducing odor is insufficient. On the other hand, if the treatment time is too long, the odor reduction effect is not improved. Therefore, a treatment time of 3 minutes to 2 hours is preferable, and a treatment time of 5 minutes to 1 hour is particularly preferable.
- Polyarylene sulfide PAS obtained by the method for producing PAS according to the present invention has a very low content of odor components.
- the content of odorous component in PAS is 65 ppm (mg / kg-PAS) or less, preferably 50 ppm or less, more preferably 30 ppm or less, particularly preferably 20 ppm or less.
- the content of diacetone alcohol may be 35 ppm or less, preferably 30 ppm or less, more preferably 25 ppm or less
- the content of dihaloaromatic compound may be 110 ppm or less, More preferably 100 ppm or less, particularly preferably 80 ppm or less.
- PAS contains mesityl oxide and diacetone alcohol as odor components
- their total content in PAS is 100 ppm or less, preferably 70 ppm or less, more preferably 60 ppm or less, more preferably 50 ppm or less. Can be.
- p-DCB p-dichlorobenzene
- the content of p-DCB is usually 110 ppm or less, preferably 100 ppm or less, more preferably 75 ppm or less, and particularly preferably 50 ppm or less.
- the melt viscosity measured at a temperature of 310 ° C. and a shear rate of 1,216 sec ⁇ 1 is usually 1 to 100 Pa ⁇ s, preferably 2 to 80 Pa ⁇ s, particularly preferably 3 to 70 Pa ⁇ s.
- the PAS can be obtained.
- a PAS having a mass average molecular weight (Mw) of usually 10,000 to 300,000, preferably 13,000 to 200,000, particularly preferably 14,000 to 100,000 is obtained. be able to.
- the dried granular polymer collected by a screen having an opening diameter of 150 ⁇ m (100 mesh) is usually 80 to 98%, preferably 83 to 97%, particularly preferably 85 to 95%.
- a granular PAS having an average particle diameter of 50 to 1,000 ⁇ m, preferably 70 to 800 ⁇ m, more preferably 200 to 700 ⁇ m can be obtained.
- the specific surface area by the BET method by nitrogen adsorption is 0.1 to 500 m 2 / g, preferably 1 to 200 m 2 / g, more preferably 3 to 80 m 2 / g. Since PAS can be obtained, granular PAS with good detergency and excellent granularity and handleability can be obtained.
- Odor component Quantitative measurement of the odor component is performed by using the dried PAS polymer obtained in “12. Generated polymer recovery step”, mesityl oxide and diacetone alcohol, which are strongly odorous substances, and reaction raw materials.
- the residual amount of p-DCB was determined by gas chromatography (hereinafter abbreviated as GC).
- FID hydrogen flame ionization detector
- the value was determined from a calibration curve using commercially available mesityl oxide, diacetone alcohol and p-DCB.
- melt viscosity was measured with Capilograph 1-C (registered trademark) manufactured by Toyo Seiki Seisakusho Co., Ltd. using about 20 g of the dried polymer. A 1 mm ⁇ ⁇ 10 mmL flat die was used as the capillary, and the set temperature was 310 ° C. The polymer sample was introduced into the apparatus and held for 5 minutes, and then the melt viscosity was measured at a shear rate of 1,216 sec ⁇ 1 .
- Mass average molecular weight The mass average molecular weight (Mw) of the polymer was measured using a high temperature gel permeation chromatograph (GPC) SSC-7000 manufactured by Senshu Kagaku Co., Ltd. under the following conditions. The mass average molecular weight was calculated as a polystyrene equivalent value.
- Solvent 1-chloronaphthalene, Temperature: 210 °C, Detector: UV detector (360 nm), Sample injection volume: 200 ⁇ l (concentration: 0.05% by mass), Flow rate: 0.7 ml / min, Standard polystyrene: Five standard polystyrenes of 616,000, 113,000, 26,000, 8,200, and 600.
- Average particle diameter The average particle diameter of the polymer was determined by measuring the recovered dried polymer using mesh # 7 (aperture diameter 2,800 ⁇ m), # 12 (aperture diameter 1,410 ⁇ m), # 16 (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 It measured by the sieving method using (opening diameter 75 micrometers).
- the contents of the autoclave were cooled to 150 ° C., and 3,380 g of p-dichlorobenzene, 3,456 g of NMP, 19.29 g of sodium hydroxide (high purity product), and 149 g of ion-exchanged water were added.
