WO2025192516A1 - Procédé de fabrication de produit solide - Google Patents

Procédé de fabrication de produit solide

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Publication number
WO2025192516A1
WO2025192516A1 PCT/JP2025/008772 JP2025008772W WO2025192516A1 WO 2025192516 A1 WO2025192516 A1 WO 2025192516A1 JP 2025008772 W JP2025008772 W JP 2025008772W WO 2025192516 A1 WO2025192516 A1 WO 2025192516A1
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WO
WIPO (PCT)
Prior art keywords
specific
fluorine
medium
mass
mixture
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
PCT/JP2025/008772
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English (en)
Japanese (ja)
Inventor
圭司 堀
優 竹内
優樹 折戸
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
AGC Inc
Original Assignee
Asahi Glass Co Ltd
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Filing date
Publication date
Application filed by Asahi Glass Co Ltd filed Critical Asahi Glass Co Ltd
Publication of WO2025192516A1 publication Critical patent/WO2025192516A1/fr
Anticipated expiration legal-status Critical
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F14/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
    • C08F14/18—Monomers containing fluorine
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F6/00—Post-polymerisation treatments
    • C08F6/06—Treatment of polymer solutions
    • C08F6/12—Separation of polymers from solutions

Definitions

  • the present invention relates to a method for producing a solid material containing a fluorinated polymer.
  • fluorine-containing polymers have been used in a variety of applications, taking advantage of their excellent properties such as heat resistance, solvent resistance, and chemical resistance.
  • Known methods for producing fluoropolymers include solution polymerization, suspension polymerization and emulsion polymerization, and in these methods, a fluorine-containing compound having a relatively low molecular weight is used as the polymerization medium in order to give a high molecular weight copolymer and to increase the polymerization rate.
  • Patent Document 1 describes a method for producing a fluorinated polymer, in which a monomer component containing a fluorinated monomer is polymerized in a polymerization medium containing a specific fluorinated ether compound in the presence of a polymerization initiator.
  • the present invention aims to provide a method for producing a solid material containing a fluoropolymer, which allows for the easy production of a solid material containing a fluoropolymer as a main component and having a low content of low-molecular-weight fluorine-containing compounds.
  • a method for producing a solid material containing a fluoropolymer comprising contacting a mixture containing a fluoropolymer and a low-molecular-weight fluorine-containing compound with a specific medium to obtain a composition containing the fluoropolymer, the low-molecular-weight fluorine-containing compound and the specific medium, separating the specific medium from the obtained composition, and drying the composition from which the specific medium has been separated, wherein the content of units based on monomers containing a ring structure in the fluoropolymer is 10 mass% or less relative to the total mass of the fluoropolymer, the fluoropolymer does not contain an ionic functional group, and the specific medium is a hydrocarbon medium or a ketone medium which does not contain fluorine atoms or hydroxyl groups.
  • [4] The method for producing a solid material according to [1] or [2], wherein the specific medium brought into contact with the mixture is gaseous, and the mass ratio of the amount of the gaseous specific medium brought into contact with the mixture to the amount of the mixture is 3000 mass% or less.
  • [5] The method for producing a solid material according to any one of [1] to [4], wherein the Hansen solubility parameter distance between the low-molecular-weight fluorine-containing compound and the specific medium is 12 MPa 0.5 or less.
  • [6] The method for producing a solid material according to any one of [1] to [5], wherein the low-molecular-weight fluorine-containing compound does not have an ionic functional group.
  • the present invention provides a method for producing a solid material containing a fluoropolymer, which allows for the easy production of a solid material containing a fluoropolymer as a main component and having a low content of low-molecular-weight fluorine-containing compounds.
  • each component may be a single substance corresponding to the component, or two or more substances may be used in combination.
  • the content of the component refers to the total content of the substances used in combination, unless otherwise specified.
  • a combination of two or more preferred embodiments is a more preferred embodiment.
  • unit refers collectively to an atomic group derived from one molecule of the monomer formed directly by polymerization of the monomer, and an atomic group obtained by chemically converting a part of the atomic group.
  • units derived from individual monomers may be referred to by the name of the monomer followed by "unit.”
  • TFE units are units based on tetrafluoroethylene in a fluoropolymer
  • E units are units based on ethylene in a fluoropolymer.
  • solvent means a substance that is liquid at 25°C and 1013 hPa.
  • the method for producing a solid material containing a fluoropolymer of the present invention is a production method which comprises contacting a mixture containing a fluoropolymer and a low-molecular-weight fluorine-containing compound with a specific medium to obtain a composition containing the fluoropolymer, the low-molecular-weight fluorine-containing compound and the specific medium, separating the specific medium from the obtained composition, and drying the composition from which the specific medium has been separated, characterized in that in the fluoropolymer, the content of units based on a monomer containing a ring structure is 10 mass% or less relative to the total mass of the fluoropolymer, the fluoropolymer does not contain an ionic functional group, and the specific medium is a hydrocarbon medium or a ketone medium which does not contain fluorine atoms and hydroxyl groups.
  • This method makes it possible to easily produce a solid material that contains a fluoropolymer as its main component and has a low content of low-molecular-weight fluorine-containing compounds. While the details of why such a solid material can be produced are unclear, this method involves contacting a fluoropolymer that contains no more than 10 mass% of units based on monomers containing a ring structure, relative to the total mass of the fluoropolymer, and that does not contain ionic functional groups, with a specific medium that does not contain fluorine atoms or hydroxyl groups, followed by separation of the specific medium and subsequent drying.
  • the specific medium has a moderate affinity for the fluoropolymer, it is easy to extract the low-molecular-weight fluorine-containing compounds present in the fluoropolymer and allows them to be easily separated from the fluoropolymer. As a result, it is presumed that a solid material that contains a lower content of low-molecular-weight fluorine-containing compounds and that contains the fluoropolymer as its main component can be produced.
  • a fluoropolymer in which the content of units based on monomers containing a ring structure is 10 mass% or less relative to the total mass of the fluoropolymer and which does not contain an ionic functional group will also be referred to as a "specific fluoropolymer”
  • a mixture containing a specific fluoropolymer and a low-molecular-weight fluorocompound will also be referred to as a "specific mixture”
  • a hydrocarbon medium which does not contain fluorine atoms and does not contain hydroxyl groups will also be referred to as a "specific hydrocarbon medium”
  • a ketone-based medium which does not contain fluorine atoms and does not contain hydroxyl groups will also be referred to as a "specific ketone-based medium”
  • the specific hydrocarbon medium and the specific ketone-based medium will also be collectively referred to as a "specific medium”.
