WO2020023102A1 - Poudres résineuses contenant du fluor fonctionnalisées et méthodes de formation associées - Google Patents

Poudres résineuses contenant du fluor fonctionnalisées et méthodes de formation associées Download PDF

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Publication number
WO2020023102A1
WO2020023102A1 PCT/US2019/032142 US2019032142W WO2020023102A1 WO 2020023102 A1 WO2020023102 A1 WO 2020023102A1 US 2019032142 W US2019032142 W US 2019032142W WO 2020023102 A1 WO2020023102 A1 WO 2020023102A1
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group
fluorine
functional group
powder
functionalized
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PCT/US2019/032142
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English (en)
Inventor
Masatoshi Abe
Shigeru Aida
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Agc Chemicals Americas, Inc.
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Priority to JP2021501339A priority Critical patent/JP2021532218A/ja
Publication of WO2020023102A1 publication Critical patent/WO2020023102A1/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
    • 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
    • C08F214/262—Tetrafluoroethene with fluorinated vinyl ethers
    • 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
    • C08F214/265—Tetrafluoroethene with non-fluorinated comonomers
    • 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
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
    • C08F8/32—Introducing nitrogen atoms or nitrogen-containing groups by reaction with amines

Definitions

  • the invention generally relates to functionalized fluorine-containing resinous powders and methods for forming same, and more specifically to functionalized fluorine-containing resinous powders having one or more reactive groups formed by reacting functionalized ethylene/tetrafluoroethylene or functionalized tetrafluoroethylene/perfluoroalkylvinylether copolymer powders with compounds having reactive functional groups reactive with the functional groups of such copolymer powders.
  • An ethylene/tetrafluoroethylene copolymer (sometimes alternatively referred to as an ETFE copolymer, or simply ETFE) and a tetrafluoroethylene/perfluoroalkylvinyl ether copolymer (sometimes alternatively referred to as an PFA copolymer, or simply PFA) each, respectively, have characteristics excellent in, for example, heat resistance, chemical resistance, water resistance, oil resistance, weather resistance, aging resistance, gas barrier properties, fuel barrier properties, release properties, non-stickiness, antifouling properties, dye adhesion resistance and unelution properties.
  • ETFE copolymers and PFA copolymers are employed in various fields such as semiconductor industries, aircraft or automobile industries, food manufacturing industries and medical industries.
  • non-functionalized ETFE or PFA copolymers have poor bonding or adhesion to other substrates due to their low affinity to other compounds, based on the characteristics of a fluorine atom bonded to their main chains.
  • functional groups may be improved.
  • the present invention is directed to a method for forming a functionalized fluorine- containing resinous powder.
  • the method comprises providing a fluorine-containing powder having at least one functional group; providing a compound having at least one reactive functional group reactive with the at least one functional group; combining a solvent with the fluorine- containing powder and the compound to form a mixture, wherein the fluorine-containing powder is not dissolved in the solvent; and reacting one of the at least one reactive functional group of the compound with a corresponding one of the at least one functional group from the non-dissolved fluorine-containing powder to form the functionalized fluorine-containing resinous powder including at least one of the at least one reactive functional group.
  • the present invention is also directed to functionalized fluorine-containing resinous powders having at least one of the at least one reactive functional groups formed from the methods described above.
  • the present invention is also directed to a functionalized fluorine-containing resinous powder comprising the reaction product of reactants comprising a fluorine-containing powder having at least one functional group and selected from an ethyl ene/tetrafluoroethylene copolymer powder having at least functional group and a tetrafluoroethylene/perfluoroalkylvinylether copolymer powder having at least one functional group; and a compound having at least one reactive functional group reactive with said at least one functional group, wherein the functionalized fluorine-containing resinous powder includes and at least one of said at least one reactive functional group and has an average particle diameter size of 400 micrometers or less.
  • the present invention is also directed to a functionalized fluorine-containing resinous powder having at least one reactive functional group and an average particle diameter size of 400 micrometers or less, with the functionalized fluorine-containing resinous powder comprising repeating units derived from tetrafluoroethylene, repeating units derived from ethylene or perfluoroalkylvinylether, and repeating units derived from a polymerizable compound having an unsaturated bond and a functional group.