- the ratio (g / mol) of NMP / charged sulfur source (hereinafter abbreviated as “charge S”) in the can is 375
- p-DCB / charge S (mol / mol) is 1.060
- the (mol / mol) was 1.50
- the NaOH / charge S (mol / mol) was 1.060.
- Example 1 Add 100 g of 100 mg / L hydrogen peroxide solution to 50 g of the wet cake (water content 60%) obtained in Reference Example 1, and stir at 30 ° C. for 15 minutes under the conditions of stirring PPS and hydrogen peroxide as an oxidizing aqueous solution. Treated with water (oxidizing aqueous solution treatment step). The PPS after the hydrogen peroxide treatment was stirred and washed five times for 20 minutes with ion-exchanged water. Thereafter, the polymer was separated by sieving and then dried in a constant temperature bath at 100 ° C. for 24 hours to obtain a PPS polymer (produced polymer recovery step).
- the polymer thus obtained had a yield of 89%, an average particle size of 355 ⁇ m, a specific surface area of 38 m 2 / g, a melt viscosity of 30 Pa ⁇ s and a mass average molecular weight of 32,000. I didn't feel it.
- Comparative Example 1 When the same treatment as in Example 1 was carried out except that hydrogen peroxide was not added to 50 g of the wet cake (water content 60%) obtained in Reference Example 1, the obtained polymer “feels odor”. It was those. The results of GC measurement are shown in Table 1.
- Example 2 Examination of hydrogen peroxide concentration
- the PPS of Example 2 was obtained by treating in the same manner as in Example 1 except that the concentration of hydrogen peroxide in the hydrogen peroxide solution was changed.
- the polymer was “no odor”.
- Extraction of odor components from the obtained PPS and GC measurement confirmed that the amount of odor components remaining in the resin decreased as the hydrogen peroxide concentration increased.
- the results of GC measurement are shown in Table 2 together with the previous Comparative Example 1.
- Example 3 and [Comparative Example 2] Examination of treatment time
- the PPS of Example 3 was obtained by treating in the same manner as in Example 1 except that the treatment time with hydrogen peroxide was changed.
- the polymer was “no odor”. As the treatment time is extended, a decrease in the amount of odorous components remaining in the resin is observed.
- the polymer of Comparative Example 2 to which no hydrogen peroxide solution was added was “feeling odor”.
- the results of GC measurement in Example 3 and Comparative Example 2 are shown in Table 3.
- Example 4 The wet cake separated and recovered in the separation step of Reference Example 1 was subjected to contact treatment under the conditions of stirring at 30 ° C. for 15 minutes using the hydrogen peroxide solution of Example 1 without passing through the washing step (oxidation property). solution treatment step).
- the PPS after treatment with hydrogen peroxide solution was stirred and washed with ion-exchanged water 5 times for 20 minutes, and then sieved to separate and collect the polymer, followed by drying in a constant temperature bath at 100 ° C. for 24 hours.
- the PPS after drying was “no odor”.
- Example 5 and [Comparative Example 3]
- 1,000 g of the liquid from which the polymer was separated from the reaction liquid was combined with 500 g of washing waste liquid obtained by washing the polymer with a mixed liquid of ion-exchanged water and acetone in the washing process.
- the separation liquid used in Example 5 was recovered.
- the amount of acetone in the separated liquid was 20% by mass, and GC measurement showed mesityl oxide 224 ppm, diacetone alcohol 229 ppm, and p-DCB 63 ppm.
- hydrogen peroxide water having a concentration of 10% by mass was added until the hydrogen peroxide concentration in the separation liquid reached 100 mg / L, stirred at 30 ° C.
- the remaining or generated odor-causing substances can be removed to a low level at the time of polymerization of polyarylene sulfide, washing and recovery.
- the polyarylene sulfide obtained by the production method of the present invention is generally melted by extrusion molding, injection molding, compression molding, etc. It is suitable for application of processing methods, and can be suitably used in a wide range of fields such as sealants and coating agents for electronic parts, electric / electronic devices, and automotive devices.
- the odor of the liquid after separation of PAS from the reaction liquid containing the produced polymer or the washing waste liquid after washing the polyarylene sulfide with an organic solvent is obtained. Can be reduced. As a result, the deodorizing process does not require a great deal of effort, the recycling use of organic solvents and the like is promoted, and it can contribute to the solution of resource environment problems, and has great industrial utility.
