WO2024257869A1 - Copolymère, composition, et corps moulé - Google Patents

Copolymère, composition, et corps moulé Download PDF

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Publication number
WO2024257869A1
WO2024257869A1 PCT/JP2024/021742 JP2024021742W WO2024257869A1 WO 2024257869 A1 WO2024257869 A1 WO 2024257869A1 JP 2024021742 W JP2024021742 W JP 2024021742W WO 2024257869 A1 WO2024257869 A1 WO 2024257869A1
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Prior art keywords
copolymer
units
mol
formula
amount
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English (en)
Japanese (ja)
Inventor
大輔 田口
瑞菜 豊田
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AGC Inc
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Asahi Glass Co Ltd
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Priority to CN202480039121.9A priority Critical patent/CN121311515A/zh
Priority to JP2025528024A priority patent/JPWO2024257869A1/ja
Publication of WO2024257869A1 publication Critical patent/WO2024257869A1/fr
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    • 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
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/02—Ethene
    • 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
    • C08F214/00—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
    • C08F214/18—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
    • C08F214/00—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
    • C08F214/18—Monomers containing fluorine
    • C08F214/26—Tetrafluoroethene
    • 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
    • C08F216/00—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 an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
    • C08F216/12—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 an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an ether radical
    • C08F216/14—Monomers containing only one unsaturated aliphatic radical
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or 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; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or 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; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/12—Compositions of homopolymers or 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; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C08L27/18—Homopolymers or copolymers or tetrafluoroethene

Definitions

  • the present invention relates to a copolymer, a composition, and a molded article.
  • Ethylene/tetrafluoroethylene copolymer (hereinafter also referred to as "ETFE") is excellent in heat resistance, weather resistance, electrical insulation, non-adhesiveness, water repellency, oil repellency, etc., and is characterized by high moldability and mechanical strength among fluororesins. Therefore, a variety of molded products such as electric wire coverings, tubes, sheets, films, filaments, pump casings, joints, packings, linings, coatings, etc. are manufactured by melt molding methods such as extrusion molding, blow molding, injection molding, and rotational molding.
  • Patent Document 1 discloses an ethylene/tetrafluoroethylene copolymer including a copolymer having polymerized units based on tetrafluoroethylene, polymerized units based on ethylene, and polymerized units based on (perfluorobutyl)ethylene.
  • ETFE When ETFE is used as a constituent material of a molded article, it is required that the article be excellent in various performances. Specifically, the molded article is required to have low nitrogen permeability and low yellowness and excellent surface properties.
  • the present inventors have evaluated a molded article formed using the ETFE described in Patent Document 1 and have found that there is room for improvement at least in terms of nitrogen permeability.
  • the present invention aims to provide a copolymer that can form a molded article having low nitrogen permeability and yellowness and excellent surface properties. It also aims to provide a composition containing the copolymer, and a molded article obtained by molding the copolymer.
  • a copolymer comprising a unit based on tetrafluoroethylene, a unit based on ethylene, and either or both of a unit based on a compound represented by formula (1) and a unit based on a compound represented by formula (2), the total content of the units based on tetrafluoroethylene and the units based on ethylene is 80.0 to 99.7 mol % based on all units contained in the copolymer, the content of the units based on tetrafluoroethylene is 49.0 mol % or more and less than 56.0 mol % based on the total content of the units based on tetrafluoroethylene and the units based on ethylene, the content of units based on the compound represented by formula (1) or the compound represented by formula (2) is 0.3 to 1.3 mol % based on all units contained in the copolymer, A copolymer having a melt flow rate of 33
  • CZ 2 CX(CF 2 ) m Y Formula (1)
  • CF 2 CF-O-(CF 2 ) n F Formula (2)
  • X, Y and Z each independently represent a hydrogen atom or a fluorine atom
  • m represents an integer of 2 to 6.
  • n represents an integer of 1 to 6.
  • a copolymer comprising the above-mentioned tetrafluoroethylene-based units, the above-mentioned ethylene-based units, and units based on the compound represented by formula (1), The copolymer according to [1], wherein the content of units based on the compound represented by formula (1) is 0.3 to 1.3 mol % based on all units contained in the copolymer.
  • a composition comprising the copolymer according to [1] or [2].
  • a solid composition comprising the copolymer according to [1] or [2] and having a water content of 0.02 to 0.8% by mass.
  • the present invention provides a copolymer that can form a molded article having low nitrogen permeability and yellowness and excellent surface properties.
  • the present invention also provides a composition containing the copolymer, and a molded article obtained by molding the copolymer.
  • a numerical range expressed using “to” means a range that includes the numerical values before and after “to” as the lower and upper limits.
  • unit refers collectively to an atomic group derived from one molecule of the above-mentioned monomer that is formed directly by polymerization of the monomer, and an atomic group obtained by chemically converting a part of the above-mentioned atomic group.
  • a unit derived from an individual monomer will be referred to by the name of the monomer with "unit” added.
  • the "TFE unit” is a unit based on tetrafluoroethylene in the copolymer
  • the "E unit” is a unit based on ethylene in the copolymer
  • the "A unit” is a unit based on a compound represented by formula (1) or (2) described below.
  • the copolymer of the present invention (hereinafter also referred to as "the present copolymer") contains E units, TFE units, and A units within respective predetermined ranges.
  • the present copolymer has a melt flow rate of 33 to 50 g/10 min measured under conditions of a temperature of 297° C. and a load of 49 N in accordance with ASTM D3159.