  • the methods for forming the functionalized fluorine-containing resinous powders of the present invention are simple and do not require special equipment associated with melting the fluorine-containing powder having at least one functional group in order to be reacted with the compound. Still further, the methods do not require expensive solvents needed for dissolving the fluorine-containing powder having at least one functional group. Still further, the functionalized fluorine-containing resinous powders are easily integrated into further products without the need for subsequent steps associated with adjusting particle size. Even still further, the functionalized fluorine-containing resinous powder of the present invention can easily be introduced to form molded materials or prepregs (such as carbon fiber prepregs).
  • the present invention is directed to a functionalized fluorine-containing resinous powder having at least one reactive functional group (sometimes alternatively referred to simply as a functionalized fluorine-containing resinous powder) that is formed from a fluorine-containing powder having at least one functional group (sometimes alternatively referred to simply as a fluorine-containing powder) and a compound having at least one reactive functional group (sometimes alternatively referred to simply as a compound) reactive with the at least one functional group.
  • a functionalized fluorine-containing resinous powder having at least one reactive functional group (sometimes alternatively referred to simply as a functionalized fluorine-containing resinous powder) that is formed from a fluorine-containing powder having at least one functional group (sometimes alternatively referred to simply as a fluorine-containing powder) and a compound having at least one reactive functional group (sometimes alternatively referred to simply as a compound) reactive with the at least one functional group.
  • the functionalized fluorine-containing resinous powder is formed by combining a solvent with the fluorine-containing powder and the compound to form a mixture, wherein the fluorine-containing powder is not dissolved in the solvent.
  • the process proceeds by reacting one of the at least one reactive functional group of the compound with a corresponding one of the at least one functional group from the non-dissolved fluorine-containing powder to form a reaction product.
  • the reaction product comprises the functionalized fluorine-containing resinous powder and includes at least one of the at least one reactive functional group.
  • the functionalized fluorine-containing resinous powder having at least one reactive functional group has an average particle diameter size of 400 micrometers or less, or such as 80 micrometers or less, or such as 60 micrometers or less.
  • the formed functionalized fluorine-containing resinous powder having at least one reactive functional group may also have a melting point of 150 degrees Celsius or higher, and/or may have a specific gravity of 1.5 or more as measured by Test Method A of ASTM D792 - 13 (as used hereinafter, any reference to specific gravity is in accordance with Test Method A of ASTM D792 - 13).
  • the fluorine-containing powder used to form the functionalized fluorine-containing resinous powder is in the form of an ethylene/tetrafluoroethylene (ETFE) copolymer powder having at least one functional group (alternatively referred to below as functional group-containing ETFE), while in other embodiments the fluorine-containing powder is in the form a tetrafluoroethylene/perfluoroalkylvinylether copolymer powder having at least one functional group (alternatively referred to below as functional group-containing PFA).
  • ETFE ethylene/tetrafluoroethylene
  • PFA tetrafluoroalkylvinylether copolymer powder having at least one functional group
  • the fluorine-containing powder may include both the ethylene/tetrafluoroethylene copolymer powder having at least one functional group and the tetrafluoroethylene/perfluoroalkylvinylether copolymer powder having at least one functional group.
  • the molar ratio of repeating units derived from tetrafluoroethylene and repeating units derived from ethylene in an ETFE copolymer powder having a functional group formed by the copolymerization process is from 70/30 to 30/70, such as from 65/35 to 35/65, such as from 60/40 to 40/60.
  • the molar ratio of repeating units derived from tetrafluoroethylene and repeating units derived from perfluoroalkylvinylether in a PFA copolymer powder having a functional group formed by the copolymerization process is from 99.5/0.5 to 80/20, such as from 95/5 to 85/65.
  • the functional group of the fluorine-containing powder may be an anhydride group, carbonyl group, a hydroxy group, an isocyanate group, or an epoxy group (i.e., the functional group is selected from an anhydride group, carbonyl group, a hydroxy group, an isocyanate group, and an epoxy group).
  • an anhydride group is preferred, wherein this anhydride group is reacted with an amine group as the reactive functional group from the compound to form an imide bond in the resultant functionalized fluorine-containing resinous powder, as will be described further below.