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Abstract
Description
(a)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、ポリマーを生成する重合工程;
(b)重合工程後、生成したポリマーを含有する反応液からポリマーを分離して回収する分離工程;
(c)回収したポリマーを、水、有機溶媒、及び、水と有機溶媒との混合溶液からなる群より選ばれる少なくとも一種の洗浄液を用いて洗浄した後、ポリマーを分離して回収する洗浄工程;及び、
(d)回収したポリマーを酸化性水溶液と接触処理させる酸化性水溶液処理工程;
を含むポリアリーレンスルフィドの製造方法が提供される。
本発明では、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。
本発明で使用するジハロ芳香族化合物は、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。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い。
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。
本発明では、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。
本発明では、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、各種相分離剤(重合助剤)を用いることが好ましい。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。
重合工程の前工程として、脱水工程を配置して反応系内の水分量を調節することが好ましい。脱水工程は、望ましくは不活性ガス雰囲気下、有機アミド溶媒とアルカリ金属硫化物とを含む混合物を加熱して反応させ、蒸留により水を系外へ排出する方法により実施する。硫黄源としてアルカリ金属水硫化物を用いる場合には、アルカリ金属水硫化物とアルカリ金属水酸化物とを含む混合物を加熱して反応させ、蒸留により水を系外へ排出する方法により実施する。
本発明では、脱水工程後、系内に残存する混合物に、必要に応じてアルカリ金属水酸化物及び水を添加することができる。特に、硫黄源としてアルカリ金属水硫化物を用いる場合には、脱水時に生成した硫化水素に伴い生成するアルカリ金属水酸化物のモル数と脱水前に添加したアルカリ金属水酸化物のモル数と脱水後に添加するアルカリ金属水酸化物のモル数の総モル数が、脱水工程後に系内に存在する硫黄源1モル当たり1.00~1.09モル、より好ましくは1.00超過1.09モル以下となり、かつ、水のモル数が仕込み硫黄源1モル当たり0.02~2.0モル、好ましくは0.05~2.0モル、より好ましくは0.5~2.0モルとなるように調整することが望ましい。仕込み硫黄源の量は、〔仕込み硫黄源〕=〔総仕込み硫黄モル〕-〔脱水後の揮散硫黄モル〕の式により算出される。
重合工程は、脱水工程終了後の混合物にジハロ芳香族化合物を仕込み、有機アミド溶媒中で硫黄源とジハロ芳香族化合物を加熱することにより行われる。脱水工程で用いた反応槽とは異なる重合槽を使用する場合には、重合槽に脱水工程後の混合物とジハロ芳香族化合物を投入する。脱水工程後、重合工程前には、必要に応じて、有機アミド溶媒量や共存水分量などの調整を行ってもよい。また、重合工程前または重合工程中に、重合助剤その他の添加物を混合してもよい。
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、該ジハロ芳香族化合物の転化率が80~99%のポリマーを生成させる前段重合工程;並びに、
相分離剤の存在下、重合反応系内に生成ポリマー濃厚相と生成ポリマー希薄相とが混在する相分離状態で重合反応を継続させる後段重合工程;
を含む少なくとも2段階の重合工程により重合反応を行うことが好ましい。
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、仕込み硫黄源1モル当たり0.02~2.0モルの水が存在する状態で、170~270℃の温度で重合反応させて、該ジハロ芳香族化合物の転化率が80~99%のポリマーを生成させる前段重合工程;並びに、
仕込み硫黄源1モル当たり2.0モル超過10モル以下の水が存在する状態となるように重合反応系内の水量を調整するとともに、245~290℃の温度に加熱することにより、重合反応系内に生成ポリマー濃厚相と生成ポリマー希薄相とが混在する相分離状態で重合反応を継続させる後段重合工程;
を含む少なくとも2段階の重合工程により重合反応を行うことがより好ましい。
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。
本発明の製造方法において、重合反応後の生成PASポリマーの分離回収処理は、通常の重合反応後の生成PASポリマーの分離回収処理工程と同様の方法により行うことができる。分離工程としては、重合反応終了後、生成PASポリマーを含有する反応液である生成物スラリーを冷却した後、必要により水などで生成物スラリーを希釈してから、濾別することにより、反応液から生成PASを分離して回収することができる。
