WO2019004170A1 - Procédé de fabrication de résine de sulfure de polyarylène - Google Patents

Procédé de fabrication de résine de sulfure de polyarylène Download PDF

Info

Publication number
WO2019004170A1
WO2019004170A1 PCT/JP2018/024119 JP2018024119W WO2019004170A1 WO 2019004170 A1 WO2019004170 A1 WO 2019004170A1 JP 2018024119 W JP2018024119 W JP 2018024119W WO 2019004170 A1 WO2019004170 A1 WO 2019004170A1
Authority
WO
WIPO (PCT)
Prior art keywords
mol
polyarylene sulfide
sulfide resin
range
dehydration
Prior art date
Application number
PCT/JP2018/024119
Other languages
English (en)
Japanese (ja)
Inventor
早織 奈良
渡邉　英樹
将哉 角木
拓 茨木
井上　敏
Original Assignee
Dic株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Dic株式会社 filed Critical Dic株式会社
Priority to JP2019526915A priority Critical patent/JP6866923B2/ja
Publication of WO2019004170A1 publication Critical patent/WO2019004170A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
    • C08G75/02—Polythioethers
    • C08G75/0204—Polyarylenethioethers
    • C08G75/025—Preparatory processes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L81/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen or carbon only; Compositions of polysulfones; Compositions of derivatives of such polymers
    • C08L81/02—Polythioethers; Polythioether-ethers

