WO2020032171A1 - Procédé de purification et procédé de production de poly(sulfure d'arylène) - Google Patents

Procédé de purification et procédé de production de poly(sulfure d'arylène) Download PDF

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Publication number
WO2020032171A1
WO2020032171A1 PCT/JP2019/031355 JP2019031355W WO2020032171A1 WO 2020032171 A1 WO2020032171 A1 WO 2020032171A1 JP 2019031355 W JP2019031355 W JP 2019031355W WO 2020032171 A1 WO2020032171 A1 WO 2020032171A1
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Prior art keywords
polyarylene sulfide
pas
crude
solvent
carbonated water
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PCT/JP2019/031355
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English (en)
Japanese (ja)
Inventor
渡辺　創
渡邉　英樹
井上　敏
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Dic株式会社
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Priority to JP2020532073A priority Critical patent/JPWO2020032171A1/ja
Publication of WO2020032171A1 publication Critical patent/WO2020032171A1/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
    • C08G75/0277—Post-polymerisation treatment
    • C08G75/0281—Recovery or purification

Definitions

  • the present invention relates to a method for purifying and producing polyarylene sulfide (hereinafter sometimes abbreviated as PAS). More specifically, as compared with conventional refining methods using various strong acids (hydrochloric acid, sulfuric acid, etc.), it is possible to reduce the corrosiveness to manufacturing equipment and molds during molding, and to improve the quality of polyarylene sulfide.
  • the present invention relates to a purification method and a production method that can be performed.
  • Another object of the present invention is to provide polyarylene sulfide which is suitable as a material for a wide range of uses such as various molding materials, films, fibers, electric / electronic parts, automobile parts, and paints.
  • a typical polyphenylene sulfide (hereinafter sometimes abbreviated as PPS) is usually N-methyl-2-pyrrolidone, N, N-dimethyl, as described in Patent Document 1 and the like.
  • PPS polyphenylene sulfide
  • relatively polar organic solvents such as acetamide and N-methyl- ⁇ -caprolactam
  • alkali metal sulfide represented by sodium sulfide or alkali metal sulfide represented by sodium hydrosulfide and sodium hydroxide represented by sodium sulfide Obtained by reacting an alkali metal hydroxide with a polyhaloaromatic compound represented by p-dichlorobenzene (see Patent Document 1).
  • the polymerization reaction is usually carried out under high temperature and pressure and under alkaline conditions, and as the polymerization reaction proceeds, salt is generated.
  • the so-called crude reaction product after the polymerization reaction includes at least polyarylene sulfide and alkali metal halide. And, in addition, unreacted raw materials, cyclic or linear oligomers, and the following structural formula (1)
  • Ar is an aryl group having a halogen atom
  • R 1 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms or a cyclohexyl group
  • R 2 represents an alkylene group having 3 to 5 carbon atoms
  • X represents a hydrogen atom or an alkali metal atom
  • a compound represented by -NR 1 R 2 COOX group is sometimes referred to as carboxyalkylamino group (hereinafter sometimes referred to as carboxyalkylamino group-containing compound).
  • carboxyalkylamino group-containing compound a compound represented by -NR 1 R 2 COOX group
  • the polyarylene sulfide is produced, as a raw material for producing the polyarylene sulfide, for example, when the amide solvent is N-methyl-2-pyrrolidone and the polyhalo aromatic compound is p-dichlorobenzene, the carboxyalkylamino group
  • the amide solvent is N-methyl-2-pyrrolidone
  • the polyhalo aromatic compound is p-dichlorobenzene
  • CP-MABA Hydrogen-type
  • CP-MABA alkali-metal salt type
  • CP-MABA Na-salt type
  • the crude reaction product after the polymerization reaction is taken out to a suitable container, and the solvent contained therein is removed by a suitable means (e.g., vacuum distillation, centrifugation, screw decanter, vacuum filtration, pressure filtration, etc.). Depending on the method, it can be separated and recovered and reused (here, this operation is referred to as “desolvation”), or, if necessary, further purified and reused.
  • a suitable means e.g., vacuum distillation, centrifugation, screw decanter, vacuum filtration, pressure filtration, etc.
  • the slurry containing the polyarylene sulfide contained in the crude reaction product (hereinafter, crude polyarylene sulfide) is generally subjected to water washing and filtration repeatedly, Polyarylene sulfide can be obtained by drying after removing impurities such as salt and alkaline substances.
  • the polyarylene sulfide thus obtained is used for fibers, films, paints, compounds for injection molding materials and fiber reinforced composite materials, etc. due to its excellent chemical resistance, electrical properties, and mechanical properties.
  • impurities contained in polyarylene sulfide generate gas during melt processing, corrode injection molds and processing equipment, have poor adhesion to paint supports, and have the effect of reinforcing fibers in composite materials. Due to poor adhesion and the like, it has been desired to reduce the amount of impurities in polyarylene sulfide.
