WO2023089872A1 - Procédé pour la production de résine de poly(sulfure d'arylène) modifiée - Google Patents

Procédé pour la production de résine de poly(sulfure d'arylène) modifiée Download PDF

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Publication number
WO2023089872A1
WO2023089872A1 PCT/JP2022/029049 JP2022029049W WO2023089872A1 WO 2023089872 A1 WO2023089872 A1 WO 2023089872A1 JP 2022029049 W JP2022029049 W JP 2022029049W WO 2023089872 A1 WO2023089872 A1 WO 2023089872A1
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Prior art keywords
container
raw material
gas
pas resin
reforming
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PCT/JP2022/029049
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English (en)
Japanese (ja)
Inventor
麻朗 竹中
高志 古沢
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Dic株式会社
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Application filed by Dic株式会社 filed Critical Dic株式会社
Priority to JP2023504050A priority Critical patent/JP7302759B1/ja
Publication of WO2023089872A1 publication Critical patent/WO2023089872A1/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
    • 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
    • C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules

Definitions

  • the present disclosure relates to a method for producing a modified polyarylene sulfide resin.
  • Polyarylene sulfide resins (hereinafter also abbreviated as "PAS resins”) typified by polyphenylene sulfide resins (hereinafter abbreviated as “PPS resins”) are excellent in heat resistance, chemical resistance, etc. Therefore, it is widely used for electrical and electronic parts, automobile parts, plumbing parts, fibers, films, and the like.
  • each type of PAS which is roughly classified into crosslinked PAS resin (also referred to as high molecular weight PAS resin), linear PAS resin or semi-crosslinked PAS resin
  • Various methods for modifying the PAS resin such as increasing the molecular weight, increasing the viscosity, or increasing the purity, have been studied as methods for producing the resin.
  • a method for producing a crosslinked PAS resin mainly used for injection molding crude PAS obtained by reacting a sulfidating agent with a polyhalogenoaromatic compound in the presence of an organic polar solvent is prepared. , after removing the by-produced salt by washing with water, a method of oxidative cross-linking is adopted.
  • Patent Document 1 a container rotation type heating device is used, which is provided with a gas introduction section for introducing oxygen-containing gas and a gas exhaust section for discharging internal gas by heating particulate PPS resin to a temperature below its melting point.
  • a method of curing PPS resin is disclosed.
  • the container rotating type heating device described in Patent Document 1 does not use a stirring blade, for example, a stirring blade such as a fixed container heating and mixing device with a double spiral stirring blade is used. It is said that problems (uneven curing, decrease in yield, removal of adhesion layer) caused by agglomeration and adhesion solidification of PPS resin particles in a heating and mixing device are less likely to occur.
  • Patent Document 2 discloses a method for producing a high molecular weight PAS resin using a screw mixing type heating device, a conical screw mixing type heating device, or a high-speed rotating blade mixing type heating device. Then, according to Patent Document 2, by using the fixed container heating device described in Patent Document 2 and adopting a predetermined gas flow, the conventional fixed container heating and mixing with double spiral stirring blades It is said that the problem of the device or container rotating type heating device can be avoided.
  • Patent Document 1 suffers from structural problems of the container rotating type heating device used, such as heat transferability, mixability of raw material components, or product recovery (for example, recovery of high-temperature products, product recovery rate, etc.), the productivity of the oxidatively crosslinked PAS resin is inferior, and low-molecular-weight components in the obtained PAS resin (mainly low-boiling volatile oligoarylene sulfides ) (hereinafter referred to as low-molecular-weight impurities) was insufficiently removed. Therefore, in any type of PAS resin production method, if the technique of Patent Document 1 is used, the raw material components are not uniformly dispersed and mixed, making it difficult to control the molecular weight.
  • the technique of Patent Document 1 if the technique of Patent Document 1 is used, the raw material components are not uniformly dispersed and mixed, making it difficult to control the molecular weight.
  • Patent Document 2 is not only insufficient in removing low-molecular-weight impurities, but the technique of Patent Document 2 uses a mixing device equipped with a rotating blade for stirring. Friction between the rotating blades and the container tends to generate metal powder, which causes a problem of contamination (metal contamination, deformed resin contamination) in the next step.
  • contamination metal contamination, deformed resin contamination
  • the technique of Patent Document 2 is used to produce a linear PAS resin, it will not be possible to ensure the high purity that is its advantage, and as a result, There is a possibility that the low hygroscopic property of the rubber cannot be effectively exhibited.
  • PAS resin solid matter the PAS resin component adhering to the inner wall of the container or the stirring blade (hereinafter referred to as PAS resin solid matter) is further aggregated, or pressed against the inner wall of the container or the lid of the container by the stirring blade or stirring shaft. If the PAS resin adheres firmly to the inner wall of the container or the bottom surface of the container, there is no chemical that dissolves in an environment of 200 ° C or less due to the characteristics of PAS resin (for example, PPS resin). It is extremely difficult to remove the PAS resin adhering to the inner wall or the bottom of the container.
  • PAS resin solid matter the PAS resin component adhering to the inner wall of the container or the stirring blade
  • An object of the present invention is to provide a method for producing a modified PAS resin with reduced
  • the present inventors have made extensive studies to solve the various problems described above. As a result, the inventors have found that the various problems described above can be solved by using a predetermined reforming apparatus and adopting a heat treatment and a gas supply control process under predetermined conditions, and have completed the present invention.
  • the present disclosure includes a tapered container portion capable of accommodating a raw material component including a PAS resin, and along the inner wall of the container portion, from the bottom portion to the upper portion of the container portion, and further from the upper portion to the center side of the container portion.
  • a reforming treatment apparatus equipped with a stirring mechanism forms a circulation flow in which the raw material components circulate to the bottom through the reforming gas (g S ) atmosphere, and the raw material components are heated to the melting point T of the PAS resin.
  • a method for producing a modified PAS resin by heating to a temperature of less than m comprising: The reforming gas (g s ) is supplied into the container part and the gas (g d ) inside the container part is discharged outside the container part, and the raw material component introduced into the container part is transferred to the circulating flow. a heat treatment step of heating the raw material component to below the melting point Tm by a heating means while circulating by and a gas supply control step of controlling the supply amount of the reforming gas (g S ) per minute within the range of 0.1 to 100% of the volume of the container part. It is a manufacturing method of PAS resin.
  • the present disclosure while suppressing the aggregation of PAS resins that tend to fuse at high temperatures, the formation of solidified PAS resins that adhere to the inner wall of the container is suppressed and prevented, and the concentration and contamination of low-molecular-weight impurities are suppressed. It is possible to produce a modified PAS resin with reduced According to the present disclosure, a high yield of modified PAS resin can be produced.
  • FIG. 1 is a schematic vertical cross-sectional view of a main part of a reforming treatment apparatus 1 according to this embodiment.
  • 2 is a perspective view of the stirring member 2 of FIG. 1.
  • FIG. 3 is a perspective view of the stirring member 2 of another aspect of this embodiment.
  • FIG. 4 is a schematic vertical cross-sectional view of the reforming apparatus 1 of another aspect of this embodiment.
  • the PAS resin contained as a raw material component is heated to a temperature lower than the melting point Tm of the PAS resin in an atmosphere of a reforming gas (g S ) used to modify the PAS resin by using a modification apparatus.
  • the reforming apparatus includes a tapered container portion capable of containing the raw material component including the PAS resin, and along the inner wall of the container portion, from the bottom portion of the container portion to the upper portion, and further from the upper portion to the container portion. It has a stirring mechanism that forms a circulation flow in which the raw material components circulate to the bottom through the center side of the part.
  • a stirring mechanism that forms a circulation flow in which the raw material components circulate to the bottom through the center side of the part.
  • the PAS resin solid matter is an amorphous (e.g., granular or tabular) mass generated in the manufacturing process of the modified PAS resin, and the PAS resin adhering to the inner wall of the container.
  • the PAS resin adhered matter can be visually observed as described in the Examples section below.
  • modification refers to increasing the molecular weight of the PAS resin contained as a raw material component for the purpose of improving the properties of the PAS resin contained as a raw material component or eliminating the drawbacks of the PAS resin, Increasing the viscosity of the PAS resin contained as a raw material component, purifying the PAS resin contained as a raw material component, copolymerizing with other monomers, blending with other polymer materials, or plasticizing , Mixing with additives such as curing agents or stabilizers.
  • the above-mentioned increase in molecular weight means that the amount of change (%) in the peak molecular weight (M top ) of the molecular weight distribution before and after the modification treatment is a predetermined value or more, that is, the modification treatment apparatus of the present embodiment.
  • the increase in viscosity is represented by the amount of change (%) in the melt viscosity before and after performing the heat treatment step and the gas supply control step of the present embodiment using the reforming apparatus of the present embodiment.