  • the copolymer can form a molded article having low nitrogen permeability and yellowness and excellent surface properties, and although the details of the reason for this are not yet clear, it is believed that the content of A units, which are either or both of units based on a compound represented by formula (1) and units based on a compound represented by formula (2) described below, is 0.3 to 1.3 mol % relative to the total units contained in the copolymer, and the copolymer has a melt flow rate of 33 to 50 g/10 min.
  • a molded product with excellent surface properties means a molded product with excellent surface smoothness and in which the occurrence of flow marks (flow marks of the copolymer) is suppressed.
  • the nitrogen permeation of the obtained molded body is suppressed because the content of A units is 1.3 mol % or less based on the total units contained in the copolymer, and therefore the free volume of the polymer chains of the copolymer is reduced.
  • the melt flow rate of 33 g/10 min or more leads to shorter molecular chains and a lower refractive index, which contributes to the lower yellowness of the resulting molded article.
  • the melt flow rate of 50 g/10 min or less suppresses the inclusion of air bubbles in the copolymer during molding (particularly injection molding), resulting in a molded product with excellent surface properties.
  • This copolymer contains TFE units based on tetrafluoroethylene, E units based on ethylene, and A units based on a compound represented by formula (1) or a compound represented by formula (2).
  • CZ 2 CX(CF 2 ) m Y Formula (1)
  • CF 2 CF-O-(CF 2 ) n F Formula (2)
  • X, Y and Z each independently represent a hydrogen atom or a fluorine atom
  • m represents an integer of 2 to 6.
  • n represents an integer of 1 to 6.
  • X and Z are preferably a hydrogen atom in terms of polymerizability.
  • Y is preferably a fluorine atom.
  • m is preferably an integer of 2 to 6, and more preferably an integer of 4.
  • Specific examples of the compound represented by formula (2) include CF 2 ⁇ CF-O-(CF 2 ) F, CF 2 ⁇ CF-O-(CF 2 ) 2 F, CF 2 ⁇ CF-O-(CF 2 ) 3 F, 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.
  • CF 2 ⁇ CF-O-(CF 2 ) 3 F which corresponds to the compound in which n is 3, is preferred.
  • the present copolymer may contain, as A units, either a unit based on a compound represented by formula (1) (hereinafter also referred to as "A1 units”) or a unit based on a compound represented by formula (2) (hereinafter also referred to as “A2 units”), or may contain both A1 units and A2 units. That is, when the present copolymer contains both A1 units and A2 units, the "content of A units” means the total content of A1 units and the content of A2 units.
  • the content of A units is 0.3 to 1.3 mol % based on the total units contained in the copolymer.
  • the content of A units is 0.3 mol % or more based on the total units contained in the copolymer, a molded article having excellent surface properties can be formed.
  • the content of A units is preferably 0.5 to 1.3 mol % based on the total units contained in the copolymer, in view of a well-balanced and excellent suppression of nitrogen permeation and surface properties.
  • the present copolymer a copolymer containing TFE units, E units and A1 units, or a copolymer containing TFE units, E units and A2 units is preferred, and from the viewpoint of excellent long-term folding resistance, a copolymer having E units, TFE units and A1 units is more preferred.
  • the present copolymer is a copolymer containing TFE units, E units, and A1 units
  • the content of the A1 units is 0.3 to 1.3 mol% based on the total units contained in the present copolymer, and from the above-mentioned viewpoints, it is preferably 0.5 to 1.3 mol%.
  • the content of the A2 units is 0.3 to 1.3 mol% based on the total units contained in the present copolymer, and from the above-mentioned viewpoints, it is preferably 0.6 to 1.3 mol%.
  • the total content of TFE units and E units is 80.0 to 99.7 mol % based on all units contained in the present copolymer.
  • the total content of TFE unit and E unit is preferably 85.0 mol% or more, more preferably 88.0 mol% or more, from the viewpoint of excellent long-term heat resistance.
  • the total content of TFE unit and E unit is preferably 99.5 mol% or less, from the viewpoint of excellent durability against repeated load.
  • the content of the TFE units is 49.0 mol % or more and less than 56.0 mol % based on the total content of the TFE units and the E units.
  • the content of the TFE units is preferably from 50.0 to 56.0 mol %, more preferably from 52.0 to 56.0 mol %, based on the total content of the TFE units and the E units, from the viewpoint of excellent heat resistance.
  • the content of TFE units is preferably 40.0 to 54.9 mol%, more preferably 45.0 to 54.5 mol%, and particularly preferably 50.0 to 54.5 mol%, based on the total units contained in the copolymer. If the content is equal to or greater than the lower limit, the heat resistance of the molded article will be superior, and if the content is equal to or less than the upper limit, the mechanical properties of the molded article will be superior.
  • the content of E units is preferably 36.0 to 50.0 mol%, more preferably 40.0 to 48.0 mol%, and particularly preferably 42.0 to 47.0 mol%, based on the total units contained in the copolymer. If it is equal to or greater than the lower limit, the mechanical properties of the molded article will be superior, and if it is equal to or less than the upper limit, the heat resistance of the molded article will be superior.
  • the present copolymer may contain units based on other monomers than tetrafluoroethylene, ethylene, the compound represented by formula (1) and the compound represented by formula (2).
