WO2023053529A1 - Procédé de production de résine de poly (sulfure d'arylène), résine de poly(sulfure d'arylène), composition de résine de poly (sulfure d'arylène) et article moulé en résine de poly(sulfure d'arylène) - Google Patents

Procédé de production de résine de poly (sulfure d'arylène), résine de poly(sulfure d'arylène), composition de résine de poly (sulfure d'arylène) et article moulé en résine de poly(sulfure d'arylène) Download PDF

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WO2023053529A1
WO2023053529A1 PCT/JP2022/013800 JP2022013800W WO2023053529A1 WO 2023053529 A1 WO2023053529 A1 WO 2023053529A1 JP 2022013800 W JP2022013800 W JP 2022013800W WO 2023053529 A1 WO2023053529 A1 WO 2023053529A1
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polyarylene sulfide
pas resin
sulfide resin
resin
test piece
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PCT/JP2022/013800
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English (en)
Japanese (ja)
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拓 茨木
まい 池田
高志 古沢
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Dic株式会社
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Priority to JP2022547720A priority Critical patent/JP7228109B1/ja
Publication of WO2023053529A1 publication Critical patent/WO2023053529A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
    • C08G75/02—Polythioethers
    • C08G75/0204—Polyarylenethioethers
    • C08G75/025—Preparatory processes
    • C08G75/0259—Preparatory processes metal hydrogensulfides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
    • C08G75/02—Polythioethers
    • C08G75/0204—Polyarylenethioethers
    • C08G75/0277—Post-polymerisation treatment
    • C08G75/0281—Recovery or purification
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
    • C08G75/02—Polythioethers
    • C08G75/0204—Polyarylenethioethers
    • C08G75/0286—Chemical after-treatment
    • C08G75/029—Modification with organic compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • 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 method for producing a polyarylene sulfide resin, a polyarylene sulfide resin, a polyarylene sulfide resin composition, and a polyarylene sulfide resin molded product.
  • PAS resins Polyarylene sulfide resins
  • PPS resins polyphenylene sulfide resins
  • the PAS resin used for the above applications maximizes its functions by combining various additives such as glass fibers, fillers, elastomers, and the like. Therefore, controlling the interfacial reactivity between an additive such as glass fiber and the PAS resin and the reactivity between the elastomer and the PAS resin is an essential technology for the functional expression of the obtained PAS resin (parts).
  • Patent Literature 1 discloses a technique related to a PAS resin having higher reactivity with epoxysilane than conventional PAS resins.
  • the functional group at the molecular end of the PAS resin which is a factor that greatly contributes to the reactivity of the interface between the PAS resin and a different material, is not studied at all.
  • the PAS resin has a unique circumstance that it is polymerized at a high temperature of 200° C. or higher and under a high pressure. As a result, many side reactions occur during the polymerization of the PAS resin, resulting in the presence of various functional groups at the molecular ends of the PAS resin, which greatly contribute to the reactivity.
  • the high heat resistance/chemical resistance of PAS resins limits the analytical prescriptions, and the present situation is that the amounts of various functional groups have not yet been quantified.
  • controlling the reactivity of the interface between the PAS resin and different materials by the molecular terminal structure of the PAS resin is a technique with a very high barrier, but various applications are expected, so it is requested by various technical fields. It is a technology that is being used.
  • the present invention provides a PAS resin molded article having excellent mechanical strength, particularly tensile strength, and small variation in physical properties between lots, a highly reactive resin and resin composition constituting the article, and furthermore,
  • the object is to provide a manufacturing method.
  • the present inventors have made intensive research and repeated experiments.
  • the above problems can be solved by using a specific polyarylene sulfide resin evaluated by the zeta potential value according to the streaming potential method under specific conditions.
  • the present invention comprises a step (1) of polymerizing a PAS resin, A method for producing a PAS resin, comprising the steps (2) of purifying the PAS resin to prepare a purified PAS resin, and (3) evaluating a test piece formed from at least a portion of the purified PAS resin.
  • the step (3) is a test piece preparation step (3-1) in which the test piece is obtained by solidifying the molten PAS resin obtained by melting the purified PAS resin;
  • a method for producing a PAS resin, comprising a discrimination step (3-3) of discriminating a PAS resin having a zeta potential value in the range of -50 to -65 mV as measured in the step (3-2).
  • the present invention is a PAS resin whose surface zeta potential value of the test piece at pH 7.8 to 8.2 is in the range of -50 to -65 mV.
  • the present invention provides a PAS resin having a surface zeta potential value in the range of -50 to -65 mV, wherein the surface zeta potential value is measured from a test piece having at least a portion of the PAS resin.
  • a PAS resin having a zeta potential value on the surface of the test piece at pH 7.8 to 8.2 in the range of -50 to -65 mV and a substance having a reactive functional group are blended, It is a PAS resin composition.
  • the molded article of the present invention is obtained by melt-molding the PAS resin composition described above.
  • the PAS resin obtained by the production method according to any one of claims 1 to 3 and a substance having a reactive functional group are blended and melted. Having a kneading step, and The zeta potential value of the surface of the test piece at pH 7.8 to 8.2 of the PAS resin is in the range of -50 to -65 mV.
  • the method for producing a molded product of the present invention is characterized by including the step of melt-molding the PAS resin composition obtained by the production method described above.
  • the present invention by quantifying and determining the surface characteristics of the PAS resin with high accuracy, it is possible to obtain a resin having specific reactivity with higher accuracy than in the past.
  • the resin by using the resin, it is possible to provide a PAS molded article having less variation in physical properties, excellent mechanical strength, particularly excellent tensile strength, a resin composition constituting the PAS molded article, and a method for producing the same.
  • FIG. 1 is a schematic diagram showing an example of a method for measuring zeta potential by streaming potential method.
  • the method for producing a PAS resin according to the present embodiment includes a step (1) of polymerizing a PAS resin, a step (2) of purifying the PAS resin to prepare a purified PAS resin, and the purification step. and a step (3) of evaluating a test piece made from at least a portion of the purified PAS resin.
  • the step (3) comprises a test piece preparation step (3-1) in which the purified PAS resin is melted to prepare a molten PAS resin, and then the molten PAS resin is solidified to obtain the test piece;
  • the method for producing a PAS resin of the present embodiment for the purpose of evaluating the surface properties of the obtained PAS resin, after preparing a test piece as an evaluation sample from at least a part of the PAS resin, the By measuring the zeta potential of the test piece, the surface characteristics of the obtained PAS resin are grasped. As a result, it is possible to quantify the surface characteristics of the PAS resin with high accuracy, so that it is possible to identify resins having more uniform reactivity than conventional methods. As a result, it is possible to provide a PAS resin molded product with little variation in physical properties and excellent mechanical strength, particularly excellent tensile strength, and a method for producing the same.
  • PAS resin obtained through the purification treatment of step (2) is referred to as purified PAS resin
  • molten PAS resin the PAS resin obtained through the purification treatment of step (2)
  • purified PAS resin the PAS resin obtained through the purification treatment of step (2)
  • molten PAS resin the PAS resin obtained through the purification treatment of step (2)
  • molten PAS resin the PAS resin obtained through the purification treatment of step (2)
  • molten PAS resin molten PAS resin
  • Step (1) is a step of polymerizing a PAS resin.