  • Formula (2): ⁇ (melt viscosity of modified PAS resin after heat treatment step and gas supply control step) - (melt viscosity of PAS resin contained as a raw material component before heat treatment step and gas supply control step ) ⁇ /(melt viscosity of PAS resin contained as raw material component before heat treatment step and gas supply control step) ⁇ 100 is 10% or more.
  • the above-mentioned high purification refers to the concentration of low-molecular-weight impurities (the amount of gas generated (mass% ))
  • Expression (3) represented by the amount of change (%): ⁇ (Concentration of low-molecular-weight impurities in PAS resin contained as raw material components before heat treatment step and gas supply control step (gas generation amount (mass%)))-(heat treatment step and gas supply control step Concentration of low-molecular-weight impurities in the modified PAS resin (gas generation amount (mass%))) ⁇ /(Low molecular weight impurity content of the PAS resin contained as a raw material component before the heat treatment step and the gas supply control step) It means that the concentration of molecular weight impurities (gas generation amount (mass %)) ⁇ 100 is 10% or more.
  • the amount of gas generated (% by mass) calculated by the method described in the Examples column is used as an example of an indicator of the concentration of low-molecular-weight impurities.
  • the PAS resin contained as a raw material component refers to the PAS resin before being subjected to the heat treatment step and the gas supply control step of the present embodiment using the reforming apparatus of the present embodiment. It is also called raw material PAS resin. Therefore , the raw material PAS resin is a PAS resin that has not yet been modified. to 150,000, or PAS resins with a low molecular weight impurity concentration of 1.0 mass % or more.
  • the method for measuring the melt viscosity at 300° C. uses the measuring method described in the Examples section.
  • the peak molecular weight (M top ) of the molecular weight distribution of the PAS resin of the present embodiment can be measured using gel permeation chromatography (GPC) under the following conditions using six types of monodisperse polystyrene for calibration. can.
  • GPC gel permeation chromatography
  • low molecular weight impurities refer to volatile oligoarylene sulfides, which are produced as by-products in the PAS polymerization reaction stage and have peak molecular weights (M top ) in the molecular weight distribution of less than 1000.
  • M top peak molecular weights
  • a PAS resin is mentioned.
  • the volatile oligoarylene sulfide the following general formulas (1) and (2): (In the above general formulas (1) and (2), each Y 1 independently represents a halogen atom (fluorine atom, chlorine atom, bromine atom, etc.)) and / or 3 Including polymer components.
  • the lower limit of the dimer component and/or trimer component is preferably 50% by mass or more, more preferably 70% by mass or more, and still more preferably It can be 80% by mass or more.
  • the upper limit may be preferably 100% by mass or less, more preferably 95% by mass or less, and even more preferably 90% by mass or less.
  • the content of the dimer component and/or the trimer component in the volatile oligoarylene sulfide can be any combination of the above lower limit and the above upper limit.
  • a raw material component containing a commercially available raw PAS resin or a raw material component containing a raw PAS resin obtained by the polymerization process described below is stirred with a stirring mechanism.
  • modifying the PAS resin as a raw material component a product having desired mechanical properties or moldability can be obtained.
  • the reforming treatment apparatus of the present embodiment includes a tapered container portion capable of accommodating raw material components including a raw material PAS resin, and along the inner wall of the container portion, from the bottom portion of the container portion to the upper portion, and further from the upper portion.
  • a stirring mechanism is provided for forming a circulation flow in which the raw material components circulate to the bottom portion through the center side of the container portion.
  • FIG. 1 is a schematic vertical cross-sectional view of the main part of the reforming apparatus in this embodiment.
  • a lid portion 11 that is attached to the opening portion OP2 and that can be opened and closed to take out raw material components or contents, and a space V (or a recess) between the bottom portion that is the lid portion 11 and the top portion that is the first opening portion OP1.
  • the reforming apparatus 1 is a tapered cylinder having a first opening OP1 and a second opening OP2 having an opening diameter d2 smaller than the opening diameter d1 of the first opening OP1.
  • a discharge port 9 for discharging gas (g d ) in 4 an input port 10 for inputting raw material components including the raw material PAS resin, and a content (raw material) in the container part 4 attached to the second opening OP2. and an openable and closable lid 11 for taking out the component or product P).
  • the stirring member 2 preferably has rotary blades. Furthermore, it is preferable that the maximum rotation diameter of the rotor blade is 50 to 99% of the diameter d1 .
  • the first opening OP1 is closed by a top plate T having an inlet 10 for charging raw material components including the raw material PAS resin and a discharge port 9 for discharging the gas (g d ) in the container part 4.
  • the second opening OP2 is closed by the openable/closable lid portion 11, the inside of the container portion 4, that is, the space V is sealed.
  • the supply port 8, the discharge port 9 and the input port 10 can also be closed by known closing means.
  • FIG. 1 shows an example of a so-called inverted truncated cone-shaped cylindrical body as an example of the container part 4 as a whole. Therefore, the first opening OP1 and the second opening OP2 of the inverted truncated cone-shaped cylindrical body are both circular, and the centers of both openings are coaxial centers (or the first opening OP1 and the second opening and the portion OP2 are coaxial circles). As a result, the symmetry of the rotating shaft 2 a within the container portion 4 can be maintained, and a uniform circulation flow can be easily formed within the container portion 4 .
  • FIG. 1 shows an example of a so-called inverted truncated cone-shaped cylindrical body as an example of the container part 4 as a whole. Therefore, the first opening OP1 and the second opening OP2 of the inverted truncated cone-shaped cylindrical body are both circular, and the centers of both openings are coaxial centers (or the first opening OP1 and the second opening and the portion OP2 are coaxial circles).
  • a stirring apparatus having a rotating shaft 2a is provided so that the long axis of the rotating shaft 2a is provided on the coaxial center line between the first opening OP1 and the second opening OP2.
  • An example in which the member 2 is attached and the stirring member 2 is accommodated in the container portion 4 is shown.
  • the top plate T that closes the first opening OP1 is also circular, and the top plate T and the first opening OP1 are coaxial circles. show.
  • the ratio d 1 /d 2 between the diameter d 1 of the first opening OP1 and the diameter d 2 of the second opening OP2 is preferably 1.1 to 10.0.
  • the diameter d1 of the first opening OP1 refers to the maximum length among the lengths connecting any two points on the outer circumference of the first opening OP1
  • the diameter d2 of the second opening OP2 is also It means the maximum length among the lengths connecting any two points on the outer circumference of the second opening OP2.
  • a double-helical rotor blade is shown as an example of the stirring member 2 , and the double-helical rotor blade also has a tapered shape following the shape of the container part 4 .
  • the stirring member 2 includes a rotating shaft 2a (a rotating shaft used for the stirring member 2) extending from the top plate T side (upper side) of the container portion 4 to the lid portion 11 side (lower side) in the container portion 4.
  • the strip-shaped rotor blades are blades that extend three-dimensionally and continuously in the vertical direction within the container portion 4 and reach the lower region of the container portion 4 .
  • the reforming treatment apparatus 1 is provided with a stirring mechanism, and the stirring mechanism stirs the raw material component containing the PAS resin filled in the tapered container portion 4 .
  • the stirring mechanism includes a tapered container portion 4 and a stirring member 2 following the shape of the tapered container portion 4 .
  • the agitating member 2 having a rotating blade housed in the space V in the container portion 4 is detachably attached to the tapered container portion 4 . Therefore, by rotating the rotating shaft 2a of the stirring member 2 provided with the rotating blades at a constant speed or at a non-uniform speed, co-rotation of the container part 4 and the stirring member 2 is suppressed, and sufficient stirring performance is obtained. can be Then, when the stirring member 2 having the rotating blades rotates around the rotating shaft 2a, the stirring member 2 moves along the inner wall of the container from the bottom to the top of the container, and further from the top to the center of the container.
  • a circulation flow is formed in which the raw material components circulate to the bottom.
  • the raw material component containing the PAS resin filled in the lid portion 11 side (bottom portion) of the container portion 4 flows along the inner wall of the container portion 4 from the bottom portion of the container portion 4 to the upper portion, and further from the upper portion to the container portion 4. It is circulated to the bottom via the central side.
  • the rotor has a single-axis double helix structure. That is, as one of the preferable forms of the stirring member 2, as shown in FIG. 1, it is preferable that the rotating blade has a double helix structure with respect to one rotating shaft 2a which is a single shaft. This makes it easier to form a circulation flow.
  • the rotating shaft 2a is one single shaft. Further, the rotating shaft 2a is connected and fixed to the central portion of the top plate T. As shown in FIG. In FIG. 1, the rotating shaft 2a is composed of two rod-shaped bodies having different thicknesses, but may be rod-shaped bodies having the same thickness or tapered rod-shaped bodies. Furthermore, in FIG. 1, an example in which seven supporting members (2b 1 , 2b 2 , 2b 3 , 2b 4 , 2b 5 , 2b 6 , 2b 7 ) are attached radially outward to the rotating shaft 2a.