回収したPASをそのまま、以下に述べる酸化性水溶液で接触処理することもできるが、好ましくは、酸化性水溶液による接触処理に先だって、回収したPASを、水、有機溶媒、及び、水と有機溶媒との混合溶液からなる群より選ばれる少なくとも一種の洗浄液によって洗浄処理を行う洗浄工程を設け、副生アルカリ金属塩やオリゴマーをできるだけ少なくするためにPASの洗浄を行うことが、酸化性水溶液による接触処理の効果を高める上で、より好ましい。
本発明においては、回収したPASを酸化性水溶液と接触させて処理する酸化性水溶液処理工程を実施する。酸化性水溶液処理工程の実施は、「9.分離工程」後であれば1回でも複数回でもよく、「9.分離工程」で分離回収したPASに対して行ってもよいし、「9.分離工程」で分離回収したPASに対して行われる「10.洗浄工程」の途中または終了後に洗浄液を分離して回収したPASに対して行ってもよい。
酸化性水溶液処理工程の後に、水による洗浄を行い、あるいは行わずに、濾別によってPASポリマーを分離し、その後、乾燥を行って、生成したPASポリマーを回収する。
本発明においては、さらに、分離工程において重合反応液からポリマーを分離した液、及び、前記洗浄工程においてポリマーを分離した洗浄液の排液からなる群より選ばれる少なくとも一種の分離液を、酸化性水溶液と接触させる分離液の処理工程、すなわち、酸化性水溶液による分離液の処理工程を実施することができる。
本発明によるPASの製造方法によって得られるPASは、臭気成分の含有量が極めて少ないものである。例えば、PAS中の臭気成分の含有量について、臭気成分であるメシチルオキシドの含有量を65ppm(mg/kg-PAS)以下、好ましくは50ppm以下、より好ましくは30ppm以下、特に好ましくは20ppm以下のものとすることができ、同じくジアセトンアルコールの含有量を、35ppm以下、好ましくは30ppm以下、より好ましくは25ppm以下のものとすることができ、同じくジハロ芳香族化合物の含有量を、110ppm以下、より好ましくは100ppm以下、特に好ましくは80ppm以下のものとすることができる。また、PASに、臭気成分として、メシチルオキシド及びジアセトンアルコールが含まれる場合は、PAS中のそれらの合計含有量を100ppm以下、好ましくは70ppm以下、より好ましくは60ppm以下、さらに好ましくは50ppm以下のものとすることができる。
PASポリマー及び分離液の臭気は、「6段階臭気強度表示法」に準じて3人の検査者が判定し、全員が、「0:無臭」、「1:やっと感知できるにおい」または「2:何のにおいであるかがわかる弱いにおい」のいずれかの判定をしたときは、「臭気を感じない」と評定し、それ以外のときは、「臭気を感じる」と評定した。
臭気成分の定量測定は、「12.生成ポリマー回収工程」で得られた乾燥後のPASポリマーを用いて、臭気が強い物質であるメシチルオキシド及びジアセトンアルコールと、反応原料であるp-DCBの残存量について、ガスクロマトグラフィー(以下、GCと略記する。)によって行った。
装置:株式会社日立製作所製G-3000、
検出器:FID(水素炎イオン化検出器)230℃、
気化室温度:200℃、
カラム:DB-WAX、0.53mmφ×15m、df(膜厚み)=1.0μm、
カラム温度:80℃(1分)、昇温速度10℃/分で220℃まで昇温し、220℃(1分)、
キャリアーガス:ヘリウム 4.7ml/分(10kPa)、
サンプル量:2μl。
溶融粘度の測定は、乾燥したポリマー約20gを用いて、株式会社東洋精機製作所製キャピログラフ1-C(登録商標)により行った。キャピラリーとして1mmφ×10mmLのフラットダイを使用し、設定温度を310℃とした。ポリマー試料を装置内に導入し、5分間保持した後、剪断速度1,216sec-1で溶融粘度を測定した。
ポリマーの質量平均分子量(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-7000を用いて、以下の条件で測定した。質量平均分子量は、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:0.05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。
ポリマーの平均粒径は、回収した乾燥ポリマーを、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。
ポリマー粒子の比表面積は、以下の装置と条件により測定した。
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
20リットルのオートクレーブに、N-メチル-2-ピロリドン(以下、NMPと略記)6,004gと水硫化ナトリウム水溶液(NaSH:濃度62質量%、Na2Sを28g含む)2,000g、水酸化ナトリウム(NaOH:濃度74質量%)1,191gを仕込んだ。水酸化ナトリウム/硫黄源(NaOH/S)のモル比は0.997であり、NaOH/NaSHのモル比は1.012であった。これらの各濃度の水硫化ナトリウム及び水酸化ナトリウムは、残余の成分として、水和水などの水分を含有するものである。