  • the carbonyl group contained in the functional group-containing ETFE, or contained in the functional group-containing PFA is a carboxy group, an alkoxycarbonyl group, a halogeno-carbonyl group, a carbonate group, an anhydride group, an aldehyde group, a ketone group or the like, and is most preferably an anhydride group.
  • both carbon atoms of the acid anhydride may be connected to the main chain of the functional group-containing ETFE or PFA, or either one of them may be connected thereto.
  • the functional groups that are part of the functional group- containing ETFE, or the functional group-containing PFA are polymerized into the respective functional group-containing ETFE or PFA copolymer from monomers having functional groups.
  • the monomer having a functional group (alternatively referred to herein as a polymerizible compound having an unsaturated bond and a functional group) may be used alone or in combination as a mixture of two or more of them.
  • the monomer having a carbonyl group may, for example, be an unsaturated polycarboxylic acid anhydride such as itaconic anhydride, citraconic anhydride, bicyclo[2.2.
  • l]hept-5-ene-2,3-dicarboxylic anhydride or maleic anhydride an unsaturated carboxylic acid monomer such as acrylic acid, methacrylic acid, maleic acid, maleic acid monomethyl ester, fumaric acid, itaconic acid, citraconic acid, crotonic acid or bicyclo[2.2.
  • l]hepto-2,3-en-5,6-dicarboxylic acid an unsaturated carboxylic acid ester monomer such as methyl acrylate, methyl methacrylate, dimethyl maleate, methyl fumarate, methyl methacrylate, diethyl citraconate, diethyl fumarate, dimethyl itaconate, diethyl citraconate, perfluoroacrylic acid fluoride, l-fluoroacrylic acid fluoride, acrylic acid fluoride, acrylic acid chloride, l-trifluoromethacrylic acid fluoride or perfluorobutenoic acid; an unsaturated aldehyde monomer such as acrolein or croton aldehyde; or vinylene carbonate. Itaconic anhydride, citraconic anhydride, bicyclo[2.2. l]hept-5-ene-2,3-dicarboxylic anhydride or maleic anhydride is particularly preferred.
  • the monomer having a functional group other than an carbonyl group that may be used include a monomer having a hydroxy group such as allyl alcohol, crotyl alcohol, 2-methyl allyl alcohol, methyl vinyl carbinol, 3-butene-l-ol or 2-vinyl oxyethanol; a monomer having an amino group such as allylamine; a monomer having a vinyl group such as 1,3- butadiene, l,4-pentadiene, l,5-hexadiene, isoprene, 2-methyl- l,4-pentadiene, l,3-pentadiene or 2- methyl-l,5-hexadiene; and a monomer having an epoxy group such as vinyl ethylene oxide, 1,2- epoxy-5-hexene, allyl glycidyl ether or glycidyl methacrylate.
  • a monomer having a hydroxy group such as allyl alcohol, crotyl alcohol, 2-
  • additional other monomers may also be included in the copolymerization process used in forming the respective ETFE fluorine-containing powder or PFA fluorine-containing powder having at least one functional group.
  • these additional monomers may be used in combination with e.g. a hydrocarbon olefin monomer having at most three carbon atoms such as propylene or isobutyrene; a vinyl ester such as vinyl acetate; and a vinyl ether such as ethyl vinyl ether or cyclohexyl vinyl ether.
  • a hydrocarbon olefin monomer having at most three carbon atoms such as propylene or isobutyrene
  • a vinyl ester such as vinyl acetate
  • a vinyl ether such as ethyl vinyl ether or cyclohexyl vinyl ether.
  • the process for producing a ETFE or PFA fluorine-containing powder having at least one functional group is not particularly limited, and it is possible to employ a method wherein tetrafluoroethylene, ethylene or perfluoroalkylvinylether, the monomer including a functional group (such as the monomer including an anhydride functional group as described above), and the another monomer (as also described above) as the case requires, are introduced into a reactor, and then copolymerized by means of a radical polymerization initiator and a chain transfer agent which are commonly employed.