  • the problem to be solved by the present invention is to use an alkali metal halide or a carboxyalkylamino group-containing compound in polyarylene sulfide at a lower pressure without using a strong acid, and to prepare an alkali metal in polyarylene sulfide.
  • a method for purifying polyarylene sulfide which can efficiently reduce halides and carboxyalkylamino group-containing compounds, and a method for producing polyarylene sulfides in which alkali metal halides and carboxyalkylamino group-containing compounds in polyarylene sulfide are low. May be.
  • the inventors of the present application have found that when introducing carbon dioxide gas or carbonated water into the system and bringing carbon dioxide gas or carbonated water into contact with the crude polyarylene sulfide, the crude polyarylene sulfide becomes porous. By forming particles, it has been found that even at a lower temperature or at a low pressure, it is possible to efficiently reduce alkali metal halides and carboxyalkylamino group-containing compounds in polyarylene sulfide. Thus, the present invention has been completed.
  • the present invention provides a slurry containing a crude polyarylene sulfide by desolvating a crude reaction product containing a polyarylene sulfide obtained by reacting a polyhalo aromatic compound with a sulfide agent in an organic polar solvent.
  • a step of obtaining a crude product a slurry containing the crude polyarylene sulfide is brought into contact with water and a solvent containing an oxygen atom having 1 to 3 carbon atoms to make the crude polyarylene sulfide have a specific surface area of 30 m 2 / g or more.
  • a step of bringing the obtained porous particles into contact with carbonated water comprising the steps of:
  • the present invention also relates to a method for producing polyarylene sulfide, comprising a step of purifying polyarylene sulfide by the above-described purification method.
  • an alkali metal halide or a carboxyalkylamino group-containing compound in a polyarylene sulfide is treated at a lower temperature or under a low pressure without using a strong acid, and the alkali in the polyarylene sulfide is treated.
  • a method for purifying a polyarylene sulfide capable of efficiently reducing a metal halide or a carboxyalkylamino group-containing compound, and a method for producing a polyarylene sulfide having a low content of an alkali metal halide or a carboxyalkylamino group-containing compound in the polyarylene sulfide. Can be provided.
  • the present invention provides a slurry containing a crude polyarylene sulfide by desolvating a crude reaction product containing a polyarylene sulfide obtained by reacting a polyhalo aromatic compound with a sulfidizing agent in an organic polar solvent.
  • Polyarylene sulfide is usually prepared by reacting at least one polyhaloaromatic compound with at least one sulfidizing agent in an organic polar solvent such as N-methyl-2-pyrrolidone under appropriate polymerization conditions. And synthesized.
  • the polyhalo aromatic compound used in the present invention is, for example, a halogenated aromatic compound having two or more halogen atoms directly bonded to an aromatic ring, and specifically, p-dichlorobenzene, o- Dichlorobenzene, m-dichlorobenzene, trichlorobenzene, tetrachlorobenzene, dibromobenzene, diiodobenzene, tribromobenzene, dibromonaphthalene, triiodobenzene, dichlorodiphenylbenzene, dibromodiphenylbenzene, dichlorobenzophenone Dihaloaromatic compounds such as dibromobenzophenone, dichlorodiphenylether, dibromodiphenylether, dichlorodiphenylsulfide, dibromodiphenylsulfide, dichlorobiphenyl, dibromobiphenyl, and mixtures thereof.
  • the compounds may
  • a polyhalo aromatic compound having three or more halogen substituents in one molecule may be used as a branching agent, if desired.
  • Such polyhalo aromatic compounds include, for example, 1,2,4-trichlorobenzene, 1,3,5-trichlorobenzene, 1,4,6-trichloronaphthalene and the like.
  • polyhalo aromatic compounds having a functional group having an active hydrogen such as an amino group, a thiol group, or a hydroxyl group
  • 2,6-dichloroaniline, 2,5-dichloroaniline Dihaloanilines such as 2,3,4-dichloroaniline and 2,3-dichloroaniline; 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'-dichlorodiphenylether and 2,4'-diamino-2 ', 4-dichlorodiphenylether And compounds in which an amino group is replaced with a thiol group or a hydroxyl group in these mixtures.
  • a hydrogen atom bonded to a carbon atom forming an aromatic ring is replaced with another inert group, for example, an active hydrogen-containing polyhalo group such as an alkyl group.
  • Aromatic compounds can also be used.
  • active hydrogen-containing polyhalo aromatic compounds preferred are active hydrogen-containing dihalo aromatic compounds, and particularly preferred is dichloroaniline.
  • polyhalo aromatic compound having a nitro group examples include mono- or dihalonitrobenzenes such as 2,4-dinitrochlorobenzene and 2,5-dichloronitrobenzene; 2-nitro-4,4'-dichlorodiphenyl ether; Dihalonitrodiphenyl ethers; dihalonitrodiphenylsulfones such as 3,3'-dinitro-4,4'-dichlorodiphenylsulfone; 2,5-dichloro-3-nitropyridine, 2-chloro-3,5 Mono- or dihalonitropyridines such as dinitropyridine; or various dihalonitronaphthalenes.