  • the number of supporting members can be changed as appropriate depending on the radius of the start point, the radius of the end point, the number of turns, or the total length of the spiral drawn by the belt-shaped rotor.
  • a preferred embodiment of the stirring member 2 will be described later with reference to FIGS. 2 and 3.
  • FIG. 1 Furthermore, in FIG. 1, seven support members (2b 1 , 2b 2 , 2b 3 , 2b 4 , 2b 5 , 2b 6 , 2b 7 ) are attached perpendicular to the longitudinal direction of the rotating shaft 2a. 7 supporting members (2b 1 , 2b 2 , 2b 3 , 2b 4 , 2b 5 , 2b 6 , 2b 7 ) are separated into two supporting members (a total of 14 supporting members).
  • FIG. 1 shows an example in which the rotating shaft 2a is connected and fixed to the central portion of the top plate T, but as a modified example, the rotating shaft 2a is inserted into a through hole provided in the central portion of the top plate T.
  • the top plate T may be connected to the top plate T and the rotating shaft 2a may be attached so as to rotate independently.
  • a rotary motor (not shown) may be attached so as to be connected and fixed to the rotary shaft 2a as power for rotating the stirring member 2 of the stirring mechanism.
  • the stirring member 2 in this embodiment preferably has a rotary blade. Furthermore, the maximum rotation diameter of the rotor blade is preferably 50 to 99% of the diameter d1 of the first opening OP1, more preferably 60 to 90%. When the maximum rotation diameter of the rotor blades of the stirring member 2 is 50 to 99% of the diameter d1 of the first opening OP1, it becomes easier to form a circulation flow. In FIG.
  • the maximum rotation diameter of the rotor blade represents twice the starting point radius of the spiral drawn by the belt-shaped rotor blade, so the maximum rotation diameter of the belt-shaped rotor fixed to the support member 2b1 is the diameter d1 can be 50-99% of the Further, as described above, since the rotating shaft 2a is connected and fixed to the center of the first opening OP1, the length of the supporting member 2b7 corresponds to the maximum rotating diameter of the rotating blade.
  • the input port 10 formed in the top plate T communicates with the space V. Therefore, when the raw material components including the raw PAS resin are input from the input port 10, the raw material components including the raw PAS resin will flow into the container part 4 (space V).
  • the supply port 8 for injecting the reforming gas (g S ) and the discharge port 9 for discharging the gas (g d ) in the container part 4 (or in the space V) communicate with the space V as well as the inlet 10 . It is Therefore , by supplying the reforming gas (g S ) to the supply port 8 , the reforming gas (g S ) can be atmosphere.
  • the gas (g d ) includes gas generated by reforming (for example, oxidation reaction) of the raw material PAS resin, by exhausting the gas (g d ) in the container part 4, the inside of the container part 4 can be kept constant, the reforming gas (g S ) atmosphere (for example, gas phase oxidizing atmosphere or inert gas atmosphere).
  • the reforming gas (g S ) atmosphere for example, gas phase oxidizing atmosphere or inert gas atmosphere.
  • the reforming gas (g S ) is supplied into the container portion 4 through a supply port 8 provided so as to communicate with the container portion 4 .
  • a supply port 8 provided so as to communicate with the container portion 4 .
  • other gases hydrogen gas, carbon dioxide gas, etc.
  • the reforming gas (g S ) concentration contained in the gas supplied into the container 4 through the supply port 8 is in the range of 1 to 100%.
  • the reforming gas (g S ) concentration referred to here means the amount (volume %) of the reforming gas (g S ) contained in the gas supplied into the container part 4 per minute.
  • the concentration range of the reforming gas (g S ) is preferably set according to the type of the reforming gas (g S ).
  • the concentration of the inert gas in the gas supplied into the container part 4 per minute is preferably 93 to 100% by volume, more Preferably 95 to 100% by volume, more preferably 97 to 100% by volume, even more preferably 99 to 100% by volume.
  • oxygen or a gas containing oxygen for example, air
  • the oxygen concentration in the gas supplied into the container part 4 per minute should be 1% by volume or more.
  • the lower limit of the oxygen concentration in the reforming gas (g S ) is preferably 1% by volume or more, 5% by volume or more, 7% by volume or more, 11% by volume or more, or 13% by volume or more.
  • the upper limit of the oxygen concentration in the reforming gas (g S ) is 100% by volume or less, 80% by volume or less, 60% by volume or less, 34% by volume or less, 27% by volume or less, or 21% by volume or less. is preferred.
  • the preferred range of oxygen concentration in the reforming gas (g S ) can be any combination of the above upper limit and the above lower limit.
  • the reforming gas (g S ) when the reforming gas (g S ) is a gas containing oxygen, it is supplied into the container portion 4 through the supply port 8 provided so as to communicate with the container portion 4, It is preferable that the concentration of oxygen contained in the gas supplied into the container part 4 per minute at the supply port 8 is in the range of 1 to 21% by volume.
  • the concentration of oxygen contained in the gas supplied into the container part 4 per minute at the supply port 8 is in the range of 1 to 21% by volume, the inside of the container part 4 (or the inside of the space V) can be easily gas-phase oxidized. It can be made sexual.
  • the oxygen concentration at the supply port 8 refers to the concentration of oxygen existing between the inlet and the outlet of the supply port 8.
  • An oxygen sensor for example, UEGO (Universal Exhaust Gas Oxygen ) sensor
  • UEGO Universal Exhaust Gas Oxygen
  • the reforming gas (g S ) is an inert gas
  • it is supplied into the container portion 4 through the supply port 8 provided so as to communicate with the container portion 4
  • the concentration of the inert gas contained in the gas supplied into the container portion 4 per minute at the supply port 8 is in the range of 99 to 100% by volume.
  • the inert gas concentration contained in the gas supplied into the container part 4 per minute at the supply port 8 is in the range of 99 to 100% by volume, the inside of the container part 4 (or the inside of the space V) can be easily made inert. It can be under an active gas atmosphere.
  • a method for supplying the reforming gas (g S ) and a method for discharging the gas (g d ) in the container portion 4 known means can be employed. For example, by fluidly connecting a compressing device (for example, a compressing pump) for compressing and supplying the reforming gas (g S ) to the supply port 8 via the compressing pipe body, the reforming gas (g S ) can be supplied. Furthermore, by fluidly connecting a suction device to the discharge port 9 via a tubular body, the gas (g d ) inside the container part 4 (or inside the space V) can be discharged.
  • the position of the supply port 8 in the container part 4 is not particularly limited.
  • the reforming gas (g S ) (for example, oxygen , a gas containing 1% by volume or more of oxygen or an inert gas) may be supplied.
  • the reforming gas (g S ) is a gas containing oxygen
  • the distance between the supply port 8 and the discharge port 9 is the container It is preferably provided on a (substantially) diagonal line that can have the maximum value in the portion 4 .
  • the position of the supply port 8 in the container part 4 is on the lid part 11 side (lower part of the container part 4) in consideration of the contact probability between the raw material components including the raw material PAS resin and the reforming gas (g S ). is set in
  • the inlets or outlets 6 and 7 for the heat medium or refrigerant are not communicated with the space V. As shown in FIG.
  • FIG. 1 shows the openable/closable lid portion 11 in a closed state.
  • the contents contained in the container portion 4 raw material components including the raw material PAS resin, products P obtained by chemical reaction of the raw material components, etc.
  • the openable and closable lid portion 11 is provided at the bottom portion of the container portion 4, not only can the product P immediately after the modification treatment (for example, oxidative cross-linking reaction or volatilization of low-molecular-weight components) be recovered in a short time, For example, even contents in the middle of the reaction can be recovered in a short time.
  • the modification treatment for example, oxidative cross-linking reaction or volatilization of low-molecular-weight components
  • the opening/closing mechanism of the lid portion 11 is not particularly limited.
  • the lid portion 11 is rotatably pivotally supported with respect to the container portion 4 by an opening/closing mechanism configured to be slidably movable in the separating and contacting direction, or by a rotating member such as a hinge that connects the lid portion 11 and the container portion 4 .
  • An opening and closing mechanism, etc., which are used, are mentioned.
  • the lid portion 11 and the container portion 4 may be fixed by a known locking portion.
  • a drift plate 3 is provided between the stirring member 2 and the gas discharge port 9 (top surface side in FIG. 1). Due to the rotation of the stirring member 2, the drift plate 3 moves the raw material components including the raw material PAS resin that have moved from the lid portion 11 side to the drift plate 3 side along the inner wall of the container portion 4 toward the rotating shaft 2a side (first opening). It can be a plate material that is unevenly distributed in the central part of the part OP1 and dropped.
  • a temperature control jacket 5 covering the outer surface of the container part 4 has a space for accommodating a heat medium or a coolant inside. , 7 by injecting and discharging a heat medium or a refrigerant.