  • the step of contacting the specific mixture with the specific medium to obtain a composition containing the specific fluorine-containing polymer, the low-molecular-weight fluorine-containing compound and the specific medium is also referred to as the "contacting step”
  • the step of separating the specific medium from the composition is also referred to as the “separating step”
  • the step of drying the composition from which the specific medium has been separated is also referred to as the “drying step”.
  • the specific mixture containing the specific fluorine-containing polymer and the low-molecular-weight fluorine-containing compound is contacted with the specific medium, and the contacting step results in a composition containing the specific fluorine-containing polymer, the low-molecular-weight fluorine-containing compound, and the specific medium (hereinafter also referred to as the "first composition").
  • the specific fluorine-containing polymer is a polymer which contains units derived from at least one fluorine-containing monomer, in which the content of units derived from a monomer containing a ring structure is 10 mass % or less based on the total mass of the fluorine-containing polymer, and which does not contain an ionic functional group.
  • the specific fluorine-containing polymer can be obtained, for example, by polymerizing a monomer component containing a fluorine-containing monomer (excluding a monomer containing any one of ionic functional groups).
  • the fluorine-containing monomer used in the production of the specific fluorine-containing polymer is preferably a compound which contains a fluorine atom and a polymerizable unsaturated bond, but which does not contain a ring structure or an ionic functional group, and examples thereof include the following compounds.
  • Tetrafluoroethylene hereinafter also referred to as "TFE”
  • chlorotrifluoroethylene examples thereof include the following compounds.
  • Tetrafluoroethylene hereinafter also referred to as "TFE”
  • chlorotrifluoroethylene chlorotrifluoroethylene.
  • Compounds represented by the following formula 1 compounds represented by the following formula 2
  • fluoroolefins which may have an ether bond such as vinylidene fluoride (VDF), vinyl fluoride (VF), trifluoroethylene, and hexafluoroisobutylene (HFIB) (excluding TFE and CTFE).
  • VDF vinylidene fluoride
  • VF vinyl fluoride
  • X, Y, and Z each independently represent a hydrogen atom or a fluorine atom
  • m represents an integer of 1 to 6.
  • n represents an integer of 1 to 6.
  • (1) is preferred, and TFE is more preferred, because it has even better heat resistance, chemical resistance, weather resistance, and the like.
  • the fluorine-containing monomer may be used alone or in combination of two or more kinds.
  • X is preferably a hydrogen atom from the viewpoint of polymerization reactivity.
  • Y is preferably a hydrogen atom.
  • Z is preferably a fluorine atom.
  • m is preferably an integer of 2 to 6, more preferably an integer of 3 to 6, and even more preferably 3 or 4.
  • Specific examples of the compound represented by formula 2 include CF 2 ⁇ CF-O-(CF 2 )F (perfluoromethyl vinyl ether (PMVE)), CF 2 ⁇ CF-O-(CF 2 ) 2 F, CF 2 ⁇ CF-O-(CF 2 ) 3 F (perfluoropropyl vinyl ether (PPVE)), CF 2 ⁇ CF-O-(CF 2 ) 4 F, CF 2 ⁇ CF-O-(CF 2 ) 5 F, and CF 2 ⁇ CF-O-(CF 2 ) 6 F, with PMVE and PPVE being preferred and PMVE being more preferred.
  • PMVE and PPVE perfluoromethyl vinyl ether
  • CF 2 ⁇ CF-O-(CF 2 ) 2 F perfluoromethyl vinyl ether
  • PPVE perfluoropropyl vinyl ether
  • CF 2 ⁇ CF-O-(CF 2 ) 4 F perfluoropropyl vinyl ether
  • the specific fluorine-containing polymer may contain units based on monomers other than the fluorine-containing monomer.
  • monomers include chain hydrocarbons having an unsaturated bond at the ⁇ -position, such as ethylene (hereinafter also referred to as "E"), propylene, and butene.
  • E chain hydrocarbons having an unsaturated bond at the ⁇ -position
  • ethylene, propylene, or 1-butene is preferred, and ethylene is more preferred, in view of the excellent physical properties such as heat resistance and mechanical properties of the resulting polymer.
  • the content of units based on monomers containing a ring structure is 10% by mass or less, and preferably 5% by mass or less, relative to the total mass of the fluoropolymer.
  • the lower limit is not particularly limited and may be 0% by mass.
  • the content of units based on monomers containing a ring structure in the specific fluoropolymer may be below the detection limit of the measurement method described in the examples.
  • the specific fluorine-containing polymer does not contain an ionic functional group.
  • the fluoropolymer does not contain an ionic functional group means that the content of units derived from monomers having ionic functional groups relative to all units contained in the fluoropolymer is 0.001 mol% or less, preferably 0.0001 mol% or less, more preferably 0 mol%. It is also preferable that the content of units derived from monomers having ionic functional groups relative to all units contained in the specific fluoropolymer is below the detection limit of the measurement method described in the Examples.
  • Examples of the ionic functional group include an anionic functional group and a cationic functional group.
  • anionic functional groups include acid groups such as sulfonic acid groups, carboxylic acid groups, sulfate groups, phosphonic acid groups, and phosphate groups, salts of the acid groups, and precursor groups of the acid groups.
  • Counter ions that form salts with the acid groups include metal cations and quaternary ammonium cations.
  • the precursor groups of the acid groups refer to groups that can be converted into the acid groups by treatments such as hydrolysis and acidification.
  • Examples of cationic functional groups include basic groups such as quaternary ammonium groups, salts of the basic groups, and precursor groups of the basic groups.
  • Examples of counter ions that form salts with the basic groups include anions formed by removing at least one proton from an inorganic acid or an organic acid.
  • the precursor groups of the basic groups refer to groups that can be converted into the basic groups by treatment such as hydrolysis.
  • a polymer containing TFE units is preferred, a polymer containing TFE units and E units, a polymer containing TFE units and PMVE units or a polymer containing TFE units and PPVE units is more preferred, a polymer containing TFE units and E units or a polymer containing TFE units and PMVE units is more preferred, a polymer containing TFE units and E units is even more preferred, a polymer containing TFE units and E units and at least one of units based on a compound represented by formula 1 and units based on a compound represented by formula 2 is particularly preferred, and a polymer containing TFE units, E units and units based on a compound represented by formula 1 is most preferred.