  • mono- or dihalonitrobenzenes such as 2,4-dinitrochlorobenzene and 2,5-dichloronitrobenzene
  • 2-nitro-4,4'-dichlorodiphenyl ether Dihalonitrodiphenyl ethers
  • dihalonitrodiphenylsulfones such
  • the alkali metal sulfide used in the present invention includes lithium sulfide, sodium sulfide, rubidium sulfide, cesium sulfide and a mixture thereof.
  • Such an alkali metal sulfide can be used as a hydrate, an aqueous mixture or an anhydride.
  • the alkali metal sulfide can also be derived by a reaction between the alkali metal hydrosulfide and the alkali metal hydroxide.
  • alkali metal hydroxide may be added in order to react with a small amount of alkali metal hydrosulfide or alkali metal thiosulfate in the alkali metal sulfide.
  • organic polar solvent used in the present invention examples include N-methyl-2-pyrrolidone, formamide, acetamide, N-methylformamide, N, N-dimethylacetamide, 2-pyrrolidone, N-methyl- ⁇ -caprolactam, ⁇ -caprolactam , Hexamethylphosphoramide, tetramethylurea, N-dimethylpropyleneurea, amideurea of 1,3-dimethyl-2-imidazolidinonic acid, and lactams; sulfolane such as sulfolane and dimethylsulfolane; benzonitrile and the like Nitriles; ketones such as methylphenylketone and mixtures thereof.
  • the polymerization conditions of the sulfidizing agent and the polyhaloaromatic compound are generally at a temperature of 200 to 330 ° C., and the pressure is substantially lower than the polymerization solvent and the polyhaloaromatic compound as the polymerization monomer.
  • the range should be such that the liquid layer is kept in a liquid phase, and is generally selected from the range of 0.1 to 20 MPa, preferably 0.1 to 2 MPa.
  • the reaction time varies depending on the temperature and pressure, but is generally in the range of 10 minutes to 72 hours, preferably 1 hour to 48 hours.
  • a form obtained by reacting a crude reaction product by continuously or intermittently adding a polyhaloaromatic compound and an organic polar solvent in the presence of a sulfidizing agent and an organic polar solvent is also included. I do.
  • the crude reaction product containing the polyarylene sulfide obtained by the polymerization reaction is subjected to suitable means (e.g., vacuum distillation, centrifugation, screw decanter, vacuum filtration, pressure filtration, etc.). After the organic polar solvent is separated and removed, a slurry containing crude polyarylene sulfide can be obtained.
  • suitable means e.g., vacuum distillation, centrifugation, screw decanter, vacuum filtration, pressure filtration, etc.
  • the slurry containing the crude polyarylene sulfide is brought into contact with water and a solvent containing an oxygen atom having 1 to 3 carbon atoms, whereby the crude polyarylene sulfide has a specific surface area of 30 [m 2 / g].
  • a step of forming porous particles in the above range.
  • an appropriate amount of water is added to the slurry containing at least the crude polyarylene sulfide obtained in the previous step, and the slurry is washed.
  • the temperature at the time of adding water is not particularly limited, but is preferably from 10 ° C. or higher, more preferably from 20 ° C. or higher, preferably 120 ° C. or lower, more preferably 100 ° C. or lower, and still more preferably 80 ° C. or lower. .
  • the solid-liquid separation is performed by filtration or the like to obtain a slurry.
  • the amount of water used in one washing is not particularly limited, but is preferably 20 parts by mass or more, more preferably 50 parts by mass or more, and still more preferably 100 parts by mass, based on 100 parts by mass of polyarylene sulfide. To 10,000 parts by mass, preferably 5,000 parts by mass or less, more preferably 2,000 parts by mass or less.
  • the slurry is brought into contact with a slurry containing crude polyarylene sulfide and washed.
  • the temperature at which the organic solvent is added is not particularly limited, but is preferably in the range of 10 ° C or higher, more preferably 20 ° C or higher, preferably 90 ° C or lower, more preferably 70 ° C or lower.
  • the amount of the organic solvent used in one washing is not particularly limited, but is preferably 20 parts by mass or more, more preferably 50 parts by mass or more, and still more preferably 100 parts by mass based on 100 parts by mass of polyarylene sulfide. The amount is at least 5,000 parts by mass, preferably at most 5,000 parts by mass, more preferably at most 1,800 parts by mass, still more preferably at most 600 parts by mass.
  • the slurry containing the crude polyarylene sulfide may be brought into contact with water and a solvent containing an oxygen atom having 1 to 3 carbon atoms in any order, and the slurry containing the crude polyarylene sulfide is contacted with water and washed.