  • the other monomers include fluoroolefins (e.g., vinyl fluoride, vinylidene fluoride, trifluoroethylene, hexafluoropropylene, hexafluoroisobutylene, etc., excluding the compounds represented by formula (1) and formula (2)), CF 2 ⁇ CFORf 1 SO 2 X 1 (wherein Rf 1 is a perfluoroalkylene group having 1 to 10 carbon atoms which may contain an oxygen atom between the carbon atoms, and X 1 is a halogen atom or a hydroxyl group), CF 2 ⁇ CFORf 2 CO 2 X 2 (wherein Rf 2 is a perfluoroalkylene group having 1 to 10 carbon atoms which may contain an oxygen atom between the carbon atoms, and X 2 is a hydrogen
  • the content of the units based on the other monomers is preferably 2.0 mol % or less, more preferably 1.0 mol % or less, based on all units contained in the present copolymer.
  • the present copolymer is preferably one comprising TFE units, E units and A units, and more preferably one comprising TFE units, E units and A1 units.
  • the melt flow rate (hereinafter, also referred to as "MFR") of the present copolymer is 33 to 50 g/10 min.
  • MFR melt flow rate
  • the MFR of the present copolymer is preferably from 33 to 45 g/10 min in view of achieving a good balance between yellowness and surface properties.
  • a specific example of a method for controlling the MFR of the present copolymer within the above range is a method for adjusting the molecular weight of the present copolymer.
  • the MFR of the present copolymer means the mass of the present copolymer flowing out of an orifice having a diameter of 2 mm and a length of 8 mm in 10 minutes, measured under conditions of a temperature of 297° C. and a load of 49 N in accordance with ASTM D3159.
  • the melting point of the present copolymer is preferably 245° C. or higher, more preferably 248° C. or higher, and particularly preferably 249° C. or higher, in terms of superior crack resistance.
  • the upper limit of the melting point of the present copolymer is preferably 290° C. or lower, more preferably 280° C. or lower, and particularly preferably 270° C. or lower, in view of excellent moldability of the present copolymer.
  • Specific examples of the method for adjusting the melting point of the present copolymer to fall within the above range include a method of lowering the polymerization temperature during the production of the present copolymer, and a method of adjusting the content of A units in the present copolymer.
  • the melting point of the present copolymer is the temperature corresponding to the endothermic peak when the present copolymer is heated at a rate of 10° C./min in an air atmosphere using a differential scanning calorimeter.
  • the present copolymer can be produced by using the above-mentioned monomers (ethylene, tetrafluoroethylene, and one or both of the compound represented by formula (1) and the compound represented by formula (2)) by a known method such as bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization, etc., among which, it is preferably produced by solution polymerization.
  • a polymerization initiator, a polymerization medium, a chain transfer agent, etc. can be used.
  • the polymerization initiator is preferably a radical polymerization initiator having a half-life of 10 hours at a temperature of 0 to 100° C., and particularly 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 is preferably 0.01 to 0.9 parts by mass, particularly preferably 0.05 to 0.5 parts by mass, based on 100 parts by mass of the monomer used.
  • the polymerization medium may be a perfluorocarbon, a hydrofluorocarbon, a hydrofluoroether, etc. Specific examples of the polymerization medium include the polymerization media exemplified in WO 2013/015202.
  • the polymerization medium may be used alone or in combination of two or more kinds.
  • the amount of the polymerization medium used is preferably 5 times or more, more preferably 7 times or more, by mass ratio to the amount of the monomers used, and is preferably 20 times or less, more preferably 17 times or less.
  • 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 from the viewpoint of higher chain transfer constant and higher stability of the end group of the copolymer, at least one selected from the group consisting of alcohols and hydrocarbons is more preferred, and alcohols are particularly preferred.
  • the alcohols methanol or ethanol is particularly preferred.
  • methanol is particularly preferred from the viewpoint of reactivity and availability.
  • Two or more chain transfer agents may be used.
  • the amount of the chain transfer agent used is preferably 0.001 times or more, more preferably 0.005 times or more, based on the amount of the monomer used, in terms of mass ratio, and is preferably 5 times or less, more preferably 4 times or less.
  • the polymerization temperature is preferably 15 to 60° C., more preferably 20 to 58° C., and particularly preferably 25 to 55° C. If the polymerization temperature is 15° C. or higher, the polymerizability is excellent. If the polymerization temperature is 60° C. or lower, the melting point of the present copolymer can be improved.
  • the polymerization pressure is preferably from 0.5 to 3.0 MPa, particularly preferably from 0.9 to 2.5 MPa.
  • the polymerization time is preferably from 1 to 12 hours.
  • composition of the present invention contains the above-mentioned present copolymer. Since the present composition contains the present copolymer, by using the present composition, a molded article having low nitrogen permeability and yellowness and excellent surface properties can be formed.
  • the content of the present copolymer is preferably from 50% by mass to less than 100% by mass, more preferably from 70% by mass to less than 100% by mass, and particularly preferably from 90% by mass to less than 100% by mass, based on the total mass of the present composition.
  • the solid composition of the present invention (hereinafter also referred to as “the present solid composition”) contains the present copolymer, and the TOC (total organic carbon) elution amount relative to the surface area of the present solid composition is 1,000 to 63,000 ⁇ g/ cm2 . Since the adhesive strength after a hot water resistance test is high, the TOC elution amount is preferably 50,000 or less, and more preferably 30,000 or less. Since the tensile strength after a heat aging test is high, the TOC elution amount is preferably 2,000 or more, and more preferably 5,000 or more. Specific examples of methods for controlling the TOC elution amount of the present solid composition within the above range include methods of adjusting the purity of water used in granulating the present copolymer or the water content of the copolymer.