  • the polymerization method may be, as per se known, bulk polymerization; solution polymerization using, as a polymerization medium, an organic solvent such as a fluorinated hydrocarbon, a chlorinated hydrocarbon, a fluoro- chlorinated hydrocarbon, an alcohol or a hydrocarbon; suspension polymerization using an aqueous medium as a polymerization medium and, if necessary a suitable organic solvent; and emulsion polymerization using an aqueous medium as a polymerization medium and an emulsifier.
  • an organic solvent such as a fluorinated hydrocarbon, a chlorinated hydrocarbon, a fluoro- chlorinated hydrocarbon, an alcohol or a hydrocarbon
  • suspension polymerization using an aqueous medium as a polymerization medium and, if necessary a suitable organic solvent
  • emulsion polymerization using an aqueous medium as a polymerization medium and an emulsifier.
  • a solution polymerization is most preferred.
  • the above-described polymerization can be carried out in a batch system or continuous system operation by using a single vessel- or multi vessel-type stirring-type polymerization apparatus, a tubular polymerization apparatus or the like.
  • the radical polymerization initiator is preferably an initiator having a half-life of 10 hours at a temperature of from 0 to 100 degrees Celsius, more preferably at a temperature of from 20 to 90 degrees Celsius. It may, for example, be an azo compound such as azobisisobutyronitrile; a peroxydicarbonate such as diisopropyl peroxydicarbonate, a peroxy ester such as t-butyl peroxypivalate, t-butyl peroxyisobutyrate or t-butyl peroxyacetate; a non-fluorinated diacyl peroxide such as isobutyryl peroxide, octanoyl peroxide, benzoyl peroxide or lauroyl peroxide; a fluorinated diacyl peroxide such as (Z(CF 2 ) P COO)2 (wherein Z is a hydrogen atom, a fluorine atom or a chlorine atom, and p is an azo compound
  • the polymerization medium is at least one member selected from the group consisting of an organic solvent such as a fluorinated hydrocarbon, a chlorinated hydrocarbon, a fluoro- chlorinated hydrocarbon, an alcohol or a hydrocarbon as mentioned above, and an aqueous medium.
  • the chain transfer agent may, for example, be an alcohol such as methanol or ethanol; a chlorofluorohydrocarbon such as l,3-dichloro-l, l,2,2,3-pentafluoropropane or l, l-dichloro-l- fluoroethane; or a hydrocarbon such as pentane, hexane or cyclohexane.
  • the polymerization conditions are not particularly limited, but the polymerization temperature is usually preferably from 0 to 100 degrees Celsius, more preferably from 20 to 90 degrees Celsius. Further, the polymerization pressure is preferably from 0.1 to 10 MPa, more preferably from 0.5 to 3 MPa.
  • the polymerization time may vary depending upon the polymerization temperature, the polymerization pressure, etc. but it is usually preferably from 1 to 30 hours, more preferably from 2 to 10 hours.
  • the copolymerization ratio of such the monomer including the functional group is usually preferably at most 20 mol %, particularly preferably from 0.01 to 10 mol %, based on the total monomer content.
  • the content of repeating units derived from the polymerizible compound having an unsaturated bond and functional group is at most 20 mol %, particularly preferably from 0.01 to 10 mol %.
  • the copolymerization ratio of such the monomer including the anhydride-functional group is preferably from 0.01 to 5 mol %, based on the total monomer content.
  • the anhydride-functional group content exceeds this amount, the heat resistance, chemical resistance, etc. of the fluorine-containing powder having at least one functional group, and the corresponding heat resistance of the resultant functionalized fluorine-containing resinous compound formed in accordance with the present invention, may be impaired.
  • the fluorine-containing powder formed by the copolymerization process also has a melting point of 160 degrees Celsius or higher, and/or has a specific gravity of 1.5 or more.
  • a bonding group of the graft compound is a group which enables the non-functionalized ETFE or PFA copolymer powder to be grafted.
  • the bonding group may, for example, be an unsaturated or saturated hydrocarbon group involved in association or addition of radicals, or an amino group or phenolic hydroxy group involved in a nucleophilic reaction. Further, it may be a group which is likely to generate radicals such as a peroxy group or an azo group.
  • the bonding group is preferably a group having a carbon-carbon unsaturated bond (particularly an organic group having an a, b-unsaturated double bond at its terminals), a peroxy group or an amino group.