  • Either of the inlets or outlets 6, 7 may serve as an inlet for the heat medium or the refrigerant, or may serve as an outlet for the heat medium or the refrigerant.
  • an inflow pipe (not shown) is attached to one of the inlets or outlets 6 or 7 of the heat medium or refrigerant communicating with the temperature control jacket 5, and an outflow pipe (not shown) is attached to the other.
  • a heat medium or refrigerant circulator (not shown) is connected to the inflow pipe (not shown) and the outflow pipe (not shown), and the heat medium or refrigerant is pumped to the container part 4 can be adjusted.
  • the heat medium or refrigerant inlet or outlet 6 in FIG. 7 may be used as an outlet.
  • the heat medium can be appropriately selected depending on the desired temperature, and any heat medium that is liquid at a temperature of 100° C. or higher can be used.
  • Glycol-based or silicone-based heat medium oil such as ethylene glycol, pressurized water (for example, water at 150° C.), and steam having a boiling point of 100° C. or higher can be used.
  • Examples of the above refrigerant can be appropriately selected depending on the desired temperature, and for example, ammonia, isobutane, hydrocarbons, CFC substitutes, etc. can be used.
  • a temperature control jacket 5 for example, the temperature of the raw material components in the container 4 can be controlled within a temperature range of 100 to 280.degree. Within this temperature range, the raw material PAS resin in the raw material components can be easily heated to near the melting point Tm or the entire raw material components.
  • FIG. 2 is a perspective view of essential parts of the stirring member 2 shown in FIG.
  • the stirring member 2 includes a rotary shaft 2a connected and fixed to the central portion of the top plate T, and a plurality of support members (2b 1 , 2b 2 , 2b 3 , 2b 4 , 2b ) attached to the rotary shaft 2a. 5 , 2b 6 , 2b 7 ) and two strip - shaped rotor blades 2c ( stirring (used in member 2).
  • the support members (2b 1 , 2b 3 , 2b 5 ) and the support members (2b 2 , 2b 6 ) are perpendicular to each other in their longitudinal directions and extend outward in the radial direction of the rotating shaft 2a.
  • the support member 2b7 is attached to the rotating shaft 2a such that the longitudinal direction thereof is inclined at a predetermined angle with respect to the longitudinal direction of the support members ( 2b2 , 2b6 ).
  • the strip-shaped rotor blade 2c is a continuous spiral blade in which the strip draws a spiral shape around the rotation shaft 2a.
  • the stirring member 2 includes a support member 3a attached to the rotating shaft 2a between the top plate T and the support member 2b1 , and a pair of deflection plates fixed to each of the support members 3a. 3.
  • the stirring member 2 has the helical rotor blades 2c
  • the rotation of the rotor blades 2c forms a helical vortex more effectively. It becomes easier to form a circulation flow in which the raw material components circulate from the top to the bottom through the center of the container part 4 from the top to the bottom.
  • the number of turns of the spiral is not particularly limited, and is preferably 1 to 10 turns.
  • the spiral of the strip-shaped rotor blade 2c shown in FIG. 2 has 1.25 turns.
  • the total length of the spiral is preferably 1 to 50 m, more preferably 1.1 to 30 m, even more preferably 1.2 to 15 m.
  • the starting radius of the spiral (for example, 1/2 of the length of the support 2b1 ) is 25-49.5% of the diameter d1 of the first opening.
  • the end point radius of the spiral (for example, half the length of the support member 2b7 ) is preferably 25-49.5% of the diameter d1 of the second opening OP2.
  • Examples of the cross-sectional shape 2d of the belt-like rotor blade 2c include a thin plate, a (substantially) circular body, a (substantially) elliptical shape, and a polygonal shape such as a triangle.
  • the rotation of the strip-shaped rotor blade 2c having a three-dimensional structure agitates the raw material components in the container 4 more efficiently in the vertical direction.
  • the gap between the outer end surface of the rotor blade 2c and the inner peripheral wall of the container portion 4 is preferably set to a range of 1 to 50%, preferably 1 to 10%, of the diameter d1 of the first opening OP1.
  • the rotating shaft 2a is composed of two rod-shaped bodies having different thicknesses, but the rotating shaft 2a may be a rod-shaped body having the same thickness or a tapered rod-shaped body. Furthermore, in FIG.
  • the support members (2b 1 , 2b 2 , 2b 3 , 2b 4 , 2b 5 , 2b 6 , 2b 7 ) are configured so that the major axis direction of the support member is outside the radial direction around the rotation axis 2a.
  • the start point radius, end point radius, number of turns or total length of the spiral drawn by the belt-shaped rotor blade 2c for example, the start point radius, end point radius, number of turns of the spiral described above
  • the method of attaching the supporting members (for example, 2b 1 to 2b 7 , 3b, etc.) to the rotating shaft 2a is not particularly limited as long as the supporting members are firmly fixed to the rotating shaft 2a.
  • FIG. 2 shows an example in which a support member 3a and a pair of deflection plates 3 are attached radially outwardly of the rotating shaft 2a. And these mounting methods can be changed as appropriate.
  • FIG. 3 is a perspective view of essential parts showing another embodiment of the stirring member 2.
  • the stirring member 2 in FIG. 3 includes a rotary shaft 2a connected and fixed to the central portion of the top plate T, and a plurality of support members (2b 1 , 2b 2 , 2b 3 , 2b 4 , 2b 5 ) attached to the rotary shaft 2a. , 2b 6 , 2b 7 ) and one belt-like rotor 2c fixed to a plurality of support members (2b 1 , 2b 2 , 2b 3 , 2b 4 , 2b 5 , 2b 6 , 2b 7 ), I have.
  • the single strip-shaped rotary blade 2c is a continuous spiral blade in which the strip draws a spiral shape around the rotary shaft 2a.
  • the main difference between the stirring member 2 shown in FIG . 3 and the stirring member 2 shown in FIG . is the number of strip-shaped rotor blades 2c fixed to the . More specifically, in the stirring member 2 shown in FIG. 2, two belt-like bodies are spirally wound around the rotating shaft 2a so as to taper toward the second opening side as the rotor blades 2c. is. On the other hand, in the stirring member 2 shown in FIG. 3, a belt-like body as the rotor blade 2c is spirally wound around the rotating shaft 2a so as to taper toward the second opening side.
  • the number of strips forming the spiral is not particularly limited, and is preferably 1 to 10, for example.
  • the rotation of the rotor blades 2c forms a helical vortex more effectively. It becomes easier to form a circulation flow in which the raw material components circulate from the top to the bottom through the center of the container part 4 from the top to the bottom.
  • FIG. 1 When the raw material components including the raw PAS resin are blended from the inlet 10 into the space V in the tapered container portion 4, and the stirring member 2 equipped with the double-helical rotor blades rotates around the rotating shaft 2a, As indicated by the arrow in FIG. 1, the raw material PAS resin is distributed along the inner wall of the container 4 from the bottom to the upper part of the container 4, and further from the upper part of the inner wall of the container 4 toward the center of the container 4 (rotating shaft 2a side).
  • the stirring mechanism of the reforming apparatus 1 can form a circulating flow in which the raw material components containing move, and furthermore, the raw material components circulate from the upper part of the center part of the container part 4 to the bottom part of the container part 4 .
  • a predetermined amount of reforming gas (g s ) is supplied into the container 4 from the gas supply port 8, and if necessary, the gas (g d ) in the container 4 is discharged through the gas discharge port 9.
  • the inside of the container part 4 is controlled to have a predetermined amount of reforming gas (g S ) atmosphere, and the raw material components including the raw material PAS resin are circulated by the circulation flow.
  • the modified PAS resin is produced by heating the raw material components containing the raw PAS resin for a predetermined time below the melting point Tm of the raw PAS resin (for example, 100 to 280° C.) using the temperature control jacket 5. do. Thereafter, as shown in FIG. 4, the openable and closable lid portion 11 is opened, and the modified PAS resin, which is the product P, can be recovered. Also, for example, as shown in FIG. A vacuum pump 13 fluidly connected to the gas outlet 9 may be used to reduce the pressure in the container 4 and supply the reforming gas (g S ) from the gas supply port 8 . Furthermore, the amount of the reforming gas (g S ) supplied into the container portion 4 per minute is controlled within the range of 0.1 to 100% by volume of the volume of the container portion 4 .
  • a rotary motor (not shown) may be attached on the top plate T as a power for rotating the stirring member 2 of the stirring mechanism.
  • the rotary motor is started, for example, rotation of the top plate T itself in FIG.
  • the rotor blades attached to the shaft 2a (for example, the spiral rotor blades 2c in FIG. 2) also rotate to more effectively form a spiral vortex.
  • the screw rotation speed of the rotor blade is preferably 10 to 100 rpm, more preferably 20 to 90 rpm.