参考例1で得たウェットケーキ(含水率60%)50gに100mg/L濃度の過酸化水素水100gを添加し、30℃、15分間撹拌の条件下、PPSを酸化性水溶液である過酸化水素水で処理した(酸化性水溶液処理工程)。過酸化水素水処理後のPPSをイオン交換水により20分間ずつ5回の攪拌洗浄を行った。その後、篩分してポリマーを分離し、次いで、100℃の恒温槽で24時間乾燥を行い、PPSポリマーを得た(生成ポリマー回収工程)。このようにして得られたポリマーは、その収率が89%、平均粒径が355μm、比表面積が38m2/g、溶融粘度が30Pa・s、質量平均分子量32,000であり、「臭気を感じない」ものであった。
参考例1で得たウェットケーキ(含水率60%)50gに、過酸化水素水を添加しなかった以外は、実施例1と同様に処理したところ、得られたポリマーは、「臭気を感じる」ものであった。GC測定の結果を表1に示す。
過酸化水素水の過酸化水素の濃度を変えた以外は、実施例1と同様に処理して、実施例2のPPSを得たところ、得られたポリマーは、「臭気を感じない」ものであった。得られたPPSからの臭気成分を抽出し、GC測定すると、レジン中に残存する臭気成分量は、過酸化水素濃度の増加に伴い減少することが確認された。先の比較例1とともに、GC測定の結果を表2に示す。
過酸化水素水による処理時間を変えた以外は、実施例1と同様に処理して実施例3のPPSを得たところ、得られたポリマーは、「臭気を感じない」ものであった。処理時間が延長するに従いレジン中に残存する臭気成分量の減少が認められる。過酸化水素水を添加しなかった比較例2のポリマーは、「臭気を感じる」ものであった。実施例3及び比較例2のGC測定の結果を表3に示す。
参考例1の分離工程において分離・回収したウエットケーキを、洗浄工程を経ることなく、実施例1の過酸化水素水を用いて、30℃、15分間撹拌の条件下に接触処理した(酸化性水溶液処理工程)。過酸化水素水処理後のPPSをイオン交換水により20分間ずつ5回の攪拌洗浄を行った後、篩分しポリマーを分離・回収し、100℃の恒温槽で24時間乾燥を行った。乾燥後のPPSは、「臭気を感じない」ものであった。このPPSから臭気成分を抽出し、GC測定したところ、メシチルオキシド27ppm、ジアセトンアルコール31ppmであり、ポリマー中に残存する臭気成分量の減少が認められ、また、p-DCBも98ppmに減少していた。
参考例1の分離工程において、反応液からポリマーを分離した液1,000gと、洗浄工程においてポリマーをイオン交換水とアセトンとの混合液により洗浄して得られた洗浄排液500gとを合わせて、実施例5に用いる分離液を回収した。該分離液中のアセトン量は20質量%であり、GC測定したところ、メシチルオキシド224ppm、ジアセトンアルコール229ppm、p-DCB63ppmであった。該分離液に、濃度10質量%の過酸化水素水を、分離液中の過酸化水素濃度が100mg/Lとなるまで添加し、30℃で、約3分間撹拌した後、静置して、合計1時間分離液を処理した(分離液の処理工程)ところ、分離液は、臭気の強さが処理前に比べて低減した。過酸化水素水を添加しなかった比較例3とともに、GC測定の結果を表4に示す。
Claims (13)
- 以下の(a)、(b)及び(d)の工程、または、(a)~(d)の工程:
(a)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、ポリマーを生成する重合工程;
(b)重合工程後、生成したポリマーを含有する反応液からポリマーを分離して回収する分離工程;
(c)回収したポリマーを、水、有機溶媒、及び、水と有機溶媒との混合溶液からなる群より選ばれる少なくとも一種の洗浄液を用いて洗浄した後、ポリマーを分離して回収する洗浄工程;及び、
(d)回収したポリマーを酸化性水溶液と接触処理させる酸化性水溶液処理工程;
を含むポリアリーレンスルフィドの製造方法。 - (e)前記分離工程において反応液からポリマーを分離した液、及び、前記洗浄工程においてポリマーを分離した洗浄液の排液からなる群より選ばれる少なくとも一種の分離液を、酸化性水溶液と接触処理させる分離液の処理工程;
をさらに含む請求項1記載の製造方法。 - 酸化性水溶液が過酸化水素水である請求項1または2記載の製造方法。
- 過酸化水素の使用量が、ポリアリーレンスルフィド100質量部に対して0.005~50質量部である請求項3記載の製造方法。
- 有機溶媒がアセトンを含むものである請求項1または2記載の製造方法。
- 前記重合工程が、
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て、該ジハロ芳香族化合物の転化率が80~99%のポリマーを生成させる前段重合工程;並びに、
相分離剤の存在下、重合反応系内に生成ポリマー濃厚相と生成ポリマー希薄相とが混在する相分離状態で重合反応を継続させる後段重合工程;
を含む少なくとも2段階の重合工程である請求項1または2記載の製造方法。 - 前記重合工程が、
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、仕込み硫黄源1モル当たり0.02~2.0モルの水が存在する状態で、170~270℃の温度で重合反応させて、該ジハロ芳香族化合物の転化率が80~99%のポリマーを生成させる前段重合工程;並びに、