Definitions

  • the present invention relates to a highly efficient method for producing linear high molecular weight polyarylene sulfide resin.
  • Polyarylene sulfide resins represented by polyphenylene sulfide resin (hereinafter sometimes abbreviated as “PPS resin”) (hereinafter sometimes abbreviated as “PAS resin”) are heat resistant, It has excellent chemical resistance and is widely used for electrical and electronic parts, automobile parts, water heater parts, fibers, film applications, and the like.
  • a hydrous alkali metal sulfide or less than 1 mole of N-methylpyrrolidone per mole of the hydrous alkali metal sulfide and a polyhaloaromatic compound are mixed and the mixture is azeotroped
  • a method of obtaining a slurry containing fine particulate anhydrous alkali metal sulfide by dehydration, and then heating the same to carry out a polymerization reaction see, for example, Patent Documents 1 and 2).
  • the obtained polyarylene sulfide resin contains metal atoms derived from the metal member eluted by the consumption of the metal member in the contact portion, it is also difficult to remove these metal atoms in a normal cleaning operation.
  • thinning of molded articles using polyarylene sulfide resin is also progressing, and polyarylene sulfide resin of higher quality than before is required, and metal derived from a reaction device in polyarylene sulfide resin
  • the reduction of atomic content has been an urgent issue.
  • the problem to be solved by the present invention is a method for producing a polyarylene sulfide resin in which a dihaloaromatic compound and a sulfidizing agent are subjected to a polymerization reaction in the presence of an aliphatic cyclic compound which can be opened by hydrolysis. It is an object of the present invention to provide a method for suppressing the corrosion of production equipment and reducing the content of metal atoms derived from the production equipment in the resulting polyarylene sulfide resin.
  • the present inventors dehydrate the sulfidizing agent containing water and the aliphatic cyclic compound which can be opened by hydrolysis in the presence of the dihaloaromatic compound. At that time, it is carried out under reduced pressure, and compared with the case where it is carried out under the atmospheric pressure, that is, compared to the case where it is carried out under atmospheric pressure, corrosion of the contact portion can be reduced. It has been found that the content of the metal atom derived from can be reduced, and the present invention has been completed.
  • the present invention is a method for producing a polyarylene sulfide resin, wherein a dihaloaromatic compound and a sulfidizing agent are reacted in the presence of an aliphatic cyclic compound that can be opened by hydrolysis.
  • the liquid temperature of the sulfidizing agent containing water and the aliphatic cyclic compound capable of ring-opening by hydrolysis is from 30 [kPa abs] to at most atmospheric pressure until the liquid temperature is in the range of 90 to 150 ° C.
  • the present invention relates to a method for producing a polyarylene sulfide resin, comprising the dehydration step (1) of obtaining a mixture by reacting while dehydrating in the range of kPa abs] or less.
  • a step of producing a polyarylene sulfide resin by the above production method the obtained polyarylene sulfide resin, a filler, a thermoplastic resin other than the polyarylene sulfide resin, an elastomer, and two or more functional groups Having a step of blending at least one other component selected from the group consisting of a crosslinkable resin having the above and a silane coupling agent, heating to a temperature above the melting point of the polyarylene sulfide resin, and melt kneading
  • the present invention relates to a method for producing a polyarylene sulfide resin composition characterized by
  • the present invention comprises a polyarylene sulfide resin molded article characterized by comprising a step of producing a polyarylene sulfide resin composition by the above production method, and a step of melt-molding the obtained polyarylene sulfide resin composition.
  • the method for producing the polyarylene sulfide resin of the present invention is
  • the liquid temperature of the sulfidizing agent containing water and the aliphatic cyclic compound capable of ring-opening by hydrolysis is from 30 [kPa abs] to at most atmospheric pressure until the liquid temperature is in the range of 90 to 150 ° C.
  • a dihalo aromatic compound is further added, liquid temperature heats to the range of 90 to 170 degreeC, and pressure is 30 [kPa abs] to 80 [
  • the reaction is characterized by having a dehydration step (1) of obtaining a mixture by reacting while dehydrating in the range of kPa abs] or less. The details will be described below.
  • the present invention provides a sulfidizing agent containing water and an aliphatic cyclic compound capable of ring-opening by hydrolysis until the liquid temperature is in the range of 90 ° C. or more to 150 ° C. or less, from 30 kPa abs or more
  • the reaction is carried out while dehydrating under a pressure in the range of atmospheric pressure or less, and a dihaloaromatic compound is further added, and the liquid temperature is heated to a range of 90 ° C.
  • the reaction is carried out while dehydrating in the range of 80 [kPa abs] or less, and a dehydration step (1) for obtaining a mixture is essential.
  • the dehydration step (1) is a step of reacting a sulfidizing agent containing water and an aliphatic cyclic compound which can be opened by hydrolysis in the presence of a dihaloaromatic compound while dehydrating.
  • a sulfidizing agent containing water and an aliphatic cyclic compound which can be opened by hydrolysis in the presence of a dihaloaromatic compound while dehydrating.
  • the dihaloaromatic compound used in the present invention acts as a solvent for securing the fluidity of the resulting mixture in the dehydration step (1), but can be used as a polymerization raw material in the subsequent polymerization step.
  • the dihaloaromatic compound used in the present invention include p-dihalobenzene, m-dihalobenzene, o-dihalobenzene, 2,5-dihalotoluene, 1,4-dihalonaphthalene, 1-methoxy-2,5-dihalobenzene, 4,4'-Dihalobiphenyl, 3,5-dihalobenzoic acid, 2,4-dihalobenzoic acid, 2,5-dihalonitrobenzene, 2,4-dihalonitrobenzene, 2,4-dihaloanisole, p , P′-dihalodiphenyl ether, 4,4′-dihalobenzophenone, 4,4′-di
  • p-dichlorobenzene from the viewpoint that the mechanical strength and moldability of the finally obtained polyarylene sulfide resin will be particularly excellent when the linear polyarylene sulfide resin is efficiently produced.
  • M-dichlorobenzene, 4,4'-dichlorobenzophenone and 4,4'-dichlorodiphenyl sulfone are preferred, and p-dichlorobenzene is particularly preferred.
  • 1,2,3-trihalobenzene and 1,2,4-trihalobenzene together with the above dihaloaromatic compound.
  • 1,3,5-trihalobenzene, 1,2,3,5-tetrahalobenzene, 1,2,4,5-tetrahalobenzene or 1,4,6-trihalonaphthalene in combination preferable.
  • the halogen atom contained in each of the above compounds is also preferably a chlorine atom or a bromine atom, and more preferably a chlorine atom.
  • the amount of the dihaloaromatic compound added is preferably 0.2 mol or more, more preferably 0.3 mol or more, preferably 5. It is in the range of 0 mol or less, more preferably 2.0 mol or less. If it is 0.2 mol or more, it is preferable from the viewpoint of securing the fluidity of the mixture, and if it is 5.0 mol or less, the total amount of heat necessary for heating can be suppressed, and it is preferable from the viewpoint of excellent productivity.
  • alkali metal sulfide or alkali metal hydrosulfide and alkali metal hydroxide can be mentioned.
  • alkali metal sulfides and alkali metal hydrosulfides are used as raw materials of polyarylene sulfide resin as so-called hydrates containing crystal water, and in that case, the solid content concentration is preferably 10% by mass.
  • the liquid or solid hydrate is used preferably in the range of 35% by mass or more, preferably 80% by mass or less, more preferably 65% by mass or less.
  • alkali metal sulfide used in the present invention examples include compounds such as lithium sulfide, sodium sulfide, potassium sulfide, rubidium sulfide and cesium sulfide. These may be used alone or in combination of two or more. Among these alkali metal sulfides, sodium sulfide and potassium sulfide are preferable, and sodium sulfide is particularly preferable.
  • alkali metal hydroxide examples include, for example, lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide and cesium hydroxide. Among these, lithium hydroxide and sodium hydroxide and potassium hydroxide are particularly preferable, and sodium hydroxide is particularly preferable.
  • the alkali metal hydroxide is preferably used as an aqueous solution, and its concentration is preferably in the range of 10% by mass to 50% by mass.