  • the molar ratio of TFE units to PMVE units is preferably 80.0/20.0 to 30.0/70.0, more preferably 75.0/25.0 to 35.0/65.0, and even more preferably 70.0/30.0 to 40.0/60.0.
  • the molar ratio of TFE units to E units is preferably 20.0/80.0 to 80.0/20.0, more preferably 30.0/70.0 to 70.0/30.0, and even more preferably 50.0/50.0 to 65.0/35.0, in order to obtain a molded article made from the specific fluoropolymer with better heat resistance, weather resistance, chemical resistance, resistance to chemical permeation, mechanical strength, melt moldability, etc.
  • the content of TFE units is preferably 45.00 to 69.99 mol%, more preferably 48.00 to 64.90 mol%, and even more preferably 50.00 to 64.50 mol%, based on all units contained in the specific fluorine-containing polymer. If it is not less than the above-mentioned lower limit, the chemical resistance and heat resistance during long-term use of the molded article will be better, and if it is not more than the above-mentioned upper limit, the mechanical properties of the molded article will be better.
  • the content of E units is preferably 30.00 to 54.99 mol%, more preferably 35.00 to 51.90 mol%, and even more preferably 35.00 to 49.50 mol%, based on all units contained in the specific fluorine-containing polymer. If it is not less than the above-mentioned lower limit, the mechanical properties of the molded article will be better, and if it is not more than the above-mentioned upper limit, the heat resistance and weather resistance during long-term outdoor use of the molded article will be better.
  • the total content of TFE units and E units is preferably 90.00 mol% or more, more preferably 95.00 mol% or more, and even more preferably 97.00 mol% or more, based on all units contained in the specific fluoropolymer, and may be 100.00 mol% or less.
  • the total content of TFE units and E units is preferably 99.00 mol% or less, more preferably 99.50 mol% or less, based on all units contained in the specific fluoropolymer.
  • the content of the other units is preferably 0.01 to 10.00 mol %, more preferably 0.10 to 5.00 mol %, and even more preferably 0.50 to 4.00 mol %, based on the total units contained in the specific fluoropolymer. If the content is above the lower limit, a molded product with excellent abrasion resistance can be formed, and if it is below the upper limit, a molded product with excellent dimensional stability can be formed.
  • the specific fluorine-containing polymer can be produced, for example, by polymerizing the above-mentioned monomer components by a known method.
  • the polymerization method include bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization, and among these, solution polymerization or suspension polymerization is preferred.
  • a polymerization initiator, a polymerization medium, a chain transfer agent, etc. can be used.
  • the polymerization initiator used for producing the specific fluorine-containing polymer is preferably a radical polymerization initiator having a half-life of 10 hours at a temperature of 0 to 100° C., more preferably a radical polymerization initiator having a temperature of 20 to 90° C.
  • Specific examples of the polymerization initiator include various polymerization initiators exemplified in WO 2013/015202.
  • the polymerization initiator may be used alone or in combination of two or more kinds.
  • the amount of the polymerization initiator used can be appropriately changed depending on the type of polymerization initiator and polymerization reaction conditions, but is usually about 0.01 to 5% by mass of the polymerization initiator based on the total mass of the monomer components.
  • Examples of the polymerization medium include fluorine-containing solvents, and also include the polymerization media exemplified in WO 2013/015202.
  • fluorine-containing solvents include perfluorocarbons (PFCs), chlorofluorocarbons (CFCs), hydrofluorocarbons (HFCs), hydrochlorofluorocarbons (HCFCs), hydrofluoroethers (HFEs), hydrochlorofluoroethers (HCFEs), hydrofluoroolefins (HFOs), hydrochlorofluoroolefins (HCFOs), and hydrofluorothioethers.
  • the structure of the fluorine-containing solvent may be any of linear, branched, and cyclic.
  • the fluorine-containing solvent preferably has 3 to 10 carbon atoms, more preferably 3 to 8 carbon atoms.
  • the fluorine-containing solvent is preferably PFC, CFC, HFC, HCFC, HFE or HCFE, more preferably HFC or HFE , and examples thereof include CF3CH2OCF2CF2H (AE -3000), C6F13H (AC-2000), C7F15H , perfluorocyclobutane , HCF2CF2CH2OCF2CF2H , CF3CFHCF2OCF3 , CF3 ( CF2 ) 2OCH3 , ( CF3 ) 2CFOCH3 , CF3 ( CF2 ) 3OCH3 , ( CF3 ) 2CFCF2OCH3 , CF3 (CF 2 ) 3 OCH 2 CH 3 , (CF 3 ) 2 CFCF 2 OCF 2 CH 3 , or CF 3 CF 2 CF(OCH 3 )CF(CF 3 ) 2 are more preferred, and AE-3000, AC-2000, CF 3 (CF 2 ) 3 OCH
  • the boiling point of the polymerization medium is preferably from 20 to 120° C., more preferably from 40 to 100° C., and even more preferably from 50 to 90° C.
  • the boiling point of the polymerization medium is preferably 100° C. or lower.
  • the polymerization medium may be used alone or in combination of two or more.
  • the amount of the polymerization medium used is preferably 5 times or more, more preferably 7 times or more, and preferably 20 times or less, more preferably 17 times or less, by mass ratio relative to the total mass of the monomer components.
  • a chain transfer agent In the production of the specific fluorine-containing polymer, it is preferable to use a chain transfer agent. By polymerizing the monomer components in the presence of a chain transfer agent, it becomes easier to adjust the molecular weight of the specific fluorine-containing polymer to be produced.
  • the chain transfer agent may be any known agent generally used in polymerization reactions.
  • alcohols such as methanol, ethanol, 2,2,2-trifluoroethanol, 2,2,3,3-tetrafluoropropanol, 1,1,1,3,3,3-hexafluoroisopropanol, 2,2,3,3,3-pentafluoropropanol, etc.
  • hydrocarbons such as n-pentane, n-hexane, cyclohexane, etc.
  • hydrofluorocarbons such as CF 2 H 2 , etc.
  • ketones such as acetone, etc.
  • mercaptans such as methyl mercaptan, etc.
  • esters such as methyl acetate, ethyl acetate, etc.
  • ethers such as diethyl ether, methyl ethyl ether, etc.
  • At least one selected from the group consisting of alcohols, hydrocarbons and hydrofluorocarbons is preferred, more preferably at least one selected from the group consisting of alcohols and hydrocarbons, and even more preferably alcohols, in view of a larger chain transfer constant and high stability of the end groups of the specific fluorine-containing polymer.
  • alcohols methanol or ethanol is particularly preferred.