仕込み硫黄源1モル当たり2.0モル超過10モル以下の水が存在する状態となるように重合反応系内の水量を調整するとともに、245~290℃の温度に加熱することにより、重合反応系内に生成ポリマー濃厚相と生成ポリマー希薄相とが混在する相分離状態で重合反応を継続させる後段重合工程;
を含む少なくとも2段階の重合工程である請求項1または2記載のポリアリーレンスルフィドの製造方法。 - 前記後段重合工程において、
仕込み硫黄源1モル当たり2.0モル超過10モル以下の水が存在する状態となるように重合反応系内の水量を調整するとともに、
有機カルボン酸金属塩、有機スルホン酸金属塩、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、及びパラフィン系炭化水素類からなる群より選ばれる少なくとも一種の相分離剤を、仕込み硫黄源1モルに対して0.01~3モルの範囲内で存在させる請求項7記載のポリアリーレンスルフィドの製造方法。 - 前記重合工程に先立って、
有機アミド溶媒、アルカリ金属水硫化物を含有する硫黄源、及び該アルカリ金属水硫化物1モル当たり0.95~1.05モルのアルカリ金属水酸化物を含有する混合物を加熱して反応させ、該混合物を含有する系内から水を含む留出物の少なくとも一部を系外に排出する脱水工程;並びに、
脱水工程の後、系内に残存する混合物に、必要に応じてアルカリ金属水酸化物及び水を添加して、脱水時に生成した硫化水素に伴い生成するアルカリ金属水酸化物のモル数と脱水前に添加したアルカリ金属水酸化物のモル数と脱水後に添加するアルカリ金属水酸化物のモル数の総モル数が、脱水工程後に系内に存在する硫黄源1モル当たり1.00~1.09モルとなり、かつ、水のモル数が仕込み硫黄源1モル当たり0.02~2.0モルとなるように調整する仕込み工程;
を配置する請求項1または2記載のポリアリーレンスルフィドの製造方法。 - 請求項1または2記載のポリアリーレンスルフィドの製造方法によって製造された、メシチルオキシドの含有量が65ppm以下であるポリアリーレンスルフィド。
- 請求項1または2記載のポリアリーレンスルフィドの製造方法によって製造された、ジアセトンアルコールの含有量が35ppm以下であるポリアリーレンスルフィド。
- 請求項1または2記載のポリアリーレンスルフィドの製造方法によって製造された、ジハロ芳香族化合物の含有量が110ppm以下であるポリアリーレンスルフィド。
- 請求項1または2記載のポリアリーレンスルフィドの製造方法によって製造された、メシチルオキシド及びジアセトンアルコールの合計含有量が100ppm以下であるポリアリーレンスルフィド。
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2015152032A1 (ja) * | 2014-03-31 | 2015-10-08 | 株式会社クレハ | ポリアリーレンスルフィドの製造方法 |
WO2020032171A1 (ja) * | 2018-08-10 | 2020-02-13 | Dic株式会社 | ポリアリーレンスルフィドの精製方法および製造方法 |
WO2021117795A1 (ja) * | 2019-12-11 | 2021-06-17 | Dic株式会社 | ポリアリーレンスルフィド、その精製方法および製造方法 |
Families Citing this family (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2016536376A (ja) | 2013-09-25 | 2016-11-24 | ティコナ・エルエルシー | 低ハロゲン含量のポリアリーレンスルフィドを形成する方法 |
US9617387B2 (en) | 2013-09-25 | 2017-04-11 | Ticona Llc | Scrubbing process for polyarylene sulfide formation |
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WO2016133739A1 (en) * | 2015-02-19 | 2016-08-25 | Ticona Llc | Method for forming a high molecular weight polyarylene sulfide |
WO2016133740A1 (en) | 2015-02-19 | 2016-08-25 | Ticona Llc | Method of polyarylene sulfide precipitation |
WO2016133738A1 (en) | 2015-02-19 | 2016-08-25 | Ticona Llc | Method for forming a low viscosity polyarylene sulfide |
WO2016153610A1 (en) | 2015-03-25 | 2016-09-29 | Ticona Llc | Technique for forming a high melt viscosity polyarylene sulfide |