  • the solid composition contains the copolymer, and the water content relative to the mass of the solid composition is preferably 0.02 to 0.8% by mass.
  • the water content is preferably 0.5% by mass or less, and more preferably 0.3% by mass or less, since the amount of TOC eluted is reduced.
  • the water content is preferably 0.03% by mass or more, and more preferably 0.04% by mass or more, since the tensile strength after a heat aging test is increased.
  • a specific example of a method for controlling the water content of the present solid composition to fall within the above range is to extend the time for which the present copolymer is kept at 100° C. or higher during drying after granulation.
  • the present composition may contain other components in addition to those described above.
  • specific examples of such other components include resins other than the present copolymer, heat stabilizers, antioxidants, colorants, ultraviolet absorbers, fillers, crosslinking agents, crosslinking assistants, and organic peroxides.
  • the content of the other components is preferably 0.0000001 to 70 parts by mass, more preferably 0.0000005 to 60 parts by mass, and particularly preferably 0.000001 to 50 parts by mass, per 100 parts by mass of the present copolymer in the present composition.
  • the method for producing this composition includes melt-kneading this copolymer with the above-mentioned components, which are used as necessary, by a known method.
  • the molded article of the present invention is obtained by molding the present copolymer or the present composition. Since the present molded article contains the present copolymer, the present molded article has low nitrogen permeability and yellowness and also has excellent surface properties. Specific examples of molding methods include injection molding, extrusion molding, blow molding, press molding, rotational molding, and electrostatic coating.
  • the molded product is preferably molded by press molding. Injection molding is also preferred because it is possible to obtain an injection molded product with a beautiful appearance without corroding the mold used for molding.
  • molded articles of the present invention include nuts, bolts, joints, 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 present copolymer, the present composition or the above-mentioned molded article can be used for the following applications.
  • Fuel transfer components such as O-rings, square rings, tubes, packing, valve core materials, hoses, and seals used in automobile fuel systems and peripheral devices, as well as hoses and seals used in automobile AT devices; Carburetor flange gaskets, shaft seals, valve stem seals, sealing materials, hoses, etc.
  • Examples 1 to 11 are working examples, and Examples 12 to 17 are comparative examples. However, the present invention is not limited to these examples.
  • the various measurement and evaluation methods are as follows.
  • MFR Melt Flow Rate
  • the melting point (°C) of the copolymer was determined from the endothermic peak observed when the copolymer was heated to 300°C at a rate of 10°C/min in an air atmosphere using a differential scanning calorimeter (product name "DSC7020", manufactured by Hitachi High-Tech Science Corporation).
  • the copolymer obtained in each example was press molded in the range of the melting point of the copolymer + 50 ° C ⁇ 20 ° C (for example, 280 ° C to 320 ° C when the melting point of the copolymer is 250 ° C) to obtain a film having a thickness of 200 ⁇ m and a film having a thickness of 0.1 mm.
  • the press molding was performed using a hot press machine (Tester Sangyo Co., Ltd. "SA-301").
  • SA-301 Hot press machine
  • a dumbbell-shaped test piece as defined in JIS K6301 No. 3 was cut out from the obtained film having a thickness of 1 mm.
  • the tensile elongation (unit: %) of this test piece was measured in accordance with the method of ASTM D-3159 using a Strograph (manufactured by Toyo Seiki Seisakusho Co., Ltd.) by setting the distance between the gripping jigs to 35 mm and pulling the test piece at a pulling speed of 200 mm/min in a room temperature (temperature 23 ⁇ 2° C.) environment.
  • the test piece was placed in a gear oven (forced circulation air heating aging tester) (manufactured by Toyo Seiki Seisakusho Co., Ltd.) and subjected to a heat exposure treatment.
  • the temperature was set to 250°C for 24 hours after placement.
  • the tensile elongation of the test piece after the heat treatment was measured in the same manner as above.
  • the tensile elongation ratio after the heat treatment was calculated based on the tensile elongation ratio before the heat treatment being 100%, and the evaluation was performed according to the following criteria.
  • YI Yellow Index
  • YI value YI value is less than 4.3.
  • ⁇ YI value is 4.3 or more.
  • oxygen permeability was measured using a differential pressure gas permeability meter (L100-5000 type gas permeability meter, manufactured by Systech Illinois) in accordance with JIS K7126-1:2006.
  • the oxygen permeability values were obtained at a permeation area of 50.24 cm 2 , a test temperature of 70° C., and a test humidity of 0% RH.
  • the oxygen permeability coefficient was calculated according to the following formula. A larger oxygen permeability coefficient value indicates higher oxygen permeability.
  • Oxygen permeability coefficient ( cm3 mm/( m2 24h atm)) GTR x d
  • GTR Oxygen permeability ( cm3 /( m2 ⁇ 24h ⁇ atm))
  • d film thickness (mm) (Evaluation Criteria)
  • ⁇ Oxygen permeability coefficient is 2.6 or less.
  • ⁇ Oxygen permeability coefficient exceeds 2.6.