  • an alkali metal hydrosulfide used by this invention lithium hydrosulfide, sodium hydrosulfide, potassium hydrosulfide, rubidium hydrosulfide, cesium hydrosulfide etc. are mentioned, for example. These may be used alone or in combination of two or more.
  • sodium hydrosulfide and potassium hydrosulfide are preferable, and sodium hydrosulfide is particularly preferable.
  • an alkali metal hydrosulfide can also be obtained by reacting hydrogen sulfide with an alkali metal hydroxide, one prepared in advance outside the reaction system may be used.
  • N-methyl-2-pyrrolidone hereinafter sometimes abbreviated as NMP
  • N-cyclohexyl-2-pyrrolidone N-methyl- ⁇ -caprolactam
  • formamide acetamide
  • N-methylformamide N
  • N N
  • Aliphatic cyclic amide compounds such as -dimethylacetamide, 2-pyrrolidone, ⁇ -caprolactam, hexamethylphosphoramide, tetramethylurea, N-dimethylpropyleneurea, 1,3-dimethyl-2-imidazolidinonic acid, amidourea And lactams.
  • aliphatic cyclic amide compounds, particularly NMP are preferable in terms of good reactivity.
  • the amount of the aliphatic cyclic compound to be charged is preferably in the range of 0.01 mol or more and 4.0 mol or less with respect to 1 mol of sulfur atom of the sulfidizing agent, but it is more preferable.
  • it is preferably in the range of 0.01 or more, preferably in the range of 0.9 mol, more preferably 0. It is less than 9 moles, more preferably in the range of 0.5 moles or less.
  • the temperature of the solution is 90 ° C. or more, preferably 110 ° C. or more, more preferably 120 ° C. or more, and the sulfidizing agent containing water and the aliphatic cyclic compound capable of ring opening by hydrolysis.
  • the temperature of the solution is 90 ° C. or more, preferably 110 ° C. or more, more preferably 120 ° C. or more, and the sulfidizing agent containing water and the aliphatic cyclic compound capable of ring opening by hydrolysis.
  • the temperature of the solution is 90 ° C. or more, preferably 110 ° C. or more, more preferably 120 ° C. or more, and the sulfidizing agent containing water and the aliphatic cyclic compound capable of ring opening by hydrolysis.
  • the addition time of the dihaloaromatic compound is not particularly limited, but the dehydration progress is preferably 30% or more, more preferably 40% or more and 70% or less, more preferably More preferably, it is at a point in the range of 60% or less.
  • the degree of progress of dehydration is determined by measuring the total amount of water in the reaction system before the start of the dehydration step (1) and subtracting the total amount of water in the reaction system after the completion of the desired dehydration step (1)
  • the target moisture content of the distilled water (hereinafter referred to as the target distilled water content) is set, and the present moisture content of the distilled water according to the progress of dehydration in the dehydration step
  • the water content can be measured to obtain “current water content to be distilled” / “target water content to be distilled” ⁇ 100 (%).
  • an error range of ⁇ 20% shall be acceptable.
  • the isolated aliphatic cyclic compound, the aliphatic cyclic compound and the dihaloaromatic compound separated from water are preferably returned to the reaction system, but if not returned, they correspond to the azeotropically distilled amount. If an aliphatic cyclic compound or a dihaloaromatic compound is additionally charged, or after considering the azeotropically distilling amount, an excess of the aliphatic cyclic compound or the dihaloaromatic compound may be charged in advance. Good.
  • water is discharged out of the reaction system by dehydration treatment, and the aliphatic cyclic compound that can be opened by hydrolysis is hydrolyzed, and at the same time, an anhydrous sulfidizing agent
  • anhydrous sulfidizing agent Preferably, it is a process in which anhydrous alkali metal sulfide is formed. If excess water is present in the reaction system after dehydration treatment, a large amount of by-products are generated in the subsequent polymerization step to induce growth end termination reaction, and chain extension reaction of polyarylene sulfide resin, As a result, it tends to inhibit viscosity increase or high molecular weight formation.
  • the total water content in the reaction system after the dehydration step (1) be as small as possible. Specifically, it is preferably 0. 1 per mol of sulfur atoms of the sulfidizing agent used in the dehydration step (1).
  • the amount of water is in the range of more than 1 mol, more preferably 0.6 mol or more, preferably 0.99 mol or less, more preferably 0.96 mol or less.
  • the total water content in the reaction system refers to water consumed for hydrolysis of the aliphatic cyclic compound, crystal water remaining in a small amount in the sulfidizing agent, and other water present in the reaction system. It is the total mass of all.
  • the amount of water existing in the reaction system after the dehydration step (1) be in a range of 0.4 mol or less per 1 mol of sulfur atom of the sulfidizing agent in the reaction system. It is more preferable that the ratio be in the range of 0.4 mol or less from the limit, and it is further preferable that the ratio be in the range of 0.03 mol or more to 0.11 mol or less as a range excellent in the efficiency of dehydration.
  • the amount of water existing in the reaction system refers to water excluding water consumed for hydrolysis of the aliphatic cyclic compound out of the total amount of water in the reaction system, that is, water of crystallization, H 2
  • the total amount of water (hereinafter, these are called “crystal water, etc.”) actually present in the reaction system as O, etc. is said.
  • an optional aprotic polar organic solvent may be added to the mixture obtained in the dehydration step (1), and water may be distilled off to carry out dehydration as an optional step.
  • the charged amount of the aprotic polar solvent into the reaction system is preferably in the range of 0.5 mol or more and 5 mol or less with respect to 1 mol of sulfur atom of the sulfidizing agent Is preferably added. If the amount of water existing in the reaction system is within the range of less than 0.03 mol with respect to 1 mol of sulfur atom of the sulfidizing agent, the dehydrating efficiency tends to be greatly reduced.
  • the amount of water contained in the reaction system at the end of the dehydration step (2) relative to 1 mol of sulfur atoms of the sulfidizing agent can be adjusted in the range of less than 0.03 mol, preferably in the range of less than 0.03 mol from the detection limit, and more preferably, in the range of from the detection limit or more to 0.01 mol or less.
  • Dehydration in the dehydration step (2) can be carried out under the conditions where the liquid temperature is in the range of 90 ° C. to 220 ° C., and in the range of 30 kPa abs to 202 kPa abs.
  • the liquid temperature is preferably 90 ° C. or more, more preferably 110 ° C. or more, still more preferably 130 ° C. or more to 160 ° C. or less Is preferably 30 kPa abs or more, more preferably 35 kPa abs or more, and still more preferably 40 kPa abs or more, preferably 80 kPa while heating to a temperature of 150 ° C. or less. abs] or less, more preferably 70 [kPa abs] or less, still more preferably 60 [kPa abs] or less From the viewpoint of performing the dehydration while the pressure was reduced it can be efficiently dehydrated at lower liquid temperature.
  • the mixture obtained through the dehydration step (1) is heated in the range of 0.4 mol or less of the existing water content in the reaction system to 1 mol of the dihaloaromatic compound.
  • a polymerization step to cause a polymerization reaction.
  • dehydration step (2) is performed after dehydration step (1), the mixture obtained through dehydration step (2) is present in the reaction system relative to 1 mol of dihaloaromatic compound.
  • the polymerization reaction can be carried out by heating in the range of less than 0.03 mol of water content.
  • the polymerization reaction proceeds by heating the mixture obtained through the dehydration step (1) to the dehydration step (2) to a range of 200 ° C. or more and 300 ° C. or less in a closed reaction vessel. Process.
  • the polymerization reaction conditions are not particularly limited, but a temperature at which the polymerization reaction can easily proceed, that is, a range of 200 ° C. or more and 300 ° C. or less, preferably 210 ° C. or more and 280 ° C. or less, More preferably, the reaction is performed in the range of 215 ° C. or more and 250 ° C. or less.
  • the dihaloaromatic compound which is the polymerization raw material is charged azeotropically by distillation in addition to being charged in the dehydration step (1), the dihaloaromatic compound is taken into consideration after considering the amount to be azeotropically distilled off.
