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WO2023243205A1 - Procédés de production d'un polymère de thioéther sulfone aromatique, composition et article moulé - Google Patents

Procédés de production d'un polymère de thioéther sulfone aromatique, composition et article moulé Download PDF

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Publication number
WO2023243205A1
WO2023243205A1 PCT/JP2023/014955 JP2023014955W WO2023243205A1 WO 2023243205 A1 WO2023243205 A1 WO 2023243205A1 JP 2023014955 W JP2023014955 W JP 2023014955W WO 2023243205 A1 WO2023243205 A1 WO 2023243205A1
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WO
WIPO (PCT)
Prior art keywords
alkali metal
aromatic
polymer
thioether sulfone
sulfone polymer
Prior art date
Application number
PCT/JP2023/014955
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English (en)
Japanese (ja)
Inventor
智理 鶴岡
Original Assignee
Dic株式会社
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Publication date
Application filed by Dic株式会社 filed Critical Dic株式会社
Priority to JP2024502521A priority Critical patent/JP7691647B2/ja
Publication of WO2023243205A1 publication Critical patent/WO2023243205A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
    • C08G75/02—Polythioethers
    • C08G75/0204—Polyarylenethioethers
    • 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
    • C08G75/20—Polysulfones
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L81/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen or carbon only; Compositions of polysulfones; Compositions of derivatives of such polymers