  • Nitrogen permeability was measured using a 0.1 mm thick film in accordance with JIS K7126-1:2006 using a differential pressure gas permeability meter (L100-5000 type gas permeability meter, manufactured by Sytech Illinois). The nitrogen permeability was measured at a permeation area of 50.24 cm 2 , a test temperature of 70° C., and a test humidity of 0% RH.
  • TOC elution amount The amount of TOC (total organic carbon) eluted was measured in accordance with SEMI F57 "Specification for polymeric materials and components for use in ultrapure water and chemical supply systems.” 30 g of a sample (solid composition obtained in the Example) and a PFA container to be used were pre-washed with ultrapure water in accordance with SEMI F40. 30 g of the pre-washed sample was placed in a pre-washed PFA container, 100 mL of ultrapure water was poured into it to completely immerse it, and the container was sealed and subjected to elution at 85° C. ⁇ 3° C. for 7 days. The concentration of each component in the eluate was measured using a TOC-L CPH (manufactured by Shimadzu Corporation) to determine the amount of elution relative to the surface area.
  • TOC-L CPH manufactured by Shimadzu Corporation
  • the moisture content was measured by the following procedure. Using an infrared moisture meter "FD610" (Kett Electric Laboratory), the moisture content was measured from the mass loss rate before and after the test under conditions of a drying temperature of 140°C, a time static mode of 10 minutes, and a sample (solid composition obtained in the Examples) mass of 100 g.
  • FD610 infrared moisture meter
  • the coating process and the baking process were each performed four times, and a coated article was obtained in which a coating layer made of powder with a thickness of about 250 ⁇ m was formed on the substrate.
  • ⁇ Hot water resistance test (PCT peel test)> The coating film formed on the coating test piece was cut with a cutter knife in a lateral direction at intervals of 10 mm. At one end of the coating test piece where there was no primer layer, the outermost layer and the topcoat layer were peeled off from the substrate to obtain a gripping area.
  • the gripping area was fixed to the chuck of a tensile tester, and the 90° peel strength (unit: N/cm) was measured at a pulling speed of 50 mm/min. Based on the measured value, the adhesive strength was evaluated according to the following criteria.
  • ASAHIKLIN registered trademark
  • AE-3000 fluorine-based organic solvent
  • the MFR of copolymer 1 was 33g/10min, and the melting point was 259°C. Pure water was added to the obtained copolymer 1, and the mixture was heated with stirring to remove the solvent. Next, water was removed from the mixture of pure water and copolymer 1, and drying was carried out by maintaining a drying temperature of 100° C. or higher for 1.9 hours to obtain solid composition 1. After drying, the TOC elution amount of solid composition 1 was 13,300 ⁇ g/cm 2 , and the water content was 0.14 mass%.
  • Example 2 Copolymer 2 of Example 2 was obtained in the same manner as in Example 1, except that the amount of PFBE and the amount of methanol initially charged into the polymerization tank were changed to 4.7 g and 7.1 g, respectively, the amount of the polymerization initiator solution initially charged was changed to 1.3 mL, and the amount of PFBE continuously charged during polymerization was changed to an amount equivalent to 0.4 mol % based on the total moles of TFE and ethylene.
  • the MFR of copolymer 2 was 33 g/10 min, and the melting point was 266° C.
  • Example 2 Drying was carried out in the same manner as in Example 1, except that the drying was carried out so as to maintain a state of 100° C. or higher for 4.6 hours, to obtain Solid Composition 2.
  • the TOC elution amount of the solid composition after drying was 5,900 ⁇ g/cm 2 , and the water content was 0.03 mass %.
  • Example 3 Copolymer 3 of Example 3 was obtained in the same manner as in Example 1, except that the amount of PFBE and the amount of methanol initially charged into the polymerization tank were changed to 2.9 g and 6.0 g, respectively, the amount of the polymerization initiator solution initially charged was changed to 3.1 mL, and the amount of PFBE continuously charged during polymerization was changed to an amount equivalent to 1.0 mol % relative to the total moles of TFE and ethylene.
  • the MFR of copolymer 3 was 35 g/10 min and the melting point was 260° C.
  • Example 3 Drying was carried out in the same manner as in Example 1, except that the drying was carried out so as to maintain a state of 100° C. or higher for 4.6 hours, to obtain Solid Composition 3.
  • the TOC elution amount of the solid composition after drying was 11,600 ⁇ g/cm 2 , and the water content was 0.12 mass %.
  • Example 4 Copolymer 4 of Example 4 was obtained in the same manner as in Example 1, except that the amount of PFBE and the amount of methanol initially charged into the polymerization tank were changed to 1.5 g and 6.7 g, respectively, the amount of the polymerization initiator solution initially charged was changed to 2.2 mL, and the amount of PFBE continuously charged during polymerization was changed to an amount equivalent to 0.7 mol % relative to the total moles of TFE and ethylene.
  • the MFR of copolymer 4 was 37 g/10 min, and the melting point was 263° C.
  • Example 4 Drying was carried out in the same manner as in Example 1, except that the drying was carried out so as to maintain a state of 100° C. or higher for 3.0 hours, to obtain Solid Composition 4.
  • the TOC elution amount of the solid composition after drying was 9,100 ⁇ g/cm 2 , and the water content was 0.08 mass %.
  • Example 5 Copolymer 5 of Example 5 was obtained in the same manner as in Example 1, except that the amount of PFBE and the amount of methanol initially charged into the polymerization tank were changed to 3.9 g and 5.7 g, respectively, the amount of the polymerization initiator solution initially charged was changed to 3.8 mL, and the amount of PFBE continuously charged during polymerization was changed to an amount equivalent to 1.2 mol % based on the total moles of TFE and ethylene.