  • the amount of the chain transfer agent used is preferably 0.001 times or more, more preferably 0.005 times or more, and is preferably 5 times or less, more preferably 4 times or less, based on the total mass of the monomer components.
  • the polymerization temperature is preferably from 5 to 100°C, more preferably from 50 to 80°C.
  • the polymerization pressure is preferably 0.1 to 10 MPaG, more preferably 0.5 to 3 MPaG.
  • the polymerization time is preferably from 1 to 30 hours, more preferably from 2 to 20 hours.
  • the content of the specific fluorine-containing polymer in the specific mixture is preferably 80 to 100 mass% and more preferably 95 to 100 mass% based on the total mass of the specific mixture.
  • Low molecular-weight fluorine-containing compound refers to a compound that contains fluorine atoms and has a molecular weight (weight average molecular weight (Mw) when there is a molecular weight distribution; the same applies hereinafter) of 3,000 or less.
  • the molecular weight of the low-molecular-weight fluorine-containing compound is preferably 3,000 or less, more preferably 1,000 or less, and is preferably 180 or more, more preferably 100 or more.
  • the molecular weight of the low-molecular-weight fluorine-containing compound can be measured by a gas chromatograph mass spectrometer (GC-MS).
  • the low-molecular-weight fluorine-containing compound is a compound that does not have an ionic functional group.
  • the ionic functional group is synonymous with the ionic functional group not contained in the specific fluorine-containing polymer.
  • Examples of the low molecular weight fluorine-containing compound contained in the specific mixture include fluorine-containing solvents used as polymerization media in the production of the specific fluorine-containing polymer.
  • the fluorine-containing solvent is preferably PFC, CFC, HFC, HCFC, HFE or HCFE, more preferably HFC or HFE , and examples thereof include CF3CH2OCF2CF2H (AE -3000), C6F13H (AC-2000), C7F15H , perfluorocyclobutane , HCF2CF2CH2OCF2CF2H , CF3CFHCF2OCF3 , CF3 ( CF2 ) 2OCH3 , ( CF3 ) 2CFOCH3 , CF3 ( CF2 ) 3OCH3 , ( CF3 ) 2CFCF2OCH3 , CF3 (CF 2 ) 3 OCH 2 CH 3 , (CF 3 ) 2 CFCF 2 O
  • Examples of the low-molecular-weight fluorine-containing compound contained in the specific mixture include fluorine-containing emulsifiers used in the production of the specific fluorine-containing polymer, including preferred embodiments thereof.
  • fluorine-containing emulsifiers include C 2 F 5 OCF 2 CF 2 OCF 2 COONH 4 (EEA), C 8 H 5 F 13 O 3 S (6:2 FTS), CF 3 CF 2 CF 2 OCF(CF 3 )COONH 4 (HFPO-DA), and CF 3 OCF 2 CF 2 CF 2 OCFHCF 2 COONH 4 , with EEA being preferred.
  • the content of the low-molecular-weight fluorine-containing compound contained in the specific mixture is, for example, 50% by mass or less, preferably 25% by mass or less, more preferably 10% by mass or less, even more preferably 5% by mass or less, particularly preferably 3% by mass or less, and most preferably 2% by mass or less, relative to the total mass of the specific mixture.
  • the lower limit of the content of the low-molecular-weight fluorine-containing compound is not particularly limited, and examples of the lower limit of the content of the low-molecular-weight fluorine-containing compound include 1 ppb by mass, 25 ppb by mass, 100 ppb by mass, 1 ppm by mass, 10 ppm by mass, and 100 ppm by mass.
  • the content of the low-molecular-weight fluorine-containing compound in the specific mixture can be measured by headspace gas chromatography/mass spectrometry (HS-GC/MS). Detailed analytical conditions will be described in the examples below.
  • the specific mixture may contain components other than the specific fluorine-containing polymer and the low-molecular-weight fluorine-containing compound.
  • other components include components (monomer components, polymerization medium, chain transfer agent, etc.) used in the production of the specific fluorine-containing polymer that are not included in the low-molecular-weight fluorine-containing compound, and water.
  • the content of the other components contained in the specific mixture is preferably 5% by mass or less, more preferably 1% by mass or less, and may be 0% by mass or more, relative to the total mass of the specific mixture.
  • the specific mixture may be in the form of, for example, powder, granules (beads), pellets, threads, etc., and from the viewpoint of making it easier to obtain a solid product with a lower content of low-molecular-weight fluorine-containing compounds, powder or granules (beads) are preferred, with powder being more preferred.
  • the specific mixture can be produced, for example, by polymerizing a monomer component containing a fluorine-containing monomer having neither a ring structure nor an ionic functional group in the presence of a fluorine-containing solvent corresponding to a low-molecular-weight fluorine-containing compound.
  • the detailed production method is as described in the method for producing the specific fluorine-containing polymer.
  • the specific mixture is preferably a granule obtained by mixing a slurry containing the specific fluorine-containing polymer and the low-molecular-weight fluorine-containing compound obtained by polymerization of the above-mentioned monomer components with water, granulating the obtained mixture by heating with stirring, and then removing the polymerization solvent and water.
  • the specific medium is a specific hydrocarbon medium or a specific ketone-based medium.
  • the specific hydrocarbon medium is a hydrocarbon medium that does not contain a fluorine atom and does not contain a hydroxyl group
  • the specific ketone medium is a medium that has a ketone group, does not contain a fluorine atom, and does not contain a hydroxyl group.
  • the specific medium is preferably a specific hydrocarbon medium, from the viewpoint of achieving better effects of the present invention.
  • the specific medium is preferably in a gaseous or liquid state when it comes into contact with the specific mixture, and more preferably in a liquid state, in order to enable more efficient contact with the specific mixture.
  • a specific medium that is in a liquid state when brought into contact with a specific mixture will also be referred to as a “specific solvent,” and a specific medium that is in a gaseous state when brought into contact with a specific mixture will also be referred to as a "specific gas.”
  • the specific hydrocarbon medium is preferably a compound consisting of only hydrogen atoms and carbon atoms, or a compound consisting of only hydrogen atoms, carbon atoms and chlorine atoms, and more preferably a compound consisting of only hydrogen atoms and carbon atoms.
  • the specific hydrocarbon medium may have a cyclic structure such as an alicyclic ring or an aromatic ring, but is preferably an aliphatic hydrocarbon having no cyclic structure, and more preferably a straight-chain aliphatic hydrocarbon.