  • Step (Sw) a solvent containing an oxygen atom having 1 to 3 carbon atoms in any order
  • Step (Sw) a solvent containing 1 to 3 carbon atoms to wash it
  • Step (Sw) ”) or the step (Sw) may be performed after the step (Ss). Each step can be performed together or alternately, any one or more times.
  • oxygen atom-containing solvent having 1 to 3 carbon atoms to be brought into contact with the slurry containing the crude polyarylene sulfide for example, at least one selected from the group consisting of alcohol solvents and ketone solvents can be mentioned.
  • alcohol solvents also referred to as alcohol solvents
  • examples of alcohol solvents include methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, t-butyl alcohol, ethylene glycol, propylene glycol, trimethylolpropane, and benzyl.
  • Alcohols having 10 or less carbon atoms such as alcohols; 2-methoxyethyl alcohol, 2-ethoxyethyl alcohol, 1-methoxy-2-propyl alcohol, 1-ethoxy-2-propyl alcohol, 3-methoxy-1-butyl alcohol Alcohols having 10 or less carbon atoms containing an ether bond, such as, 2-isopropoxyethyl alcohol; alcohols having 10 or less carbon atoms containing a ketone group, such as 3-hydroxy-2-butanone; Dorokishiiso number of carbon atoms containing acid ester groups such as methyl or the like is 10 ppm alcohol are exemplified.
  • ketone solvent also referred to as a ketone solvent
  • examples of the ketone solvent include acetone, methyl ethyl ketone, cyclohexanone, ⁇ -butyl lactone, and N-methylpyrrolidinone.
  • the present invention relates to porous particles having a specific surface area of 30 [m 2 / g] or more by contacting crude polyarylene sulfide with water and the organic solvent one or more times, and contacting the same.
  • the porous particles Preferably, have a range of 43 m 2 / g or more and 200 m 2 / g or less, more preferably 60 m 2 / g or more and 120 m 2 / g or less. Range of porous particles.
  • the carboxyalkylamino group-containing compound in the crude polyarylene sulfide can be easily reduced, which is preferable.
  • the carboxyalkylamino group-containing compound contained in the crude polyarylene sulfide is preferably in the range of 1000 ppm or less per g of the polyarylene sulfide, more preferably 400 ppm or less, and 1 ppm or more. It is preferable to set the content in the range described above, because the effect of reducing impurities, particularly alkali metal halides, by washing with carbonated water described later becomes more excellent.
  • the present invention has a step of subsequently contacting the obtained porous particles with carbonated water.
  • the conditions for bringing the porous particles obtained in the previous step into contact with carbonated water are preferably 10 ° C. or higher, more preferably 20 ° C. or higher, preferably 100 ° C. or lower, more preferably 80 ° C. or lower.
  • the pressure gauge pressure
  • the conditions of temperature and pressure are within these ranges, in addition to the effects of excellent quality, in particular, the improvement of the mechanical properties by improving the reactivity with the epoxysilane-based silane coupling agent, the shortening of the isothermal crystallization time, etc.
  • a polyarylene sulfide having a reduced impurity concentration such as an alkali metal halide or a compound containing a carboxyalkylamino group in the polyarylene sulfide can be obtained.
  • the ratio of the alkali metal halide in the polyarylene sulfide is preferably not more than 1000 ppm, more preferably not more than 700 ppm, and still more preferably not more than 500 ppm, per gram of the polyarylene sulfide.
  • Can be reduced to The lower limit is not particularly limited, but is 20 ppm or more.
  • the ratio of the compound (1) represented by the structural formula (1) is preferably 1000 [ppm] or less, more preferably 500 [ppm] or less, and still more preferably 300 / g / g of the polyarylene sulfide. It can be reduced to the range of [ppm] or less.
  • the lower limit is not particularly limited, but is preferably 50 ppm or more.
  • One of the advantages of the present invention is that when the purification method using carbonated water of the present invention is used, there is almost no corrosion to metals under ordinary purification temperature conditions (100 ° C. or less), and the present apparatus can cope.
  • relatively inexpensive materials having corrosion resistance of about SUS304 can withstand corrosion, only the equipment cost advantage from the material side of the apparatus as compared with other acids can be mentioned.
  • One of the advantages of the present invention is that when other acids remain in the polyarylene sulfide (especially chloride ions and sulfate ions are likely to remain in the polymer), mold corrosion during molding and molding of the molded product may occur. Although it is a major cause of deterioration in physical properties, in the case of the purification method using carbonated water of the present invention, it is easy to remove even in a water washing step which is a later step, and it is also decomposed and scattered from polyarylene sulfide even in a drying step, so other It is difficult to cause corrosion of molds such as acids and deterioration of physical properties of molded products.
  • one of the advantages of the present invention is that when a strong acid other than carbonated water is used, a large amount of water and the number of times of washing are required after washing with the strong acid in order to remove the acid remaining in the polyarylene sulfide.