Definitions

  • the present invention relates to aromatic thioether sulfone polymers, compositions, and methods for producing molded articles.
  • resin materials have been widely used for optical materials such as optical lenses, prism sheets, and parts for organic light emitting diode devices (OLED) due to their excellent processability and productivity. Furthermore, due to the trend toward smaller and lighter optical members, resin materials with a high refractive index are required. Conventional resins generally have a refractive index of 1.30 to 1.70, and there are almost no general-purpose materials with a refractive index exceeding 1.70.
  • a common approach to increasing the refractive index of resins is to introduce substituents with high molar refraction, small molar volume, and high specific gravity into molecules according to the Lorentz-Lorentz equation. That is, introduction of halogen atoms and sulfur atoms is said to be effective. Since sulfur atoms have high polarizability, stability, and ease of introduction into polymers, sulfur-containing resins for various optical materials have been reported. For example, a compound having a thiourethane skeleton is disclosed as a sulfur-containing resin. However, this compound has low heat resistance and has problems in use under high temperature conditions (Patent Document 1, Patent Document 2, Patent Document 3).
  • aromatic polythioethers have a high sulfur content in the resin skeleton and a very high density, so they are promising high refractive materials.
  • aromatic thioether sulfone polymers are highly transparent because they are amorphous resins, and they also have excellent heat resistance due to their high glass transition temperature of about 220°C, making them optical materials that can be used even under high-temperature conditions. It is expected that However, in the conventionally reported production methods of aromatic thioether sulfone polymers, the resulting resins are colored and lack transparency, so their use as optical materials has been avoided (Patent Document 4, Patent Document 5).
  • the problem to be solved by the present invention is to provide an aromatic thioether sulfone polymer, a composition, and a method for producing molded articles that have a high refractive index, little coloration, and high transparency.
  • the present inventors conducted extensive studies and found that in the presence of a hydrous sulfonic solvent, a dihaloaromatic compound and (i) an alkali metal sulfide, or (ii) an alkali metal hydrosulfide It has been found that by polymerizing the aromatic thioether sulfone and an alkali metal hydroxide, it is possible to provide an aromatic thioether sulfone polymer that has a high refractive index, has little coloring, and is highly transparent.
  • the present disclosure involves polymerizing a dihaloaromatic compound and (i) an alkali metal sulfide, or (ii) an alkali metal hydrosulfide and an alkali metal hydroxide in a water-containing sulfonic solvent.
  • the present invention relates to a method for producing an aromatic thioether sulfone polymer.
  • oligomer a polymer having 2 to 40 repeating units (a mixture of dimers to 40-mers) may be referred to as an "oligomer.”
  • this embodiment an embodiment of the present invention (hereinafter referred to as “this embodiment”) will be described in detail, but the present invention is not limited to the following description, and can be modified in various ways within the scope of the gist. It can be implemented by
  • the method for producing an aromatic thioether sulfone polymer according to the first embodiment of the present disclosure includes combining a dihaloaromatic compound and (i) an alkali metal sulfide, or (ii) an alkali metal sulfide in a water-containing sulfonic solvent. It is characterized by polymerizing a hydrosulfide and an alkali metal hydroxide.
  • the method for producing an aromatic thioether sulfone polymer according to the second embodiment of the present disclosure includes: A step of polymerizing a dihaloaromatic compound and (i) an alkali metal sulfide, or (ii) an alkali metal hydrosulfide and an alkali metal hydroxide in a water-containing sulfonic solvent to obtain a crude reaction mixture ( 1), step (2) of crushing the crude reaction mixture; The method includes a step (3) of contacting the crushed crude reaction mixture with a polar organic solvent and then performing solid-liquid separation to obtain a solid phase component (A). The details will be explained below.
  • the hydrous sulfonic solvent used in this embodiment is a mixture of water and a sulfonic solvent.
  • the sulfonic solvent include compounds having one or more sulfone groups, such as diphenylsulfone (DPS), dimethylsulfoxide, diethylsulfone, diisopropylsulfone, and sulfolane (1,1-dioxothyrane).
  • DPS diphenylsulfone
  • dimethylsulfoxide diethylsulfone
  • diisopropylsulfone diisopropylsulfone
  • sulfolane 1,1-dioxothyrane
  • dihaloaromatic compounds having functional groups with active hydrogen such as amino groups, thiol groups, and hydroxyl groups
  • functional groups with active hydrogen such as amino groups, thiol groups, and hydroxyl groups
  • specific examples include 2,6-dichloroaniline and 2,5-dichloroaniline.
  • 2,2'-diamino-4,4'-dichlorodiphenyl ether 2,4'-diamino-2',4-di
  • dihaloaminodiphenyl ethers such as chlordiphenyl ether, and compounds in which the amino group is replaced with a thiol group or a hydroxyl group in a mixture thereof.
  • active hydrogen-containing dihaloaromatic compounds in which the hydrogen atom bonded to the carbon atom forming the aromatic ring in these active hydrogen-containing dihaloaromatic compounds are substituted with other inert groups, such as hydrocarbon groups such as alkyl groups.
  • Aromatic compounds can also be used.
  • dihaloaromatic compounds having a nitro group examples include dihalonitrobenzenes such as 2,4-dinitrochlorobenzene and 2,5-dichloronitrobenzene; Halonitro diphenyl ethers; Dihalonitro diphenyl sulfones such as 3,3'-dinitro-4,4'-dichloro diphenyl sulfone; 2,5-dichloro-3-nitropyridine, 2-chloro-3,5-dinitro Mono- or dihalonitropyridines such as pyridine; or various dihalonitronaphthalenes; 9,9-bis(4-chlorophenyl)fluorene, 9,9-bis(4-bromophenyl)fluorene, 9,9-bis( 4-iodophenyl)fluorene, 9,9-bis(4-chloro-3-methylphenyl)fluorene, 9,9-bis(4-bromo-3-methylphenyl)fluoren
  • an alkali metal sulfide, or an alkali hydrosulfide and an alkali metal hydroxide (hereinafter sometimes referred to as a sulfidating agent) are used as raw materials.
  • the alkali metal sulfide includes lithium sulfide, sodium sulfide, rubidium sulfide, cesium sulfide, and mixtures thereof.
  • Such alkali metal sulfides can be used as hydrates or aqueous mixtures or as anhydrides.
  • an alkali metal sulfide can also be derived by a reaction between an alkali metal hydrosulfide and an alkali metal hydroxide. Note that a small amount of alkali metal hydroxide may be added in order to react with alkali metal hydrosulfide and alkali metal thiosulfate, which are usually present in a small amount in the alkali metal sulfide.
  • the alkali metal hydrosulfide includes lithium hydrogen sulfide, sodium hydrogen sulfide, rubidium hydrogen sulfide, cesium hydrogen sulfide, and mixtures thereof.
  • Such alkali metal hydrosulfides can be used as hydrates or aqueous mixtures or as anhydrides.
  • the molar ratio of the dihaloaromatic compound to the sulfidating agent is preferably in the range of 0.95 to 1.2 (mol/mol), more preferably 1.00 to 1.10 (mol/mol). ) is within the range. If it is smaller than 0.95 (mol/mol), a decomposition reaction may occur or the resulting aromatic copolymer may have poor thermal stability; if it is larger than 1.2 (mol/mol), polymerization may The reaction may be difficult to proceed and it may be difficult to increase the molecular weight.
  • the conditions for polymerizing the sulfidating agent and the dihaloaromatic compound in the presence of the above-mentioned water-containing sulfonic solvent are generally at a temperature of 150 to 330°C, and at a pressure that substantially removes the polymerization solvent and the dihaloaromatic compound as the polymerization monomer.
  • the pressure should be within a range such that the pressure is maintained in the 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 temperature and pressure, but is generally in the range of 10 minutes to 72 hours, preferably in the range of 1 hour to 10 hours.