  • the MFR of copolymer 5 was 39 g/10 min and the melting point was 259° C. Drying was carried out in the same manner as in Example 1 to obtain Solid Composition 5.
  • the TOC elution amount of the solid composition after drying was 13,400 ⁇ g/cm 2 , and the water content was 0.14 mass %.
  • Example 6 Copolymer 6 of Example 6 was obtained in the same manner as in Example 1, except that the amount of PFBE and the amount of methanol initially charged into the polymerization tank were changed to 0.6 g and 7.2 g, respectively, the amount of the polymerization initiator solution initially charged was changed to 1.6 mL, and the amount of PFBE continuously charged during polymerization was changed to an amount equivalent to 0.5 mol % based on the total moles of TFE and ethylene.
  • the MFR of copolymer 6 was 40 g/10 min and the melting point was 265° C.
  • Example 6 Drying was carried out in the same manner as in Example 1, except that the drying was carried out so as to maintain a state of 100° C. or higher for 1.3 hours, to obtain Solid Composition 6.
  • the TOC elution amount of the solid composition after drying was 6,000 ⁇ g/cm 2 , and the water content was 0.20 mass %.
  • Example 7 Copolymer 7 of Example 7 was obtained in the same manner as in Example 1, except that the amount of PFBE and the amount of methanol initially charged into the polymerization tank were changed to 2.0 g and 6.6 g, respectively, the amount of the polymerization initiator solution initially charged was changed to 2.5 mL, and the amount of PFBE continuously charged during polymerization was changed to an amount equivalent to 0.8 mol % based on the total moles of TFE and ethylene.
  • the MFR of copolymer 7 was 42 g/10 min, and the melting point was 262° C.
  • Example 7 Drying was carried out in the same manner as in Example 1, except that the drying was carried out by maintaining a state of 100° C. or higher for 2.7 hours, to obtain Solid Composition 7.
  • the TOC elution amount of the solid composition after drying was 9,900 ⁇ g/cm 2 , and the water content was 0.09 mass %.
  • Example 8 Copolymer 8 of Example 8 was obtained in the same manner as in Example 1, except that the amount of PFBE and the amount of methanol initially charged into the polymerization tank were changed to 3.5 g and 6.1 g, respectively, the amount of the polymerization initiator solution initially charged was changed to 3.4 mL, and the amount of PFBE continuously charged during polymerization was changed to an amount equivalent to 1.1 mol % relative to the total moles of TFE and ethylene.
  • the MFR of copolymer 8 was 44 g/10 min and the melting point was 260° C.
  • Example 8 Drying was carried out in the same manner as in Example 1, except that the drying was carried out so as to maintain a state of 100° C. or higher for 2.1 hours, to obtain a solid composition 8.
  • the TOC elution amount of the solid composition after drying was 12,500 ⁇ g/cm 2 , and the water content was 0.13 mass %.
  • Example 9 Copolymer 9 of Example 9 was obtained in the same manner as in Example 1, except that the amount of PFBE and the amount of methanol initially charged into the polymerization tank were changed to 0.6 g and 7.4 g, respectively, the amount of the polymerization initiator solution initially charged was changed to 1.6 mL, and the amount of PFBE continuously charged during polymerization was changed to an amount equivalent to 0.5 mol % based on the total moles of TFE and ethylene.
  • the MFR of copolymer 9 was 50 g/10 min and the melting point was 265° C.
  • Example 9 Drying was carried out in the same manner as in Example 1, except that the drying was carried out by maintaining a state of 100° C. or higher for 3.7 hours, to obtain Solid Composition 9.
  • the TOC elution amount of the solid composition after drying was 7,400 ⁇ g/cm 2 , and the water content was 0.06 mass %.
  • ASAHIKLIN registered trademark
  • the MFR of copolymer 12 was 35g/10min, and the melting point was 271°C. Pure water was added to the obtained copolymer 10, and the mixture was heated with stirring to remove the solvent in the same manner as in Example 1. Next, water was removed from the mixture of pure water and copolymer 10, and drying was performed by maintaining a drying temperature of 100° C. or higher for 2.3 hours.
  • the TOC elution amount of solid composition 10 after drying was 11,500 ⁇ g/cm 2 , and the water content was 0.12 mass%.
  • Example 11 Copolymer 11 of Example 11 was obtained in the same manner as in Example 10, except that the amount of PPVE and the amount of methanol initially charged into the polymerization vessel were changed to 25.3 g and 16.8 g, respectively, and the amount of PPVE continuously charged during the polymerization was changed to an amount equivalent to 0.6 mol % based on the total moles of TFE and ethylene.
  • the MFR of copolymer 11 was 36 g/10 min, and the melting point was 275° C.
  • Example 11 Drying was carried out in the same manner as in Example 1, except that the drying was carried out so as to maintain a state of 100° C. or higher for 3.3 hours, to obtain a solid composition 11.
  • the TOC elution amount of the solid composition after drying was 8,250 ⁇ g/cm 2 , and the water content was 0.07 mass %.
  • Example 12 Copolymer 12 of Example 12 was obtained in the same manner as in Example 1, except that the amount of PFBE and the amount of methanol initially charged into the polymerization tank were changed to 2.5 g and 6.6 g, respectively, the amount of the polymerization initiator solution initially charged was changed to 2.8 mL, and the amount of PFBE continuously charged during polymerization was changed to an amount equivalent to 0.9 mol % relative to the total moles of TFE and ethylene.