  • the step (1) is not particularly limited, and a known polymerization method can be applied depending on the chemical structure of the target PAS resin.
  • the zeta potential value of the surface of the test piece which is an evaluation sample formed from at least a part of the obtained PAS resin, tends to be in the range of -50 to -65 mV.
  • the method of polymerizing the PAS resin that can be applied to the present embodiment is not particularly limited. (Manufacturing method 2) in a polar solvent in the presence of an alkali metal sulfide and/or alkali metal hydrosulfide (hereinafter sometimes abbreviated as a sulfidation agent) agent, etc.
  • the method of (manufacturing method 2) is versatile and preferable.
  • an alkali metal salt of carboxylic acid or sulfonic acid, or an alkali hydroxide may be added in order to adjust the degree of polymerization.
  • an alkali metal salt of a carboxylic acid or a sulfonic acid, or an alkali hydroxide may be added during the reaction in order to adjust the degree of polymerization.
  • a polar organic solvent and / or a dihalogeno aromatic compound is further added to the low water content solid. and, if necessary, a dihalogeno aromatic compound in the presence of a solid alkali metal sulfide and an aprotic polar organic solvent.
  • a polyhalogeno aromatic compound or other copolymerization components are added, and an alkali metal hydrosulfide and an organic acid alkali metal salt are added in an amount of 0.01 to 0.9 mol per 1 mol of the sulfur source.
  • Particularly preferred is a method of conducting the reaction while controlling the amount of water in the reaction system within the range of 0.02 mol or less per 1 mol of the aprotic polar organic solvent (see WO2010/058713 pamphlet).
  • the polymerization method using the above production method 2 more specifically, at least one polyhalogenoaromatic compound and at least one
  • a reaction mixture (slurry) containing a PAS resin obtained by reacting with a sulfidating agent under appropriate polymerization conditions will be described below.
  • a form obtained by reacting the slurry in the presence of a sulfidating agent and an organic solvent while continuously or intermittently adding a polyhalogenoaromatic compound and/or an organic solvent is also included. do.
  • the polyhaloaromatic compound used in the present embodiment is, for example, a halogenated aromatic compound having two or more halogen atoms directly bonded to an aromatic ring, specifically 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' -dihalodiphenyl sulfone, 4,4'-dihalodiphenyl sulfox
  • dihalogeno aromatic compounds may be used alone or in combination of two or more.
  • Polyhalogeno aromatic compounds other than dihalogeno aromatic compounds include 1,2,3-trihalobenzene, 1,2,4-trihalobenzene, 1,3,5-trihalobenzene, 1,2,3,5- tetrahalobenzene, 1,2,4,5-tetrahalobenzene, 1,4,6-trihalonaphthalene and the like. Moreover, you may block-copolymerize these compounds.
  • dihalogenated benzenes preferred are those containing 80 mol % or more of p-dichlorobenzene.
  • the polyhalogeno aromatic compounds described above may be used alone or in combination of two or more.
  • the halogen atoms contained in each halogenoaromatic compound are preferably chlorine atoms and/or bromine atoms.
  • a polyhalogeno aromatic compound having 3 or more halogen substituents in one molecule may be used as a branching agent as desired.
  • examples of such polyhalogenoaromatic compounds include 1,2,4-trichlorobenzene, 1,3,5-trichlorobenzene, 1,4,6-trichloronaphthalene and the like.
  • polyhalogeno aromatic compounds having functional groups with active hydrogen such as amino groups, thiol groups, hydroxyl groups, etc.
  • 2,6-dichloroaniline and 2,5-dichloroaniline 2,4-dichloroaniline, 2,3-dichloroaniline and other dihaloanilines
  • 2,3,4-trichloroaniline, 2,3,5-trichloroaniline, 2,4,6-trichloroaniline 3, trihaloanilines such as 4,5-trichloroaniline
  • dihaloaminodiphenyl ethers such as 2,2'-diamino-4,4'-dichlorodiphenyl ether and 2,4'-diamino-2',4-dichlorodiphenyl ether and compounds in which an amino group is replaced with a thiol group or a hydroxyl group in a mixture thereof.
  • active hydrogen-containing polyhalogens in which the hydrogen atoms bonded to the carbon atoms forming the aromatic ring in these active hydrogen-containing polyhalogeno aromatic compounds are substituted with other inert groups, for example, hydrocarbon groups such as alkyl groups.
  • Aromatic compounds can also be used.
  • the active hydrogen-containing dihalogenoaromatic compounds are preferred, and dichloroaniline is particularly preferred.
  • polyhalogenoaromatic compounds having a nitro group examples include mono- or dihalonitrobenzenes such as 2,4-dinitrochlorobenzene and 2,5-dichloronitrobenzene; 2-nitro-4,4'-dichlorodiphenyl ether and the like. dihalonitrodiphenyl ethers; 3,3′-dinitro-4,4′-dichlorodiphenyl sulfones such as dihalonitrodiphenyl sulfones; 2,5-dichloro-3-nitropyridine, 2-chloro-3,5 - mono- or dihalonitropyridines such as dinitropyridine; or various dihalonitronaphthalenes.
  • Polar organic solvents include formamide, acetamide, N-methylformamide, N,N-dimethylacetamide, tetramethylurea, N-methyl-2-pyrrolidone, 2-pyrrolidone, N-methyl- ⁇ -caprolactam, ⁇ -caprolactam, Amides such as hexamethylphosphoramide, N-dimethylpropylene urea, 1,3-dimethyl-2-imidazolidinoic acid, ureas and lactams; sulfolane, sulfolane such as dimethylsulfolane; nitriles such as benzonitrile; methyl Mention may be made of ketones such as phenyl ketone and mixtures thereof, among which N-methyl-2-pyrrolidone, 2-pyrrolidone, N-methyl- ⁇ -caprolactam, ⁇ -caprolactam, hexamethylphosphoramide, N -Dimethylpropylene urea, amides having an
  • the sulfidation agent used in this embodiment includes alkali metal sulfides and/or alkali metal hydrosulfides.
  • Alkali metal sulfides include lithium sulfide, sodium sulfide, rubidium sulfide, cesium sulfide and mixtures thereof. Such alkali metal sulfides can be used as hydrates or as aqueous mixtures or as anhydrates. Alkali metal sulfides can also be derived from the reaction between alkali metal hydrosulfides and alkali metal hydroxides. A small amount of alkali metal hydroxide may be added to react with alkali metal hydrosulfide and alkali metal thiosulfate, which are usually present in trace amounts in alkali metal sulfide.
  • Alkali metal hydrosulfides include lithium hydrogen sulfide, sodium hydrogen sulfide, rubidium hydrogen sulfide, cesium hydrogen sulfide, and mixtures thereof. Such alkali metal hydrosulfides can be used as hydrates or as aqueous mixtures or as anhydrates.
  • the alkali metal hydrosulfide is used together with the alkali metal hydroxide.