  • a polymerizable compound having an unsaturated bond and acid anhydride residue such as maleic anhydride, itaconic anhydride, citraconic anhydride or bicyclo[2.2.
  • l]hept-5-ene-2,3-dicarboxylic anhydride an unsaturated carboxylic acid such as acrylic acid, methacrylic acid, maleic acid, maleic acid monomethyl ester, fumaric acid, itaconic acid, citraconic acid, crotonic acid or bicyclo[2.2.
  • unsaturated carboxylic acid such as acrylic acid, methacrylic acid, maleic acid, maleic acid monomethyl ester, fumaric acid, itaconic acid, citraconic acid, crotonic acid or bicyclo[2.2.
  • l]hept-5-ene-2,3-dicarboxylic anhydride an unsaturated carboxylic ester such as methyl acrylate, methyl methacrylate, dimethyl maleate, methyl fumarate, methyl methacrylate, diethyl citraconate, diethyl fumarate, dimethyl itaconate or diethyl citraconate; and an unsaturated aldehyde such as acrolein or crotonaldehyde; may, for example, be mentioned.
  • the polymerizable compound having an unsaturated bond and acid anhydride residue such as maleic anhydride, itaconic anhydride, citraconic anhydride or bicyclo[2.2. l]hept-5-ene-2,3-dicarboxylic anhydride is particularly preferred.
  • the method for producing the fluorine-containing powder having at least one functional group with the grafted functional group is preferably a method wherein peroxy carbonate or peroxy ester is used as a radical polymerization initiator for producing ETFE, or appropriately selecting a chain transfer agent, thereby to introduce a carbonyl group at the terminals of the polymer.
  • the peroxy carbonate is preferably diisopropyl peroxy carbonate, di-n- propylperoxy carbonate, t-butyl peroxyisopropyl carbonate, bis(4-t-butylcyclohexyl)peroxy carbonate, di-2-ethylhexyl peroxy carbonate or the like.
  • a compound having at least one reactive functional group reactive with the at least one functional group is also used to form the functionalized fluorine-containing resinous powder having at least one of the at least one reactive functional group.
  • the number of reactive functional groups in the compound may be 1 or at least 2.
  • the reactive functional group in the compound is preferably a hydroxy group, an amino group, a carbonyl group, an isocyanate group, an epoxy group, a vinyl group, and a nitrile group, more preferably a hydroxy group or an amino group, most preferably an amino group.
  • the compound includes at least one reactive functional group that reacts with an anhydride-functional group of the fluorine-containing polymer to form an imide group in the functionalized fluorine containing resinous powder.
  • the compound preferably includes at least one amino group.
  • exemplary compounds having one reactive functional group which can react with the functional group of the fluorine-containing powder is a compound represented by R-X.
  • X is a hydroxy group, an amino group, a mercapto group, an isocyanate group or an epoxy group
  • R is -H
  • an alkyl group it may be linear, branched or circular
  • an alkyl group it may be linear, branched or circular
  • Exemplary compounds having one reactive functional group include methanol, ethanol, hexanol, octanol, dodecanol, sodium hydroxymethane sulfmate, nitroethanol, 4-hydoxypropionitrile, 2- ethoxy ethanol, hydroxyacetonitrile, 2-bromoethanol, N,N-dimethylaminoethanol, 2- (trimethoxysilyl)ethanol, phenol, benzyl alcohol, 4-hydroxypyridine, allyl alcohol, ammonia, methylamine, ethylamine, hexylamine, octylamine, dodecylamine, 3-aminopropionitrile, methoxyethylamine, 4-aminomorpholine, 2-bromoethylamine, N,N-dimethylethylenediamine, trimethoxysilylmethylamine,
  • exemplary compounds having two reactive functional groups include, but are not limited to, ethylene diamine, l,3-diaminopropane, l,4-diaminobutane, 1,5- diaminopentane, l,6-diaminohexane, 1, 4-cyclohexyl diamine, l,4-phenylene diamine, p-xylylene diamine, l,2-bis(2-aminoethoxy)ethane, tris(2-aminoethyl)amine, tris(3-aminopropyl)amine, ethylene glycol, 1, 3-propanediol, l,6-hexadiol, diethylene glycol, hydroquinone, 1,4- benzenedimethanol, l,2,4-butanetriol, l,3,5-cyclohexanetriol, meso-erythritol, 3,6-dioxa-l,8-
  • One preferred compound having two reactive amino functional groups used in the Example below, is l,6-diaminohexane (also known as hexamethylene diamine, or HMD).