  • the MFR of copolymer 12 was 29 g/10 min, and the melting point was 261° C.
  • Example 12 Drying was carried out in the same manner as in Example 1, except that the drying was carried out so as to maintain a state of 100° C. or higher for 3.3 hours, to obtain a solid composition 12.
  • the TOC elution amount of the solid composition after drying was 11,400 ⁇ g/cm 2 , and the water content was 0.11 mass %.
  • Example 13 Copolymer 13 of Example 13 was obtained in the same manner as in Example 1, except that the amount of PFBE and the amount of methanol initially charged into the polymerization tank were changed to 4.9 g and 5.4 g, respectively, the amount of the polymerization initiator solution initially charged was changed to 4.4 mL, and the amount of PFBE continuously charged during polymerization was changed to an amount equivalent to 1.4 mol % based on the total moles of TFE and ethylene.
  • the MFR of copolymer 13 was 41 g/10 min, and the melting point was 257° C.
  • Example 13 Drying was carried out in the same manner as in Example 1, except that the drying was carried out so as to maintain a state of 100° C. or higher for 1.6 hours, to obtain a solid composition 13.
  • the TOC elution amount of the solid composition after drying was 15,000 ⁇ g/cm 2 , and the water content was 0.17 mass %.
  • Example 14 Copolymer 14 of Example 14 was obtained in the same manner as in Example 1, except that the amount of PFBE and the amount of methanol initially charged into the polymerization tank were changed to 3.5 g and 6.6 g, respectively, the amount of the polymerization initiator solution initially charged was changed to 3.4 mL, and the amount of PFBE continuously charged during polymerization was changed to an amount equivalent to 1.1 mol % relative to the total moles of TFE and ethylene.
  • the MFR of copolymer 14 was 64 g/10 min, and the melting point was 260° C.
  • Example 14 Drying was carried out in the same manner as in Example 1, except that the drying was carried out so as to maintain a state of 100° C. or higher for 2.1 hours, to obtain a solid composition 14.
  • the TOC elution amount of the solid composition after drying was 12,700 ⁇ g/cm 2 , and the water content was 0.13 mass %.
  • Example 15 Copolymer 15 of Example 15 was obtained in the same manner as in Example 1, except that the amount of PFBE and the amount of methanol initially charged into the polymerization tank were changed to 0.66 g and 9.9 g, respectively, the amount of the polymerization initiator solution initially charged was changed to 1.0 mL, and the amount of PFBE continuously charged during polymerization was changed to an amount equivalent to 0.2 mol % based on the total moles of TFE and ethylene.
  • the MFR of copolymer 15 was 40 g/10 min, and the melting point was 268° C. Drying was carried out in the same manner as in Example 1 to obtain Solid Composition 15.
  • the TOC elution amount of the solid composition after drying was 15,000 ⁇ g/cm 2 , and the water content was 0.14 mass %.
  • Example 16 Copolymer 16 of Example 16 was obtained in the same manner as in Example 1, except that the amount of PFBE and the amount of methanol initially charged into the polymerization tank were changed to 3.9 g and 5.7 g, respectively, the amount of the polymerization initiator solution initially charged was changed to 3.8 mL, and the amount of PFBE continuously charged during polymerization was changed to an amount equivalent to 1.2 mol % based on the total moles of TFE and ethylene.
  • the MFR of copolymer 16 was 39 g/10 min, and the melting point was 259° C.
  • Example 16 Drying was carried out in the same manner as in Example 1, except that the drying was carried out so as to maintain a state of 100° C. or higher for 0.5 hours, to obtain a solid composition 16.
  • the TOC elution amount of the solid composition after drying was 64,000 ⁇ g/cm 2 , and the water content was 0.89 mass %.
  • Example 17 Copolymer 17 of Example 17 was obtained in the same manner as in Example 1, except that the amount of PFBE and the amount of methanol initially charged into the polymerization tank were changed to 3.9 g and 5.7 g, respectively, the amount of the polymerization initiator solution initially charged was changed to 3.8 mL, and the amount of PFBE continuously charged during polymerization was changed to an amount equivalent to 1.2 mol % based on the total moles of TFE and ethylene.
  • the MFR of copolymer 17 was 39 g/10 min, and the melting point was 259° C.
  • Drying was also carried out in the same manner as in Example 1, except that drying was carried out so as to maintain a state of 100° C. or higher for 6.8 hours, to obtain Solid Composition 17.
  • the TOC elution amount of the solid composition after drying was 980 ⁇ g/cm 2 , and the water content was 0.01 mass %.
  • Table 1 shows the composition of the copolymer in each example, as well as the measurement and evaluation results of the copolymer.
  • TFE units (mol %) indicates the content (unit: mol %) of TFE units relative to all units contained in the copolymer.
  • E units (mol %) indicates the content (unit: mol %) of E units relative to all units contained in the copolymer.
  • TFE/(TFE+E) (mol %) indicates the content of TFE units relative to the total content of TFE units and E units (unit: mol %).
  • the column “A units (mol %)” indicates the content (unit: mol %) of A units relative to all units contained in the copolymer.