  • the compound of the group is previously charged in excess in the dehydration step, or the dihaloaromatic compound is additionally charged until the polymerization step is started, and the ratio of the dihaloaromatic compound in the reaction system is the sulfur atom of the sulfidizing agent It is preferably in the range of preferably 0.8 mol or more, more preferably 0.9 mol or more, preferably 1.2 mol or less, more preferably 1.1 mol or less, particularly preferably equimolar to 1 mol. Adjust for reaction.
  • the amount of water existing in the reaction system at the start of polymerization is preferably as small as possible, for example, in the range of 0.4 mol or less, preferably in the range of the detection limit (mol) or less per 1 sulfur atom of the sulfidizing agent. It is preferably in the range of 0.4 mol or less, more preferably 0.11 mol or less, still more preferably 0.08 mol or less, particularly preferably 0.03 mol or less, most preferably 0.01 mol or less.
  • water is produced, so that at the end of the polymerization reaction of the polymerization step, water is produced in the range of 0.1 mol or more and 0.3 mol or less per mol of sulfur atom of the sulfidizing agent.
  • the above range is preferably satisfied after the point at which the conversion of the dihaloaromatic compound exceeds 80% by mole, more preferably after the point at which the conversion of the dihaloaromatic compound exceeds 60% by mole, more preferably immediately after the start of the polymerization.
  • Conversion rate (%) (charged amount-residual amount) / charged amount ⁇ 100
  • the amount charged represents the mass of the dihaloaromatic compound charged into the reaction system
  • the “remaining amount” represents the mass of the dihaloaromatic compound remaining in the reaction system.
  • the reaction mixture containing the polyarylene sulfide resin obtained by the polymerization reaction can be subjected to a post-treatment step.
  • the post-treatment step may be any known method and is not particularly limited. For example, after completion of the polymerization reaction, the reaction mixture is first added as it is or after adding an acid or a base, under reduced pressure or normal pressure.
  • the solvent is distilled off with water, and the solid after evaporation is washed once or twice or more with a solvent such as water, acetone, methyl ethyl ketone or alcohols, followed by neutralization, water washing, filtration and drying, or After completion of the polymerization reaction, the reaction mixture contains a solvent such as water, acetone, methyl ethyl ketone, alcohols, ethers, halogenated hydrocarbons, aromatic hydrocarbons, aliphatic hydrocarbons (soluble in the polymerization solvent used, and Solid solvent such as polyarylene sulfide resin and inorganic salt by adding at least a solvent which is a poor solvent to polyarylene sulfide resin as a precipitant The product was precipitated, and these were separated by filtration, washed and dried, or after completion of the polymerization reaction, the reaction mixture was added with a reaction solvent (or an organic solvent having equivalent solubility to a low molecular weight polymer) and stirred.
  • the drying of the polyarylene sulfide resin may be performed in vacuum, or may be performed in the air or in an inert gas atmosphere such as nitrogen.
  • the polyarylene sulfide resin thus obtained can be used as it is for various molding materials and the like, but may be oxidized and crosslinked by heat treatment in air or oxygen-enriched air or under reduced pressure conditions.
  • the temperature of the heat treatment is preferably in the range of 180 ° C. or more to 270 ° C. or less, although it varies depending on the target crosslinking treatment time and the treatment atmosphere.
  • the heat treatment may be carried out in a molten state of the polyarylene sulfide resin at a temperature above the melting point of the polyarylene sulfide resin using an extruder or the like, but the possibility of thermal degradation of the polyarylene sulfide resin is increased. It is preferable to carry out at a temperature of 100 ° C. or less.
  • the reaction device used in each of the above steps in the method for producing a polyarylene sulfide resin of the present invention is a raw material, that is, a dihaloaromatic compound, a sulfidizing agent, an alkali catalyst, etc. Part, or all, of the contact portion with the group cyclic compound, the mixture obtained through the dehydration step, and the polymerization reactant including the polyarylene sulfide resin obtained after the polymerization reaction is composed of titanium, zirconium or nickel alloy It is preferable from the viewpoint of corrosion resistance to use the same.
  • reaction apparatus examples include batch type reaction containers (autoclave, reaction kettle) equipped with stirring blades inside, reaction containers (polymerization line) such as continuous reaction containers, stirring blades, baffles and the like.
  • the batch type reaction vessel may be any vessel capable of holding the raw material, the mixture or the polymerization reaction inside the reaction vessel, and is composed of, for example, a top cover, a body and a bottom, and if necessary
  • a structure having a sealable structure and a structure having a stirring blade, an axis transmitting power to the stirring blade, a baffle plate, and a temperature control serpentine inside is preferable from the viewpoint of excellent stirring efficiency.
  • a stirring blade an anchor type stirring blade, a turbine type stirring blade, a screw type stirring blade, a double helical type stirring blade, etc. are mentioned. It is preferable from the viewpoint of facilitating heat conduction and heat control that the lower end of the baffle plate is installed near the bottom surface of the reaction vessel and the upper end of the baffle plate is extended to the position where it comes out of the liquid surface.
  • the continuous reaction vessel includes, for example, a tubular reactor in which a plurality of mixing elements without moving parts are fixed, a polymerization line in which the tubular reactors are connected in series, or a plurality of tubulars What forms a continuous annular polymerization line which has a structure which connects a reactor and circulates a part of reaction liquid to the raw material inlet of the said tubular reactor is mentioned.
  • These continuous reaction containers can feed raw materials and transfer reaction liquid by a plunger pump or the like.
  • reaction vessel is further equipped with various measuring devices such as a thermometer, a pressure gauge, a safety valve and the like, and the piping and the open / close valve leading to the steam device outside thereof, a condenser, a decanter, a distillate (a decanter Organic layer component) Distillation equipment such as return line, distillate (water layer component of decanter) distillation line, and pressure reduction valve such as pressure control valve, vacuum pump, hydrogen sulfide capture device, etc. Is preferred.
  • various measuring devices such as a thermometer, a pressure gauge, a safety valve and the like, and the piping and the open / close valve leading to the steam device outside thereof, a condenser, a decanter, a distillate (a decanter Organic layer component) Distillation equipment such as return line, distillate (water layer component of decanter) distillation line, and pressure reduction valve such as pressure control valve, vacuum pump, hydrogen sulfide capture device, etc. Is preferred.
  • the contact portion may preferably be composed entirely of the nickel alloy.
  • the nickel alloy used herein preferably has a chromium content in the range of 43% to 47% by mass, and a molybdenum content in the range of 0.1% to 2% by mass. And the remainder is an alloy composed of nickel and unavoidable impurities.
  • Tungsten, iron, cobalt and copper preferably have a content below the detection limit.
  • the term "unavoidable impurities” means a trace amount of impurities which are technically difficult to remove.
  • a carbon atom contained in the alloy in a proportion of 3% by mass or less, preferably 1% by mass or less, more preferably the detection limit or less is mentioned.
  • the polyarylene sulfide resin obtained by the manufacturing method of the present invention described in detail above includes a filler, a thermoplastic resin other than the polyarylene sulfide resin, an elastomer, a crosslinkable resin having two or more functional groups, At least one other component selected from the group consisting of silane coupling agents is compounded, and heated to a temperature equal to or higher than the melting point of the polyarylene sulfide resin, and then melt-kneaded through the process of polyarylene sulfide resin composition It can be done.
  • a fibrous filler for example, a fibrous filler, an inorganic filler, etc. are mentioned.