  • the carbon number of the specific hydrocarbon medium is preferably 1 to 8, more preferably 2 to 6, and even more preferably 3 to 6, in view of the temperature and pressure during handling being close to normal temperature and normal pressure.
  • hydrocarbon media include, for example, methane, ethane, propane, n-butane, isobutane, n-pentane, 2-methylbutane, 2,2-dimethylpropane, n-hexane, 2-methylpentane, 2,2-dimethylbutane, n-heptane, and n-octane, with propane, n-butane, n-pentane, or n-hexane being preferred.
  • the specific ketone medium is preferably a compound consisting only of oxygen atoms, carbon atoms, and hydrogen atoms, and having a ketone group, and more preferably a compound consisting only of oxygen atoms, carbon atoms, and hydrogen atoms, having a ketone group, and having no oxygen atoms other than the oxygen atoms derived from the ketone group.
  • the specific ketone medium preferably has 3 to 8 carbon atoms, more preferably 3 or 4, from the viewpoint of compatibility with the specific fluorine-containing polymer.
  • Preferred specific ketone media include, for example, acetone, methyl ethyl ketone, diethyl ketone, acetophenone, and cyclohexanone, with acetone or methyl ethyl ketone being more preferred, and acetone being even more preferred.
  • the Hansen solubility parameter distance ( ⁇ HSP) between the specific medium and the low-molecular-weight fluorine-containing compound is preferably 13.5 MPa 0.5 or less, more preferably 12 MPa 0.5 or less, and even more preferably 8 MPa 0.5 or less.
  • ⁇ HSP may be 0 MPa 0.5 .
  • ⁇ HSP is equal to or less than the above upper limit, a solid product containing a lower amount of low-molecular-weight fluorine-containing compounds can be produced.
  • Hansen solubility parameters are the solubility of a substance divided into three components (dispersion term ⁇ D, polar term ⁇ P, and hydrogen bonding term ⁇ H) and expressed in three-dimensional space.
  • the dispersion term ⁇ D indicates the effect of dispersion forces
  • the polar term ⁇ P indicates the effect of dipole-dipole forces
  • the hydrogen bonding term ⁇ H indicates the effect of hydrogen bonding forces.
  • the ⁇ HSP (unit: MPa 0.5 ) between the specific medium and the low-molecular-weight fluorine-containing compound is calculated from the following formula (D).
  • ⁇ D1 represents the dispersion term in the HSP of a particular medium
  • ⁇ P1 represents the polar term in the HSP of a particular medium
  • ⁇ H1 represents the hydrogen bonding term in the HSP of a particular medium
  • ⁇ D2 represents the dispersion term in the HSP of the low-molecular-weight fluorine-containing compound
  • ⁇ P2 represents the polar term in the HSP of the low-molecular-weight fluorine-containing compound
  • ⁇ H2 represents the hydrogen bond term in the HSP of the low-molecular-weight fluorine-containing compound.
  • the above ⁇ D1, ⁇ P1 and ⁇ H1 are the numerical values obtained by multiplying the dispersion term, polar term or hydrogen bond term of each specific media by the mass content of each specific media and adding them up.
  • the above ⁇ D2, ⁇ P2 and ⁇ H2 are the numerical values obtained by multiplying the dispersion term, polar term or hydrogen bond term of each low molecular weight fluorine-containing compound by the mass content of each low molecular weight fluorine-containing compound and adding them up.
  • Hansen solubility parameters are described in Charles M. Hansen, Hansen Solubility Parameters: A Users Handbook (CRC Press, 2007). Furthermore, by using computer software Hansen Solubility Parameters in Practice (HSPiP), the Hansen solubility parameters of compounds for which literature values are not known can be easily estimated from their chemical structures.
  • HSPiP (ver. 5) is used, and the values are applied to compounds whose HSPs are registered in the database.
  • an estimated value calculated based on the Y-MB method using HSPiP may be used.
  • the specific medium is preferably a compound that does not dissolve the specific fluorine-containing polymer.
  • the term "compound that does not dissolve the specific fluorine-containing polymer” means a compound in which the amount of the specific fluorine-containing polymer that dissolves at a temperature not exceeding 23°C is less than 1 mass %.
  • Methods for contacting the specific mixture with the specific medium include, for example, immersing the specific mixture in the specific solvent, passing the specific solvent through a pipeline containing the specific mixture, passing a specific gas through a column filled with the specific mixture, and filling a container containing the specific mixture with the specific gas.
  • a method for contacting the specific mixture with the specific medium a method of immersing the specific mixture in the specific solvent or a method of passing the specific solvent through a pipeline in which the specific mixture is placed is preferred, as this method provides better uniformity throughout the system, and a method of immersing the specific mixture in the specific solvent is more preferred.
  • the specific mixture When the specific solvent is passed through a pipeline containing the specific mixture, the specific mixture may be repeatedly brought into contact with the specific solvent while circulating the specific solvent. In other words, a circulation process may be performed in which the specific solvent that has passed through the specific mixture is returned to the upstream side of the specific mixture and passed through the specific mixture again.
  • a specific gas when a specific gas is passed through a column packed with a specific mixture, the specific mixture may be repeatedly brought into contact with the specific gas while circulating the specific gas. That is, a circulation process may be performed in which the specific gas that has passed through the specific mixture is returned to the upstream side of the specific mixture and passed through the specific mixture again.
  • the mass ratio of the amount of the specific solvent to the amount of the specific mixture is preferably 10% by mass or more, more preferably 100% by mass or more, and is preferably 3000% by mass or less, more preferably 2000% by mass or less. If the mass ratio is equal to or greater than the lower limit, the effects of the present invention are more excellent. Furthermore, if the mass ratio is equal to or less than the upper limit, the economic efficiency is more excellent.
  • the specific mixture is immersed in the specific solvent, or when the specific mixture is passed through the specific solvent only once, the amount of the specific solvent brought into contact with the specific mixture is equal to the amount of the specific solvent used for the contact.
  • the amount of the specific solvent brought into contact with the specific mixture means the cumulative amount of the specific solvent passed, which is obtained by multiplying the amount of the specific solvent used for the contact by the number of times the passing-through process is repeated.
  • the contact time between the specific mixture and the specific solvent is preferably 0.5 hours or more, more preferably 1 hour or more, and preferably 3 hours or less, more preferably 2 hours or less. If the contact time is equal to or greater than the lower limit, the effects of the present invention are more excellent. Furthermore, if the contact time is equal to or less than the upper limit, the economic efficiency is more excellent.