  • the amount of water used after washing with carbonated water can be reduced, and the number of times of washing can be reduced. Therefore, this method is very advantageous in terms of process capability, and can be said to be a method suitable for environmental measures.
  • the present invention provides a polyarylene by contacting an aqueous solution in which the solubility of carbonic acid is controlled by controlling the pressure and temperature of the system by blowing carbon dioxide gas into an airtight container or apparatus, for a suitable period of time (eg, 5 minutes or longer).
  • a purification method characterized in that the molecular end of sulfide is converted from a basic end (SNa type end) to an acidic end (SH type end), wherein the SNa group present at the molecular chain end of polyarylene sulfide is SH.
  • the concentration of carbon dioxide (derived carbonate ions) in carbonated water depends on the solubility of carbon dioxide in water, and more specifically follows Henry's law at the temperature and pressure.
  • carbon dioxide gas may be bubbled into water in an open container or a closed container or piping, or may be press-fitted, or continuously using a hollow fiber membrane module or the like. Carbon dioxide may be dissolved in water.
  • the solid content concentration in the system is preferably a ratio of 1 to 50% by weight.
  • the contact between the polyarylene sulfide particles and the carbonated water is favorably performed, and the purification efficiency is suitable and more preferable.
  • the amount of carbonated water is not particularly limited, but is preferably 50 to 10,000 parts by mass, more preferably 100 to 5,000 parts by mass, and still more preferably 200 to 2,000 parts by mass, per 100 parts by mass of polyarylene sulfide. When the amount of carbonated water is within this range, the contact between the polyarylene sulfide particles and the carbonated water is performed favorably, and the purification efficiency is suitable and more preferable.
  • the contact between carbonated water and porous particles of polyarylene sulfide can be performed in an open-type container having a stirring blade inside the container and a filter disposed at the bottom at the bottom. It is not necessary to carry out in a hermetically sealed or hermetically sealed container having a mixing function, but naturally it can also be carried out in such a container.
  • the embodiment of the present invention is, as described above, in an organic polar solvent, after desolvating a crude reaction product containing a polyarylene sulfide obtained by reacting a polyhalo aromatic compound with a sulfidizing agent, A polyarylene sulfide having a specific surface area of 30 [m 2 / g] or more by contacting with an organic solvent to form porous particles, and contacting the obtained porous particles with carbonated water. It relates to a purification method.
  • Another embodiment of the present invention relates to a method for producing polyarylene sulfide, comprising a step of purifying polyarylene sulfide by the purification method.
  • the polyarylene sulfide obtained through the purification method of the present invention may be dried as it is, or may be appropriately washed with water or an organic solvent, then solid-liquid separated and dried.
  • Drying is performed by heating to a temperature at which a solvent such as water is substantially evaporated. Drying may be performed under vacuum, or may be performed in air or under an inert atmosphere such as nitrogen.
  • the polyarylene sulfide obtained by the production method of the present invention can be used as it is for conventional molding materials and the like, but can be thickened by heat treatment in air or oxygen-enriched air or under reduced pressure. After performing such a thickening operation as needed, it may be used for various molding materials. Since the heat treatment temperature varies depending on the treatment time and the atmosphere in which the treatment is performed, it cannot be unconditionally specified. If the heat treatment temperature is lower than 180 ° C., the rate of thickening is extremely slow, and the productivity is poor, which is not preferable.
  • the heat treatment may be performed in a molten state at a temperature higher than the melting point of the polymer using an extruder or the like. However, from the viewpoint of the possibility of deterioration of the polymer or workability, it is preferable to carry out the reaction at a temperature higher than the melting point plus 100 ° C.
  • the polyarylene sulfide obtained by the present invention is, as in the past, blended with a filler or other resin, melt-kneaded, directly or once formed into pellets, and then subjected to injection molding, extrusion molding, compression molding, blow molding.
  • a filler or other resin melt-kneaded, directly or once formed into pellets, and then subjected to injection molding, extrusion molding, compression molding, blow molding.
  • a molded article having excellent heat resistance, moldability, dimensional stability, and the like can be obtained.
  • the filler include a fibrous filler and an inorganic filler.
  • a small amount of a mold release agent, a colorant, a heat stabilizer, an ultraviolet stabilizer, a foaming agent, a rust inhibitor, a flame retardant, a lubricant, a cup as an additive during the molding process without departing from the object of the present invention.
  • a ring agent can be included.
  • the following synthetic resins and elastomers can be mixed and used.
  • the elastomer include polyolefin rubber, fluorine rubber, and silicone rubber.
  • a molded article obtained by melt-molding the polyarylene sulfide of the present invention or a resin composition containing the same has excellent heat resistance, dimensional stability and the like as PPS obtained by a conventional method.