  • fibrous fillers include glass fibers, carbon fibers, silane glass fibers, ceramic fibers, aramid fibers, metal fibers, fibers such as potassium titanate, silicon carbide, calcium sulfate and calcium silicate, and natural fibers such as wollastonite Can be used.
  • inorganic filler barium sulfate, calcium sulfate, clay, viroferrite, bentonite, sericite, zeolite, mica, mica, mica, talc, atalpulgite, ferrite, calcium silicate, calcium carbonate, magnesium carbonate, glass beads, etc. It can be used.
  • various additives such as a mold release agent, a colorant, a heat resistant stabilizer, an ultraviolet light stabilizer, a foaming agent, a rust inhibitor, a flame retardant, a lubricant and the like can be contained as an additive during molding processing.
  • blended with the polyarylene sulfide resin composition of this invention polyester, a polyamide, a polyimide, a polyether imide, a polycarbonate, a polyphenylene ether, a polysulfone, a polyether sulfone , Polyetheretherketone, polyetherketone, polyarylene, polyethylene, polypropylene, polytetrafluorinated ethylene, polydifluorinated ethylene, polystyrene, ABS resin, epoxy resin, silicone resin, silicone resin, phenolic resin, urethane resin, liquid crystal polymer, etc.
  • the proportion of the thermoplastic resin other than the polyarylene sulfide resin is preferably 1 part by mass or more, more preferably 3 parts by mass or more, and still more preferably 5 parts by mass or more with respect to 100 parts by mass of the polyarylene sulfide resin.
  • the amount is preferably 300 parts by mass or less, more preferably 100 parts by mass or less, still more preferably 45 parts by mass or less.
  • thermoplastic elastomer As an elastomer mixed with the polyarylene sulfide resin composition of the present invention, it is mentioned that a thermoplastic elastomer is used.
  • thermoplastic elastomers include polyolefin elastomers, fluorine elastomers and silicone elastomers. In the present specification, thermoplastic elastomers are classified not into the thermoplastic resin but into elastomers.
  • the elastomer (especially the thermoplastic elastomer) preferably has a functional group capable of reacting with a hydroxy group or an amino group.
  • a functional group capable of reacting with a hydroxy group or an amino group.
  • Such functional groups include epoxy group, carboxy group, isocyanate group, oxazoline group, and the formula: R (CO) O (CO)-or R (CO) O- (wherein R represents one or more carbon atoms) And a group represented by the following 8 alkyl groups:
  • the thermoplastic elastomer having such a functional group can be obtained, for example, by copolymerization of an ⁇ -olefin and a vinyl polymerizable compound having the above functional group.
  • Examples of the ⁇ -olefins include ⁇ -olefins in the range of 2 to 8 carbon atoms such as ethylene, propylene and butene-1.
  • Examples of the vinyl polymerizable compound having a functional group include, for example, ⁇ , ⁇ -unsaturated carboxylic acids such as (meth) acrylic acid and (meth) acrylic acid esters and alkyl esters thereof, maleic acid, fumaric acid, itaconic acid and the like.
  • Other ⁇ , ⁇ -unsaturated dicarboxylic acids having 4 to 10 carbon atoms and derivatives thereof (mono- or di-esters and acid anhydrides thereof), glycidyl (meth) acrylates and the like can be mentioned.
  • an epoxy group a carboxy group, and a formula: R (CO) O (CO)-or R (CO) O-(wherein R represents an alkyl group having a carbon number of 1 to 8).
  • Ethylene-propylene copolymers and ethylene-butene copolymers having at least one functional group selected from the group consisting of groups represented by) are preferable from the viewpoint of improvement in toughness and impact resistance.
  • the proportion of the elastomer varies depending on the type and application, but can not be generally defined, but for example, preferably 1 part by mass or more, more preferably 3 parts by mass or more, with respect to 100 parts by mass of the polyarylene sulfide resin.
  • the amount is preferably in the range of 5 parts by mass or more, preferably 300 parts by mass or less, more preferably 100 parts by mass or less, and still more preferably 45 parts by mass or less. When the content of the elastomer is in these ranges, an even more excellent effect can be obtained in securing the heat resistance and the toughness of the molded article.
  • the crosslinkable resin blended in the polyarylene sulfide resin composition has two or more functional groups.
  • the functional group include epoxy group, phenolic hydroxyl group, amino group, amido group, carboxy group, acid anhydride group, and isocyanate group.
  • an epoxy resin, a phenol resin, and a urethane resin are mentioned, for example.
  • the compounding amount of the crosslinkable resin is preferably 1 part by mass or more, more preferably 3 parts by mass or more, still more preferably 5 parts by mass or more, preferably 300 parts by mass or less with respect to 100 parts by mass of the polyarylene sulfide resin. It is more preferably in the range of 100 parts by mass or less, still more preferably 30 parts by mass or less. When the compounding amount of the crosslinkable resin is in these ranges, the effect of improving the rigidity and heat resistance of the molded article can be particularly remarkably obtained.
  • silane coupling agent blended with the polyarylene sulfide resin composition of the present invention for example, ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -glycidoxypropyltriethoxysilane, ⁇ - (3,4-epoxy) Examples include cyclohexyl) ethyltrimethoxysilane, ⁇ -glycidoxypropylmethyldiethoxysilane, and ⁇ -glycidoxypropylmethyldimethoxysilane.
  • the compounding amount of the silane compound is, for example, preferably 0.01 parts by mass or more, more preferably 0.1 parts by mass or more, preferably 10 parts by mass or less, more preferably 100 parts by mass of the polyarylene sulfide resin. It is a range of 5 parts by mass or less. When the compounding quantity of a silane compound exists in these ranges, the effect of the compatibility improvement with polyarylene sulfide resin and said other component is acquired.
  • the polyarylene sulfide resin composition of the present invention may further contain other additives such as a mold release agent, a colorant, a heat resistant stabilizer, an ultraviolet light stabilizer, a foaming agent, a rust inhibitor, a flame retardant and a lubricant.
  • additives such as a mold release agent, a colorant, a heat resistant stabilizer, an ultraviolet light stabilizer, a foaming agent, a rust inhibitor, a flame retardant and a lubricant.
  • the compounding quantity of an additive is the range of 1 mass part or more and 10 mass parts or less with respect to 100 mass parts of polyarylene sulfide resin, for example.
  • the polyarylene sulfide resin composition can be obtained, for example, in the form of a pellet-like compound or the like by a method of melt-kneading the polyarylene sulfide resin obtained by the above method and the other components.
  • the temperature of the melt-kneading is, for example, preferably in the range of 250 ° C. or more, more preferably 290 ° C. or more, preferably 350 ° C. or less, more preferably 330 ° C. or less.
  • Melt-kneading can be performed using a twin-screw extruder etc.
  • the polyarylene sulfide resin composition according to the present embodiment may be melt-formed by various melt processing methods such as injection molding, extrusion molding, compression molding and blow molding alone or in combination with materials such as the other components. Thus, it can be processed into a molded article excellent in heat resistance, moldability, dimensional stability and the like. Since the polyarylene sulfide resin composition of the present invention has a low metal content, it enables easy production of high-quality molded articles, particularly thin-walled molded articles excellent in insulation.
  • the polyarylene sulfide resin obtained by the production method of the present invention and the composition thereof also have various properties such as the inherent heat resistance and dimensional stability of the polyarylene sulfide resin, and thus, for example, connectors, printed boards and seals Electrical and electronic parts such as molded parts, automobile parts such as lamp reflectors and various electric parts, interior materials for various buildings, aircrafts and automobiles, or precision parts such as office equipment parts, camera parts and watch parts It is widely useful as a material for various molding processes such as injection molding or compression molding, or extrusion molding of composites, sheets, pipes and the like, or pultrusion, or as materials for fibers or films.
  • various molding processes such as injection molding or compression molding, or extrusion molding of composites, sheets, pipes and the like, or pultrusion, or as materials for fibers or films.