  • the method of introducing the raw material components including the raw material PAS resin into the container portion 4 of the reforming apparatus 1 is not particularly limited, but may be carried out by a constant feeder such as a rotary feeder or a vibrating feeder. Moreover, the raw material components including the raw material PAS resin may be supplied as they are. The above is the description of the reforming treatment apparatus 1 of the present embodiment. The raw material components including the raw material PAS resin, the reforming gas (g s ) and gas (g d ), the heat treatment step, and the gas supply control step will be described below.
  • the melt viscosity at 300° C. is preferably in the range of 1 Pa s or more, more preferably 3 Pa s or more. range, more preferably 5 Pa s or more, preferably 9000 Pa s or less, more preferably 7000 Pa s or less, still more preferably 4000 Pa s or less, 1000 Pa s or less Certain PAS resins are mentioned.
  • the peak molecular weight (M top ) is preferably in the range of 10,000 or more, more preferably in the range of 15,000 or more, and still more preferably in the peak molecular weight (M top ) of 15,000 or more.
  • M top ) is in the range of 20000 or more and 150000 or less, more preferably the peak molecular weight (M top ) is in the range of 100000 or less, more preferably the peak molecular weight (M top ) is in the range of 90000 or less. mentioned.
  • the concentration of low molecular weight impurities is preferably 1% by mass or more and 5% by mass or less, and more preferably the concentration of low molecular weight impurities is 1% by mass or more and 4% by mass or less. and more preferably a PAS resin having a low-molecular-weight impurity concentration of 1% by mass or more and 3% by mass or less.
  • powder of the raw material PAS resin which is commercially available or obtained by the polymerization process described later, or agglomerated particles obtained by further compressing and pulverizing the powder can be used. .
  • Pellet-like material obtained by melt-kneading powder or agglomerated particles of raw PAS resin can also be used.
  • the use of raw material PAS resin powder, agglomerated particles, or a mixture thereof as a raw material in particular maintains good heat conduction to the raw material PAS resin, and improves compatibility with the reforming gas (g S ). It is preferable from the viewpoint of widening the contact area.
  • the reforming gas (g S ) is oxygen or a gas containing 1% by volume or more of oxygen
  • the use of a raw material PAS resin in the form of powder or agglomerated particles expands the contact area with oxygen and causes oxidation.
  • the cross-linking reaction can be performed uniformly.
  • agglomerated particles are used alone as the raw material PAS resin, or when the presence ratio of agglomerated particles in the mixture is high, a large amount of the raw material PAS resin can be introduced into the container portion, and a long residence time can be secured. In addition, clogging of the bag filter and reduction in yield due to scattering of powder can be prevented.
  • the content of the agglomerated particles or the mixture that passes through a test sieve with an opening of 0.3 mm according to Japanese Industrial Standard Z 8801 is preferably 50% by mass or less, particularly preferably 30% by mass. % or less.
  • the "raw material component containing the raw material PAS resin” means that the content of the raw material PAS resin is 50% by mass or more with respect to the total amount (100 mass) of the raw material components blended in the reforming apparatus 1. , preferably 60% by mass or more and 100% by mass or less.
  • Production Methods 1 to 4 Representative examples of the polymerization process applicable to the present embodiment include, for example, Production Methods 1 to 4 below.
  • Method of self-condensing by adding other copolymerization components (manufacturing method 4): A diiodo aromatic compound and elemental sulfur are combined in the presence of a polymerization inhibitor that may have a functional group such as a carboxy group or an amino group. , method of melt polymerization while reducing pressure Of the above production methods 1 to 4, the above (production method 2) method is versatile and preferred. During the reaction, 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.
  • a hydrous sulfidation agent is introduced into a mixture containing a heated organic polar solvent and a dihalogeno aromatic compound at such a rate that water can be removed from the reaction mixture, and dihalogeno is produced in the organic polar solvent.
  • a method for producing a raw material PAS resin by controlling the range of (see JP-A-07-228699), and a dihalogeno aromatic compound and necessary in the presence of a solid alkali metal sulfide and an aprotic polar organic solvent If so, 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 of an organic acid alkali metal per 1 mol of the sulfur source.
  • Particularly preferred is the one obtained by a method of reacting while controlling the amount of water in the salt and reaction system in the range of 0.02 mol or less per 1 mol of the aprotic polar organic solvent (see WO2010/058713 pamphlet). .
  • a reaction mixture containing a PAS resin obtained by reacting at least one polyhalogenoaromatic compound and at least one sulfidating agent in an organic solvent under appropriate polymerization conditions (A process for obtaining a slurry) will be described as an example.
  • the polyhalogenoaromatic compound in the present embodiment is a halogenated aromatic compound having two or more halogen atoms directly bonded to an aromatic ring. called a compound.
  • the dihalogenoaromatic compounds include p-dihalobenzene, m-dihalobenzene, o-dihalobenzene, 2,5-dihalotoluene, 1,4-dihalonaphthalene, 1-methoxy-2,5-dihalobenzene, 4,4 '-dihalobiphenyl, 3,5-dihalobenzoic acid, 2,4-dihalobenzoic acid, 2,5-dihalonitrobenzene, 2,4-dihalonitrobenzene, 2,4-dihaloanisole, p,p' -dihalodiphenyl ether, 4,4'-dihalobenzophenone, 4,4'-dihalodiphenyl sulfone, 4,4'
  • 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, if 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.
  • active hydrogen-containing polyhaloaromatic compounds preferred are active hydrogen-containing dihalogenoaromatic compounds, and particularly preferred is dichloroaniline.
  • 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.
  • the raw PAS resin must be dissolved in an organic solvent, so the organic solvent used must be able to dissolve the PAS resin under certain conditions.
  • the conditions for dissolving the starting material PAS resin may be room temperature or heating, but currently known solvents require heating to a certain temperature in order to dissolve the PAS resin having a molecular weight above a certain level.
  • Organic solvents capable of dissolving the PAS resin include N-methyl-2-pyrrolidone, formamide, acetamide, N-methylformamide, N,N-dimethylacetamide, 2-pyrrolidone, N-methyl- ⁇ -caprolactam, ⁇ -caprolactam, hexamethylphosphoramide, tetramethylurea, N-dimethylpropyleneurea, amidourea of 1,3-dimethyl-2-imidazolidinoic acid and lactams; sulfolanes such as sulfolane, dimethylsulfolane; benzonitrile ketones such as methylphenylketone; other solvents such as polyethylene dialkyl ether, 1-chloronaphthalene, diphenyl sulfide and the like.
  • Alkali metal sulfides used in this embodiment 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.
  • the polymerization reaction of the PAS resin is carried out by reacting the above alkali metal sulfide or alkali metal hydrosulfide and alkali metal hydroxide, which are called so-called sulfidating agents, with the polyhalogenoaromatic compound in the presence of these organic polar solvents. .
  • the polymerization temperature of the raw material PAS resin in the present embodiment should be in the range of 200 to 330° C.
  • the pressure should be such that the polyhalogenoaromatic compound, which is the polymerization solvent and the polymerization monomer, is substantially kept in the liquid layer, It is generally selected from the range of 0.1 to 20 MPa, preferably from the range of 0.1 to 2 MPa.
  • the reaction time varies depending on the temperature and pressure, it is generally in the range of 10 minutes to 72 hours, preferably 1 hour to 48 hours.
  • the reaction mixture containing the raw material PAS resin obtained by the polymerization step is subjected to an appropriate means (a vacuum distillation method, a centrifugal separation method, a screw decanter method, a vacuum filtration method, a heating method, etc.) in the purification treatment described below.
  • an appropriate means a vacuum distillation method, a centrifugal separation method, a screw decanter method, a vacuum filtration method, a heating method, etc.
  • a suitable method such as pressure filtration can be selected) to separate and remove the organic solvent, after which the crude PAS resin can be recovered.
  • a reaction mixture containing a raw material PAS resin obtained by reacting at least one polyhalogenoaromatic compound with at least one alkali metal sulfide as a sulfidating agent in an organic solvent It is preferable to be a step of obtaining a slurry). Therefore, in the polymerization step, the organic solvent, the polyhalogeno aromatic compound, and the alkali metal sulfide, which are added as raw materials, only need to be brought into contact to allow the polymerization reaction to proceed. At least one selected from the group consisting of group compounds and the alkali metal sulfides may not be added in an amount necessary for the polymerization reaction from the charging stage.
  • At least one selected from the group consisting of the organic solvent, the polyhalogenoaromatic compound, and the alkali metal sulfide is continuously added until the polymerization reaction is completed, in order to make the amount of raw materials charged necessary for the polymerization reaction. It may be reacted while being added gradually or intermittently.
  • a purification treatment for purifying the raw material PAS resin obtained from the polymerization step may be performed.
  • the purification treatment in this embodiment is not particularly limited, and a known purification treatment can be applied according to the chemical structure of the raw material PAS resin, which is the target product.