  • the molar content of the reactive functional group in the compound is at least 2 times more, such as greater than 2 times more, than the molar content of functional group in the fluorine-containing powder. Stated another way, the molar ratio of reactive functional group of the compound to the molar content of the functional group of the fluorine-containing powder is greater than or equal to 2: 1.
  • a solvent is also included in the method for forming the functionalized fluorine-containing resinous powder.
  • the solvent is mixed with the fluorine-containing powder and the compound during the reaction process.
  • the solvent does not dissolve the fluorine-containing powder at a temperature below of the melting point of the fluorine-containing powder under atmospheric pressure or a pressurized condition, such as at a temperature below 250 degree Celsius.
  • the solvent in certain embodiments, may dissolve the compound into a dissolved state, while in other embodiments the compound may remain in a non-dissolved state such as in a dispersed state.
  • the compound is either in a dissolved state or non-dissolved state in the solvent, while the fluorine-containing powder is in a non-dissolved state in the solvent, during the subsequent or simultaneous process of reacting the compound with the fluorine-containing powder to form the functionalized fluorine-containing resinous powder.
  • a “dissolved state”, used herein with respect to the compound and solvent means a state wherein a mixture of the compound and the solvent is transparent and homogeneous at a certain temperature, by visual evaluation after mixing them sufficiently.
  • a non- dissolved state used herein with respect to the fluorine-containing powder and the solvent (or between the compound and the solvent), means a state wherein a mixture of fluorine-containing powder and the solvent (or compound and solvent) is not transparent or otherwise is not homogeneous at a certain temperature, as determined by visual evaluation after mixing them sufficiently.
  • Suitable solvents that can be used in the present invention are solvents that may or may not dissolve the compound at a temperature below the melting temperature of the fluorine-containing powder, but do not dissolve the fluorine-containing powder at these same temperatures.
  • Exemplary solvents include, but are not limited to acetic acid, acetone, acetonitrile, 1- butanol, 2-butanol, 2-butanone, t-butyl alcohol, carbon tetrachloride, chlorobenzene, chloroform, 1, 2-dichloroethane, diethyl ether, di ethylene glycol, di ethylene glycol dimethyl ether, 1,2- dimethoxy-ethane, dimethylether, dimethyl formamide, dimethyl sulfoxide, dioxane, ethanol, ethyl acetate, ethylene glycol, glycerin, heptane, hexamethylphosphoramide, hexamethylphosphorous triamide, hexane, methanol, methyl t-butyl ether, methylene chloride, N- methyl-2-pyrrolidinone, nitromethane, pentane, petroleum ether, l-propanol, 2-propan
  • Exemplary additional solvents that can be used, with the proviso that such a solvent or solvents do not dissolve the fluorine-containing powder including at least one anhydride-functional group, can be found in paragraphs [0052], [0053], and [0059-0063] of ETS 2013/0046062.
  • One particular preferred solvent that is used in the Example below is diisopropyl ketone (DIPK).
  • DIPK diisopropyl ketone
  • the content of the fluorine-containing powder, prior to the heating step of the method described below is less from 1 to 120 parts by mass per 100 parts by mass of the solvent.
  • the process for forming the functionalized fluorine-containing resinous powder in accordance with the present invention includes, in general, mixing the fluorine- containing powder and the compound in a solvent and reacting one at least one of the reactive functional groups of the compound with a corresponding one of the functional groups of the fluorine-containing powder.
  • the process or forming the functionalized fluorine-containing resinous powder in accordance with the present invention includes first providing the fluorine-containing powder having at least one functional group as described above.
  • the fluorine-containing powder can be either the ethylene/tetrafluoroethylene copolymer powder having at least one functional group or the tetrafluoroethylene/perfluoroalkylvinylether copolymer powder having at least one functional group, or combinations of both powders, as described above.