  • Electric and electronic parts such as molded parts, automotive parts such as lamp reflectors and various electrical parts, interior materials for various buildings, aircraft and automobiles, and precision parts such as OA equipment parts, camera parts, watch parts, etc. It can be widely used as injection molded / compressed molded products, or extruded / pull molded products such as fibers, films, sheets and pipes.
  • CP-MABA in the filtrate was prepared by adding the mobile phase as it was and measured.
  • hydrochloric acid was added to the aqueous solution as a filtrate to adjust the pH of the aqueous solution to 4.
  • brown oily CP-MABA hydrogen type
  • Chloroform was added thereto to extract a brown oily substance.
  • the aqueous phase was discarded because it contained N-methyl-2-pyrrolidone and its ring-opened product, 4-methylaminobutyric acid (hereinafter abbreviated as "MABA").
  • MABA 4-methylaminobutyric acid
  • HPLC measurement From the well stirred solution, 1 ml was sampled, and 9 ml of the HPLC mobile phase was added thereto, and the filtrate was used as a measurement sample. The measurement sample was subjected to HPLC measurement, and the concentration in the liquid was determined from the peak area and the calibration curve at the same retention time as the standard sample prepared by the following method.
  • the HPLC measurement conditions are as follows.
  • Measurement Method 2 Method of Analyzing Specific Surface Area (BET Specific Surface Area) Tristar II3020 manufactured by Shimadzu Corporation was used for measuring the specific surface area. After the sample was put into the cell, it was degassed, replaced with helium, cooled, and replaced with nitrogen to measure the specific surface area.
  • the kettle After heating and distilling 27.3 kg of water, the kettle was sealed. The DCB distilled off azeotropically during the dehydration was separated by a decanter and returned to the kettle at any time. After the completion of the dehydration, the anhydrous sodium sulfide composition was dispersed in the DCB. Furthermore, the internal temperature was cooled to 160 ° C, NMP 47.492 kg (479 mol) was charged, and the temperature was raised to 185 ° C. When the pressure reached 0.00 MPa, the valve connected to the rectification column was opened, and the internal temperature was raised to 200 ° C. over 1 hour. At this time, cooling and valve opening were controlled so that the outlet temperature of the rectification column was 110 ° C. or lower.
  • the mixed vapor of the distilled DCB and water was condensed by a condenser, separated by a decanter, and the DCB was returned to the kettle.
  • the amount of distilled water was 179 g.
  • the internal temperature was raised from 200 ° C. to 230 ° C. over 3 hours, and after stirring for 1 hour, the temperature was raised to 250 ° C. and stirred for 1 hour. After the reaction was completed, the internal temperature of the autoclave was raised from 250 ° C. to 235 ° C.
  • Example 1 400 g of the PPS mixture obtained in Synthesis Example 1 and 634 g of isopropyl alcohol were placed in a flask and mixed by stirring at 40 ° C. for 30 minutes. The slurry was filtered under reduced pressure with a Kiriyama funnel, compacted from above, and 422 g of isopropyl alcohol was further added from above. The mixture was poured into portions and filtered. Further, the cake prepared by the filtration was transferred to a beaker, crushed into a powder with a spoonful, 634 g of water at 70 ° C. was poured therein, and the mixture was stirred and mixed for 30 minutes.
  • the slurry was filtered under reduced pressure with a Kiriyama funnel, compacted from above, and 845 g of water at 70 ° C. was poured from the top into several portions and filtered. 8 g of the cake was crushed, sampled, dried in a hot air drier at 120 ° C. for 4 hours, and the resin content was analyzed. As a result, the specific surface area was 79 [m 2 / g], and the content of CP-MABA in the resin was 207 [ppm]. The cake was transferred to a beaker, and 636 g of carbonated water was poured into the beaker and mixed with stirring for 1 hour.
  • the slurry was filtered under reduced pressure with a Kiriyama funnel, compacted from above, and 848 g of carbonated water was poured from above in several portions and filtered.
  • the cake produced by the filtration was transferred to a vat, crushed into powder with a spoon, and dried at 120 ° C. for 4 hours.
  • As a result of analyzing the amount of sodium in the obtained resin it was 300 [ppm].
  • Example 2 317 g of methanol was used instead of 634 g of isopropyl alcohol, and 634 g of methanol was used instead of 422 g of isopropyl alcohol, and the rest was carried out under the same conditions as in Example 1.
  • the specific surface area was 83 [m 2 / g]
  • the content of CP-MABA in the resin was 52 [ppm].
  • the amount of carbonated water was changed to 845 g instead of 636 g, and the other conditions were the same as in Example 1.
  • As a result of analyzing the amount of sodium in the obtained resin it was 290 [ppm].
  • Example 3 The amount of isopropyl alcohol was changed from 634 g to 1056 g, the amount of isopropyl alcohol was changed from 422 g to 845 g, and the rest was carried out under the same conditions as in Example 1.
  • the specific surface area was 75 [m 2 / g]
  • the content of CP-MABA in the resin was 125 [ppm].