  • Measurement by gas chromatograph is performed by Shimadzu gas chromatography “GC 2014” (column: column “G300” manufactured by Chemical Substances Evaluation Research Corporation, carrier gas: helium, measurement column conditions: 140 ° C. for 5 minutes ⁇ 3 ° C.) Temperature / 200 ° C. for 20 minutes).
  • GC 2014 Shimadzu gas chromatography
  • column “G300” manufactured by Chemical Substances Evaluation Research Corporation
  • carrier gas helium
  • measurement column conditions 140 ° C. for 5 minutes ⁇ 3 ° C.
  • Temperature / 200 ° C. for 20 minutes In order to determine the phenol concentration, first, a standard curve was prepared with a standard sample. Next, a peak area of the same retention time as that of the standard sample was obtained from the chromatogram obtained by measuring the supernatant prepared above.
  • the concentration in the solution was determined from the peak area and the calibration curve, and the number of moles of phenol was calculated as a percentage per 1 mole of sulfide agent (1 mole of sulfur atoms in total) (hereinafter "mol% / S" ).
  • the water content was measured by a Karl Fischer volumetric titration method using a Karl Fischer moisture measuring device (AQV-300 manufactured by Hiranuma Sangyo Co., Ltd.).
  • the detection limit is 6.0 ⁇ 10 ⁇ 6 mol with respect to 1 mol of sulfur atom.
  • Example 1 Dehydration process (1) Thermometer, heating device, titanium stirring blade and pressure gauge, raw material (pDCB) storage tank, raw material (NMP) storage tank, decompression device (pressure control valve, vacuum pump and recovery device of scattered hydrogen sulfide) and distillation
  • pDCB raw material
  • NMP raw material storage tank
  • decompression device pressure control valve, vacuum pump and recovery device of scattered hydrogen sulfide
  • distillation To an autoclave made of a nickel alloy (Ni-Cr-Mo alloy containing 45% by mass of chromium, 1% by mass of molybdenum and 1% by mass of molybdenum) connected to the apparatus (refraction column, condenser and decanter) respectively , NMP 29.7 parts by mass (0.3 molar parts), 45 wt% NaSHaq.
  • Ni-Cr-Mo alloy Ni-Cr-Mo alloy containing 45% by mass of chromium, 1% by mass of molybdenum and 1%
  • p-DCB dichlorobenzene
  • the autoclave containing the mixture obtained in the dehydration step was placed under a nitrogen atmosphere, and the valve was closed to seal the reaction system.
  • the liquid temperature was set to 160 ° C., 415.8 parts by mass (4.2 mol parts) of NMP previously set in the raw material storage tank was opened by a valve leading to the raw material storage tank, pumped out from the piping and charged in the autoclave . Then, the temperature was raised to 220 ° C. and stirred for 2 hours, and then the temperature was raised to 250 ° C. and stirred for 1 hour.
  • the final pressure was 373 [kPa abs]. Then, it cooled to room temperature.
  • the autoclave containing the mixture obtained in the dehydration step was placed under a nitrogen atmosphere, and the valve was closed to seal the reaction system.
  • the liquid temperature was set to 160 ° C., 415.8 parts by mass (4.2 mol parts) of NMP previously set in the raw material storage tank was opened by a valve leading to the raw material storage tank, pumped out from the piping and charged in the autoclave . Then, the temperature was raised to 220 ° C. and stirred for 2 hours, and then the temperature was raised to 250 ° C. and stirred for 1 hour.
  • the final pressure was 373 [kPa abs]. Then, it cooled to room temperature.
  • the valve of the pipe from the autoclave to the distillation apparatus was closed to complete the dehydration.
  • the inside of the autoclave after the dehydration reaction was in a slurry state in which a particulate anhydrous sodium sulfide composition was dispersed in DCB, and the remaining amount of water was 0.31 mol per 1 mol of sulfur atoms present in the autoclave.
  • the melt viscosity of the obtained PPS resin was 65 Pa ⁇ s
  • the amount of phenol produced was 0.1 mol%
  • the total metal content of chromium, molybdenum and nickel was 23 ppm.
  • the valve of the pipe from the autoclave to the distillation apparatus was closed to complete the dehydration.
  • the total amount of total water distilled out of the system by dehydration was 49.4 parts by mass.
  • the inside of the autoclave after the dehydration reaction was in a slurry state in which particulate anhydrous sodium sulfide composition was dispersed in DCB, and the remaining amount of water was 3 moles per 1 sulfur atom in the autoclave.
  • Example 2 The part to be “an autoclave whose inner wall (wetted part) is a nickel alloy (Ni-Cr-Mo alloy containing 45% by mass of chromium, 1% by mass of molybdenum and the remainder of nickel)” is The same procedure as in Example 1 was performed except that "the inner wall (wetted portion) was an autoclave made of titanium".
  • the valve of the pipe from the autoclave to the distillation apparatus was closed to complete the dehydration.
  • the inside of the autoclave after the dehydration reaction was in the form of a slurry in which fine particulate anhydrous sodium sulfide composition was dispersed in DCB, and the remaining amount of water was 0.29 mol per mol of sulfur atoms present in the autoclave.
  • the melt viscosity of the obtained PPS resin was 67 Pa ⁇ s
  • the amount of phenol produced was 0.08 mol%
  • the metal content of titanium was below the detection limit value.
  • the valve of the pipe from the autoclave to the distillation apparatus was closed to complete the dehydration.
  • the inside of the autoclave after the dehydration reaction was in the form of a slurry in which fine particulate anhydrous sodium sulfide composition was dispersed in DCB, and the remaining amount of water was 0.27 moles per mole of sulfur atoms present in the autoclave.
  • the melt viscosity of the obtained PPS resin was 65 Pa ⁇ s
  • the amount of phenol produced was 0.09 mol%
  • the metal content of titanium was 5 ppm.
  • Comparative example 4 The part to be “an autoclave whose inner wall (wetted part) is a nickel alloy (Ni-Cr-Mo alloy containing 45% by mass of chromium, 1% by mass of molybdenum and the remainder of nickel)” is The same procedure as in Comparative Example 2 was followed except that "the inner wall (wetted portion) was an autoclave made of titanium".
  • the valve of the pipe from the autoclave to the distillation apparatus was closed to complete the dehydration.
  • the total amount of total water distilled out of the system by dehydration was 50.2 parts by mass.
  • the inside of the autoclave after the dehydration reaction was in a slurry state in which a particulate anhydrous sodium sulfide composition was dispersed in DCB, and the remaining amount of water was 2.8 moles per mole of sulfur atoms present in the autoclave.
  • Example 3 "Then, the valve of the pipe leading from the autoclave to the distillation apparatus is opened, dehydration is started under atmospheric pressure, and the temperature is raised to a liquid temperature of 128 ° C.” "After that, the valve of the pipe leading from the autoclave to the distillation apparatus was opened, dehydration was started under atmospheric pressure, and the liquid temperature was raised to 105 ° C.”, "Next, while continuing the dewatering, open the valve of the piping that leads to the decompression device, and reduce the pressure from atmospheric pressure to 47 [kPa abs] at a rate of -6.6 [kPa abs] / min and The temperature of the solution was gradually raised to 147 ° C.
  • the valve of the pipe from the autoclave to the distillation apparatus was closed to complete the dehydration.
  • the inside of the autoclave after the dehydration reaction was in a slurry state in which a particulate anhydrous sodium sulfide composition was dispersed in DCB, and the remaining amount of water was 0.3 mol per 1 sulfur atom present in the autoclave.
  • the melt viscosity of the obtained PPS resin is 62 Pa ⁇ s
  • the amount of phenol produced is 0.1 mol%
  • the total metal content of chromium, molybdenum and nickel is below the detection limit
  • Example 4 "Next, while continuing the dewatering, open the valve of the piping that leads to the decompression device, and reduce the pressure from atmospheric pressure to 47 [kPa abs] at a rate of -6.6 [kPa abs] / min and The temperature of the solution was gradually raised to 147 ° C. at a rate of 0.1 ° C./min, and finally the portion was dehydrated while maintaining the solution temperature of 147 ° C. at 47 kPa abs.
  • the valve of the pipe from the autoclave to the distillation apparatus was closed to complete the dehydration.
  • the inside of the autoclave after the dehydration reaction was in a slurry state in which a particulate anhydrous sodium sulfide composition was dispersed in DCB, and the remaining amount of water was 0.3 mol per 1 sulfur atom present in the autoclave.
  • the melt viscosity of the obtained PPS resin is 65 Pa ⁇ s
  • the amount of phenol produced is 0.09 mol%
  • the total metal content of chromium, molybdenum and nickel is below the detection limit value