  • the purification treatment of the raw material PAS resin (reaction mixture containing the PAS resin) obtained by the polymerization step is not particularly limited, but examples thereof include the following purification treatments 1 to 5.
  • Purification process 1 After the completion of the polymerization reaction, the reaction mixture (slurry) 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 (crude PAS resin) is washed once or twice with a washing solvent such as water, a reaction solvent (or an organic solvent having an equivalent solubility for the low-molecular-weight polymer), acetone, methyl ethyl ketone, or alcohols, and then neutralized, washed with water, a method of filtering and drying;
  • Purification process 2 After the polymerization reaction is completed, the reaction mixture (slurry) is added with solvents such as water, acetone, methyl ethyl ketone, alcohols, ethers, halogenated hydrocarbons, aromatic hydrocarbons, and aliphatic hydrocarbons (organic A solvent that is soluble in the solvent and is a poor solvent for at least the PAS resin) is added as a precipitant to precipit
  • Purification process 3 After completion of the polymerization reaction, the reaction mixture (slurry) was added with a reaction solvent (or an organic solvent having an equivalent solubility to the low-molecular-weight polymer) and stirred, followed by filtration to remove the low-molecular-weight polymer. a method of washing the solid (crude PAS resin) with a washing solvent such as water, acetone, methyl ethyl ketone or alcohols once or twice or more, followed by neutralization, washing with water, filtration and drying; Purification process 4: After completion of the polymerization reaction, water is added as a washing solvent to the reaction mixture (slurry) and washed with water. A method of acid-treating with an acid and drying.
  • a reaction solvent or an organic solvent having an equivalent solubility to the low-molecular-weight polymer
  • Purification process 5 After the completion of the polymerization reaction, the solid (crude PAS resin) obtained by filtering the reaction mixture (slurry) is washed with a solvent if necessary. washing with a reaction solvent once or twice or more, washing with water, filtering and drying, and the like.
  • the raw PAS resin may be dried in a vacuum, or in air or in an atmosphere of an inert gas such as nitrogen. good.
  • the purification treatment in the present embodiment involves adding a washing solution to the reaction mixture (slurry) containing the raw material PAS resin obtained in the polymerization step or the crude PAS resin, which is the solid content of the reaction mixture (slurry), and washing and filtering. and drying.
  • each of the washing treatment in which the washing solvent is added, the filtration treatment and the drying treatment can be optionally performed at least once or more than once.
  • the term "crude PAS resin" as used herein refers to a solid content obtained by subjecting the reaction mixture (slurry) containing the raw material PAS resin obtained in the polymerization step to solid-liquid separation one or more times.
  • the reforming gas (g S ) in the present embodiment is a general term for gases used for reforming the raw material PAS resin, and the reforming gas itself does not need to directly reform the raw material PAS resin.
  • the reforming gas (g S ) atmosphere in the present embodiment means that one volume of the reforming gas (g S ) is contained in the entire volume (100% by volume) of the atmosphere containing the reforming gas (g S ). % or more.
  • the reforming gas (g S ) in the present embodiment is preferably at least one selected from the group consisting of oxygen, an oxygen-containing gas, and an inert gas.
  • the oxygen-containing gas is preferably a gas (for example, air) containing 1% by volume or more of oxygen in the entire reforming gas (g S ) (100% by volume).
  • the reforming gas (g S ) in the present embodiment is oxygen or a gas containing 1% by volume or more of oxygen (for example, air)
  • the inside of the container can be easily made into a gas-phase oxidizing atmosphere.
  • the atmosphere contains 1% by volume or more of oxygen with respect to the entire volume of the reforming gas (g S ) atmosphere, the oxidative cross-linking reaction of the raw material PAS resin will easily proceed as a vapor-phase oxidizing atmosphere. .
  • the term "vapor-phase oxidizing atmosphere” refers to a mixed gas atmosphere containing oxygen, in which oxygen accounts for 1% by volume or more of the total volume of the mixed gas (100% by volume).
  • the reforming gas (g S ) is oxygen or a gas containing oxygen
  • the inert gas refers to a stable gas typified by rare gas elements or nitrogen that is unlikely to cause chemical reactions, for example, at least one selected from the group consisting of nitrogen, helium, and argon. is preferred.
  • the inert gas may be a mixed inert gas in which two or more inert gases are mixed.
  • the reforming gas (g S ) in the present embodiment is an inert gas
  • the inside of the container can be easily made into an inert gas atmosphere.
  • the concentration of low-molecular-weight impurities can be reduced by selecting an inert gas as the reforming gas (g S ). .
  • the "inert gas atmosphere” in this specification is a mixed gas atmosphere containing an inert gas, and the inert gas is 99% by volume or more with respect to the total volume (100% by volume) of the mixed gas.
  • the atmosphere that occupies when the reforming gas (g S ) is an inert gas, it is particularly preferable to make the inside of the container part an inert gas atmosphere. This makes it easier to reduce the concentration of low-molecular-weight impurities.
  • a known method can be adopted as a method for measuring the reforming gas (g S ) concentration. For example, it can be carried out with a detector such as various sensors, gas chromatography, gas detection tube, etc., using a predetermined container or gas suction pump.
  • the method for producing the modified PAS resin in this embodiment has a heat treatment step.
  • a reforming gas (g S ) is supplied into a container provided in a reforming apparatus and a gas (g d ) in the container is discharged to the outside of the container,
  • This is a step of heating the raw material components containing the raw material PAS resin by a heating means to a temperature lower than the melting point Tm of the PAS resin while circulating the raw material components containing the raw material PAS resin put into the container in a circulating flow.
  • the inside of the container portion is placed under the reforming gas (g S ) atmosphere (for example, under a vapor-phase oxidizing atmosphere or under an inert gas atmosphere).
  • the raw material is A raw material component containing a PAS resin is heated below the melting point Tm of the PAS resin.
  • the raw material PAS resin While the raw material components including the raw material PAS resin are circulated by the convective circulating flow in the container, the raw material PAS resin is heated to a predetermined temperature in the reforming gas (g S ) atmosphere, thereby promoting the modification of the raw material PAS resin.
  • the reforming gas (g S ) atmosphere While the raw material components including the raw material PAS resin are circulated by the convective circulating flow in the container, the raw material PAS resin is heated to a predetermined temperature in the reforming gas (g S ) atmosphere, thereby promoting the modification of the raw material PAS resin.
  • the reforming gas (g S ) when oxygen or a gas containing 1% by volume or more of oxygen is used as the reforming gas (g S ), it is heated to a predetermined temperature in a gas-phase oxidizing atmosphere, so that oxidation and cross-linking can be performed uniformly. The reaction proceeds more easily, and the reaction time of the raw material components including the raw material PAS resin is shortened.
  • an inert gas when used as the reforming gas (g S ), it is heated to a predetermined temperature in an inert gas atmosphere, so low-molecular-weight impurities can be reduced.
  • the reforming gas (g S ) can be appropriately selected according to the intended use of the resulting modified PAS resin.
  • the time for heating the raw material components including the raw material PAS resin to below the melting point Tm of the PAS resin by the heating means is preferably 1 to 100 hours, more preferably 1 to 50 hours. , more preferably 1 to 10 hours.
  • the temperature of the raw material components introduced into the container is preferably controlled within the range of 100 to 280°C, more preferably within the range of 150 to 280°C. Heating the raw material components including the raw material PAS resin to the above range is preferable from the viewpoint of shortening the treatment time.
  • a temperature control jacket is used to supply the heat medium or refrigerant into the inlet or outlet of the heat medium or refrigerant. Temperature control is performed by injecting and discharging and circulating the heat medium or refrigerant in the temperature control jacket.
  • the method for producing a modified PAS resin in this embodiment has a gas supply control step.
  • the gas supply control step the amount of reforming gas (g S ) supplied per minute is controlled within a range of 0.1 to 100% of the volume of the container provided in the reforming apparatus. It is a process to do.
  • the gas supply control step supplies the reforming gas (g S ) into the container provided in the reforming apparatus and supplies the gas in the container to the outside of the container in the heat treatment step.
  • g d is a step of maintaining the inside of the container under the reforming gas (g S ) atmosphere in conjunction with the operation of discharging g d ).
  • the range of 0.1 to 100% of the volume of the container part is 0.1 with respect to the total volume (100% by volume) of the space V described above in the column of “reforming treatment device” and FIG. Refers to the range of up to 100%.
  • the gas supply control step may be performed at any timing or period between before the heat treatment step and after the heat treatment step, and the gas supply control step is continued during the heat treatment step. preferably. Thereby, the inside of the container can be kept under the atmosphere of the reforming gas (g S ).
  • the amount of reforming gas (g S ) supplied per minute is It is preferable to control within the range of 1 to 50% of the volume of the container provided.