US11407861B2 (en) | 2019-06-28 | 2022-08-09 | Ticona Llc | Method for forming a polyarylene sulfide |
CN115279734A (zh) | 2019-12-20 | 2022-11-01 | 提克纳有限责任公司 | 形成聚芳硫醚的方法 |
Citations (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS59168032A (ja) * | 1983-03-15 | 1984-09-21 | Kureha Chem Ind Co Ltd | 高溶融粘度をもつ芳香族スルフイド重合体の製造方法 |
JPS62253626A (ja) * | 1986-04-28 | 1987-11-05 | Kureha Chem Ind Co Ltd | ポリアリ−レンスルフイドの製造方法 |
JPH02232375A (ja) * | 1989-01-14 | 1990-09-14 | Bayer Ag | ポリアリーレンスルフイドの成形物の金属化方法 |
JPH04218531A (ja) * | 1990-11-19 | 1992-08-10 | Toopuren:Kk | 高熱安定性ポリアリーレンスルフィド樹脂の製造方法および組成物 |
JPH05255235A (ja) * | 1992-01-27 | 1993-10-05 | Phillips Petroleum Co | ポリスルフイド類の精製法 |
JPH08134216A (ja) * | 1994-11-02 | 1996-05-28 | Dainippon Ink & Chem Inc | 硫黄系ガス発生量の少ないポリアリーレンスルフィドの製造方法 |
JPH11169870A (ja) * | 1997-12-16 | 1999-06-29 | Dainippon Ink & Chem Inc | ポリアリーレンスルフィド製造時の排水処理方法 |
JP2003275773A (ja) * | 2002-03-22 | 2003-09-30 | Dainippon Ink & Chem Inc | ポリフェニレンスルフィドの排水処理方法 |
WO2004060973A1 (ja) * | 2002-12-27 | 2004-07-22 | Kureha Chemical Industry Company, Limited | ポリアリーレンスルフィドの製造方法及び洗浄方法、並びに洗浄に使用した有機溶媒の精製方法 |
JP2005194312A (ja) * | 2003-12-26 | 2005-07-21 | Kureha Chem Ind Co Ltd | ポリアリーレンスルフィド及びその製造方法 |
JP2005225931A (ja) * | 2004-02-12 | 2005-08-25 | Kureha Chem Ind Co Ltd | ポリアリーレンスルフィド及びその製造方法 |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE4314737A1 (de) | 1993-05-04 | 1994-11-10 | Hoechst Ag | Zweistufige Oxidation von Polyarylensulfiden |
DE19751239A1 (de) | 1997-11-19 | 1999-05-20 | Ticona Gmbh | Oxidation von Polyarylensulfiden |
JP2004182840A (ja) | 2002-12-03 | 2004-07-02 | Idemitsu Petrochem Co Ltd | ポリアリーレンスルフィド樹脂及びその組成物、並びにこれらの製造方法 |
JP2009079317A (ja) | 2007-09-26 | 2009-04-16 | Toray Ind Inc | ポリアリーレンスルフィド酸化物からなる紙及びその製造方法 |
KR101287729B1 (ko) * | 2009-05-18 | 2013-07-19 | 가부시끼가이샤 구레하 | 폴리아릴렌술피드 및 그의 제조 방법 |
-
2011
- 2011-10-18 WO PCT/JP2011/073939 patent/WO2012070335A1/ja active Application Filing
- 2011-10-18 CN CN201180056570.7A patent/CN103228705B/zh not_active Expired - Fee Related
- 2011-10-18 US US13/989,714 patent/US9096723B2/en not_active Expired - Fee Related
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Patent Citations (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS59168032A (ja) * | 1983-03-15 | 1984-09-21 | Kureha Chem Ind Co Ltd | 高溶融粘度をもつ芳香族スルフイド重合体の製造方法 |