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne un procédé de fabrication de résine de sulfure de polyarylène selon lequel un composé dihalogéno-aromatique et un agent de sulfuration sont mis en réaction de polymérisation, en présence d'un composé cyclique aliphatique permettant une ouverture de cycle par hydrolyse, et selon lequel la corrosion d'un dispositif de fabrication est évitée, et la teneur en atomes métalliques provenant du dispositif de fabrication dans la résine de sulfure de polyarylène obtenue, est réduite. Plus précisément, l'invention fournit un procédé de fabrication de résine de sulfure de polyarylène qui présente une étape de déshydratation (1) au cours de laquelle l'agent de sulfuration qui contient de l'eau et le composé cyclique aliphatique permettant une ouverture de cycle par hydrolyse sont mis en réaction simultanément à une déshydratation, la température de liquide se trouvant dans une plage supérieure ou égale à 90°C et inférieure ou égale à 150°C, sous une pression dans une plage supérieure ou égale à ３０〔ｋＰａ ａｂｓ〕 et inférieure ou égale à la pression atmosphérique, puis, le composé dihalogéno-aromatique est ajouté, un chauffage est effectué dans une plage de température de liquide supérieure ou égale à 90°C et inférieure ou égale à 170°C, une réaction à lieu simultanément à une déshydratation dans une plage de pression supérieure ou égale à ３０〔ｋＰａ ａｂｓ〕 et inférieure ou égale à ８０〔ｋＰａ ａｂｓ〕, et un mélange est obtenu.
PCT/JP2018/024119 2017-06-29 2018-06-26 Procédé de fabrication de résine de sulfure de polyarylène WO2019004170A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2019526915A JP6866923B2 (ja) 2017-06-29 2018-06-26 ポリアリーレンスルフィド樹脂の製造方法