  • these fluorine- containing powder of either of the powders are formed in a solution polymerization process, as described above.
  • the fluorine-containing powder, the compound, and the solvent are mixed together to form a mixture, wherein the fluorine-containing powder is not dissolved in the solvent (and hence remains in a non-dissolved state).
  • the compound is dissolved in the solvent and is therefore in a dissolved state, whereas in other embodiments the compound remains in a non-dissolved state.
  • one of the at least one reactive functional group of the compound reacts with a corresponding one of the at least one functional group of the functional groups of the fluorine- containing powder to form the functionalized fluorine-containing resinous powder having at least one reactive functional group.
  • the mixture is heated to a temperature from 30 degrees Celsius to a temperature below the melting point of the fluorine-containing powder, such as less than 250 degrees Celsius.
  • the heating of the mixture is believed to increase the flowability of the compound and/or of the fluorine-containing powder, therein promoting the reaction of the one reactive functional group of the compound with the corresponding one functional group of the fluorine- containing powder.
  • the heating step proceeds for a sufficient period of time to ensure the reaction of the one reactive functional group of the compound with the corresponding one functional group of the fluorine-containing powder.
  • the molar content of the reactive functional group is preferably greater than the molar content of functional group, and more preferably wherein the molar ratio is 2: 1 or higher, as described above. Even more preferably, the compound, or at least a portion of the compound, has two or more reactive functional groups per molecule (i.e., is difunctional or higher) to ensure that the functionalized fluorine-containing resinous powder includes the at least one reactive group (i.e., the functionalized fluorine-containing resinous powder includes the at least one reactive group contributed from the compound).
  • the functionalized fluorine-containing resinous powder includes a reactive functional group that is selected from an amino group, an amide group, a carbonyl group, a hydroxy group, an isocyanate group, an epoxy group, a vinyl group and a nitrile group.
  • the reactive functional group is contributed from the compound during the reaction.
  • reaction continues for a sufficient amount of time to ensure reaction of the one reactive functional group of the compound s with the corresponding one functional group of the fluorine-containing powder, typically while maintaining the temperature from 30 degrees Celsius to a temperature below the melting point of the fluorine-containing powder, as noted above.
  • a sufficient amount of time, or sufficient time may vary depending upon the compositions of the components of the mixture, but typically occurs with a time period between a few minutes and a few hours.
  • the temperature of the mixture is reduced below 30 degrees Celsius, which may result in a powder precipitate being formed.
  • the solvent is then removed, resulting in a powder product remaining.
  • the powder product i.e., the functionalized fluorine-containing resinous powder
  • the resultant functionalized fluorine-containing resinous powder when analyzed, has a particle diameter size of 400 micrometers or less, a melting point of 150 degrees Celsius or more, and a specific gravity of 1.5 or more.
  • the functionalized fluorine-containing resinous powder, formed in accordance with the present invention offers numerous advantages in terms of the resultant product, processing and subsequent use over known methods.
  • the process is simple and does not require special equipment associated with melting the fluorine-containing powder having the at least one functional group in order to be reacted with the compound.
  • the methods do not require expensive solvents needed for dissolving the fluorine-containing powder having the at least one functional group.
  • the functionalized fluorine-containing resinous powder is formed has a particle diameter size of 400 micrometers or less and provide advantages in terms of adhesive properties over functionalized fluorine-containing powders not having the additional reactive functional group contributed by the compound.
  • Such compounds may also retain, or may enhance, further properties of heat resistance, chemical resistance, water resistance, oil resistance, weather resistance, aging resistance, gas barrier properties, fuel barrier properties, release properties, non stickiness, antifouling properties, dye adhesion resistance and unelution properties, as compared with a functionalized fluorine-containing ETFE or PFA copolymer powder or non-functionalized ETFE or PFA copolymer powder.
  • the functionalized fluorine-containing resinous powder is easily integrated into further products, such as molded materials or prepregs (such as carbon fiber prepregs), without requiring an additional processing step for reducing particle diameter size that are associated with a solid, functionalized fluorine-containing resinous powder formed by a different method.