  • oxygen or a gas containing oxygen is supplied into the container portion through a supply port provided in the container portion provided in the reforming apparatus, and It is preferable that the oxygen concentration is in the range of 1 to 21%.
  • an inert gas is supplied into the container portion through a supply port provided in the container portion provided in the reforming apparatus, and the inert gas concentration at the supply port is 99 to 100%.
  • a method for supplying/discharging the reforming gas (g S ) known means can be adopted. For example, by fluidly connecting a pumping device for compressing and supplying the reforming gas (g S ) to the supply port via a pumping tube, the reforming gas (g S ) is fed into the container section. can supply to Further, if a discharge port for discharging the gas (g d ) in the container is provided so as to communicate the inside of the container with the outside, the gas (g d ) is discharged to the outside. Furthermore, if necessary, the gas (g d ) inside the container part 4 (or inside the space V) may be discharged by fluidly connecting a suction device to the discharge port via a tubular body.
  • the raw material PAS resin is heated to a temperature below the melting point Tm of the raw material PAS resin in a vapor-phase oxidizing atmosphere using a modification apparatus.
  • a method for producing a modified PAS resin by heating a raw material component containing the a heat treatment step of discharging the gas (g d ) in the container portion, and heating the raw material component with a heating means to a temperature lower than the melting point T m while circulating the raw material component introduced into the container portion by a circulating flow; and a gas supply control step of controlling the amount of the oxygen-containing gas supplied per minute within a range of 1 to 50% of the volume of the container.
  • the reforming apparatus includes a tapered container portion capable of accommodating raw material components including the raw material PAS resin, and along the inner wall of the container portion, from the bottom portion of the container portion to the top, and further from the top to the above.
  • the raw material component containing the raw material PAS resin is obtained by a polymerization step of polymerizing the raw material PAS resin.
  • the aggregation of the PAS resins which tend to fuse at high temperatures, is further suppressed, the formation of PAS resin adherents adhered to the inner wall of the container is suppressed and prevented, and contamination is further reduced.
  • a modified PAS resin is produced by heating a raw material component including a raw PAS resin to a temperature below the melting point Tm of the PAS resin in an inert gas atmosphere using a modification apparatus.
  • an inert gas is supplied into the container mounted in the reforming apparatus, the gas (g d ) in the container is discharged to the outside of the container, and the gas (g d ) is introduced into the container.
  • a heat treatment step of heating the raw material components to less than the melting point Tm by a heating means while circulating the raw material components with a circulating flow, and the supply amount of the inert gas per minute is the volume of the container part.
  • the reforming apparatus includes a tapered container portion capable of containing the raw material component including the PAS resin, and along the inner wall of the container portion, from the bottom portion of the container portion to the upper portion, and further from the upper portion to the container portion. It has a stirring mechanism that forms a circulation flow in which the raw material components circulate to the bottom through the center side of the part. Furthermore, it is preferable that the raw material component containing the raw material PAS resin is obtained by a polymerization step of polymerizing the raw material PAS resin.
  • Modified PAS Resin The modified PAS resin obtained by the production method of the present embodiment can be appropriately blended with various fillers in order to impart properties such as strength, heat resistance, and dimensional stability depending on the application.
  • the filler is not particularly limited, but includes fibrous fillers, non-fibrous fillers, and the like.
  • fibrous fillers include fibers such as glass fiber, carbon fiber, silane glass fiber, ceramic fiber, aramid fiber, metal fiber, potassium titanate, silicon carbide, calcium sulfate, calcium silicate, and natural fibers such as wollastonite. Fiber etc. can be used.
  • non-fibrous fillers examples include barium sulfate, calcium sulfate, clay, pyroferrite, bentonite, sericite, zeolite, mica, mica, talc, attalpalgite, ferrite, calcium silicate, calcium carbonate, and magnesium carbonate. , glass beads, etc. can be used.
  • additives during molding processing a small amount of coloring agents, antistatic agents, antioxidants, heat stabilizers, ultraviolet stabilizers, ultraviolet absorbers, foaming agents, flame retardant Retardants, flame retardant aids, rust inhibitors, and mold release agents (metal salts and esters of fatty acids having 18 to 30 carbon atoms including stearic acid and montanic acid, polyolefin waxes such as polyethylene, etc.)
  • additives may be included in the modified PAS resin.
  • synthetic resins and elastomers such as those described below can also be mixed and used in the same manner.
  • These synthetic resins include polyester, polyamide, polyimide, polyetherimide, polycarbonate, polyphenylene ether, polysulfone, polyethersulfone, polyetheretherketone, polyetherketone, polyarylate, polyethylene, polypropylene, polytetrafluoroethylene, Polyethylene difluoride, polystyrene, ABS resins, epoxy resins, silicone resins, phenol resins, urethane resins, liquid crystal polymers and the like can be mentioned, and elastomers can include polyolefin rubbers, fluororubbers, silicone rubbers and the like.
  • the modified PAS resin obtained by the production method of the present embodiment has heat resistance, moldability, and dimensional stability by various melt processing methods such as injection molding, extrusion molding, compression molding, and blow molding. etc.
  • various melt processing methods such as injection molding, extrusion molding, compression molding, and blow molding. etc.
  • electrical and electronic parts such as connectors, printed circuit boards, and sealed molded products
  • automotive parts such as lamp reflectors and various electrical parts, interior materials for various buildings, aircraft, automobiles, etc.
  • OA equipment parts It can be widely used as injection molding/compression molding products such as precision parts such as camera parts and watch parts, or extrusion molding/pultrusion molding such as fibers, films, sheets and pipes.
  • the melt viscosity (Pa s) of the modified PAS resin in the present embodiment is preferably 2 or more, more preferably 3 or more, still more preferably 5 or more, preferably 10000 or less, and more preferably 8000 or less. , 5000 or less.
  • the modified PAS resin in the present embodiment has a peak molecular weight (M top ) of preferably 15,000 or more, more preferably 20,000 or more, even more preferably 30,000 or more, and preferably 170,000 or less, more preferably 150,000 or less, 100,000 or less is more preferable.
  • the content of low molecular weight impurities in the modified PAS resin in the present embodiment is preferably 0.9% by mass or less with respect to the total amount (100% by mass) of the modified PAS resin, It is more preferably 0.7% by mass or less, and even more preferably 0.5% by mass or less.
  • a preferred range for each physical property of the modified PAS resin can be any combination of the above upper limit and the above lower limit.
  • Example 1 30 kg of a raw material PPS resin having a melt viscosity (V6) of 22 Pa ⁇ s was passed through a reforming apparatus 1 ( (Also referred to as apparatus A.). Next, air is introduced from the gas supply port 8 attached to the bottom of the reforming device 1 at a flow rate of 2 L/min (4%/min of the effective capacity of the reforming device 1), and the gas at the top is While performing a gas supply control step of exhausting air from the discharge port 9, the inside temperature of the container part 4 is raised to 250 ° C. in 3 hours using the temperature control jacket 5 that can be filled with a heat medium. Stirring was continued at temperature for an additional 7 hours.
  • the rotational speed of the rotary blade which is the stirring member 2
  • the lid portion 11 was opened without lowering the internal temperature from 250° C., and the modified PPS resin after the heat treatment was recovered.
  • the yield of the modified PPS resin after heat treatment was 29.5 kg (yield: 98.3%), and adherence of PPS resin deposits between the inner wall of the container part 4 and the rotor blade was observed. I didn't.
  • the modified PPS resin after heat treatment had a yellowish brown color, a melt viscosity (V6) of 152 Pa s, and a concentration of low-molecular-weight impurities (amount of gas generated during melting) of 0.28% by mass. .
  • the modified PPS resin has a peak molecular weight (M top ) of 33,000, which is 10% or more higher than the peak molecular weight (M top ) of the raw material PPS resin before modification (M top ) of 25,000. confirmed.
  • the concentration of low-molecular-weight impurities in the raw material PPS resin (the amount of gas generated during melting) before the gas supply control step and the heat treatment was performed was 1.0% by mass.
  • the formation of PPS resin deposits in the container portion 4 could not be confirmed.
  • Example 2 It was carried out in the same manner as in Example 1, except that the internal temperature of the container part 4 was raised to 230° C. over 2 hours, and the stirring was continued at that temperature for 21 hours.
  • the yield was 29.7 kg (yield 99.0%), and adhesion of PPS resin deposits between the inner wall of the container part 4 and the rotor blades was not observed.
  • the melt viscosity (V6) of the modified PPS resin after heat treatment was 155 Pa ⁇ s, and the concentration of low-molecular-weight impurities (the amount of gas generated during melting) was 0.29% by mass.
  • Example 2 the concentration of low-molecular-weight impurities (the amount of gas generated during melting) in the raw PPS resin before the gas supply control step and the heat treatment was 1.0% by mass.