  • the specific mixture is immersed in the specific solvent, the above contact time corresponds to the immersion time, and when the specific solvent is passed through the specific mixture, the above contact time corresponds to the passing time of the specific solvent.
  • the mass ratio of the amount of the specific gas to the amount of the specific mixture is preferably 10% by mass or more, more preferably 100% by mass or more, and preferably 3000% by mass or less, more preferably 2000% by mass or less. If the mass ratio is equal to or greater than the lower limit, the effect of the present invention is more excellent. Furthermore, if the mass ratio is equal to or less than the upper limit, the economic efficiency is more excellent.
  • the amount of specific gas brought into contact with the specific mixture is equal to the amount of specific gas used for the contact.
  • the amount of specific gas brought into contact with the specific mixture means the cumulative amount of gas passed, which is obtained by multiplying the amount of specific gas used for the contact by the number of times the passing process is repeated.
  • the contact time between the specific mixture and the specific gas is preferably 0.5 hours or more, more preferably 1 hour or more, and preferably 3 hours or less, more preferably 6 hours or less. If the contact time is equal to or greater than the lower limit, the effect of the present invention is more excellent. Furthermore, if the contact time is equal to or less than the upper limit, the economic efficiency is more excellent.
  • the above contact time corresponds to the time during which both the specific mixture and the specific gas are present in the container, and when a specific gas is passed through the specific mixture, the above contact time corresponds to the time during which the specific gas is passed through the specific mixture.
  • the temperature at which the specific mixture is brought into contact with the specific medium in the contacting step is preferably in the range of 20 to 150°C, more preferably in the range of 50 to 120°C, and even more preferably in the range of 70 to 110°C, from the viewpoint of easily obtaining a solid product with a lower content of low-molecular-weight fluorine-containing compounds.
  • the separation step the specific medium is separated from the first composition containing the specific fluorine-containing polymer, the low-molecular-weight fluorine-containing compound, and the specific medium obtained in the contacting step.
  • the separation step gives a composition containing at least the specific fluorine-containing polymer (hereinafter also referred to as the "second composition").
  • a known separation method can be applied.
  • known solid-liquid separation methods such as filtration, decantation, and centrifugation can be used.
  • a separation method using a known solid-gas separator such as a cyclone or a bag filter may be used.
  • a method for separating the specific medium from the first composition a method in which the specific solvent is separated from the first composition by filtration to obtain the second composition is preferred from the viewpoint of simplicity and economy.
  • a second contacting step may be carried out in which the obtained second composition is brought into contact with a second hydrocarbon medium (second specific medium) that contains neither fluorine atoms nor hydroxyl groups
  • a second separation step may be carried out in which the second hydrocarbon medium is separated from the obtained composition containing the fluorinated polymer and the second hydrocarbon medium.
  • the number of repetitions is preferably 2 to 6 sets, more preferably 2 to 4 sets, where one contact and one separation is one set.
  • the contact and separation in each set may be the same or different.
  • the second specific medium may be the same as the specific medium described above, including preferred embodiments.
  • the contact and separation steps in each set are the same as those described in the contact step and separation step, including preferred embodiments.
  • the total contact time in each set is preferably 1 hour or more, more preferably 3 hours or more, and preferably 6 hours or less, more preferably 3 hours or less.
  • the drying step the second composition containing the specific fluorine-containing polymer obtained in the separation step is dried to obtain a solid material containing the specific fluorine-containing polymer.
  • Methods for drying the second composition include known drying treatments such as natural drying, heating, air blowing, reduced pressure, etc. These drying treatments may be performed alone or in combination. Natural drying means leaving the product at room temperature (23° C.) for a predetermined period of time. Dryers used for the drying treatment include, for example, ovens, dryers, and vacuum dryers.
  • the drying temperature is preferably in the range of 20 to 250°C, more preferably in the range of 60 to 250°C, and even more preferably in the range of 100 to 160°C.
  • the drying time is preferably in the range of 1 to 48 hours, more preferably in the range of 1 to 24 hours.
  • the resulting second composition when contact and separation are repeated, after the first contact and separation to obtain the second composition, the resulting second composition may be subjected to a drying treatment before being contacted with the second specific medium. Details of the drying treatment, including preferred embodiments, are as described below in the drying step.
  • a solid material containing the specific fluoropolymer as a main component can be obtained as the final product.
  • “Containing as a main component” means that the content of the specific fluoropolymer relative to the total mass of the solid material is 50 mass% or more.
  • the content of the specific fluorine-containing polymer in the solid matter is preferably 50% by mass or more and less than 100% by mass, more preferably 70% by mass or more and less than 100% by mass, still more preferably 90% by mass or more and less than 100% by mass, and particularly preferably 99% by mass or more and less than 100% by mass, relative to the total mass of the solid matter.
  • the content of low-molecular-weight fluorine-containing compounds contained in the solid material obtained by this method is, for example, 0.1% by mass or less, preferably 0.01% by mass or less, more preferably 0.005% by mass or less, even more preferably 0.001% by mass or less, even more preferably 1 ppm by mass or less, particularly preferably 100 ppb by mass or less, and most preferably 25 ppb by mass or less, relative to the total mass of the solid material, in order to achieve a low environmental impact for the molded product.
  • the content of low-molecular-weight fluorine-containing compounds in the solid material may be 0 ppb by mass.
  • the content of the specific medium contained in the solid material obtained by this method is, for example, 10% by mass or less, preferably 5% by mass or less, more preferably 2% by mass or less, even more preferably 1% by mass or less, particularly preferably 1000 ppm by mass or less, and most preferably 100 ppm by mass or less, relative to the total mass of the solid material.
  • the content of low-molecular-weight fluorine-containing compounds in the solid material may be 0% by mass.
  • the solid may be in the form of granules, powder, pellets, threads, etc., with powder or granules (beads) being preferred, and powder being more preferred.
  • the solid obtained by the above drying may be melted using an extruder and molded into other shapes such as pellets or threads.
  • the solid material can be used to produce a molded body.
  • the molded article can be obtained by molding the above-mentioned solid material or a composition containing the solid material. Specific examples of molding methods include injection molding, extrusion molding, blow molding, press molding, rotational molding, electrostatic painting, and spray molding.
  • compositions containing solids include kneaded products obtained by melt-kneading a solid and other components used as needed using a known method.
  • specific examples of other components include resins other than the specific fluorine-containing polymer, heat stabilizers, antioxidants, colorants, ultraviolet absorbers, fillers, crosslinking agents, crosslinking aids, and organic peroxides.