  • the alkali metal hydroxide include lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, and cesium hydroxide. These may be used alone, or two or more of them may be mixed. You can use it as Among these, lithium hydroxide, sodium hydroxide and potassium hydroxide are preferred because they are readily available, and sodium hydroxide is particularly preferred.
  • the method for producing the PAS resin used in the present embodiment can also use a hydrous sulfidation agent as a raw material. It is preferable to use it for the polymerization reaction of the resin. Further, when the amount of the aprotic polar solvent charged is small, for example, when it is less than 1 mol with respect to 1 mol of sulfur atoms in the sulfidation agent, in the presence of the polyhaloaromatic compound, the hydrous sulfidation agent and the non- It is preferred to dehydrate the protic polar solvent.
  • aprotic polar solvent and hydrous alkali metal sulfide or hydrous alkali hydrosulfide and alkali metal hydroxide as hydrous sulfidating agent are charged into a reaction vessel equipped with a distillation apparatus.
  • a temperature at which water is removed azeotropically specifically, in the range of 300 ° C. or less, preferably in the range of 80 to 220 ° C., more preferably in the range of 100 to 200 ° C., and water is removed by distillation. It is carried out by discharging out of the system.
  • dehydration is performed until the amount of water in the system in which the polymerization reaction is performed is 5 mol or less, more preferably in the range of 0.01 to 2.0 mol, per 1 mol of the sulfur atom of the sulfidating agent. is preferred.
  • the polymerization conditions for the PAS resin generally range from a temperature of 200 to 330° C., and the pressure should be such that the polymerization solvent and the polyhaloaromatic compound, which is the polymerization monomer, are substantially kept in the liquid phase. is selected from the range of 0.1 to 20 MPa, preferably from the range of 0.1 to 2 MPa.
  • the amount of the polyhaloaromatic compound charged is in the range of 0.2 mol to 5.0 mol, preferably in the range of 0.8 to 1.3 mol, more preferably in the range of 0.8 to 1.3 mol, per 1 mol of the sulfur atom of the sulfidating agent. It is prepared so as to be in the range of 0.9 to 1.1 mol.
  • the amount of the aprotic polar solvent charged is in the range of 1.0 to 6.0 mol, preferably in the range of 2.5 to 4.5 mol, per 1 mol of the sulfur atom of the sulfidating agent. adjust.
  • the polymerization reaction is preferably carried out in the presence of a small amount of water, and the proportion thereof is preferably adjusted appropriately in consideration of the polymerization method, the molecular weight of the resulting polymer, and productivity.
  • the dehydration operation is carried out so that the amount becomes 2.0 mol or less, preferably 1.6 mol or less per 1 mol of the sulfur atom of the sulfidation agent, and the dehydration is performed in the presence of the polyhaloaromatic compound.
  • the operation is 0.9 mol or less, preferably 0.05 to 0.3 mol, more preferably 0.01 to 0.02 mol or less.
  • Dehydration operation may be performed so that the range of
  • polymerizing the sulfidating agent and the polyhaloaromatic compound in the presence of the polar organic solvent include, for example: 1) A method using a polymerization aid such as an alkali metal carboxylate or lithium halide, 2) A method using a branching agent such as an aromatic polyhalogen compound, 3) a method of conducting a polymerization reaction in the presence of a small amount of water and then adding water to further polymerize; 4) a method of cooling the gas phase portion of the reaction vessel during the reaction between the alkali metal sulfide and the aromatic dihalogen compound to condense a portion of the gas phase in the reaction vessel and reflux it to the liquid phase; 5) reacting an alkali metal sulfide, or a hydrous alkali metal hydrosulfide and an alkali metal hydroxide with an amide, urea or lactam having an aliphatic cyclic structure in the presence of a polyhaloaromatic compound while dehydrating; a
  • the coarse slurry containing the PAS resin obtained in step (1) is subjected to suitable means (e.g., vacuum distillation method, centrifugal separation method, screw decanter method, vacuum filtration method, pressure filtration method, etc.).
  • suitable means e.g., vacuum distillation method, centrifugal separation method, screw decanter method, vacuum filtration method, pressure filtration method, etc.
  • a suitable method can be selected) to separate and remove the organic solvent, and then the crude PAS resin (the PAS resin that has not undergone the purification step) can be recovered.
  • the total amount of the organic solvent used from the charging of the raw materials to the completion of the polymerization reaction is preferably in a ratio of 1 to 6 mol per 1 mol of the sulfidating agent, which is the sulfur source.
  • the amount of the organic solvent initially charged is preferably 0.01 to 0.50 mol with respect to 1 mol of the sulfidating agent, which is the sulfur source.
  • Examples of the acid under the condition (c) include saturated fatty acids such as carbonic acid, oxalic acid, formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, and monochloroacetic acid; acrylic acid, crotonic acid, oleic acid, and the like; aromatic carboxylic acids such as unsaturated fatty acids, benzoic acid, phthalic acid and salicylic acid; dicarboxylic acids such as oxalic acid, maleic acid and fumaric acid; organic acids such as methanesulfonic acid and sulfonic acids such as p-toluenesulfonic acid; Inorganic acids such as sulfuric acid, sulfurous acid, nitric acid, nitrous acid or phosphoric acid may be mentioned.
  • Examples of the hydrogen salt under the condition (c) include sodium hydrogen sulfate, disodium hydrogen phosphate, sodium hydrogen carbonate, and the like. Organic acids that cause less corrosion to metal members
  • step (1) of the present embodiment when the above condition (a) is adopted, the concentration of the PAS resin during polymerization is increased, so that the ring-opened product of the aliphatic cyclic compound is added to the end of the PAS resin. can exhibit a certain zeta potential value because it is easier for In step (1) of the present embodiment, if the above condition (b) is adopted, the concentration of the PAS resin during polymerization increases, so that the ring-opened product of the aliphatic cyclic compound is attached to the end of the PAS resin. A specific zeta potential value can be exhibited because the reaction that occurs is likely to proceed.
  • the acidic component is included in the PAS resin, and the acidic component oozes out in the purification step, resulting in terminal functionalization of the PAS resin.
  • Certain zeta potential values can be exhibited because some of the groups ion exchange and protonate.
  • Step (2) purification step
  • a known purification treatment can be applied according to the chemical structure of the PAS resin to be evaluated, etc.
  • the slurry containing the PAS resin obtained in the step (1) it is preferable to add a washing solution to the crude PAS resin, which is the solid content of the slurry, and perform washing treatment, filtration treatment and drying treatment.
  • each of the washing treatment, filtration treatment and drying treatment can be optionally performed at least once or more than once.
  • the purification treatment of the PAS resin (slurry containing the PAS resin) obtained in step (1) is not particularly limited.
  • the reaction mixture is used as it is, or after adding an acid or base, the solvent is distilled off under reduced pressure or normal pressure, and then the solid after solvent distillation is treated with water, a reaction solvent (or an equivalent solubility in a low-molecular-weight polymer).
  • a reaction solvent or an organic solvent having an equivalent solubility to the low-molecular-weight polymer
  • the drying method in the above refining treatment is not particularly limited, and it is preferable to dry at a drying temperature of 120-270°C.