  • the total content of TFE units and E units is 80.0 to 99.7 mol% based on the total content of all units contained in the copolymer
  • the content of TFE units is 49.0 mol% or more and less than 56.0 mol% based on the total content of TFE units and E units
  • the content of A units is 0.3 to 1.3 mol% based on the total units contained in the copolymer
  • the MFR is 33 to 50 g/10 min
  • Table 2 shows the measurement results and evaluation results of the solid compositions of each example.
  • TFE units (mol %) indicates the content (unit: mol %) of TFE units relative to all units contained in the copolymer.
  • E units (mol %) indicates the content (unit: mol %) of E units relative to all units contained in the copolymer.
  • TFE/(TFE+E) (mol %) indicates the content of TFE units relative to the total content of TFE units and E units (unit: mol %).
  • the column “A units (mol %)” indicates the content (unit: mol %) of A units relative to all units contained in the copolymer.

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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)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

L'invention fournit un copolymère qui permet de former un corps moulé dont la perméabilité à l'azote et le jaunissement sont faibles, et qui présente en outre une excellente qualité de surface. L'invention fournit fournit également une composition et un corps moulé.　Le copolymère de l'invention contient une unité tétrafluoroéthylène, une unité éthylène, et une unité à base d'un composé représenté par la formule (1) ＣＺ２＝ＣＸ（ＣＦ２）ｍＹ et/ou à base d'un composé représenté par la formule ＣＦ２＝ＣＦ－Ｏ－（ＣＦ２）ｎＦ (2). La teneur totale en unité tétrafluoroéthylène et en unité éthylène est comprise entre ８０,０ et ９９,７% en moles pour l'ensemble des unités contenues dans ledit copolymère. La teneur en unité tétrafluoroéthylène est supérieure ou égale à 49,0% en moles et inférieure à 56,0% en moles pour la teneur totale en unité tétrafluoroéthylène et en unité éthylène. La teneur en unité à base de composé représenté par la formule (1) ou la formule (2), est comprise entre 0,3 et 1,3% en moles pour l'ensemble des unités contenues dans le copolymère. L'indice de fluidité à chaud est compris entre ３３ et ５０ｇ／１０ minutes.
PCT/JP2024/021742 2023-06-16 2024-06-14 Copolymère, composition, et corps moulé Pending WO2024257869A1 (fr)

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Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4919709B1 (fr) * 1970-01-20 1974-05-20
DE4131746A1 (de) * 1991-09-24 1993-03-25 Hoechst Ag Fasern aus tetrafluorethylen-copolymeren, verfahren zu deren herstellung und deren verwendung
WO2010123002A1 (fr) * 2009-04-21 2010-10-28 ダイキン工業株式会社 Copolymère éthylène/tétrafluoroéthylène, fil électrique et poudre de résine fluorée pour moulage par rotation
WO2013146704A1 (fr) * 2012-03-26 2013-10-03 旭硝子株式会社 Composition d'élastomère fluoré, procédé pour la produire, corps moulé, produit réticulé et fil métallique revêtu
WO2017018353A1 (fr) * 2015-07-28 2017-02-02 旭硝子株式会社 Copolymère, procédé pour le produire, matériau de résine pour gainage de câble électrique, et câble électrique
WO2017082417A1 (fr) * 2015-11-13 2017-05-18 旭硝子株式会社 Copolymère et composition le contenant
WO2018008563A1 (fr) * 2016-07-04 2018-01-11 旭硝子株式会社 Film et procédé pour sa production
WO2018008562A1 (fr) * 2016-07-04 2018-01-11 旭硝子株式会社 Film de copolymere d'éthylène-tétrafluoroéthylène et procédé pour sa production
JP2021067338A (ja) * 2019-10-25 2021-04-30 Ａｇｃ株式会社 積層ホース
WO2022138768A1 (fr) * 2020-12-24 2022-06-30 ダイキン工業株式会社 Procédé de production de polymère fluoré

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4919709B1 (fr) * 1970-01-20 1974-05-20
DE4131746A1 (de) * 1991-09-24 1993-03-25 Hoechst Ag Fasern aus tetrafluorethylen-copolymeren, verfahren zu deren herstellung und deren verwendung
WO2010123002A1 (fr) * 2009-04-21 2010-10-28 ダイキン工業株式会社 Copolymère éthylène/tétrafluoroéthylène, fil électrique et poudre de résine fluorée pour moulage par rotation
WO2013146704A1 (fr) * 2012-03-26 2013-10-03 旭硝子株式会社 Composition d'élastomère fluoré, procédé pour la produire, corps moulé, produit réticulé et fil métallique revêtu
WO2017018353A1 (fr) * 2015-07-28 2017-02-02 旭硝子株式会社 Copolymère, procédé pour le produire, matériau de résine pour gainage de câble électrique, et câble électrique
WO2017082417A1 (fr) * 2015-11-13 2017-05-18 旭硝子株式会社 Copolymère et composition le contenant
WO2018008563A1 (fr) * 2016-07-04 2018-01-11 旭硝子株式会社 Film et procédé pour sa production
WO2018008562A1 (fr) * 2016-07-04 2018-01-11 旭硝子株式会社 Film de copolymere d'éthylène-tétrafluoroéthylène et procédé pour sa production
JP2021067338A (ja) * 2019-10-25 2021-04-30 Ａｇｃ株式会社 積層ホース
WO2022138768A1 (fr) * 2020-12-24 2022-06-30 ダイキン工業株式会社 Procédé de production de polymère fluoré

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