  • the amount of carbonated water was changed to 1584 g instead of 636 g, and the other conditions were the same as in Example 1.
  • As a result of analyzing the amount of sodium in the obtained resin it was 200 [ppm].
  • Example 4 The procedure was performed under the same conditions as in Example 1 except for using 221 g of ethanol instead of 634 g of isopropyl alcohol and 422 g of ethanol instead of 422 g of isopropyl alcohol.
  • the specific surface area was 60 [m 2 / g]
  • the content of CP-MABA in the resin was 450 [ppm].
  • the steps were performed under the same conditions as in Example 1.
  • As a result of analyzing the amount of sodium in the obtained resin it was 230 [ppm].
  • Example 5 845 g of acetone was used instead of 634 g of isopropyl alcohol, and 845 g of acetone was used instead of 422 g of isopropyl alcohol, and the rest was performed under the same conditions as in Example 1.
  • the specific surface area was 43 [m 2 / g]
  • the content of CP-MABA in the resin was 399 [ppm].
  • the amount of carbonated water was changed to 845 g instead of 636 g, and the amount of carbonated water was changed to 1267 g instead of 848 g.
  • As a result of analyzing the amount of sodium in the obtained resin it was 340 [ppm].
  • Example 6 1056 g of ethanol was used instead of 634 g of isopropyl alcohol, and 845 g of ethanol was used instead of 422 g of isopropyl alcohol, and the rest was performed under the same conditions as in Example 1.
  • the specific surface area was 102 [m 2 / g]
  • the content of CP-MABA in the resin was 57 [ppm].
  • the amount of carbonated water was 422 g instead of 636 g, and the amount of carbonated water was 422 g instead of 848 g.
  • As a result of analyzing the amount of sodium in the obtained resin it was 380 [ppm].
  • Example 7 The procedure was carried out under the same conditions as in Example 1, except that 634 g of isopropyl alcohol was replaced by 211 g of methanol, and 422 g of isopropyl alcohol was replaced by 422 g of methanol.
  • the specific surface area was 75 [m 2 / g]
  • the content of CP-MABA in the resin was 187 [ppm].
  • the amount of carbonated water was 422 g instead of 636 g, and the amount of carbonated water was 1267 g instead of 848 g.
  • As a result of analyzing the amount of sodium in the obtained resin it was 350 [ppm].
  • the specific surface area was 78 [m 2 / g], and the content of CP-MABA in the resin was It was 3246 [ppm].
  • the cake was transferred to a beaker, 845 g of carbonated water was poured therein, and the mixture was stirred and mixed for 1 hour.
  • the slurry was filtered under reduced pressure with a Kiriyama funnel, compacted from above, and further filtered and poured from above with 1267 g of carbonated water in several portions.
  • the cake produced by the filtration was transferred to a vat, crushed into powder with a spoon, and dried at 120 ° C. for 4 hours. As a result of analyzing the amount of sodium in the obtained resin, it was 930 [ppm].
  • the temperature was lowered to room temperature, the slurry was filtered under reduced pressure with a Kiriyama funnel, compacted from above, and 845 g of 70 ° C. water was poured from above into several portions and filtered.
  • the cake was crushed, 8 g was sampled, dried by a hot air drier at 120 ° C. for 4 hours, and the resin was analyzed.
  • the specific surface area was 8 [m 2 / g], and the content of CP-MABA in the resin was It was 849 [ppm].
  • the cake was transferred to a beaker, 845 g of carbonated water was poured therein, and the mixture was stirred and mixed for 1 hour.
  • the slurry was filtered under reduced pressure with a Kiriyama funnel, compacted from above, and further filtered and poured from above with 1267 g of carbonated water in several portions.
  • the cake produced by the filtration was transferred to a vat, crushed into powder with a spoon, and dried at 120 ° C. for 4 hours.
  • As a result of analyzing the amount of sodium in the obtained resin it was 1200 [ppm].

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  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)

Abstract

L'invention concerne un procédé de purification de poly(sulfure d'arylène) (PAS) qui permet de réduire efficacement des halogénures de métal alcalin et des composés contenant un groupe carboxyalkylamino dans le PAS par traitement des halogénures de métal alcalin et des composés contenant un groupe carboxyalkylamino dans le PAS sous une basse pression sans utiliser d'acide fort et un procédé de production de PAS présentant un faible niveau d'halogénures de métal alcalin et de composés contenant un groupe carboxyalkylamino dans le PAS. Plus particulièrement, l'invention concerne un procédé de purification de PAS, le procédé comprenant une étape d'élimination d'un solvant à partir d'un produit de réaction brut qui contient du PAS et qui est obtenu par réaction d'un composé polyhalogénoaromatique et d'un agent de sulfuration dans un solvant polaire organique et obtention d'une suspension contenant du PAS brut, une étape de mise en contact de la suspension contenant du PAS brut avec de l'eau et un solvant contenant un atome d'oxygène pour façonner le PAS brut en particules poreuses présentant une aire de surface spécifique de 30 m2/g ou plus et une étape de mise en contact des particules poreuses obtenues avec de l'eau gazéifiée ; et un procédé de production de PAS, le procédé présentant les étapes susmentionnées.