  • the atmosphere of the drying treatment includes under vacuum, under reduced pressure, under nitrogen or inert gas inert gas atmosphere, under oxidizing atmosphere such as oxygen or air, and under mixed gas atmosphere of air and nitrogen.
  • the drying time is preferably 0.5 to 53 hours.
  • the filtration treatment is not particularly limited as long as it is a method capable of solid-liquid separation, and examples include a method of solid-liquid separation using a filter, a centrifuge, or the like.
  • Specific purification conditions include the following conditions (d) to (f).
  • step (2) it is preferable to acid-treat the crude PAS resin with a predetermined amount or more of an acid solution. More preferably, the acid treatment is performed using an acid solution of about twice the total weight of the PAS resin.
  • the pH of the acid solution used in the acid treatment of (d) is preferably 6 or less.
  • step (2) it is preferable to wash with hot water of 140 to 260° C. with 1.5 to 10 times the total weight of the PAS resin.
  • the terminal functional groups of the PAS resin can be protonated by an ion exchange reaction.
  • the acid used for the acid solution is not particularly limited as long as an acid solution having a pH of 6 or less can be prepared, and the acid under the condition (c) above can be used.
  • the step (1 ) or in the step (2) an acid may be added to the PAS resin.
  • the preferred purification step of the present embodiment is solid-liquid separation of the PAS resin (including slurry) obtained in step (1) or the slurry containing the PAS resin obtained in step (1). It includes acid treatment by adding an acid solution to the crude PAS resin, which is a solid content.
  • step (2) is the PAS resin (including slurry) obtained in step (1) or crude PAS, which is the solid content of the slurry containing the PAS resin obtained in step (1).
  • the crude PAS resin is subjected to acid treatment by adding an acid solution one or more times.
  • Step (3) in the present embodiment is a step of evaluating a test piece produced from at least part of the PAS resin obtained through steps (1) and (2).
  • the step (3) includes a test strip preparation step (3-1), a zeta potential measurement step (3-2) and a discrimination step (3-3).
  • step (3) of the present embodiment the chemical properties of the PAS resin, which is the raw material of the test piece, are quantified based on the zeta potential value of the surface of the test piece, which is an evaluation sample formed from the PAS resin. Accordingly, it is not necessary to evaluate the entire amount of the PAS resin obtained through steps (1) and (2), and it is sufficient to evaluate the PAS resin obtained through steps (1) and (2). Since the step (3) in the present embodiment makes it possible to identify a PAS resin having a zeta potential value within a predetermined range, the surface characteristics of the PAS resin can be quantified with high accuracy, and the PAS resin can be distinguished and sorted.
  • Step (3-1) is a step of melting the PAS resin obtained in steps (1) and (2) to prepare a molten PAS resin, and then solidifying the molten PAS resin to prepare a test piece.
  • the test piece preparation step in the present embodiment comprises extracting at least part of the PAS resin obtained in steps (1) to (2), melting it once, and then solidifying the melted PAS resin.
  • the test piece of the present embodiment is preferably in an amorphous state.
  • amorphous state refers to a state in which no crystalline phase exists in the PAS resin constituting the test piece, and more specifically, the following condition (i) is satisfied.
  • (i) In the DSC measurement of the PAS resin film which is the test piece, when the temperature range from 40 ° C. to 350 ° C. is raised at 20 ° C./min, an exothermic peak accompanying crystallization occurs between 100 ° C. and 200 ° C. is not confirmed.
  • the chemical properties of the PAS resin are quantified using the zeta potential value of the surface of the test piece made from the PAS resin.
  • the reason why the reactivity of the PAS resin is evaluated from the surface chemical properties is that the PAS resin has extremely high chemical resistance.
  • PPS resin which is a particularly preferred embodiment of PAS resin
  • the presence of a solvent capable of dissolving the PPS resin at 200° C. or lower has not yet been found. This is because there is practically no technique for directly evaluating the molecular ends in the PAS resin, which greatly contributes to reactivity. Therefore, in the present invention, by using a specific test piece as a reference, the characteristics of the PAS resin, which is the constituent material of the test piece, are grasped.
  • the method of melting the PAS resin to prepare the molten PAS resin is not particularly limited as long as the PAS resin can be heated and melted, and known heating means can be employed. Specific examples include a hot plate, hot air/cold air circulating constant temperature oven, microwave or (far) infrared heater, or hot press.
  • the heating time for heating the PAS resin using the heating means is not particularly limited as long as the PAS resin is melted, and is, for example, about 30 seconds to 10 minutes.
  • the temperature for melting the PAS resin may be the melting point of the PAS resin or higher, preferably 300° C. or higher and 400° C. or lower. Since the PAS resin undergoes an oxidative cross-linking reaction at a temperature of 200° C. or higher, it may be thermally melted in a non-oxidizing inert gas atmosphere.
  • the PAS resin may be heated and melted through the sheet body.
  • the sheet body preferably has a melting point higher than that of the PAS resin and preferably has a hydrophobic surface.
  • a PAS resin for example, a powdered PAS resin
  • the sheet body is heated using a heating means to melt the PAS resin. It is preferable to prepare a molten PAS resin by As another method, a PAS resin (for example, solid or powdered purified PAS resin) is sandwiched between a pair of sheets, and then the pair of sheets is heated by heating means.
  • the sheet body it is preferable to melt the PAS resin by heating one of the pair of sheet bodies to prepare a molten PAS resin.
  • the sheet body By using the sheet body, it is possible to easily collect the test piece in which the molten PAS resin is solidified.
  • the sheet body preferably has releasability. As a result, the test piece can be easily collected without the solidified PAS resin adhering to it, so that damage to the appearance characteristics (cracking, rough skin, etc.) can be reduced, or breakage of the test piece can be suppressed.
  • the material of the sheet body must have a melting point higher than that of the PAS resin, and examples thereof include metal materials (martensitic stainless steel such as SUS404C), fluororesins, polyimides, and ceramics.
  • metal materials martensitic stainless steel such as SUS404C
  • fluororesins include polytetrafluoroethylene (PTFE), tetrafluoroethylene/perfluoroalkyl vinyl ether copolymer (PFA), tetrafluoroethylene/ethylene copolymer (ETFE), tetrafluoroethylene/hexafluoropropylene copolymer polymer (FEP), polyvinylidene fluoride (PVDF) or ethylene-chlorotrifluoroethylene copolymer (ECTFE).
  • the fluororesin may contain an inorganic filler such as glass fiber, if necessary.
  • the method of solidifying the molten PAS resin includes a method of solidifying the molten PAS resin by cooling.
  • the cooling may be natural cooling or rapid cooling, and rapid cooling is preferred.
  • a known cooling means can be employed as the cooling method. Examples of the cooling means include rolls whose surface temperature can be adjusted (cooling rolls), air knives, immersion in water (a water tank, etc.), and direct or indirect contact with metal materials at 35° C. or lower.
  • the test piece of the present embodiment is preferably made of amorphous PAS resin.