  • the above temperature range is preferably a reaction temperature of 180°C or higher because it is easy to obtain an aromatic thioether sulfone polymer with a sufficiently high molecular weight, and side reactions such as depolymerization are difficult to occur, and a high molecular weight product can be stably produced. It is preferable to carry out the reaction at 300° C. or lower because it is easy to obtain.
  • the crude reaction product is obtained by reacting the dihaloaromatic compound and the hydrous sulfonic solvent in the presence of the sulfidating agent and the hydrous sulfonic solvent while continuously or intermittently adding the dihaloaromatic compound and the hydrous sulfonic solvent.
  • Step (3) is a step in which the crushed crude reaction mixture is brought into contact with a polar organic solvent and then subjected to solid-liquid separation to obtain the solid phase component (A).
  • the degree of separation and removal of the water-containing sulfone solvent is not particularly limited, it is preferable that the solid content ratio (solid content concentration) in the solid phase component (A) is based on 100 parts by mass of the solid phase component (A). is 40 parts by mass or more, more preferably 50 parts by mass or more, still more preferably 55 parts by mass or more.
  • the upper limit is not limited, it is preferably 100 parts by mass or less, more preferably less than 100 parts by mass, and even more preferably 99 parts by mass or less.
  • the aromatic thioether sulfone polymer obtained by the above production method has excellent melt stability, so the rate of viscosity change during retention is small.
  • the viscosity change rate is preferably 10% or less, more preferably 8% or less. Note that the viscosity change rate in the present disclosure can be measured by the method described in Examples.
  • the method for producing a composition according to the present embodiment includes a step of blending the aromatic thioether sulfone polymer produced by the above method with another substance and melt-kneading the mixture.
  • the aromatic thioether sulfone polymer obtained by the production method according to the present embodiment may contain other substances such as a mold release agent, a coloring agent, a heat stabilizer, an ultraviolet stabilizer, and a foaming agent to the extent that the effects of the present invention are not impaired. It can be used as a composition by containing additives such as additives, rust preventives, flame retardants, lubricants, coupling agents, and fillers.
  • additives such as additives, rust preventives, flame retardants, lubricants, coupling agents, and fillers.
  • the filler known and commonly used materials can be used as long as they do not impair the effects of the present invention. Examples include inorganic fillers.
  • fibrous fillers such as glass fiber, carbon fiber, silane glass fiber, ceramic fiber, aramid fiber, metal fiber, potassium titanate, silicon carbide, calcium silicate, wollastonite, natural fiber, etc. It can also be used for glass beads, glass flakes, barium sulfate, clay, pyrophyllite, bentonite, sericite, mica, talc, attapulgite, ferrite, calcium silicate, calcium carbonate, glass beads, zeolite, milled fiber, calcium sulfate, etc.
  • Non-fibrous fillers can also be used.
  • the aromatic thioether sulfone polymer obtained by the production method according to the present embodiment is further mixed with the following synthetic resins and elastomers as other substances to the extent that the effects of the present invention are not impaired. It can also be used as an object.
  • These synthetic resins include polyester, polyamide, polyimide, polyetherimide, polycarbonate, polyphenylene ether, polysulfone, polyether sulfone, polyether ether ketone, polyether ketone, polyarylene, polyarylene sulfide, polyethylene, polypropylene, polytetra
  • Examples include fluorinated ethylene, polydifluoroethylene, polystyrene, ABS resin, epoxy resin, silicone resin, phenol resin, urethane resin, liquid crystal polymer, etc.
  • elastomers include polyolefin rubber, fluororubber, silicone rubber, etc. It will be done.
  • the melt-kneading machine is preferably a twin-screw kneading extruder from the viewpoint of dispersibility and productivity, for example, a discharge rate of the resin component in the range of 5 to 500 (kg/hr) and a screw rotation speed of 50 to 500 (rpm). It is preferable to melt and knead while appropriately adjusting the range, and melt and knead under conditions such that the ratio (discharge amount/screw rotation speed) is in the range of 0.02 to 5 (kg/hr/rpm). is even more preferable. Further, the addition and mixing of each component to the melt-kneading machine may be performed simultaneously or may be performed separately.
  • the position of the side feeder is preferably such that the ratio of the distance from the extruder resin input part (top feeder) to the side feeder to the total screw length of the twin-screw kneading extruder is 0.1 or more, and 0. More preferably, it is .3 or more. Moreover, it is preferable that this ratio is 0.9 or less, and it is more preferable that it is 0.7 or less.
  • the aromatic thioethersulfone polymer composition according to the present embodiment obtained by melt-kneading as described above has a morphology in which the aromatic thioethersulfone polymer forms a continuous phase and other essential components and optional components are dispersed.
  • the aromatic thioethersulfone polymer composition according to the present embodiment is produced by a known method, for example, by extruding the molten polymer composition into a strand shape, and then forming the composition into pellets, chips, granules, and powder. After processing into a form such as, it is preferable to perform preliminary drying at a temperature range of 100 to 150°C as necessary.
  • the method for producing a molded article according to the present embodiment includes the step of melt-molding the aromatic thioethersulfone polymer composition obtained by the method for producing an aromatic thioethersulfone polymer composition according to the present embodiment described above. .
  • the aromatic thioether sulfone polymer composition can be molded by various molding methods such as injection molding, compression molding, extrusion molding of composites, sheets, pipes, etc., pultrusion molding, blow molding, and transfer molding.
  • various molding conditions are not particularly limited, and molding can be performed by a general method.
  • aromatic thioether sulfone polymer and polymer composition is not particularly limited, and can be used as various products.
  • electrical/electronic parts such as connectors, printed circuit boards, and molded seals
  • automotive parts such as lamp reflectors and various electrical components, interior materials for various buildings, aircraft, automobiles, etc., OA equipment parts, camera parts, etc.
  • precision parts such as watch parts.
  • optical materials such as plastic lenses such as eyeglass lenses, camera lenses, and prism lenses, hard coating agents, antireflection films, prism lenses, and LED sealing materials.
  • Example 1-Step (2) After the polymerization was completed, the reaction solution was cooled to room temperature and solidified. The solidified crude reaction mixture was collected in a mixer ("Sample Mill” manufactured by Kyoritsu Riko Co., Ltd.) and crushed. The D50 of the crude reaction mixture after crushing was 40 ⁇ m.
  • Example 1-Step (3) The crushed crude reaction mixture was collected in a container and washed three times with a mixed solvent of acetone and methanol (mass ratio 1:1) and with hot water (70°C). Thereafter, the solid phase component collected by filtration was dried at 120° C. for 2 hours under normal pressure, and then further dried under reduced pressure at 150° C. for 5 hours to obtain a polymer (1). Table 1 shows the properties of the obtained polymer.
  • the aromatic thioether sulfone polymer obtained by the production method of the example has a high refractive index, less coloring, and high transparency. Furthermore, the amount of gas generated and the rate of change in viscosity were small, indicating excellent thermal stability.