  • the modified PPS resin had a peak molecular weight (M top ) of 33,000, and compared with the peak molecular weight (M top ) of the raw material PPS resin before modification of 25,000, the amount of change in the peak molecular weight (M top ) was was confirmed to increase by 10% or more.
  • the formation of the PPS resin adhered matter could not be confirmed in the container portion 4 after the modification treatment.
  • Example 3 Air is introduced from the gas supply port 8 formed at the bottom of the reforming apparatus 1 at a flow rate of 20 L/min (40%/min of the internal volume of the container), and the internal temperature reaches 250°C using a heat medium. The procedure was carried out in the same manner as in Example 1, except that the temperature was raised in 3 hours to 3 hours, and the stirring was continued at this temperature for 5 hours. The yield was 29.7 kg (yield 98.9%), and adhesion of PPS resin deposits between the inner wall of the container part 4 and the rotor blades was not observed.
  • the melt viscosity (V6) of the modified PPS resin after heat treatment was 170 Pa ⁇ s, and the concentration of low-molecular-weight impurities (the amount of gas generated during melting) was 0.26% by mass.
  • the concentration of low-molecular-weight impurities (the amount of gas generated during melting) in the raw material PPS resin before the gas supply control step and the heat treatment was 1.0% by mass.
  • the modified PPS resin had a peak molecular weight (M top ) of 34,000, and compared to the peak molecular weight (M top ) of the raw material PPS resin before modification of 25,000, the amount of change in the peak molecular weight (M top ) was was confirmed to increase by 10% or more.
  • the formation of the PPS resin adhered matter could not be confirmed in the container portion 4 after the modification treatment.
  • Example 4 Nitrogen as an inert gas is introduced at a flow rate of 2 L/min (4%/min of the internal volume of the container) from the gas supply port 8 formed at the bottom of the reforming apparatus 1, and the internal temperature is increased using a heat medium. The procedure was carried out in the same manner as in Example 1, except that the temperature was raised to 250° C. over 3 hours, and stirring was continued at that temperature for 7 hours. The yield was 29.55 kg (yield 98.5%), and adhesion of PPS resin deposits between the inner wall of the container part 4 and the rotor was not observed.
  • the modified PPS resin after heat treatment was grayish white, had a melt viscosity (V6) of 41 Pa ⁇ s, and had a concentration of low-molecular-weight impurities (amount of gas generated during melting) of 0.27% by mass.
  • the concentration of low-molecular-weight impurities in the raw material PPS resin (the amount of gas generated during melting) before the gas supply control step and the heat treatment was performed was 1.0% by mass.
  • the modified PPS resin has a peak molecular weight (M top ) of 28,000 , which is the peak molecular weight (M top ) of the raw material PPS resin before modification, which is 25,000. was confirmed to increase by 10% or more.
  • the formation of the PPS resin adhered matter could not be confirmed in the container portion 4 after the modification treatment.
  • Example 1 60 kg of the same PPS resin (melt viscosity (V6) 22 Pa s) as in Example 1 was placed in the apparatus described in Japanese Patent Application Laid-Open No. 7-242746, that is, an effective capacity equipped with a gas introduction device and a heat medium circulation jacket. A 100 L conical screw mixing type heating device (described in FIG. 1 of JP-A-7-242746: also referred to as device B) was charged. Next, air is introduced into the container at a flow rate of 16 L / min (16% / min of the internal volume of the container), and the internal temperature is raised to 250 ° C. using a heat medium in 4 hours. Hold for 7 hours.
  • the rotational speed of the agitator was 1 rpm for the screw revolution axis and 36 rpm for the rotation axis. Thereafter, the lid of the container was opened without lowering the internal temperature from 250° C. to obtain a PPS resin product after the reaction.
  • the yield was 46.8 kg (78% yield), and adherence of PPS resin deposits to the inner wall of the processing vessel was observed.
  • the melt viscosity (V6) of the PPS resin after heat treatment was 152 Pa ⁇ s, and the amount of gas generated during melting was 0.55% by mass.
  • the conical screw mixing type heating apparatus (apparatus B) used in Comparative Example 1 was arranged along the inner wall of the container from the bottom to the top of the container, and further from the top to the center of the container. No circulation flow was formed in which raw material components circulated to the bottom.
  • Example 2 15 kg of the same PPS resin (melt viscosity (V6) 22 Pa s) as in Example 1 was added to the apparatus described in JP-A-62-205127, that is, the full capacity equipped with a gas introduction device and a heat medium circulation jacket. was charged in a 50 L vessel rotating double cone heating device (described in FIG. 1 of Japanese Patent Application Laid-Open No. 205127/1987: also referred to as device C). Next, the rotation of the container is started at a rotation speed of 3 rpm, air is introduced into the container at a flow rate of 2 L/min (4%/min of the internal volume of the container), and the internal temperature reaches 250°C using a heat medium.
  • a 50 L vessel rotating double cone heating device described in FIG. 1 of Japanese Patent Application Laid-Open No. 205127/1987: also referred to as device C.
  • the rotation of the container is started at a rotation speed of 3 rpm, air is introduced into the container at a flow rate of 2 L/min (
  • the temperature was raised to 5 hours and held at that temperature for an additional 8 hours.
  • the lid of the container was opened without lowering the internal temperature from 250° C.
  • the PPS resin adhered to the lid, and no PPS resin was obtained. Adherence of PPS resin deposits was also observed on the inner wall of the processing vessel.
  • the melt viscosity (V6) of the PPS resin after heat treatment was 154 Pa ⁇ s, and the amount of gas generated during melting was 0.54% by mass.
  • the conical screw mixing type heating apparatus (apparatus C) used in Comparative Example 1 was arranged along the inner wall of the container from the bottom to the top of the container, and further from the top to the center of the container. No circulation flow was formed in which raw material components circulated to the bottom.
  • Example 3 60 kg of the same PPS resin (melt viscosity (V6) 22 Pa s) as in Example 1 was placed in the apparatus described in Japanese Patent Application Laid-Open No. 7-242746, that is, an effective capacity equipped with a gas introduction device and a heat medium circulation jacket.
  • a 100 L conical screw mixing type heating device (described in FIG. 1 of JP-A-7-242746: also referred to as device B) was charged.
  • nitrogen as an inert gas is introduced into the container at a flow rate of 16 L/min (16%/min of the internal volume of the container), and the internal temperature is raised to 250 ° C. using a heat medium in 4 hours, It was held at that temperature for an additional 7 hours.
  • the rotational speed of the agitator was 1 rpm for the screw revolution axis and 36 rpm for the rotation axis. Thereafter, the lid of the container was opened without lowering the internal temperature from 250° C. to obtain a PPS resin product after the reaction.
  • the yield was 47.4 kg (79% yield), and adherence of PPS resin deposits to the inner wall of the processing vessel was observed.
  • the melt viscosity (V6) of the PPS resin after heat treatment was 41 Pa ⁇ s, and the amount of gas generated during melting was 0.54% by mass.
  • the conical screw mixing type heating apparatus (apparatus B) used in Comparative Example 3 was arranged along the inner wall of the container from the bottom to the top of the container, and further from the top to the center of the container. No circulation flow was formed in which raw material components circulated to the bottom.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)

Abstract

L'invention concerne un procédé pour la production d'une résine de poly(sulfure d'arylène) (PAS) avec lequel la formation d'une substance adhérant à la résine de PAS qui adhère à la paroi interne d'un récipient est supprimée et évitée, l'agrégation de résines de PAS étant en même temps supprimée, et la contamination est réduite. Plus précisément, l'invention porte sur un procédé pour la production d'une résine de PAS, dans lequel un composant matière première contenant une résine de PAS est modifié par chauffage du composant matière première à une température au-dessous du point de fusion Tm de la résine de PAS dans une atmosphère d'un gaz de modification au moyen d'un appareil de modification pourvu d'une partie récipient pouvant contenir le composant matière première et d'un mécanisme d'agitation pour former un flux de circulation, le procédé comprenant : une étape de traitement thermique consistant à apporter le gaz de modification dans la partie récipient, la décharge du gaz présent dans la partie récipient vers l'extérieur de la partie récipient et le chauffage du composant matière première à une température au-dessous du point de fusion Tm à l'aide d'un moyen de chauffage, le composant matière première introduit dans la partie récipient étant en même temps amené à circuler par le flux de circulation ; et une étape de réglage d'apport de gaz consistant à régler la quantité d'apport du gaz de modification par minute dans la plage de 0,1 à 100 % du volume de la partie récipient.
PCT/JP2022/029049 2021-11-16 2022-07-28 Procédé pour la production de résine de poly(sulfure d'arylène) modifiée WO2023089872A1 (fr)

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Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4245399A (en) * 1978-04-26 1981-01-20 Schering Aktiengesellschaft Material dryer with air and screw agitator

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4245399A (en) * 1978-04-26 1981-01-20 Schering Aktiengesellschaft Material dryer with air and screw agitator

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