  • a method for producing such an amorphous PAS resin it is preferable to solidify the molten PAS resin by rapidly cooling it. By rapid cooling, it is possible to produce an amorphous PAS resin that does not contain a crystalline phase. Therefore, it becomes easier to uniformly evaluate the PAS resin even by surface measurement, and it becomes an index of reactivity in the molten state. This is preferable from the viewpoint of ease of use.
  • the PAS resin obtained through steps (1) and (2) is melted and then cooled at a rate of 10 ° C./second or more. It is more preferable to cool at a speed of 100° C./s or less. Moreover, the cooling rate is preferably maintained in the temperature range from 400° C. to at least the Tg of the PAS resin. As a result, the PAS resin can be solidified in an amorphous state, the PAS resin can be uniformly evaluated even by surface measurement, and the measurement can easily serve as an index of reactivity in the molten state. In the present embodiment, it is preferable to cool the molten PAS resin at a cooling rate of 10° C./sec or more and 100° C./sec or less to the Tg or less of the PAS resin, preferably 90° C. or less.
  • the molten PAS resin may be solidified through the sheet body for the purpose of easily obtaining a test piece of a predetermined size.
  • Another method for solidifying the molten PAS resin is to solidify the molten PAS resin between the pair of sheet bodies by cooling at least one of a pair of sheet bodies placed so as to sandwich the molten PAS resin.
  • test piece it is preferable to collect the test piece by As a result, the test piece can be easily collected without the solidified PAS resin adhering to it, so that deterioration of the appearance characteristics (thickness, etc.) can be reduced, or breakage of the test piece can be suppressed.
  • the test piece in the present embodiment is an example of the object to be measured for zeta potential measurement. ) must be provided. Therefore, in the step (3-1) of the present embodiment, a test piece having a certain shape, size and thickness is prepared as an object to be measured for convenience of zeta potential measurement. It is considered that the test piece in this embodiment is not particularly limited as long as it does not affect the measured value itself for each zeta potential measurement as much as possible.
  • test piece is 4.5 to 5.5 cm (length) ⁇ 2.5 to 3.5 cm (width) ⁇ 0.05 to 0.15 cm (thickness) for convenience of zeta potential measurement.
  • a film-like PAS resin is used.
  • shape, size, thickness, etc. of the test piece are not particularly limited as long as they do not affect the zeta potential measurement value itself as much as possible.
  • a flat plate (film-like including) and is preferably a step of producing a test piece composed of a PAS resin in an amorphous state.
  • the "length and width of the test piece” are measured using vernier calipers.
  • the “thickness of the test piece” means that the test piece is cut at 5 points in the longitudinal direction at 8 mm intervals in the direction perpendicular to the longitudinal direction, and 5 test pieces at 5 mm intervals in the width direction on each cut surface.
  • the thickness of the film was measured using a TH-104 film thickness measuring machine (manufactured by Tester Sangyo Co., Ltd.), and refers to the average value of the thickness of a total of 25 points.
  • the surface of the test piece or the surface of the sheet body may be surface-treated for the purpose of suppressing variation in measured values.
  • the surface treatment method is not particularly limited, and can be appropriately selected from known methods within a range that does not impair the characteristics of the test piece. For example, degreasing with an organic solvent such as acetone in which the PAS resin is insoluble is mentioned.
  • the step (3-2) is a step of measuring the zeta potential of the surface of the test piece obtained in the test piece preparation step by streaming potential method.
  • the zeta potential value as an index of the surface properties of the PAS resin, it is possible to relatively easily measure the surface properties of the evaluation sample and to easily grasp the properties of the PAS resin.
  • the fluctuation range (variation coefficient) of the zeta potential value due to the measurement is smaller than in the viscosity increase measurement using the conventional MFR.
  • the step (3-2) in the present embodiment is preferably a step of measuring the zeta potential of the surface of the test piece by the streaming potential method under conditions of pH 7.8 to 8.2.
  • the zeta potential measurement conditions within the range of pH 7.8 to 8.2 not only the variation in the measured values is further reduced, but also the absolute value of the observed zeta potential value itself can be increased. can.
  • the amount of difference in zeta potential value increases, so that it becomes easier to detect the difference in zeta potential value between the same or different PAS resins, and it becomes easier to evaluate the properties of the PAS resins with higher accuracy.
  • the zeta potential in the present embodiment is measured within a pH range of 7.8 to 8.2 using streaming potential method.
  • the zeta potential by streaming potential method is generated by forming an electric double layer at the solid-liquid interface between the test piece and the electrolytic solution. It is calculated from the Helmholtz-Smolkowschki equation by measuring the difference between the laminar flow of the solution, the viscosity of the electrolyte solution, and the dielectric constant of the electrolyte solution. The measurement of zeta potential by the streaming potential method will be described below with reference to FIG.
  • Compressed air or an inert gas may also be used to sweep away the electrolyte solution 3 with a constant pressure difference ( ⁇ P) to create a flow. Then, using the values of the laminar flow velocity difference (or pressure difference), the viscosity of the electrolytic solution 3, the dielectric constant of the electrolytic solution 3, etc., measured by the above principle, the following Helmholtz-Smoluchowski formula formula:
  • I str represents the streaming current
  • U str represents the streaming potential
  • ⁇ p represents the differential pressure
  • ⁇ represents the viscosity of the electrolyte solution
  • ⁇ r ⁇ ⁇ 0 represents the electrolyte solution.
  • KB represents the electrical conductivity
  • L/A represents the parameters of the channel.
  • the electrolytic solution that can be used to measure the zeta potential is preferably an aqueous solution containing a monovalent-monovalent electrolyte, such as an aqueous potassium chloride solution, an aqueous sodium chloride solution, an aqueous lithium chloride solution, an aqueous potassium hydroxide solution, An aqueous sodium hydroxide solution or an aqueous lithium hydroxide solution may be mentioned.
  • a monovalent-monovalent electrolyte such as an aqueous potassium chloride solution, an aqueous sodium chloride solution, an aqueous lithium chloride solution, an aqueous potassium hydroxide solution, An aqueous sodium hydroxide solution or an aqueous lithium hydroxide solution may be mentioned.
  • the pH-adjusting acid or alkali used when measuring the zeta potential a general acid or alkali aqueous solution is used, and HCl or KOH is mainly used.
  • the electrolyte concentration in the electrolytic solution is preferably 0.1 to 1000 mmol/L.
  • a buffer solution may be used as an electrolytic solution that can be used.
  • the buffer solution can be appropriately selected according to the pH conditions to be measured.
  • the buffer solution refers to a weak acid and its salt (conjugate base), or a mixed solution of a weak base and its salt (conjugate acid), which can be combined to adjust the desired pH.
  • phosphate buffer MES buffer, Tris buffer or HEPES buffer
  • CHES buffer solution TAPS buffer solution, or Bicine buffer solution is mentioned.
  • the pH of the electrolytic solution used in step (3-2) in the present embodiment is preferably in the range of 7.8 to 8.2. electrolyte solution is used.
  • the conductivity of the zeta potential electrolyte solution in this embodiment may be in the range of 14-15 mS/m.
  • the pH and conductivity measurement methods in this specification are measured using a pH and conductivity meter (SurPASS3 (Anton Paar)).