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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)
  • Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)

Abstract

L'invention concerne des procédés de production d'un polymère de thioéther sulfone aromatique, une composition de polymère de thioéther sulfone aromatique, et un article moulé en polymère de thioéther sulfone aromatique, qui ont tous un indice de réfraction élevé et présentent moins de coloration et une transparence élevée. Plus en détail, ce procédé de fabrication d'un polymère de thioéther sulfone aromatique est caractérisé par la polymérisation, dans un solvant à base de sulfone hydraté, d'un composé aromatique dihalogéné et (i) d'un sulfure de métal alcalin ou (ii) d'un hydrosulfure de métal alcalin et d'un hydroxyde de métal alcalin.
PCT/JP2023/014955 2022-06-14 2023-04-13 Procédés de production d'un polymère de thioéther sulfone aromatique, composition et article moulé WO2023243205A1 (fr)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS61168629A (ja) * 1985-01-22 1986-07-30 Asahi Glass Co Ltd 芳香族ポリスルホン／ポリチオエ−テルスルホン共重合体の製造方法
JPH0268146A (ja) * 1988-09-01 1990-03-07 Asahi Glass Co Ltd 新規な架橋構造を有する陰イオン交換体
JPH0450246A (ja) * 1990-06-19 1992-02-19 Asahi Chem Ind Co Ltd 多孔性ポリマーの精製方法
JPH04275335A (ja) * 1991-03-02 1992-09-30 Toray Philips Petroleum Kk ポリフェニレンスルフィドスルホンの製造方法
JPH07252359A (ja) * 1994-03-16 1995-10-03 Sekisui Chem Co Ltd 芳香族ポリスルフィドスルホン樹脂
JP2017114923A (ja) * 2015-12-21 2017-06-29 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 (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS61168629A (ja) * 1985-01-22 1986-07-30 Asahi Glass Co Ltd 芳香族ポリスルホン／ポリチオエ−テルスルホン共重合体の製造方法
JPH0268146A (ja) * 1988-09-01 1990-03-07 Asahi Glass Co Ltd 新規な架橋構造を有する陰イオン交換体
JPH0450246A (ja) * 1990-06-19 1992-02-19 Asahi Chem Ind Co Ltd 多孔性ポリマーの精製方法
JPH04275335A (ja) * 1991-03-02 1992-09-30 Toray Philips Petroleum Kk ポリフェニレンスルフィドスルホンの製造方法
JPH07252359A (ja) * 1994-03-16 1995-10-03 Sekisui Chem Co Ltd 芳香族ポリスルフィドスルホン樹脂
JP2017114923A (ja) * 2015-12-21 2017-06-29 Dic株式会社 ポリアリーレンスルフィド樹脂の製造方法

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JPWO2023243205A1 (fr) 2023-12-21

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