PCT/JP2019/031355 2018-08-10 2019-08-08 Procédé de purification et procédé de production de poly(sulfure d'arylène) WO2020032171A1 (fr)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2019006923A (ja) * 2017-06-27 2019-01-17 東ソー株式会社 ポリアリーレンスルフィドおよびその製造方法
WO2021117795A1 (fr) * 2019-12-11 2021-06-17 Dic株式会社 Poly(sulfure d'arylène), et procédé de purification et procédé de production associés
JP2021098815A (ja) * 2019-12-23 2021-07-01 Dic株式会社 ポリアリーレンスルフィド、その精製方法および製造方法
JP7318843B1 (ja) * 2022-05-10 2023-08-01 Dic株式会社 ポリアリーレンスルフィドの精製方法及び製造方法
WO2023218735A1 (fr) * 2022-05-10 2023-11-16 Dic株式会社 Procédé de purification et procédé de production de sulfure de polyarylène

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JPS51144495A (en) * 1975-05-27 1976-12-11 Phillips Petroleum Co Process for polymerizing allylene and sulfide
JPH06192421A (ja) * 1992-10-23 1994-07-12 Phillips Petroleum Co ポリ（アリーレンスルフィド）ポリマーの製造法
WO2003048231A1 (fr) * 2001-12-03 2003-06-12 Kureha Chemical Industry Company, Limited Procede de purification continue de sulfure de polyarylene
JP2005264030A (ja) * 2004-03-19 2005-09-29 Dainippon Ink & Chem Inc ポリアリーレンスルフィドの精製方法
WO2006027985A1 (fr) * 2004-09-06 2006-03-16 Kureha Corporation Procédé servant à produire du sulfure de polyarylène
WO2012070335A1 (fr) * 2010-11-26 2012-05-31 株式会社クレハ Procédé de production de polysulfure d'arylène, et polysulfure d'arylène
JP2015040284A (ja) * 2013-08-23 2015-03-02 Dic株式会社 ポリアリーレンスルフィド樹脂多孔質体およびその製造方法
WO2015166838A1 (fr) * 2014-04-30 2015-11-05 株式会社クレハ Procédé de production de polysulfure d'arylène, et appareil pour sa production
JP2017071752A (ja) * 2015-10-05 2017-04-13 Dic株式会社 ポリアリーレンスルフィド樹脂の製造方法

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS51144495A (en) * 1975-05-27 1976-12-11 Phillips Petroleum Co Process for polymerizing allylene and sulfide
JPH06192421A (ja) * 1992-10-23 1994-07-12 Phillips Petroleum Co ポリ（アリーレンスルフィド）ポリマーの製造法
WO2003048231A1 (fr) * 2001-12-03 2003-06-12 Kureha Chemical Industry Company, Limited Procede de purification continue de sulfure de polyarylene
JP2005264030A (ja) * 2004-03-19 2005-09-29 Dainippon Ink & Chem Inc ポリアリーレンスルフィドの精製方法
WO2006027985A1 (fr) * 2004-09-06 2006-03-16 Kureha Corporation Procédé servant à produire du sulfure de polyarylène
WO2012070335A1 (fr) * 2010-11-26 2012-05-31 株式会社クレハ Procédé de production de polysulfure d'arylène, et polysulfure d'arylène
JP2015040284A (ja) * 2013-08-23 2015-03-02 Dic株式会社 ポリアリーレンスルフィド樹脂多孔質体およびその製造方法
WO2015166838A1 (fr) * 2014-04-30 2015-11-05 株式会社クレハ Procédé de production de polysulfure d'arylène, et appareil pour sa production
JP2017071752A (ja) * 2015-10-05 2017-04-13 Dic株式会社 ポリアリーレンスルフィド樹脂の製造方法

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2019006923A (ja) * 2017-06-27 2019-01-17 東ソー株式会社 ポリアリーレンスルフィドおよびその製造方法
WO2021117795A1 (fr) * 2019-12-11 2021-06-17 Dic株式会社 Poly(sulfure d'arylène), et procédé de purification et procédé de production associés
JP2021098815A (ja) * 2019-12-23 2021-07-01 Dic株式会社 ポリアリーレンスルフィド、その精製方法および製造方法
JP7318843B1 (ja) * 2022-05-10 2023-08-01 Dic株式会社 ポリアリーレンスルフィドの精製方法及び製造方法
WO2023218735A1 (fr) * 2022-05-10 2023-11-16 Dic株式会社 Procédé de purification et procédé de production de sulfure de polyarylène

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