  • the temperature for measuring the zeta potential in the present embodiment is preferably around room temperature (22 to 28° C.).
  • the step (3-2) in this embodiment uses the following conditions as an example.
  • ⁇ Type of electrolytic solution KCl aqueous solution
  • Ultrapure water used for electrolytic solution ASTM I grade
  • ⁇ Concentration of electrolytic solution 1 mmol/L
  • ⁇ Electrolytic solution conductivity 14 to 15 mS/m
  • ⁇ Measurement temperature 20 to 28°C ⁇ pH: 7.8 to 8.2
  • ⁇ Cell type Clamp cell ⁇ Cell material: PVDF ⁇ Gap between cell and test piece (evaluation sample): adjusted to 100 to 120 ⁇ m ⁇ Measurement pressure range: 200 to 450 mbar
  • the step (3-3) in this embodiment is a discrimination step of discriminating PAS resins having a zeta potential value in the range of -50 to -65 mV as measured by the zeta potential measurement step.
  • the zeta potential of the surface of the test piece is measured at a predetermined pH (for example, pH 3 to 9)
  • a reactive functional group for example, , a functional group containing an oxygen atom or a nitrogen atom
  • the reactivity of the prepared PAS resin is naturally considered to be high.
  • the zeta potential values of test pieces having the same molecular weight of PAS resin as constituent components are compared, it is confirmed that the reactivity of the PAS resin used in the test piece having a large zeta potential value tends to be high.
  • the zeta potential value of the PAS resin is -50 mV or more, the hot water resistance of the PAS resin tends to decrease.
  • the zeta potential value is -65 mV or less, the reactivity between the PAS resin and the substance having a reactive functional group tends to decrease.
  • a step (selection step) of selecting a PAS resin having a specific zeta potential may be included after the determination step of step (3-3). Thereby, a PAS resin having a specific reactivity can be selected. If the selected lot of resin has the same zeta potential, the reactivity with a substance having a reactive functional group will also be the same, so the mechanical strength etc. when made into a resin composition or molded product can be the same. . Therefore, by sorting using the zeta potential as an index, it is possible to obtain a molded article with less variation in physical properties between lots and a resin composition constituting the molded article than when the degree of viscosity increase, which is a conventional index, is used. .
  • the PAS resin composition according to the present embodiment has a zeta potential on the surface of the test piece at pH 7.8 to 8.2 obtained through the above steps (1) to (3) in the range of -50 to -65 mV.
  • the PAS resin contained in the PAS resin composition of the present embodiment exhibits high reactivity because it has a zeta potential value within a specific range.
  • a resin composition is prepared by melt-kneading another raw material, particularly a substance having a reactive functional group, and a PAS resin having a zeta potential value within a specific range
  • the PAS resin and the reactive functional group are produced. It exhibits excellent mechanical strength because it reacts well with substances.
  • the PAS resin contained in the PAS resin composition has a zeta potential value within a specific range, variations in reactivity are reduced, and as a result, variations in the physical properties of the entire PAS resin composition are reduced. .
  • the substance having a reactive functional group in the present embodiment is not particularly limited as long as it is a substance having a reactive functional group capable of interacting (including chemical bonding) with the PAS resin. It is preferably one or more substances selected from the group consisting of agents, elastomers, epoxy resins, and surface-treated inorganic fillers. Substances having suitable reactive functional groups are described below.
  • the PAS resin composition according to this embodiment preferably contains a silane coupling agent.
  • the silane coupling agent is not particularly limited as long as it does not impair the effects of the present invention, but a functional group capable of reacting with at least one group selected from the group consisting of a hydroxyl group, an amino group, a carboxyl group, and a salt of a carboxyl group.
  • a silane coupling agent having Such functional groups include epoxy group, amino group, hydroxyl group, carboxyl group, mercapto group, isocyanate group, oxazoline group, and formula: R (CO) O (CO) - or R (CO) O - (in the formula, R represents an alkyl group having 1 to 8 carbon atoms.).
  • Examples of such silane coupling agents include epoxy groups such as ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -glycidoxypropyltriethoxysilane, ⁇ -(3,4-epoxycyclohexyl)ethyltrimethoxysilane, and the like.
  • the silane coupling agent is an optional component, and the ratio when blending is not particularly limited.
  • it is preferably 0.3 parts by mass or more with respect to 100 parts by mass of the PAS resin. , more preferably 0.4 parts by mass or more, more preferably 0.5 parts by mass or more.
  • it is more preferably 10 parts by mass or less, more preferably 8 parts by mass or less, relative to 100 parts by mass of the PAS resin. , 6 parts by mass or less.
  • the PAS resin composition according to this embodiment preferably contains an elastomer.
  • the elastomer By including the elastomer, the toughness and thermal shock resistance of the PAS resin composition can be further enhanced. From the same point of view, it is preferable to use a thermoplastic elastomer as the elastomer.
  • the thermoplastic elastomer is not particularly limited as long as it does not impair the effects of the present invention. Examples of the thermoplastic elastomer include polyolefin-based elastomers, fluorine-based elastomers, and silicone-based elastomers.
  • the elastomer (particularly thermoplastic elastomer) preferably has a functional group capable of reacting with at least one group selected from the group consisting of hydroxyl group, amino group, carboxyl group and carboxyl group.
  • Such functional groups include epoxy group, amino group, hydroxyl group, carboxyl group, mercapto group, isocyanate group, oxazoline group, and formula: R (CO) O (CO) - or R (CO) O - (in the formula, R represents an alkyl group having 1 to 8 carbon atoms.).
  • a thermoplastic elastomer having such a functional group can be obtained, for example, by copolymerizing an ⁇ -olefin and a vinyl polymerizable compound having the functional group.
  • Examples of ⁇ -olefins include ⁇ -olefins having 2 to 8 carbon atoms such as ethylene, propylene and butene-1.
  • Examples of the vinyl polymerizable compound having the functional group include ⁇ , ⁇ -unsaturated carboxylic acids and their alkyl esters such as (meth)acrylic acid and (meth)acrylic acid esters, maleic acid, fumaric acid, itaconic acid and Other examples include ⁇ , ⁇ -unsaturated dicarboxylic acids having 4 to 10 carbon atoms and derivatives thereof (mono- or diesters, acid anhydrides thereof, etc.), glycidyl (meth)acrylate, and the like.
  • an epoxy group a carboxyl group, and a formula: R (CO) O (CO) - or R (CO) O - (wherein R represents an alkyl group having 1 to 8 carbon atoms)
  • R represents an alkyl group having 1 to 8 carbon atoms
  • Ethylene-propylene copolymers and ethylene-butene copolymers having at least one functional group selected from the group consisting of the groups represented are preferred from the standpoint of improving toughness and impact resistance.
  • the elastomer is an optional component, but the ratio when blending is not particularly limited. 1 part by mass or more, preferably 1 part by mass or more, preferably 30 parts by mass or less, more preferably 20 parts by mass or less, and even more preferably 15 parts by mass or less.
  • the PAS resin composition according to the present embodiment preferably contains an epoxy resin.