  • a 500 milliliter three neck flask was utilized to perform the reaction, in which a water flux line was coupled to one of the necks of the flask. Nitrogen gas was introduced through a second neck in the flask for five minutes, and a magnetic stir bar was placed into a third neck of the flask.
  • Example A and Sample B Two separate samples (Sample A and Sample B) of low temperature melt ETFE copolymers including at least one anhydride-functional group, sold under the tradename Fluon® by AGC Chemicals, Europe) were placed into a three-neck flask, along with hexamethylene diamine (HMD, specific gravity 0.89) and diisopropyl ketone (DIPK, specific gravity 0.81) (see Tables 1A and 1B below).
  • HMD hexamethylene diamine
  • DIPK diisopropyl ketone
  • the flask was sealed, the stir bar was implemented with an air-driven stirrer, and the flask was placed on a heating mantle. Cooling water was into the flux line through the right flask by opening water control valve. The mantle heater was turned on to heat the flask for 2 at a temperature of 123 degrees Celsius to control the boiling point of the DIPK. During this process, the HMD dissolved into the DIPK, while the Samples A and B, respectively, were not dissolved.
  • the mantle heater was turned off, and the temperature within the flask was returned to room temperature. A precipitate was observed in the flask, which was filtered. The filtered powder was dried on an aluminum plate for a day. The obtained powder of each sample was rinsed with additional DIPK at least two times and was dried on an aluminum plate in an oven for 3 hours.

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Abstract

Une méthode de formation d'une poudre résineuse contenant du fluor fonctionnalisée comprend la fourniture d'une poudre contenant du fluor ayant au moins un groupe fonctionnel et un composé ayant au moins un groupe fonctionnel réactif réagissant avec le ou les groupes fonctionnels. Un solvant est combiné avec la poudre contenant du fluor et le composé pour former un mélange, la poudre contenant du fluor n'étant pas dissoute dans le solvant. L'un parmi le ou les groupes fonctionnels réactifs du composé dissous est mis à réagir avec un groupe fonctionnel correspondant du ou des groupes fonctionnels de la poudre non dissoute pour former la poudre résineuse contenant du fluor fonctionnalisée comprenant au moins l'un du ou des groupes fonctionnels réactifs. La poudre résineuse contenant du fluor fonctionnalisée formée a un diamètre moyen de particule de 400 micromètres ou moins, tel que 80 micromètres ou moins.
PCT/US2019/032142 2018-07-27 2019-05-14 Poudres résineuses contenant du fluor fonctionnalisées et méthodes de formation associées WO2020023102A1 (fr)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7192638B2 (en) * 2001-05-09 2007-03-20 Daikin Industries, Ltd. Fluorine-containing coating composition, primer for ETFE-based coatings, and coated article
US20130053493A1 (en) * 2010-04-16 2013-02-28 Asahi Glass Company, Limited Method for producing fluorinated copolymer composition, coating composition, article having coating film, and molded product
US20140342155A1 (en) * 2012-02-22 2014-11-20 Asahi Glass Company, Limited Fluorinated copolymer composition, molded product and electric wire
US20170088651A1 (en) * 2014-06-24 2017-03-30 Asahi Glass Company, Limited Ethylene/tetrafluoroethylene copolymer, method for its production, powder coating material and molded article

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6559238B1 (en) * 1998-06-29 2003-05-06 E. I. Du Pont De Nemours And Company Thermally cross-linked fluoropolymer
JP2001081261A (ja) * 1999-09-09 2001-03-27 Asahi Glass Co Ltd アニオン交換体ポリマー溶液

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7192638B2 (en) * 2001-05-09 2007-03-20 Daikin Industries, Ltd. Fluorine-containing coating composition, primer for ETFE-based coatings, and coated article
US20130053493A1 (en) * 2010-04-16 2013-02-28 Asahi Glass Company, Limited Method for producing fluorinated copolymer composition, coating composition, article having coating film, and molded product
US20140342155A1 (en) * 2012-02-22 2014-11-20 Asahi Glass Company, Limited Fluorinated copolymer composition, molded product and electric wire
US20170088651A1 (en) * 2014-06-24 2017-03-30 Asahi Glass Company, Limited Ethylene/tetrafluoroethylene copolymer, method for its production, powder coating material and molded article

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