  • the content of the other components is preferably from 0.0000001 to 70 parts by mass, more preferably from 0.0000005 to 60 parts by mass, and even more preferably from 0.000001 to 50 parts by mass, per 100 parts by mass of the specific fluorine-containing polymer in the composition.
  • molded articles include nuts, bolts, fittings, films, bottles, gaskets, wire coatings, tubes, hoses, pipes, valves, sheets, seals, packing, tanks, rollers, containers, cocks, connectors, filter housings, filter cages, flow meters, pumps, wafer carriers, and wafer boxes.
  • the molded article may be a coating film formed using a solid material.
  • a method for forming a coating film include a method for forming a coating film using a solid material or a composition containing a solid material by rotational molding, electrostatic coating, or spray molding.
  • the thickness of the coating film is preferably 1 ⁇ m to 10 mm, more preferably 50 ⁇ m to 5 mm, and even more preferably 100 ⁇ m to 3 mm.
  • the above solid or molded product can be used for the following purposes.
  • Food packaging films, lining materials for fluid transfer lines used in food manufacturing processes, packings, sealing materials, and fluid transfer components for food manufacturing equipment such as sheets;
  • Fuel transfer components such as O-rings, tubes, packings, valve core materials, hoses and seals used in automobile fuel systems and peripheral devices, as well as hoses and seals used in automobile automatic transmission devices; Carburetor flange gaskets, shaft seals, valve stem seals, sealing materials and hoses used in automobile engines and peripheral devices, as well as other automobile parts such as automobile brake hoses, air conditioner hoses, radiator hoses and electrical wire covering materials;
  • Chemical liquid transfer components for semiconductor manufacturing equipment such as O-rings, tubes, packings, valve core materials, hoses, seal materials
  • a mixture containing a fluoropolymer having a specific structure and a low-molecular-weight fluorine-containing compound is treated with a specific medium to reduce the content of the low-molecular-weight fluorine-containing compound in the solid material containing the fluoropolymer.
  • the content of the low-molecular-weight fluorine-containing compound can also be reduced by using supercritical CO2 instead of the specific medium.
  • the low-molecular-weight fluorine-containing compound whose content can be reduced by supercritical CO 2 include the above-mentioned low-molecular-weight fluorine-containing compounds, and fluorine-containing emulsifiers are preferred.
  • the supercritical CO 2 used in the treatment is preferably at a temperature of 31° C. or higher and a pressure of 7.38 MPa or higher.
  • Examples 2 to 5 and 8 to 11 are working examples, and Examples 1, 6 and 7 are comparative examples. However, the present invention is not limited to these examples.
  • the various measurement and evaluation methods are as follows.
  • Y-axis AE-3000 concentration of standard solution for creating calibration curve [unit: ng/2 ⁇ L]
  • the calibration curve was obtained by linear approximation using the least squares method, and the correlation coefficient was 0.993.
  • Fluoropolymer 1 contained neither units derived from a monomer having a ring structure nor ionic functional groups. Furthermore, AE-3000, a low-molecular-weight fluorine-containing compound, was contained in Mixture 1. The contents of the low-molecular-weight fluorine-containing compound relative to the total mass of Mixture 1 (unit: mass ppb) are shown in the table below.
  • Example 1 Mixture 1 obtained in Production Example 1 was dried in an oven at 120° C. for 6 hours to obtain solid matter 1. The contents of the low-molecular-weight fluorine-containing compounds contained in the solid material 1 measured by the above method are shown in the table below.
  • Example 2 ⁇ Contact, separation> A 0.25 L stainless steel reactor was charged with 20 g of Mixture 1 obtained in Production Example 1, and then the reactor was sealed and the outside of the reactor was cooled with liquid nitrogen. Next, 16.7 g of propane (specific medium) was introduced into the reactor while being liquefied, thereby bringing Mixture 1 into contact with propane, and the reactor was then heated and maintained at an internal temperature of 90°C for 1 hour. After 1 hour, Composition 2-A containing fluoropolymer 1, AE-3000, and propane was removed from the reactor. Next, a membrane filter with 10 ⁇ m openings was placed on a Buchner funnel, and composition 2-A was poured into it to perform solid-liquid separation of propane from composition 2-A, thereby obtaining composition 2-B containing fluoropolymer 1.
  • composition 2-B was dried in an oven at 120° C. for 5 hours to obtain solid matter 2.
  • the content of the low-molecular-weight fluorine-containing compound contained in solid matter 2 is shown in the table below.
  • Example 3 The same treatment as in Example 2 was carried out except that 14.0 g of n-butane (specific medium) was used instead of 16.7 g of propane, to obtain a solid material 3 containing a fluoropolymer 1.
  • n-butane specific medium
  • propane 16.7 g
  • the contents of the low-molecular-weight fluorine-containing compounds contained in the solid material 3 are shown in the table below.
  • Example 4 ⁇ Contact, separation> A 0.25 L stainless steel reactor was charged with 20 g of the mixture 1 obtained in Production Example 1 and 16.3 g of n-pentane (specific medium), and then the reactor was sealed. The reactor was then heated and maintained at an internal temperature of 90°C for 1 hour. After 1 hour, composition 4-A containing fluoropolymer 1, AE-3000, and n-pentane was removed from the reactor. Next, n-pentane was separated from composition 4-A by filtration to obtain composition 4-B containing fluoropolymer 1.
  • Example 5 The same treatment as in Example 4 was carried out except that 16.7 g of n-hexane (specific medium) was used instead of 16.3 g of n-pentane, to obtain a solid material 5 containing a fluoropolymer 1.
  • the contents of the low-molecular-weight fluorine-containing compounds contained in the solid material 5 are shown in the table below.
  • Example 6 The same treatment as in Example 4 was carried out except that 17.3 g of methanol was used instead of 16.3 g of n-pentane, to obtain a solid material 6 containing a fluoropolymer 1.
  • the contents of the low-molecular-weight fluorine-containing compounds contained in the solid material 6 are shown in the table below.
  • Example 7 The same treatment as in Example 4 was carried out except that 17.8 g of 1-propanol was used instead of 16.3 g of n-pentane, to obtain solid matter 7 containing a fluoropolymer 1.
  • the contents of the low-molecular-weight fluorine-containing compounds contained in solid matter 7 are shown in the table below.