  • the epoxy resin is not particularly limited as long as it does not impair the effects of the present invention. Examples include bisphenol type epoxy resins such as bisphenol A type and bisphenol F type; glycidyl ester type epoxy resins; glycidyl amino type epoxy resins; and epoxy resins having a polyarylene ether structure.
  • the epoxy resin is an optional component, but the ratio at the time of blending is not particularly limited. parts or more, more preferably 5 parts by mass or more, preferably 30 parts by mass or less, more preferably 20 parts by mass or less, and still more preferably 15 parts by mass or less.
  • the amount of active groups in the curing agent is 0.1 equivalents or less, more preferably 0.01 equivalents or less, and most preferably 0 equivalents, ie, absent.
  • the PAS resin composition according to the present embodiment preferably contains a surface-treated inorganic filler.
  • these inorganic fillers known and commonly used materials can be used as long as they do not impair the effects of the present invention. and inorganic fillers.
  • fibers such as glass fiber, carbon fiber, silane glass fiber, ceramic fiber, aramid fiber, metal fiber, potassium titanate, silicon carbide, calcium silicate, wollastonite, and fibrous filler such as natural fiber are used.
  • Non-fibrous fillers can also be used.
  • Specific examples of the surface treatment agent for surface-treating the inorganic filler include epoxy-based compounds, isocyanate-based compounds, silane-based compounds, titanate-based compounds, borane treatment, ceramic coating, and the like. Among them, epoxy-based compounds and silane-based compounds are preferred.
  • the inorganic filler is not an essential component in the present invention, and when blended, its content is not particularly limited as long as it does not impair the effects of the present invention.
  • the amount of the inorganic filler compounded is, for example, preferably 5 parts by mass or more, more preferably 10 parts by mass or more, and further preferably 20 parts by mass or more with respect to 100 parts by mass of the PAS resin. preferable.
  • it is more preferably 350 parts by mass or less, and 300 parts by mass or less with respect to 100 parts by mass of the PAS resin. More preferably, it is particularly preferably 250 parts by mass or less.
  • the PAS resin composition according to the present embodiment may contain a synthetic resin other than the PAS resin, a coloring agent, an antistatic agent, an antioxidant, a heat stabilizer, an ultraviolet stabilizer, an ultraviolet absorber, Additives such as foaming agents, flame retardants, flame retardant aids, rust inhibitors, and coupling agents (hereinafter referred to as "other components") may be included.
  • the other components are, for example, preferably 0.01 parts by mass or more and preferably 1000 parts by mass or less with respect to 100 parts by mass of the PAS resin, depending on the purpose and application so as not to impair the effects of the present invention. It may be used after adjusting as appropriate.
  • Examples of the synthetic resin include polyester resin, polyamide resin, polyimide resin, polyetherimide resin, polycarbonate resin, polyphenylene ether resin, polysulfone resin, polyethersulfone resin, polyetheretherketone resin, polyetherketone resin, poly Synthetic resins such as arylene resins, polyethylene resins, polypropylene resins, polytetrafluoroethylene resins, polydifluoroethylene resins, polystyrene resins, ABS resins, phenol resins, urethane resins, and liquid crystal polymers can be used.
  • the synthetic resin is not an essential component, and the mixing ratio is not particularly limited as long as it does not impair the effects of the present invention, and can be appropriately selected according to each purpose.
  • the PAS resin composition according to the present embodiment it can be about 5 parts by mass or more and 15 parts by mass or less with respect to 100 parts by mass of the PAS resin.
  • the ratio of the PAS resin to the total of the PAS resin and the synthetic resin is preferably (100/115) or more, more preferably (100/105) or more, on a mass basis.
  • the method for producing a PAS resin composition according to the present embodiment includes a step of blending the PAS resin obtained through the above steps (1) to (3) and a substance having a reactive functional group, and melt-kneading them. and the zeta potential value of the surface of the test piece at pH 7.8 to 8.2 of the PAS resin is in the range of -50 to -65 mV.
  • the PAS resin composition according to the present embodiment contains each essential component and optionally optional components.
  • the essential components and optional components are the same as those described in the PAS resin composition according to the present embodiment.
  • the method of blending and kneading the essential components and optional components is not particularly limited, but a method of blending the essential components and optionally optional components and melt-kneading them, more specifically, a tumbler if necessary Alternatively, a method of homogeneously dry-mixing with a Henschel mixer or the like and then introducing into a twin-screw extruder to melt-knead may be used.
  • Melt-kneading is carried out in a temperature range in which the resin temperature is equal to or higher than the melting point of the PAS resin, preferably the melting point +10°C or higher, more preferably the melting point +10°C or higher, further preferably the melting point +20°C or higher, Preferably, the melting point is +100° C. or lower, more preferably, the melting point is +50° C. or lower.
  • melt-kneader a twin-screw kneading extruder is preferable from the viewpoint of dispersibility and productivity. It is preferable to melt-knead while appropriately adjusting the range of and melt-kneading under conditions where the ratio (discharge rate / screw rotation speed) is in the range of 0.02 to 5 (kg / hr / rpm). is more preferred. Moreover, addition and mixing of each component to the melt-kneader may be performed simultaneously, or may be performed separately.
  • the ratio of the distance from the extruder resin input part (top feeder) to the side feeder with respect to the total screw length of the twin-screw kneading extruder is preferably 0.1 or more, and 0 .3 or more is more preferable. Also, the ratio is preferably 0.9 or less, more preferably 0.7 or less.
  • the PAS resin composition according to the present embodiment obtained by melt-kneading in this manner has a morphology in which the PAS resin forms a continuous phase and other essential components and optional components are dispersed.
  • the PAS resin composition according to the present embodiment is processed into pellets, chips, granules, powder, and the like by a known method, for example, extruding the resin composition in a molten state into strands. After that, it is preferable to perform pre-drying in a temperature range of 100 to 150° C., if necessary.
  • the molded article according to this embodiment is obtained by melt-molding the PAS resin composition according to this embodiment described above. Further, the method for producing a molded product according to the present embodiment is characterized by having a step of melt-molding the PAS resin composition obtained by the above-described method for producing a PAS resin composition according to the present embodiment.
  • the molded article according to the present embodiment uses the PAS resin composition according to the present embodiment as a material, physical properties such as mechanical strength are maintained at a high level, and excellent moist heat resistance and moldability are realized. It has the effect of
  • the PAS resin composition can be molded by injection molding, compression molding, extrusion molding of composites, sheets, pipes, etc., pultrusion molding, blow molding, transfer molding, and the like. Also suitable for injection molding applications.
  • various molding conditions are not particularly limited, and molding can be performed by a general method.
  • the resin temperature is in the range of the melting point of the PAS resin or higher, preferably the melting point +10°C or higher, more preferably the melting point +10°C to the melting point +100°C, further preferably the melting point +20°C.
  • the PAS resin composition After passing through the step of melting the PAS resin composition in a temperature range of up to the melting point +50° C., it may be molded by injecting it into a mold from the resin discharge port. At that time, the mold temperature may also be set within a known temperature range, for example, room temperature (approximately 23°C) to 300°C, preferably 120 to 180°C.