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2017-127441 2017-06-29
JP2017127441 2017-06-29
JP2018070828 2018-04-02
JP2018-070828 2018-04-02

Publications (1)

Publication Number Publication Date
WO2019004170A1 true WO2019004170A1 (fr) 2019-01-03

Family

ID=64741596

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2018/024119 WO2019004170A1 (fr) 2017-06-29 2018-06-26 Procédé de fabrication de résine de sulfure de polyarylène

Country Status (2)

Country Link
JP (1) JP6866923B2 (fr)
WO (1) WO2019004170A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US12018129B2 (en) 2022-09-06 2024-06-25 Ticona Llc Extraction technique for recovering an organic solvent from a polyarylene sulfide waste sludge

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6123627A (ja) * 1984-07-11 1986-02-01 Kureha Chem Ind Co Ltd ポリアリーレンスルフィドの製造法
JPH0245531A (ja) * 1988-08-05 1990-02-15 Idemitsu Petrochem Co Ltd ポリアリーレンスルフィドの製造方法
JPH0335023A (ja) * 1989-06-30 1991-02-15 Idemitsu Petrochem Co Ltd ポリアリーレンスルフィドの製造方法
JPH09278888A (ja) * 1996-04-16 1997-10-28 Idemitsu Petrochem Co Ltd ポリアリーレンスルフィド製造用機器およびそれを用いたポリアリーレンスルフィドの製造方法
WO2010058713A1 (fr) * 2008-11-21 2010-05-27 Dic株式会社 Procédé de fabrication d'une résine de poly(sulfure d'arylène)

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6123627A (ja) * 1984-07-11 1986-02-01 Kureha Chem Ind Co Ltd ポリアリーレンスルフィドの製造法
JPH0245531A (ja) * 1988-08-05 1990-02-15 Idemitsu Petrochem Co Ltd ポリアリーレンスルフィドの製造方法
JPH0335023A (ja) * 1989-06-30 1991-02-15 Idemitsu Petrochem Co Ltd ポリアリーレンスルフィドの製造方法
JPH09278888A (ja) * 1996-04-16 1997-10-28 Idemitsu Petrochem Co Ltd ポリアリーレンスルフィド製造用機器およびそれを用いたポリアリーレンスルフィドの製造方法
WO2010058713A1 (fr) * 2008-11-21 2010-05-27 Dic株式会社 Procédé de fabrication d'une résine de poly(sulfure d'arylène)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US12018129B2 (en) 2022-09-06 2024-06-25 Ticona Llc Extraction technique for recovering an organic solvent from a polyarylene sulfide waste sludge

Also Published As

Publication number Publication date
JPWO2019004170A1 (ja) 2020-03-26
JP6866923B2 (ja) 2021-04-28

Similar Documents

Publication Publication Date Title
JP4761173B2 (ja) ポリアリ−レンスルフィド樹脂の製造方法
JP4296527B2 (ja) 酸基含有ポリアリ−レンスルフィド樹脂の製造方法
KR101759185B1 (ko) 블로우 중공 성형품용 수지 조성물, 블로우 중공 성형품 및 제조 방법
KR101324269B1 (ko) 폴리아릴렌설피드 수지의 제조 방법
JP4953020B2 (ja) ポリアリ−レンスルフィド樹脂の製造方法
JP5012131B2 (ja) ポリアリーレンスルフィド樹脂の製造方法
JP6866924B2 (ja) ポリアリーレンスルフィド樹脂の製造方法
JP6939882B2 (ja) ポリアリーレンスルフィド樹脂の製造方法
JP6866923B2 (ja) ポリアリーレンスルフィド樹脂の製造方法
JP6808926B2 (ja) ポリアリーレンスルフィド樹脂の製造方法
JP7172020B2 (ja) ポリアリーレンスルフィド樹脂の製造方法
JP6691660B2 (ja) ポリアリーレンスルフィド樹脂の製造方法
JP2018154691A (ja) ポリアリーレンスルフィド樹脂の製造方法
JP6972591B2 (ja) ポリアリーレンスルフィド樹脂の製造方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 18822837

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2019526915

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 18822837

Country of ref document: EP

Kind code of ref document: A1