  • Example 8 ⁇ Contact, separation> A 0.05 L SUS tubular reactor was charged with 10 g of the mixture 3 obtained in Production Example 3, and then the reactor was sealed. Next, the bomb and the reactor were heated so that the temperature inside the reactor reached 90°C, and gaseous n-butane (specific medium) was introduced into the reactor at a pressure of 0.1 MPaG. n-butane was circulated into the reactor while adjusting the aperture of the outlet valve so that the introduction rate was 7 g/h. After stopping the flow of n-butane one hour after the start of the flow, the reactor was opened, and composition 8-A containing fluoropolymer 1 and AE-3000 was removed from the reactor. Since the n-butane that had come into contact with the mixture was in a gaseous state, solid-liquid separation was not necessary.
  • composition 8-A was dried in an oven at 120° C. for 5 hours to obtain a solid 8.
  • the content of the low-molecular-weight fluorine-containing compound contained in the solid 8 is shown in the table below.
  • Table 1 shows the type and content (unit: mass ppb) of the low molecular weight fluorine-containing compound contained in the specific mixture, the type of hydrocarbon medium used, the mass ratio (unit: mass%) of the amount of hydrocarbon medium to the amount of the specific mixture contacted, the contact treatment time, the drying treatment time, and the content (unit: mass ppb) of the low molecular weight fluorine-containing compound contained in the obtained solid.
  • the "HSP distance [MPa 0.5 ]" column of "Hydrocarbon medium” shows the HSP distance (unit: MPa 0.5 ) between the low molecular weight fluorine-containing compound and the hydrocarbon medium used in each example.
  • the column “Medium/Mixture Ratio” indicates the mass ratio (unit: mass %) of the amount of hydrocarbon medium to the amount of a specific mixture.
  • the column “Residual rate of low molecular weight fluorine-containing compounds” indicates the ratio (unit: mass %) of the content of low molecular weight fluorine-containing compounds contained in the solid matter to the content of low molecular weight fluorine-containing compounds contained in the specific mixture.
  • Example 9 Mixture 2 was contacted with n-butane (specific medium, HSP distance 6.4) in the same manner as in Example 2, except that mixture 2 was used instead of mixture 1.
  • Composition 9-A containing fluoropolymer 1, AE-3000, and n-butane was taken out of the reactor.
  • n-butane was separated from composition 9-A by filtration, to obtain composition 9-B containing fluoropolymer 1.
  • the obtained composition 9-B was dried in an oven at 120°C for 1 hour to obtain composition 9-C.
  • the content of the low-molecular-weight fluorine-containing compound contained in composition 9-C was 208 ppb by mass relative to the total mass of composition 9-C.
  • composition 9-C was contacted with n-butane in the same manner as in the first contact and separation described above, except that composition 9-C was used instead of mixture 2, to give composition 9-D containing fluoropolymer 1, AE-3000 and n-butane, and then n-butane was separated from composition 9-D by filtration to give composition 9-E containing fluoropolymer 1.
  • the resulting composition 9-E was dried in an oven at 120° C. for 3 hours to obtain a solid 9.
  • the content of the low-molecular-weight fluorine-containing compound contained in the solid material 9 was 23 ppb by mass relative to the total mass of the solid material 9.
  • Example 9 it was confirmed that in Example 9 as well, a solid product containing a fluoropolymer as a main component and having a small content of low-molecular-weight fluorine-containing compounds was obtained.
  • Example 10 A 0.25 L stainless steel reactor was charged with 49.5 g of the mixture 1 obtained in Production Example 1 and 98.9 g of acetone (specific medium, HSP distance 5.6), and then the reactor was sealed. The reactor was then heated and maintained at an internal temperature of 80°C for 1 hour. After 1 hour, composition 10-A containing fluoropolymer 1, AE-3000, and acetone was removed from the reactor. Furthermore, acetone was separated from composition 10-A by a filtration operation, to obtain composition 10-B containing fluoropolymer 1.
  • composition 10-C Similar to the first contact and filtration/separation described above, the step of contacting composition 10-B with acetone and filtration/separation was added two more times, so that a total of three contacts and filtration/separations were repeated to obtain composition 10-C.
  • the resulting composition 10-C was dried in an oven at 150° C. for 5 hours to obtain a solid 10.
  • the content of the low-molecular-weight fluorine-containing compound contained in the solid material 10 was 27 ppb by mass relative to the total mass of the solid material 10 .
  • Example 11 The same contact and filtration separation as in Example 10 were repeated three times in total, except that methyl ethyl ketone (specific medium, HSP distance 4.0) was used as the specific medium instead of acetone, to obtain Composition 11-C.
  • the resulting composition 11-C was dried in an oven at 150° C. for 1 hour to obtain a solid 11.
  • the content of the low-molecular-weight fluorine-containing compound contained in the solid material 11 was 80 ppb by mass relative to the total mass of the solid material 11 .
  • solid products containing a fluoropolymer as the main component and having a small content of low-molecular-weight fluorine-containing compounds were obtained.

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Abstract

La présente invention a pour objectif de fournir un procédé de fabrication qui permet de fabriquer facilement un produit solide qui comprend un polymère contenant du fluor comme composant principal de telle sorte que le produit solide contient une petite quantité d'un composé contenant du fluor de faible poids moléculaire.　Selon la présente invention, un procédé de fabrication d'un produit solide qui comprend un polymère contenant du fluor consiste à mettre en contact un milieu spécifique avec un mélange qui comprend un polymère contenant du fluor et un composé contenant du fluor de faible poids moléculaire, à séparer le milieu spécifique de la composition résultante et à sécher la composition dont le milieu spécifique a été séparé. Le polymère contenant du fluor ne contient pas plus de 10 % en masse d'unités sur la base de monomères qui comprennent une structure cyclique par rapport à la masse totale du polymère contenant du fluor, le polymère contenant du fluor ne comprend pas de groupes fonctionnels ioniques, et le milieu spécifique est un milieu hydrocarboné ou un milieu cétone et ne comprend pas d'atomes de fluor ou de groupes hydroxyle.
PCT/JP2025/008772 2024-03-12 2025-03-10 Procédé de fabrication de produit solide Pending WO2025192516A1 (fr)

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US5886293A (en) * 1998-02-25 1999-03-23 The United States Of America As Represented By The Secretary Of The Navy Preparation of magnesium-fluoropolymer pyrotechnic material
JP2001350265A (ja) * 2000-06-09 2001-12-21 Asahi Glass Co Ltd レジスト組成物
JP2004502786A (ja) * 2000-06-13 2004-01-29 ハイドロ−ケベック 低いＴｇを示すフッ化ビニリデンを主成分とする、架橋性ブロモスルホン化フルオロエラストマー
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