  • Products using the molded article according to the present embodiment are not particularly limited, and can be used for the following various applications.
  • electrical and electronic parts such as connectors, printed circuit boards, and sealed molded products
  • automobile parts such as lamp reflectors and various electrical parts
  • interior materials for various buildings, aircraft, and automobiles It can be widely used as injection molding/compression molding products such as precision parts such as watch parts, extrusion molding/pultrusion molding products such as fibers, films, sheets, and pipes, and 3D printer modeling products.
  • the p-DCB distilled azeotropically was separated with a decanter and returned to the kettle as needed.
  • the internal temperature of the autoclave was cooled to 160°C, and 29.486 kg (297 mol) of NMP was supplied, 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. bottom.
  • the final pressure was 0.28 MPa.
  • the bottom valve of the autoclave is opened, NMP is extracted into a 150 L vacuum stirring dryer with stirring blades while the pressure is reduced, and then the NMP is sufficiently removed by stirring at 150 ° C. for 2 hours under reduced pressure, and the powder is obtained.
  • a mixture (A-1) of PPS resin and salts was obtained.
  • the resulting water-containing cake and 600 g of ion-exchanged water were placed in a 1 L autoclave equipped with a stirrer, stirred at 220° C. for 30 minutes, cooled to room temperature, and filtered. Added and filtered. After that, 600 g of carbonated water having a pH of 4 at 20° C. was added and filtered, and further 600 g of ion-exchanged water at 70° C. was added and filtered. The resulting water-containing cake was dried in a hot air circulation dryer at 120° C. for 6 hours to obtain a white powdery PPS resin. The same operation was repeated to obtain 3 lots of PPS resin.
  • Example (1-3) Evaluation of PPS resin 0.5 g of the obtained PPS resin was weighed and sandwiched between two glass fiber-containing polytetrafluoroethylene resin sheets (Nitto Denko Co., Ltd., Nitoflon). Heated for 1 minute using a hot plate heated to 350°C. At this time, the PPS resin melted, so that it was pressed from above with a metal plate heated to 350° C. to form a film with a thickness of 0.1 cm.
  • the two polytetrafluoroethylene resin sheets sandwiching the film-like molten PPS resin were transferred from the hot plate onto a metal plate at room temperature (28° C.), and immediately The melted PPS resin was solidified by sandwiching it from above with metal plates at room temperature (28° C.) and cooling down to room temperature (28° C.). Thereafter, the solidified film-like PPS resin was cut into 5 cm ⁇ 3 cm pieces to obtain amorphous test pieces. It was confirmed by DSC measurement that the test piece was in an amorphous state.
  • Example (2-2) Purification and Preparation of PPS Resin To 417 g of the mixture (B-1), 1000 g of ion-exchanged water at 70° C. was added, stirred for 20 minutes, and filtered. After repeating this operation once more, the resulting water-containing cake and 600 g of ion-exchanged water were supplied to a 1 L autoclave equipped with a stirrer and stirred at 160° C. for 30 minutes. After cooling to room temperature, 600 g of ion-exchanged water at 70° C. was added to the resulting water-containing cake, followed by filtration. The resulting water-containing cake was dried in a hot air circulation dryer at 120° C. for 6 hours to obtain a white powdery PPS resin. The same operation was repeated to obtain 3 lots of PPS resin.
  • Example (2-3) Evaluation of PPS resin In the same manner as in Example 1, the zeta potential value of the surface of the obtained PPS resin test piece was measured. Table 1 shows the results.
  • Comparative Example (1-2) Purification and Preparation of PPS Resin The procedure was carried out in the same manner as in Example 1-2, except that the temperature of the ion-exchanged water used for washing and the stirring temperature were all set to 70°C. A PPS resin was obtained. The same operation was repeated to obtain 3 lots of PPS resin.
  • Comparative Example (2-1) Polymerization of PPS Resin The same procedure as in Example 2-1 was performed except that oxalic acid dihydrate was not added at 200° C. during cooling.
  • Comparative example (3) The degree of increase in viscosity of the PPS resin when epoxysilane was added was measured, and lots of PPS resin having a degree of increase in viscosity of 9.0 to 9.1 times were selected. Also, in the same manner as in Example 1, the zeta potential values of the surfaces of the selected PPS resin test pieces were measured. The results are shown in Table 1
  • DSC measurement of PPS resin 4 mg was taken from a film-shaped PPS resin test piece prepared for zeta potential measurement, and 20% from 40 ° C. to 350 ° C. was measured using a differential scanning calorimeter (DSC), Perkin Elmer's DSC8500. The temperature was raised at °C/min. Since no exothermic peak due to crystallization of the resin was observed between 100° C. and 200° C., it was confirmed that each film-like test piece was in an amorphous state.
  • DSC differential scanning calorimeter

Abstract

La présente invention concerne: un article moulé en résine poly(sulfure d'arylène) (PAS) qui a peu de variation de réactivité et possède une résistance mécanique uniforme, en particulier une résistance à la traction; une résine et une composition de résine à partir desquelles l'article moulé est constitué; et leur procédé de production. Plus spécifiquement, l'invention concerne un procédé de production de résine PAS comprenant une étape (1) pour la polymérisation d'une résine PAS, une étape (2) pour le raffinement de la résine PAS pour préparer une résine PAS raffinée, et une étape (3) pour l'évaluation d'une éprouvette formée à partir d'au moins une partie de la résine PAS raffinée, l'étape (3) comprenant une étape de production d'éprouvette pour obtenir l'éprouvette par solidification de résine PAS fondue qui est obtenue par fusion de la résine PAS raffinée, une étape de mesure de potentiel zêta pour la mesure du potentiel zêta de la surface de l'éprouvette par un procédé de potentiel d'écoulement à un pH de 7,8 à 8,2, et une étape de distinction pour la distinction d'une résine PAS pour laquelle la valeur de potentiel zêta mesurée dans l'étape ci-dessus est dans la plage de -50 mV à -65 mV.
PCT/JP2022/013800 2021-09-28 2022-03-24 Procédé de production de résine de poly (sulfure d'arylène), résine de poly(sulfure d'arylène), composition de résine de poly (sulfure d'arylène) et article moulé en résine de poly(sulfure d'arylène) WO2023053529A1 (fr)

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Citations (3)

* Cited by examiner, † Cited by third party
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JP2020070445A (ja) * 2018-10-31 2020-05-07 東レ株式会社 粒状ポリアリーレンスルフィドの製造方法
JP2021113279A (ja) * 2020-01-20 2021-08-05 東ソー株式会社 ポリアリーレンスルフィドの製造方法
JP2021130792A (ja) * 2020-02-21 2021-09-09 東レ株式会社 ポリアリーレンスルフィドの製造方法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2020070445A (ja) * 2018-10-31 2020-05-07 東レ株式会社 粒状ポリアリーレンスルフィドの製造方法
JP2021113279A (ja) * 2020-01-20 2021-08-05 東ソー株式会社 ポリアリーレンスルフィドの製造方法
JP2021130792A (ja) * 2020-02-21 2021-09-09 東レ株式会社 ポリアリーレンスルフィドの製造方法

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