JPS62253626A (ja) * | 1986-04-28 | 1987-11-05 | Kureha Chem Ind Co Ltd | ポリアリ−レンスルフイドの製造方法 |
JPH02232375A (ja) * | 1989-01-14 | 1990-09-14 | Bayer Ag | ポリアリーレンスルフイドの成形物の金属化方法 |
JPH04218531A (ja) * | 1990-11-19 | 1992-08-10 | Toopuren:Kk | 高熱安定性ポリアリーレンスルフィド樹脂の製造方法および組成物 |
JPH05255235A (ja) * | 1992-01-27 | 1993-10-05 | Phillips Petroleum Co | ポリスルフイド類の精製法 |
JPH08134216A (ja) * | 1994-11-02 | 1996-05-28 | Dainippon Ink & Chem Inc | 硫黄系ガス発生量の少ないポリアリーレンスルフィドの製造方法 |
JPH11169870A (ja) * | 1997-12-16 | 1999-06-29 | Dainippon Ink & Chem Inc | ポリアリーレンスルフィド製造時の排水処理方法 |
JP2003275773A (ja) * | 2002-03-22 | 2003-09-30 | Dainippon Ink & Chem Inc | ポリフェニレンスルフィドの排水処理方法 |
WO2004060973A1 (ja) * | 2002-12-27 | 2004-07-22 | Kureha Chemical Industry Company, Limited | ポリアリーレンスルフィドの製造方法及び洗浄方法、並びに洗浄に使用した有機溶媒の精製方法 |
JP2005194312A (ja) * | 2003-12-26 | 2005-07-21 | Kureha Chem Ind Co Ltd | ポリアリーレンスルフィド及びその製造方法 |
JP2005225931A (ja) * | 2004-02-12 | 2005-08-25 | Kureha Chem Ind Co Ltd | ポリアリーレンスルフィド及びその製造方法 |
Cited By (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2015152032A1 (ja) * | 2014-03-31 | 2015-10-08 | 株式会社クレハ | ポリアリーレンスルフィドの製造方法 |
JP6077175B2 (ja) * | 2014-03-31 | 2017-02-08 | 株式会社クレハ | ポリアリーレンスルフィドの製造方法 |
KR101758039B1 (ko) | 2014-03-31 | 2017-07-13 | 가부시끼가이샤 구레하 | 폴리아릴렌 설파이드의 제조방법 |
US9896548B2 (en) | 2014-03-31 | 2018-02-20 | Kureha Corporation | Method of producing polyarylene sulfide |
WO2020032171A1 (ja) * | 2018-08-10 | 2020-02-13 | Dic株式会社 | ポリアリーレンスルフィドの精製方法および製造方法 |
JPWO2020032171A1 (ja) * | 2018-08-10 | 2020-09-17 | Dic株式会社 | ポリアリーレンスルフィドの精製方法および製造方法 |
WO2021117795A1 (ja) * | 2019-12-11 | 2021-06-17 | Dic株式会社 | ポリアリーレンスルフィド、その精製方法および製造方法 |
JPWO2021117795A1 (ja) * | 2019-12-11 | 2021-12-09 | Dic株式会社 | ポリアリーレンスルフィド、その精製方法および製造方法 |
JP7031797B2 (ja) | 2019-12-11 | 2022-03-08 | Dic株式会社 | ポリアリーレンスルフィド、その精製方法および製造方法 |
CN114729123A (zh) * | 2019-12-11 | 2022-07-08 | Dic株式会社 | 聚芳硫醚、其纯化方法和制造方法 |
Also Published As
Publication number | Publication date |
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CN103228705A (zh) | 2013-07-31 |
US20130253147A1 (en) | 2013-09-26 |
JP5781086B2 (ja) | 2015-09-16 |
CN103228705B (zh) | 2015-04-29 |
JPWO2012070335A1 (ja) | 2014-05-19 |
US9096723B2 (en) | 2015-08-04 |
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